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High Rate and Stable Solid-State Lithium Metal Batteries Enabled by Electronic and Ionic Mixed Conducting Network Interlayers Zhengxin Zhu, Lei-Lei Lu, Yichen Yin, Jiaxin Shao, Bao Shen, and Hong-Bin Yao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b02184 • Publication Date (Web): 23 Apr 2019 Downloaded from http://pubs.acs.org on April 23, 2019

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ACS Applied Materials & Interfaces

High Rate and Stable Solid-State Lithium Metal Batteries Enabled by Electronic and Ionic Mixed Conducting Network Interlayers Zhengxin Zhu†, Lei-Lei Lu†, Yichen Yin, Jiaxin Shao, Bao Shen, Hong-Bin Yao* Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Hefei Science Center of CAS, Department of Applied Chemistry, Center for Micro- and Nanoscale Research and Fabrication, University of Science and Technology of China, Hefei, Anhui 230026, China. † These authors contributed equally *Corresponding author. [email protected]

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Abstract All solid-state lithium (Li) metal batteries (SSLMBs) are attractive for prospective electrochemical energy storage systems on account of their high energy densities and good safeties. However, the incompatible interface between solid-state electrolyte (SSE) and Li metal anode limits the ability of SSLMBs. Here, a three dimensional (3D) electronic and ionic mixed conducting interlayer is proposed to improve the interfacial affinity in SSLMBs. The 3D electronic and ionic mixed conducting interlayer is composed of Sn/Ni alloy layer coated Cu nanowire (Cu@SnNi) network. The Li plating demonstrates that the Cu@SnNi network can possess fast Li+ ion transport channels from the Li metal to the LiFePO4, acting as a stable interlayer between Li metal and solid polymer electrolyte. Noticeably, solid-state LiFePO4/Li cell with a Cu@SnNi interlayer exhibits an excellent rate capability (133 mAh g−1, 2 C; 100 mAh g−1, 5 C) in comparison to low rate performance of the cell without the interlayer (117 mAh g−1, 2 C; 60 mAh g−1, 5 C). This unique structure design of electronic and ionic mixed conducting interlayer provides an alternative strategy to improve the performance of SSLMBs.

Keywords: Mixed conductor, interlayer, solid-state, lithium metal anode, lithium-tin alloy


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Introduction Although rechargeable lithium (Li) ion batteries have achieved great success in portable electronics in the past decades, their limited theoretical energy densities are hard to satisfy future demand in electric vehicles and grid-scale energy storage.1,

2

To explore electrode

materials for high energy density batteries, many high capacity anode materials including Sn,3, 4

Si,5, 6 and Li metal,7, 8 have been considered. Among them, Li metal anode has attracted

intensive attention due to its highest theoretical specific capacity (3860 mAh g-1) and lowest redox potential (-3.04 V vs. standard hydrogen electrode).9-12 However, in traditional liquid Li metal batteries, the fragile solid electrolyte interface (SEI) cannot form good protection to prevent the dendritic growth of Li and the continuous reaction between liquid electrolyte and Li metal, leading to serious safety issue and low Coulombic efficiency of Li metal batteries.13, 14

Although much effort has been made to improve the stability of Li metal anodes in liquid

electrolyte systems via various artificial SEI designs, the intrinsic high-reactivity of Li metal and the flammability of organic electrolytes are still huge obstacles for achieving high safety of Li metal batteries.7, 15-20 Using non-flammable solid-state electrolytes (SSEs) to replace liquid electrolyte is hopeful to solve the safety issue of Li metal batteries.21-24 Presently, SSEs are categorized into inorganic solid electrolytes (ISEs) and solid polymer electrolytes (SPEs).25-28 Although high ionic conductivity of ISEs has been achieved in recent years, the poor rigid solid-solid interfacial contacts between ISEs and electrodes lead to complex manufacture and low active material mass loading of all solid-state Li metal batteries (SSLMBs).21, 29 Compared to ISEs, SPEs possess good flexibility and high processibility, enabling compact contact with electrodes,



meanwhile simplifying the manufacture process of SSLMBs.26,

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30-34

However, the conflict

between the mechanical strength and ionic conductivity of SPEs limited their applications in SSLMBs.26,

35-37

In this scenario, to enable high performance of SSLMBs, an alternative

strategy is highly desirable beside only focusing on the design of high performance SSEs.38 Especially, the low surface area and drastic interfacial fluctuation of planar Li metal anode during cycling are non-negligible for further improving the performance of SSLMBs.36, 37 Recently, three dimensional (3D) electronic conductive networks have exhibited the capability to enhance the performance of Li metal anode via reducing the effective current density in liquid electrolyte system.19, 38-42 Unfortunately, unlike the liquid electrolyte, SSEs barely has the fluidity to provide good Li+ ion conductive channels within 3D network electrode. Therefore, the construction of mixed electronic and ionic conductive 3D network is necessary in solid-state Li metal anode. Very recently, Hu et al. have introduced a mixed electronic and ionic conductor at both the cathode-electrolyte and the Li metal anode-electrolyte interfaces and demonstrated the improved Li+ ion transfer in SSLMBs.41, 43 In the proposed design, high Li+ ionic transport is prerequisite for such 3D mixed electronic and ionic conducting network and the Li+ ion diffusion coefficient of lithiated carbon nanotubes (10−14-10−13 cm2 s−1) reported by Hu et al. is still low.18,

