Marine-Biomass-Derived Porous Carbon Sheets with a Tunable N

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Functional Nanostructured Materials (including low-D carbon)

Marine Biomass-Derived Porous Carbon Sheets with Tuneable N-Doping Content for Superior Sodium Ion Storage Yaqi Guo, Wei Liu, Ruitao Wu, Lanju Sun, Yuan Zhang, Yongpeng Cui, Shuang Liu, Huanlei Wang, and Baohong Shan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b14304 • Publication Date (Web): 15 Oct 2018 Downloaded from http://pubs.acs.org on October 15, 2018

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ACS Applied Materials & Interfaces

Marine Biomass-Derived Porous Carbon Sheets with Tuneable N-Doping Content for Superior Sodium Ion Storage

Yaqi Guo, Wei Liu,* Ruitao Wu, Lanju Sun, Yuan Zhang, Yongpeng Cui, Shuang Liu, Huanlei Wang and Baohong Shan

School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China. Corresponding authors: *E-mail: [email protected]

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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 It is highly desirable to synthesis the electrode materials of sodium ion storage devices from sustainable precursors via green methods. In this work, we fabricated an unique N,O dual-doped biocarbon nanosheet (CBCS) with hierarchical porosity by direct pyrolysis of low-cost cuttle bones and simple air oxidation activation (AOA) technique. With prolonging AOA time, thickness of the carbon sheets could be reduced controllably (from 35 nm to 5 nm), which may lead to tunable preparation for carbon nanosheets with certain thickness. Besides, an unexpected increase of

N doping amount from 7.5 at% to 13.9 at% was observed after AOA,

demonstrating the unique role of AOA in tuning the doped heteroatoms of carbon matrix. This was also the first example of increasing N doping content in carbons by treatment in air. More importantly, by optimizing the thickness of carbon sheets and heteroatom doping via AOA, superior sodium capacity–cycling retention–rate capability combinations was achieved. Specifically, a current state of the art Na+ storage capacity of 640 mAh g-1 was obtained, which was comparable with the lithium ion storage in carbon materials. Even after charging/discharging at large current densities (2 A g-1 and 10 A g-1) for 10000 cycles, the asobtained samples still retained the capacities of 270 mAh g-1 and 138 mAh g-1, respectively, with more than 90% retention. The assembled sodium ion capacitors (NICs) also delivered a high integrated energy-power densities (36 kWh kg−1 at an ultra-high power density of 53000 W kg−1) and good cycling stability (90.5% of capacitance retention after 8000 cycles at 5 A g−1).

Keywords: cuttle bones; air oxidation activation; biomass-derived carbon; multi-heteroatom doped; sodium ion capacitor

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1. Introduction The intensive development of lithium ion batteries (LIBs) supports a number of portable devices as well as smart grid applications. However, the problem of low power density limits the application of LIBs for large-scale energy storage and electric vehicles.1-4 Recently, hybrid energy storage devices are developed. These devices combine the advantages of batteries and supercapacitors (SCs) within one system, which can maintain high energy density of batteries and achieve a higher power output like SCs.5-7 As a typical example of hybrid energy storage devices, lithium-ion capacitors (LICs) made up of different materials have been extensively studied these years. However, like LIBs, the high cost and scarcity of lithium resources cause an uncertain factor of their wide application.5, 8-13 In this context, sodium-ion capacitors (NICs) are promising alternatives to LICs due to their analogous physical/chemical features with lithium and high- abundance of sodium.14-22 As a very emerging field, there are many researches about NICs that focus on optimizing sodium ion electrode materials, ranging from carbon, metals/alloy to oxides and sulfides.23-25 Among these materials, carbon outstands due to its cheap, lightweight and fine performance in commercial LIBs and SCs.26 Given sodium ions do not reversibly intercalate into graphite easily, a range of hard carbons with various nanostructures and good sodium ion storage ability have been developed. Particularly, carbon derived from natural biomass receives great interests due to its abundant structural configurations, low cost, high abundance, rapid regeneration and environmental friendliness.27-29 So far, many biomass-derived carbonaceous materials were prepared via various natural biomass materials, including human hair30, pig bones31, peanut skins32, leaves33, 34, corncobs35, kelps36, clover stem37, cornstalk38, etc. Meanwhile, thanks to the chemical diversity of the natural resources, biocarbon enriched with heteroatoms (such as N, O, S) can be fabricated readily. Among these heteroatoms, nitrogen/oxygen dual-doping is widely applied since biomass generally contains nitrogen rich components.15, 17-19, 36, 39 This dual-heteroatom doping can not only provide additional charge storage capacity by binding of Na+ to the N-based associated defects or oxygen functional groups, but also enhance the 3



