Route of Irreversible Transformation in Layered Tin Thiophosphite and

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Route of Irreversible Transformation in Layered Tin Thiophosphite and Enhanced Lithium Storage Performance Eldho Edison, Apoorva Chaturvedi, Hao Ren, Sivaramapanicker Sreejith, Chwee Teck Lim, and Srinivasan Madhavi ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b01357 • Publication Date (Web): 26 Sep 2018 Downloaded from http://pubs.acs.org on September 28, 2018

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ACS Applied Energy Materials

Route of Irreversible Transformation in Layered Tin Thiophosphite and Enhanced Lithium Storage Performance Eldho Edison,a Apoorva Chaturvedi,a Hao Ren,a Sivaramapanicker Sreejith, *b,c Chwee Teck Lim*b,c,d and Srinivasan Madhavi*a a

School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang

Avenue, 639977, Singapore. b

the Center for Advanced 2D Materials, National University of Singapore, 6 Science Drive 2,

117546, Singapore. c

Biomedical Institute for Global Health Research and Technology, National University of

Singapore, 14 Medical Drive, 117546, Singapore. d

Department of Biomedical Engineering, National University of Singapore, 2 Engineering Drive

3, 117581, Singapore.

ACS Paragon Plus Environment

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KEYWORDS: lithium-ion batteries, metal thiophosphites, metal chalcogenides, anode, conversion, alloying

ABSTRACT

Novel materials with high lithium-storage capacities are indispensable to substantially increase the gravimetric and volumetric energy densities of lithium-ion batteries. In this context, metal thiophosphites (MTPs) possessing a layered structure are considered as ideal candidates to serve as alkali-ion hosts. Herein, the lithium storage properties of layered tin thiophosphite (SnPS3) crystals have been investigated in coin-cell configuration. The results reveal that SnPS3 undergoes a conversion and alloying reaction to deliver high lithiation capacities. The SnPS3 anode delivered a significant lithiation capacity of ~800 mAh g-1 at a specific current of 100 mA g-1. Moreover, the layered structure was able to accommodate the volume changes upon (de)lithiation as evident from its excellent cycling stability. Additionally, the SnPS3 anode demonstrated excellent rate capability as well and delivered ~315 mAh g-1 at a high specific current of 2 A g-1. Furthermore, the lithium-storage mechanism was investigated through cyclic voltammetry and ex-situ X-ray diffraction and X-ray photoelectron spectroscopy studies. Studies of SnPS3 anode in a full cell configuration by coupling with commercial LiNi0.33Co0.33Mn0.33O2 cathode is also presented. The outstanding electrochemical performance demonstrated by the SnPS3 anode calls for further research into this novel class of metal thiophosphites for energy storage applications.


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Introduction Ever since their inception in the 1990’s, lithium-ion batteries have been deployed in a myriad of applications ranging from portable devices like mobile phones and laptops to high energy and power expending electric vehicles. In the past decade, the pursuit of novel materials that can deliver higher energy densities than the conventional graphite anode spawned the research on “beyond intercalation” based materials.1-5 The primary objective was to develop high energy and high power batteries by making use of alloying and conversion-based materials that offer high gravimetric as well as volumetric energy densities. In this regard, lithium-alloying materials such as Sn, Si, P, among others, are of great interest as they offer manifold lithium storage capacities when compared to the conventional graphite anode.6-8 Additionally, metal chalcogenides such as MoS2, TiS2 and SnS2 have been intensely investigated as alkali-ion hosts and were found to deliver high storage capacities by means of reversible conversion reactions.4, 914

However, the alloying and conversion anodes present the challenges of rapid capacity fading

due to the extreme volume changes and the accompanied pulverization and loss of electrical contact. Metal thiophosphites (MTPs) are an intriguing class of layered materials with diverse tunable electrical, chemical and magnetic properties.15 The MTPs have layers of metal and phosphorous atoms sandwiched between the sulfur layers and this layered structure facilitates the intercalation of alkali metal ions. On account of their layered structure, MTPs have demonstrated anisotropic electrical and mechanical properties and additionally, the localization of magnetic moments in the metal ions has revealed magnetic behavior.16 Recently, Du and others, synthesized and characterized monolayers of 2D MTPs and investigated the semiconducting properties. The cleavage energies of the MPTs were calculated and found to be less than that of


