Phosphorus: An Anode of Choice for Sodium ion Batteries - ACS

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Phosphorus: An Anode of Choice for Sodium ion Batteries Jiangfeng Ni, Liang Li, and Jun Lu ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.8b00312 • Publication Date (Web): 06 Apr 2018 Downloaded from http://pubs.acs.org on April 6, 2018

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ACS Energy Letters

Phosphorus: An Anode of Choice for Sodium-ion Batteries Jiangfeng Ni*a, Liang Li*a, and Jun Lu*b a

College of Physics, Optoelectronics and Energy, Center for Energy Conversion Materials & Physics

(CECMP), Soochow University, Suzhou 215006, P. R. China b

Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue,

Lemont, Illinois 60439, United States

Abstract Phosphorus (P) offers a high theoretical capacity of 2596 mAh g−1, and thus has been intensively pursued as one of the most promising anodes for sodium-ion batteries. However, sodium storage in P anodes is facing significant technical challenges in terms of poor conductivity, large volume swelling, and unstable solid-electrolyte interphase. These challenges need to be well mitigated before P material can be deployed in full batteries. In this perspective, we summarize the latest research progress in the development of P anodes. We focus on the design principle and criteria of efficient P anodes and materials strategies that mainly leverage on the knowledge accumulated for lithium anode of silicon. We also highlight the decisive role that theoretical simulation and in situ techniques play in addressing these difficulties associated with P materials.

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Sodium-ion batteries (SIBs) are a core energy storage device that can meet the needs for scalable and affordable stationary applications such as smart grid and renewable energy.1-4 Sharing a similar storage mechanism, SIBs could be a complementary alternative to current Li-ion technology. They adopt earth abundant elements and low-cost raw materials, and could offer energy and power fully comparable to current Li-ion systems, given that high-capacity anode is coupled with P2-Na2/3Fe1/2Mn1/2O2 cathode. Versatile sodium (Na) anode materials have been developed, but mostefforts have been devoted to hard-carbon materials, which usually exhibit a capacity limited to around 200 mAh g−1.5-6 Alloying type materials are capable of offering a larger capacity versus carbon with suitable sodiation potentials.7 Among the possible candidates for Na anode, phosphorus (P) has captured the most interest because of its extremely high theoretical capacity of 2596 mAh g−1,8 as well as an abundant resource and environmental benignity. P is the most abundant pnictogen element, ranking 11 in the Earth’s crust with an abundance of 0.105%. It has three most common allotropes of white P, red P and black P, with strikingly different structures illustrated in Figure 1.9 White P consists of tetrahedral P4 molecules, in which each atom is bound to the other three atoms by a single bond. White P is the least stable and the most toxic of the allotropes, and therefore it is in principle ruled out in SIB application. Red P is much more stable and can be directly obtained from white P by mild heating (~250 °C) or exposing to sunlight. Red P has a chain-like structure which can be viewed as a derivative of P4 wherein one P-P bond is broken, and one additional bond is formed with the neighboring tetrahedron.Black P is the most thermodynamically stable allotrope, and can be prepared by heating P under high pressure. It has remarkably different properties from other allotropes as it is black, flaky, and composed of puckered sheets of linked atoms, reminiscent of graphite. Pure red P is electronically insulating and was formerly considered electrochemically inactive toward Li+ ions, while black P is a semiconductor with a narrow bandgap of 0.34 eV and thus suitable for energy storage.10 In 2007, Park and Sohn have successfully transformed red P into orthorhombic black P using a high-energy mechanical milling technique at ambient temperature and pressure.11As Figure 2 shows, the resultant black P delivered a high lithiationcapacity of 1814 mAh g−1. Lithiation in black P involves a series of reactions from P→LixP→LiP→Li2P→Li3P. This opens up a new stage for the research of P based lithium anodes. By limiting the content of red P (~30%), an average capacity of 750 mAh g−1 (2413 mAh g−1 based on red P) can be sustained over 55 cycles.12 The success of P anode in Li storage inspires the research on its application in Na. Although experimental studies suggest that Na3P is the final sodiation product of P, identification on other phases upon the sodiation process remains unclear due to their amorphous nature. Therefore, theoretical simulation based on first-principles study could provide valuable insight into the sodiation process.13 By ab initio study, Mayo et al. have pointed out sodiation in P is analogous to lithiation, although the sodiation potential 2