conductivity of carbon by providing additional free electrons contributing to the conduction band of carbons.40-45 Despite these advantages of heteroatom self-doping, it is difficult to control and tuning the doping ratios of carbonaceous materials due to the relative stable components in biomass. Therefore, the associated regulation approaches of heteroatom doping still need to be investigated to achieve satisfying performance. Besides heteroatoms doping, structural design is another way to improve the Na+ storage performance of carbon materials. Although many biomass has natural pores and channels in the structures, their size is generally ranged in macroscale, causing small surface area and undesirable electrochemical performance. Consequently, proper activation methods need to be performed to increase the porosity and defects of bio-derived carbon. Though activators like KOH, NaOH, et al. are widely applied for biomass-derived carbon activation, they transform most biostructures into analogous porous textures, which thus reduce the scientific interests for biomass-derived carbon to a large extent.46-53 In contrast, air oxidation activation (AOA) is a mild activation technique, which not only cause limited influence on biostructures, but also is cheap and green (without any additional agents). So far, little study concentrating on using AOA for the carbon materials of sodium ion storage has been done. Specifically, the influence of AOA on bio-derived carbon with heteroatom doping is not yet to be fulfilled. Herein, we employed cuttlebone as precursors to fabricate biomass-derived carbon materials via simple pyrolysis and air oxidation activation. In the pyrolysis process, chitin films were supported by CaCO3 framework to form the cuttlebone-derived carbonaceous sheets (CBCS) with numerous nanopores and high N,O doping level. Interestingly, the AOA process further adjusted the element components of CBCS efficiently, leading to very high N (13.9 at %) and O (14.0 at %) doping amount. More importantly, by tuning the nanostructure and doping amount of CBCS, the air oxide activated CBCS (CBCS-A) delivered a state of the art Na+ storage performance with a discharge capacities of 640 mAh g-1 at 0.1 A g-1. Even at the high current density of 10 A g-1, the activated CBCS could still retain 138 mAh g-1 after 10000 cycles with almost 90% retention. In addition, the assembled NICs with CBCS-A as anode and 4


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KOH/NaOH activated CBCS as cathode exhibited superior energy storage performance as well as good cycling performance.

2. Experimental 2.1. Material Synthesis The cuttlebones were purchased from the market of Qingdao. In a typical synthesis, the cuttlebones with hard outer shell removed were cut into small pieces. These pieces were carbonized under nitrogen atmosphere at 600 oC for 1 h with a heating rate of 3 oC min-1 in a tube furnace and then cooled down naturally. And then, carbon sheets materials were obtained after washing with 1M HCl and sufficient deionized water followed by freeze-drying procedure. The cuttlebones-derived carbon sheets were denoted as CBCS (the yield is about 0.5-1.0%). The CBCS sample was further activated under air ﬂow at 300°C for 1, 2, 3, 5 and 8h, resulting in final samples denoted as CBCS-Ax, where x represented the activation time. To obtain the cathode materials, the CBCS was thoroughly mixed with sodium hydroxide and potassium hydroxide in 1:1:2 mass ratios of NaOH: KOH: CBCS. The obtained product was heated to 700 oC for 1h under nitrogen atmosphere with a heating rate of 3 oC min-1. After cooling to room temperature, the sample (labeled as CBC-C) was washed several times with 1 M HCl and deionized water to neutrality. 2.2 Material characterization The morphologies and microstructure of the samples were examined by scanning electron microscope (SEM, Philip XL30) and transmission electron micrographs (TEM, JEM-2010). The carbon structures were analyzed by X-ray diffraction (XRD, German Bruker D8) with Cu Kα radiation operated from 2θ = 5-70°and Raman spectrum on a micro-Raman spectrometer (LabRAM HR800). Surface element compositions were analyzed with X-ray photoelectron spectroscopy analysis (XPS Thermo ESCALAB 250). An elemental analyzer (EA) was employed to confirm the content of C, N on a vario EL instrument. The N2 sorption isotherms were measured at 77K to confirm the specific surface area and porosity on a surface 5



