Ni3N Nanocrystals Decorated Reduced Graphene Oxide with High

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NiN Nanocrystals Decorated Reduced Graphene Oxide with High Ionic Conductivity for Stable Lithium Metal Anode Lingfei Zhao, Wenhui Wang, Xixia Zhao, Zhen Hou, Xiaokun Fan, Yulian Liu, and Zewei Quan ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.9b00014 • Publication Date (Web): 14 Mar 2019 Downloaded from http://pubs.acs.org on March 17, 2019

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ACS Applied Energy Materials

Ni3N Nanocrystals Decorated Reduced Graphene Oxide with High Ionic Conductivity for Stable Lithium Metal Anode Lingfei Zhao, Wenhui Wang, Xixia Zhao, Zhen Hou, Xiaokun Fan, Yulian Liu, Zewei Quan*

Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, Guangdong 518055, P.R. China. * Correspondence author. E-mail: [email protected] (Z. Q.)

Abstract Lithium (Li) metal is the ultimate choice of anode material for high energy density rechargeable Li batteries, yet its practical application has been seriously hindered due to fast capacity decay, infinite volume expansion, and uncontrolled dendrite formation. Herein, we report the utilization of Ni3N nanocrystals decorated nitrogen doped reduced graphene oxide (Ni3N@N-RGO) coated Cu as stable host for lithium metal anode. The uniformly-distributed Ni3N nanocrystals can be in-situ converted into Li3N, which leads to high ionic conductivity and homogenous Li-ion flux distribution of the 3D N-RGO matrix. As a result, the Ni3N@N-RGO/Cu electrode presents a stable Li plating/strapping for 1400 h at 1 mA cm-2 with a small overpotential of ~30 mV. The improved electrochemical stability is demonstrated as the smooth and dense surfaces of the plated metallic Li on Ni3N@N-RGO/Cu electrode over 300 cycles. The Li||LiFePO4 full cells with Li/Ni3N@N-RGO/Cu anode present improved rate and cycling performances. These results indicate that improving

the

ionic

conductivity

of

3D

graphene

based

hosts

with

uniformly-distributed Ni3N nanocrystals is a feasible approach for stable Li metal anode. Key words: Lithium metal, Anode, Batteries, Ni3N nanocrystals, Li3N, Ionic conductivity, Host.

ACS Paragon Plus Environment

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1. INTRODUCTION The past decades has witnessed the booming of Li ion batteries (LIBs) as power sources for various portable devices,1,2 whereas traditional anode materials are reaching their capacity limits and facing challenges especially for high energy density and high power density applications.3-5 Li metal possesses a high theoretical capacity of 3,860 mA h g–1 and the lowest electrochemical potential (-3.04 V vs. the standard hydrogen electrode) among anode candidates for Li batteries,6,7 making it an ideal anode for high energy density Li batteries.8 However, the application of Li metal anode has been seriously hindered by low Coulombic efficiency, unstable solid electrolyte interphase (SEI), infinite volume expansion, and potential safety hazard of internal short circuit derived from dendrite formation.9 Several approaches have been proposed to address the above issues, including constructing Li protective layer,10-16 designing stable host,17-22 regulating electrolyte composition,23-32 and modifying separators.33,34 Plenty of researches have reported that a stable host is effective to suppress Li dendrite growth,35-38 among which graphene based 3D porous matrixes are of particular interests due to their high surface area to reduce the effective local current density, good electronic conductivity for fast charge transfer, and large void spaces to buffer the volume changes during Li plating/stripping.39-47 However, the low ionic conductivity of graphene is a major concern that impedes its application. As one of the well-known Li ion conductor with a high room-temperature conductivity of ≈10−3 S cm−1, Li3N have been utilized to modify the Li-ion conductivity of planar hosts and achieved promising performances.48 Recently, a thin coating layer of Cu3N on Cu was achieved by reactive sputtering, which can be converted into Li3N during first discharge process, leading to a homogenous and high Li-ion flux to inhibit Li dendrite formation.49 Therefore, the modification of graphene with Li3N is a promising approach to achieve high Li+ ion conductive graphene matrixes as Li metal host. In this work, Ni3N nanocrystals decorated nitrogen doped reduced graphene


