Co3O4 [email protected] porous carbon composites as anode materials with superior lithium storage performance

Accepted Manuscript Co3O4 nanoparticles@MOF-5-derived porous carbon composites as anode materials with superior lithium storage performance Yuanyuan Fu, Yanfei Li, Rihui Zhou, Yuzhe Zhang, Shouhui Chen, Yonghai Song, Li Wang PII:

S0925-8388(18)31215-5

DOI:

10.1016/j.jallcom.2018.03.338

Reference:

JALCOM 45568

To appear in:

Journal of Alloys and Compounds

Received Date: 8 January 2018 Revised Date:

18 March 2018

Accepted Date: 27 March 2018

Please cite this article as: Y. Fu, Y. Li, R. Zhou, Y. Zhang, S. Chen, Y. Song, L. Wang, Co3O4 nanoparticles@MOF-5-derived porous carbon composites as anode materials with superior lithium storage performance, Journal of Alloys and Compounds (2018), doi: 10.1016/j.jallcom.2018.03.338. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT

Co3O4 Nanoparticles@MOF-5-Derived Porous Carbon Composites as Anode Materials with Superior Lithium Storage Performance

RI PT

Yuanyuan Fu, Yanfei Li, Rihui Zhou, Yuzhe Zhang, Shouhui Chen, Li Wang and Yonghai Song∗ Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Key Laboratory of Chemical Biology, Jiangxi Province, College of Chemistry and Chemical

AC C

EP

TE D

M AN U

SC

Engineering, Jiangxi Normal University, Nanchang 330022, China.

∗Corresponding author: Tel/Fax: +86 791 88120862. E-mail: [email protected] (Y. Song).

ACCEPTED MANUSCRIPT

Co3O4 Nanoparticles@MOF-5-Derived Porous Carbon

2

Composites as Anode Materials with Superior Lithium

3

Storage Performance

RI PT

1

Yuanyuan Fu, Yanfei Li, Rihui Zhou, Yuzhe Zhang, Shouhui Chen, Yonghai Song and Li Wang∗

M AN U

5

SC

4

6

Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Key Laboratory of

8

Chemical Biology, Jiangxi Province, College of Chemistry and Chemical Engineering, Jiangxi

9

Normal University, Nanchang, 330022, China.

12

13

EP

11

AC C

10

TE D

7

∗Corresponding author: Tel/Fax: +86 791 88120861. E-mail: [email protected] (L. Wang). 1

ACCEPTED MANUSCRIPT 1

Abstract A new route to load Co3O4 nanoparticles (NPs) on MOF-5 (MOF-5 was composed of 1,4-

3

benzenedicarboxylate (BDC) and Zn2+ via coordination bond (Zn4O(BDC)3•(DMF)8(C6H5Cl)),

4

where MOF indicates metal-organic framework) derived hierarchically porous carbon (MDPC) was

5

proposed. Various techniques including scanning electron microscopy, transmission electron

6

microscopy, Raman spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy,

7

thermogravimetric analysis and electrochemical methods were used to characterize the

8

Co3O4NPs@MDPC. The results showed that the MDPC contained mesopores obtained by

9

vaporizing ZnONPs and micropores came from MOF-5 self. Lots of nano-sized Co3O4NPs formed

10

in MDPC’s mesopores. The vast micropores of MDPC provided an effective channel for the

11

transport of Li+ when it was used as anode materials for lithium ion batteries (LIBs). The MDPC

12

prevented Co3O4NPs from agglomerating effectively, which remained robust for superior rate

13

capability during repeated lithiation/delithiation process. And the as-prepared Co3O4NPs@MDPC

14

composites remained 94% reversible capacity from the second cycle. Furthermore, the as-prepared

15

Co3O4NPs@MDPC anode manifested outstanding capability of 587.2 mA h g-1 at 2000 mA g-1 after

16

200 cycles, apparently superior to that of other Co3O4NPs@PC. The high capacity especially at

17

high current density and exceptional rate capability of Co3O4NPs@MDPC manifested it is a

18

promising anode material for LIBs.

19

Keywords: Lithium ion batteries; Porous carbon; Co3O4 nanoparticles; Metal-organic framework

AC C

EP

TE D

M AN U

SC

RI PT

2

2

ACCEPTED MANUSCRIPT 1

Introduction Lithium ion batteries (LIBs) are of vital importance in modern life [1,2]. Although graphite is still

3

a widely used anode material for LIBs, its low theoretical capacity has not met demands of modern

4

life [3,4]. Accordingly, various metal oxide nanomaterials have been proposed for LIBs’ anodes [5-

5

9]. Among various metal oxide nanomaterials, Co3O4 nanomaterial is one of the most promising

6

anode materials owing to its high theoretical capacity and low cost [10,11]. However, their structure

7

destruction due to the huge expansion of volume in the lithation/delithation process would cause the

8

increase of irreversible capacity. Furthermore, the poor electron transfer and Li+ diffusion also

9

hindered Co3O4 nanomaterials as LIBs’ anode materials.

M AN U

SC

RI PT

2

To overcome these limitations, one approach is to load Co3O4 nanomaterials on carbon materials

11

including graphene [4,12,13], carbon nanotubes [14-16], porous carbon [17,18], etc. These carbon

12

materials could enhance electron transfer of Co3O4 nanomaterials. Their good mechanical properties

13

could also alleviate structure collapse partly. Among these carbon materials, the porous carbon (PC)

14

derived from bio-waste materials has attracted special attention because of its bountiful supply,

15

natural hierarchical pores and low cost [19-21]. Some good works have been performed by loading

16

Co3O4 nanomaterials on the PC derived from bio-waste materials such as crawfish shell-derived N-

17

doped PC [22], animal bones-derived PC networks [23], watermelon-derived carbonaceous

18

hydrogel [24], etc. However, the biological sources have inhomogeneous internal structures in the

19

different regions, which may result in poor reproducibility. Co3O4 nanomaterials are only loaded on

20

the outer surface of PC, which still makes the structure of Co3O4 nanomaterials easy to collapse

AC C

EP

TE D

10

3

ACCEPTED MANUSCRIPT during the lithation/delithation process. Furthermore, it remains a large challenge for large-scale

2

manufacture if the bio-waste materials are unable to access instantly. Another method is to prepare

3

Co3O4 nanomaterials@PC by calcining Co-metal organic framework (MOF) [25-29]. However,

4

only a few Co3O4 and a large number of Co were formed through calcining Co-MOF. It also is

5

difficult to form uniform Co3O4 nanomaterials through calcining Co-MOF owing to Co3O4

6

aggregating at high temperature [30,31].

