Lithiophilic Ag Nanoparticle Layer on Cu Current Collector towards

Subscriber access provided by UNIV OF DURHAM

Energy, Environmental, and Catalysis Applications

Lithiophilic Ag Nanoparticle Layer on Cu Current Collector towards Stable Li Metal Anode Zhen Hou, Yikang Yu, Wenhui Wang, Xixia Zhao, Qian Di, Qianwen Chen, Wen Chen, Yulian Liu, and Zewei Quan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b01521 • Publication Date (Web): 01 Feb 2019 Downloaded from http://pubs.acs.org on February 3, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 19 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

ACS Applied Materials & Interfaces

Lithiophilic Ag Nanoparticle Layer on Cu Current Collector towards Stable Li Metal Anode Zhen Hou,†,‡,‖ Yikang Yu,‡,‖ Wenhui Wang,‡,‖ Xixia Zhao,‡ Qian Di,‡ Qianwen Chen,†,‡ Wen Chen,†,‡ Yulian Liu,‡ and Zewei Quan*,‡ †

School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001,

P. R. China ‡

Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen,

Guangdong 518055, P. R. China KEYWORDS: lithium metal anode, lithiophilic layer, Li nucleation, Li dendrite, Ag nanoparticle, Cu current collector

ABSTRACT: The intractable hurdles of low Coulombic efficiency and dendritic Li formation during repeated deposition/stripping process hinder commercial use of Li metal anode for nextgeneration battery systems. Achieving uniform Li nucleation is one of the effective strategies to address these issues, and it is of practical importance to realize it on commercial Cu current collector that is lithiophobic. Herein, we design a nanostructured Ag lithiophilic layer on Cu foil via an electroless plating process for Li metal current collector. The deposition of lithiophilic Ag particles that are homogeneously distributed on Cu foil can reduce the nucleation overpotential, realizing uniform Li nucleation and subsequent flat Li plating. As a result, a stable cycle stability

ACS Paragon Plus Environment

1

ACS Applied Materials & Interfaces 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

Page 2 of 19

up to 360 h (1 mA cm-2) and an average Columbic efficiency of 94.5% for 100 cycles (1 mA cm2

) are achieved. Furthermore, CuAg full cells with LiFePO4 as cathode exhibit good cycle

performances and low polarization voltage. This approach provides another facile way for stable lithium metal anode.

1. INTRODUCTION

Lithium ion batteries (LIBs) have promoted the development of portable electronic devices and significantly changed our lifestyle.1 However, the conventional LIBs using graphite (limited capacity of 372 mAh g-1) as anodes are getting closer to their theoretical specific energy density, unable to satisfy the relentlessly growing requirements of high energy density storage systems.2-6 Lithium metal is considered as one of the promising anodes for constructing next-generation systems due to its high theoretical specific capacity (~3860 mAh g-1) and the lowest redox potential (-3.04 V).7-14 However, the non-uniform Li deposition during cycles leads to Li dendrite growth that potentially cause thermal runaway and explosion hazard.15,16 Besides, the infinite volumetric variations of the Li metal anode give rise to the crack of the solid-electrolyte interphase (SEI), and the repetitive consumption of Li metal and electrolyte, engendering the low Coulombic efficiencies.17,18 Such issues impede the commercial use of Li metal anode. Considerable efforts have been made to tackle these problems such as electrolyte composition optimization,19-21 artificial SEI construction,22-24 separator modification,25-27 and current collector design.28-35 In addition, introducing lithiophilic modification has been reported to enhance lithiophilic nature of the Li hosts for better combination with lithium, as lithiophilic sites can serve as Li nucleation seeds to enable its flat and uniform deposition, thus effectively suppressing Li dendrite plague.35,36 Recently, Cui and co-workers found selective Li deposition


2

Page 3 of 19 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


on various metal substrates, and demonstrated that the utilization of metal nanoparticles seeds without obvious overpotential was conducive to uniform Li nucleation.37 Hu et al. reported the carbon nanofibers anchored with ultrafine Ag nanoparticles by rapid Joule heating enable a low overpotential (∼25 mV) and uniform lithium deposition as the Ag nanoparticles can alloy with Li, which in return serve as the Li nucleation seeds.38 Furthermore, recent efforts are being devoted to the modification/design of Cu current collectors for practical use, as Cu foils are the commonly adopted current collectors in battery industry.39-41 However, there are only a few reports on the construction of the lithiophilic Cu foil.42,43 Yang et al. constructed Cu current collector with lithiophilic CuO nanosheets via NH4OH etching at 60 oC for 8 h, realizing uniform and stable Li deposition at 0.5 mA cm−2 (700 h).42 Lu et al. reports the lithiophilic Cu-CuO-Ni hybrid structure prepared via three-step approach (magnetron sputtering-annealing-hydrogen plasma treatment), showing improved Li plating behavior.43 Herein, we present the design and fabrication of advanced Cu current collectors that are coated with homogeneous lithiophilic Ag nanoparticles (denoted as CuAg current collector) via a simple, facile and effective electroless plating process, which is conducted at room temperature for several minutes. Compared with bare Cu current collector, these as-synthesized CuAg-1.5 current collectors display much lower nucleation overpotentials (-50 mV at 1 mA cm-2, about 21% of Cu current collector) as the Ag nanopartilces can alloy with Li to form lithiophilic layer. Such features enable the uniform Li nucleation and plating on CuAg-1.5 current collector with smooth surface, which is distinct from the rough structure of bare Cu foil. Therefore, an improved cycling life up to 360 h at 1 mA cm−2 is achieved on the CuAg-1.5 current collector, which is more than twice that of the commercial Cu foil (130 h). Moreover, good cycling