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graphite.17 Of late, Carmen and group investigated a library of MTPs with several transition metal or p-metal ions for their magnetic and electrochemical properties.18 The oxygen evolution reaction and excellent lithium storage performance of nickel thiophosphite was recently investigated by Raksha and group.19 Among the various MTPs, SnPS3 exhibits a monoclinic structure and was previously investigated for its optoelectronic and magnetic properties.20-21 Assuming full conversion reaction, SnPS3 exhorts the potential to deliver high lithium storage capability with the formation of LixSn and LiyP phases. Interestingly, Huang and group recently investigated the pseudocapacitive sodium storage of SnPS3.22 However, the performance of SnPS3 as a lithium-ion battery anode was yet to be explored. As both Sn and P are known for the high gravimetric and volumetric lithium storage capacities, we hypothesized that the SnPS3 anode could deliver high lithium storage capacity. Moreover, the layered structure of the SnPS3 crystals were also assumed to aid the cycling stability by buffering the volume changes accompanying the lithiation/delithiation cycles. Herein, we have grown phase pure SnPS3 crystals via chemical vapour transport technique with elemental tin, phosphorous and sulphur as the starting materials. The as-grown crystals were used as the active material in conventional battery fabrication technique and evaluated as lithium-ion battery anode. The layered structure was found to facilitate excellent lithium storage with superior cycling stability and enhanced rate capabilities. The SnPS3 anode delivered a lithiation capacity of over 800 mAh g-1 at a specific current of 100 mA g-1, which is more than twice that of the conventional graphite anode used in commercial lithium-ion batteries. Also, a remarkable lithiation capacity of ~315 mAh g-1 was achieved at a high current rate of 2 A g-1. Additionally, the lithium storage mechanism was evaluated through electrochemical cyclic voltammetry and ex-situ X-ray diffraction and X-ray photoelectron


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spectroscopy studies. Moreover, preliminary studies of the SnPS3 crystals were carried out in a full-cell assembly. The study would open the doors for the investigation of similar unexplored materials in the class of metal thiophosphites that would deliver high energy density and long calendar life for a wide range of applications.

Results and discussions The SnPS3 crystals were grown via chemical transport route starting from elemental Sn, P and S precursors. (The synthesis process is detailed in Section 1.1 of the Supporting Information.) The as-synthesized SnPS3 crystals were characterized by powder X-ray diffraction (XRD) to evaluate the phase purity and crystallinity. As shown in Figure 1, the Bragg reflections agree well with the monoclinic crystal system in the P1c1 space group (ICSD-25357) and the sharp diffraction peaks attest the crystallinity of the as-grown sample.23 The crystal structure of the layered, monoclinic SnPS3 phase is illustrated in Figure 1b. As seen, the Sn and P atoms are sandwiched between the layers of S atoms. Furthermore, the chemical states of the elements were investigated by X-ray photoelectron spectroscopy (XPS). The XPS survey spectrum shown in Figure S1 indicates the presence of the elements Sn, P and S. The high resolution XPS spectra shown in Figure 1c has Sn (3d5/2) and Sn (3d3/2) peaks at 486.01 eV and 494.41 eV respectively, with spin orbital splitting of 8.4 eV corresponding to the Sn2+ state.24 The P (2p3/2) and P (2p1/2) peaks were observed at binding energies 130.86 eV and 132.28 eV respectively while the S (2p3/2) and S (2p1/2) peaks at 161.02 eV and 162.35 eV respectively. The XRD and XPS results confirm the formation of phase-pure SnPS3 crystals.


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Figure 1. Phase characterization of SnPS3 crystals (a) X-ray diffraction pattern of the assynthesized SnPS3 crystals (b) Crystal structure of layered, monoclinic SnPS3.25 (c) High resolution XPS spectra of the Sn, P, and S elements in the crystal. Furthermore, the morphology of the as-synthesized crystals was observed using scanning electron microscopy and is presented in Figure S2. The size of individual segments of SnPS3 flakes was of the order of micrometers and had uniform elemental distribution of Sn, P and S as evident from the energy dispersive X-ray (EDX) spectrum. The high-resolution transmission electron microscopy (HR-TEM) images (Figure 2a) reveals a composition of highly ordered crystalline two-dimensional sheets of SnPS3. The lattice fringes could be indexed to the (21-3) plane and the corresponding FFT (Fast Fourier Transform) is presented in the Figure 2b inset. The bright spots observed in the selected area electron diffraction (SAED) pattern further attest


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the crystallinity and matches well with the d-spacing’s of the SnPS3 phase as indexed in Figure 2c.

