Multiporous core-shell structured [email protected] carbon towards high-performance lithium-ion batteries

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Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries Jing Lin a, Lei Yu c,*, Qujiang Sun b,**, Fangkuo Wang a, Yong Cheng b,***, Sheng Wang a, Xu Zhang a a

Department of Chemical and Chemical Engineering, Hefei Normal University, Hefei, 230601, Anhui, China State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun, 130022, Jilin, China c Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei, 230031, Anhui, China b

highlights

graphical abstract


MnO@NeC with multiporous coreshell structure is synthetized.
High lithium storage capacity and rate capability of MnO@NeC are confirmed.
The high performance is studied by kinetic analysis and electrochemical process.
High rate capabilities of lithium ion full battery are constructed.

article info

abstract

Article history:

It is imminently to seek for high energy density in addition to a sensational lifetime of

Received 15 August 2019

lithium-ion batteries (LIBs) to meet growing requisition in the energy storage application.

Received in revised form

Anode containing metal oxide composite is being thoroughly investigated for their higher

15 October 2019

capacity than that of the commercial graphite. A multiporous core-shell structured metal

Accepted 12 November 2019

oxide composite anode possessing the excellent capacity and superb lifespan for LIBs is

Available online xxx

designed. In detail, metal oxide (i.e., MnO) is encapsulated in N-doped carbon shell (MnO@N eC) via coprecipitation-annealing technique. During annealing, abundant void space

Keywords:

among MnO cores/between MnO cores and NeC shells is obtained. This space can effica-

Metal oxides

ciously buffer volume changes of MnO upon cycles. Benefiting from the unique structure

Lithium-ion batteries

and heteroatom doping, the capacity of MnO@NeC microcube anode exhibits 576 mAh g1

MnO

at 5 A g1 with an ultra-long lifespan more than 3500 cycles. The connection between the

Core-shell structure

electrode characteristics and structure is concurrently examined by adopting kinetic

N-doped carbon

analysis. Finally, a full lithium-ion battery is presented, applying the MnO@NeC (anode)

* Corresponding author. ** Corresponding author. *** Corresponding author. E-mail addresses: [email protected] (L. Yu), [email protected] (Q. Sun), [email protected] (Y. Cheng). https://doi.org/10.1016/j.ijhydene.2019.11.083 0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved. Please cite this article as: Lin J et al., Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.083

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and Nick-rich layered oxide (cathode). It is believed that structural designing with heteroatom doping can be utilized in vaster fields for superior capabilities. © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Introduction Highly efficient and green energy storage systems have been demanded to cope with the global energy shortage. Lithiumion batteries (LIBs) have been applied in a lot of areas (e.g., electric vehicles, electricity grid storage, etc.) for their outstanding lifetime as well as energy density [1e12]. However, the theoretical capacity of predominant mercantile graphite is impoverished, and its rate property is also weak [13]. It cannot satisfy the upsurging requirements of new generation high-energy LIBs. Accordingly, it is urgent to foster the novel electrode materials exhibiting higher capacity, longer lifespan, and improved rate performance. Transition metal oxides (TMOx, CoO [14,15], CuO [16], NiO [17], MnO [18,19], etc.) have been broadly analyzed as anode material for LIBs on account of the fantastic capacity and costefficient price. In particular, MnO has been considered to be the most promising alternative on account of natural enrichment, moderate potential, wonderful theoretical capacity (756 mAh g1) and ecofriendly [20e24]. However, the intrinsically poor electronic conductivity, serious aggregation in addition to manifest volumetric change throughout lithiation and delithiation reactions greatly restrict its application for LIBs [25,26]. To address the above issues, modifying nanosized active materials with various carbon (e.g., rGO [27e30], CNTs [31e34], CNFs [20], etc.) is available, leading to an enhanced electron conductivity. Another good approach is to design various structures of active materials [35e48], such as coreshell structure, in which the shell (i.e., carbon) provides beneficial conductivity and mechanical stability to constrain the active core (i.e., MnO), undergoing large volumetric expansion. Herein, a multiporous core-shell structure is introduced to address the related issues, in which the porous structure and voids between shell and core can offer ample space to buffer the volume changes upon the cycles. In detail, the multiporous core-shell MnO@NeC is prepared via a coprecipitationannealing route by using PDA as the carbon source and N source. Benefiting from the super architecture and heteroatom-doping, the acquired MnO@NeC anode material exhibits excellent rate capacities (1009 mAh g1 at 0.1 A g1, 335 mAh g1 at 5 A g1), along with an enhanced lifespan (576 mAh g1 at 5 A g1 over 3500 cycles), revealing immense application foreground as one progressive electrode for LIBs.