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oxide (Ni3N@N-RGO) composite coated commercial Cu is reported as a host for metallic Li. The well-distributed Ni3N nanocrystals on the N-RGO matrix can be in-situ converted into Li3N nanocrystals to achieve high Li-ion conductivity of the host. As a result, the Ni3N@N-RGO/Cu electrode exhibits stable Li plating/stripping for a prolonged period of 1400 h at 1 mA cm-2 with a small overpotential of ~30 mV, as well as a smooth, densified and dendrite-free Li surface for over 300 cycles.

1. EXPERIMENTAL SECTION 2.1 Preparation of the Ni3N@N-RGO composite. All the reagents were of analytical grade and used as received without further purification. Graphene oxide solution (GO) was prepared by modified Hummer’s method as reported previously.50 Typically, 50 mg GO solution (concentration ~8 mg/mL) was added into a 100 mL beaker, then 0.5 mL of Ni(Ac)2 aqueous solution (0.525 M) and 2.0 mL of hexamethylenetetramine (HMT, 0.525 M) aqueous solution were dropped into the GO solution in sequence under magnetic stirring. Proper amount of deionized water (DI) was added into the solution to standardize the total volume of the solution to 40 mL. After stirred for another 20 min, the solution was transferred into a 50 mL Teflon-lined stainless-steel autoclave, maintained at 120 oC for 12 h and cooled down to room temperature naturally. The mixture was centrifuged, washed with DI water and absolute ethanol for several times and then freezing dried. Finally, the sample was treated at 380 oC for 3 h under ammonia flow, followed by cooling down to room temperature at the rate of 10 oC/min (denoted as Ni3N@N-RGO). As contrast, N-RGO was prepared with identical conditions except the addition of Ni(Ac)2 and HMT. 2.2 Characterizations. The morphologies of the samples were characterized by field emission scanning electron microscope (FE-SEM, S-4800, Hitachi, Japan) equipped with vacuum transfer system. Transmission electron microscopy (TEM) images and high resolution transmission electron microscopy (HRTEM) images were taken with TEM Tecnai F30 (FEI) at an accelerating voltage of 300 kV. XRD patterns were recorded on an X-Ray diffractometer (Rigaku SmartLab) with Cu K radiation



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(λ = 0.15418 nm) at a voltage of 45 kV and a current of 200 mA. Raman spectra were detected on ARC-SP 2558 spectrometers (Princeton Instruments). XPS spectra were recorded on a PHI 5000 VersaProbe II (ULVAC-PHI, INC, Japan) system with a microfocused (100 µm, 25 W, 15 kV) monochromatic Al-Kα radiation source. Thermogravimetric Analysis (TGA) was performed on a Setaram thermometer (SETSYS EVO 18) from 30 to 800 oC under air atmosphere with a heating rate 5 oC/min.

The BET (Brunauer Emmett-Teller) surface area was measured on an

automated surface area analyzer (ASAP2420-4MP). 2.3 Electrochemical measurements. The coin-type cells were tested at 25 oC on a Neware battery testing system. The working electrodes were prepared by mixing Ni3N@N-RGO (or N-RGO) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)

