rGO Composite as Long Cycle Life Anode material for

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NiGaO/rGO Composite as Long Cycle Life Anode material for Lithium Ion Batteries Yongmin Huang, Jiaxing Ouyang, Xun Tang, Yao Yang, Jiangfeng Qian, Juntao Lu, Li Xiao, and Lin Zhuang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b21581 • Publication Date (Web): 30 Jan 2019 Downloaded from http://pubs.acs.org on January 31, 2019

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ACS Applied Materials & Interfaces

NiGa2O4/rGO Composite as Long Cycle Life Anode material for Lithium Ion Batteries Yongmin Huang1§, Jiaxing Ouyang1§, Xun Tang1, Yao Yang2, Jiangfeng Qian1, Juntao Lu1, Li Xiao*1, Lin Zhuang*1 1College

of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, China

2Department

of Chemistry and Chemical Biology, Cornell University, Ithaca, New York, 14853, USA

*Corresponding

authors. E-mail: [email protected]; [email protected].

Y. H. and J. O. contributed equally.

§

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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

Abstract This work reports a novel Ga-based material, NiGa2O4, which is typically used as a photo-catalyst for water splitting, as anode for LIB with long cycling life. High surface area rGO has been used as the conductive substrate to avoid the aggregation of NiGa2O4 nanoparticles (NPs). Because the size and the shape of NiGa2O4 is very sensitive to the pH of the precursor, ethylene glycol has been employed as the solvent, as well as the reduction agent to reduce GO, in order to avoid using extra surfactants and also to avoid the variation of pH of the precursor. The obtained NiGa2O4/rGO composite possesses high capacity and long cycling life (2000 cycles, 2 A/g), with NiGa2O4 NPs around 3-4 nm that uniformed distributed on rGO surface. Full cell performance with LiCoO2 as cathode has also been studied, with the average loss of 0.04% per cycle after 100 cycles (C/2 of LiCoO2). The long cycling life of the composite was ascribed to the self-healing feature of Ga0 formed during charging. Keywords: gallium, self-healing, NiGa2O4, lithium ion batteries, rGO Introduction The development of high capacity and long cycling life electrode materials is vital for the competitiveness of Li-ion batteries (LIBs) in energy storage 1-4. Recently, gallium (Ga) has attracted great attention for its self-healing feature potentially to solve the pulverization issue of the LIB anode upon charge/discharge 5-9. The reversible lithium storage behavior of Ga was found in 2004 5, but the self-healing property of liquid Ga during lithiation/delithiation has not been revealed until recently 8. By using in situ TEM, Zhang and Liang found that during lithiation process, Ga will transform into solid lithium-gallium alloys, and obvious cracks were observed after the formation of these solid alloys 8. Because of the self-healing property of Ga, these cracks gradually disappeared during the delithiation process of the alloys. The disappearance of the cracks can reduce the capacity loss caused by electrode pulverization, hence improve the cycleability of electrode materials. To promote the durability of Ga-based anode, bulk Ga were replaced by Ga nanodroplets 9. Porous carbon, reduced graphene oxide (rGO) and carbon nanotube (CNT) has been used as substrate to prevent Ga particles


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from aggregation 6, 10. New types of Ga-based materials, including GaN, GaSx, Ga2O3 and Ga2Se3, were also investigated to obtain higher lithium storage capacity 11-21. In this work, we report a novel Ga-based material, NiGa2O4, for LIB anode. NiGa2O4 is a semiconductor that is typically used as a transparent film for water splitting, a photo-catalyst that catalyzes the hydrogen evolution reaction (HER)

22-24.

We found that upon properly synthesizing, it can be a superior LIB anode material. In order to maximize the intrinsic properties of NiGa2O4, reduced graphene oxide (rGO) was employed to act as a conductive additives. The high specific surface area of rGO is expected to largely prevent the aggregation of the NiGa2O4 NPs by forming a NiGa2O4/rGO composite, and its excellent electronic conductivity is expected to maximize the lithium storage performance of the NiGa2O4 NPs

25-33.

