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Endowing Lithium Metal Surface with Self-healing Property via Insitu Gas-solid Reaction for High-performance Lithium Metal Batteries Yang Nan, songmei li, Mengqi Zhu, Bin Li, and Shubin Yang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b07942 • Publication Date (Web): 16 Jul 2019 Downloaded from pubs.acs.org on July 19, 2019

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ACS Applied Materials & Interfaces

Endowing Lithium Metal Surface with Self-Healing Property via In-Situ Gas-Solid Reaction for High-Performance Lithium Metal Batteries Yang Nan, Songmei Li*, Mengqi Zhu, Bin Li*, Shubin Yang Key Laboratory of Aerospace Advanced Materials and Performance of Ministry of Education, School of Materials Science & Engineering Beihang University Beijing, 100191, China *E-mail: [email protected], [email protected]

ABSTRACT: The property of solid electrolyte interphase (SEI) layer is of prime importance for the performance of lithium metal anodes. Replacing the spontaneously formed inhomogeneous and unstable SEI layer with a high-performance artificial SEI is an effective strategy. Herein, a self-healing SEI layer with high lithium ion conductivity and stable framework to address the issues of poor performance of lithium metal anode is achieved. C, Li2S and LiI are uniformly distributed on lithium surface via a “sauna” reaction between CS2-I2 mixed steam and metal lithium, which has the potential to apply to large-scale preparation. The obtained SEI layer possesses high mechanical strength and facilitated lithium ion transport capability, which are inherited from the amorphous C and lithium compounds (Li2S and LiI). Most importantly, LiI component can migrate through the electrolyte and cover the exposed lithium caused by flaws and cracks, leading to a self-healing property. As a result, the C-Li2S-LiI@Li electrodes exhibits excellent electrochemical performance with low overpotential and long lifespan.

KEYWORDS Li metal anodes, lithium dendrites, SEI, sauna reaction, self-healing

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INTRODUCTION Metal lithium, with extremely high theoretical specific capacity, low density and the lowest negative electrochemical potential, is considering as an ideal anode candidate for high energy density rechargeable lithium batteries. 1-7 However, the application of lithium anode is severally deterred by issues of the uncontrollable dendrite growth and inevitable production of dead lithium, which induced safety hazards and short cycling lifespan.

8-14

Therefore, circumventing the unstable interphase of lithium metal anode

such as building an artificial SEI layer on lithium remains a highly anticipated target.

Until now, artificial SEI layers or protective films consist of various materials or components have been widely explored, such as PEO (LiTFSI), 15 LiF-PVDF-HFP, 16 Al2O3 nanoparticles,

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graphene,

18-19

hexagonal boron nitride (h-BN),

20

lithium

halides, 21-26 lithium salts, 27-33 etc. In general, a splendid artificial SEI layer ought to satisfy the following conditions: Firstly, it should be stable under cell environment during long cycles; Secondly, it should possess sufficient Li-ion conductivity and electron insulation to insure that Li-ion could quickly pass though the SEI layer and deposit under it; Thirdly, it should have enough mechanical strength (shear modulus G > GLi=3.4 GPa)

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to suppress the dendrites growth and buffer the volume change.

Nevertheless, no matter how splendid the artificial SEI is, the flaws and cracks on lithium anode surface are ineluctable during long cycle process. Thus, introducing selfhealing mechanism in lithium anodes is necessary and pregnant to deal with the dendrites growth and prolong life-span. Very recently, Li et al. 35 found that extensive surface migration of Li would be triggered by the heat occurred from high current density and leaded to dendrites healing behavior. Similarly, melting lithium metal anodes 36-37 and liquid metal alloys 38-41 were also utilized to obtain a self-healing metal anode without dendrites. However, to the best of our knowledge, artificial SEI layers with self-healing behavior are rarely mentioned.