SC

RI PT

1

Hence, a new route to load Co3O4 nanoparticles (NPs) on MDPC (MOF-5 was composed of 1,4-

8

benzenedicarboxylate (BDC) and Zn2+ via coordination bond, Zn4O(BDC)3•(DMF)8(C6H5Cl))-

9

derived PC) was developed. Herein, lots of nano-sized Co3O4NPs were formed in the mesopores of

10

MDPC which was formed by vaporizing ZnONPs. The vast micropores of MDPC originated from

11

the MOF-5 increased the specific surface area and facilitated the transport of Li+. The MDPC

12

prevented Co3O4NPs from agglomerating, which remained robust for superior rate capability during

13

repeated lithiation/delithiation process.

14

2. Experimental

15

2.1. Reagents and chemicals

AC C

EP

TE D

M AN U

7

16

Zn(NO3)2·6H2O and BDC were obtained from Aladdin Industrial Corporation (Shanghai, China).

17

Co(CH3COO)2·4H2O was obtained from Sigma-Aldrich and ammonia (25−28 wt%) was purchased

18

from Tianjin Yongda Chemical Reagent Factory (Tianjin, China). Dimethyl formamide (DMF) as

19

well as ethanol served as solvent were obtained from Guangdong Xilong Chemical Reagent Factory

20

(Guangzhou, China). All chemical reagents were used without further purification. Polyvinylidene 4

ACCEPTED MANUSCRIPT fluoride (PVDF) and carbon black were obtained from Guangdong Xilong Chemical Reagent

2

Factory (Guangzhou, China). Metallic Li foil (0.6 mm thickness, 99.9%) was purchased from

3

Tianjin Zhongneng (Tianjin, China) and copper foil (10 µm thickness) came from Guangzhou

4

Jiayuan Company (Guangzhou, China). Millipore-Q System (18.2 MΩ cm) was used to purify tap

5

water into ultra-pure water.

6

2.2. Preparation of MDPC.

SC

RI PT

1

MOF-5 was prepared via a typical method. Briefly, 1.00 g of BDC and 5.45 g of Zn (NO3)2·6H2O

8

were ultrasonic dissolved in 150 mL of DMF. And then, the obtained homogeneous solution was

9

transferred into a 250 mL of round flask and subsequently heated to 120 ºC for 4 h in oil bath. Next,

10

the raw product was washed with DMF for several times to remove adherent impurity. After dried at

11

60 ºC in vacuum oven, pure MOF-5 cube was obtained. As a sacrificial template, the as-mentioned

12

MOF-5 was carbonized at 1000 ºC for 3 h at N2 flowing with a heating rate of 5 ºC min-1. Finally,

13

the MDPC cube was successfully prepared. The detailed preparation process was diagrammatized

14

in Fig. 1.

15

2.3. Preparation of Co3O4NPs@MDPC composites

AC C

EP

TE D

M AN U

7

16

In a typical procedure, 50 mg of the as-prepared MDPC was dispersed into 96 mL of ethanol and

17

then was treated under ultrasonic process for 30 min. Subsequently, 4.4 mL of ultrapure water, 0.36

18

g of Co(CH3COO)2·4H2O and 2 mL of 28% ammonia was added into the turbidity solution under

19

stirring, respectively. Subsequently, the mixture was stirred in oil bath at 80 ºC for 20 h. And then,

20

the solution was sealed in a 100 mL Teflon-lined autoclave, and hold at 150 ºC for 3.5 h. The black 5

ACCEPTED MANUSCRIPT precipitate, Co3O4NPs@MDPC composites, was collected via centrifugation-rinsing cycles and

2

dried at 60 ºC overnight. A control sample was prepared in a similar condition by the addition of

3

100 mg MDPC (denoted as Co3O4NPs@MDPC-100). The detailed preparation process was

4

diagrammatized in Fig. 1. "Here Fig. 1"

5

2.4. Characterization

SC

6

RI PT

1

Scanning electron microscopy (SEM) images were obtained on a HITACHI S3400 performed at

8

an acceleration voltage of 20 kV with an Energy dispersive X-ray analyzer (EDXA). Powder X-ray

9

diffraction (XRD) analysis was carried out on a D/Max 2500 V/PC X-ray powder diffractometer

10

using Cu Kα radiation. X-ray photoelectron spectroscopy (XPS) analysis was obtained by an

11

ESCALAB 250Xi spectrometer (ThermoFisher Scientific Co., United States). Thermogravimetric

12

analysis (TGA) was acquired on SDT 2960 accompanied with a ramping rate about 10 ºC min-1.

13

After exhausting the samples at 200 ºC, N2 adsorption/desorption isotherm was analyzed at liquid

14

nitrogen temperature (Tristar 3000) and used to calculate the Brunauer−Emmett−Teller (BET)

15

specific surface areas. Transmission electron microscopy (TEM) images were obtained by JEOL

16

JEM-2100 microscopes with an acceleration voltage of 200 kV.