characterization analyzer (Micromeritics 3 FlexTM). The thermogravimetry and differential thermal analysis (TG-DTA, METTLER TOLEDO DGA-DSC2 analyzer). The sample decomposition was further evaluated by temperature programmed oxidation (TPO) reactions in a fixed–bed reactor with the effluent gases (CO, CO2 and NOx) monitored by an infrared spectrometer (Thermo Nicolet iS10). During the measurements, about 30 mg sample was sandwiched by quartz wool in a tubular quartz reactor. An air flow (1 L/min) with a gas hourly space velocity (GHSV) of 30,000 h-1 was fed. The reactor temperature was then ramped to 800 °C at a heating rate of 10 °C min-1. 2.3 Electrochemical measurements All working electrodes were prepared by mixture the slurry of active material, carbon black (as a conductive agent) and PVDF (as a binder) with a mass ratio of 8:1:1. This slurry was evenly coated on stainless steel foil as working electrodes, while the counter and reference electrode was Na metal foil to assemble a half-cell. Separator was Celgard 2400 microporous polypropylene membrane. 1 M NaClO4 in ethylene carbonate(EC): diethyl carbonate ethylene carbonate (DEC) (v:v = 1:1) was used as electrolyte. The mass loading of active materials in the anode electrode was ~0.9 mg cm-2. Galvanostatically charged-discharged was carried out by using a battery measurement system (Land, CT2001A). The cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) experiment were conducted by using an electrochemical workstation (Zahner Zennium). For NICs, the half-cell was galvanostatically charge-discharge for 3 cycles at 0.1 A g-1 using CBCS-A3 or CBCS material as working electrode. And then, a NIC device was assembled by employing prelithiated CBCS-A3 or CBCS as anode and CBC-C as cathode with the mass ratio of 1:3. The galvanostatically charge-discharge, CV, and EIS measurements of the NICs were conducted by using a Zahner Zennium electrochemical work station at room temperature. The power density (P, W kg-1) and energy density (E, Wh kg-1) were calculated based on chargedischarge profiles through the following formula:

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V  I m Pt E 3600 V  Vmin V  max 2

(1)

P=

(2) (3)

where I (A) represents the discharge current, m (kg) represents the total mass of both electrodes, t (s) is the discharge time, Vmax (V) and Vmin (V) are the voltage at beginning and end of the discharge after the IR drop.

3. Results and Discussion 3.1. Physicochemical characterization Intercalation anode air oxidation activation

CBCS-A

chitin bio-films

Na+ ClO4-

CaCO3 wall

KOH/NaOH mixed activation

cuttlebone

Adsorption cathode

CBCS-C

Figure 1. Schematic illustration of material synthesis process and the relevant anode - cathode charge storage mechanisms in NIC. Cuttlebone, the skeleton of cuttlefish, is a biomass waste of food processing which mainly composes of CaCO3 and chitin with a natural three-dimensional ordered assembly.54-56 Figure 1 illustrates the synthesis process for the electrode materials and the relevant cathode/anode kinetic mechanisms of NICs. Cuttlebone has a chamber-like framework in form of mineralized 7



CaCO3 sheets arranging in parallel layers that separated by S-shaped pillars. The internal wall of the resultant architecture is attached by abundant chitin bio-films. When the cuttlebone is pyrolysed, chitin can provide C, N and O species required for the formation of N,O dual-doped carbons, while CaCO3 crystals act as hard templates for porosity control. After removing CaCO3 by soaking the samples in HCl solution, the resultant 3D carbon framework collapses into numerous carbon sheets. Notably, different from previously reported cases using chemical activators such as KOH, a simple physical activation approach, AOA was carried out in our case. Just by heating directly in air flow at low temperature is enough to achieve the optimization of the microstructure and surface functional modification of carbon materials. The as-obtained carbon material labeled as CBCS-A was utilized as anode materials. For cathode materials, a chemical activation with KOH-NaOH mixture was employed to fabricate cuttlebone-derived active carbon with large surface area and rich porosity, which favored the enhancement of capacitance behaviors. The obtained cuttlebone-derived carbons were labeled as CBC-C.

Figure 2 SEM images of (a) cuttlebone and (b, c) CBCS, TEM images of (d,e) CBCS, (f) HRTEM image of CBCS, and (g) EDS element mapping of CBCS. 8


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The microstructure and morphology of cuttlebone and CBCSs were investigated by electroscopic technologies. As depicted in Figure 2a, the highly organized chamber-like structure contained a chitin organic framework. Although the intact chamber-like architecture collapsed during pyrolysis, interconnected carbon sheets were retained well. The as-obtained CBCSs exhibited continuous and smooth texture without any CaCO3 residues (Figure 2b). As demonstrated in an enlarged picture of the samples’ edge part (Figure 2c), the average thickness of CBCSs ranged from 30 to 40 nm. TEM observations further disclosed the inner structure of CBCSs. Interestingly, as shown in figure 2d, there were numerous bright spots distributing homogeneously on the surface of carbon sheets. The high magnification TEM image suggested that these bright spots were not holes but ball-like pores with a diameter about 20 nm (Figure 2e). These nanopores came possibly from original biostructure, which were retained in carbonization and set evenly on the surface or inside the carbon sheets of CBCSs. The HRTEM micrograph (Figures 2f and S1) indicated that CBCS was almost in amorphous state but with partially ordered graphene domains, resulting in pseudographitic arrays. The dilated intergraphene spacing was approximately 0.37 nm according to the intensity profile for the line scan across the lattice fringes. Since chitin was a modified polysaccharide that contains oxygen and nitrogen, lots of O and N atoms could dope into carbon matrix during hydrolysis to form N, O dual-doped carbonaceous materials. This was confirmed by TEM-EDS mapping analysis (Figure 2g), which revealed the uniform distribution of nitrogen and oxygen atoms in the carbon sheets.