In this contribution, a self-healing artificial SEI layer is achieved through a “sauna”


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reaction between mixed CS2-I2 steam and metal lithium belt. Such a sauna reaction is not only an easily controllable method but also a large-scale preparation strategy. Based on the solid-gas reaction, the obtained SEI layer composes of unfirmly dispersed porous carbon framework and lithium ion conductive components (Li2S and LiI). More importantly, the LiI component could migrate through the electrolyte to the flaws and cracks on the artificial SEI layers and regenerate a LiI-contained SEI layer on newly exposed lithium metal, exhibiting a self-healing behavior. Hence, symmetric battery with C-Li2S-LiI@Li electrodes exhibits low overpotential (37 mV at 1 mA cm-2) and stable cycling over 600 hours. In addition, Li-Li4Ti5O12 full cell with C-Li2S-LiI@Li anode shows high capacity (110 mAh g-1) and capacity retention (≥97%) over 800 cycles at 4 C.

EXPERIMENTAL SECTION Synthesis of C-Li2S-LiI@Li electrode. CS2-I2 mixed precursor solution was prepared by adding 1.5 mg I2 into 100 μL CS2 (Shanghai Macklin Biochemical Co., Ltd, China) with sufficient oscillation. Two pieces of lithium wafers (Φ16 mm

0.4

mm, China Energy Lithium Co., Ltd.) were fully rolled into a strip with a thickness of about 100 μm and then attached onto a clean copper foil. The lithium strip and CS2-I2 mixed precursor solution were put into a reaction kettle with a volume of 50 mL. The reaction kettle was heated to 110 ℃ and kept for 0.5 hour. After natural cooling, the lithium strip with C-Li2S-LiI SEI layer was carefully stripped from the copper foil. The synthesis of C-Li2S@Li electrode was similar to that of C-Li2S-LiI@Li, and the main difference was that the precursor solution was composed of 100 μL CS2 without I2. And so on, for the synthesis of LiI@Li electrode. All these processes were operated in a glovebox (DELLIX, China) with Ar protection.

Synthesis of Li4Ti5O12 cathode. Li4Ti5O12 (LTO), acetylene black and PVDF (Taiyuan Lizhiyuan Battery Company, China) were mixed together with a mass ratio



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of 8:1:1 and a total mass of 30 mg. 300 μL NMP (Xilong Chemical Engineering Ltd., China) was added into the mixed powder and then fully grinded until the mixture became slurry. The slurry was applied evenly onto electrode slices and then dried in a vacuum oven at 60 ℃ for 12 h. The LTO content on each electrode slice was approximately 2.0 mg.

Structural Characterization. SEM, TEM, XPS and XRD were performed via JEOL 7500, JEM 2100, Thermo Scientific Escalab 250Xi and Rigaku D/Max 2500, respectively.

Electrochemical tests. The electrochemical measurements were carried out via a Land electrochemical testing system, utilizing 1 M LiPF6 and 1% VC in EC: DMC: EMC=1:1:1 vol% as electrolyte, polypropylene as separator and 2032 cells. EIS tests were carried out from 100 kHz to 0.1 Hz at 10 mV.

RESULTS AND DISCUSSION As illustrated in Figure 1, a “sauna” reaction was carried out at 110 ℃ to in-situ build a SEI layer on lithium surface. Under such temperature, mixed solution composed of CS2 (boiling point 46.5 ℃) and I2 (sublimation point ~45 ℃) is easily vaporized, while lithium belt with melting point 180 ℃ is stable. I2 with strong oxidizing property could react with lithium to form LiI, which is an excellent Li-ion conductor.

42

The

reaction products between CS2 gas and lithium are C and Li2S, 43 which could act as a SEI framework and another Li-ion conductor, 44 respectively. Such a C-Li2S-LiI SEI layer possesses high intensity and facilitated li-ion transportation ability, which are inherited from the amorphous C and lithium compounds (Li2S and LiI).


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Figure 1. The schematic diagram of the “sauna” reaction.