(II). After that, II was added into I and stirred vigorously, then heated at 50  C for 9 h. The generating MnCO3 was collected by filtering, washing and finally freeze-drying. Synthesis of MnCO3@PDA. 0.1 g MnCO3 was added to 200 mL Tris-buffer (0.01 M, pH ¼ 8.5) under ultrasonic for 1 h. 0.2 g dopamine hydrochloride (98%, Aladdin) was dispersed into the above suspension afterward. The suspension was magnetically stirred for 12 h at room temperature. Finally, the sample was filtered, washed, then freeze-dried. Synthesis of MnO@NeC. The MnCO3@PDA was handled  under argon shield at 700  C for 2 h. The heating rate was 5 C/ min. Then MnO@NeC was successfully obtained. In contrast, the bare MnO was prepared by calcining MnCO3 at 700  C for 2 h under argon atmosphere. Sample characterization. X-ray diffraction (XRD) was accomplished with a Bruker D8 power X-ray diffractometer utilizing Cu radiation. Hitachi S-4800 field emission scanning electron microscope (SEM) was employed to collect the surface appearance of samples. Microstructure features of products were observed by the FEI Tecnai G2 S-Twin transmission electron microscope (TEM). The electronic states and elements of composites were confirmed, applying an X-ray photoelectron spectrometer taking advantage of Al Ka radiation (XPS, ESCALABMKLL). BET superficial area and porosity were estimated from N2 adsorption/desorption tests, performed by a Micromeritics ASAP 2010 apparatus. Distribution of pore size was conducted with the adsorption isotherms by the Barrett-Joyner-Halenda (BJH) approach. Electrochemical measurements. The coin-type cells were fabricated to characterize the electrochemical properties of products. Samples (70 wt%), carbon black (20 wt%), together with poly (vinylidene fluoride) binder (10 wt%) mixed with Nmethy1-2-pyrrolidone were ground uniformly. Next, the slurry was spread on clean Cu foil then dried for 12 h at 60  C in a vacuum oven. Then the prepared electrode foil was pressed at 5 MPa and punched into disks afterward. Half cells (CR2025) were assembled in the glove box. The pure metallic Li foil was regarded as a counter electrode. Commercial LiPF6 (1 M) in a mixed solvent of ethyl carbonate, including diethyl carbonate (1:1, v/v), was an electrolyte. The separator was Celgard 2400 membrane. Electrochemical performance measurement was taken on the BTS (NEW WARE) battery measurement system. A cyclic voltammogram (CV) test was implemented using the Biologic VMP3 electrochemical workstation. The electrochemical impedance spectroscopy (EIS) test was performed from 10 mHz to 100 kHz at room temperature by Biologic VMP3 electrochemical workstation.

Experimental section Preparation of MnCO3. First, 5 mmol MnSO4, 35 mL ethanol and 50 mmol (NH4)2SO4 were dissolved into a 1 L beaker filled with 350 mL deionized (DI) water. The product was labeled as I. Next, 50 mmol NH4HCO3 was dissolved by 350 mL DI water

Results and discussion The fabrication procedure of MnO@NeC is presented in Fig. 1. Firstly, MnCO3 precursor with a diameter ranging from 1.6 to

Please cite this article as: Lin J et al., Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.083

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Fig. 1 e Diagrammatic sketch of synthesizing MnO and MnO@NeC composite.