in

a

weight

ratio

of

90:10

with

proper

amount

of

N-methyl-2-pyrrolidinone, and the mixture was milled in a micro miller (4000 r/min, 18 min) to form homogeneous slurry. The slurry was coated onto copper foil (coating thickness 20 m), vacuum dried at 60 ºC for 12 h, and then tailored into disks with a diameter of 16 mm unless otherwise specified. Coin-type cells (LIR2025) were assembled in an argon-filled glove box (moisture and oxygen ＜ 0.2 ppm) with Celgard polypropylenes as separators, lithium foils as both counter and reference electrodes, 100 µL electrolyte with 1 M LiTFSI in mixture solvent of 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL), (1:1 by volume) and 2% LiNO3 as addictive. For symmetrical Li||Li cell tests, 10 mA h cm-2 of Li were pre-deposited onto the working electrodes (N-RGO/Cu, and Ni3N@N-RGO/Cu) and they were denoted as Li/N-RGO/Cu and Li/Ni3N@N-RGO/Cu, respectively. Both charging and discharging were cut off with a fixed time of 60 min at a current density of 1 mA cm-2. To evaluate the Coulombic efficiency, the working electrodes were cut into discs with diameter of 12 mm, and the batteries were first cycled at 0.01~1 V (vs. Li/Li+) at 0.5 mA cm−2 for 3 cycles to remove surface contaminations and form stable SEI. For Li||LiFePO4 full cells, the cathodes were LiFePO4 mixed with Super P and PVDF in a weight ratio of 80:10:10 (diameter: 16 mm, mass loading: ~3 mg cm−2), and the anodes were Li/N-RGO/Cu and Li/Ni3N@N-RGO/Cu. Electrochemical


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impedance spectroscopy (EIS) was recorded with the amplitude of 10 mV at the frequency range of 100 kHz to 5 mHz (Bio-Logic VSP electrochemical workstation).

2. RESULTS AND DISCUSSION

Figure 1. Phase and morphology characterizations of the sample. (a, b) SEM images, (c) TEM image, (d) HRTEM images, (e) elemental mapping images, and (f) XRD pattern of the sample.

The synthesis procedure for the composite is illustrated in Figure S1. The Ni(OH)2@RGO precursor was prepared via a hydrothermal process, in which the GO was reduced into RGO and Ni(OH)2 was simultaneously growing onto the RGO surfaces. The precursor composite was then converted into Ni3N@N-RGO by calcination under ammonia flow. Phase and morphology characterizations of the as-obtained products are presented in Figure 1. SEM images (Figure 1a, b), TEM image (Figure 1c) and HRTEM images (Figure 1d) of the as-obtained products show



that nanocrystals with an average diameter of 10.2 ± 0.3 nm (Figure S2) are well distributed on the RGO sheets. Elemental mapping images (Figure 1e) of the sample exhibit the uniform distribution of C, N, and Ni elements. XRD pattern (Figure 1f) of the sample can be allocated to Ni3N phase and the bump at 20~30o results from the diffraction of RGO sheets. The nanocrystals show a lattice distance of ~0.232 nm in the HRTEM image (Figure 1d), which can be indexed as the (002) lattice planes of the hexagonal Ni3N phase. Raman analysis (Figure S3a) exhibits typical D band and G band for RGO at 1348 and 1588 cm-1, and the peaks below 1000 cm-1 can be assigned to Ni3N.51 TGA analysis (Figure S3b) under air flow shows a mass loss of 77.10% from 300 to 650 ºC, corresponding to the decomposition of N-RGO and transformation of Ni3N into NiO (Figure S3b inset). Therefore, the weight ratio of the Ni3N nanocrystals in the composite is determined to be ~19.42%.

Figure 2. (a) XPS spectra, and high resolution (b) C 1s, (c) N 1s, (d) Ni 2p spectra of the Ni3N@N-RGO sample.

XPS characterization was performed to further confirm the constitution of the sample. The spectra of the sample (Figure 2a) present the peaks corresponding to the binding energy of C 1s, N 1s, O 1s, and Ni 2p. The fitted results of the C 1s spectra (Figure 2b) exhibit two peaks corresponding to the C-C/C=C (284.6 eV) and C-N


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(286.0 eV) bonds, respectively. The fitted N 1s spectra display three peaks (Figure 2c), which can be assigned to Ni-N (398.0 eV), pyridinic nitrogen (399.0 eV), and pyrrolic nitrogen (400.2 eV), respectively. Therefore, it can be deduced that N atoms were doped into the RGO matrix. The fitted Ni 2p spectra (Figure 2d) exhibit a dominate peak at 853.9 eV that originates from the Ni-N bond, and other two peaks at 856.5 and 862.2 eV that correspond to the Ni 2p and satellite. Based on the above results, we can conclude that the Ni3N@N-RGO composite was successful synthesized.

