Dual Lithiophilic Structure for Uniform Li Deposition - ACS Applied

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Dual Lithiophilic Structure for Uniform Li Deposition Shouyi Yuan, Junwei Lucas Bao, Chao Li, Yong-Yao Xia, Donald G. Truhlar, and Yong-Gang Wang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b19654 • Publication Date (Web): 25 Feb 2019 Downloaded from http://pubs.acs.org on February 27, 2019

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ACS Applied Materials & Interfaces

Dual Lithiophilic Structure for Uniform Li Deposition Shouyi Yuan,† Junwei Lucas Bao,# Chao Li, † Yongyao Xia, † Donald G. Truhlar*# and Yonggang Wang*†

† Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institution of New Energy, Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, Shanghai, 200433, China E-mail: [email protected].

# Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, State of Minnesota, MS 55455-0431, USA E-mail: [email protected]

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KEYWORDS: Li deposition • dual lithiophilic Structure • metal organic framework • Ag nanoparticles • nucleation overpotential

ABSTRACT : The development of Li metal anode is hindered by the Li dendrites arising from the random deposition of Li metal during cycles. Hence, uniform deposition of Li during repeated cycles is crucial for the development of Li metal batteries. However, it is difficult to regulate Li deposition due to convection in the electrolyte. Here, we employ a dual lithiophilic structure composed of polar metal organic framework (MOF) and highly conductive Ag nanoparticles, and we show that it brings about uniform lithium deposition. The binding energy for Li is increased by the abundant oxygen sites and large surface area of the MOF, and concomitantly the uniform distribution of Li nuclei can be achieved with a low nucleation overpotential. When highly conductive lithiophilic Ag is incorporated into the MOF, the binding energy for Li is further increased and the nucleation


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overpotential is decreased to nearly zero. As a result, Li platting and stripping on the Ag@MOF (i.e., Ag@HKUST-1) substrate exhibits a Coulombic efficiency (CE) of 97% over 300 cycles and a high areal capacity of 5 mAh cm-2 without dendrite formation.

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INTRODUCTION


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Lithium metal anodes have attracted considerable attention for their use in Li metal batteries such as lithium–sulfur batteries and lithium–air batteries because lithium metal anodes deliver the highest theoretical specific capacity (3860 mAh g-1) among all the anode materials and the lowest electrochemical potential (-3.04 V versus S.H.E.).[1-4] While steady progress has been made on the cathode side of next-generation batteries,[510]

the growth of lithium dendrites that cause short circuits upon repeated plating and

stripping at the anode still remains a challenge. Lithium dendrites also promote side reactions that increase the polarization, and the detachment of Li dendrite from the current collector leads to “dead lithium” with capacity loss.[1] Therefore, there is a critical need to inhibit the growth of lithium dendrites during repeated Li plating and stripping. Various strategies have been employed to address the issue, and they can be classified into three categories: (1) optimizing the electrolyte to stabilize the Li metal anode,[11-16] (2) engineering a high-modulus artificial solid electrolyte interface to prevent the penetration of lithium dendrite,[17-19] and (3) designing structured anodes.[20-25]


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The electrodeposition of lithium during charging involves two steps. The first step is ion diffusion as the electric field and concentration gradient drive Li ions to the anode, where they deposit randomly on the substrate. The second step is electron transfer, in which the adsorbed Li ions pick up electrons from the substrate and are eventually converted to metallic lithium. Because the ion-diffusion step is much slower than the electron transfer step, it is the rate-determining step of electrodeposition. [1] Unfortunately, due in part to convection in the liquid electrolyte, it is very difficult to constrain the Li ions to be deposited in a regular fashion. As a result, nonuniformly distributed Li nuclei will grow on the substrate,[26] and the deposited Li metal tends to be highly dendritic, which causes electrochemical hot spots and triggers filamentary growth.

The growth of lithium dendrites has also been modeled in terms of Sand’s time  as follows:[1,3-5]

  D

e2C02( a  Li  )2 4J2a2

(1)


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where  is a measure of the initiation time for dendrite growth, D is the diffusion coefficient,

e is the electronic charge, C0 is the initial Li ion concentration, μa and μLi+ are anionic and cationic mobilities, and J is current density. The inverse proportionality of Sand’s time to

J2 suggests that smaller J will bring about longer cycle life before Li dendrite growth. For a given electrode current, a high specific surface area decreases the local current density and should therefore lead to a more stable electrode.

Another factor important for uniform deposition is the nucleation overpotential of Li, and recently, some lithiophilic materials with low nucleation overpotentials for Li have been demonstrated to lead to more uniform Li deposition with less formation of Li dendrites. [2638]

(The Li nucleation overpotential(μn) is defined as the energy barrier for heterogeneous

nucleation during electrochemical plating of Li.) Therefore, we are motivated to search for a Li host with large surface area and low overpotential for Li nucleation.

Metal organic frameworks (MOFs), which are composed of inorganometallic nodes and organic ligands, represent a class of porous materials with large surface area and abundant polar functional groups.[39,40] The polar functional groups are able to induce the


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uniform nucleation of Li on the substrate. At the same time, the large surface area of the MOF lowers the local current density. However, the insulating nature of most MOFs has restricted their application in batteries. Here we employ a dual lithiophilic structure, composed of a MOF, in particular HKUST-1,[41] permeated with conductive lithiophilic Ag nanoparticles, to promote the uniformity of Li deposition. We find that strong binding of Li to the polar functional groups of the MOF and to the lithiophilic Ag nanoparticles reduces the overpotential for Li nucleation to nearly zero. Furthermore, the large surface area of HKUST-1 lowers the local current density, the nano-porous structure of the MOF matrix provides space for the initial Li nucleation, and the highly conductive Ag seeds in the MOF matrix improve the conductivity, which facilitates electron transfer. We found that the Ag@HKUST-1 substrate exhibits a long life of over 300 cycles with a high CE of 97% at a current density of 0.5 mA cm-2. When the deposition amount of Li was increased to 5 mAh cm-2, a high CE over 98.5% was also achieved for 50 cycles.