44

The Li-alloys (e.g., Li-Sn alloy) exhibit much faster Li+ ion

diffusion coefficient of 6.6×10−8-5.6×10−7 cm2 s−1 than lithiated carbon nanotubes at room temperature.7, 45 It has been demonstrated that the Li-Sn alloy layer can be used as a surface protection layer of planar Li metal anode due to its good wettability to SSE and high Li+ ionic conductivity.46 Herein, we reported a 3D Sn/Ni alloy layer coated copper nanowires (CuNWs) network


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(Cu@SnNi) as an electronic and ionic mixed conducting interlayer to improve the performance of SSLMBs. The Sn/Ni alloy layer was coated onto a 3D CuNWs network via galvanostatical electrodeposition to form a 3D Cu@SnNi interlayer. In our fabricated Cu@SnNi interlayer, the Li+ ions flowed in the lithiated Sn/Ni alloy layer and electrons flowed along the CuNWs, thus forming a mixed electronic and ionic conductor to facilitate charge transfer to endow homogeneous electron/ion flux distribution in the interlayer. As results, the solid-state LiFePO4/Li cell with a Cu@SnNi interlayer exhibited an excellent rate capability (133 mAh g−1, 2 C; 100 mAh g−1, 5 C) and good cycling stability (only 13% capacity decay after 200 cycles at 1 C), compared with low rate performance (117 mAh g−1, 2 C; 60 mAh g−1, 5 C) and short cycling life (short circuit after 30 cycles at 1 C) of the cell without the interlayer. Experimental Section Synthesis of copper nanowires (CuNWs) CuNWs were synthesized according to previously reported method42. In brief, the aqueous solution was composed of ethylenediamine (10 mL), hydrazine (342 μL), Cu(NO3)2 (20 mL, 0.2 M), and NaOH (670 mL, 15 M) in 1000 mL of round bottom flask. Then, the mixture was stirred to form a homogenous solution and heated at 80 oC under stirring at 200 rpm for 80 minutes. Gradually, the yielded CuNWs floated on the surface of the solution. After the reaction, the subnatant was decanted from the flask and the obtained CuNWs were dispersed in an aqueous solution of hydrazine (3 wt%) by hand shake, and then washed by hydrazine (3 wt%) aqueous solution and ethanol each for 3 times. The final CuNWs were stored in 5 mL of ethanol solution at room temperature to minimize the oxidation. The concentration of the obtained CuNW solution approaches to 24 mg mL-1.



Fabrication of CuNWs membrane CuNWs (2mL) ethanol solution was poured into an organic glass (2 × 2 cm) mould and evaporated the solvent at room temperature forming a NW interpenetrated membrane. Finally, the membrane was treated with an annealed process for 4 h at 450 oC under H2/Ar (5%/95%) atmosphere. In this annealing process, the amorphous Cu(OH)2 on the surface of CuNWs could be reduced to Cu and the junctions of CuNWs were infused together, which largely enhanced the conductivity of the CuNWs membrane. Fabrication of CuNWs network with a Sn/Ni alloy layer coating (Cu@SnNi) The Sn/Ni alloy layer was were manufactured on the CuNWs membrane from an aqueous solution by electrodeposition. The aqueous electrodeposition solution was composed of NiSO4 (0.075 M), SnSO4 (0.175 M), K4P2O7 (0.5 M), glycine (0.125 M), and NH4OH (5 mL L–1). The counter electrode of Pt and working electrode of CuNWs membrane were immersed in the electrodeposition solution. And the current density of 5 mA cm-2 performed for ~45 min. Finally, the received Cu@SnNi membrane was annealed for 4 h at 450 oC by H2/Ar (5%/95%) atmosphere. The typical thickness of as-fabricated Cu@SnNi membrane was 60-70 μm. Preparation of solid poly(ethylene oxide)-lithium bis(trifluoromethanesulfonimidate) (PEOLiTFSI) polymer composite electrolyte 3 g of PEO (Mw = 600000) and 1.0875 g of LiTFSI to give [EO]: [Li] ratio of 18:1 were homogeneous mixed in anhydrous acetonitrile (ACN). The obtained solution (50 mL) was then cast into a Teflon evaporating dish (10 × 10 cm). A membrane was obtained by evaporating the solvent naturally about 12 h and drying at 60 oC in a vacuum oven about 1 day to remove a little water. The typical thickness of as-fabricated PEO solid electrolyte membrane was ~250


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μm. Fabrication of the LiFePO4 (LFP) cathode For making LFP cathode, LFP (1.3 g), carbon black (0.3 g), PEO (0.2936 g) and LiTFSI (0.1064 g) were mixed in ACN by a planetary ball mill (PM100, Retsch, German), and then pasted on a Al foil with an active quality of ~2.0 mg cm−2. Finally, the foil was dried at 60 oC about 1 day. Electrochemical tests The galvanostatic intermittent titration technique (GITT) measurements of the electrodes using pre-lithiated 3D Cu@SnNi membrane were conducted on a Bio-Logic VMP3 electrochemical working station at room temperature. The test procedure composed of cycles that include 15 min galvanostatic discharge pulse (0.2 mA cm-2) and 20 min of relaxation time until the discharge capacity increasing to 5 mAh cm-2. For solid-state cells, the Li foil as the anode, PEO-electrolyte membrane as the solid electrolyte and LFP as the cathode were assembled in a 2032-type coin cell with a 3D Cu@SnNi interlayer or not. To strengthen the contact of 3D Cu@SnNi interlayer with Li foil, the 3D Cu@SnNi membrane was firstly pressed onto Li metal surface and then removed the loosely contacted non-uniform Cu@SnNi NWs before assembling the cells. The operated voltage of full cell was set at 2.5-3.8 V on Land multichannel test system. The Li metal deposition was tested at 0.02 mA cm-2 for pre-lithiation and then at 0.05 mA cm-2 for Li plating on Land multichannel test system. Electrochemical impedance spectra was collected by Bio-Logic VMP3 electrochemical working station with a frequency at 0.1 MHz-100 mHz. The electrochemical tests were carried out in an oven at the temperature of 60 oC.



