Gold nanocrystals with variable index facets as highly effective cathode catalysts for lithium–oxygen batteries
Source abstract
Abstract
Cathode catalysts are the key factor in improving the electrochemical performance of lithium–oxygen (Li–O2) batteries via their promotion of the oxygen reduction and oxygen evolution reactions (ORR and OER). Generally, the catalytic performance of nanocrystals (NCs) toward ORR and OER depends on both composition and shape. Herein, we report the synthesis of polyhedral Au NCs enclosed by a variety of index facets: cubic gold (Au) NCs enclosed by {100} facets; truncated octahedral Au NCs enclosed by {100} and {110} facets; and trisoctahedral (TOH) Au NCs enclosed by 24 high-index {441} facets, as effective cathode catalysts for Li–O2 batteries. All Au NCs can significantly reduce the charge potential and have high reversible capacities. In particular, TOH Au NC catalysts demonstrated the lowest charge-discharge overpotential and the highest capacity of ~20 298 mA h g−1. The correlation between the different Au NC crystal planes and their electrochemical catalytic performances was revealed: high-index facets exhibit much higher catalytic activity than the low-index planes, as the high-index planes have a high surface energy because of their large density of atomic steps, ledges and kinks, which can provide a high density of reactive sites for catalytic reactions. Gold nanocrystals with high-index facets improve the electrochemical performance of lithium–oxygen batteries, find scientists in Australia. The high energy densities of lithium–oxygen batteries make them attractive for powering electric vehicles. The researchers investigated three differently shaped gold nanocrystals — cubic, truncated octahedral and trisoctahedral nanocrystals — for their effectiveness as cathode catalysts for lithium–oxygen batteries. They found that all three nanocrystals significantly reduced the charge potential while possessing high reversible capacities. Furthermore, the trisoctahedral nanocrystals, which have the highest index facets among three nanocrystals, exhibited the lowest charge–discharge overpotential and highest capacity. The researchers attribute the improved catalytic performance of crystals with high-index facets to higher index planes having greater surface energies resulting from the large density of atomic steps, ledges and kinks, which act as reactive sites for catalytic reactions. Polyhedral Au nanocrystals enclosed by a variety of index facets are prepared: cubic Au NCs enclosed by {100} facets; truncated octahedral Au NCs enclosed by {100} and {110} facets; and trisoctahedral Au NCs enclosed by 24 high-index {441} facets. It is found that high index facets exhibit much higher catalytic activity toward oxygen reduction and oxygen evolution reactions in Li–O2 batteries.
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Research context
OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Electrocatalysts for Energy Conversion
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (44)
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1. Bruce, P. G ., Freunberger, S. A ., Hardwick, L. J . & Tarascon, J.-M . Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012).10.1038/nmat3191 ↗
2. Whittingham, M. S . Lithium batteries and cathode materials. Chem. Rev. 104, 4271–4302 (2004).10.1021/cr020731c ↗
3. Mitchell, R. R ., Gallant, B. M ., Thompson, C. V . & Shao-Horn, Y . All-carbon-nanofiber electrodes for high-energy rechargeable Li–O2 batteries. Energy Environ. Sci. 4, 2952–2958 (2011).10.1039/c1ee01496j ↗
4. Li, F ., Zhang, T . & Zhou, H . Challenges of non-aqueous Li-O2 batteries: electrolytes, catalysts, and anodes. Energy Environ. Sci. 6, 1125–1141 (2013).10.1039/c3ee00053b ↗
5. McCloskey, B ., Bethune, D ., Shelby, R ., Girishkumar, G . & Luntz, A . Solvents’ critical role in nonaqueous lithium–oxygen battery electrochemistry. J. Phys. Chem. Lett. 2, 1161–1166 (2011).10.1021/jz200352v ↗