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EXPERIMENT SECTION


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Fabrication of nano Ag particles: The nano Ag particles were fabricated via the ethanol reduction method

[42].

Typically, 1.3 g polyvinyl pyrrolidone (PVP) (MW=1300000) was

dissolved in the anhydrous ethanol under sonication for 1 hour. Then, AgNO3 was also dissolved in the ethanol under sonication. The as-obtained solution was refluxed at 80°C for 2 hours until the solution turned from colorless transparent to golden yellow, indicating the formation of nano Ag particle in the solution. The as-synthesized nano Ag solution was kept in the refrigerator. Fabrication of HKUST-1: The HKUST-1 was synthesized according to the previous report.[43] Cu(NO3)2 (0.966 g) was dissolved in the deionized water to form solution A. 1,3,5benzenetricarboxylic acid was also dissolved into the anhydrous ethanol to form solution B. Then, solution A was mixed with solution B under vigorous stirring. Subsequently, 1ml ethanolamine was added to the mixture. Immediately, blue precipitate was formed, indicating the formation of HKUST-1. The mixture was kept stirring overnight. The precipitate was washed several times using anhydrous ethanol and collected by centrifugation. The precipitate was then immersed in the anhydrous ethanol for 48 hours to activate the HKUST-1 particles. Finally, the sample was dried under vacuum at 160°C. Fabrication of Ag@HKUST-1: the Ag@HKUST-1 was fabricated by a pre-confinement method. Briefly, 10ml Nano Ag gel solution was previously added into Cu(NO3)2 solution to form solution A. Then, 1,3,5-benzenetricarboxylic acid was also dissolved into the anhydrous ethanol to form solution B. Solution A was mixed with solution B under vigorous stirring. Subsequently, 1 ml ethanolamine was added to the mixture. Immediately, blue precipitate was formed, indicating the formation of HKUST-1. The mixture was kept stirring overnight. Then, the precipitate was washed several times using anhydrous ethanol and collected by


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centrifugation. The as-obtained precipitate was then immersed in the anhydrous ethanol for 48 hours to activate the Ag@HKUST-1 particle. Finally, the sample was dried under vacuum at 160°C. Fabrication of the electrode: The electrode was prepared by mixing the as-prepared MOF particles, Super P, and polyvinylidene fluoride (PVdF) in a ratio of 7:2:1. Then the mixture was dissolved in the NMP solvent and slurried on a copper foil. The electrode was then dried at 80°C under vacuum to remove the NMP solvent. The average cathode loading based on the total weight of cathode is about 1.2-1.5 mg cm-2. The electrode was punched into disk with a diameter of 12mm. The electrode area is 1.13 cm-2. For comparison, the Cu foil was also used as electrode for Li deposition. The Cu foil was washed with dilute HCl solution under sonication and then wiped with ethanol to remove the impurity on the surface. Cell assembly: CR2016 coin cells was assembled in a glove box filled with pure argon. Li foil was employed as both counterpart electrode and reference electrode. The two electrodes were separated by a Celgard separator infiltrated with 1,3-Dioxolane /Ethylene glycol dimethyl ether (DOL/DME) (1:1)-(1 M Lithium bis(trifluoromethylsulphonyl)imide (LiTFSI) electrolyte containing 2 wt% LiNO3 additives). The cells were then cycled on a Landt Cycler (Wuhan Land Electronic Co. Ltd.). Characterization: The Fourier transform infrared (FTIR) spectrum was carried out on a NICOLET 6700 spectrometer. The FTIR was measured in transmission geometry with a KBr powder pellet. Powder X-ray diffraction (XRD) measurements were performed on a Bruker D8 advanced diffractometer at 40 kV, 40 mA for Cu Kα. SEM was carried out on a FE-SEM S-4800. For ex-situ SEM, the cell was first discharged to deposit a certain amount of Li on the electrode in the CR2016 coin cell and then the electrode was extracted from the cell and washed with DME for