Characterizations Powder diffraction X-ray (PXRD) patterns were collected on a Philips X’Pert PRO SUPER Xray diffractometer monochromatized Cu Kα radiation. A Hitachi HT-7700 transmission electron microscope (TEM), and the energy dispersive X-ray spectroscopy (EDS) elemental mapping were was employed to visualize the morphologies elemental compositions of Cu@SnNi NW. A JEOL-6700F scanning electron microscope (SEM) was used to observe the morphologies and elemental compositions of Cu@SnNi NWs. Results and Discussion To demonstrate the nature of mixed electronic and ionic conducting of our proposed interlayer, the ionic and electronic conductivity of the interlayer were first tested. It is notable that the fabricated CuNWs, Cu@SnNi networks and lithiated Cu@SnNi interlayer were with good electronic conductivities (Figure S1a, b and S2) which can guarantee the fast transfer of electrons in the interlayer. The Li+ ion conductivity (σ) of lithiated Cu@SnNi interlayer was determined via galvanostatic intermittent titration technique (Figure S3, details in Supporting Information). At the initial stage, the high σ of the Cu@SnNi interlayer (2.4×10-2-8.8×10-2 S cm-1) proved that the Cu@SnNi interlayer could serve as a good Li+ ion conductivity (Table S1). Therefore, the lithiated Cu@SnNi interlayer is a good electronic and ionic conductor. The proposed mechanism of mixed electronic and ionic conducting 3D Cu@SnNi interlayer design for improving the performance of SSLMBs is illustrated in Figure 1. In the incipient charging process of solid-state LiFePO4/Li cell, the Li+ ions flow from LiFePO4 cathode to the solid polymer electrolyte and then to 3D Cu@SnNi interlayer and meanwhile electrons flow through the Li foil to reach the Cu@SnNi interlayer as well. As a consequence, the Sn/Ni alloy layer


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on the surface of CuNWs is gradually lithiated to form Li-Sn alloy layer, which can serve as a fast Li+ ion transport channel in the interlayer. In the subsequent discharging process of the cell, the Li+ ions provided by the Li metal anode can flow through the lithiated Li-Sn alloy layer to the solid polymer electrolyte and then to LiFePO4 cathode. After several charging/discharging cycles, a highly electronic and ionic mixed conducting lithiated 3D Cu@SnNi interlayer is formed in the cell and can serve as an interconnected host with high surface area to largely increase electrochemical reaction kinetics and accommodate the Li plating. Therefore, the rate and cycling performance of as-fabricated solid-state LiFePO4/Li cell are improved.

Figure 1. Schematic illustration of the working mechanism of SSLMBs based a 3D electronic and ionic mixed conducting interlayer based on polymer electrolyte. LFP: LiFePO4 cathode, PEO: poly(ethylene oxide) electrolyte. To fabricate the mixed electronic and ionic conducting interlayer, 3D CuNWs networks were prepared according to our previously reported method42 and Cu@SnNi networks were prepared



via electrodeposition of Sn/Ni alloy on the surface of CuNWs. Characterizations of TEM, EDS mapping, and SEM were made to reveal the morphological evolution of nanowires (NWs) during the preparation process of 3D Cu@SnNi networks. Figure 2a shows that the freestanding CuNWs membrane (inset in Figure 2a) is composed of interconnected CuNWs. After Sn/Ni alloy electrodeposition, Sn/Ni alloy layer was uniformly coated onto the surface of CuNWs (Figure 2b). As the result, the membrane was from red to gray (inset in Figure 2b) and the diameter of NWs increased from an average size of 145 to 398 nm (Figure 2c, d). The phase of Sn/Ni alloy layer in as-fabricated Cu@SnNi membrane was confirmed as Ni3Sn2 by PXRD (Figure S4). The typical TEM image of Cu@SnNi NWs (Figure 2e) shows that Sn/Ni alloy layer around the CuNW behaves a smooth surface demonstrating the homogenous electrodeposition of this alloy layer. EDS mapping images (Figure 2f-i) further confirm that the elemental distributions of Sn and Ni predominately locate on the edge of CuNW indicating the core/shell structure of as-obtained Cu@SnNi NWs. Moreover, the cross-sectional SEM image and corresponding EDS mappings of as-fabricated 3D Cu@SnNi network (Figure S5) demonstrate that Sn/Ni alloy coating is fully distributed in the whole 3D Cu@SnNi network.