2 mm (Figure S2) was synthetized through a facile and effective coprecipitation procedure. Thus the polydopamine was coated outside the MnCO3 microcubes to form MnCO3@PDA intermediates. Finally, the multiporous core-shelled MnO@NeC microcubes were obtained with the help of annealing MnCO3@PDA intermediates at 700  C for 2 h under argon shield (i.e., MnCO3 / MnO þ CO2). The external dopamine shell was carbonized in the meantime to form the Ndoped carbon layer. Fig. 2a and Figure S1 show the XRD patterns of MnO@NeC composite and MnCO3, respectively. All peaks of MnO@NeC and MnCO3 are well fitted to MnO (JCPDS no. 07e0230) and MnCO3 (JCPDS no. 44e1472), individually. The amorphous carbon formed from PDA is determined from the broad signal at about 25 . XPS is conducted to confirm the detail element information of the composite. Mn, C, O and N are inspected by XPS, respectively. The MnII is judged by the distinct banding energy of Mn 2p1/2 and Mn 2p3/2 centered at both 653.46 and 641.63 eV. The representative energy discrepancy is about 11.9 eV (Fig. 2b) [24,42]. Moreover, the datum of C and particularly N are encapsulated in Fig. 2c. Firstly, the primary signal at 284.6 eV in the C 1s spectrum assigns to sp [2]-hybridized graphitic carbon (C]C). Peaks at 285.25, 286.35, and 288.95 eV correspond to CeC, CeN and C]O configurations, respectively [32]. Four peaks located at 398.4 eV, 399.1 eV, 400.7 eV and 403.4 eV are observed in Fig. 2d which correspond to pyridinic (N1), pyrrolic (N2), graphitic (N3) and oxidized (N4) type of N species [36,38]. Another characteristic of MnO@NeC is the salient superficial area about 132 m2 g1 and rich pores, as characterized by the type-IV isotherm in N2 adsorption/ desorption measurements (Fig. 2eef). The morphology and construction features of products were examined through FESEM and TEM in Figs. 3 and 4. The morphology from MnCO3@PDA to the products (MnO@NeC) can be preserved after annealing, illustrating the stable structural constancy of MnCO3@PDA and the practicability of this method (Fig. 3). In the case of MnO@NeC, top view SEM image (Fig. 3d) shows a smooth surface, corresponding to the NeC coating layer. Particularly, there is enough void space inside the MnO@NeC microcubes (Fig. 4), which can inhibit the volume variation during cycling. The interplanar spacing of lattice fringes is 0.22 nm which matches commendably to

(200) lattice plane of fcc MnO [49e53], establishing the existence of MnO. Particularly, the carbon content in the MnO@NeC can be finely controlled as low as 10.8 wt% based on this strategy (Figure S3). The preponderance of MnO@NeC over that of MnO is manifested in Fig. 5a. High average capacity of 994 mAh g1 at 1.0 A g1 is delivered in the continuous 500 cycles. While this value is much classier than 397 mAh g1 of MnO (Figure S6a). The capacity of MnO decays critically and cannot keep over 50 cycles. This confirms the significance of the N-doped carbon framework since it can furnish an improved electronic conductivity along with enough defects to store more ions. Moreover, MnO@NeC has ascending drift in capacity upon cycles, which results from the activation of MnO and the formation of Mn3þ or Mn4þ during the cycling process (Figure S4 and S5). Subsequently, a further study on the electrochemical reactions of MnO@NeC is performed in Fig. 5b. Four signals located about at 1.78 V, 1.48 V, 0.71 V and 0.07 V in the first cathodic scan, representing reduction of higher oxidation state manganese to Mn2þ, the formation of SEI and the reduction of Mn(II) (2Liþ þ MnO þ 2e / Mn þ Li2O), respectively [20,54e59]. During the subsequent anodic scans, a strong signal centered at 1.26 V expresses the decomposition of Li2O and regeneration of MnO (Mn þ Li2O / MnO þ 2e þ 2Liþ). An expansive signal around at 2.26 V illustrates a further oxidation of Mn2þ [40]. Subsequently, a new signal appearing at 0.28 V indicates the enhanced kinetics and irreversible phase transformation [39,47,48]. Note that the good approach of CV curves throughout cycling further proves terrific durability of MnO@NeC in the course of repeated cycles. Fine discharge/charge profiles of MnO@NeC at different ampere densities are demonstrated in Fig. 5c, which can correspond to the above CV results. As shown in Fig. 5d, the high capability of the MnO@NeC microcubes was verified by the rate test. The capacities of MnO@NeC microcubes are 1009, 837, 665, 533, 398, 335, 216 and 136 mAh g1 at current densities of 0.1, 0.2, 0.5, 1, 2, 4, 5, 10 and 15 A g1, respectively, which are much higher than those of MnO (Figure S6b). After the discharge current density goes back from 15 A g1 to 0.1 A g1, the capacity of MnO@NeC electrode can recover to 1019 mAh g1 without manifest capacity fading in the following cycles. The results confirm the

Please cite this article as: Lin J et al., Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.083

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Fig. 2 e (a) XRD graphs of MnO@NeC. (bed) XPS spectrograms for (b) Mn 2p, (c) C 1s and (d) N 1s, (e) N2 adsorption-desorption isotherm, (f) and the curve of the pore size distribution for MnO@NeC composite.