Figure 3. Performances of N-RGO/Cu and Ni3N@N-RGO/Cu electrodes for Li metal accommodation. (a) Initial Li nucleation overpotentials at 1 mA cm-2; (b) Columbic efficiencies of Li||Li symmetrical cells at 1 mA cm-2; (c) Cycling performances of the symmetrical cells at 1 mA cm-2 with areal capacity of 1 mA h cm-2.

Electrochemical measurements were carried out to investigate the ability of the N-RGO/Cu and Ni3N@N-RGO/Cu electrodes to accommodate metallic Li. The voltage profiles during the initial Li deposition onto the electrodes at 1 mA cm−2 are presented in Figure 3a. The voltage profile for N-RGO/Cu electrode drops to a dip at -0.150 V and then gradually rises to a platform at -0.044 V, giving rise to the initial Li



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nucleation overpotential of 0.106 V. In comparison, the Ni3N@N-RGO/Cu electrode possesses a much lower Li nucleation overpotential of 0.036 V (with voltage dip and voltage platform at -0.116 and -0.080 V, respectively), which probably originates from the improved Li-ion conductivity of the Ni3N@N-RGO composite. Similar trend on Li nucleation overpotentials are observed at the current density of 0.05 and 0.5 mA cm−2

(Figure

S4a,b).

The

smaller

Li

nucleation

overpotential

of

the

Ni3N@N-RGO/Cu electrode is beneficial to uniform Li nucleation, which may improve the cycling stability of the metallic Li on the electrode. As presented in Figure 3b, the CE for Li/N-RGO/Cu electrode after 3 cycles of activation is stable at first, and then become deteriorate after ~450 cycles. The low reversibility (i.e. CE) may be derived from the inherent non-uniform nucleation behavior and reactive nature of metallic Li, which would lead to the formation of mossy Li and the repeated generation and broken of SEI. In comparison, the Li/Ni3N@N-RGO/Cu electrode presents a stable and high average CE of ~98.6% over 600 cycles. The presence of the uniformly distributed Ni3N nanocrystals with high ionic conductivity in Li/Ni3N@N-RGO/Cu results in homogenous Li-ion flux distribution, which facilitates the smooth Li plating/stripping as well as the formation of stable SEI, thus leading to improved CE. Long-term cycling performances of the symmetrical cells at 1 mA cm-2 are presented in Figure 3c. It can be seen clearly in the inset detailed figures that the voltage profile for Li metal anode on N-RGO/Cu remains stable for ~450 h, and then the voltage hysteresis gradually increases and the voltage platforms become ﬂuctuant. The increased voltage hysteresis probably originates from the “whisker growth” of mossy and dendrite Li accompanied with large overpotential,52 which is also a typical phenomenon for Li/Li symmetrical cells.48 Meanwhile, the fluctuation of the voltage platforms may be derived from the detachment of the dead Li and the unstable SEI.40 While, the Li metal anode with Ni3N@N-RGO/Cu host presents a long cycle lifetime of ~1400 h with a small overpotential of ~30 mV. The cycling performances (Figure S5) of the symmetrical cells at higher current density (3 mA cm-2) present a similar trend. That is, the incorporation of Ni3N significantly improves the electrochemical performance of


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N-RGO/Cu host, despite the slightly reduced BET surface area (Figure S6) which is generally detrimental to the cycle stability due to the higher effective local current density for Li plating/stripping. Moreover, the specific capacity of the anode based on the mass of the metallic Li and Ni3N@N-RGO host is 2525 mA h/g (Table S1), which is competitive among various anode materials for lithium ion batteries.