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Figure 2. Characterizations of 3D CuNWs and Cu@SnNi networks. (a) Cross-sectional SEM image of 3D CuNWs network (inset is corresponding photograph). (b) Cross-sectional SEM image of 3D Cu@SnNi network (inset is corresponding photograph). (c) Diameter distribution statistics of CuNWs network. (d) Diameter distribution statistics of Cu@SnNi network. e) TEM image of Cu@SnNi NW. (f-i) The overlapped and individual elemental mapping image of Cu, Sn, Ni of Cu@SnNi NW, respectively. To demonstrate the homogeneous lithiation guidance role of Sn/Ni layer in 3D network interlayer (Figure 3a), the Li plating behaviors on 3D CuNWs and Cu@SnNi networks were both investigated in 2032 coin cell by counter electrode of Li foil and solid electrolyte of PEOLiTFSI composite. The areal capacity of Li metal plating in 3D NW network was set as 5 mAh cm-2 at 0.05 mA cm-2. Before Li metal plating, the tested cells were discharged to a cut-off



voltage of 0 V (vs. Li+/Li) at 0.02 mA cm-2 to guarantee the full lithiation of Sn/Ni alloy layer. The voltage profile of the cell based on the 3D CuNWs network (Figure 3b, black line) showed a rapid fluctuation at a low plating capacity of Li (1.85 mAh cm-2), which indicates short circuit of cell probably caused by the irregular Li dendritic growth on the surface of CuNWs that close to the PEO-LiTFSI electrolyte. In contrast, the voltage profile of cell based on 3D Cu@SnNi network (Figure 3b, red line) showed a flat Li plating plateau even after Li plating of 5 mAh cm-2. To further show the spatial distribution of Li metal plated in the 3D networks, crosssectional SEM characterizations were conducted on the 3D CuNWs and Cu@SnNi networks after Li plating of 5 mAh cm−2. Figure 3c shows the Li was irregularity plated in the interior pores of 3D CuNWs networks (marked out by the green color) and the diameter of the CuNWs only slightly increased from 145 to 196 nm (Figure 3d). In contrast, the inner pores of 3D Cu@SnNi network were not filled by the irregularly plated bulk Li metal, which indicates that the Li homogenously distributed on the surface of Cu@SnNi NWs (Figure 3e). As the result, the average diameter of Cu@SnNi NWs largely increased from 398 to 578 nm (Figure 3f). The homogeneously plating of Li in the 3D Cu@SnNi network is attributed to the plating guidance role of lithiated Sn/Ni layer formed in the initial pre-lithiation process. To demonstrate the consistence of Li plating behaviors in the 3D Cu@SnNi network, the morphologies of as-plated Li metal in the network under different conditions were further characterized. With the plating current density increasing to 0.2 mA cm-2, the plated Li metal was still homogeneously coated on the surface of NWs (Figure S6a, b), which indicates that the 3D Cu@SnNi network can guide the homogeneous Li deposition even under a higher current density. With the plating capacity increasing to 10 mAh cm-2, the 3D porous network structure of Cu@SnNi is still


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maintained only with the thickening of the NWs (Figure S6c, d). All these half-cell Li plating studies implied that the Li+ ions can flow through the 3D Cu@SnNi network along the lithiated Sn/Ni alloy layer, which means that as-fabricated 3D Cu@SnNi network has the potential to act as an electronic and ionic mixed conducting interlayer between the PEO-electrolyte and Li metal anode to enhance the interfacial affinity, Li+ ions transport capability, and eliminate the Li dendritic growth.



Figure 3. The plating behavior study of Li metal in 3D CuNWs and Cu@SnNi networks. (a) Schematic illustration of the process of Li metal plating in 3D CuNWs and Cu@SnNi networks. (b) Li plating voltage profiles of 3D CuNWs and Cu@SnNi networks at 0.02 mA cm-2 for lithiation and then 0.05 mA cm-2 for Li metal plating. (c, d) Cross-sectional SEM image and diameter distribution statistics of 3D CuNWs networks after Li plating. (e, f) Crosssectional SEM image and diameter distribution statistics of 3D Cu@SnNi networks after Li plating. To show the potential of electronic and ionic mixed conducting 3D Cu@SnNi network as an


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interlayer in SSLMBs, the Li/PEO-electrolyte/CuNWs-Li and Li/PEO-electrolyte/Cu@SnNiLi asymmetry cells were firstly assembled and tested at 0.2 mA cm-2 with a Li plating/stripping capacity of 1 mAh cm-2. Figure 4a shows the initial Li plating can be processed in the cell based on CuNWs interlayer with a stable voltage profile but the voltage of stripping process quickly reached to 3V with a very limited amount of Li that stripped out. This reason could be put down to the fact that the interlayer of CuNWs network can not provide efficient Li+ ions conducting channels to promote the Li stripping from the Li metal electrode. However, when the 3D Cu@SnNi network was used as the interlayer, the Li plating/stripping behavior in the asymmetry cell was totally different. As shown in Figure 4b, the 3D Cu@SnNi network was firstly lithiated and then the Li plating with a stable voltage profile was followed. During the Li stripping process, the voltage gradually increased to ~1 V rather than the immediate increase over 3 V as behaved in the cell using CuNWs interlayer. Impressively, with more cycles processing, the Li stripping voltage profile became more flat with a stripping voltage around 0.4 V indicating an activation process of the 3D Cu@SnNi interlayer to form efficient Li+ ions transport channels. The interfacial resistance after the lithiation is lower than that of pristine sample revealed by electrochemical impedance spectroscopy (EIS) analysis (Figure S7), which further indicates that the lithiation process of Cu@SnNi interlayer could improve the Li+ ions transport. To further show the effectiveness of the electronic and ionic mixed conducting network, the cycling performance of the Li/PEO-electrolyte/Li cells was also tested. Figure S8 shows the Li/PEO-electrolyte/Cu@SnNi-Li cell exhibited longer cycling stability (more than 200 h) in comparison to short cycling life of the cell without Cu@SnNi interlayer (less than 130 h). To demonstrate the structural stability of the interlayer, after several cycles of Li plating