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the SEM investigation. All the samples are stored in glovebox filled with argon. The samples were transferred into SEM with minimal air exposure. The element mapping was carried out by energy dispersive X-ray spectroscopy (EDS) in conjunction with the SEM. The TEM was performed on a JEOL JEM-2100 F microscope (Japan) operated at 200 kV. To investigate the electronic conductivity of the MOF particles, powder electronic conductivity measurement was carried out on the Powder Resistance Meter (FZ-2010, Changbao Analysis Co. Ltd, Shanghai, China) at a pressure of 4Mpa. The XPS analysis was obtained on a PHI VersaProbe 1 scanning XPS microprobe equipped with Al (Kα) source and argon ion sputter gun with an air-free transfer vessel. In addition, the specific surface area is investigated by Brunauer-Emmett-Teller (BET) method. The samples for BET measurement were degassed at 200oC under vacuums overnight. Computational Method: Geometry optimizations, which include the optimizations of the coordinates of all atoms inside the unit cell, the cell parameters, and the volume of the cell, are performed with spin-polarized density functional theory using the Perdew−Burke−Ernzerhof exchange-correlation functional[44] with Grimme’s D3 damped dispersionterms employing the Becke-Johnson damping function.[45] For Li atom adsorbing on the (111) face of Cu, a 5-layer 2×2 slab model was used, in which the bottom two Cu layers are fixed in their bulk geometry, and Li is adsorbed at the hollow sites with 1:1 (4Li:4Cu) coverage; a 40 Å vacuum layer is added between the slabs, and a dipole correction is applied along the z-axis. Spin-polarized calculations are performed with the projector augmented wave method[46,47], in which for Li atom the 1s and 2s electrons are treated explicitly, for H atom the 1s electrons are treated explicitly, and for other atoms the core electrons are frozen while all valence electrons are treated explicitly. The planewave kinetic energy cutoff is 700 eV, and the precision (“PREC”) is set to be “accurate”. We use Γ-point-centered 9×9×9 Monkhorst−Pack k points for sampling the Brillouin zone,[48,49] except


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that for the slab model we use 9×9×1, and for computing isolated atoms (which are put in a large asymmetric cell) we only use the Γ point. Periodic electronic structure calculations were done using VASP code. [50] 

RESULT AND DISCUSSION

The Cu3(1,3,5-benzenetricarboxylate)2 (HKUST-1) particles employed here are composed of Cu(II) nodes and carboxylate linkers (Figures 1a1 and 1b1), and they were prepared according to a previous report.[39] The HKUST-1 is a kind of Metal organic framework, which is composed of Cu2+ metal center and 1,3,5-benzenetricarboxylic acid ligand. This metal organic frameworks contains an internal intersecting 3D system of large square-shaped pore (9 Å by 9 Å).[41] Ag was incorporated into the MOF through a preconfinement method[43] in which the Ag nanoparticles are introduced into the solution before the formation of HKUST-1. After stirring at room temperature for 20 h, the HKUST1 matrix is formed and Ag nanoparticles are embedded into the matrix of HKUST-1 (see the Experiment Section for details). To characterize the morphology of HKUST-1 and Ag@HKUST-1 particles, TEM was carried out. As shown in Figures 1a2 and 1b2, both HKUST-1 and Ag@HKUST-1 particles are highly crystalline, displaying the shape of a


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rhombus. In addition, the C, O, N, and Cu elements are uniformly distributed in the HKUST-1 matrix (Figure 1a3). Figure 1b3 shows the composition of Ag@HKUST-1. We found that Ag is uniformly distributed in the MOF matrix.

We also obtained SEM images of HKUST-1 and Ag@HKUST-1 (Figure S1). As shown in Figure S1, these also show rhombus-shaped crystals. To gain insight into the structure of the MOF particles, the PXRD patterns of Ag, HKUST-1 and Ag@HKUST-1 particles were obtained (Figure S2). It can be identified in Figure S2 that no peak of Ag nanoparticles is observed in the PXRD pattern, indicating the fully incorporation of Ag into the matrix of HKUST-1. To further investigate the composition of the HKUST-1, Fourier transform infrared spectra, BET surface area analysis and V-T pore distribution were also carried out (see Figures S3, S4, and S5 and the accompanying discussion). As shown in Figure S3, the HKUST-1 and Ag@HKUST-1 exhibit almost identical FT-IR spectrum. In addition, as shown in Figure S4 and Figure S5, the pristine HKUST-1 shows an ultrahigh surface area of 2300 m2/g and a pore volume of 0.77cc/g. However, when Ag nanoparticles are embedded into the matrix of HKUST-1, the surface area and the pore volume


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of Ag@HKUST-1 sharply decreases to 82m2/g and 0.007cc/g. The results suggest the pore of HKUST-1 is clogged by the Ag nanoparticles. Powder electronic conductivity measurements was carried out to investigate the conductivity of the substrates. The results show that the electronic conductivity of Ag and pristine HKUST-1 particles are 8.2×107 S cm-1 and 5.3×10-6 S cm-1 respectively. When the nano Ag particles are incorporated into the MOF matrix, the electronic conductivity increases to 0.33 S cm-1, which is much higher than that of pristine HKUST-1 composites.

To confirm the structural stability of the MOF substrate during discharge, ex-situ XPS was carried out. Figure S6a shows the initial discharge profiles of HKUST-1; three plateaus are observed. The two plateaus above 1 V correspond to Li ion insertion into the MOF matrix, whereas the plateau below 1 V is attributed to the formation of a solid electrolyte interphase (SEI) due to the decomposition of LiNO3 in the electrolyte. Figures S6b shows the Li 1s XPS spectrum of HKUST-1 after discharging to 0V. It is observed that the peaks in Li 1s XPS spectrum are mainly assigned to RCOOLi and ROLi, indicating that the intercalation process of Li involves the reaction of Li with organic moiety of


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HKUST-1. In addition, the Cu 2p XPS spectrums before and after discharge (Figure S6c and Figure S6d) remain unchanged, indicating the stability of Cu metal center during cycle. These results suggest, consistently with previous reports,

[51]

that Li storage in

HKUST-1 does not occur by the conventional conversion mechanism involving the metal ions of the MOF but rather occurs by the redox participation of the organic ligands. Most significant though is that the structure and morphology (Figure S7) of HKUST-1 remain stable during repeated cycles.