6. Lu, Y.-C ., Kwabi, D. G ., Yao, K. P. C ., Harding, J. R ., Zhou, J . & Zuin, L . The discharge rate capability of rechargeable Li–O2 batteries. Energy Environ. Sci. 4, 2999–3007 (2011).10.1039/c1ee01500a ↗
7. Lu, Y.-C ., Crumlin, E. J ., Veith, G. M ., Harding, J. R ., Mutoro, E ., Baggetto, L ., Dudney, N. J ., Liu, Z . & Shao-Horn, Y . In situ ambient pressure X-ray photoelectron spectroscopy studies of lithium-oxygen redox reactions. Sci. Rep. 2, 715 (2012).10.1038/srep00715 ↗
8. Hsieh, Y.-C ., Zhang, Y ., Su, D ., Volkov, V ., Si, R ., Wu, L ., Zhu, Y ., An, W ., Liu, P ., He, P ., Ye, S ., Adzic, R. R . & Wang, J. X . Ordered bilayer ruthenium–platinum core-shell nanoparticles as carbon monoxide-tolerant fuel cell catalysts. Nat. Commun 4, 2466 (2013).10.1038/ncomms3466 ↗
9. Xu, J.-J ., Wang, Z.-L ., Xu, D ., Zhang, L.-L . & Zhang, X.-B . Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries. Nat. Commun. 4, 2438 (2013).10.1038/ncomms3438 ↗
10. Black, R ., Lee, J. H ., Adams, B ., Mims, C. A . & Nazar, L. F . The role of catalysts and peroxide oxidation in lithium–oxygen batteries. Angew. Chem. 125, 410–414 (2013).10.1002/ange.201205354 ↗
11. Hummelshøj, J ., Luntz, A . & Nørskov, J . Theoretical evidence for low kinetic overpotentials in Li–O2 electrochemistry. J. Chem. Phys. 138, 034703 (2013).10.1063/1.4773242 ↗
12. Tao, A. R ., Habas, S . & Yang, P . Shape control of colloidal metal nanocrystals. Small 4, 310–325 (2008).10.1002/smll.200701295 ↗
13. Somorjai, G. A . & Blakely, D . Mechanism of catalysis of hydrocarbon reactions by platinum surfaces. Nature 258, 580–583 (1975).10.1038/258580a0 ↗
14. Tian, N ., Zhou, Z. Y ., Sun, S. G ., Ding, Y . & Wang, Z. L . Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Science 316, 732–735 (2007).10.1126/science.1140484 ↗
15. Peng, Z. Q ., Freunberger, S. A ., Chen, Y. H . & Bruce, P. G . A reversible and higher-rate Li–O2 battery. Science 337, 563–566 (2012).10.1126/science.1223985 ↗
16. Ming, T ., Kou, X ., Chen, H ., Wang, T ., Tam, H. L ., Cheah, K. W ., Chen, J. Y . & Wang, J . Ordered gold nanostructure assemblies formed by droplet evaporation. Angew. Chem. 47, 9685–9690 (2008).10.1002/anie.200803642 ↗
17. Amadon, B ., Jollet, F . & Torrent, M . Gamma and beta cerium: LDA+U calculations of ground-state parameters. Phys. Rev. B 77, 155104(155101)–155104(155110) (2008).
18. Gonze, X ., Amadon, B ., Anglade, P.-M ., Beuken, J.-M ., Bottin, F ., Boulanger, P ., Bruneval, F ., Caliste, D ., Caracas, R ., Côté, M ., Deutsch, T ., Genovese, L ., Ghosez, Ph ., Giantomassi, M ., Goedecker, S ., Hamann, D. R ., Hermet, P ., Jollet, F ., Jomard, G ., Leroux, S ., Mancini, M ., Mazevet, S ., Oliveira, M. J. T ., Onida, G ., Pouillon, Y ., Rangel, T ., Rignanese, G.-M ., Sangalli, D ., Shaltaf, R ., Torrent, M ., Verstraete, M. J ., Zerah, G . & Zwanziger, J. W . ABINIT: first-principles approach to material and nanosystem properties. Comput. Phys. Commun. 180, 2582–2615 (2009).10.1016/j.cpc.2009.07.007 ↗
19. Perdew, J. P . & Wang, Y . Accurate and simple analytic representation of the electron-gas correlation-energy. Phys. Rev. B 45, 13244–13249 (1992).10.1103/PhysRevB.45.13244 ↗
20. Tasker, P. W . Stability of Ionic-Crystal Surfaces. J. Phys. C Solid St 12, 4977–4984 (1979).10.1088/0022-3719/12/22/036 ↗
21. Yu, Y ., Zhang, Q ., Liu, B . & Lee, J. Y . Synthesis of nanocrystals with variable high-index Pd facets through the controlled heteroepitaxial growth of trisoctahedral Au templates. J. Am. Chem. Soc. 132, 18258–18265 (2010).10.1021/ja107405x ↗
22. Tian, N ., Zhou, Z.-Y . & Sun, S.-G . Platinum metal catalysts of high-index surfaces: from single-crystal planes to electrochemically shape-controlled nanoparticles. J. Phys. Chem. C 112, 19801–19817 (2008).10.1021/jp804051e ↗
23. Van Hove, M . & Somorjai, G . A new microfacet notation for high-Miller-index surfaces of cubic materials with terrace, step and kink structures. Surf. Sci. 92, 489–518 (1980).10.1016/0039-6028(80)90219-8 ↗
24. Wang, Z. L . Transmission electron microscopy of shape-controlled nanocrystals and their assemblies. J. Phys. Chem. B 104, 1153–1175 (2000).10.1021/jp993593c ↗