and striping, the morphology of interlayer was characterized by SEM. Two stages of delithiation (a) and lithiation (b) were selected to compare the morphology of Cu@SnNi network marked in the Figure S9. As shown in Figure S10a, the average diameter of Cu@SnNi NWs increased from 398 to 518 nm after several cycles of de-lithiation and lithiation (Figure S10c) and the NWs structure still maintained. In the next lithation and deposition process, the obvious NWs structure of network was also observed (Figure S10b) and the average diameter of NWs slightly increased from 518 to 616 nm (Figure S10d) without structure collapse. These results demonstrated that the lithiated Cu@SnNi interlayer could be as a stable and effective Li+ ion conducting network and induce Li plating. To demonstrate the efficiency of 3D Cu@SnNi interlayer in SSLMBs, the performance of LiFePO4/PEO-electrolyte/Cu@SnNi-Li cell was evaluated and compared to that of LiFePO4/PEO-electrolyte/Li cell. Figure 4c shows the charge/discharge voltage profiles of first six cycles at 0.1 C (1 C = 170 mA g-1) of as-fabricated LiFePO4/PEO-electrolyte/Cu@SnNi-Li cell. It seems that the cell would need an activation process to reach the normal charge/discharge voltage profiles of the LiFePO4/PEO-electrolyte/Li cell (Figure S11) in accord with the results as shown in the half cell of Li/PEO-electrolyte/Cu@SnNi-Li (Figure 4b). After finishing the activation process, the Coulombic efficiency (CE) of the cell can reach to near 100%. In contrast, the cell using CuNWs network as an interlayer delivered low discharge capacity (73 mAh g-1), Coulombic efficiency (47.5%) and very fast capacity decay due to the poor Li+ ions transport in as-used CuNWs network (Figure S12a). In addition, the cell using the Sn foil as an interlayer also delivered very low discharge capacity (14.5 mAh g1)

because it is hard to activate the dense Sn layer to be Li+ ions conductive during the initial


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charging process (Figure S12b). These poor performances of control cells indicate that the 3D Cu@SnNi network interlayer played a crucial role on promoting the charge transfer in the solid-state cell owing to its mixed electronic and ionic conductive characteristic.

Figure 4. Electrochemical performances of different solid-state cells. (a), (b) Voltage profiles of Li/PEO-electrolyte/CuNWs-Li cell and Li/PEO-electrolyte/Cu@SnNi-Li cell at 0.2 mA cm2 with a Li plating/stripping capacity of 1 mAh cm-2, respectively. (c) Charge/discharge voltage profiles of LiFePO4/PEO-electrolyte/Cu@SnNi-Li cell at 0.1 C (1 C = 170 mA g-1) in the first six cycles. (d) EIS spectra of LiFePO4/PEO-electrolyte/Li and LiFePO4/PEOelectrolyte/Cu@SnNi-Li cells after 1 cycle and after 45 cycles. (e) Rate capability comparison



of LiFePO4/PEO-electrolyte/Li and LiFePO4/PEO-electrolyte/Cu@SnNi-Li cells. (f) Cycling performance of LiFePO4/PEO-electrolyte/Li and LiFePO4/PEO-electrolyte/Cu@SnNi-Li cells at 1 C.

The EIS analysis further proved the fast charge transfer at the Li-Cu@SnNi/PEO-electrolyte interface. As shown in Figure 4d, the semicircle of high frequency range pointed out the interfacial resistance between Li-Cu@SnNi/PEO-electrolyte or Li/PEO-electrolyte. In the LiFePO4/PEO-electrolyte/Cu@SnNi-Li cell, a low interfacial resistance of ~55 Ω after 1 cycle was observed and it increased only a little to ~70 Ω after 45 cycles. In comparison, the LiFePO4/PEO-electrolyte/Li cell showed a large interfacial resistance of ~90 Ω after 1 cycle and a much larger value of ~110 Ω after 45 cycles due to the drastic interfacial fluctuation of planner Li metal anode during cycling. The rate performance of the cell with Cu@SnNi interlayer was tested and compared with the cell without the interlayer as well. As shown in Figure S13, it is apparent that the solid cell with a 3D Cu@SnNi interlayer exhibited a much better rate performance in comparison to the cell without an interlayer. The discharge capacity of the cell with a 3D Cu@SnNi interlayer reached up to 133 and 100 mAh g−1 at 2 and 5 C, respectively but the cell without the interlayer only delivered discharge capacity of 117 and 60 mAh g−1 at 2 and 5 C, respectively (Figure 4e). The cycling stability of LiFePO4/PEOelectrolyte/Li and LiFePO4/PEO-electrolyte/Cu@SnNi-Li cells was further evaluated at 1 C. As shown in Figure 4f, the solid-state cell with a Cu@SnNi interlayer exhibited good cycling stability (0.065% decay per cycle) with 87% capacity retention after 200 cycles from 149.5 to 129.5mAh g-1. In contrast, the abnormal CE occurred in the cell using pure PEO based electrolyte without the interlayer only after 30 cycles due to the partial short circuit resulting from the deterioration of the interface between PEO-electrolyte and Li metal 30, 47.


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Conclusions In summary, we reported a 3D Cu@SnNi network as an electronic and ionic mixed conducting interlayer to improve the performance of SSLMBs. The mixed electronic and ionic conducting interlayer design for SSLMBs displayed fast Li+ ion transport from the anode to the cathode and stable network structure. As the results, the 3D networks can accommodate Li metal and the excellent rate capability can be realized in the cell of LiFePO4/PEO-electrolyte/Li using 3D Cu@SnNi interlayer between the Li metal and PEO-electrolyte. The fabricated LiFePO4/PEOelectrolyte/Cu@SnNi-Li solid cell exhibited high rate capability (133 mAh g−1, 2 C; 100 mAh g−1, 5 C) and good cycling stability (0.065% decay each cycle for 200 cycles at 1 C). The proposed 3D mixed electronic and ionic conducting interlayer design will open a new avenue to fabricated high performance SSLMBs.