Figure 4. (a) EIS and (b) graphs of Z’ plotted against -1/2 at the low frequency range for the N-RGO/Cu and Ni3N@N-RGO/Cu electrodes after first Li stripping.

To understand how the incorporation of the Ni3N nanocrystals improves the stability of N-RGO/Cu host for Li metal anode, the Ni3N@N-RGO/Cu electrodes after first plating/stripping cycle was characterized. XRD analysis of the sample detached from the Ni3N@N-RGO/Cu electrode (Figure S7) presents two diffraction peaks at 2 = 34.3o and 37.8o corresponding to the diffraction for Li3N (JCPDS No.22-0680), and the diffractions at 2 = 44.5o and 51.8o originate from metallic Ni (JCPDS No.04-0850). Therefore, it is deduced that the Ni3N in the composite can be in-situ converted into Li3N and Ni during the first Li deposition/stripping cycle. To evaluate the Li+ ion transfer properties of the electrodes, EIS of the electrodes after first stripping were tested (Figure 4a). The EIS of the electrodes exhibit two semicircles in the high frequency range for the resistance of the SEI (RSEI), the resistance of the charge-transfer process (Rct), and straight lines in the low frequency range for the semi-infinite Warburg diffusion process, respectively. It can be seen that the RSEI for Ni3N@N-RGO/Cu electrode is smaller than that for N-RGO/Cu. As presented in Figure 4b, the Z’ of the electrodes have linear relationships with -1/2, and the Li+ ion diffusion coefficients for N-RGO/Cu and Ni3N@N-RGO/Cu are



determined to be 3.7  10-18, and 5.0  10-17 cm2 s-1, respectively. The higher Li-ion conductivity of the Ni3N@N-RGO/Cu electrode should be derived from the Li3N converted from Ni3N nanocrystals in the first cycle. The uniform distribution of the Ni3N nanocrystals can improve the homogeneity of the Li-ion flux distribution. Therefore, it can be deduced that the decreased nucleation overpotential, enhanced CE performances, and improved cycling stability of the Ni3N@N-RGO host are mainly attributed to high Li-ion conductivity and uniform Li-ion flux distribution.

Figure 5. Morphology evolutions of the metallic Li on N-RGO/Cu: (a-c); and Ni3N@N-RGO/Cu: (d-f) electrodes after cycling. (a), (d) after first cycle; (b), (e) after 30 cycles; (c), (f) after 300 cycles. Scale bar: 20 m.

To further understand the improved electrochemical performance of metallic Li on the Ni3N@N-RGO/Cu electrode, morphology evolutions of the electrodes upon cycling was investigated via SEM. SEM images of the electrodes before cycling (Figure S8a,e) demonstrate that the N-RGO and Ni3N@N-RGO coatings on the Cu substrates are of similar morphology. After first Li plating with a capacity of 1 mA h g-1, metallic Li on the N-RGO (Figure 5a, Figure S8b) and Ni3N@N-RGO (Figure 5d, Figure S8f) are homogenously plating on the sheets. After 30 cycles, the majority of the Li on the N-RGO (Figure 5b, Figure S8c) is still evenly distributed except occasionally appeared small Li lumps. As for the metallic Li on the Ni3N@N-RGO (Figure 5e, Figure S8g), the homogenous morphology is retained. After 300 cycles, significant changes are observed on the electrodes. Although some of the Li can be


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retained on the N-RGO sheets, many Li lumps are detected with porous morphology (Figure 5c, Figure S8d), which may be caused by repeated SEI broken and regeneration. The porous Li is generally considered as the initial stage of mossy and dendritic Li formation, and breaking of the porous Li would result in dead Li causing irreversible capacity decay.52 Notably, the metallic Li on the Ni3N@N-RGO/Cu electrode (Figure 5f, Figure S8h) shows a smooth and dense surface even after 300 cycles, which is consistent with its superior cycling stability (Figure 3c). These morphology evolutions of the Li metal are in accordance with the cycling performances of the electrodes. It is reasonable to attribute the stable, densified and dendrite-free Li accommodation of the Ni3N@N-RGO/Cu electrode to the fast and even Li-ion transfer derived from the well-distributed Ni3N nanocrystals.