3


Page 4 of 19

performances and low polarization voltage are also demonstrated in [email protected]|| LiFePO4 full cells. 2. EXPERIMENTAL SECTION 2.1. Fabrication of CuAg Current Collectors. Firstly, one piece of commercial Cu foil (18 μm in thickness) was cleaned in ethanol and acetone with ultrasonication. After drying, it was immersed in the chemical plating solution containing both silver plating solution and reducing solution at the volume ratio of 1:1 at room temperature for different reaction times (1 minute, 1.5 minutes, 2 minutes, and 3minutes), separately. The obtained samples are denoted as CuAg-X, where “X” represents reaction time. The silver plating solution was prepared by adding ammonia (NH3·H2O) into 10 mL of silver nitrate (AgNO3) solution (0.117 g/mL) until it turned to transparent, and then 10 mL of sodium hydroxide (NaOH) solution (0.05 g/mL) was mixed with the solution. Finally, ammonia was slowly dropped into the solution until it became limpid. For the preparation of the reducing solution, 45 g of glucose (C6H12O6), 4 g of tartaric acid (C4H6O6) and 100 mL of ethanol were dissolved into 1000 mL deionized water. After being washed with deionized water and alcohol for some times, the samples were dried under vacuum at 60 °C for 12 h. The CuAg foils were cut into circular disks with a diameter of 1.6 cm as current collector for further coin cell assembly. 2.2. Structure and Morphology Characterizations. X-ray diffraction (XRD) measurements were conducted on an X-ray power diffractometer (Rigaku SmartLab) with Cu Kα radiation (λ =1.54 Å). Scanning electron microscope (SEM) images were obtained on a field-emission SEM (FE-SEM, ZEISS Merlin) at 5 kV. To investigate the Li deposition morphology on Cu or CuAg current collectors, cells were disassembled in argon-filled glove box. The current collectors were


4

Page 5 of 19 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


gently washed by DME to remove residual electrolyte and lithium salt before SEM characterizations. 2.3. Electrochemical Measurements. CR2032 coin-type cells were assembled with Celgard separators using CuAg or Cu current collector (working electrode) and Li foil (counter/reference electrode). 1 M LiTFSI in the solvent of DOL/DME (1:1, by volume) with 2 wt% LiNO3 additives was used as the electrolyte unless otherwise specified, and 60 μL of this electrolyte was employed in each coin cell. These coin cells were tested on Neware Battery Testing System. To evaluate the Coulombic efficiency (CE), the current collector was first deposited with 1 mAh cm2

of Li and then stripped to cut-off voltage of 0.5 V (versus Li+/Li) at 1 mA cm-2. The CE was

acquired according to the ratio of Li stripping capacity to depositon capacity in each cycle. To evaluate the cycling stability, 10 mAh cm-2 of Li was first plated on bare Cu and CuAg current collectors, and then these coin cells were cycled with cycling capacity of 1 mAh cm-2 at 1 mA cm-2. Electrochemical impedance spectroscopy (EIS) test was performed under a BioLogic electrochemical workstation (VSP) with the frequency range of 105 Hz to 10-1 Hz with an amplitude of 5 mV. Full cells were assembled using CuAg-1.5 or Cu foil with preelectrodeposited Li (10 mAh cm-2) and LiFePO4, and are denoted as [email protected]||LFP and Li@Cu||LFP, respectively. LFP electrodes with a mass loading (~7 mg cm-2) were prepared by mixing commercial LiFePO4 powder, PVDF and Super P with a mass ratio of 80:10:10 (diameter: 16 mm). Prior to cycling, all cells were initially cycled five times at 0.1 C for electrochemical activation. After that, these full cells were measured between 2.4 V and 4 V at different current rates. 3. RESULTS AND DISSCUTION


