Mesoporous ZnMn2O4 Microtubules Derived from a Biomorphic

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Energy, Environmental, and Catalysis Applications

Mesoporous ZnMn2O4 microtubules derived from a biomorphic strategy for high performance lithium/sodium ion batteries Xiangwei Luo, Xiuyun Zhang, Lin Chen, Lin Li, Guisheng Zhu, Guangcun Chen, Dongliang Yan, Huarui Xu, and Aibing Yu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b10111 • Publication Date (Web): 05 Sep 2018 Downloaded from http://pubs.acs.org on September 5, 2018

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ACS Applied Materials & Interfaces

Mesoporous ZnMn2O4 microtubules derived from a biomorphic strategy for high performance lithium/sodium ion batteries Xiangwei Luo a, Xiuyun Zhang a, Lin Chen b, Lin Li a, Guisheng Zhu a, Guangcun Chen c, Dongliang Yan a,*, Huarui Xu a, Aibing Yu d a

Guangxi Key Laboratory of Information Materials, Guilin University of Electronic

Technology, Guilin 541004, PR China b

Department of Material and Chemistry Engineering, Pingxiang University,

Pingxiang 337055, PR China c

Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences,

Suzhou 215123, PR China d

Department of Chemical Engineering, Monash University, Clayton, Vic 3800,

Australia

Corresponding author E-mail addresses: [email protected] (DL Yan) Tel.: +86 773 2291159 Fax.: +86 773 2191903

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ABSTRACT ZnMn2O4 microtubules (ZMO-MT) with a mesoporous structure are fabricated by a novel yet effective biomorphic approach employing cotton fiber as a biotemplate. The fabricated ZMO-MT has approximately an inner diameter of 8.5 µm and wall thickness of 1.5 µm. Further, the sample of ZMO-MT displays a large specific surface area of 48.5 m2 g-1. When evaluated as a negative materials for Li-ion batteries, ZMOMT demonstrates an improved cyclic performance with charge capacities of 750.4 and 535.2 mAh g-1 after 300 cycles, under current densities of 200 and 500 mA g-1, respectively. Meanwhile, ZMO-MT exhibits superior rate performances with high reversible discharge capacities of 614.7 and 465.2 mAh g-1 under high rates of 1000 and 2000 mA g-1, respectively. In sodium ion batteries applications, ZMO-MT delivers excellent high discharge capacities of 102 and 71.4 mAh g-1 after 300 cycles under 100 and 200 mA g-1, respectively. An excellent rate capability of 58.2 mAh g-1 under the current density of 2000 mA g-1 can also be achieved. The promising cycling performance and rate capability could be benefited from the unique one-dimensional mesoporous microtubular architecture of ZMO-MT, which offers a large electrolyte/electrode accessible contact area and short diffusion distance for both of ions and electrons, buffering the volume variation originated from the repeated ion intercalation/deintercalation processes.

Keywords: biomorphic, microtubules, mesoporous, ZnMn2O4, lithium/sodium ion batteries


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1. INTRODUCTION Zinc manganate (ZnMn2O4) is an attractive electric storage material because of its high theoretical capacity, nontoxicity, as well as low cost, and thus, it has been widely studied for potential applications in various energy storage fields, like lithium ion batteries (LIBs) and sodium ion batteries (SIBs)1-2. Nevertheless, ZnMn2O4 anode still shows an unsatisfactory cycling stability because of the volume change resulting from repeated ion intercalation/deintercalation processes. To solve this problem, design and construction of a special morphology is a common and efficient way to improve the electrochemical properties of ZnMn2O4 anode materials, which display shapedependent performances. Therefore, tests on various special morphologies of ZnMn2O4, such as ball-in-ball1, nanorods3, nanowires4, hollow microspheres5, flowers6, hexahedrons7 and nanosheets8 have been reported. Among these architectures, one-dimensional (1D) micro/nano-structured tubular electrodes have drawn considerable attention since they possess the advantages of both the onedimensional and hollow structures9. For instance, Zhang et al.10 prepared ZnMn2O4 hollow nanotubes (NTs) of approximately 100 nm in diameter by integrating ZnMn2O4 with carbon nanotubes (CNTs), and the as-prepared ZnMn2O4 hollow NTs showed excellent electrochemical properties when used as anodes in LIBs. In addition, ZnMn2O4 tubular arrays on a titanium substrate through a reactive template route have been reported by Kim et al.11. An electrochemical test showed that the as-fabricated ZnMn2O4 tubular arrays displayed an outstanding long-term stability and a high Coulombic efficiency. Further, Mondal reported the preparation of ZnMn2O4/carbon nanotube by a hydrothermal approach, which showed an acceptable electrochemical performance12. Unfortunately, the 1D ZnMn2O4 tubular structure synthesized by the above-mentioned route involves tedious or multistep procedures, which have some