Figure 6. Performances of the Li||LiFePO4 full cells with Li/Ni3N@N-RGO/Cu and Li/N-RGO/Cu as anodes: (a) Charge-discharge profiles at various rates; (b) rate capabilities and cycling performances.

To evaluate the practical application of the anodes, rate and cycling performances (Figure 6) of the full cells with LiFePO4 cathode have been studied. The gaps (Figure 6a) between the charge/discharge voltage plateaux of the full cells with Li/Ni3N@N-RGO/Cu and Li/N-RGO/Cu anodes are gradually enlarged with increasing rates, indicating larger overpotential at higher rates. The specific capacities of the cells with Li/Ni3N@N-RGO/Cu anode at 0.05, 0.5, 1, 2, 5, 10, and 20 C are 168.4, 150.8, 136.0, 118.8, 95.4, 77.9, and 59.5 mA h g–1, which are slightly higher than that for Li/N-RGO/Cu at the same rates. Such results imply improved rate capability of the Ni3N decorated anode, which may be derived from increased Li+ ion conductivity in the presence of Ni3N nanocrystals. The cells were cycled at 1 C after



cycling at various rates (Figure 6b). The full cells with the Ni3N decorated anode show improved cycle stability compared with the pristine N-RGO coated electrode. These results reveal that the Ni3N@N-RGO coating on Cu foil can improve the stability of the Li metal anode, thereby facilitating its practical applications.

3. CONCLUSIONS Ni3N@N-RGO composite coated Cu is rationally designed as stable host for Li metal anode. The Ni3N@N-RGO/Cu electrode exhibited stable, densified and dendrite-free Li accommodation, which can be attributed to the high Li-ion conductivity of in-situ generated Li3N nanocrystals. The Ni3N@N-RGO/Cu electrode presented enhanced cycling stability during metallic Li plating/stripping. Morphology evolutions also confirmed the cycling stability of the metallic Li on Ni3N@N-RGO/Cu electrode with smooth and densified surfaces. The Li||LiFePO4 full cells with Li/Ni3N@N-RGO/Cu anode present improved rate and cycling performances compared with that for Li/ N-RGO/Cu anode. These results suggest that modifying the graphene based 3D porous hosts with uniformly-distributed Ni3N nanocrystals to achieve high ionic conductivity is a feasible approach for stable host of Li metal anode.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: ****. Schematic illustration of the materials preparation, average size of the Ni3N nanocrystals, Raman and TGA analysis, nitrogen adsorption isotherms of the samples, initial Li nucleation overpotentials of various electrodes, cycling performances of the symmetrical cells at higher current density, XRD pattern of the electrode after first Li stripping, morphology evolutions of the metallic Li on the electrodes (PDF).

AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] (Z. Q.), Tel: +86-755-88018399.


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ORCID Zewei Quan: 0000-0003-1998-5527 Lingfei Zhao: 0000-0003-3683-4210 Wenhui Wang: 0000-0002-2449-619X Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENTS This work was supported by the National Natural Science Foundation of China (NSFC) (No. 51772142), Development and Reform Commission of Shenzhen Municipality (Novel Nanomaterial Discipline Construction Plan), and Shenzhen Science and Technology Innovation Committee (Nos. JCYJ20170412152528921, KQJSCX20170328155428476).



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Anatase

TiO2

Nanocrystal

Anchored

on

N,S-RGO

as

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Ni3N Nanocrystals Decorated Reduced Graphene Oxide with High

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