5


Page 6 of 19

The CuAg current collector was fabricated from Cu foil via a simple and scalable electroless plating procedure. Typically, the lithiophilic Ag layer was constructed by immersing one piece of Cu foil in chemical silver plating solution for several minutes (Figure 1a). The in situ reaction can be described as44: 2 [Ag(NH3)2]+ + Cu → 2 Ag + [Cu(NH3)4]2+

(1)

6 [Ag(NH3)2]+ + C4H4O62- + 8 OH- → 6 Ag + 2 C2O42- + 12 NH3 + 6 H2O

(2)

The characteristic diffraction peaks of face-centered cubic (fcc) Ag (PDF#04-0783) at 38.1° and 44.3°corresponding to the (111) and (200) facets begin to appear (Figure 1b). The relative intensity of Ag phase gradually increases with extending reaction time, indicating more Ag are produced. The increase of reaction times leads to the formation of larger Ag particles and more compact Ag coatings (Figure 1c-1f and Figure S1). As for CuAg-1.5 and CuAg-2 samples, their surfaces are uniformly covered with Ag nanoparticles. It should be noted that the following discussions are mostly focused on CuAg-1.5 sample, as it exhibits the best electrochemical performances, which will be discussed below.


6

Page 7 of 19 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


Figure 1. (a) Schematic of the fabrication of CuAg sample from commercial Cu foil, and the typical images of bare Cu foil and the CuAg sample are shown in the upper section; (b) XRD spectra of bare Cu foil and CuAg samples with different reaction times; SEM images of bare Cu foil (c) and CuAg samples synthesized via different electroless plating times including 1 minute (d), 1.5 minutes (e), and 2 minutes (f). The scale bars in (c-f) represent 1 μm. To directly demonstrate the lithiophilicity difference of the current collectors before and after surface modification, the molten Li was placed onto these current collectors (Figure S2). Molten Li can be spontaneously spread out on the CuAg-1.5 sample surface because of the existence of lithiophilic Ag layer, while it condenses into a droplet on the commercial Cu current collector. The phenomenon accords with lithiophilic property of the Ag nanoparticles reported previously.37-38 The nucleation overpotential (ηn), which is calculated based on the difference between the voltage dip and the stable voltage platform, is considered as a metric to estimate the heterogeneous nucleation barrier at the beginning of Li deposition. The ηn is closely related to


7


Page 8 of 19

the lithiophilic properties of the substrate.45 According to the discharge profiles of bare Cu foil (Figure 2a), the voltage rapidly declines to -303 mV and then gradually stabilizes at -63 mV, resulting in a sharp voltage tip and a large ηn of -240 mV. In contrast, CuAg-1.5 sample presents a much lower ηn of -52 mV with smoother voltage tip at -102 mV and stable voltage platform at 50 mV. The first charge/discharge voltage profile of CuAg-1.5 sample is similar to that of

Figure 2. (a) Voltage curves of Li nucleation at 1 mA cm-2 on bare Cu foil and CuAg-1.5 sample; Galvanostatic discharge and charge voltage curves at 1 mA cm-2 of (b) Cu and (c) CuAg; SEM images of bare Cu current collectors with Li deposition of (d) 1 mAh cm-2, (e) 2 mAh cm-2; and after Li stripping (f) 1 mAh cm-2, (g) 2 mAh cm-2 (strip to 0.5 V); SEM images of CuAg sample current collectors with Li deposition of (h) 1 mAh cm-2, (i) 2 mAh cm-2; and after Li stripping (j) 1 mAh cm-2, (k) 2 mAh cm-2 (strip to 0.5 V) (Scale bar: 20 μm).


8

Page 9 of 19 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


previously reported Ag anode (Figure S3),46 manifesting the alloy reaction between Ag and Li. These results clearly prove that the nanostructured Ag layer can alloy with Li to form lithiophilic layer that can effectively minimize nucleation barriers, which is favorable to achieve uniform Li nucleation.45 The deposited Li morphology evolution of bare Cu foil and lithiophilic CuAg sample during plating/stripping process is monitored by SEM. The coin-type cells were assembled with bare Cu foil or CuAg-1.5 sample (working electrode) and Li foil (counter/reference electrode). A fixed current density (1 mA cm-2) was used for the cells and the voltage was collected against time (Figure 2b,c) during one complete plating/stripping process for 2 mAh cm-2 of Li. After 1 mAh cm−2 of Li was deposited on bare Cu foil, a loose and rough surface and Li particles with varied sizes are observed (Figure 2d), indicating the non-uniform Li nucleation and deposition. When Li plating capacity increase to 2 mAh cm−2, the uneven surface still exists on Cu foil (Figure 2e). In addition, many Li particles grow into Li filaments due to a self-exacerbated non-uniform Li growth. On the contrary, a flat and compact surface has been manifested on CuAg-1.5 sample, which is uniformly covered with nodule-like Li with similar sizes (Figure 2h). With plating capacity of 2 mAh cm-2, the CuAg-1.5 sample demonstrates a much smoother and denser surface compared with bare Cu foil (Figure 2i). After stripping 1 mAh cm-2 of Li, bare Cu foil presents a rough surface (Figure 2f), while the CuAg-1.5 sample surface remains smooth, demonstrating the uniform Li stripping (Figure 2j). The difference of Li stripping behavior is more clearly revealed by the SEM images at absolutely stripped state (strip to cut-off voltage of 0.5 V). Bare Cu foil shows a porous structure with some “dead Li’’ (Figure 2g and Figure S4), whereas the morphology of CuAg-1.5 sample is quite similar to its initial state, demonstrating the excellent reversibility of Li deposition/stripping process. The excellent reversibility of deposition/stripping