17

2.5. Electrochemical measurements

AC C

EP

TE D

M AN U

7

18

The working electrode was derived from homogeneous slurry which includes active materials,

19

acetylene black and PVDF with a weight ratio of 8:1:1. The mixture were added into N-methyl

20

pyrrolidinone, and then dispersed evenly on copper foil. Next, the working electrodes were kept at 6

ACCEPTED MANUSCRIPT 60 ºC in a vacuum oven overnight. The thickness of loading active material was 50 µm. The target

2

material loaded on copper foil was about 1.0 mg cm-2 and the total weight of active materials in the

3

works electrode was about 0.96 mg. The separator is a Celgard 2300 microporous polypropylene

4

film. The half-cell was assembled in an argon-filled glove box. The electrolyte was composed of 1.0

5

M LiPF6 added in a solvent mixed with ethylene carbonate, diethyl carbonate and dimethyl

6

carbonate. Finally, galvanostatic charging/discharging test were carried out at voltage range from

7

3.0 to 0.01 V versus Li/Li+ on a Neware BTS test system (Shenzhen, China). Cyclic

8

voltammograms (CVs) and electrochemical impedance spectroscopy (EIS) were determined by a

9

CHI 760E electrochemical workstation which comes from Shanghai CH Instruments. EIS

10

was conducted by applying a perturbation voltage of 5 mV and DC open circuit voltage in the

11

frequency range of 100 kHz-0.01 Hz at room temperature. And cells were poised at the selected

12

potential for longer than 5 min before measurement. A traditional three-electrode system, lithium

13

metal acted as the counter and reference electrode and target materials acted as the working

14

electrode, was employed in the above electrochemical test.

15

3. Results and discussion

16

3.1 Characterization of MDPC

AC C

EP

TE D

M AN U

SC

RI PT

1

17

As shown in Fig. 2A, MOF-5 was a cube with a side length of ~30 µm. The high resolution

18

image demonstrated that the MOF-5 cube possessed a flat but ravine surface (Inset in Fig. 2A).

19

When annealed at 1000 ºC under N2 flowing, Zn was firstly transformed into ZnONPs and then was

20

vaporized completely [32]. The as-obtained MDPC inherited the cubic morphology and generated a 7

ACCEPTED MANUSCRIPT large number of pores as shown by Fig. 2B. These visible pores might derive from the evaporation

2

of ZnONPs. TEM image (Fig. 2C) showed that MDPC also contained many meso-/micro-pores

3

which might come from MOF-5 self. The elements mapping image (Fig. 2D) and EDS analysis of

4

MDPC (Fig. 2E) did not display the element of Zn, indicating that the Zn was evaporated

5

completely. Raman spectroscopy of MDPC (Fig. 2F) displayed two typical peaks of carbon, which

6

confirmed that the organic ligands were converted into carbon. The XRD diffraction peaks of MOF-

7

5 disappeared and no obvious peaks was observed in MDPC (Fig. 2G), further confirming the

8

successful transformation. N2 adsorption/desorption isotherms (Fig. 2H) showed that the MOF-5

9

cube had a specific surface of 732 m2 g-1, total pore volume of 0.33 cm3 g−1 and a mean pore

10

diameter of 1.80 nm, which implied that it was a kind of meso-/microporous material. After heat

11

treatment, the specific surface area, the total pore volume and the mean pore diameter of MDPC

12

were increased to 2550 m2 g-1, 2.22 cm3 g−1 and 3.5 nm, respectively (Fig. 2H). It clearly suggested

13

that the removal of Zn from MOF-5 could effectively enlarge both the pore volume and the pore

14

size in MDPC. The larger pores might be used to load nanomaterials.

16

SC

M AN U

TE D

EP

AC C

15

RI PT

1

"Here Fig. 2"

3.2. Characterization of Co3O4NPs@MDPC

17

MDPC was used as a host to load Co3O4NPs in its pores. As shown in Fig. 3A, the cubic shape of

18

MDPC was still commendably maintained after the growth of Co3O4NPs. The visible pores became

19

small and many granular-like Co3O4NPs were anchored on the surface and holes of MDPC. No

20

aggregation and clusters were observed. The elements mapping image (Fig. 3D) showed that the 8

ACCEPTED MANUSCRIPT Co3O4NPs were uniformly formed on the surface and holes of MDPC. TEM image of Co3O4

2

NPs@MDPC displayed that abundant black grains was encapsulated in carbon framework and were

3

2.5-3 nm or so (Fig. 3B). HRTEM image (Fig. 3C) confirmed that the stripe spacing of two

4

different adjacent fringes was 0.23 nm and 0.28 nm, which were contributed to the (222) and (220)

5

crystal faces of Co3O4 (JCPDS card NO. 43-1003), respectively. The result clearly proved that

6

nano-sized Co3O4NPs were successfully formed in the pores and surface of MDPC. SEM image

7

(Fig. S1, Supporting Information) of Co3O4NPs@MDPC-100 showed that its shape still maintained

8

but many Co3O4NPs were covered on the surface, which might have a negative effect on the cycle

9

stability and the rate capability.

M AN U

SC

RI PT

1

XRD pattern of Co3O4NPs@MDPC (Fig. 3E) displayed three distinct peaks at 36.9°, 45.1° and

11

64.9° which were corresponding to the (311), (400) and (440) diffraction planes of cubic Co3O4

12

phase, respectively [5,33]. The result indicated that cubic Co3O4NPs were loaded in the pores of

13

MDPC. Raman spectra (Fig. 3F) revealed the short-range local structure of Co3O4NPs@MDPC.

14

Besides, the D band and G band assigned to the carbon substrate as well as two characteristic peaks

15

belonged to Co3O4NPs appeared. The peak at 473 cm-1 was related to the Eg symmetry, whereas the

16

peak at 678 cm-1 was ascribed to A1g species which originated from the octahedral sites [34]. N2

17

adsorption/desorption isotherm of Co3O4NPs@MDPC exhibited characteristic IV curve with H4

18

hysteresis loop (Fig. 3G). After loading of Co3O4NPs, Brunauer-Emmet-Teller surface area, the

19

total pore volume and the mean pore diameter of Co3O4NPs@MDPC reduced to 629 m2 g-1, 0.523

20

cm3 g−1 and 1.325 nm, respectively. The result clearly indicated that of the Co3O4NPs covered not

AC C

EP

TE D

10

9

ACCEPTED MANUSCRIPT 1

only on the surface but also in the interior of MDPC. The Co3O4NPs@MDPC still had vast meso-

2

/micro-pores, which was benefit for the ion diffusion and mass transfer. To give in-depth understanding of chemical composition and valence state of Co3O4NPs

4

@MDPC, XPS was performed. The survey XPS spectrum (Fig. 3H) showed that the Co3O4NPs