disadvantages such as high-cost, complexity and requirement of special instruments. Hence, developing an effective, simple and economic approach to synthesis tubular ZnMn2O4 is significant and necessary. Recently, natural biomaterials such as cotton13-14, bagasse15, corn stalk16, protein17, yeast18-19, pollen20 and legume21 each have been used as a biotemplate to synthesis of biomorphic functional materials. These natural species present highly optimized, unique material systems after stringent natural selection processes of billions of years22-23. By elaborately replicating these structural systems, we can obtain biomorphic functional materials with a subtle micro-nanostructure, which are barely attainable by traditional synthesized strategies24-25. With their unique structural advantages, these novel biomorphic materials are, therefore, expected to demonstrate amazing applicable properties22-25. To date, 1D micro/nano-structured tubular ZnO26, NiO27, SiO228 and Al2O329 have been successfully synthesized through the use of different biomaterials, and their performances have been quite intriguing in gas adsorption and energy storage/conversion applications. Herein, ZnMn2O4 microtubules with a mesoporous structure are successfully synthesized via a simple and effective biomorphic strategy employing cotton fiber as a biotemplate, and the lithium/sodium storage performances of the as-fabricated samples are studied.

2. EXPERIMENTAL SECTION The ZMO-MT is prepared via a biomorphic route as illustrated in Figure 1. The detailed preparation procedures and characterization methods are shown in the


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Supporting Information. For comparison, bulk ZnMn2O4 is synthesized in a similar procedure, but without using cotton.

Figure 1 Schematic illustration of the formation of ZMO-MT

3. RESULTS AND DISSUSSION The XRD pattern of the as-fabricated sample can be seen in Figure 2a. All the diffraction peaks can be well ascribed to a body-centered-tetragonal zinc manganate with space group of I41/amd (JCPDS, no. 24-1133) (a=b= 5.7205 Å, c= 9.2674 Å;), suggesting that the pure ZnMn2O4 with a spinel structure has been successfully fabricated. The FT-IR spectrum of the as-obtained ZMO-MT is given in Figure 2b. The absorption peak at ~3450 cm-1 can be attributed to the stretching vibrations of OH and adsorbed water from the atmosphere30. Two absorption bands can be detected at ~1636 and 1384 cm-1, which correspond to the C=C stretching and -COOsymmetrical stretching, respectively31. Two peaks locate at ~622 and ~550 cm-1 are related to the Zn-O and Mn-O vibrations32, respectively.



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(a)

(b)

(c)


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(d)

(e)

(f)

Figure 2 (a) XRD pattern; (b) FT-IR spectrum; and (c) XPS spectrum of survey spectrum, (d) Zn2p, (e) Mn2p, and (f) O1s for ZMO-MT