Graphene oxide

(GO) has been used as the precursor of rGO in this work. The surface of GO is rich in functional groups, which are nucleation sites for the growth of metal oxides

34.

A

large number of nucleation sites not only ensure good dispersion of the metal oxide on the GO, but also ensure good electronic contact between the two in the final composite

35.

In order to obtain an rGO composite with uniform metal oxide

dispersion, a key to synthesize is that the solution of GO and other precursors have to be homogeneous and stable

36-41.

Dispersing agents or surfactants, such as

poly(vinylpyrrolidone) (PVP), are commonly used to increase the dispersion of GO, bringing in complicated following removal washing steps 42-44. In addition, reductants, such as NaBH4, hydrazine, citric acid or vitamin C, is needed to reduce GO to rGO 45-50.

However, these methods are not suitable for synthesizing NiGa2O4/rGO

composite in this work, because the pH value of the precursor solution will change by adding certain reduce agents, but the size and shape of NiGa2O4 NPs are very sensitive to the pH of the precursors. According to Zhou’s work, changing in the pH value of the precursor solution resulted in a 5-fold change in the particle size of the NiGa2O4 NPs (from 10 nm to 50 nm), and the morphology of the NiGa2O4 NPs also changed from sphere shape to octahedral accordingly 23. Herein, in order to avoid the use of reduce agents that may change the pH of the precursor solution, ethylene glycol was utilized as the solvent, as well as the reducing



agent for GO reduction. It can also act as a surfactant to disperse graphene oxide because of its relatively higher viscosity

51-53.

Ga(ACAC)3 and Ni(CH3OO)2·4H2O

have been used as precursors for NiGa2O4 because of their good solubility in ethylene glycol. NiGa2O4/rGO composite can be obtained by a facile one-pot solvent thermal method

54-55,

and pyrolysis were further used to remove the small molecules and

increase the crystalline structure of the sample

56.

The obtained NiGa2O4 NPs

dispersed uniformly on rGO surface, and the particle size was well controlled. The NiGa2O4/rGO composite exhibits high reversible capacity and long cycleability. The composite was also successfully used as an anode with LiCoO2 cathode to form a full cell. The full cell exhibited excellent reversibility and stability, and the capacity retention is 96% (100 cycles) under a C/2 rate of LiCoO2 (average loss 0.04% per cycle). The long cycling life of the composite was ascribed to the self-healing feature of Ga0 according to the mechanism study. Experimental section Preparation of NiGa2O4@rGO. NiGa2O4/rGO composite was synthesized via a solvent-thermal method, and then by a calcination process. For example, 0.05 g graphene oxide (GO, Nanjing XFNANO Materials Tech Co. Ltd) and 50 mL ethylene glycol (AR, Sinopharm Chemical) were mixed in 100 mL glass beaker and form a dispersion by ultra-sonication. The 0.280 g of gallium (III) acetylacetonate (Ga(ACAC)3, 99.9%, Aladdin Chemistry) and 0.095 g of Nickel-II-acetate tetrahydrate (Ni(CH3OO)2·4H2O, AR, Sinopharm Chemical) was further added to the above dispersion and ultrasonically dispersed. The obtained mixture was further treated by solvent thermal method, centrifugal washing, freeze-drying and calcination process to obtain the NiGa2O4/rGO composite. The experimental detail is similar to our previous work 19, except that the solvent-thermal time is 12 h, and the calcination is under 500°C for 2 h. Structural characterization. The NiGa2O4/rGO composite was characterized by X-ray diffraction (XRD, Rigaku Miniflex600, Cu K,  = 1.5406 Å, 10° to 80°, 5°/min for the as prepared sample, and 2°/min for the disassembled cell ex situ tests),