5

@MDPC mainly contained C, O and Co elements. As shown in inset a (Fig. 3H), C1s spectrum of

6

Co3O4NPs@MDPC was resolved into three peaks. Two evident ones at 284.7 eV and 285.5 eV

7

were ascribed to C-C bond and C-O bond, respectively. Another weak peak at 287.7 eV was related

8

to O-C=O group [22,28]. It was noteworthy that some oxygen-containing functional groups formed

9

on the surface of amorphous and graphite carbon frames during the carbonization. As shown in

10

high-resolution spectrum of O1s (inset b in Fig. 3H), the peaks were unfolded into lattice Co-O

11

bond in Co3O4NPs centered at 530.0 eV, adsorbed O on Co3O4NPs surface centered at 531.5 eV and

12

oxygen from surface water at 531.6 eV [6,35]. Furthermore, the high-resolution spectrum of Co2p

13

(inset c in Fig. 3H) showed two prominent peaks at 780.0 eV and 795.1 eV, assigned to Co2p3/2 and

14

Co2p1/2 orbits, respectively. The binding splitting was 15.1 eV which matched well with those in the

15

previous literatures [36,37]. Besides, the Co2p3/2 peak could be fitted with two peaks located at

16

780.9 eV and 779.8 eV, indicating that the Co3O4NPs@MDPC consisted of tetrahedral Co2+ and

17

octahedral Co3+ [36]. The existence of Co3O4NPs could effectively enhance the energy storage on

18

the basis of pure PC.

19 20

AC C

EP

TE D

M AN U

SC

RI PT

3

"Here Fig. 3” 3.3. Application of Co3O4NPs@MDPC as anode materials for LIBs 10

ACCEPTED MANUSCRIPT For exploring the lithium embedded mechanism of Co3O4NPs@MDPC, the first three CVs of

2

Co3O4 NPs@MDPC composites were presented in Fig. 4A in the voltage range from 0.01 V to 3 V

3

at 0.2 mV s-1. In the first discharge process, the broad peak appeared at 0.68 V was ascribed to the

4

irreversible reaction to form solid electrolyte interphase (SEI) film [29]. Besides, the sharp peak

5

centered at 0.91 V was mainly attributed to the transformation of Co3O4NPs into metallic cobalt as

6

well as the formation of Li2O [38]. Another two distinct peaks located at 1.4 V and 1.9 V was

7

resulted from the reduction of oxygen functional groups on the surface [32]. In the subsequent

8

cycles, the cathodic peak at 0.91 V was shifted to 0.94 V, which was correspond to conversion of

9

Co3O4 into metallic cobalt. In the first anodic scan, one peak was record at around 2.09 V, which

10

was due to the oxidation of metallic cobalt back into Co3O4 and the decomposition of Li2O [39,40].

11

In addition, the subsequent cycles almost overlapped with each other, revealing good

12

electrochemical stability. Fig. 4B displayed the electrochemical charging/discharging profiles of

13

Co3O4NPs@MDPC at 100 mA g-1 in the voltage window between 0.01 V and 3.0 V for the 1st, 2nd,

14

3rd, 50th and 100th. After 50 cycles, the electrode of Co3O4NPs@MDPC delivered the specific

15

charging and discharging capacities of 1014 mA h g-1 and 873 mA h g-1, respectively. The

16

coulumbic efficiency still remained as high as 99.1% after 100 cycles. The good capacities and

17

coulumbic efficiency just came from the specific construction: many small Co3O4NPs were loaded

18

in the pores of MDPC.

19 20

AC C

EP

TE D

M AN U

SC

RI PT

1

"Here Fig. 4" To gain insights into the long-term cycle performance, Fig. 5A exhibited the cycling ability of 11

ACCEPTED MANUSCRIPT MDPC, Co3O4NPs@MDPC and Co3O4NPs@MDPC-100 at 2000 mA g-1. After 200 cycles at large

2

current density, the specific capacity of Co3O4NPs@MDPC still maintained 587.2 mA h g-1, which

3

displayed larger capacity and better capacity retention than that of pure MDPC (only 87.8 mA h g-1)

4

and that of Co3O4NPs@MDPC-100 (559.5 mA h g-1). It was remarkable that the combination of

5

Co3O4NPs with PC could not only improve electrochemical performance and cycling stability of

6

Co3O4NPs, but also partially promote the specific capacity of carbon materials [41]. The lithium ion

7

storage at a current density of 2000 mA g-1 was of vital importance in practical application. What’s

8

more, the good cycling stability might be credited to the embedding of Co3O4NPs into MDPC

9

matrix, which provided strain accommodation against structure collapsing during the repeated

10

lithium uptake and removal process. And the CoNPs produced in the discharge process can act as a

11

catalyst to effectively facilitate reversible transformation of some SEI components, resulting in

12

superior lithium ion storage capacity [38,42,43].

TE D

M AN U

SC

RI PT

1

EIS of Co3O4NPs@MDPC, Co3O4NPs@MDPC-100 and MDPC were displayed in Fig. 5B. The

14

diameter of the semicircle of Co3O4NPs@MDPC in high frequency region represented the low

15

charge transfer resistance between electrolyte and electrode contact interface of Co3O4

16

NPs@MDPC, owing to the superior electron transport of carbon framework. The slope line of

17

Co3O4NPs@MDPC in low frequency region, which was more inclined to the Z’ axis, implied a

18

lower Warburg resistance due to the well diffusion of Li+ in the electrode, resulting in the enhanced

19

electrochemical property.

20

AC C

EP

13

To further evaluate the electrochemical properties, the rate capability of Co3O4NPs@MDPC, 12

ACCEPTED MANUSCRIPT Co3O4NPs@MDPC-100 and MDPC were shown in Fig. 5C. The Co3O4NPs@MDPC exhibited

2

excellent rate performance, which achieved capacities of 1418.7, 1388.5, 1162.8, 927.1, and 650

3

mA h g-1 at various current densities of 100, 200, 500, 1000, and 2000 mA g-1. When the current

4

density was back to 100 mA g-1, the specific capacity even increased to 1500.8 mA h g-1, which

5

might be due to the synthetic effect between PC matrix and the appropriate amount of Co3O4NPs as

6

well as the complete structures of Co3O4NPs. In addition, SEM image of Co3O4NPs@MDPC after

7

100 cycles was presented in Fig. S2 (Supporting Information). It was noticeable that the

8

morphology still kept well, suggesting that the pores of carbon skeleton could significantly alleviate

9

the structural strain during the lithiation/delithiation.