SEM, EDS, TEM and XPS were performed to find out the composition of the achieved C-Li2S-LiI SEI. The top view SEM image of the layer (Figure 2a) shows a homogeneous flat surface and the selective area EDS mappings (Figure 2b) illustrate the uniformly distributed element of carbon, iodine and sulfur, indicating that the obtained SEI perfectly covers on the lithium surface almost without flaws or cracks. Side view SEM image (Figure 2c) reveals that the C-Li2S-LiI layer exhibits a consistent thickness of ~8 μm, and the corresponding EDS mappings (Figure 2d) show that the element of carbon, iodine and sulfur uniform distributed on the section. After the lithium compounds in the artificial SEI layers were removed, the residual carbon exhibits a porous structure (Figure 2e-f), which acts as a framework for lithium compounds. Furthermore, the high-resolution transmission electron microscopy (HRTEM) image (Figure. 2g) and the fast Fourier transform (FFT) pattern (Figure. 2h) demonstrates the amorphous form of the obtained carbon, which supplies sufficient strength for the SEI layer. The hardness of the electrodes with artificial SEI was measured via a Shore A type durometer (Figure S3), and the hardness values are significantly higher in the presence of carbon framework (72.4 HV for C-Li2S-LiI@Li, 72.7 HV for C-Li2S@Li, 62.0 HV for LiI@Li and 63.2 HV for bare Li). Such a result reveals that the C-Li2S-LiI@Li electrode exhibits a relatively tougher surface which



might efficiently suppress the dendrites growth.

In the high-resolution I 3d XPS spectrum of C-Li2S-LiI SEI layer (Figure 2i), there are two peaks at around 619.10 eV and 630.63 eV, which are assigned to I 3d5/2 and I 3d3/2, indicating the existence of LiI. 24 The amorphous carbon is corroborated by the C-C bond at 284.87 eV in the C 1s XPS spectrum (Figure 2j), while the existence of compound Li2S is confirmed by the high-resolution S 2s XPS spectrum with a peak of 161.89 eV and 163.09 eV (Figure 2k). The existences of C=O, CO32- could be attributed to the native passivation coating on metal lithium. Similarly, the surface of LiI@Li is composed of LiI, while Li2S and C make up the C-Li2S SEI (Figure S4 and S5). Although carbon itself is conductive, the SEI layer on the whole is nonconductive (Figure S6), because the carbon in this layer is coated and interlaced with nonconductive LiI and Li2S. 45

Figure 2．(a) SEM image and (b) EDS mapping (I, C, S) on top view of C-Li2S-LiI@Li. (c) SEM image and (d) EDS mapping (I, C, S) on side view of C-Li2S-LiI@Li. (e) TEM image and (f) EDS mapping of the obtained carbon. (g) HRTEM image and (h) FFT pattern of the HRTEM image.


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High resolution (i) I 3d, (j) C 1s and (k) S 2p XPS spectra of C-Li2S-LiI@Li.

Li-Li symmetrical cell tests were conducted to estimate the Li plating/stripping processes on lithium anode. As presented in Figure 3a, a flat and stable voltage profiles over 600 hours are acquired by utilizing C-Li2S-LiI@Li electrodes, while unstable and undulating voltage profiles are observed in terms of C-Li2S@Li, LiI@Li and bare Li electrodes. In detail, the C-Li2S-LiI@Li exhibits a lower potential hysteresis of 37 mV (Figure 3b), comparing to that of the LiI@Li (41 mV), C-Li2S@Li (51 mV) and bare Li (57 mV) electrode (Figure 3c-e), which indicates low polarization behavior or internal resistance. Furthermore, internal resistance of different electrodes is confirmed by performing electrochemical impedance spectroscopy (EIS) of symmetrical cells after 50 cycles. As illustrated in Figure S7 and Table S1, the C-Li2S-LiI@Li electrode exhibits the lowest charge transfer resistance of 156.4 Ω, while that of LiI@Li CLi2S@Li and bare Li electrode are 175.8 Ω, 380.7 Ω and 244.1 Ω, respectively. The average potential polarizations at higher current densities of 2 mA cm-2 and 3 mA cm-2 are respectively 75 mV and 120 mV without significant increase for over 200 cycles (Figure 3f-h).