Figure 1. (a1) Structure of HKUST-1; (a2) TEM images of HKUST-1 (a3) corresponding EDS mapping of HKUST-1; (b1) structure of Ag@HKUST-1; (b2) TEM images of Ag@HKUST-1; (b3) corresponding EDS mapping of Ag@HKUST-1


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The binding energy was calculated by density functional theory (DFT), using the PBED3(BJ)[44,45] exchange-correlation functional and periodic boundary conditions with the VASP code[50]. The unit cell has the formula Cu12C72H24O48 without Ag and Ag4Cu12C72H24O48 with Ag, and we included four Li in each unit cell. The average binding energy was calculated as ∆E/4, where ∆E=E (4 Li in U)-4E(Li)-E(U), in which U denotes the unit cell.

As shown in Figure 2a, Cu foil exhibits the weakest average binding energy, only 1.62 eV, for Li atoms among all the substrates. However, when employing HKUST-1, the average binding energy increased to 3.02 eV. The DFT calculations indicate that the Li atoms tend to adsorb on the lithiophilic oxygen sites in the HKUST-1 matrix. Furthermore, when lithiophilic Ag nanoparticles were incorporated into the MOF matrix, the binding energy further increased to 3.14 eV for Ag@HKUST-1 substrate. The strong binding energy between Li and the MOF matrix reduces the nucleation overpotentials, which promotes more uniform deposition of Li metal on the MOF substrate.


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The nucleation overpotentials of Li on various substrates were measured at 0.05 mA cm-2. The nucleation overpotential (μn) is defined as the difference between the tip voltage and the later stable mass-transfer-controlled plateau.[23] As shown in Figure 2b, a sharp voltage drop to -26 mV was observed for Cu substrate, which then recovers to -6 mV (blue). Hence, the nucleation overpotential for Cu substrate is 20 mV. In contrast, the voltage drop for HKUST-1 is much smoother; there is a drop to -16.0 mV (red) and a recovery to -7 mV, corresponding to a nucleation overpotential of 9 mV. When Ag nanoparticles are incorporated into the matrix of HKUST-1, the nucleation overpotential further is further reduced to 3 mV; this decrease of Li nucleation overpotential is consistent with the DFT calculations showing stronger favorable interaction of Li with Ag@HKUST 1 than with HKUST-1. We see large discharge slopes in the first discharge of both samples, and these are attributed to the irreversible lithiation process of the MOF in the first cycle (Figure S8). After the first cycle, the large discharge slopes disappear (Figure S9), while the nucleation overpotentials remain unchanged. The result suggests that the discharge slopes arise from the irreversible Li intercalation at the first cycle.


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Figure 2. a). PBE-D3-BJ computed averaged binding energy (eV per Li atom) between Li atom and Cu substrate, HKUST-1 substrate, and Ag@HKUST-1 substrate; b) Nucleation overpotential of Li on Cu substrate (green), on HKUST-1 substrate (blue), and on Ag@HKUST-1 (red); c) Schematic illustration of electrodeposition process of Li on the MOF substrate with Super P and PVDF and on the Cu substrate.

Figure 2c schematically illustrates the Li deposition process on the MOF substrate and Cu substrate. For the electrodeposition of Li metal, Li ions are driven to the substrates by the electric field and the concentration gradient of electrolyte. When Li ions reach the


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surface of the current collectors, they obtain electrons from the current collectors and start to nucleate. For MOF substrates, the Li ions tend to adsorb on the lithiophilic sites in the MOF matrix (especially – according to the DFT results – on the oxygen sites of the MOF), and this promotes uniform Li nucleation in the pore. For comparison, when employing Cu as the substrate, ball-like Li nuclei are formed on the planar Cu, and these lead to protrusions on the surface of Cu foil. The subsequently arriving Li ions tend to adsorb on these protrusions due to the high charge on the tip. As a result, needle-like Li dendrites are formed on planar Cu foil.

The detail deposition process on the MOF particles is schematically illustrated in Figure 3. As shown in Figure 3, the initial Li-platting prefers to occur in the pores of Ag@HKUST-1, because the nano-Ag are highly conductive and lithiophilic. After initial platting, the Ag@HKUST-1 filled with Li can serve as the nuclei for the further Li-plating, which leads to the dendrite-free deposition on the outer surface of Ag@HKUST-1. High Resolution Ex-situ SEM images of the electrode at different Li-plating depths indicate that


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the Li prefers to coat on the outer surface of the Ag@HKUST-1 particles, rather than the lithiophobic Super P. (Figure S10)

Further Li Deposition

Initial Nucleation Stage

Li Ag Pristine Ag@HKUST-1 particles

Uniform Li nucleation in the pore of MOF particles

Uniform metallic Li coated on the surface of MOF particles

Figure 3. Schematically illustration of Li deposition on the Ag@HKUST-1 substrate. Figure 4a shows the SEM image of Cu foil with varying amounts of Li deposited on it at 0.5 mA cm-2. The surface of Cu foil is very smooth before Li deposition. However, when depositing 1 mAh cm-2 of Li on the Cu foil, ball-like Li nuclei and needle-like Li dendrites were formed on the planar Cu. When the deposition was increased to 5 mAh cm-2, needlelike Li dendrites were clearly observed on the Cu foil, and the Li dendrites became much thicker. However, when HKUST-1 and Ag@HKUST-1 were employed as substrates,


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neither of them showed dendrites during deposition of 1 mAh cm-2 Li on the substrates (Figures 4b and 4c). Even when the amount of Li on the substrate increased to 5 mAh cm-2, the HKUST-1 and Ag@HKUST-1 substrates remains smooth. The result suggests that the Ag@HKUST-1 is able to suppress Li dendrites.