M AN U

SC

RI PT

1

"Here Fig. 5"

10

In order to gain a intimate comparison, the eletrochemical properties of various carbon/cobalt-

TE D

11

based composites were listed in Table 1. When

comparing with other materials, the Co3O4

13

NPs@MDPC displayed superior specific capacity, cycle life and distinguished rate performance,

14

which could be attributed to the porous structure of MDPC matrix, good electrical conductivity and

15

uniformly coated lots of nano-sized Co3O4NPs: (1) The pores of MDPC provided high surface for

16

loading Co3O4NPs uniformly and buffered the volume variation during the charging/discharging

17

process; (2) The MDPC substrate with stable strength prevented Co3O4NPs from aggregating and

18

fragmenting; (3) The synergic effect of nano-sized Co3O4NPs and mesoporous structure shortened

19

the pathway for Li+ diffusion and charge transfer, thus effectively enhancing the electrochemical

20

properties.

AC C

EP

12

13

ACCEPTED MANUSCRIPT "Here Table 1"

1

2

4. Conclusions In a word, the Co3O4NPs@MDPC composites were fabricated by loading nano-sized Co3O4NPs

4

(2.5-3.0 nm) on pores of MDPC. The porous cubic nanostructures manifested a long stable cycle

5

ability and outstanding discharging/charging specific capacity of 587.2 mA h g-1 at high current

6

density of 2000 mA g-1 after 200 cycles, which made it to be a promising material in anode field.

7

The enhanced electrochemical performance might be related to the following aspects: (1) The

8

supported MDPC matrix alleviated the volume strain during lithium ion insertion/extraction process.

9

(2) The porous structure of MDPC provided large specific surface area for loading lots of nano-

10

sized Co3O4NPs uniformly and the encapsulated nano-sized Co3O4NPs with stable strength were

11

incapable of aggregating and fragmenting; (3) The synergic effect of nano-sized Co3O4NPs and

12

mesoporous structure provided a shortened transfer path for lithium ions and electrons, thus

13

effectively enhancing the electrochemical properties. The method using the MOF-derived template

14

could be applied to prepare other porous composites anode materials for new generation energy

15

storage devices.

16

Acknowledgements

AC C

EP

TE D

M AN U

SC

RI PT

3

17

This work was financially supported by This work was financially supported by National Natural

18

Science Foundation of China (21465014 and 21765009), Science and Technology Support Program

19

of Jiangxi Province (20123BBE50104 and 20133BBE50008), Ground Plan of Science and

20

Technology Projects of Jiangxi Educational Committee (KJLD14023), and Scientific Research 14

ACCEPTED MANUSCRIPT 1

Foundation of Jiangxi Education Commission (GJJ160288).

AC C

EP

TE D

M AN U

SC

RI PT

2

15

ACCEPTED MANUSCRIPT References

2

[1] L. Ji, Z. Lin, M. Alcoutlabi, X. Zhang, Recent developments in nanostructured anode materials

3

for rechargeable lithium-ion batteries, Energy Environ. Sci. 4 (2011) 2682-2699.

4

[2] D. Mohanty, B. Mazumder, A. Devaraj, A.S. Sefat, A. Huq, L.A. David, E.A. Payzant, J. Li, D.L.

5

Wood, C. Daniel, Resolving the degradation pathways in high-voltage oxides for high-energy-

6

density lithium-ion batteries; Alternation in chemistry, composition and crystal structures, Nano

7

Energy 36 (2017) 76-84.

8

[3] W. Wang, X. Song, C. Gu, D. Liu, J. Liu, J. Huang, A high-capacity NiCo2O4@reduced

9

graphene oxide nanocomposite Li-ion battery anode, J. Alloys Compd. 741 (2018) 223-230.

M AN U

SC

RI PT

1

[4] Z. Wu, W. Ren, L. Wen, L. Gao, J. Zhao, Z. Chen, G. Zhou, F. Li, H. Cheng, Graphene anchored

11

with Co3O4 nanoparticles as anode of lithium ion batteries with enhanced reversible capacity and

12

cyclic performance, ACS Nano 4 (2010) 3187-3194.

13

[5] C. Bai, S. Wei, D. Deng, X. Lin, M. Zheng, Q. Dong, A nitrogen-doped nano carbon

14

dodecahedron with Co@Co3O4 implants as bifunctional electrocatalyst for efficient overall water

15

splitting, J. Mater. Chem. A 5 (2017) 9533-9536.

16

[6] M. Yu, Z. Wang, C. Hou, Z. Wang, C. Liang, C. Zhao, Y. Tong, X. Lu, S. Yang, Nitrogen-doped

17

Co3O4 mesoporous nanowire arrays as an additive-free air-cathode for flexible solid-state zinc-air

18

batteries, Adv. Mater. 29 (2017) 1602868.

19

[7] G. Huang, S. Xu, S. Lu, L. Li, H. Sun, Micro-/nanostructured Co3O4 anode with enhanced rate

20

capability for lithium-ion batteries, ACS Appl. Mater. Inter. 6 (2014) 7236-7243.

AC C

EP

TE D

10

16

ACCEPTED MANUSCRIPT [8] S.V. Gnedenkov, D.P. Opra, S.L. Sinebryukhov, V.G. Kuryavyi, А.Y. Ustinov, V.I. Sergienko,

2

Structural and electrochemical investigation of nanostructured C:TiO2–TiOF2 composite

3

synthesized in plasma by an original method of pulsed high-voltage discharge, J. Alloys Compd.

4

621 (2015) 364-370.

5

[9] S. Wang, Q. Li, W. Pu, Y. Wu, M. Yang, MoO3–MnO2 intergrown nanoparticle composite

6

prepared by one-step hydrothermal synthesis as anode for lithium ion batteries, J. Alloys Compd.