Fig. 3 e SEM images of (aeb) bare MnO including (ced) MnO@NeC at different resolutions.

superiorities of MnO@NeC composite profiting from multiporous core-shell architecture and hetero-atom components of the shell. Moreover, the capacity and cycle function of the composite is shown at 2 and 5 A g1 (Fig. 5e and g), where an average capacity is 906 and 576 mAh g1 over 800 and 3500 cycles with an outstanding Coulombic efficiency of nearly 99.5%. In addition, three-stage cycling behavior of cycling performance can be observed: (i) capacity fading in the first 30 cycles, which is caused by the formation of SEI and voltage hysteresis; (ii) Capacity recovery stage from 31 to 400 cycles

thanks to the activation of electrode materials and the interfacial storage of lithium; (iii) Capacity stabilization stage after 400 cycles. Moreover, the morphology of MnO@NeC can be is stabilized when the electrode was cycled at 1.0 A g1 for 30 cycles, demonstrating the good structural stability of MnO@NeC upon (de-)lithiation process (Figure S7). Reaction kinetics of MnO@NeC composite and MnO were explored first by EIS (Fig. 6aeb, Table S1). The charge transfer resistance (Rct) of MnO@NeC (43.5 U) is abated by a wide margin compared with MnO (147.1 U), confirming its

Please cite this article as: Lin J et al., Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.083

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Fig. 4 e (aeb) TEM images of MnO@NeC. The inset shows its HRTEM image.

Fig. 5 e (a) Cycling constancy at 1 A g¡1, (b) CV curves at 0.1 mV s¡1, (c) voltage vs. capacity profile, (d) rate capabilities and (e) cycling feature at 2 A g¡1 of MnO@NeC. (f) Rate feature of MnO@NeC compared with other electrode materials containing MnO (g) and its high-rate characteristic at 5 A g¡1.

preferable electronic conductivity than MnO. The diffusion coefficient of lithium ions (DLiþ) is obtained by the following formula: DLi ¼

R2 T2 2A2 n4 F4 C2 s2

where R, T, A, n, F, C and s are gas constant, absolute temperature, the surface area of the anode, number of electrons per molecule during oxidation, Faraday constant, the concentration of Liþ and Warburg coefficient, separately. s is calculated via the linear fitting of Z0 versus u1/2 ðZ0 ¼ ðR0 þRct Þ þsu1=2 Þ (Fig. 6b) [60,61]. The DLiþ of MnO@NeC is

6.88  1014 cm2 s1, which is higher than that of MnO (1.76  1014 cm2 s1). The raised DLiþ is attributed to the considerable pores in NeC construction and abundant voids among MnO particles, which contributes to the infiltration of electrolyte and migration of Liþ as well as cuts down the Liþ diffusion distance. The kinetics analysis for MnO@NeC was deeply investigated by CV. Four signals in Fig. 6c labeled as peak 1, peak 2, peak 3 and peak 4 are used to recognize the association between peak current (i) and scan rate (v) which abides by the following formula: i ¼ avb (a and b are both constants) [61]. The value of b at four peaks are 0.73, 0.69, 0.76, and 0.83

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Fig. 6 e (a, b) EIS of MnO@NeC and MnO (Inset is the equivalent models). (c) Cyclic voltammogram of MnO@NeC composite. (d) The connection between logarithm (i) and logarithm (v). (e) Capacity analysis of capacitive (green part) and diffusioncontrolled contribution at 1.0 mV s¡1. (f) The proportion of capacitive and diffusion-controlled contribution at diverse rates. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

individually, as acquired through the slope of log i versus log v displayed in Fig. 6d. MnO@NeC undergoes a collective behavior of diffusion-controlled Liþ insertion (b ¼ 0.5) and surface-controlled charge storage process (b ¼ 1) [62,63]. Consequently, the effect of battery behavior and capacitance can be characterized by the total current i. Total current i can be broken into a diffusion-controlled section which is consistent to v1/2 and capacitive section which is proportional to v [57].