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ACS Energy Letters

(~0.3V, vs. Na+/Na) is much lower than that of lithiation (~0.8 V, vs. Li+/Li).8 In 2013, Qian et al.14 and Kim et al.15 have almost simultaneously reported amorphous composite consisting of 70% red P and 30% carbon as sodium anode. A reversible capacity beyond 1500 mAh g−1 is sustained over several tens of cycles. Since their pioneering work, grand efforts have been devoted to searching for highly active and stable P electrodes.Because P and Si share several common features upon sodiation and lithiation, respectively, such as poor electrical conduction (or poor interlayer conduction for black P), huge volume change of 400%, and unstable solid-electrolyte interphase (SEI).16 The identification of similarities in the materials suggests that they can share principles and criteria of design, and thus knowledge accumulation for Si anode can be directly transplanted to assist the research of P electrodes. In this perspective, we will briefly summarize the latest development of P material for SIBs and try to highlight major technical challenges facing P rather than to give an exhausting overview of related work (excellent reviews can be found in literature17-21). We specifically identify these challenges from the comparison of P with Si, as in many regards, sodiation of P resemble lithiation of Si. By such a comparison, we hope this perspectivecould provide valuable insights to the design and practical deployment of anode materials with large capacity.

Issues facing P anode Conductivity issue. Red P is commercially available and cheap, well adapted to scalable electrochemical application, and thus will be the focus of the discussion in this perspective. Despite its harsh synthesis, black P is appealing for high-power and energy application owing to its narrow band gap. Hence, typical examplespertaining to black P will also be discussed. As is generally known, the conduction of electrode materials is playing the key role. Pure Si is a semiconductor with an electrical conductivity of 4×10−6 S cm−1, while red P is a molecular crystal with a much lower conductivity of ~10−14 S cm−1 at room temperature.10 Huang et al. have demonstrated carbon coating could improve the Si nanowire electrodes.22 By analogy, red P can be improved with carbon wrapping, which can be realized by several ways such as doping (introduction of carbon into P bulk), compositing (strong interaction between carbon and P), and hybridizing (weak interaction between carbon and P). The most common wrapping is realized by mixing red P with carbon nanoparticles (such as carbon black) via ball-milling.14-15 Through this vigorous milling process, red P clusters are dispersed in a conductive carbon matrix. Nonetheless, this approach generally involves long balling duration (24-100 h) and heavy loading of carbon (≥ 30 wt.%), and the disperse has not always been homogeneous.23 Consequently, the resulted P/C composite only affords a modest capacity of about 1000 mAh g−1 based on the mass of the composite, and the rate capacity is yet satisfactory. To decrease the carbon portion, additional conductive agents such as Cu24 and Ti2P25 has been incorporated, resulting in improvement 3