9


Page 10 of 19

process on CuAg-1.5 sample is further supported by the morphology after 150 cycles (Figure 3a,b). The CuAg-1.5 sample shows a smoother and denser texture with nodule-like Li, which is completely different from loose structure with mossy Li observed on bare Cu foil. In short, the homogeneous Ag nanoparticles with low Li nucleation overpotential could serve as Li nucleation sites to induce the metallic Li growth on Cu current collector with smooth surface, which remedies the self-exacerbated uneven Li growth on pristine Cu foil. The aforementioned uniform Li nucleation behavior in the CuAg-1.5 sample opens up the

Figure 3. SEM images of (a) bare Cu foil, and (b) CuAg-1.5 sample after 150 cycles at 1 mA cm-2; Voltage–time curves of Li anode deposition/stripping of bare Cu foil and CuAg-1.5 sample with (c) a cycling capacity of 1 mAh cm-2 at 1 mA cm-2 and (d) a cycling capacity of 2 mAh cm-2 at 2 mA cm-2; (e) Coulombic efficiencies of the Cu foil and CuAg-1.5 sample with an areal capacity of 1 mAh cm-2 at 1 mA cm-2 using 5 wt% LiNO3 additives; (f) The Nyquist curves of bare Cu foil and CuAg-1.5 sample in symmetrical cells after 100 cycles with a cycling capacity of 1 mAh cm-2 at 1 mA cm-2.


10

Page 11 of 19 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


opportunity to guide the following Li deposition/stripping process to realize enhanced cycle life of Li metal anodes. The CuAg-1.5 sample shows a long-term stability up to 360 h, which is more than twice that of the commercial Cu current collector (130 h) (Figure 3c). To further investigate the improved performance of CuAg-1.5 sample, we conduct cycling at a higher current density (2 mA cm−2) with a higher cycling capacity (2 mAh cm-2) (Figure 3d). The CuAg-1.5 sample exhibits stable cycling for 200 h with a small overpotential (~90 mV), while there are severe fluctuations with large overpotential (~170 mV) for bare Cu foil. Compared with bare Cu foil, the much better cycle stability of CuAg-1.5 sample is consistent with the more uniform and better stability of Li plating/stripping behavior (Figure 2). To tentatively investigate the coating effect of Ag nanoparticles, the electrochemical performances of decorated samples with different electroless plating times were evaluated (Figure S5). The voltage fluctuations of CuAg-1, CuAg2 and CuAg-3 samples arise around 200 h, 320 h and 210 h, respectively. This is because the partial exposure of Cu substrate in CuAg-1 sample may induce non-uniform Li nucleation and further exacerbate the subsequent plating/stripping process, while the crowed and larger Ag nanoparticles in CuAg-2 sample and CuAg-3 sample probably cannot tolerate the volumetric variation and hinder the diffusion of Li.42 The performances of the Cu foil and CuAg-1.5 samples were further examined by the CE, which is a critical parameter for assessing the reversibility of continual Li deposition/stripping. The CE of CuAg-1.5 sample could be stabilized at ~98% for ~50 cycles and presents the average CE of 94.5 % for 100 cycles at 1 mA cm-2 (cycling capacity of 1 mAh cm-2), while bare Cu foil presents a stable CE of ~95% for only 20 cycles and a rapid decay to less than 65% after 30 cycles (Figure 3e). The fluctuant voltage curves with obviously increased voltage hysteresis are shown on bare Cu foil (Figure S6a). On the contrary, the charge/discharge curves of the CuAg-