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Figure 3. (a,b) SEM, (c,d) TEM and (e,f)HRTEM of CBCS-A3 and CBCS-A8, respectively and (g) Raman spectra and (h,i) Nitrogen desorption-adsorption isotherms and the pore size distributions.

For AOA, the CBCS samples were heated in air for 3h and 8h, which were labeled as CBCSA3 and CBCS-A8, respectively. As displayed in figures 3a, 3b and S2, with prolonging air oxidation activation, the thickness (from ca.17 nm of CBCS-A3 to ca. 5 nm of CBCS-A8) of carbon sheets reduced obviously as accompanying with the rougher surface of carbon sheets, while the mesopores in CBCS became less and smaller due to intensive carbon oxidation (Figures. 3c and 3d). Figures.3e and 3f suggested that the lattice fringe disappeared gradually with prolonging AOA treatment, leading to a more disordering carbon structure. To gain responding insights, XRD, Raman and BET tests were carried out. Figure S3 showed the XRD 10


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patterns of all samples. Clearly, there were a broad peak centered at 24ºand a weak one at around 43 º corresponding to the (002) and (100) reflections of carbons, indicating their amorphous feature.62 Raman spectra of CBCS, CBCS-A3, and CBCS-A8 are shown in figure 3g, in which two peaks at 1350 and 1600 cm-1 could be assigned to the D-band (disordered carbon or defective graphitic structures) and G-band (the graphitic layers and the tangential vibration of the carbon atoms), respectively.57 The IG/ID ratios reduced from 1.14 of CBCS to 0.96 and 0.88 for CBCS-A3 and CBCS-A8, indicating more defects and structural distortion formed in the carbon matrix with prolonging the AOA time. Overall the trend observed by Raman agreed with the TEM results. The N2 desorption-adsorption isotherms and pore size distributions are shown in Figures 3h and 3i, respectively. The former was performed to investigate the porosity of the samples. As shown in Figure 3h, the isotherms of all the samples exhibited the IV-type curve with a distinct increase in the low-pressure range and the hysteresis loop at P/Po = 0.4-0.99, suggesting a hierarchically porous structure. The distribution of pore size shown in figure 3i demonstrated the coexistence of micropores and mesopores. Meanwhile, it can be noticed in Table 1 that the micropore volume increases apparently in CBCS-A3 compared with CBCS, demonstrating the positive effect of the AOA treatment in creating micropores. Notably, CBCS-A3 exhibited obviously more robust porosity in comparison with CBCS, demonstrating the positive effect of the AOA treatment in creating small pores. However, activation for too long time in turn reduced the samples’ porosity, which was the case of CBCSA8. The BET specific surface areas of CBCS, CBCS-A3, and CBCS-A8 were 535, 1488, and 845 m2 g−1, respectively, suggesting their analogous tread with the porosity. As a consequence, it was suggested that the AOA treatment could improve the porosity and enhance the surface area efficiently, which thereby favored large specific capacity and good rate performance. Nevertheless, long-term AOA was unfavourable due to the quick thickness decrease of carbon sheets, which led to small surface area and poor porosity.

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a

d

N5

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g

OI OII

N6

b N6

N

OIII

NQ N5

OI

e

OII

O

Initial carbon structure OIII

NQ

c N6

N5

eh

OI

f

N

OII

OIII

NQ

O

carbon structure after AOA Figure 4. (a-c) high resolution XPS N1s and (d-f) O 1s spectra of CBCS, CBCS-A3 and CBCSA8, and (g,h) the schematic illustration for the structures of carbon materials without and with AOA treatment.

Table 1 Physical and electrochemical properties of CBCS, CBCS-A3 and CBCS-A8 samples. Sample

BET (m2 g-1)

total pore volume

(cm3 g-1)

micropore volume

IG/ID

Elemental analysis (at%)

XPS composition (at%)

N1s

O1s

(cm3 g-1) C

N

O

C

N

O

N-6

N-5

N-Q

OI

OII

OIII

CBCS

535

0.55

0.02

1.14

85.2

7.2

7.6

86.6

7.5

5.9

23.1

61.1

15.8

44.6

47.0

8.4

CBCS-A3

1489

1.09

0.27

0.96

78.5

8.4

13.1

80.6

8.9

10.5

25.8

59.4

14.8

48.8

45.9

5.3

CBCS-A8

846

0.71

0.13

0.88

70.8

12.9

16.3

72.1

13.9

14.0

31.2

57.2

11.6

54.0

43.3

2.7

AOA not only influenced the microstructure of carbon sheets, but also determined the total heteroatom composition and the ratios of various nitrogen/oxygen moieties. According to the results of XPS analysis (Table 1), the CBCS possessed high surface content of N (7.5 at%) and 12