7

663 (2016) 148-155.

8

[10] M.V. Reddy, G.V. Subba Rao, B.V.R. Chowdari, Metal oxides and oxysalts as anode materials

9

for Li ion batteries, Chem. Rev. 113 (2013) 5364-5457.

M AN U

SC

RI PT

1

[11] R. Hu, H. Zhang, Y. Bu, H. Zhang, B. Zhao, C. Yang, Porous Co3O4 nanofibers surface-

11

modified by reduced graphene oxide as a durable, high-rate anode for lithium ion battery,

12

Electrochim. Acta 228 (2017) 241-250.

13

[12] M. Jing, M. Zhou, G. Li, Z. Chen, W. Xu, X. Chen, Z. Hou, Graphene-embedded Co3O4 rose-

14

spheres for enhanced performance in lithium ion batteries, ACS Appl. Mater. Inter. 9 (2017) 9662-

15

9668.

16

[13] Y. Dou, J. Xu, B. Ruan, Q. Liu, Y. Pan, Z. Sun, S. Dou, Atomic layer-by-layer Co3O4/graphene

17

composite for high performance lithium-ion batteries, Adv. Energy Mater. 6 (2016) 1501835.

18

[14] N. Du, H. Zhang, B. Chen, J. Wu, X. Ma, Z. Liu, Y. Zhang, D. Yang, X. Huang, J. Tu, Porous

19

Co3O4 nanotubes derived from Co4(CO)12 clusters on carbon nanotube templates: A highly efficient

20

material for Li-battery applications, Adv. Mater. 19 (2007) 4505-4509.

AC C

EP

TE D

10

17

ACCEPTED MANUSCRIPT [15] D. Gu, W. Li, F. Wang, H. Bongard, B. Spliethoff, W. Schmidt, C. Weidenthaler, Y. Xia, D.

2

Zhao, F. Schüth, Controllable synthesis of mesoporous peapod-like Co3O4@carbon nanotube arrays

3

for high-performance lithium-ion batteries, Angew. Chem. Int. Ed. 54 (2015) 7060-7064.

4

[16] G. Huang, F. Zhang, X. Du, Y. Qin, D. Yin, L. Wang, Metal organic frameworks route to in situ

5

insertion of multiwalled carbon nanotubes in Co3O4 polyhedra as anode materials for lithium-ion

6

batteries, ACS Nano, 9 (2015) 1592-1599.

7

[17] J. Tang, S. Wu, T. Wang, H. Gong, H. Zhang, S.M. Alshehri, T. Ahamad, H. Zhou, Y. Yamauchi,

8

Cage-type highly graphitic porous carbon–Co3O4 polyhedron as the cathode of lithium–oxygen

9

batteries, ACS Appl. Materi. Inter. 8 (2016) 2796-2804.

M AN U

SC

RI PT

1

[18] Y. Hou, J. Li, Z. Wen, S. Cui, C. Yuan, J. Chen, Co3O4 nanoparticles embedded in nitrogen-

11

doped porous carbon dodecahedrons with enhanced electrochemical properties for lithium storage

12

and water splitting, Nano Energy 12 (2015) 1-8.

13

[19] J. Wu, L. Zuo, Y. Song, Y. Chen, R. Zhou, S. Chen, L. Wang, Preparation of biomass-derived

14

hierarchically porous carbon/Co3O4 nanocomposites as anode materials for lithium-ion batteries, J.

15

Alloys Compd. 656 (2016) 745-752.

16

[20] F. Chen, J. Yang, T. Bai, B. Long, X. Zhou, Biomass waste-derived honeycomb-like nitrogen

17

and oxygen dual-doped porous carbon for high performance lithium-sulfur batteries, Electrochim.

18

Acta 192 (2016) 99-109.

19

[21] D. Xu, S. Xin, Y. You, Y. Li, H. Cong, S. Yu, Built-in carbon nanotube network inside a

20

biomass-derived hierarchically porous carbon to enhance the performance of the sulfur cathode in a

AC C

EP

TE D

10

18

ACCEPTED MANUSCRIPT Li-S battery, Chem. Nanomat. 2 (2016) 712-718.

2

[22] L. Wang, Y. Zheng, X. Wang, S. Chen, F. Xu, L. Zuo, J. Wu, L. Sun, Z. Li, H. Hou, Y. Song,

3

Nitrogen-doped porous carbon/Co3O4 nanocomposites as anode materials for lithium-ion batteries,

4

ACS Appl. Mater. Inter. 6 (2014) 7117-7125.

5

[23] J. Guan, Z. Zhang, J. Ji, M. Dou, F. Wang, Hydrothermal synthesis of highly dispersed Co3O4

6

nanoparticles on biomass-derived nitrogen-doped hierarchically porous carbon networks as an

7

efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions, ACS Appl. Mater.

8

Inter. 9 (2017) 30662-30669.

9

[24] L. Wu, T. Wen, L. Guo, S. Yang, X. Wang, W. Xu, Biomass-derived sponge-like carbonaceous

M AN U

SC

RI PT

1

hydrogels and aerogels for supercapacitors, ACS Nano 7 (2013) 3589-3597.

11

[25] G. Fang, J. Zhou, C. Liang, A. Pan, C. Zhang, Y. Tang, X. Tan, J. Liu, S. Liang, MOFs

12

nanosheets derived porous metal oxide-coated three-dimensional substrates for lithium-ion battery

13

applications, Nano Energy 26 (2016) 57-65.

14

[26] L. Zhang, H. Wu, X. Lou, Metal–organic-frameworks-derived general formation of hollow

15

structures with high complexity, J. Am. Chem. Soc. 135 (2013) 10664-10672.

16

[27] Y. Wu, J. Meng, Q. Li, C. Niu, X. Wang, W. Yang, W. Li, L. Mai, Interface-modulated

17

fabrication of hierarchical yolk–shell Co3O4/C dodecahedrons as stable anodes for lithium and

18

sodium storage, Nano Res. 10 (2017) 2364-2376.