i ¼ k1 v þ k2 v1=2 wherein k1 and k2 are constants, calculated by plotting iv1/2 versus v1/2. According to the above discussion, a few conclusions can be concluded: i) diffusion-controlled battery behaviors occupy 71.1e52.4% of the whole capacity contribution as growing the rate from 0.3 to 1.50 mV s1, indicating the dominance of diffusion-controlled (Fig. 6eef); ii) capacitive

Fig. 7 e (a) Diagrammatic sketch of full lithium-ion battery included MnO@NeC (anode) and LiNi0.8Co0.1Mn0.1O2 (cathode). (b) Charge-discharge curves of both MnO@NeC and LiNi0.8Co0.1Mn0.1O2. (c) Cyclic voltammetry curves, (d) rate property, (e) and cyclical stability at 0.5C (1C ¼ 200 mA g¡1) for the full battery.

Please cite this article as: Lin J et al., Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.083

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contribution affects the overall capacity significantly at high v. These analyses certify that the multiporous microcubes architectures and hetero-atom components are foremost resulting in the sterling capacity and marvelous rate capabilities. All these advantages were further confirmed by the full battery with classy performance when MnO@C was acted as an anode and the Ni-rich layered oxide was cathode (e.g., LiNi0.8Co0.1Mn0.1O2, around 200 mAh g1), as summarized in Fig. 7a. The battery shows an appreciable energy/power density, resulted from a preferable capacity of MnO@C (about 995 mAh g1). The capacity ratio of anode/cathode of the designed full battery is about 1.1 (Fig. 7b). The homologous specific capacity of cathode and anode are 205 and 995 mAh g1, separately. The electrochemical properties are tested by CV curves (Fig. 7c). The full battery can be stabilized quickly even in the first cycle, in which the following CV profiles overlap well. The full Li-ion battery reveals fantastic rate capabilities. The discharge capacity can be obtained at 97.5%, 92.2%, 78.1%, 66.5% and 54.1% (vs. 191 mAh g1) under the rate of 0.2, 0.5, 1, to 5C, separately (Fig. 7d, Fig. S8a). More importantly, the appreciable cycle stability and great (dis-)charge profiles are expressed at 0.5C (1C ¼ 200 mA g1) in Figure S8b. The battery exhibits 100 mAh g1 together with a capacity retention of 67.7% after 100 recharge cycles (Fig. 7e). These current results in this paper demonstrate that the MnO@NeC has a high potential value as an anode in LIBs due to the quicker Liþ diffusion rate inside multiporous microcubes and impressive capacitive contribution for Liþ storage at the high rate.

Conclusion In summary, a facile and efficient strategy for carbon modification by a coprecipitation-annealing route is demonstrated, in which a hierarchical metal oxide MnO decorated with heteroatom mingled carbon NeC is introduced. MnO@NeC shows a terrific capacity of 1009 mAh g1 and excellent rate capacity at 15 A g1 over 3500 cycles as a consequence of the profitable structure and composition. Furthermore, a new lithium battery of MnO@NeC | LiNi0.8Co0.1Mn0.1O2 with the appreciable peculiarities of high rate performance over 5C (1C ¼ 200 mA g1) is presented. This general method is suitable for other electrode materials for higher capabilities. The obtained high rate lithium-ion battery can content the widespread requirement in the high energy storage devices.

Acknowledgements This work was supported by the Nature Science Research Project of Anhui province (1908085QE172); the National Science Foundation of China (NSFC) (41504143); the Teaching and research project of Hefei normal university (2018jy22); the Excellent Young Talents in University of Anhui Province (gxyq2018055); and the Natural Science

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Foundation of the Education Department of Anhui Province (KJ2019A0731).

Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.ijhydene.2019.11.083.

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Please cite this article as: Lin J et al., Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.083

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Please cite this article as: Lin J et al., Multiporous core-shell structured MnO@N-Doped carbon towards high-performance lithium-ion batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.083