Associated Content Supporting Information The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org. Photograph of measurement of the resistance of CuNWs and Cu@SnNi membranes, the measurement of electronic and ionic conductivity of lithiated Cu@SnNi interlayer, the PXRD of Cu@SnNi nanowires, cross-sectional SEM image and mapping of 3D Cu@SnNi network, SEM images of 3D Cu@SnNi networks under different current density and plating capacity, EIS spectra of Li/PEO-electrolyte/Cu@SnNi-Li cell before and after cycle, discharge/charge voltage profiles of Li/PEO-electrolyte/Cu@SnNi-Li and Li/PEO-electrolyte/Li cells at 0.2 mA cm−2 with a Li plating/stripping capacity of 1 mAh cm-2, SEM image of Cu@SnNi networks



of the full charge and discharge in Li/PEO-electrolyte/Cu@SnNi-Li cell, galvanostatic charge/discharge voltage profiles of LiFePO4/PEO-electrolyte/Li cell at 0.1 C, cycling performance of LiFePO4/PEO-electrolyte/CuNWs-Li and LiFePO4/PEO-electrolyte/Sn-Li foil cells at 0.1 C, the corresponding galvanostatic charge/discharge voltage profiles of LiFePO4/PEO-electrolyte/Cu@SnNi-Li and LiFePO4/PEO-electrolyte/Li cells (PDF) Author Information Corresponding Author. *E-mail [email protected] Author Contributions Z.X.Z., L.-L.L. obtained the experiments and characterizations. Z.X.Z., L.-L.L., Y.C.Y., J.X.S., and H.-B.Y. designed and drawn schematic illustration of the preparation process. Z.X.Z., L.L.L., and H.-B.Y. co-wrote the paper. Notes The authors declare no competing financial interest. Acknowledgements We acknowledge the funding support from the National Natural Science Foundation of China (Grant 51571184, 21501165, 21875236), the Fundamental Research Funds for the Central Universities (Grant WK2060190085), the joint Funds from Hefei National Synchrotron Radiation Laboratory (Grant KY2060000111). We thank the support from USTC Center for Micro and Nanoscale Research and Fabrication. References (1) Armand, M.; Tarascon, J. M. Building Better Batteries. Nature 2008, 451, 652-657. (2) Dunn, B.; Kamath, H.; Tarascon, J. M. Electrical Energy Storage for the Grid: A Battery of Choices. Science 2011, 334, 928-35. (3) Derrien, G.; Hassoun, J.; Panero, S.; Scrosati, B. Nanostructured Sn–C Composite as an Advanced Anode Material in High-Performance Lithium-Ion Batteries. Adv. Mater. 2007, 19, 2336-2340.


Page 20 of 24

Page 21 of 24 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


(4) Zhang, W. M.; Hu, J. S.; Guo, Y. G.; Zheng, S. F.; Zhong, L. S.; Song, W. G.; Wan, L. J. Tin-Nanoparticles Encapsulated in Elastic Hollow Carbon Spheres for High-Performance Anode Material in Lithium-Ion Batteries. Adv. Mater. 2008, 20, 1160-1165. (5) Chan, C. K.; Peng, H. L.; Liu, G.; McIlwrath, K.; Zhang, X. F.; Huggins, R. A.; Cui, Y. High-Performance Lithium Battery Anodes Using Silicon Nanowires. Nat. Nanotech. 2007, 3, 31-35. (6) Guo, S. T.; Li, H.; Li, Y. Q.; Han, Y.; Chen, K. B.; Xu, G. Z.; Zhu, Y. J.; Hu, X. L. SiO2-Enhanced Structural Stability and Strong Adhesion with a New Binder of Konjac Glucomannan Enables Stable Cycling of Silicon Anodes for Lithium-Ion Batteries. Adv. Energy Mater. 2018, 8, 1800434. (7) Liang, X.; Pang, Q.; Kochetkov, I. R.; Sempere, M. S.; Huang, H.; Sun, X. Q.; Nazar, L. F. A Facile Surface Chemistry Route to a Stabilized Lithium Metal Anode. Nat. energy 2017, 2, 17119. (8) Lin, D. C.; Liu, Y. Y.; Liang, Z.; Lee, H. W.; Sun, J.; Wang, H. T.; Yan, K.; Xie, J.; Cui, Y. Layered Reduced Graphene Oxide with Nanoscale Interlayer Gaps as a Stable Host for Lithium Metal Anodes. Nat. Nanotech. 2016, 11, 626-32. (9) Xu, W.; Wang, J. L.; Ding, F.; Chen, X. L.; Nasybulin, E.; Zhang, Y. H.; Zhang, J. G. Lithium Metal Anodes for Rechargeable Batteries. Energy Environ. Sci. 2014, 7, 513-537. (10) Guo, Y. P.; Li, H. Q.; Zhai, T. Y. Reviving Lithium-Metal Anodes for Next-Generation High-Energy Batteries. Adv. Mater. 2017, 29, 1700007. (11) Tarascon, J. M.; Armand, M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 414, 359-67. (12) Lin, D. C.; Liu, Y. Y.; Cui, Y. Reviving the Lithium Metal Anode for High-Energy Batteries. Nat. Nanotech. 2017, 12, 194-206. (13) Yang, H. J.; Guo, C.; Naveed, A.; Lei, J. Y.; Yang, J.; Nuli, Y. N.; Wang, J. L. Recent Progress and Perspective on Lithium Metal Anode Protection. Energy Storage Mater. 2018, 14, 199-221. (14) Li, S.; Jiang, M. W.; Xie, Y.; Xu, H.; Jia, J. Y.; Li, J. Developing High-Performance Lithium Metal Anode in Liquid Electrolytes: Challenges and Progress. Adv. Mater. 2018, 30, 1706375. (15) Zhu, B.; Jin, Y.; Hu, X. Z.; Zheng, Q. H.; Zhang, S.; Wang, Q. J.; Zhu, J. Poly(dimethylsiloxane) Thin Film as a Stable Interfacial Layer for High-Performance Lithium-Metal Battery Anodes. Adv. Mater. 2017, 29, 1603755. (16) Choudhury, S.; Archer, L. A. Lithium Fluoride Additives for Stable Cycling of Lithium Batteries at High Current Densities. Adv. Electron. Mater. 2016, 2, 1500246. (17) Li, X.; Zheng, J. M.; Ren, X. D.; Engelhard, M. H.; Zhao, W. G.; Li, Q. Y.; Zhang, J. G.; Xu, W. DendriteFree and Performance-Enhanced Lithium Metal Batteries through Optimizing Solvent Compositions and Adding Combinational Additives. Adv. Energy Mater. 2018, 8, 1703022. (18) Zhang, Y.; Wang, C. W.; Pastel, G.; Kuang, Y. D.; Xie, H.; Li, Y. J.; Liu, B. Y.; Luo, W.; Chen, C. J.; Hu, L. B. 3D Wettable Framework for Dendrite-Free Alkali Metal Anodes. Adv. Energy Mater. 2018, 8, 1800635. (19) Zhao, Y.; Sun, Q.; Li, X.; Wang, C. H.; Sun, Y. P.; Adair, K. R.; Li, R. Y.; Sun, X. L. Carbon Paper Interlayers: A Universal and Effective Approach for Highly Stable Li Metal Anodes. Nano Energy 2018, 43, 368375. (20) Xu, R.; Zhang, X. Q.; Cheng, X. B.; Peng, H. J.; Zhao, C. Z.; Yan, C.; Huang, J. Q. Artificial Soft-Rigid Protective Layer for Dendrite-Free Lithium Metal Anode. Adv. Funct. Mater. 2018, 28, 1705838. (21) Sun, C. W.; Liu, J.; Gong, Y. D.; Wilkinson, D. P.; Zhang, J. J. Recent Advances in All-Solid-State Rechargeable Lithium Batteries. Nano Energy 2017, 33, 363-386.