XPS was conducted to detect the constituent and valence state of element of the product (Figures 2c-2f). Typical survey spectrum (Figure 2c) indicates the coexistence of Zn, Mn and O, and C element used as the reference for calibration. Two fitting peaks at 1021.6 and 1044.7 eV can be observed from the Zn 2p spectrum (Figure 2d), which correspond to Zn 2p3/2 and Zn 2p1/2, respectively. The BE separation of about 23.1 eV between the two peaks further confirm that the presence of Zn2+ species in the sample33-34. The peaks centered at BEs of 641.6 and 653.2 eV in Mn 2p spectrum could be assigned to Mn 2p3/2 and Mn 2p1/2, respectively (Figure 2e). The BE separation of approximately 11.6 eV is consistent with Mn3+ present in ZnMn2O44,35. The high-resolution spectrum of O1s indicates two kinds of oxygen atoms in the sample (Figure 2f), of which the peaks located at 531.5 and 529.8 eV correspond to the lattice oxygen and metal oxygen bonds9 in ZnMn2O433, respectively. The SEM images reveal that the natural cotton fiber possess a microbelts-like morphology (Figure 3a). After the calcination process, however, the microbelts are rolled into a tubular morphology with an inner diameter of ~8.5 µm and a wall thickness of approximately 1.5 µm, as shown in Figures 3b and 3c. The hollow tubular structure of the sample is also clearly confirmed via the sharp contrast between the core and the edge in the TEM image (Figure 3d). The well-defined lattice fringes with a spacing of 0.304 nm can be found from the HRTEM image (Figure 3e), corresponding to the (112) crystal plane of spinel ZMO. In addition, the TEM image and corresponding EDS mapping of ZMO-MT (Figure 3f) clearly demonstrate that the key element of Zn, Mn and O are evenly distributed in the microtublue. In contrast, the bulk ZnMn2O4, which achieved from the directly calcination of precursor solution, exhibits an irregular particle morphology (Figure S2). Therefore, the cotton fiber have a determinant effect on the formation of ZMO-MT. Because of


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the gravitation effect, the top side absorbed less precursor solution than the bottom side during the impregnation and drying process. When heat treated at 700 °C, the fiber appeared to curl into a mesoporous microtubular morphology because of the different shrinkage between the bottom side and the top side, the decomposition of the precursor and release of gases generated during the heat treatment18.

(a)

(b)

(c)



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(d)

(e)


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(f)

Figure 3 SEM images of: (a) cotton fiber; (b-c) ZMO-MT; (d) TEM, (e) HRTEM and (f) the corresponding elemental mapping of ZMO-MT

A TG test was carried out on the infiltrated cotton fiber, which revealed the formation process of ZMO-MT (Figure 4(a)). A weight loss of 4.1% can be found first between 25 to 164 °C, which may be due to the vaporization of physically absorbed water13-14. The largest mass loss of 40.7% occurs from 164 to 350 °C, which is most likely ascribed to the decompositions of Zn(CH3COO)2·2H2O and Mn(CH3COO)2·4H2O15. The last significant mass loss of 21.8% is observed from 350 to 420 °C, which is related to the burning out of the cotton fiber15,18. At higher temperatures than 420 °C, the weight loss shown in the TG profile remains almost constant suggesting that all the reactions have finished and the calcination temperature of 700 °C used in this work is high enough for the fully transformation from precursor to pure spinel ZnMn2O4. Furthermore, nitrogen adsorption and desorption isotherm of the ZMO-MT reveals a type IV isotherm with a H1 type



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hysteresis loop (Figure 4(b)), implying the presence of a mesporous structure in the product14,36. Based on the DFT method, the BET surface area of ZMO-MT is estimated to be 48.5 m2 g-1 with the average pore size of 5 nm (inset in Figure 4(b)), which is larger than that of ZnMn2O4 materials reported by other groups1,5,10,37-46. Such a large BET surface area of ZMO-MT may be ascribed to the replication of the morphology and structure of natural cotton. The high specific surface area is favorable to promote the redox reaction, and thus to enhance battery performance.