19

[28] Y. Chen, J. Wu, W. Yang, Y. Fu, R. Zhou, S. Chen, L. Zhang, Y. Song, L. Wang, Zn/Fe-MOFs-

20

derived hierarchical ball-in-ball ZnO/ZnFe2O4@carbon nanospheres with exceptional lithium

AC C

EP

TE D

10

19

ACCEPTED MANUSCRIPT storage performance, J. Alloys Compd. 688 (2016) 211-218.

2

[29] X. Han, W. M. Chen, X. Han, Y. Z. Tanc, D. Sun, Nitrogen-rich MOF derived porous

3

Co3O4/N–C composites with superior performance in lithium-ion batteries, J. Mater. Chem. A, 4

4

(2016) 13040-13045.

5

[30] G. Zhuang, Y. Gao, X. Zhou, X. Tao, J. Luo, Y. Gao, Y. Yan, P. Gao, X. Zhong, J. Wang, ZIF-

6

67/COF-derived highly dispersed Co3O4/N-doped porous carbon with excellent performance for

7

oxygen evolution reaction and Li-ion batteries, Chem. Eng. J. 330 (2017) 1255-1264.

8

[31] C. Fu, G. Li, D. Luo, X. Huang, J. Zheng, L. Li, One-step calcination-free synthesis of

9

multicomponent spinel assembled microspheres for high-performance anodes of Li-ion batteries: A

M AN U

SC

RI PT

1

case study of MnCo2O4, ACS Appl. Mater. Inter. 6 (2014) 2439-2449.

11

[32] L. Zuo, S. Chen, J. Wu, L. Wang, H. Hou, Y. Song, Facile synthesis of three-dimensional

12

porous carbon with high surface area by calcining metal-organic framework for lithium-ion

13

batteries anode materials, RSC Adv. 4 (2014) 61604-61610.

14

[33]T. Ouyang, K. Cheng, S. Kong, K. Ye, Y. Gao, D. Zhang, G. Wang, D. Cao, Facile synthesis of

15

Co3O4 with different morphology and their application in supercapacitors, RSC Adv. 5 (2015)

16

36059-36065.

17

[34] L. Shen, H. Song, G. Yang, C. Wang, Hollow ball-in-ball CoxFe3-xO4 nanostructures: High-

18

performance anode materials for lithium-ion battery, ACS Appl. Mater. Inter. 7 (2015) 11063-11068.

19

[35] T. Zhai, L. Wan, S. Sun, Q. Chen, J. Sun, Q. Xia, H. Xia, Phosphate ion functionalized Co3O4

20

ultrathin

AC C

EP

TE D

10

nanosheets

with

greatly

improved 20

surface

reactivity

for

high

performance

ACCEPTED MANUSCRIPT pseudocapacitors, Adv. Mater. 29 (2017) 1604167.

2

[36] X. Chen, B. Liu, C. Zhong, Z. Liu, J. Liu, L. Ma, Y. Deng, X. Han, T. Wu, W. Hu, J. Lu,

3

Ultrathin Co3O4 layers with large contact area on carbon fibers as high-performance electrode for

4

flexible zinc-air battery integrated with flexible display, Adv. Energy Mater. 7 (2017) 1700779.

5

[37] M. Liu, X. Deng, Y. Ma, W. Xie, X. Hou, Y. Fu, D. He, Well-designed hierarchical Co3O4

6

architecture as a long-life and ultrahigh rate capacity anode for advanced lithium-ion batteries, Adv.

7

Mater. Inter. (2017) 1700553.

8

[38] L. Guo, Y. Ding, C. Qin, W. Li, J. Du, Z. Fu, W. Song, F. Wang, Nitrogen-doped porous carbon

9

spheres anchored with Co3O4 nanoparticles as high-performance anode materials for lithium-ion

M AN U

SC

RI PT

1

batteries, Electrochim. Acta 187 (2016) 234-242.

11

[39] G. Qu, H. Geng, D. Ge, J. Zheng, H. Gu, Graphene-coating mesoporous Co3O4 fibers as an

12

efficient anode material for Li-ion batteries, RSC Adv. 6 (2016) 71006-71011.

13

[40] F. Zheng, K. Shi, S. Xu, X. Liang, Y. Chen, Y. Zhang, Facile fabrication of highly porous

14

Co3O4 nanobelts as anode materials for lithium-ion batteries, RSC Adv. 6 (2016) 9640-9646.

15

[41] J. Wang, B. Gao, L. Zhang, R. Li, J. Shen, Z. Qiao, G. Yang, F. Nie, Controlled synthesis of

16

porous Co3O4–C hybrid nanosheet arrays and their application in lithium ion batteries, RSC Adv. 4

17

(2014) 30573-30578.

18

[42] X. Zhou, J. Shi, Y. Liu, Q. Su, J. Zhang, G. Du, Microwave irradiation synthesis of Co3O4

19

quantum dots/graphene composite as anode materials for Li-ion battery, Electrochim. Acta 143

20

(2014) 175-179.

AC C

EP

TE D

10

21

ACCEPTED MANUSCRIPT [43] H. Fang, S. Zhang, W. Liu, Z. Du, X. Wu, Y. Xing, Hierarchical Co3O4@multiwalled carbon

2

nanotube nanocable films with superior cyclability and high lithium storage capacity, Electrochim.

3

Acta 108 (2013) 651-659.

4

[44] W. Kang, Y. Zhang, L. Fan, L. Zhang, F. Dai, R. Wang, D. Sun, Metal-organic framework

5

derived porous hollow Co3O4/N-C polyhedron composite with excellent energy storage capability,

6

ACS Appl. Mater. Inter. 9 (2017) 10602-10609.

7

[45] X. Liu, S.W. Or, C. Jin, Y. Lv, W. Li, C. Feng, F. Xiao, Y. Sun, Co3O4/C nanocapsules with

8

onion-like carbon shells as anode material for lithium ion batteries, Electrochim. Acta 100 (2013)

9

140-146.

M AN U

SC

RI PT

1

[46] Y. Yu, D. Wang, H. He, J. Wang, W. Zhou, H. D. Abruña, Surfactant-free synthesis of hollow

11

structured Co3O4 nanoparticles as high-performance anodes for lithium-ion batteries, ACS Nano 9

12

(2015) 1775-1781.