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to some extent. A more efficient way is to deposit vapor of P into porous carbon framework, as commercialred P has a low sublimation temperature.26 This vaporization-condensation way ensures a homogeneous coverage of red P on porous carbon. Moreover, porous carbon serves as both an electrical pathway and a mechanical backbone to support P nanoparticles.27 Intrinsic flexibility and functionality render this methodology extremely effective for the synthesis of P anodes. It should be pointed out that carbon black suffers from a large junction contact resistance when used as a conductive additive.28 Carbon nanomaterials such as 1D carbon nanotube (CNT) and 2D graphene or reduced graphene oxide (rGO) show better conduction and electrical wrapping capability.29-30 They could build a better wiring network even at lower threshold versus black carbon.31-33 In this regard, Li et al. reported a simple hand-grinding mixture of microsized red P and multiwalled CNTs (7:3) affording a reversible Na capacity of 1675 mAh g−1.34 Despite its poor cycling, the simple hybrid makes a great impact in the research on Na materials. If the hybridizing process was elaborated, an unprecedented capacity retention of 80% over 2000 cycles could be achieved for CNT wired red P.35 Moreover, if the interaction between active species and CNT is chemical (strongly coupled), the activity and reversibility of materials P/CNT could be simultaneously boosted.36 Song et al. so designed a system in which red P was chemically bonded to carboxyl-groups-functionalized CNTs via P–O–C bonds.37 Due to chemical bonding-induced synergetic effects, as schematically illustrated in Figure 3, the P–CNT composite anode delivered a discharge capacity of 2134 mAh g−1 (based on the mass of P) and retained ∼92% of this value over 100 cycles. The same group has also applied this strategy to P/graphene hybrid.38 As expected, the strongly coupled hybrid showed a high sodiation activity and duration, as graphene enables good interfacial contact with particles and prevents particles from aggregation during volume variation. In all cases, the presence of functional groups is a prerequisite to fulfilling the chemical bonding. Volume swelling issue. Similar to the widely studied Si anodes, material pulverization and fracture induced by large volume swelling cause the loss of electrical contact of P electrode and thus the rapid capacity fade. A myriad of engineering strategies have been established to address this swelling issue, mainly taking profit of the advancement of knowledge accumulated for Si anode. One notable approach is to use amorphous P electrode rather than the crystalline one.14-15 The rich defects and vacancies in amorphous structure, which serve to mitigate the volume swelling and associated stress, are possibly responsible for the improvement.39 A parallel design in Si anode has previously been proposed by Cui et al.40 Another straightforward strategy is to design hollow or porous structures whose empty part provides sufficient space for the free expansion of the electrode.41-43 P nanospheres via a gas-bubble-directed solvothermal synthesis demonstrated a capacity of 1365 mAh g−1 for Na+ ions and an excellent cycling life of 600 cycles.42 Zhang et al. designed a porous P/nitrogen-doped graphene (P@GN) paper and achieved a superior capacity retention of >85% over 350 cycles.43 More 4


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ACS Energy Letters

interestingly, theyconducted a direct in situ HRTEM study of the P@GN anode upon sodiation to reveal its structural changes during Na cycling. As Figure 4 shows, the P@GN nanosheet exhibits free expansion along both longitudinal and transverse directions without trace of structural degradation even after entiresodiation. This result confirms that the porous P@GN paper can effectively buffer the volume swelling during Na uptake. This porous structures can also be realized by 3D architecture design, which allows for the free expansion of the electrode through the height direction.44-45 Alternatively, the volume swelling can be controlled by a confined space such as nanopore, as the swelling degree is proportional to the number of Na+ ion uptake per formula unit.46-47 The confinement effect of pores limits the sodiation reaction to form reversible NaxPy intermediates rather than the final unstable product of Na3P, eventually raising the cycling stability.27 A good case in point was reported by Li et al., who took ZIF-8-derived microporous carbon matrix as a confinement.48 The P composite displayed a reversible capacity of about 600 mAh g−1 at 150 mA g−1 (based on the mass of the composite) and retains a capacity of ~450 mAh g−1 at1 A g−1 after 1000 cycles. With itslayered structure and considerable in-plane electrical conductivity, black P is beneficial for realizing both high-power and energy densities.10 Carbon additives are frequently utilized in the processing of black P electrodes, severing as an elastic buffer agent that helps relieve the stress and strain associated with volume swelling.49 In some cases, black P was subject to surface engineering with purposely designed species such as rGO50 or polymer51. Such a design achieved enhanced charge transfer kinetics and super surface wettability with electrolyte. Phosphorene referring to single- or few-layer black Phas emerged as a promising 2D nanomaterial, and can be prepared by using an exfoliation method. Phosphorene has the potential application in the field of energy storage and SIB in particular.52-54 Sun et al. have designed a hybrid of a few phosphorene layers sandwiched between graphene layers showing a specificcapacity of 2,440 mAh g−1 (based on the mass of P only) and a capacity retention of 83% capacity over 100 cycles (Figure 5).55 In this case, the graphene layers work as a mechanical backbone and an electrical highway, enabling an efficient buffering of the anisotropic expansion of phosphorene layers and a rapid charge transfer between less-conductive phosphorene interlayers. SEI issue. When an anode is sodiated, a SEI will be formed on its surface due to side reactions caused mainly by the reduction of electrolytes. Depending on the type of electrode and electrolyte, a SEI layer may play a more or less protective role on the electrode structure, and significantly influence how Na+ ions move into the P (ionic transport and alloying kinetics) and how the electrons interact with the sodium (electron transport at the surface). This layer is usually dense and stable, electronically insulating but ionically conducting, in order to shut down further side reactions. Wu et al. designed a double-walled Si nanotube anodes to regulate the evolution of SEI, and achieved a retention of 85% over 6,000 times.56 Unlike Li anodes, Na anodes form a rough and nonuniform SEI 5