Figure 2. HR-TEM analysis of SnPS3 crystals. (a), (b) HR-TEM images of a segment comprising of layered SnPS3 structure. The FFT of the lattice fringes is presented in the inset (b). (c) Corresponding selected area electron diffraction pattern. The suitability of SnPS3 to host Li ions was investigated in half-cell configurations in a coin- cell assembly. (The details of the coin cell fabrication and assembly are provided in section 1.3 of supporting information.) The electrochemical performance of SnPS3 anode is presented in Figure 3. The cyclic voltammogram (Figure 3a) reveals the initial lithiation and conversion reaction of SnPS3 occurring at a voltage of ~1.65 and 1.2 V vs. Li in the first cathodic cycle.26 The broad peak at 1.2 V is absent in the subsequent cycles and indicates the irreversible phase transformation/conversion of SnPS3 upon the lithium storage.11 This is followed by small shoulder peaks at ~0.7 and 0.5 V vs. Li which could be attributed to the electrolyte decomposition and solid electrolyte formation.27 The cathodic peaks close to 0.26 and 0.15 V vs. Li corresponds to the lithiation of the extruded Sn and P to form Li4.4Sn and Li3P, consistent with the previous reports on tin and phosphide anodes.28 The broad anodic peak at ~0.5 V and the small peaks observed in the first cycle at ~0.8, 1.3, 1.8 and 2.4 V vs. Li corresponds to the de-


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lithiation reactions. The cyclic voltammograms since the second cycle overlap, which indicate the reversibility and the stability of the layered SnPS3 anode as lithium-ion host. Similarly, the potential profiles presented in Figure S3 indicate a step at ~1.7 V followed by a plateau at ~1.4 V vs. Li, indicative of the conversion reaction of SnPS3. Below 1 V vs. Li, a sloping voltage profile was observed. Similarly, a sloping potential profile without any characteristic plateau was observed from the second cycle onwards.


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Figure 3. Electrochemical performance of SnPS3 anode for lithium-ion battery. (a) Cyclic voltammogram at scan rate of 0.1 mV s-1. (b) Galvanostatic charge-discharge performance at a specific current of 0.1 A g-1 and (c) Rate test at different specific currents.


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The galvanostatic charge-discharge (GCD) tests were carried out at different cut-off voltages to enhance the cycling stability of the SnPS3 anode (Figure S4). Additionally, the effect of carboxymethyl cellulose (CMC) binder and the conventional polyvinylidene fluoride (PVDF) binder on cycling performance was also evaluated (Figure S5). The capacity retention was better for the PVDF binder-based electrode, possibly due to the better preservation of the structural integrity of the electrode. The GCD performance at the optimized voltage range of 0.2-1.5 V vs. Li is presented in Figure 3b. The initial coulombic efficiency was ~38%. However, 95% coulombic efficiency was attained in the second cycle and over 99% since the seventh cycle. The SnPS3 anode retained a lithiation capacity of 532 mAh g-1 after 100 cycles at a specific current of 100 mA g-1. The capacities and currents were calculated based on the mass of SnPS3 in the electrode. The observed downward trend is possibly due to the capacity losses incurred due to the volume expansion accompanying the lithium alloying reactions occurring in the electrode. However, the electrochemical performance of SnPS3 anode is comparable and even superior to some of the recent reports on ternary chalcogenides for lithium storage (Table S1). The layered SnPS3 also exhibited excellent high-rate performance as seen in Figure 3d, S6 and S7, although, the cycling stability at higher current rates could be further improved. However, the anode delivered a noteworthy lithiation capacity of ~315 mAh g-1 at a high specific current of 2 A g-1. This demonstrates the ability of the layered SnPS3 structure to efficiently facilitate the lithiumion and electron transport even at high current fluxes. The (de)lithiation mechanism was further investigated through ex-situ X-ray diffraction and X-ray photoelectron spectroscopy studies of the lithiated and de-lithiated SnPS3 anode at various cut-off potentials. The details of the electrode preparations for the ex-situ studies are elaborated in our previous reports as well as in the Supporting Information section 1.4.29 The ex-


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situ XRD patterns at different cut-off voltages and the corresponding potential profile are depicted in the Figure 4. The initial discharge to 1.2 V vs. Li significantly reduced the crystallinity of the SnPS3 phase upon the lithiation process. Upon discharge to 0.2 V vs. Li, the broad peaks of poorly crystallized Li4.4Sn and Li3P were visible.30-31 During the de-lithiation process, the SnPS3 structure was not recovered but weakly crystallized Sn and P Bragg peaks appeared upon charging to 1.5 V vs. Li.32-33 This amorphous Sn and P are electrochemically active in the subsequent (de)lithiation cycles.