(a)

(b)

Figure 4 (a) TG profile; and (b) Nitrogen adsorption and desorption isotherm and pore size distribution (inset) for ZMO-MT


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The initial three cyclic voltammetry of the ZMO-MT electrode tested at 0.1 mV s-1 are displayed in Figure 5a. During the initial cathodic scan, a reduction peak appears located at 1.17 V, which could be ascribed to the reduction of Mn3+ to Mn2+42. A weak peak at approximately 0.83 V can be detected, which can be assigned to the formation of solid electrolyte interface (SEI) layer37,42. The intensive reduction peak centered at 0.11 V may be attributed to the reduction of Zn2+ to Zn and Mn2+ to Mn in Li2O matrix, followed by the formation of Li-Zn alloy42 (equations 1 and 2). In the initial anodic sweep process, two peaks are found at about 1.53 V and 1.24 V, which corresponding to the oxidation of Zn0 and Mn0 to ZnO and MnO, accompanied with the disintegration of the formed Li2O matrix5,33 (equations 3 and 4). The cathodic peak moves toward 0.43 V in the subsequent cycles, which is associated with the structural rearrangement5,11. The anodic scan that followed is similar to the first one, demonstrating the same electrochemical reactions are taking place in the anodic scans. In addition, the CV curves follow the first cycle, suggesting the good reversibility and structural stability of ZMO-MT. ZnMn2O4 + 8Li+ + 8e- → Zn + 2Mn + 4Li2O

(1)

Li+ + Zn + e-↔ ZnLi

(2)

2Li2O + 2Mn ↔ 2MnO + 4Li+ + 4eLi2O + Zn ↔ ZnO + 2Li+ + 2e-


(3) (4)


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(a)

(b)

(c)


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(d)

(e)

Figure 5 (a) Cyclic voltammetry curves; (b) charge-discharge profiles; (c) cyclic life; (d) rate capabilities at various current densities; and (e) corresponding rate profiles for ZMO-MT

Figure 5b presents the galvanostatic charge/discharge plots of ZMO-MT electrode performed at 200 mA g-1. Two obvious discharge plateaus at 1.27 and 0.35 V can be observed in the initial discharge curve, which are consistent with the formation of Mn0, Zn0 and Li-Zn alloy, respectively11,42,47. The first charge and discharge capacities are 738.7 and 1034.9 mAh g-1, respectively, with a Coulombic efficiency of 71.4%. The Coulombic efficiency of the second cycle reaches 95.7% and it gradually



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stabilizes close to 100% in subsequent cycles, implying the superior reversibility of the electrode. The cycling stability of ZMO-MT anode measured under the different current densities of 200, 500 and 1000 mA g-1 for 300 cycles is shown in Figure 5c. Interestingly, the discharge capacity of the electrode undergoes an unusual variational process at 200 mA g-1, in which the capacity increased up to 186 cycles after the first certain number of cycles and then decreased slowly. The increment of the capacity is mainly associated with the reversible formation of polymeric gel-like coating, which is a common phenomenon for transition metal oxides anodes1,48-50. Finally, after 300 cycles, the discharge capacity settles at 750.4 mAh g-1 with a retention rate of 95.1% compared with the second discharge capacity. In addition, capacities of 535.2 and 366.7 mAh g-1 could be delivered at 500 mA g-1 and 1000 mA g-1 after 300 cycles, and the corresponding retention rate are found to be 80.4% and 59.5%, respectively, which illustrate a superior long-term cycling performance, outperforming the performances of other reported ZnMn2O4-based electrodes, as summarized in Table 1.

Table 1 Comparison of electrochemical properties of ZnMn2O4-based anode of past and present studies

Electrode

Reversible Capacity

Current Density

Retention

(mAh g-1)

(mA g-1)

Rate (%)

Materials


Ref. No.