(22) Zhang, J. X.; Zhao, N.; Zhang, M.; Li, Y. Q.; Chu, P. K.; Guo, X. X.; Di, Z. F.; Wang, X.; Li, H. Flexible and Ion-Conducting Membrane Electrolytes for Solid-State Lithium Batteries: Dispersion of Garnet Nanoparticles in Insulating Polyethylene Oxide. Nano Energy 2016, 28, 447-454. (23) Lin, D. C.; Yuen, P. Y.; Liu, Y. Y.; Liu, W.; Liu, N.; Dauskardt, R. H.; Cui, Y. A Silica-Aerogel-Reinforced Composite Polymer Electrolyte with High Ionic Conductivity and High Modulus. Adv. Mater. 2018, 30, 1802661. (24) Tang, W. J.; Tang, S.; Zhang, C. J.; Ma, Q. T.; Xiang, Q.; Yang, Y. W.; Luo, J. Y. Simultaneously Enhancing the Thermal Stability, Mechanical Modulus, and Electrochemical Performance of Solid Polymer Electrolytes by Incorporating 2D Sheets. Adv. Energy Mater. 2018, 8, 1800866. (25) Porz, L.; Swamy, T.; Sheldon, B. W.; Rettenwander, D.; Frömling, T.; Thaman, H. L.; Berendts, S.; Uecker, R.; Carter, W. C.; Chiang, Y. M. Mechanism of Lithium Metal Penetration through Inorganic Solid Electrolytes. Adv. Energy Mater. 2017, 7, 1701003. (26) Xue, Z. G.; He, D.; Xie, X. L. Poly(ethylene oxide)-Based Electrolytes for Lithium-Ion Batteries. J. Mater. Chem. A 2015, 3, 19218-19253. (27) Zhao, C. Z.; Zhang, X. Q.; Cheng, X. B.; Zhang, R.; Xu, R.; Chen, P. Y.; Peng, H. J.; Huang, J. Q.; Zhang, Q. An Anion-Immobilized Composite Electrolyte for Dendrite-Free Lithium Metal Anodes. Proc. Natl. Acad. Sci. USA 2017, 114, 11069-11074. (28) Zhang, J. J.; Zhao, J. H.; Yue, L. P.; Wang, Q. F.; Chai, J. C.; Liu, Z. H.; Zhou, X. H.; Li, H.; Guo, Y. G.; Cui, G. L.; Chen, L. Q. Safety-Reinforced Poly(propylene carbonate)-Based All-Solid-State Polymer Electrolyte for Ambient-Temperature Solid Polymer Lithium Batteries. Adv. Energy Mater. 2015, 5, 1501082. (29) Li, Y. T.; Zhou, W. D.; Chen, X.; Lu, X. J.; Cui, Z. M.; Xin, S.; Xue, L. G.; Jia, Q. X.; Goodenough, J. B. Mastering the Interface for Advanced All-Solid-State Lithium Rechargeable Batteries. Proc. Natl. Acad. Sci. USA 2016, 113, 13313-13317. (30) Tao, C.; Gao, M. H.; Yin, B. H.; Li, B.; Huang, Y. P.; Xu, G. W.; Bao, J. J. A Promising TPU/PEO Blend Polymer Electrolyte for All-Solid-State Lithium Ion Batteries. Electrochim. Acta 2017, 257, 31-39. (31) Yue, L. P.; Ma, J.; Zhang, J. J.; Zhao, J. W.; Dong, S. M.; Liu, Z. H.; Cui, G. L.; Chen, L. Q. All Solid-State Polymer Electrolytes for High-Performance Lithium Ion Batteries. Energy Storage Mater. 2016, 5, 139-164. (32) Zeng, X. X.; Yin, Y. X.; Li, N. W.; Du, W. C.; Guo, Y. G.; Wan, L. J. Reshaping Lithium Plating/Stripping Behavior via Bifunctional Polymer Electrolyte for Room-Temperature Solid Li Metal Batteries. J. Am. Chem. Soc. 2016, 138, 15825-15828. (33) Duan, H.; Yin, Y. X.; Zeng, X. X.; Li, J. Y.; Shi, J. L.; Shi, Y.; Wen, R.; Guo, Y. G.; Wan, L. J. In-Situ Plasticized Polymer Electrolyte with Double-Network for Flexible Solid-State Lithium-Metal Batteries. Energy Storage Mater. 2018, 10, 85-91. (34) Hu, Z. L.; Zhang, S.; Dong, S. M.; Li, W. J.; Li, H.; Cui, G. L.; Chen, L. Q. Poly(ethyl α-cyanoacrylate)Based Artificial Solid Electrolyte Interphase Layer for Enhanced Interface Stability of Li Metal Anodes. Chem. Mater. 2017, 29, 4682-4689. (35) Han, F. D.; Yue, J.; Zhu, X. Y.; Wang, C. S. Suppressing Li Dendrite Formation in Li2S-P2S5 Solid Electrolyte by LiI Incorporation. Adv. Energy Mater. 2018, 8, 1703644. (36) Hou, G. M.; Ma, X. X.; Sun, Q. D.; Ai, Q.; Xu, X. Y.; Chen, L. N.; Li, D. P.; Chen, J. H.; Zhong, H.; Li, Y.; Xu, Z. B.; Si, P. C.; Feng, J. K.; Zhang, L.; Ding, F.; Ci, L. J. Lithium Dendrite Suppression and Enhanced Interfacial Compatibility Enabled by an Ex Situ SEI on Li Anode for LAGP-Based All-Solid-State Batteries. ACS Appl. Mater. Interfaces 2018, 10, 18610-18618. (37) Zhou, W. D.; Wang, S. F.; Li, Y. T.; Xin, S.; Manthiram, A.; Goodenough, J. B. Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte. J. Am. Chem. Soc. 2016, 138, 9385-9388.