Figure 4. Morphology of Li metal anode during plating: a) Cu foil; b) HKUST-1 substrate; c) Ag@HKUST-1 substrate

In addition, high-resolution SEM was carried out on the Ag@HKUST-1 substrate with various amounts of Li plating (Figure S10). As shown in Figure S10, even after depositing


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5 mAh cm-2 of Li on the substrate, the Super P particles were still clearly seen, suggesting that Li was mainly adsorbed on the lithiophilic matrix of the MOF particles rather than on the lithiophobic Super P carbon. The morphology of the electrode after Li stripping is shown in Figure S11. It can be identified in Figure S11, after stripping, the surface of the MOF substrate remains smooth, while obvious dendrites are still found on Cu substrate. To clarify the deposition process, the ex-situ XPS spectrum of the Ag@HKUST-1 substrate before and after Li plating is shown in Figure S12.

The electrochemical performance of Li deposition was investigated with a CR2016 coin cell. Figure 5a shows the Coulombic efficiency (CE) of the Li plating and stripping process with a fixed capacity of 1 mAh cm-2 at a current density of 0.5 mA cm-2. Among all the substrates tested, the planar Cu foil exhibited the highest initial CE (88%). However, the CE of Cu dropped below 80% after only 80 cycles. The CE of HKUST-1 remains at 97% after 200 cycles, and Ag@HKUST-1 retained a CE over 97% even after 300 cycles. When the current density is increased to 1 mA cm-2, (Figure 5b), Cu foil shows the highest CE for the first several cycles. However, the CE began to fluctuate after 55 cycles. For pristine


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HKUST-1 substrates, the CE remains at 97.5% over 130 cycles. When Ag nanoparticles were introduced into the HKUST-1 matrix, the cycle life was further prolonged to 150 cycles with high CE of 97.5%. When the amount of Li plating on the substrates increased to 5 mAh cm-2 (Figure 5c), the CE of Cu foil began to fluctuate only after 15 cycles. However, for pristine HKUST-1 substrate, the cycle life extended to 40 cycles with a high CE of 98.5% and then gradually decreased. For Ag@HKUST-1 substrate, the CE maintained a value over 98.5% for 50 cycles. The corresponding voltage profiles are given in Figures S13, S14 and S15. The improved performance of Ag@HKUST-1 substrate is attributed to the dual lithiophilic structure of MOF and Ag nanoparticles in the MOF matrix, which promotes uniform Li deposition into the MOF matrix. The achieved results (i.e. CE, cycle life and capacity) are among the best performance of the recent reports about lithiophilic substrate. (See Table S1 for a comparison). It should be noted that the MOF-based substrates contain Super P (as conductive additive) and PVDF (as binder). Therefore, the Li deposition on the Cu foil coated with Super P and PVDF was also investigated for comparison, as shown in Figure S16, the Super P substrate exhibits


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inferior performance compared to the MOF substrate. (See Figure S16 and the accompanying discussion.)

To further investigate the performance of Ag@HKUST-1 substrate (Figure 5e) in a full cell, 5 mAh cm-2 Li was pre-deposited on the substrates, which was then extracted from the cell and paired with a LiFePO4 cathode to assemble a full cell. For comparison, Cu foil was also prepared in the same way for full-cell assembly (Figure 5d). As shown in Figures 5d and 5e, both the Cu@Li-LiFePO4 full cell and the Ag@HKUST-1@Li-LiFePO4 full cell exhibited an initial discharge capacity of 160 mAh cm-2 at a rate of 0.5C. The specific capacity slightly decreased to144 mAh cm-2 after 100 cycles and 137 mAh cm-2 after 150 cycles for the Ag@HKUST-1@Li-LiFePO4 full cell, corresponding to a capacity retention of 87% for 150 cycles. However, the specific discharge capacity of Cu@LiLiFePO4 full cells reduced to 137 mAh cm-2 after 100 cycles and further decreased to 120 mAh cm-2 after 150 cycles. The capacity retention for the Cu@Li-LiFePO4 full cell is only 75%. The corresponding voltage profiles of the LiFePO4 full cells are given in Figure S17,


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where it can be clearly seen that the increase of the polarization of the Cu@Li-LiFePO4 full cell is much more severe than that of the Ag@HKUST-1@Li-LiFePO4 full cell.

Figure 5. a) Coulombic efficiency of Li deposition on various substrates with a fixed capacity of 1 mAh cm-2 at 0.5 mA cm-2. b) Coulombic efficiency of Li deposition on various


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substrates at 1 mA cm-2 with a fixed capacity of 1 mAh cm-2.; c) Coulombic efficiency of Li deposition on vaious substrates at 1mA cm-2 with a fixed capacity of 5mAh cm-2; d) Cycling performance of Cu@Li-LiFePO4 full cell; e) Cycling performance of Ag@HKUST1@Li-LiFePO4 full cell.



CONCLUSION The work presented here demonstrates that uniform Li deposition can be obtained with a dual

lithiophilic structure, which is composed of polar metal organic framework and conductive Ag nanoparticles encapsulated in the MOF matrix. Owing to the abundant oxygen sites of the HKUST1 matrix and the strong binding energy Ag@HKUST-1 for Li metal, the overpotential for Li nucleation is reduced to nearly zero. As a result, the Ag@HKUST-1 substrates exhibit a long cycle life over 300 cycles with a high CE over 97% at a current density of 0.5 mA cm-2. In addition, even when the amount of Li deposited into the metal organic framework increases to 5 mAh cm-2, a high CE above 98.5% was also achieved over 50 cycles. These results are encouraging for the design of an advanced lithiophilic host for Li platting and stripping. 