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field emission scanning electron microscope (FESEM, ZEISS Merlin Compact, EHT as 5 kV), X-ray photoelectron spectroscopy (XPS, Thermo Fisher ESCALAB 250Xi spectrometer, monochromic Al Kα radiation), high-resolution transmission electron microscopy (HRTEM, FEI Tecnai G2 F30), energy-dispersive X-ray spectroscopy (EDX, Oxford Instruments X-MaxN), thermogravimetric analysis (TGA, TA Instruments Q500 Instruments Analyzer, Air atmosphere), and Raman spectroscopy (HORIBA XploRA PLUS, λ=532 nm). Electrochemical measurements. The half-cell and full cell tests were evaluated in CR2016-type coin cells, and the assembly process was described in our previous work 19. The full cell was prepared by using a delithiated LiCoO2 cathode (LiCoO2:Super P:PVDF=8:1:1 by weight, the mass loading was ca. 7 mg/cm2) and a prelithiated NiGa2O4/rGO anode (the mass ratio of anode to cathode was 1:3.5). LiCoO2 was purchased from Shenzhen Kejingstar Technology Ltd., and the SEM image of LiCoO2 is shown in Figure S1. The prelithiated NiGa2O4/rGO anode was prepared by discharging it versus metal lithium from an open-circuit voltage (OCV) to 0.05 V at 0.5 A/g. The LiCoO2 mixture slurry was prepared with the same mixing ratio as NiGa2O4/rGO, and an Al foil was used as the current collector. The delithiated LiCoO2 cathode was prepared by charging it versus metal lithium from an open-circuit voltage (OCV) to 4.30 V at C/2 rate (0.07 A/g). The full lithium-ion cell was cycled at C/2 (0.07 A/g for LiCoO2 cathode) on a LAND CT2001A battery test system between 2.50 V and 4.30 V. Results and discussion Structure analysis of NiGa2O4/rGO. According to XRD measurement, the obtained final sample shows a NiGa2O4 spinel structure pattern of the Fd3m (JCPDS#10-0114) space group (Figure 1a). The particle size of the NiGa2O4 NPs was calculated by the Scherrer formula and the full width at half-maximum (FWHM) of the (440) peak in the XRD pattern, and turns out to be 3.5 nm. The corresponding fitting curve is shown in the insert of Figure 1a. The XPS characterization results can



further reflect the chemical composition and elemental valence of the sample. As shown in Figure 1b, the energy splitting peaks on the XPS spectra are consistent with that of Ni 2p and Ga 2p (Ni 2p: 879.7 eV, 873.4 eV, 862.0 eV 855.8 eV. Ga 2p: 1144.7 eV, 1117.7) 23, 57, indicating the sample contains two metal elements of Ni and Ga. The energy levels difference between the 2p1/2 and 2p3/2 peaks is 17.6 eV for Ni 2p and 17.7 eV for Ni 2p satellite, respectively, indicting Ni is bonded with oxygen atoms in the sample. Similarly, Ga is also bonded with oxygen atom in the sample, with the energy difference between the 2p1/2 and 2p3/2 peaks to be 27.0 eV 58. Raman spectroscopy was used to investigate the defect change of carbon after GO being reduced to rGO (Figure S2). The ID/IG of NiGa2O4/rGO and GO are 1.12 and 1.08, respectively, indicating that there are more defects of carbon of NiGa2O4/rGO than GO, which will benefit the Li-ion diffusion

59-61.

SEM was used to demonstrate the

morphology of the NiGa2O4/rGO composite. As shown in Figure 2a, the 2D structure of rGO was well preserved after the multi-step synthesis. The rGO surface was uniformly covered with very small NPs (Figure 2b). By enlarging the SEM image, it can be seen that the size of those NPs are less than 10 nm, no aggregation of large particles was observed (Figure 2c). Figure 2d displays the atomically resolved HRTEM image of a typical particle nanocrystalline. The particle size is around 3-4 nm, with well identified {311} facets of NiGa2O4 spinel structure, in consistent with the XRD results. The elemental mapping images clearly demonstrate that NiGa2O4 NPs were uniformly distributed on the surface of rGO sheets. According to TGA measurement, the mass fraction of NiGa2O4 was 70% in the sample (Figure S4). Lithiation capacity and cyclability of NiGa2O4/rGO. The cyclic voltammograms of the NiGa2O4/rGO sample is shown in Figure 3a. As is shown in many other LIB anode materials, this sample also show an obviously larger reduction current in the 1st cycle comparing with that of the following cycles. This phenomenon is usually believed as the formation of a solid electrolyte interphase (SEI) layer at the 1st cycle 62-64.