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O (5.9 at%), which was in consistent with the EA results. With increasing AOA time, both N and O doping contents rose evidently. The N doping amount increased from 8.9 at% (CBCSA3) to 13.9 at% (CBCS-A8), while the O doping amount increased from 10.5 at% to 14.0 at%. The high-resolution XPS C 1s, O 1s and N 1s spectra disclosed detail information of surface functionalities as displayed in figures 4(a-f) and S4. In view of the nitrogen functionalities, three fitting peaks centered at 398.2, 400.1, and 402.7 eV were observed, corresponding respectively to pyridinic N (N-6), porrolic/pyridone N (N-5), and quaternary N (N-Q). Among them, the N-6 and N-5 moieties dominated N-doping in carbon matrix, which should endow the carbon sheets with higher chemically active and additional defects. Table 1 clearly presents the relative concentrations of N-moieties for all samples, showing a notable increase of N-6 content via prolonging the activating time. The plentiful N-containing species (especially, N-5 and N-6) could enhance the sodium ion capacity of carbon materials. For oxygen, three deconvoluted peaks could be noted in the O1s core level spectra, which correspond to different O functionalities: O-I at 531 eV (C=O/O-C=O), O-II at 532.4 eV (C-OH/C-O-C) and O-III at 535.4 eV (COOH).35,36 In all samples, O-I and O-II are the primary O-containing functional groups. Clearly, the proportion of O-I increased continuously with prolonging activation time. Since O-I is the most reactive species with unsaturated quinone bond, it could enhance the capacity of carbon materials by reversibly binding with more Na ions. The above results suggested that AOA played a novel and critical role on tuning microstructure and element composition of heteroatom doped carbon materials. More interestingly, different from the expected increase of oxygen doping amount due to carbon oxidation, the enhancement in N doping caused by prolonging AOA treatment was unreported previously. We made a primary analysis with respect to this phenomenon. As is well known, CN bonds have a higher bonding energy than C-C bonds, which confers nitrogen-containing functional groups a higher thermodynamic stability than carbons. This was confirmed by the TG and TPO results, in which NOx was released at a higher temperature than COx in pyrolysis (Figure S5). As a consequence, during the low temperature oxidation process, much less N 13



atoms lost in comparison with the carbon atoms, resulting in the relative rise of N doping amount in carbon matrix as illustrated in figure 4g and 4h. Meanwhile, the continuous breakage of C-C bonds created not only numerous micropores but also more pyridinic N moieties at the expense of quaternary N in carbon nets. This could explain why the N-6 moieties and the surface area of the samples increased after the AOA treatment. In sum, our study provided a facile approach (AOA controlling) for producing carbon materials with different microstructure and N, O contents, which made it possible to design and prepare high performance N, O dual-doped carbon electrode materials. As a successful attempt, the optimized N, O dual-doped carbon sheets in our case not only offered abundant activate sites, enhanced electrical conductivity, but also provided a high specific surface area and hierarchical porosity, which thereby exhibited a promising application potential in Na ion storage.

3.2 Electrochemical Performance 3.2.1. Electrochemical Evaluation as Anodes in Half-Cell

-0.1

1st 2nd 3rd

-0.2

-0.3

c140 120

b

0.1 Current (mA)

0.0 -0.1 -1

0.4 mV s Capacitive: 59.7%

-0.2

0.2 mV s -1 0.5

1.0

1.5

2.0

2.5

3.0

-0.3 0.0

0.5

1.0

Potential (V)

Voltage (V)

1st 2nd 3rd

2.0 1.5 1.0 0.5

-1

d

2.5

1.5 2.0 Voltage (V)

2.5

60 40

3.0

0 CBCS

CBCS-A3

e

1800

Capacity (mAh g )

3.0

80

20

Test at 0.2mV/s -0.4 0.0

0.1Ag

-1

0.2Ag

-1

0.5Ag

400

CBCS-A8 Carbon CBCS-A1 CBCS-A2 CBCS-A3 CBCS-A5 CBCS-A8

800 600

g

Diffusion controlled Capacitive

100

0.2Ag

-1

1Ag

-1

-1

2Ag

-1

5Ag

200

-1

10Ag

-1

0

0.0 0

300

600

900

1200 -1

1500

0

10

20

30

Capacity (mAh )

40 50 Cycle Number

60

500 -1

f

400

70

80 100

600

80

2A

g-1

60

300

10 A g-1

200

40

20

100 0 0

2000

4000

6000

8000

0 10000

Cycle Number

14


Coulombic efficiency (%)

Current (mA)

0.2

a

0.0

Contribution(%)

0.1

Capacity (mAh g )

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

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Figure 5. (a) CV curves of CBCS-A3, (b) capacitive (red) contribution to charge storage of CBCS-A3 anode in SIBs at 0.4 mV s−1, (c) the ratios of capacitive charge storage against the total charge storage in CBCS, CBCS-A3 and CBCS-A8, (d) the charge-discharge curves of CBCS-A3, (e) the rate performance of the CBCS and the samples treated by AOA for various time, (f) the cycle performance of CBCS-A3 at 2 and 10 A g-1, respectively, and (g) the schematic illustration of the evolution of the porosity and the pseudocapacitance in carbon matrix with prolonging AOA treatment.