13

[47] G.P. Kim, S. Park, I. Nam, J. Park, J. Yi, Preferential growth of Co3O4 anode material with

14

improved cyclic stability for lithium-ion batteries, J. Mater. Chem. A 1 (2013) 3872-3876.

15

[48] S. Chen, Y. Zhao, B. Sun, Z. Ao, X. Xie, Y. Wei, G. Wang, Microwave-assisted synthesis of

16

mesoporous Co3O4 nanoflakes for applications in lithium ion batteries and oxygen evolution

17

reactions, ACS Appl. Mater. Inter. 7 (2015) 3306-3313.

18

[49] D. Tian, X. Zhou, Y. Zhang, Z. Zhou, X. Bu, MOF-derived porous Co3O4 hollow tetrahedra

19

with excellent performance as anode materials for lithium-ion batteries, Inorg. Chem. 54 (2015)

20

8159-8161.

AC C

EP

TE D

10

22

ACCEPTED MANUSCRIPT [50] C. Li, T. Chen, W. Xu, X. Lou, L. Pan, Q. Chen, B. Hu, Mesoporous nanostructured Co3O4

2

derived from MOF template: a high-performance anode material for lithium-ion batteries, J. Mater.

3

Chem. A 3 (2015) 5585-5591.

4

[51] Y. Han, M. Zhao, L. Dong, J. Feng, Y. Wang, D. Li, X. Li, MOF-derived porous hollow Co3O4

5

parallelepipeds for building high-performance Li-ion batteries, J. Mater. Chem. A 3 (2015) 22542-

6

22546.

7

[52] F. Zheng, Z. Yin, H. Xia, Y. Zhang, MOF-derived porous Co3O4 cuboids with excellent

8

performance as anode materials for lithium-ion batteries, Mater. Lett. 197 (2017) 188-191.

M AN U

SC

RI PT

1

9

10

AC C

EP

TE D

11

23

ACCEPTED MANUSCRIPT Figure Caption

2

Fig. 1. A schematic representation of the preparation of Co3O4NPs@MDPC composites.

3

Fig. 2. SEM images of MOF-5 (A) and MDPC (B). TEM image (C) and corresponding EDX maps

4

for C, O, Zn (D) of MDPC. Raman pattern (E) of MDPC, XRD pattern (F) of MOF-5 and MDPC,

5

N2 adsorption/desorption isotherm (H) and pore size distribution (inset in H) of MOF-5.

6

Fig. 3. SEM images (A), TEM image (B), HRTEM image (C) of Co3O4NPs@MDPC and

7

corresponding EDX maps of Co3O4NPs@MDPC for C, O, Co (D). XRD pattern (E), Raman

8

pattern (F), N2 adsorption/desorption isotherm (G) and pore size distribution (inset in G), XPS

9

spectrum (H) and high-resolution XPS spectrums for C 1s, O 1s and Co 2p (inset in H) of Co3O4

M AN U

SC

RI PT

1

NPs@MDPC.

11

Fig.4. CVs measurements during the first three cycles at 0.2 mV s-1 (A). Galvanostatic

12

charging/discharging profiles (B) for the 1st,2nd,3rd ,50th,100th cycles at a current density of 100 mA

13

g-1 between 0.01 and 3.00 V of Co3O4NPs@MDPC.

14

Fig.5. Cycling performance (A) at 2000 mA g-1 and Rate capability (B) at various current densities

15

from 100 mA g-1 to 2000 mA g-1 after three cycles. EIS (C) of Co3O4NPs@MDPC, Co3O4

16

NPs/MDPC-100 and MDPC, respectively

17

.

AC C

EP

TE D

10

18

19

20 24

ACCEPTED MANUSCRIPT 1

3

Fig. 1

M AN U

4

5

6

11

12

EP

10

AC C

9

TE D

7

8

SC

RI PT

2

13

25

Fig. 2

2

M AN U

3

4

5

AC C

9

EP

8

TE D

6

7

10 11

SC

1

RI PT

ACCEPTED MANUSCRIPT

Fig. 3 26

ACCEPTED MANUSCRIPT 1

2

3

RI PT

4

5

SC

6 7

M AN U

8

9

10

12 13

AC C

EP

TE D

11

Fig. 4

14

15

16 27

ACCEPTED MANUSCRIPT 1

5

EP

4

Fig. 5

AC C

3

TE D

M AN U

SC

RI PT

2

28

ACCEPTED MANUSCRIPT 1

Table 1. Comparison of the electrochemical performance of various carbon and cobalt-based

2

composites as anode materials for LIBs. Current density

Nth

mA g−1

mA h g−1

Mesoporous Co3O4 microcubes

1780

416(60)

[7]

Graphene/Co3O4 Rose-Spheres

90

1110.8 (30)

[12]

Co3O4 @CNT

100

700 (100)

[15]

Porous Hollow Co3O4/N-C

1000

~671 (2000)

[44]

Co3O4/C nanocapsules

445

1026.9 (50)

[45]

Hollow Co3O4/C

50

880 (50)

[46]

890

709 (150)

[47]

890

548(300)

[48]

200

1052(60)

[49]

200

913 (60)

[50]

Porous Hollow Co3O4 Parallelepipeds

100

1100 (50)

[51]

Porous Co3O4 Cuboids

100

886 (60)

[52]

Co3O4 NPs@MDPC

2000

587.2 (200)

This work

References

Mesoporous Co3O4 nanoflake Porous Co3O4 Hollow Tetrahedra

4

5

AC C

3

EP

TE D

Mesoporous nanostructured Co3O4

SC

M AN U

Co3O4/C

RI PT

Active material

6

29

ACCEPTED MANUSCRIPT

Highlights


The MDPC matrix possesses a large specific surface area and good electrical conductivity.




The Co3O4NPs loading in MDPC’s pores avoided from agglomerating to endure the volume




RI PT

variation. The Co3O4NPs@MDPC exhibited good capability of 578.2 mA h g-1 at 2000 mA g-1 after 200

EP

TE D

M AN U

The Co3O4NPs@MDPC also exhibited exceptional rate capability.

AC C




SC

cycles.