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750.4/300th cycles

200

95.1

This work

535.3/300th cycles

500

80.4

This work

Loaf-like ZnMn2O4

517/100th cycles

500

~79.5

3

ZnMn2O4 nanowires

450/40th cycles

500

~75

4

ZnMn2O4 hollow

607/100th cycles

400

~80

5

626/50th cycles

100

~82.0

6

~600/100th cycles

100

~72.7

12

ZnMn2O4 nanorod

518.3/300th cycles

500

~79.9

37

ZnMn2O4/NG-H2O

~410/100th cycles

ZnMn2O4/G

~312/100th cycles

ZMO-MT

microspheres

Flower-like ZnMn2O4

MWCNTZnMn2O4 nanoparticels

~54.1 500


~52

51


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ZnMn2O4

~116/100th cycles

ZnMn2O4

361/100th cycles

ZnMn2O4 at 600 °C

430/90th cycles

ZnMn2O4 at 700 °C

500/90th cycles

ZnMn2O4 at 900 °C

370/90th cycles

ZnMn2O4 nanoplate

502/30th cycles

60

~63.5

54

ZnMn2O4

430/100th cycles

100

~61.4

55

ZnMn2O4

490/25th cycles

100

72.6

56

Nanocrystalline

569/50th cycles

100

~71.1

57

602/100th cycles

100

~75.2

58

~20

400

60

52

~43 100

~70.4

53

~52.1

nanoparticles

ZnMn2O4

ZnMn2O4 microspheres


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ZnMn2O4/15wt%AC

714/50th cycles

ZnMn2O4/75wt%AC

375/50th cycles

Pure ZnMn2O4

270/50th cycles

~89.2 100

~40.1

59

~51.9

In addition to the cyclic performance, the rate capability is also of great importance to evaluate the electrochemical properties of an electrode material. Figures 5d and 5e provide the rate capability and corresponding charge-discharge profiles of ZMO-MT at various current densities. The average capacities of 1058.1, 841.4, 723.6 and 614.7 mAh g-1 can be attained under current densities of 100, 200, 500 and 1000 mA g-1, respectively. Remarkably, a capacity of 465.2 mAh g-1 can be obtained at a higher current density of 2000 mA g-1. Further, when the current density is decreased to 100 mA g-1, the capacity returns to 862.7 mAh g-1, demonstrating an superior rate capability compared to other works 3,5,8-12,37-38,42,52-53,58,60-62.

In order to inspect the sodium storage performance of ZMO-MT electrode, the cyclic voltammetry was initially carried out at 0.1 mV s-1 in the voltage from 0.01 to 3.00 V (vs. Na/Na+) (Figure 6a). Three broad peaks located at 1.13, 0.88 and 0.49 V can be detected during the initial cathodic scan process, which correspond to the reduction of Mn3+ to Mn2+, the formation of a SEI layer, and the reduction of Zn2+ and Mn2+ to the Zn0 to Mn0, respectively2. The two weak peaks appearing at ~0.86 and ~2.20 V in the first anodic scan process can be related to the oxidation of Zn to Zn2+



and Mn to Mn2+, respectively2. In the two cycles to follow, it can be seen that the reduction peaks have vanished, which should be ascribed to the direct reduction of Mn2+ to Mn, as well as the stabilization of an as-formed SEI layer. Further, the second cycle mostly coincides with the third one, suggesting a good reversibility. The charge-discharge profiles for the ZMO-MT electrode under current density of 100 mA g-1 can be found in Figure 6b. The first charge and discharge capacities of ZnMn2O4 electrode are 100.3 and 237.7 mAh g-1, respectively, corresponding to the initial Coulombic efficiency of 42.2 %, which is superior over those of ZMO/NG and bare ZMO reported by Sekhar et al2. The Coulombic efficiency gradually increased to about 100 % in following cycles, suggesting an excellent reversibility. The cycling stability of the as-obtained ZnMn2O4 electrode under current densities of 100 and 200 mA g-1 are given in the Figure 6c. After 300 cycles at 100 mA g-1, ZMO-MT can provide discharge capacity of 102 mAh g-1, and the retention rate is estimated to be 91.1 %, which is superior to that of bare ZMO2. Meanwhile, a capacity retention of 88.4 % was maintained after 300 cycles at 200 mA g-1, indicating an excellent long-term cycling stability. Figures 6d and 6e display the rate capability of ZMO-MT. The discharge capacity of ZMO-MT decayed as the current density increases (Figure 6d). Figure 6e displays that average discharge capacities of 121.7, 77.8, 72.9 and 63.4 mAh g-1 can be achieved at 100, 200, 500 and 1000 mA g-1, respectively. Surprisingly, a capacity of 58.2 mAh g-1 can be delivered even under high current density of 2000 mA g-1. The capacity falls back to 86.5 mAh g-1 as the current density decreases to 100 mA g-1, highlighting the outstanding rate capability of ZMO-MT. Compared with those of LIBs, however, the corresponding electrochemical performances in SIBs are