Figure 3. (a) Electrochemical performances of symmetric cells with C-Li2S-LiI@Li, LiI@Li, CLi2S@Li and bare Li electrodes. (b-e) Selected stable cycle voltage profiles from figure3a. (f) Rate performances of symmetric cells with C-Li2S-LiI@Li electrodes. (g-h) Selected voltage profiles CLi2S-LiI@Li at the 100th cycle.

To study more about the Li plating/stripping behavior during cycling, the obtained Li anodes were compared with SEM. The as-obtained C-Li2S-LiI@Li appears to be more homogeneous than LiI@Li and C-Li2S@Li (Figure 4a1, b1 and c1) due to the multiformity of the products during the gas-solid reaction process, while single products are easy to form large bulks or particles. 46 The C-Li2S-LiI@Li electrode after 100 cycles exhibits a smooth morphology as the fresh electrode (Figure 4a1-a2). Even after 300 cycles, lithium dendrites are still invisible (Figure 4a3), while the cross SEM


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image and EDS mappings (I, C, S) further prove the integrity of the artificial SEI with a stale thickness of ~ 8 μm (Figure S8). As a contrast, the LiI@Li and C-Li2S@Li electrode are gradually bestrewed with dendrites during the long cycle process (Figure 4b-c). While the bare lithium electrode shows a pulverized surface with dendrites and dead lithium after only 100 cycles (Figure 4d). In fact, LiI can be used as additives in electrolyte to protect lithium metal anode due to its solubility, 21, 47 which also leads to failure of the LiI@Li electrode along with the consuming of LiI. EDS test of the membrane in symmetric cell with LiI@Li electrodes after 50 cycles was carried out. As expected, I element is found on the surface of the membrane (Figure S9). The CLi2S@Li shows poor cycling stability due to its rugged surface and relatively poor lithium-ion conductivity (Figure 4c).

Figure 4. SEM images of Li-Li cells at 1 mA cm-2 and 1 mAh cm-2. (a) C-Li2S-LiI@Li, (b) LiI@Li, (c) C-Li2S@Li and (d) bare Li. Scale bars, 50 μm.

To verify the self-healing behavior of C-Li2S-LiI SEI layer, crevasses were



prefabricated by cutting the obtained C-Li2S-LiI@Li electrodes, as illustrate in Figure 5a. The local LiI can be well reserved due to the integration with C and Li2S when the artificial SEI is intact. Once the local artificial SEI is broken during cycling and more LiI will be exposed, the local concentration of LiI in the electrolyte around the new exposed lithium will increase. Then, a LiI-contained SEI layer tends to form on the new exposed lithium surface. As a result, the LiI components in C-Li2S-LiI@Li would pay off in a long-term, which is the reason why C-Li2S-LiI@Li is superior to LiI@Li in stability (Figure 3a). To confirm the conjecture, EDS of the C-Li2S-LiI@Li electrode with prefabricated crevasse was conducted after 20 cycles at 1 mA cm-2 and 1 mAh cm-2. Element I is observed on the exposed lithium (Figure 5b-c), indicating that a LiIcontained SEI layer is reformed. At the same time, Element S is absent on the exposed lithium, due to the insolubility of Li2S in the electrolyte. The EDS results (Figure S10) of the LiI@Li, C-Li2S@Li and bare Li electrodes with prefabricated crevasses are in accord with the results above, which further verifies our conjecture. The existence of C, F, P and O elements in EDS results (Figure 5d-e, Figure S10 and S11) can be attribute to the interaction reaction between the electrolyte and lithium surface.

Figure 5. (a) The schematic diagram of self-healing behavior induced by C-Li2S-LiI SEI layer. CLi2S-LiI@Li electrode with prefabricated crevasse after 20 cycles. (b) SEM image of the crevasse. Relevant (c-d) EDS mappings (I, C) and (e) EDS pattern.