11


Page 12 of 19

1.5 sample (Figure S6b) present stable deposition/stripping behavior. The CE of CuAg-1.5 sample also outperforms that of Cu foil when the LiTFSI-DME/DOL electrolyte with 2 wt% LiNO3 additives is used (Figure S7). In summary, lithiophilic Ag nanoparticles with appropriate density facilitate the uniform Li nucleation and stable plating/stripping process, leading to a more stable cycling stability, higher CE and lower polarization of CuAg-1.5 current collector compared with bare Cu foil. The low polarization and stable cycling stability of CuAg-1.5 sample are further validated by EIS before cycling (Figure S8) and after 100 cycles (Figure 3f). The high-frequency semicircle stands for the resistance of SEI (RSEI) film and the low-frequency semicircle represents the charge-transfer resistance (Rct).47 Compared with Cu foil, a lower interfacial resistance is observed on CuAg-1.5 sample before cycling. Based on the Nyquist curves in Figure 3c, the equivalent circuit models (Figure S9) are used to determine the impedance of current collectors, as shown in Table S1. Both RSEI and Rct of CuAg-1.5 sample are smaller than those for Cu foil, especially RSEI (1.44 Ω for CuAg-1.5 sample and 37.87 Ω for Cu foil). These results clearly illustrate the significantly improved interfacial stability and favorable Li plating/stripping kinetics are enabled on CuAg-1.5 sample.48 It is evident that the deposition of lithiophilic Ag layer enables uniform Li deposition to form a stable anode/electrolyte interface for a long cycle lifetime.


12

Page 13 of 19 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


Figure 4. Cycling performances of Li@Cu||LFP and [email protected]||LFP full cells at (a) 1 C and (b) various rates ranging from 0.2 to 2 C. The loading of LiFePO4 is ~7 mg cm-2. To evaluate the practical application of the CuAg-1.5 current collector, full cells including Li@Cu||LFP and [email protected]||LFP were assembled. At 1 C (~1.1 mA cm-2, Figure 4a), [email protected]||LFP delivers capacity of ~72 mAh g-1 compared with ~55 mAh g-1 for Li@Cu||LFP counterparts. In addition, the performance of [email protected]||LFP also outperforms Li@Cu||LFP at 2 C (≈2.2 mA cm-2, Figure S10). [email protected]||LFP also exhibits higher rate capability and reduced voltage hysteresis than Li@Cu||LFP (Figure 4b and Figure S11). The improved electrochemical performances of these full cells is derived from the smoothly plated Li layer in CuAg-1.5 sample, which is enabled by the uniform lithiophilic Ag nanoparticles coating layer serving as Li nucleation seeds. The smoothly plated Li layer in return decreases the subsequent consumption of the limited Li and electrolyte in the full cell, due to the stable interface and the reduced voltage polarization for Li plating/stripping. Therefore, deeper charge/discharge of LiFePO4 (higher capacity) and higher rate performance can be realized on [email protected]||LFP full cell.


13


Page 14 of 19

4. CONCLUSIONS A commercial Cu foil with lithiophilic Ag nanoparticles coating was fabricated as the Li metal current collector by a facile, low-cost and scalable electroless plating approach. These homogeneously distributed Ag nanoparticles can alloy with Li to form lithiophilic layer and are thus beneficial to reduce nucleation overpotential, and guide Li uniform nucleation and deposition. The initial homogeneous deposition further regulates the following Li growth/stripping process, and thus a stable interface is realized with dendrite-free morphology. As a result, the CuAg-1.5 sample anode exhibits an improved lifespan up to 360 h at 1 mA cm−2, which is more than two times that of the commercial Cu foil (130 h). Furthermore, this CuAg-1.5 current collector also exhibits a high CE with average value of 94.5% for 100 cycles at 1mA cm2

. In addition, much improved cycling performance is also obtained in [email protected]||LFP full

cell. ASSOCIATED CONTENT Supporting Information Additional photographs, SEM characterizations and electrochemical measurement. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (Z.Q.) Author Contributions ‖

These authors contributed equally. The manuscript was written through contributions of all

authors. All authors have given approval to the final version of the manuscript.


14

Page 15 of 19 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


Notes There are no conflicts to declare. ACKNOWLEDGMENT This work was supported by Shenzhen Science and Technology Innovation Committee including Nos. KQJSCX20170328155428476 and KQTD2016053019134356, Development and Reform Commission of Shenzhen Municipality (Novel Nanomaterial Discipline Construction Plan), and start-up fund and Presidential fund from SUSTech.