25. Nikoobakht, B . & El-Sayed, M. A . Preparation and growth mechanism of gold nanorods (NRs) using seed-mediated growth method. Chem. Mater. 15, 1957–1962 (2003).10.1021/cm020732l ↗
26. Johnson, C. J ., Dujardin, E ., Davis, S. A ., Murphy, C. J . & Mann, S . Growth and form of gold nanorods prepared by seed-mediated, surfactant-directed synthesis. J. Mater. Chem. 12, 1765–1770 (2002).10.1039/b200953f ↗
27. Sau, T. K . & Murphy, C. J . Room temperature, high-yield synthesis of multiple shapes of gold nanoparticles in aqueous solution. J. Am. Chem. Soc. 126, 8648–8649 (2004).10.1021/ja047846d ↗
28. Millstone, J. E ., Wei, W ., Jones, M. R ., Yoo, H . & Mirkin, C. A . Iodide ions control seed-mediated growth of anisotropic gold nanoparticles. Nano Lett. 8, 2526–2529 (2008).10.1021/nl8016253 ↗
29. Ha, T. H ., Koo, H.-J . & Chung, B. H . Shape-controlled syntheses of gold nanoprisms and nanorods influenced by specific adsorption of halide ions. J. Phys. Chem. C 111, 1123–1130 (2007).10.1021/jp066454l ↗
30. Grzelczak, M ., Pérez-Juste, J ., Mulvaney, P . & Liz-Marzán, L. M . Shape control in gold nanoparticle synthesis. Chem. Soc. Rev. 37, 1783–1791 (2008).10.1039/b711490g ↗
31. Murphy, C. J ., Sau, T. K ., Gole, A. M ., Orendorff, C. J ., Gao, J ., Gou, L ., Hunyadi, S. E . & Li, T . Anisotropic metal nanoparticles: synthesis, assembly, and optical applications. J. Phys. Chem. B 109, 13857–13870 (2005).10.1021/jp0516846 ↗
32. Yu, Y ., Zhang, Q ., Lu, X . & Lee, J. Y . Seed-mediated synthesis of monodisperse concave trisoctahedral gold nanocrystals with controllable sizes. J. Phys. Chem. C 114, 11119–11126 (2010).10.1021/jp103840k ↗
33. Oh, S. H ., Black, R ., Pomerantseva, E ., Lee, J.-H . & Nazar, L. F . Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium–O2 batteries. Nat. Chem 4, 1004–1010 (2012).10.1038/nchem.1499 ↗
34. Laoire, C. O ., Mukerjee, S ., Abraham, K ., Plichta, E. J . & Hendrickson, M. A . Elucidating the mechanism of oxygen reduction for lithium-air battery applications. J. Phys. Chem. C 113, 20127–20134 (2009).10.1021/jp908090s ↗
35. Tian, N ., Zhou, Z. Y . & Sun, S. G . Electrochemical preparation of Pd nanorods with high-index facets. Chem. Commun. 12, 1502–1504 (2009).10.1039/b819751b ↗
36. Xie, X ., Li, Y ., Liu, Z.-Q ., Haruta, M . & Shen, W . Low-temperature oxidation of CO catalysed by Co3O4 nanorods. Nature 458, 746–749 (2009).10.1038/nature07877 ↗
37. Han, X. G ., He, H. Z ., Kuang, Q ., Zhou, X ., Zhang, X. H ., Xu, T ., Xie, Z. X . & Zheng, L. S . Controlling morphologies and tuning the related properties of nano/microstructured ZnO crystallites. J.Phys. Chem. C 113, 584–589 (2009).10.1021/jp808233e ↗
38. Somorjai, G. A . Chemistry in two dimensions: surfaces. Chemistry in Two Dimensions: Surfaces (1981).
39. Lebedeva, N. P ., Koper, M. T. M ., Feliu, J. M . & van Santen, R. A . Role of crystalline defects in electrocatalysis: mechanism and kinetics of CO adlayer oxidation on stepped platinum electrodes. J. Phys. Chem. B 106, 12938–12947 (2002).10.1021/jp0204105 ↗
40. Lu, Y.-C ., Gasteiger, H. A . & Shao-Horn, Y . Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries. J. Am. Chem. Soc. 133, 19048–19051 (2011).10.1021/ja208608s ↗
41. Ma, Y ., Kuang, Q ., Jiang, Z ., Xie, Z ., Huang, R . & Zheng, L . Synthesis of trisoctahedral gold nanocrystals with exposed high-index facets by a facile chemical method. Angew. Chem. 47, 8901–8904 (2008).10.1002/anie.200802750 ↗
42. Aurélie, D ., Bao, J. L ., Armstrong, G . & Bruce, P. G . An O2 cathode for rechargeable lithium batteries: the effect of a catalyst. J. Power Sources 174, 1177–1182 (2007).10.1016/j.jpowsour.2007.06.180 ↗
43. Oh, S. H . & Nazar, L. F . Oxide catalysts for rechargeable high-capacity Li–O2 batteries. Adv. Energy Mater 2, 903–910 (2012).10.1002/aenm.201200018 ↗
44. Lu, Y. C ., Gasteiger, H. A ., Parent, M. C ., Chiloyan, V . & Yang, S.-H . The influence of catalysts on discharge and charge voltages of rechargeable Li-Oxygen batteries. Electrochem. Solid-State Lett. 13, A69–A72 (2010).10.1149/1.3363047 ↗