ASSOCIATED CONTENT

The Supporting Information is available free of charge on the ACS Publications website at DOI:



AUTHOR INFORMATION


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Corresponding Author †*E-Mail:

#*

[email protected]

E-Mail: [email protected]

Author Contributions Shouyi Yuan conceived this idea and designed the experiments. Junwei Lucas Bao carried out the density functional theory calculation. Yonggang Wang, Yongyao Xia and Donald G. Truhlar directed the project. Shouyi Yuan performed the material synthesis, characterization, electrochemical measurements and data analysis. Shouyi Yuan, Yonggang Wang and Donald G. Truhlar co-wrote the paper. All authors discussed the results and commented on the Manuscript. 

ACKNOWLEDGMENT We acknowledge funding from the National Natural Science Foundation of China

(21622303), the State Key Basic Research Program of China (2016YFA0203302), and the U.S. Department of Energy, Office of Basic Energy Sciences (DE-FG02-17ER16362).



REFERENCES

(1) Chen, X.-B; Zhang, R.; Zhao, C.Z.; Zhang, Q. Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review. Chem. Rev. 2017, 117, 10403-10473.


26

Page 27 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(2) Ye, H.; Xin, S.; Yin, Y.X.; Guo, Y.G. Advanced Porous Carbon Materials for HighEfficient Lithium Metal Anodes. Adv. Energy Mater. 2017, 7, 1700530. (3) Yang, C.P.; Fu, K.; Zhang, Y.; Hitz, E.; Hu, L.B. Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid. Adv. Mater. 2017, 29, 1701169. (4) Xu, W.; Wang, J.L.; Ding, F.; Chen, X.L.; Nasybutin, E.; Zhang, Y.H.; Zhang, J.G. Lithium Metal Anodes for Rechargeable Batteries. Energy Environ. Sci. 2014, 7, 513-537. (5) Bruce, P.G.; Freunberger, S.A.; Hardwick, L.J.; Tarascon, J.M. Li-O2 and Li-S Batteries with High Energy Storage. Nat. Mater. 2012, 11, 172; (6) Yuan, S.Y.; Bao, J.L.; Wang, L.N.; Xia, Y.Y.; Truhlar, D.G.; Wang, Y.G. GrapheneSupported Nitrogen and Boron Rich Carbon Layer for Improved Performance of Lithium-Sulfur Batteries Due to Enhanced Chemisorption of Lithium Polysulfides.

Adv. Energy Mater. 2016, 6, 1501733. (7) Zhang, L.L.; Wan, F.; Wang, X.Y.; Cao, H.M.; Dai, X., Niu, Z.Q.; Wang, Y.J.; Chen J. Dual-Functional Graphene Carbon as Polysulfide Trapper for High-Performance Lithium Sulfur Batteries. ACS Appl. Mater. Inter. 2018, 10, 5594-5602.


27


Page 28 of 36

(8) Wu, B.S.; Zhang, H.Z.; Zhou, W.; Wang, M.R.; Li, X.F.; Zhang, H.M. Carbon-Free CoO Mesoporous Nanowire Array Cathode for High-Performance Aprotic Li–O2 Batteries. ACS Appl. Mater. Inter. 2015, 7, 23182-23189. (9) Wang, J.; Zhong, H. X.; Qin, Y. L.; Zhang, X. B. An Efficient Three-Dimensional Oxygen Evolution Electrode. Angew. Chem. Int. Ed. 2013, 52, 5248-5253. (10) Xu, G.Y.; Ding, B.; Nie, P.; Shen, L.F.; Dou, H.; Zhang X.G. Hierarchically Porous Carbon Encapsulating Sulfur as a Superior Cathode Material for High Performance Lithium–Sulfur Batteries. ACS Appl. Mater. Inter. 2014, 6, 194-199. (11) Yan, C.; Yao, Y.X.; Chen, X.; Chen, X.B.; Zhang, X. Q.; Huang, J.Q.; Zhang, Q. Lithium Nitrate Solvation Chemistry in Carbonate Electrolyte Sustains High-Voltage Lithium Metal Batteries. Angew. Chem. Int. Ed. 2018, 57, 1807034. (12) Zheng, J.M.; Engelhard, M.H.; Mei, D.H.; Jiao, S.H.; Polzin, B.H.; Zhang, J.G.; Xu, W. Electrolyte Additive Enabled Fast Charging and Stable Cycling Lithium Metal Batteries. Nat. Energy 2017, 2, 17012. (13) Yan, C.; Cheng, X.B.; Tian, Y.; Chen, X.; Zhang, X.Q.; Li, W.J.; Huang, J.Q.; Zhang, Q. Dual-Layered Film Protected Lithium Metal Anode to Enable Dendrite-Free Lithium Deposition. Adv. Mater. 2018, 30, e1707629.