REFERENCES 1. Zhao, Y.; Wang, L. P.; Xi, S.; Du, Y.; Yao, Q.; Guan, L.; Xu, Z. J., Encapsulating Porous SnO2 into a Hybrid Nanocarbon Matrix for Long Lifetime Li Storage. J. Mater. Chem. A 2017, 5, 25609-25617. 2. Zhou, H.; Nanda, J.; Martha, S. K.; Unocic, R. R.; Meyer, H. M., 3rd; Sahoo, Y.; Miskiewicz, P.; Albrecht, T. F., Role of Surface Functionality in the Electrochemical Performance of Silicon Nanowire Anodes for Rechargeable Lithium Batteries. ACS Appl. Mater. Interfaces 2014, 6, 7607-14. 3. Lin, Z.-Q.; Xie, J.; Zhang, B.-W.; Li, J.-W.; Weng, J.; Song, R.-B.; Huang, X.; Zhang, H.; Li, H.; Liu, Y.; Xu, Z. J.; Huang, W.; Zhang, Q., Solution-Processed Nitrogen-Rich GrapheneLike Holey Conjugated Polymer for Efficient Lithium Ion Storage. Nano Energy 2017, 41, 117-127. 4. Zhou, X.; Yu, L.; Yu, X.-Y.; Lou, X. W. D., Encapsulating Sn Nanoparticles in Amorphous Carbon Nanotubes for Enhanced Lithium Storage Properties. Adv. Energy Mater. 2016, 6, 1601177. 5. Lu, Y.; Yu, L.; Lou, X. W., Nanostructured Conversion-Type Anode Materials for Advanced Lithium-Ion Batteries. Chem. 2018, 4, 972-996. 6. Liang, J.; Hu, H.; Park, H.; Xiao, C.; Ding, S.; Paik, U.; Lou, X. W., Construction of Hybrid Bowl-Like Structures by Anchoring Nio Nanosheets on Flat Carbon Hollow Particles with Enhanced Lithium Storage Properties. Energy Environ. Sci. 2015, 8, 1707-1711. 7. Cheng, 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. 8. Lin, D.; Liu, Y.; Cui, Y., Reviving the Lithium Metal Anode for High-Energy Batteries. Nat. Nanotechnol. 2017, 12, 194-206. 9. Li, L.; Li, S.; Lu, Y., Suppression of Dendritic Lithium Growth in Lithium Metal-Based Batteries. Chem. Commun. 2018, 54, 6648-6661. 10. Xu, W.; Wang, J.; Ding, F.; Chen, X.; Nasybulin, E.; Zhang, Y.; Zhang, J.-G., Lithium Metal Anodes for Rechargeable Batteries. Energy Environ. Sci. 2014, 7, 513-537. 11. Ma, F.; Liang, J.; Wang, T.; Chen, X.; Fan, Y.; Hultman, B.; Xie, H.; Han, J.; Wu, G.; Li, Q., Efficient Entrapment and Catalytic Conversion of Lithium Polysulfides on Hollow Metal Oxide Submicro-Spheres as Lithium-Sulfur Battery Cathodes. Nanoscale 2018, 10, 56345641.