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relatively poor. Because of the sluggish kinetics and the bigger size of Na+ (0.59 Å for Li+ vs. 1.02 Å for Na+ in radius, respectively), a lot of electrode materials with excellent electrochemical properties in LIBs present relatively poor cycling performance and limited specific capacity in SIBs63.

(a)

(b)

(c)



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(d)

(e)

Figure 6 Characteristics of ZMO-MT: (a) Cyclic voltammetry curves; (b) chargedischarge profiles; (c) cyclic life; (d) rate capabilities at various current densities; and (e) corresponding rate profiles

Compared with bulk ZnMn2O4, which achieved from the direct calcination of precursor solution, the ZMO-MT displays the improved electrochemical properties (Figure S1-S4). The promising electrochemical properties of the ZMO-MT for both LIBs and SIBs may be associated with their unique features of one-dimensional mesoporous tubular architecture, stated below. First, the larger surface area of mesoporous tubular structure may increase the electrolyte/electrode accessible contact area and offer more electroactive sites, which will result in a higher specific


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capacity1,3,9. Secondly, ZMO-MT has a mesoporous structure and relatively thin tube walls, which can reduce the transmission path lengths for both Li+/Na+ and electrons, thereby significantly improving the rate capability of the electrode1,19,27. Thirdly, mesoporous hollow tubular structure of ZMO-MT can offer adequate space to alleviate volume change during the ion insertion/extraction process, thus leading to excellent cycling stability

1,27,38

. Last but not least, the one-dimensional morphology

of the ZMO-MT can partly enhance electron transfer along their 1D geometry, which results in fast mass transfer and diffusion kinetics, thus further improving the rate capability1,43,64-66. The SEM images of the ZMO-MT after 300 cycles are shown in Figure 7. It can be seen from the images that the ZMO-MT remains a well-defined microtubular structure, suggesting the excellent stability of ZMO-MT.

(a)

(b)



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Figure 7 SEM images of ZMO-MT after 300 cycles at 200 mA g-1 for: (a), LIBs and (b), SIBs

4. CONCLUSION In summary, mesoporous tubular ZnMn2O4 with an inner diameter of about 8.5 µm and wall thickness of about 1.5 µm have been successfully fabricated through a cotton-involved biotemplate strategy. Benefitted from the one-dimensional hollow features coupled with mesoporous structure, the as-prepared ZnMn2O4 electrode showed superior electrochemical properties with promising results in high capacity, rate capability and the cycling stability in both LIBs and SIBs. We are optimistic that this facile biotemplate method provides a new way of synthesizing other transition metal oxides as well, for the applications in energy storage field.

Supporting Information Detailed preparation procedures and characterization methods; XRD, XPS, SEM image and electrochemical performances for bulk ZnMn2O4; charge-discharge curves at 1 A g-1 for ZMO-MT

ACKNOWLEDGEMENTS Financial support from the grants, NSFC (51564006, 51764011), GXNSFC (2016GXNSFAA380205,

2017GXNSFDA198021,


2017GXNSFBA198075,

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AA17204063), and Innovation Project of Guet Graduate Education (2017YJCX113) is gratefully acknowledged.

References [1] Zhang, G.Q.; Yu, L.; Wu, H.B.; Lou, X.W. Formation of ZnMn2O4 Ball-in-ball Hollow Microspheres as a High-performance Anode for Lithium-ion Batteries. Adv. Mater. 2012, 24, 4609-4613. [2]

Sekhar,

B.C.;

Packiyalakshmi,

P.;

Kalaiselvi,

N.

Custom

Designed

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Mesoporous ZnMn2O4 Microtubules Derived from a Biomorphic

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