To evaluate the Na+ storage performance, electrochemical measurements in a half-cell versus sodium metal were performed. Figures 5a and S6a show the CV curves of CBCS-A3 and CBCS half-cells. In the first CV scan of CBCS-A3, a broad reduction peak at 0.8 V was generally ascribed to the formation of a solid electrolyte interphase (SEI) layer and the electrolyte decomposition[39, 57]. In the subsequent cycles, this broad peak disappeared and the resultant CV curves showed a rectangular-like shape, suggesting the pseudocapacitive Na+ storage behaviour. In comparison with the CV curve of CBCS, the CBCS-A3 sample displayed evidently a larger rectangular area, indicating more pseudocapacitance in energy storage. According to this capacitive contribution analysis,58,59 59.7% of the total capacity of CBCS-A3 was attributable to surface capacitive mechanism (figure 5b), which was the highest among all the samples (figure 5c). This mainly came from the increased N,O-moieties after air oxidation. As seen from figure 5d, the initial charge/discharge capacities of CBCS-A3 reached 1350 mAh g-1 and 695 mAh g-1, respectively, which could even rival that of the Li+ charge-storage. The initial coulombic efficiency is up to 51.5%, higher than 35.4% for CBCS (Figure. S6b), which further demonstrated the positive effect of AOA treatment. Figure 5e compares the rate performance of CBCS and the samples by AOA for various time CBCS-Ax (x= 1h, 2h, 3h, 5h, 8h) electrodes at 0.1 A g-1 to 10 A g-1. As two-dimensional carbon materials, the CBCS sample exhibited a good Na+ storage performance, which was comparable with many reported results.14-22, 60-65 To our surprise, the air oxidation activation 15



played an incredible effect on Na+ charge storage of CBCS. With prolonging the air oxidation time, the rate performance of CBCS was enhanced, resulting in an optimal performance for CBCS-A3. The discharge capacities of the CBCS-A3 electrodes at 0.1, 0.2, 0.5, 1, 2, and 5 A g-1 were 640, 524, 395, 320, 257 and 187 mAh g-1, respectively, which was more than twice higher than those of CBCS. Even at a high current density of 10 A g-1, the capacity of CBCSA3 could still maintain at 130 mAh g-1, which was much larger than CBCS electrodes (58 mAh g-1). As soon as the current density was returned to 0.2 A g-1, the capacity of CBCS-A3 recovered fast and kept stable to be 460 mAh g-1. According to Table S1, the rate performance of CBCS-A3 represented the present state of the art among various carbonaceous materials previously tested as anodes in Na half-cells. Meantime, CBCS-A3 also exhibited superior cycling performance (figure S7). As displayed in figure 5f, after 10000 charge/discharge cycles at a high current density of 2 A g-1 and 10 A g-1, the CBCS-A3 electrode remained 270 mAh g1

and 138 mAh g-1, respectively (retention > 90%), demonstrating its application potential for

long cycle life NICs. In terms of improving sodium ion storage, it was noted that the AOA treatment played a significant effect. The CBCS-A3 electrode exhibited the best performance, which could be attributed to its optimum combination of surface area, hierarchical porosity and N, O doping content, which was critical at high scan rates and in long cycles. As reported previously, heteroatoms doping could enhance surface active sites and defects that bound with sodium ions to produce pseudocapacitance.58,66,67 Pseudocapacitance exhibited a rapid sodium ion storage kinetics, which could achieve ultra-fast charge/discharge capability and excellent cycling performance. Since AOA could tune N, O doping amount and states of CBCS, it should be also able to influence the proportion of pseudocapcitance by controlling the air oxidation time (Figures 5b inset and S8). As illustrated in figure 5g, CBCS exhibited the smallest surface area and doping atom amount among samples, which was in accordance with its little pseudocapacitance. In comparison, the micropores and N, O doping derived from AOA treatment conferred CBCS-A3 relatively large surface area and abundant functional groups, 16


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which led to the enhancement of pseudocapacitance and superior performance. As for CBCSA8, its low porosity, small surface area and structural disorder in carbon sheets brought about poor conductivity. This could be told from the quick fading of the electrochemical property of CBCS-A8 regardless of its high N,O doping amount. The results of EIS measurements also supported the above analysis. As illustrated in Figure S9, the Nyquist plot for the CBCS-A3 electrode at high and moderate-frequency region showed the smallest semicircle than those of CBCS and CBCS-A8 electrodes, suggesting the smallest charge-transfer resistance of CBCSA3. At low-frequency region, the curve of CBCS-A3 was closer to the vertical curve compared with other electrodes, indicating a dominantly capacitive behavior. Based on the above results, the AOA method could be considered as an attractive approach for tuning heteroatom doping and nanostructure of bio-derived carbon materials to facilitate sodium storage.