15


Page 16 of 19

12. Zhou, B.; Guo, L.; Zhang, Y.; Wang, J.; Ma, L.; Zhang, W. H.; Fu, Z.; Peng, Z., A HighPerformance Li-O2 Battery with a Strongly Solvating Hexamethylphosphoramide Electrolyte and a Lipon-Protected Lithium Anode. Adv. Mater. 2017, 29, 1701568. 13. Zhou, Y.; Li, Z.; Lu, Y.-C., A Stable Lithium–Selenium Interface Via Solid/Liquid Hybrid Electrolytes: Blocking Polyselenides and Suppressing Lithium Dendrite. Nano Energy 2017, 39, 554-561. 14. Chen, N.; Dai, Y.; Xing, Y.; Wang, L.; Guo, C.; Chen, R.; Guo, S.; Wu, F., Biomimetic AntNest Ionogel Electrolyte Boosts the Performance of Dendrite-Free Lithium Batteries. Energy Environ. Sci. 2017, 10, 1660-1667. 15. Jana, A.; García, R. E., Lithium Dendrite Growth Mechanisms in Liquid Electrolytes. Nano Energy 2017, 41, 552-565. 16. Tikekar, M. D.; Choudhury, S.; Tu, Z.; Archer, L. A., Design Principles for Electrolytes and Interfaces for Stable Lithium-Metal Batteries. Nat. Energy 2016, 1, 16114. 17. Peng, Z.; Zhao, N.; Zhang, Z.; Wan, H.; Lin, H.; Liu, M.; Shen, C.; He, H.; Guo, X.; Zhang, J.-G.; Wang, D., Stabilizing Li/Electrolyte Interface with a Transplantable Protective Layer Based on Nanoscale Lif Domains. Nano Energy 2017, 39, 662-672. 18. Camacho-Forero, L. E.; Balbuena, P. B., Elucidating Electrolyte Decomposition under Electron-Rich Environments at the Lithium-Metal Anode. Phys. Chem. Chem. Phys. 2017, 19, 30861-30873. 19. Ding, F.; Xu, W.; Graff, G. L.; Zhang, J.; Sushko, M. L.; Chen, X.; Shao, Y.; Engelhard, M. H.; Nie, Z.; Xiao, J.; Liu, X.; Sushko, P. V.; Liu, J.; Zhang, J. G., Dendrite-Free Lithium Deposition Via Self-Healing Electrostatic Shield Mechanism. J. Am. Chem. Soc. 2013, 135, 4450-6. 20. Choudhury, S.; Archer, L. A., Lithium Fluoride Additives for Stable Cycling of Lithium Batteries at High Current Densities. Adv. Electronic Mater. 2016, 2, 1500246. 21. Zheng, J.; Engelhard, M. H.; Mei, D.; Jiao, S.; Polzin, B. J.; Zhang, J.-G.; Xu, W., Electrolyte Additive Enabled Fast Charging and Stable Cycling Lithium Metal Batteries. Nat. Energy 2017, 2, 17012. 22. Ma, L.; Kim, M. S.; Archer, L. A., Stable Artificial Solid Electrolyte Interphases for Lithium Batteries. Chem. Mater. 2017, 29, 4181-4189. 23. Yan, K.; Lee, H. W.; Gao, T.; Zheng, G.; Yao, H.; Wang, H.; Lu, Z.; Zhou, Y.; Liang, Z.; Liu, Z.; Chu, S.; Cui, Y., Ultrathin Two-Dimensional Atomic Crystals as Stable Interfacial Layer for Improvement of Lithium Metal Anode. Nano Lett. 2014, 14, 6016-22. 24. Chen, L.; Chen, K. S.; Chen, X.; Ramirez, G.; Huang, Z.; Geise, N. R.; Steinruck, H. G.; Fisher, B. L.; Shahbazian-Yassar, R.; Toney, M. F.; Hersam, M. C.; Elam, J. W., Novel Ald Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes. ACS Appl. Mater. Interfaces 2018, 10, 26972-26981. 25. Lee, H.; Ren, X.; Niu, C.; Yu, L.; Engelhard, M. H.; Cho, I.; Ryou, M.-H.; Jin, H. S.; Kim, H.-T.; Liu, J.; Xu, W.; Zhang, J.-G., Suppressing Lithium Dendrite Growth by Metallic Coating on a Separator. Adv. Funct. Mater. 2017, 27, 1704391. 26. Liu, K.; Zhuo, D.; Lee, H. W.; Liu, W.; Lin, D.; Lu, Y.; Cui, Y., Extending the Life of Lithium-Based Rechargeable Batteries by Reaction of Lithium Dendrites with a Novel Silica Nanoparticle Sandwiched Separator. Adv. Mater. 2017, 29, 1603987. 27. Zhang, W.; Tu, Z.; Qian, J.; Choudhury, S.; Archer, L. A.; Lu, Y., Design Principles of Functional Polymer Separators for High-Energy, Metal-Based Batteries. Small 2018, 14, 1703001.