28

Page 29 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(14) Pang, Q.; Liang, X.; Shyamsunder, A.; Nazar, L.F. An In Vivo Formed Solid Electrolyte Surface Layer Enables Stable Plating of Li Metal. Joule 2017, 1, 871886; (15) Suo, L.M.; Hu, Y.S.; Li, H.; Armand, M.; Chen, L.Q. A New Class of Solvent-in-Salt Electrolyte For High-Energy Rechargeable Metallic Lithium Batteries. Nat. Commun. 2013, 4, 1481. (16) Fan, X.L.; Chen, L. Borodin, O.; Ji, X.; Chen, J.; Hou, S.; Deng, T.; Zheng, J.; Yang, C.; Liou, S.C.; Amine, K.; Xu, K.; Wang, C.S. Non-flammable Electrolyte Enables Li-Metal Batteries with Aggressive Cathode Chemistries. Nat. Nano. 2018,13, 715-722. (17) Yan, J.H.; Yu, J.Y.; Ding, B. Mixed Ionic and Electronic Conductor for Li-Metal Anode Protection. Adv. Mater. 2018, 30, 1705105. (18) Zhang, W.D.; Zhuang, H.L.L.; Fan, L.; Gao, L.N.; Lu, Y.Y. A "Cation-Anion Regulation" Synergistic Anode Host for Dendrite-Free Lithium Metal Batteries. Sci.

Adv. 2018, 4, eaar4410. (19) Liao, K.M.; Wu, S.C.; Mu, X.W.; Lu, Q.; Han, M.; He, P.; Shao, Z.P.; Zhou, H.S. Developing a "Water-Defendable" and "Dendrite-Free" Lithium-Metal Anode Using a Simple and Promising GeCl4 Pretreatment Method Adv. Mater. 2018, 30, e1705711.


29


Page 30 of 36

(20) Zuo, T.T.; Wu, X.W.; Yang, C.P.; Yin, Y.X.; Huan, Y.; Li, N.W.; Guo, Y.G. Graphitized Carbon Fibers as Multifunctional 3D Current Collectors for High Areal Capacity Li Anodes. Adv. Mater. 2017, 29, 1700389. (21) Liu, S.; Wang, A.X.; Li, Q.; Wu, J.S.; Chiou, K.V.; Huang, J.X.; Luo, J.Y. Crumpled Graphene Balls Stabilized Dendrite-free Lithium Metal Anodes. Joule, 2018, 2, 184193. (22) Zheng, G.; Lee, S.W.; Liang, Z.; Lee, H. W.; Yan, K.; Yao, H.; Wang, H.; Li, W.; Shu, S.; Cui, Y. Interconnected Hollow Carbon Nanospheres for Stable Lithium Metal Anodes. Nat. Nano. 2014, 9, 618-623. (23) Lu, L.L.; Ge, J.; Yang, J.N.; Chen, S.M.; Yao, H.-B; Zhou, F.; Yu S.-H.; Free-Standing Copper Nanowire Network Current Collector for Improving Lithium Anode Performance. Nano Lett. 2016, 16, 4431. (24) Lin, D.C.; Zhao, J.; Sun, J.; Yao, H.B.; Liu, Y.Y.; Yan, K.; Cui Y.; Three-Dimensional Stable Lithium Metal Anode with Nanoscale Lithium Islands Embedded in Ionically Conductive Solid Matrix. Proc. Natl. Acad, Sci. 2017, 114, 4613–4618. (25) Yin, Y.-C., Yu, Z.-L. Ma, Z.-Y., Zhang, T.-W., Lu, Y.-Y., Ma, T., Zhou, F. Yao H.-B., Yu S.-H., Bio-Inspired Low-Tortuosity Carbon Host for High-Performance Lithium Metal Anode. Natl. Sci. Rev., 2018, https://doi.org/10.1093/nsr/nwy148.


30

Page 31 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(26) Yan, K.; Lu, Z.D.; Lee, H.W.; Xiong, F.; Hsu, P.C.; Li, Y.Z.; Zhao, J.; Chu, S.; Cui, Y. Selective Deposition and Stable Encapsulation of Lithium Through Heterogeneous Seeded Growth. Nat. Energy, 2016,1, 16010. (27) Zhang, R.; Chen, X.R.; Chen, X.; Chen, X.B.; Zhang, X.Q.; Yan, C.; Zhang, Q. Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for DendriteFree Lithium Metal Anodes. Angew. Chem. Int. Ed. 2017, 56, 7764-7768. (28) Wu, S.L.; Zhang, Z.Y.; Lan, M.H.; Yang, S.R.; Chen, J.Y.; Cai, J.J.; Shen, J.H.; Zhu, Y.; Zhang, K.L.; Zhang, W.J. Lithiophilic Cu-CuO-Ni Hybrid Structure: Advanced Current Collectors Toward Stable Lithium Metal Anodes. Adv. Mater. 2018, 30, 1705830. (29) Liu, W.; Mi, Y.; Weng, Z.; Zhong, Y.; Wang, H. Functional Metal-Organic Framework Boosting Lithium Metal Anode Performance via Chemical Interactions. Chem. Sci. 2017, 8, 4285-4291. (30) Chen, X.B.; Zhou, T.Z.; Zhang, R.; Zhao, C.Z.; Huang, J.Q.; Zhang, Q. Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries Adv. Mater. 2016, 28, 2888-2895; (31) Yang, C.P.; Yao, Y.G.; He, S.M.; Hua, X.; Emily, H.; Hu, L.B. Ultrafine Silver Nanoparticles for Seeded Lithium Deposition toward Stable Lithium Metal Anode.