The peak at 0.4 V in the negatively scan is ascribed to the lithiation reaction to

generate LixGa (x≤2), and the peak at 1.0 V in the positively scan is ascribe to the delithiation reaction to generate Ga 5-7.


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To evaluate the capacity of the NiGa2O4/rGO composite, the sample was cycled at 0.5 A/g for 90 cycles (Figure 3b). The 1st lithiation capacity was 1990.0 mAh/g, but the coulombic efficiency (CE) of the 1st cycle is relatively low (56%), which is in consistent with the CV result. The second lithiation capacity decreased to 1028.7 mAh/g, with the CE increase to 93.0%. After 90 cycles, the lithiation capacity was 967.3 mAh/g, with the CE over 99%. Figure 3c shows the rate performance test between 0.2 to 5.0 A/g. The delithiation capacity is 1371.6 mAh/g (0.2 A/g), 1225.7 mAh/g (0.5 A/g), 1115.0 mAh/g (1.0 A/g), 922.2 mAh/g (2.0 A/g) and 514.8 mAh/g (5.0 A/g). The delithiation capacity can be recover to 1430.2 mAh/g when the rate revert back to 0.2 A/g, indicating a good stability of the NiGa2O4/rGO composite. Since the lithiation capacity of NiGa2O4 is over 1000.0 mAh/g, the lithiation reaction of NiGa2O4 will include not only the formation of Ni0 and Ga0 (Equation 1), which only gives a capacity of 817.9 mAh/g, but also other reactions. To explore the discharge/charge reaction mechanism, the structure change of the NiGa2O4 composite has been investigated by ex situ XRD upon cycling. A Li2Ga XRD peak appeared when discharge the cell to 0.05 V and then vanished at 3.0 V, indicating the alloy reaction of Gallium happened during cycling (Figure 4a). No XRD patterns of Ga0 was observed in the profile, because the formed Ga0 particles is expected to be smaller than the particle size of the NiGa2O4 composite (ca. 3.5 nm), and Ga0 with this small size will be in liquid phase at room temperature 9, thus will not exhibit crystalline structure in XRD. Therefore, the formation of Ga0 in this work was measured by the valence state change of Gallium. According to the ex situ XPS measurement, the bind energy of Ga2p1/2 and Ga2p3/2 first negatively shifted when the cell discharged from open circuit potential (OCP) to 0.05 V, then positively shifted back when the cell charged to 3.0 V, indicating a transition from Ga2+ to Ga0, then to Ga2+ again (Figure 4b) 65. The further reduction from Ga0 to Li2Ga will give an extra capacity of 409.0 mAh/g 5. Thus the mechanism for the electrochemical lithiation of NiGa2O4 is proposed as following steps, which in total are expected to give a capacity of 1226.9 mAh/g.



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NiGa2O4 + 8eˉ + 8Li+ = Ni + 2Ga + 4Li2O

(Equation 1)

2Ga + 4Li+ + 4eˉ = 2Li2Ga

(Equation 2)