16

Page 17 of 19 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


28. Liu, L.; Yin, Y. X.; Li, J. Y.; Guo, Y. G.; Wan, L. J., Ladderlike Carbon Nanoarrays on 3D Conducting Skeletons Enable Uniform Lithium Nucleation for Stable Lithium Metal Anodes. Chem. Commun. 2018, 54, 5330-5333. 29. Li, Q.; Zhu, S.; Lu, Y., 3D Porous Cu Current Collector/Li-Metal Composite Anode for Stable Lithium-Metal Batteries. Adv. Funct. Mater. 2017, 27, 1606422. 30. Yang, G.; Chen, J.; Xiao, P.; Agboola, P. O.; Shakir, I.; Xu, Y., Graphene Anchored on Cu Foam as a Lithiophilic 3D Current Collector for a Stable and Dendrite-Free Lithium Metal Anode. J. Mater. Chem. A 2018, 6, 9899-9905. 31. Wang, G.; Xiong, X.; Lin, Z.; Zheng, J.; Fenghua, Z.; Li, Y.; Liu, Y.; Yang, C.; Tang, Y.; Liu, M., Uniform Li Deposition Regulated Via Three-Dimensional Polyvinyl Alcohol Nanofiber Networks for Effective Li Metal Anodes. Nanoscale 2018, 10, 10018-10024. 32. Xiong, W. S.; Xia, Y.; Jiang, Y.; Qi, Y.; Sun, W.; He, D.; Liu, Y.; Zhao, X. Z., Highly Conductive and Robust Three-Dimensional Host with Excellent Alkali Metal Infiltration Boosts Ultrastable Lithium and Sodium Metal Anodes. ACS Appl. Mater. Interfaces 2018, 10, 21254-21261. 33. Ke, X.; Cheng, Y.; Liu, J.; Liu, L.; Wang, N.; Liu, J.; Zhi, C.; Shi, Z.; Guo, Z., Hierarchically Bicontinuous Porous Copper as Advanced 3D Skeleton for Stable Lithium Storage. ACS Appl. Mater. Interfaces 2018, 10, 13552-13561. 34. Ye, H.; Xin, S.; Yin, Y. X.; Li, J. Y.; Guo, Y. G.; Wan, L. J., Stable Li Plating/Stripping Electrochemistry Realized by a Hybrid Li Reservoir in Spherical Carbon Granules with 3D Conducting Skeletons. J. Am. Chem. Soc. 2017, 139, 5916-5922. 35. Qin, L.; Xu, H.; Wang, D.; Zhu, J.; Chen, J.; Zhang, W.; Zhang, P.; Zhang, Y.; Tian, W.; Sun, Z., Fabrication of Lithiophilic Copper Foam with Interfacial Modulation toward High-Rate Lithium Metal Anodes. ACS Appl. Mater. Interfaces 2018, 10, 27764-27770. 36. Ye, H.; Zheng, Z. J.; Yao, H. R.; Liu, S. C.; Zuo, T. T.; Wu, X. W.; Yin, Y. X.; Li, N. W.; Gu, J. J.; Cao, F. F.; Guo, Y. G., Guiding Uniform Li Plating/Stripping through LithiumAluminum Alloying Medium for Long-Life Li Metal Batteries. Angew. Chem. Int. Ed. 2018, 58, 1094-1099. 37. Yan, K.; Lu, Z.; Lee, H.-W.; Xiong, F.; Hsu, P.-C.; Li, Y.; Zhao, J.; Chu, S.; Cui, Y., Selective Deposition and Stable Encapsulation of Lithium through Heterogeneous Seeded Growth. Nat. Energy 2016, 1, 16010. 38. Yang, C.; Yao, Y.; He, S.; Xie, H.; Hitz, E.; Hu, L., Ultrafine Silver Nanoparticles for Seeded Lithium Deposition toward Stable Lithium Metal Anode. Adv. Mater. 2017, 29, 1702714. 39. Zhang, Z.; Xu, X.; Wang, S.; Peng, Z.; Liu, M.; Zhou, J.; Shen, C.; Wang, D., Li2OReinforced Cu Nanoclusters as Porous Structure for Dendrite-Free and Long-Lifespan Lithium Metal Anode. ACS Appl. Mater. Interfaces 2016, 8, 26801-26808. 40. Zhao, H.; Lei, D.; He, Y.-B.; Yuan, Y.; Yun, Q.; Ni, B.; Lv, W.; Li, B.; Yang, Q.-H.; Kang, F.; 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. 41. Luo, J.; Fang, C.-C.; Wu, N.-L., High Polarity Poly(Vinylidene Difluoride) Thin Coating for Dendrite-Free and High-Performance Lithium Metal Anodes. Adv. Energy Mater. 2018, 8, 1701482.


17


Page 18 of 19

42. Zhang, C.; Lv, W.; Zhou, G.; Huang, Z.; Zhang, Y.; Lyu, R.; Wu, H.; Yun, Q.; Kang, F.; 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. 43. Wu, S.; Zhang, Z.; Lan, M.; Yang, S.; Cheng, J.; Cai, J.; Shen, J.; Zhu, Y.; Zhang, K.; Zhang, W., Lithiophilic Cu-Cuo-Ni Hybrid Structure: Advanced Current Collectors toward Stable Lithium Metal Anodes. Adv. Mater. 2018, 30, 1705830. 44. Hai, H. T.; Ahn, J. G.; Kim, D. J.; Lee, J. R.; Chung, H. S.; Kim, C. O., Developing Process for Coating Copper Particles with Silver by Electroless Plating Method. Suf. Coat. Technol. 2006, 201, 3788-3792. 45. Zhang, R.; Chen, X. R.; Chen, X.; Cheng, X. B.; Zhang, X. Q.; Yan, C.; Zhang, Q., Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes. Angew Chem. Int. Ed. 2017, 56, 7764-7768. 46. Morales, J.; Sanchez, L.; Martin, F.; Ramos-Barrado, J. R.; Sanchez, M., Synthesis, Characterization, and Electrochemical Properties of Nanocrystalline Silver Thin Films Obtained by Spray Pyrolysis. J. Electrochem. Soc. 2004, 151, A151-A157. 47. Bieker, G.; Winter, M.; Bieker, P., Electrochemical in Situ Investigations of Sei and Dendrite Formation on the Lithium Metal Anode. Phys. Chem. Chem. Phys. 2015, 17, 8670-9. 48. Lin, D.; Liu, Y.; Liang, Z.; Lee, H. W.; Sun, J.; Wang, H.; Yan, K.; Xie, J.; Cui, Y., Layered Reduced Graphene Oxide with Nanoscale Interlayer Gaps as a Stable Host for Lithium Metal Anodes. Nat. Nanotechnol. 2016, 11, 626-32.


18

Page 19 of 19 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


TOC


19

Lithiophilic Ag Nanoparticle Layer on Cu Current Collector towards

Recommend Documents