3.2.2. Electrochemical Measurement as Cathodes in Half-Cell

Figure 6 (a) SEM image of CBC-C, (b) the charge/discharge curves of CBC-C in a voltage range from 2.7 to 4.2 V, (c) the rate performance of CBC-C, (d) the cycling performance of CBC-C at 0.5 A g-1.

17



Owing to the limited surface area of CBCS and the AOA treated ones, they were undesirable to be used as cathode materials of NICs. To improve the double-layer capacitive ability for anions, a chemical activation method was employed to enlarge the surface area and porosity of the carbon materials. After being activated by a KOH–NaOH mixture, the as- obtained CBC-C materials was used as ion adsorption electrodes (a cathode) to operate at high voltages. As shown in Figure 6a, the CBC-C sample exhibited a 3D porous morphology constructed by numerous of carbon sheets. As expected, the specific BET surface area of CBC-C was enhanced remarkably (3229 m2 g-1), which should be attributed to the abundant micro/mesopores created by KOH and NaOH activation. The half cells containing CBC-C electrodes were tested between 2.7 and 4.2 V vs. Na/Na+. As indicated in figure 6b, the highly symmetrical charge/discharge profiles at various current densities manifested that CBC-C was a desirable capacitor-type cathode material. The capacity was mainly derived from electrical double layer storage of ClO4-, and/or reversible Na+ adsorption at surface defects. The corresponding rate-dependent capacities are illustrated in Figure 6c. Although the capacity was not high at small current densities, the capacity fading with increasing current density was not distinct. Moreover, the capacity retained to be 23 mAh g-1 even at the rate as high as 10 A g-1. The cycle stability of CBC-C cathode was also evaluated under a current density of 0.5 A g-1 for 10000 cycles. The results suggested the excellent cycling property with the 99% coulombic efficiency (Figure 6d). In this sense, the CBC-C materials could be regarded as one proper candidate for cathode materials of NICs. 3.2.3. Hybrid Sodium Ion Capacitors Based on CBCS-A and CBC-C Electrodes

18


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a

Na+ adsorption at Nand O- containing functional groups

ClO4-

e-

adsorption at Nand O- containing functional groups

Na+ intercalation in the carbon layer

ClO4adsorption into the pores

Na+ transportation in the channels and adsorption into the pores

c

4

2

0.03

CBCS-A3//CBC-C 1:1 CBCS-A3//CBC-C 1:2 CBCS-A3//CBC-C 1:3 CBCS-A3//CBC-C 1:4 CBCS//CBC-C

20mv 200mv 400mv

0.02

1

50mv 300mv 500mv

d

100mv

0.00

-0.01

-1

-0.02

-1

2A g -1 5A g -1 10A g -1 20A g -1 30A g -1 40A g -1 50A g

3.0

0.01

0

4.0 3.5

Potenial (V)

3

Current (mA)

: ClO4: Na+ :C :O :N

Current (A)

b

2.5 2.0 1.5 1.0 0.5 0.0

100

10

0.5

1.0

1.5 2.0 2.5 Potential (V)

360s

3.0

36s

CBCS-3A//CBC-C CBCS//CBC-C HPCNS//HPC NOFC//PSNC TiO2/RGO//PDPC

3.5

0.0

4.0 3.6s

f

0.36s

TiO2@CNT@C//AC Na2Ti3O7@CNT//PSC

1 100

V2O5/CNTs//AC Nb2O5@C//AC

1000 10000 -1 Power density (W kg )

100000

0.5

1.0

1.5 2.0 2.5 Potential (V)

3.0

3.5

4.0

0

100

200

300 400 500 Time (s)

600

700

120

Capacity Retention (%)

0.0

e -1 Energy density (W h kg )

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


5Ag

-1

100 80 60 40 20 0

0

2000

4000

6000

8000

Cycle Number

Figure 7. (a) Schematic illustration of the charge-storage mechanisms for the CBCS//CBC-C NIC; (b) CV curves of CBCS-A3//CBCS-C NICs with various mass ratios and CBCS//CBC-C NIC devices; (c) CV curves of CBCS-A3//CBCS-C NICs at various scan ratios ； (d) galvanostatic profiles of CBCS-A3//CBC-C NIC device, the high current density results being shown in Fig. S10; (e) Ragone plot of CBCS-A3//CBC-C NIC and CBCS//CBC-C NIC, and energy–power density performance comparison with state-of-the-art reported energy storage systems in literature, and (f) the cycling performance of CBCS-A3//CBC-C NIC.