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layer, because the surface film of Li anode is thick and mainly composed of organic compounds while that in Na anodes is thin and composed of inorganic compounds.5 This situation could be more serious in P anodes because a large volume change occurs during electrochemical cycling. The SEI of P cracks upon Na cycling, and the exposed fresh electrode surface is expected to result in continuous growth of thick SEI layer, leading to low Coulombic efficiency and large electrode resistance.57 To construct a stable SEI layer on the surface of P anodes, a great deal of research has been conducted already, focusing on the deployment of electrolytes additives and new binders. Electrolyte reduction at the anode side gives rise to sodium alkyl carbonates, which can be re-oxidized at the opposite cathode, thereby limiting capacity utilization and causing current inefficiency. Hence, electrolyte additives are highly desired to tune the formation and the composition of SEI. Typical additives such as fluoroethylene carbonate (FEC) and vinylidene carbonate (VC) are capable of forming a SEI film on anodes prior to electrolyte components, thereby passivating the electrodes to further side reactions with solvents. Researchers from Komaba’s group have done excellent work on this topic. They revealed an improved reversibility of red P electrode when utilizing FEC as additive, as the FEC-derived P species and sodium fluoride could suppress electrolyte decomposition.58 Using TOF-SIMS analysis, they could identify that the outermost surface layer of SEI of black P in the VC additive is composed of both inorganic and organic compounds, while that in FEC is composed mainly of inorganic compounds such as NaF and Na2CO3 (Figure 6).59However, there is much research to be done on solvents, Na supporting electrolyte salts, and additives to understand the reaction mechanisms and enable stable cycling properties. Another approach is to use polyacrylic acid or carboxymethyl cellulose instead of polyvinylidene fluoride binder, as their cross-linked interconnection is expected to increase the robustness and enhance cycle performance of the P-based materials.15 Similar methods have also been reported for Si anode using a Na-alginate binder.60

Summary and outlook Akin to Si in Li-ion system, P is promising for Na-ion technology because of its huge capacity and suitable redox potential. Utilization of phosphorus anode in practice is yet far from reality. Several core challenges including poor conductivity, large volume change, and unstable SEI, have been identified. Tackling these issues is a prerequisite for the successful deployment of phosphorus in SIBs. During the past years, remarkable material development has been achieved, largely relying on nanotechnology accumulated for Li-ion systems.61 In particular, nanostructured P/C composite could exhibit a high capacity and reasonable cyclability. However, such P/C composites that have been most explored in the literature cannot meet the practical need because they generally require a significant portion (>30 wt.%) ofcarbon, which results in alow capacity on the composite level and a low tap 6


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ACS Energy Letters

density. Hence, exploring the full capacity of P with a durable cycling and reasonable rate capability at a high loading remains a core challenge. Towards this goal, several directions might be considered. First, coupling of several strategies in one design might be a promising direction. With nanostructuring and other conductive agents, carbon portion and volume in the P/C composite can be evidently reduced. This engineering would make P/C electrode material intrinsically affordable and reproducible. Second, 3D architecture design would be another possible solution. Like Si nanowire array, 3D nanostructures of P could circumvent the volume swelling issue as they can accommodate large strain without pulverization. In addition, the direct electrical conduction, large accessible surface, and nanoscale diffusion distance offer a possibility to address the electrochemical activity issue.