Figure 4. Investigating the lithium-storage mechanism (a) Ex-situ X-ray diffraction patterns of SnPS3 anode at different cut-off voltages (b) Voltage profile of SnPS3 anode (c) Ex-situ XPS of SnPS3 anode at lithiated and delithiated states.


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The ex-situ XPS spectrum of lithiated and delithiated SnPS3 anode is presented in Figure 4c. Upon lithiation, the Sn (3d) peaks shifted to lower binding energies, indicating a lowering of the oxidation states which is expected due to the formation of LixSn phases.34 The P (2p) peaks of lithiated phase nearly vanished, however, in the delithiated electrode, the peak close to ~130.25 eV suggests the presence of elemental phosphorus in the electrode.34-35 No major shift in the S (2p) peaks was observed, probably indicating the formation of Li2S.36 From the cyclic voltammetry and ex-situ XRD and XPS investigations, the reaction mechanism of SnPS3 towards lithium can be described as follows: Initially, Li intercalation into the SnPS3 structure occurs as: SnPS3 + xLi + xe- LixSnPS3 In addition to the formation of Li2S, the first lithiation involves the extrusion of Sn and P culminating in the alloying reaction to form LixSn and LiyP phases. LixSnPS3 + yLi + ye- 3Li2S + Sn0 + P0 The subsequent reversible reaction is the alloying and dealloying of Sn and P as: Sn0 + xLi + xe-  LixSn P0 + yLi + ye-  LiyP The excellent electrochemical performance of SnPS3 anode motivated us to further investigate

the

performance

in

full

cell

configurations.

Commercial

cathode,

LiNi0.33Mn0.33Co0.33O2 (LNMC) was coupled with the SnPS3 anode. The cyclic voltammogram revealed the (de)lithiation peaks in the voltage range 2.5-4.8 V. The preliminary results seem


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promising as the full cell delivered over 92% coulombic efficiency for over 160 cycles (Figure 5). However, the capacity retention was poor (Figure S8) and needs further optimization of the anode to cathode mass ratios. The electrochemical impedance spectra of the full cell (Figure S9) could be fit to the equivalent circuit considering both anode and cathode reactions, expressed as a parallel connection of interfacial capacitance and associated charge transfer resistance with Warburg impedance in series.37


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Figure 5. Full cell configuration with LNMC cathode and SnPS3 anode (a) Schematic diagram (b) Cyclic voltammogram at 0.1 mV s-1 between 2.5-4.8 V (c) Coulombic Efficiency of the full cell

Conclusion In conclusion, we have successfully synthesized high-purity, layered SnPS3 crystals by chemical vapor transport technique and investigated its electrochemical performance as alkaliion host. The layered SnPS3 demonstrated excellent lithium storage performance and was found to accommodate the volume changes upon (de)lithiation as evident from the superior cycling stability. The SnPS3 anode delivered ~800 mAh g-1 lithiation capacity at a specific current of 0.1 A g-1 and a noteworthy ~300 mAh g-1 at a high specific current of 2 A g-1. Furthermore, the mechanism of lithium storage was elucidated through cyclic voltammetry and ex-situ X-ray diffraction and X-ray photoelectron spectroscopy studies. The SnPS3 anode was found to undergo a conversion and alloying reaction mechanism towards lithium storage. Preliminary full cell studies showed promising electrochemical performance with high coulombic efficiency. The study demonstrates the suitability of metal thiophosphites as alkali-ion hosts and calls for more research into this novel class of materials for electrochemical applications.


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ASSOCIATED CONTENT Supporting Information. A Supporting Information is available for this manuscript. Details of electrode preparation, electrochemical characterization and morphological analysis of active materials are incorporated. AUTHOR INFORMATION Corresponding Author * Dr. S. Sreejith: [email protected] ; [email protected] * Prof. Dr. C. T. Lim [email protected] * Prof. Dr. S. Madhavi [email protected] ACKNOWLEDGMENT This work was financially supported by National Research Foundation of Singapore (NRF) Investigatorship award number NRF2016NRF-NRFI001-22. We would like to thank the Facility for Analysis, Characterization, Testing and Simulation (FACTS), Nanyang Technological University, Singapore for the characterization facilities. S. S. and C. T. L acknowledge support from the National Research Foundation, Prime Minister’s Office, Singapore under medium sized center program, the Center for Advanced 2D Materials (CA2DM) and NUS-BIGHEART.


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Route of Irreversible Transformation in Layered Tin Thiophosphite and

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