Adv. Mater. 2017, 29, 1702714;


31


Page 32 of 36

(32) Lu, F.L.; Hu, L.J.; Tian, J.; Zhou, X.J.; Li, Z.; Li, C.L. In Situ Plating of Porous Mg Network Layer to Reinforce Anode Dendrite Suppression in Li-Metal Batteries. Acs

Appl. Mater. interfaces. 2018, 10, 12678-12689. (33) Foroozan, T.; Soto, F.A.; Yurkiv, V.; Sharifi-Asl, S.; Deivanayagam, R.; Huang, Z.N.; Rojaee, R.; Mashayek, F.; Balbuena, P.B.; Shahbazian ‐ Yassar R. Synergistic Effect of Graphene Oxide for Impeding the Dendritic Plating of Li. Adv. Funct. Mater. 2018, 28, 1705917; (34) Jin, C.B.; Sheng, O.W.; Luo, J.M.; Yuan, H.D.; Fang, C.; Zhang, W.K.; Huang, H.; Gan, Y.P.; Xia, Y.; Liang, C.; Zhang, J.; Tao, X.Y. 3D Lithium Metal Embedded within Lithiophilic Porous Matrix for Stable Lithium Metal Batteries. Nano Energy, 2017, 37, 177-186. (35) Zhang, C.; Lv, W.; Zhou, G.M.; Huang, Z.J.; Zhang, Y.B.; Lyu, R.Y.; Wu, H.L.; Yun, Q.B.; Kang, F.Y.; Yang, Q.H. Vertically Aligned Lithiophilic CuO Nanosheets on a Cu Collector to Stabilize Lithium Deposition for Lithium Metal Batteries. Adv. Energy.

Mater. 2018, 8, 1703404; (36) Zhao, H.; Lei, D.N.; He, Y.B.; Yuan, Y.F.; Yun, Q.B.; Ni, B.; Lv, W.; Li, B.H.; Yang, Q.H.; Kang, F.Y.; Lu, J. Compact 3D Copper with Uniform Porous Structure Derived by Electrochemical Dealloying as Dendrite-Free Lithium Metal Anode Current Collector. Adv. Energy Mater. 2018, 8, 1800266.


32

Page 33 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(37) Wang, Y.Y.; Wang, Z.J.; Lei, D.N.; Lv, W.; Zhao, Q.; Ni, B.; Liu, Y.; Li, B.H.; Kang, F.Y.; He Y.B. Spherical Li Deposited inside 3D Cu Skeleton as Anode with Ultrastable Performance. Acs Appl. Mater. Inter. 2018, 10, 20244-20249. (38) Yun, Q.B.; He, Y.B.; Lv, W.; Zhao, Y.; Li, B.H.; Kang, F.Y.; Yang, Q.H.; Chemical Dealloying Derived 3D Porous Current Collector for Li Metal Anodes. Adv. Mater. 2016, 28,6932-6939. (39) Song, B.Y.; Liu, X.Z.; Zhu, K.; Wu, S.C.; Zhou, H.S.; Metal-Organic FrameworkBased Separator for Lithium-Sulfur Batteries. Nat. Energy 2016, 1, 16094. (40) Jiang, Z.G.; Liu, T.F.; Yan, L.J.; Liu, J.; Dong, F.F.; Ling, M.; Liang, C.D.; Lin, Z. Metal-Organic Framework Nanosheets-Guided Uniform Lithium Deposition for Metallic Lithium Batteries. Energy Storage Mater. 2018, 11, 267-273. (41) Chui, S.S.Y; Lo, S.M.F; Charmant J.P.H.; Orpen A.G.; Williams I.D.; A Chemically Functionalized Nanoporous Material. Science, 1999, 283, 1148-1150. (42) Yu, H.; Yang, H.; Yao, R.; Guo, X.Z.; Preparation and Characterization of Ag Nanoparticles Embedded in Hierarchically Porous Monolithic Silica. Acta Physico-

Chimica Sinica. 2014, 30, 1384-1390.


33


Page 34 of 36

(43) Mao, Y.Y.; Li, J.W.; Ying, Y.L.; Hu, P.; Liu, Y.; Sun, L.W.; Wang, H.T.; Jin, C.H.; Peng, X.S. General Incorporation of Diverse Components Inside Metal-Organic Framework Thin Films at Room Temperature. Nat. Commun. 2014, 5, 5532. (44) Perdew, J.P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865-3868. (45) Grimme, S.; Ehrlich, S.; Goerigk, L. Effect of the Damping Function in Dispersion Corrected Density Functional Theory. J. Comp. Chem. 2011, 32, 14556-1465. (46) Kresse, G.; Hafner, J.; Abinitio Molecular-Dynamics For Liquid-Metals. Phys. Rev.

B 1993, 47, 558-561. (47) Kresse, G.; Furthmuller, J. Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set. Comput. Mater. Sci. 1996, 6, 15-50. (48) Blochl, P.E. Projector Augmented-Wave Method. Phys Rev. B 1994, 50, 1795317979. (49) Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials To the Projector Augmented-Wave Method. J. Phys. Rev. B 1999, 59, 1758-1775. (50) Monnkhorst, H.J.; Pack, J.D. Special Points For Brillouin-Zone Integrations. Phys.

Rev. B 1976, 13, 5188-5192.


34

Page 35 of 36 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(51) Maiti, S.; Pramanik, A.; Manju, U.; Mahanty, S. Cu3(1,3,5-benzenetricarboxylate)2 Metal-Organic Framework: A Promising Anode Material for Lithium-Ion Battery.

Micropor. Mesopor. Mater. 2016, 226,353-359.


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Dual Lithiophilic Structure for Uniform Li Deposition - ACS Applied

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