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Third, SEI plays a key role in the

electrode stability and current efficiency.However, SEI is compositionally complex and heterogeneous, and very sensitive to oxygen and water content, makingin situ or operando techniques a necessity.65 Forth,understanding the phase evolution upon Na+ cycling is critical to the future development of P materials.However, as Na3P is the only crystalline phase of sodium phosphides, the identification of other phases is susceptible. Thus, first principles computation using DFT might offer a fresh opportunity to probe the phase evolution.13, 66-67Fifth, when P anode comes to the practice, we need to consider its safety since white P is toxic and may remain in the materials. We might suggest a long heating process at temperatures above 250 °C to consume all white P species. Last but not least, only few works have reported full cells based on P anodes, such as P//Na3V2(PO4)3,32 P//C-Na3V2(PO4)2F3,33 and P//Na0.66Ni0.26Zn0.07Mn0.67O2.49 Due to the marked mismatch in the capacity between the anode and cathode, the design and assembly of full cells is challenging, but the knowledge accumulated for Si anodes again can be leveraged. Finally, we anticipate that these research directions could be used to predict and design highly functional and durable phosphorus anodes. With extensive efforts, the deployment of phosphate electrode in SIBs will be foreseen in the near future.

■ASSOCIATED CONTENT ■ AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (J. Ni) *E-mail: [email protected] (L. Li) *E-mail: [email protected] (J. Lu) 7



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Notes The authors declare no competing financial interest.

Biographies Prof. Jiangfeng Ni received his Ph.D. degree in Chemistry from Peking University in 2008. After three-year postdoctoral research, he moved to Soochow University, China in 2011. At present Dr. Ni is a professor of Physics and leads a team working on various types of energy storage systems. Prof. Liang Li received his Ph.D. degree from Institute of Solid State Physics, Chinese Academy of Sciences. From 2007 to 2012, he worked at the National University of Singapore, Singapore, National Institute of Advanced Industrial Science and Technology & National Institute for Materials Science, Japan, and the University of Western Ontario, Canada. Since August 2012, he is a full professor in Soochow University, China. His group (http://ecs.suda.edu.cn) focuses mainly on energy conversion materials for solar cells, photodetectors, and electrochemical batteries. His publications have generated 7000 citations. He currently has an H‐index 46. Dr. Jun Lu is a chemist at Argonne National Laboratory. His research interests focus on electrochemical energy storage and conversion technology. Dr. Lu earned his bachelor degree in Chemistry Physics from University of Science and Technology of China (USTC) in 2000. He completed his Ph.D. in the Department of Metallurgical Engineering at University of Utah in 2009 with major research on metal hydrides for reversible hydrogen storage applications.

■ACKNOWLEDGEMENTS The authors acknowledge the financial support of the National Natural Science Foundation of China (Grant Nos. 51672182, 51772197, 51422206), the Thousand Young Talents Plan, the Jiangsu Natural Science Foundation (Grant Nos. BK20151219 and BK20140009), the Key University Science Research Project of Jiangsu Province (Grant No. 17KJA430013), the 333 High-Level Talents Project in Jiangsu Province, the Six Talent Peaks Project in Jiangsu Province, and of the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). J. Lu gratefully acknowledges support from the U. S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357.