The stability of NiGa2O4/rGO is further measured by cyclablity test (Figure 3d). The capacity of NiGa2O4/rGO is 669.8 mAh/g (1000 cycles) and 621.1 mAh/g (2000 cycles), respectively. The coulumbic efficiency is over 99.4% during the cycles. This result is by far the highest cyclablity performance of Ga-based materials employed as anode material for Li-ion battery 9, 14, 18, 21. The SEM images of NiGa2O4/rGO anodes, as prepared (Figure S5A) and after 100 cycles (Figure S5B), demonstrate that the 2D structure of rGO has not collapsed after cycling. Similar carbon structure was also discovered to be stable by Zhou and Lou et al. after cycling 66. Full cell performance of NiGa2O4/rGO. To further investigate the applicability of the NiGa2O4/rGO composite, we carried out a full cell test on this composite. LiCoO2 was used as the cathode material. The full cell test is expected to reflect the reversibility of the composite under conditions closer to actual battery use. From 2.5 to 4.3 V with a discharge rate of C/2 [based on LiCoO2], the full cell shows a discharge initial capacity of 150 mAh/(g LiCoO2), and the corresponding CE is 83.5% (Figure 5a). After 100 cycles, the capacity retention rate is 96% (the average loss per cycle is 0.04%), indicating a good cycle stability (Figure 5b). Conclusion Our results show that upon appropriate synthesizing, NiGa2O4 can be a good LIB anode material. Ethylene glycol in this work acts as both solvent and reduce agent of GO, and it can also avoid the change of pH of the precursor, which can strongly influence the size and morphology of NiGa2O4 NPs according to Zhou et al 23. The size of the NiGa2O4 NPs was well controlled to be around 3-4 nm, and well distributed on the surface of rGO sheets. The NiGa2O4/rGO composite exhibited a delithiation capacity of 1372 mAh/g (0.2 A/g). The high capacity was attributed to both the conversion reaction of NiGa2O4, as well as the further lithiation reaction of Ga to generate Li2Ga, according to reaction mechanism study by ex situ XPS and XRD. The composite exhibited high cycleability (2000 cycles, 2 A/g), and a good full cell stability (an average loss of 0.04% per cycle, 100 cycles, C/2 rate of LiCoO2).


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The good stability of the composite was ascribed to the self-healing feature of Ga0 formed during discharge according to valence state characterization of Ga by XPS.

Acknowledgements: This work was supported by the National Natural Science Foundation of China (21872108, 21573167, 91545205 and 21633008), the National Key Research and Development Program (2016YFB0101203), the Fundamental Research Funds for the Central Universities (2014203020207). This work made use of TEM facilities of the Cornell Center of Materials Research, a National Science Foundation Materials Research Science and Engineering Center, under award number DMR-1120296. We are grateful to Luxi Shen at Cornell University for editing the manuscript.

Supporting Information. SEM image of LiCoO2; Raman spectroscopy of NiGa2O4/rGO and GO; Elemental mapping images of the NiGa2O4/rGO composite; TGA measurement of the NiGa2O4/rGO composite; SEM images of NiGa2O4/rGO anodes as prepared and after 100 cycles.



Figure 1. (a) XRD patterns of NiGa2O4/rGO after pyrolysis at 500oC. Insert: Curve fitting for NiGa2O4/rGO (440) diffraction peaks. (b) XPS spectra: 2p energy level of Ni and Ga in NiGa2O4/rGO.


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Figure 2. (a-c) SEM images of NiGa2O4/rGO. (d) HRTEM image of NiGa2O4/rGO.



Figure 3. (a) Cyclic voltammograms of NiGa2O4/rGO, 0.05-3.00 V vs.Li/Li+, 0.2 mV/s) (b) Discharge-charge profiles of NiGa2O4/rGO, 0.5 A/g. (c) Rate performance of NiGa2O4/rGO. (d) Cycling performance of NiGa2O4/rGO, 0.05-3.00 V vs. Li/Li+, 2.0 A/g.


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Figure 4. (a) Ex situ XRD patterns of NiGa2O4/rGO anode at various depth of charge/discharge, (b) Ex situ XPS spectra of NiGa2O4/rGO anode at various depth of charge/discharge.



Figure 5. (a) Comparison of the Li-compensated NiGa2O4/rGO/LiCoO2 full-cell and the Li metal/LiCoO2 half-cell, 1st cycle. (b) Discharge capacity of LiCoO2 in the NiGa2O4/rGO/LiCoO2 full cell in 100 cycles.


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Graphic Abstract


rGO Composite as Long Cycle Life Anode material for

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