Page 22 of 24

Page 23 of 24 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


(38) Liu, Y. Y.; Lin, D. C.; Jin, Y.; Liu, K.; Tao, X. Y.; Zhang, Q. H.; Zhang, X. K.; Cui, Y. Transforming from Planar to Three-Dimensional Lithium with Flowable Interphase for Solid Lithium Metal Batteries. Sci. Adv. 2017, 3, eaao0713. (39) Yang, C. P.; Yin, Y. X.; Zhang, S. F.; Li, N. W.; Guo, Y. G. Accommodating Lithium into 3D Current Collectors with a Submicron Skeleton towards Long-Life Lithium Metal Anodes. Nat. Commun. 2015, 6, 8058. (40) Yang, G. H.; Chen, J. D.; Xiao, P. T.; Agboola, P. O.; Shakir, I.; Xu, Y. X. 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. (41) Xu, S. M.; McOwen, D. W.; Wang, C. W.; Zhang, L.; Luo, W.; Chen, C. J.; Li, Y. J.; Gong, Y. H.; Dai, J. Q.; Kuang, Y. D.; Yang, C. P.; Hamann, T. R.; Wachsman, E. D.; Hu, L. B. Three-Dimensional, Solid-State Mixed Electron-Ion Conductive Framework for Lithium Metal Anode. Nano Lett. 2018, 18. (42) 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, 4431-7. (43) Wang, C. W.; Zhang, L.; Xie, H.; Pastel, G.; Dai, J. Q.; Gong, Y. H.; Liu, B. Y.; Wachsman, E. D.; Hu, L. B. Mixed Ionic-Electronic Conductor Enabled Effective Cathode-Electrolyte Interface in All Solid State Batteries. Nano Energy 2018, 50, 393-400. (44) Wu, X. L.; Guo, Y. G.; Su, J.; Xiong, J. W.; Zhang, Y. L.; Wan, L. J. Carbon-Nanotube-Decorated NanoLiFePO4@C Cathode Material with Superior High-Rate and Low-Temperature Performances for Lithium-Ion Batteries. Adv. Energy Mater. 2013, 3, 1155-1160. (45) Shi, J. J.; Wang, Z. G.; Fu, Y. Q. Density Functional Theory Study of Diffusion of Lithium in Li–Sn Alloys. J Mater. Sci. 2015, 51, 3271-3276. (46) 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. (47) Zhao, Y. R.; Wu, C. A.; Peng, G.; Chen, X. T.; Yao, X. Y.; Bai, Y.; Wu, F.; Chen, S. J.; Xu, X. X. A New Solid Polymer Electrolyte Incorporating Li10GeP2S12 into a Polyethylene Oxide Matrix for All-Solid-State Lithium Batteries. J. Power Sources 2016, 301, 47-53.



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