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(39) Ding, X.; Huang, Y.; Li, G.; Tang, Y.; Li, X.; Huang, Y. Phosphorus nanoparticles combined with cubic boron nitride and graphene as stable sodium-ion battery anodes. Electrochim. Acta 2017,235, 150-157. (40) Cui, L.-F.; Yang, Y.; Hsu, C.-M.; Cui, Y. Carbon-Silicon Core-Shell Nanowires as High Capacity Electrode for Lithium Ion Batteries. Nano Lett. 2009,9, 3370-3374. (41) Li, W.; Yang, Z.; Li, M.; Jiang, Y.; Wei, X.; Zhong, X.; Gu, L.; Yu, Y. Amorphous red phosphorus embedded in highly ordered mesoporous carbon with superior lithium and sodium storage capacity. Nano Lett. 2016,16, 1546-1553. (42) Zhou, J.; Liu, X.; Cai, W.; Zhu, Y.; Liang, J.; Zhang, K.; Lan, Y.; Jiang, Z.; Wang, G.; Qian, Y. Wet-chemical synthesis of hollow red-phosphorus nanospheres with porous shells as anodes for high-performance lithium-ion and sodium-ion batteries. Adv. Mater. 2017,29, 1700214. (43) Zhang, C.; Wang, X.; Liang, Q.; Liu, X.; Weng, Q.; Liu, J.; Yang, Y.; Dai, Z.; Ding, K.; Bando, Y.; Tang, J.; Golberg, D. Amorphous phosphorus/nitrogen-doped graphene paper for ultrastable sodium-ion batteries. Nano Lett. 2016,16, 2054-2060. (44) Pei, L.; Zhao, Q.; Chen, C.; Liang, J.; Chen, J. Phosphorus nanoparticles encapsulated in graphene scrolls as a high-performance anode for sodium-ion batteries. ChemElectroChem 2015,2, 1652-1655. (45) Gao, H.; Zhou, T.; Zheng, Y.; Liu, Y.; Chen, J.; Liu, H.; Guo, Z. Integrated carbon/red phosphorus/graphene aerogel 3D architecture via advanced vapor-redistribution for high-energy sodium-ion batteries. Adv. Energy Mater. 2016,6, 1601037. (46) Liang, H.; Ni, J.; Li, L. Bio-inspired engineering of Bi2S3-PPy yolk-shell composite for highly durable lithium and sodium storage. Nano Energy 2017,33, 213-220. (47) Ni, J.; Jiang, Y.; Wu, F.; Maier, J.; Yu, Y.; Li, L. Regulation of breathing CuO nanoarray electrodes for enhanced electrochemical sodium storage. Adv. Funct. Mater. 2018,28, 1707179. (48) Li, W.; Hu, S.; Luo, X.; Li, Z.; Sun, X.; Li, M.; Liu, F.; Yu, Y. Confined amorphous red phosphorus in mof-derived n-doped microporous carbon as a superior anode for sodium-ion battery. Adv. Mater. 2017,29, 1605820. (49) Xu, G. L.; Chen, Z.; Zhong, G. M.; Liu, Y.; Yang, Y.; Ma, T.; Ren, Y.; Zuo, X.; Wu, X. H.; Zhang, X.; Amine, K. Nanostructured black phosphorus/ketjenblack-multiwalled carbon nanotubes composite as high performance anode material for sodium-ion batteries. Nano Lett. 2016,16, 3955-3965. (50) Liu, H.; Tao, L.; Zhang, Y.; Xie, C.; Zhou, P.; Liu, H.; Chen, R.; Wang, S. Bridging Covalently Functionalized Black Phosphorus on Graphene for High Performance Sodium-ion Battery. Acs Appl. Mater. Interfaces 2017,9, 36849-36856. (51) Zhang, Y.; Sun, W.; Luo, Z.-Z.; Zheng, Y.; Yu, Z.; Zhang, D.; Yang, J.; Tan, H. T.; Zhu, J.; Wang, X.; Yan, Q.; Dou, S. X. Functionalized few-layer black phosphorus with super-wettability towards enhanced reaction kinetics for rechargeable batteries. Nano Energy 2017,40, 576-586. (52) Kulish, V. V.; Malyi, O. I.; Persson, C.; Wu, P. Phosphorene as an anode material for Na-ion batteries: A first-principles study. Phys. Chem. Chem. Phys. 2015,17, 13921-139218. (53) Chowdhury, C.; Karmakar, S.; Datta, A. Capping black phosphorene by h-BN enhances performances in anodes for Li and Na ion batteries. ACS Energy Lett. 2016,1, 253-259. (54) Huang, Z.; Hou, H.; Zhang, Y.; Wang, C.; Qiu, X.; Ji, X. Layer-tunable phosphorene modulated by the cation insertion rate as a sodium-storage anode. Adv. Mater. 2017,29, 1702372. (55) Sun, J.; Lee, H. W.; Pasta, M.; Yuan, H.; Zheng, G.; Sun, Y.; Li, Y.; Cui, Y. A phosphorene-graphene hybrid material as a high-capacity anode for sodium-ion batteries. Nat. Nanotechnol. 2015,10, 980-985. (56) Wu, H.; Chan, G.; Choi, J. W.; Ryu, I.; Yao, Y.; Mcdowell, M. T.; Lee, S. W.; Jackson, A.; Yang, Y.; Hu, L.; Cui, Y. 11