Li-LTO batteries were used to evalute the electrochemical property of C-Li2SLiI@Li electrode. The cycle life of the Li-LTO full cells was measured at 4 C


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(corresponding to 1.24 mA cm-2 and 0.232 A g-1 for the negative electrode), showing that C-Li2S-LiI@Li-LTO exhibits a high capacity (110 mAh g-1) and capacity retention (≥97%) over 800 cycles (Figure 6a). Capacities of C-Li2S-LiI@Li-LTO full cell at 1 C, 2 C, 4 C, 8 C and 16 C are 137, 121, 110, 104 and 95 mAh g-1 (Figure 6b), respectively, which greatly exceeds those (137, 114, 102, 92 and 81 mAh g-1, respectively) of bare Li-LTO full cell, especially at high rates. Besides, C-Li2S-LiI@LiLTO full cell shows lower midpoint discharge/charge voltage interval than bare LiLTO (Figure 6c-f and Figure S12). For example, the voltage intervals at 4 C are 120.3 mV and 196.8 mV for full cells with C-Li2S-LiI@Li and bare Li, respectively. Therefore, it’s clear that the C-Li2S-LiI@Li-LTO full cell exhibits much higher and more stable capacity than bare Li-LTO full cell due to the obtained self-healing artificial SEI layer.



Figure 6. Electrochemical properties of Li-LTO batteries. (a) The discharge capacities and coulombic efficiency at 4 C. (b) Capacities at different rates. (c-e) Discharge/charge curves at 1 C, 2 C and 4 C. (f) Midpoint discharge/charge voltage intervals at different rates.

CONCLUSION There are numerous reports of creating artificial SEI layers for lithium metal anode, and most of these reports present enhanced electrochemical performance in the aspects


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of cycling stability and voltage hysteresis. Comparing to these efforts, our work exhibits several obvious advantages. Firstly, the preparation method of gas-solid reaction insures uniformly dispersed SEI layer, which could be developed into a continuous and large-scale preparation strategy. Secondly, the obtained artificial SEI layer composes of porous carbon framework and lithium-ion conductor (Li2S and LiI), which enhances the mechanical strength and the lithium ion transport ability, respectively. In this way, the growth of lithium dendrites is suppressed and the lithium ion conductivity of SEI layer is guaranteed at the same time. More importantly, such a composite layer exhibits a self-healing behavior due to the mobility of LiI component through the electrolyte and reformation of LiI-contained SEI layer on newly exposed lithium, which further prolong the cycle stability of lithium anode.

In summary, a “sauna” reaction between CS2-I2 and lithium belt is performed to in-situ fabricate a self-healing artificial SEI layer with fast Li+ transport capacity and stiff framework. Hence, the symmetric battery utilizing C-Li2S-LiI@Li electrode exhibits low overpotential (37 mV) and stable cycling over 600h. In addition, the C-Li2SLiI@Li-LTO full cell possesses a high capacity (110 mAh g-1) and capacity retention (≥97%) over 800 cycles at 4 C. Our strategy to build self-healing artificial SEI layer offers a new thought to enhance the behavior of lithium anode and will be greatly helpful to the application of lithium metal batteries.

ASSOCIATED CONTENT Supporting Information Digital photographs, XRD pattern, hardness measurement results, SEM, EDS, XPS, characterization, EIS and full cells tests of the obtained electrodes.



AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected]. *E-mail: [email protected]. ORCID Yang Nan: 0000-0002-7975-7422 Songmei Li: 0000-0002-3729-9398 Mengqi Zhu: 0000-0002-1404-0818 Bin Li: 0000-0002-9093-3239 Shubin Yang: 0000-0001-9973-9785 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no conflict of interest.

ACKNOWLEDGEMENTS This work was supported by the National Natural Science Foundation of China (Nos. 51702010).

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Endowing the Lithium Metal Surface with Self ... - ACS Publications

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