We combined two cuttlebone derived carbons to construct hybrid NICs. Before constructing, the CBCS-A3 anode was pre-sodiated at 0.1 A g-1 for three cycles. Figure 7a showed the chargestorage mechanisms for the CBCS-A3//CBC-C NIC. Thanks to the hierarchically porosity and 19



rich N,O doping amount in carbon materials, Na+ ions were intercalated into the carbon layer or reacted with N, O moieties of anode, while ClO4- ions were absorbed in the porous framework of cathode. Since the suitable charge balance between two electrodes could achieve the high energy storage performance of NICs, the cathode/anode mass ratio was further investigated in the range of 1:1 to 1:4. Figure 7b showed the CV curves of the CBCS-A3//CBCC NIC devices with various mass ratios with comparing with CBCS//CBC-C NIC in a voltage window between 0 and 4 V. Differing to that of CBCS//CBC-C NIC, the CBCS-A3//CBC-C NICs exhibited similar rectangular-shaped CV curves without obvious redox peaks, suggesting good capacitive behavior. The optimized mass ratio of cathode to anode was identified to be 1:3 in the CBCS-A3//CBC-C NICs (Fig. S11), whose corresponding CV curves at scan rates (from 20 to 500 mV s−1) were shown in figure 7c. As the sweep rate increased to 500 mV s-1, the rectangular shape of CV curve still retained without severe distortion, demonstrating its excellent reversibility and outstanding rate capability. The charge/discharge curves of the CBCS-A3//CBC-C NIC device at various rates showed near linear slope with small IR drops (Figs. 7d and S10), which indicated the quick transport of charges in electrode materials. Figure 7e shows the Ragone plot of CBCS//CBC-C NICs and CBCS-A3//CBC-C NICs with mass ratios tested between 0 and 4.0 V. The gravimetric energy and power density was calculated on the base of the total active mass in both electrodes. Clearly, the CBCS-A3//CBCC NICs with mass ratio of 1:3 exhibited the optimal energy and power combinations. This device delivered a high energy density of 95 W h kg-1 at a power density of 1000 W kg-1. Even at a superior power density of 53000 W kg-1, an energy density of 36 W h kg-1 could be retained. This meant that a high energy of 70 W h kg-1 could be achieved when the NIC device was charged for only 25 s. These results represented the state of the art NICs and were even comparable with most of the LICs based on carbon materials for anode versus cathode (Figure 7e).17, 19, 23, 66-69 Notably, the CBCS//CBC-C NICs fabricated by CBCS as anode and CBC-C as cathode exhibited much poorer performance than the CBCS-A3//CBC-C configuration. This may be attributed to the improved Na+ storage ability of CBCS-A3 anode materials caused by 20


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AOA treatment. Figure S12 exhibited the EIS measurements. In contrast to CBCS//CBC-C NICs, the smaller equivalent series resistance (Re) value and charge-transfer resistance (Rct) of the CBCS-A3//CBC-C NIC was contributed to excellent conductivity and increased ion diffusion losses. In the low-frequency region, the straight line showed a high slope angle for CBCS-A3//CBC-C NIC. This demonstrated its better capacitive-like behavior during the cycling process, which should be attributed to the enhanced N,O-moieties functional groups by air oxidation. In addition, the CBCS-A3//CBC-C NICs showed a good cycling performance with a capacitance retention of 90.5 % after 8000 cycles at 5 A g-1 (Figure 7f), suggesting its promising prospect in practical applications.

4. Conclusions In this work, a facile pyrolysis and AOA technique was applied on cuttlebone to obtain high performance sodium storage carbon sheets. The crucial role of AOA in adjusting the element components of heteroatom doping carbon materials was observed, which provided a feasible and efficient way to tune the doping amount and configuration of CBCS. More importantly, the air oxide activated CBCS exhibited remarkable sodium ion storage performance, which overwhelmed that of the current state of the art NIBs. Meanwhile, the assembled NICs with air oxidation activated CBCS as anode and KOH/NaOH activated CBCS as cathode showed (by active mass) a combination of high energy density, power density and coulombic efficiency.

Acknowledgements This work was supported by the national natural science foundation of China (21471139), Shandong provincial key R & D plan and public welfare special program, China (NCET130530) and Shandong provincial natural science foundation, China (ZR2018MEM014).

21



Supporting Information Available: Additional TEM, SEM, XPS, XRD, TG-DSC and IPO analyses on the samples; Additional electrochemical performances of electrode materials and NIC and a table of the electrochemical performance comparison between CBCS-AS and the works reported in previous literatures (PDF).

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Marine-Biomass-Derived Porous Carbon Sheets with a Tunable N

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