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Quotes 1. Phosphorus offers a great opportunity for sodium-ion batteries because of its high theoretical capacity of 2596 mAh g−1. 2. The identification of similarities in the materials suggests that they can share principles and criteria of design, and thus knowledge accumulation for Si anode can be directly transplanted to assist the research of P electrodes 3. Perspectives highlight the decisive role that theoretical simulation and in situ techniques play in addressing these difficulties related to P materials.

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Figures

Figure 1. Structures of phosphorus allotropes of (a) white P, (b) red P and (c) black P.

Figure 2. (a, b) X-ray diffraction patterns with color photo images and TEM images with corresponding lattice spacing: a) Red p; b) black P. (c) Electrochemical behaviors of various types of phosphorus.11 Reproduced with permission. Copyright 2007, Wiley-VCH.

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Figure 3. Schematic illustration of structure evolution of the phosphorus-base anode during cycling.37 Reproduced with permission. Copyright 2015, American Chemical Society.

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Figure 4. (a) Schematic illustration of an individual P@GN nanosheet prototype sodium battery device under in situ HRTEM sodiation. (b) TEM image of the nano-SIB at the initial stage. (c−d) Time-lapse TEM images and selected area electron diffraction (SAED) patterns of sodiated P@GN nanosheet during first discharging: 15 and 120 s. (e−f) Time-dependent TEM images of desodiated P@GN nanosheet during first charging: 5 and 120 s. The insets in (b), (d), and (f) show the corresponding schematic atomic structures. The inset in (e) depicts the corresponding SAED pattern. Scale bar: 100 nm. (g) Schematic illustration of the first sodiation-desodiation process of the P@GN nanosheet.43 Reproduced with permission. Copyright 2016, American Chemical Society.

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ACS Energy Letters

Figure 5.Electrochemical characterization of the phosphorene–graphene anode for sodium-ion batteries. (a) Reversibledesodiation capacities for the first 100 galvanostatic cycles of various phosphorene–graphene electrodes with different carbon–phosphorus mole ratios (C/P) of 1.39, 2.07, 2.78 and 3.46, between 0.02 and 1.5 V at a current density of 0.05 A g−1. (b) Galvanostatic discharge–charge curves of the phosphorene–graphene (48.3 wt% P) anode plotted for the first, second and 50th cycles. (c) Volumetric and mass capacities at different current densities (from 0.05 to 26 A g−1). (d) Reversible desodiation capacity and Coulombic efficiency for the first 100 galvanostatic cycles of the phosphorene/graphene (48.3 wt% P) anode tested under different currents. (e) HRTEM image of the cross-section of the phosphorene–graphene hybrid. Scale bar, 2 nm.55 Reproduced with permission. Copyright 2015, Nature publishing group.

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Figure 6.TOF-SIMS positive ion spectra for the black P/PANa electrodes after the second charge/discharge cycle in 1.0 mol dm−3 NaPF6/EC/DEC: (a) additive-free, (b) FEC, and (c) VC.59 Reproduced with permission. Copyright 2016, American Chemical Society.

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ACS Energy Letters

Table of Content 352x235mm (72 x 72 DPI)


Phosphorus: An Anode of Choice for Sodium ion Batteries - ACS

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