Amino Acid Protic Ionic Liquids: Multifunctional Carbon Precursor for N

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Amino Acid Protic Ionic Liquids: Multifunctional Carbon Precursor for N/S co-doped Hierarchically Porous Carbon Materials towards Supercapacitive Energy Storage Hua Zhou, Yanmei Zhou, Li Li, Yonghong Li, Xiaoqiang Liu, Peng Zhao, and Bin Gao ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b00279 • Publication Date (Web): 26 Apr 2019 Downloaded from http://pubs.acs.org on April 26, 2019

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ACS Sustainable Chemistry & Engineering

Amino Acid Protic Ionic Liquids: Multifunctional Carbon Precursor for N/S co-doped Hierarchically Porous Carbon Materials towards Supercapacitive Energy Storage Hua Zhou,a,b Yanmei Zhou,*a Li Li,a Yonghong Li,a Xiaoqiang Liu,a Peng Zhaoa and Bin Gaoc a

Henan Joint International Research Laboratory of Environmental Pollution Control Materials,

College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China b Key

Laboratory for Advanced Silicon Carbide Materials, Research Center of Functional

Materials, Kaifeng University, Kaifeng 475004, China c

Department of Agricultural and Biological Engineering, University of Florida, Gainesville, FL

32611, United States Corresponding author: Tel: +86-371-22868833-3422; Fax: +86-371-23881589 E-mail address: [email protected] (Yanmei Zhou)

ACS Paragon Plus Environment

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ABSTRACT: Amino acid (AA) is abundant in the nature as the basic constituent unit of waste proteins. Amino acid protic ionic liquids (AA-PILs) rich in C, N, O and S elements can be easily synthesized, making it a promising potential precursor of N/S co-doped carbon materials for high-performance supercapacitors. A series of 21 AA-PILs were prepared and directly carbonized with various carbon yields due to the different alkyl group of AA-PILs, indicating that the carbon yield of aromatic AA-PILs was much higher than aliphatic and heterocyclic AAPILs. To further develop the electrochemical properties, hierarchical porous carbon materials were prepared via activation, possessing high surface area, micro-mesopores structure and excellent electrical conductivity. The prepared Lys-K2CO3 exhibited ultrahigh specific capacitance of 350 F g-1 at 1 A g-1 with almost 100% specific capacitance retention after 5000 cycles at 5 A g-1 in 6 M KOH electrolyte for a three-electrode system. The symmetric supercapacitors can light up a red bulb, demonstrating the application potential in energy storage devices. These results will help to develop techniques for the synthesis and fabrication of N/S codoped carbon electrode materials for supercapacitors, providing new strategy for the realization of natural waste proteins energy utilization.

KEYWORDS: Amino acid protic ionic liqulds; N/S co-doped carbon materials; Hierarchically structures, Supercapacitors

INTRODUCTION The recycling of waste natural biomass was an effective alternative for sustainable development of society and environmental protection. Renewable animals, plants, and microscopic resources rich in protein were abundant in the world, with the advantage of large amount and rapid regeneration.1 How to formulate a beneficial strategy for the use of the waste


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materials has been a hot research topic of concern. The waste proteins of animal bone, hair, agriculture and forestry biomass were made up of natural amino acid, which were composed of carbon, oxygen, nitrogen and sulfur elements, making it a promising precursor to prepare N/S co-doped carbon materials.2-8 The N, S and O heteroatoms can create polar functional groups on the surface of carbon materials, regulating the electron donor-acceptor performance of carbon materials for supercapacitors.9 The introduction of heteroatoms will increase the surface wettability and electrical conductivity, providing the pseudocapacitance through surface faradaic reaction.10-17 Doping heteroatoms was considered as an effective method to improve the specific capacitance of carbon materials. In consequence, it will be a light way to develop in situ N/S codoped carbon materials for high-performance supercapacitors via heating natural amino acid rich in heteroatoms, achieving the realization of natural biomass energy utilization. Hierarchically porous carbon materials have attracted much attention due to the unique nanostructure of reasonable aperture size and high surface area, such as purification18-23, supercapacitors24-26 and ion batteries.27-29 For electrode materials in supercapacitors, it has proved that macropores can offer the shortest diffusion distance, mesopores will serve as the fast ion transport expressway, and micropores provide the maximized space sites in the chargedischarge process, suggesting the potential large specific capacitance.30-32 Besides, micromesopores porous carbon materials were considered as the most promising electrode materials of all the hierarchical porous carbon materials, indicating much larger surface area and more superior chemical and cycling stabilities.33 Therefore, it’s still an increasing demand for developing N/S co-doped porous carbon materials with abundant micropores and mesopores from carbonaceous materials by facile method.


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Until now, amino acid ionic liquids have emerged and were designed for green solvents, catalyst and adsorbent containing multi-functional groups, due to the less toxic and biodegrable.34-37 A few carbon materials derived from amino acid have also been reported in recent years.38-41 However, amino acid ionic liquids were seldom considered as carbon precursors and then applied for high-performance supercapacitors, especially AA-PILs in which amino acid acted as cations. In addition, it was considered that AA-PILs have some advantages in several aspects. Compared with traditional precursors, the synthesis of AA-PILs and the entire carbonization process were very simple, which didn’t need complex procedures or heteroatom source as depicted in Table S1. AA-PILs exhibited particular chemical composition and easily regulated molecular structure, so the derived carbon materials were predictable and controllability in the structure and morphology. As a result, AA-PILs can be considered as a multifunctional carbon precursor for N/S co-doped hierarchically porous carbon materials. Therefore, it aroused our interest to exploit N/S co-doping carbon materials from AA-PILs for high-performance supercapacitors. Herein, a series of 21 AA-PILs were synthesized by an acid-base reaction, and were directly carbonized with different carbon yields and electrochemical performance. In addition, N/S codoped hierarchically porous carbon materials with specific capacitance were prepared via activation method. As expected, the as-synthesized materials were consist of abundant micropores and developed mesopores, which not only possesses ultrahigh surface area but also provides rapid transport pathways for electrolyte ions. Finally, the electrochemical properties of the hierarchically porous carbon materials were investigated in 6 M KOH electrolyte for supercpacitors applications. The excellent electrochemical performance indicated that it was an attractive way that bio-based ionic liquids were used as the carbon source.


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EXPERIMENTAL SECTION Preparation of carbon materials A series of AA-PILs were prepared according to our previous work42 as shown in Figure. S1 (Supporting information), and were directly carbonized at 900 ℃ in a tubular furnace in N2 atmosphere for 2 h. The carbon materials obtained from AA-PILs were denoted by the original amino acid, for example the carbon materials from [Lys][HSO4]2 was named as Lys. Furthermore, the Lys and Trp were activated by NH4Cl, KOH and K2CO3 at a weight ration 1 : 2 at 900 ℃ for 2 h under nitrogen gas flow as depicted in Scheme 1. The as-resulted samples were washed with 1 M HCl solution and distilled water several times and dried at 80 ℃ overnight, labeled as Lys-NH4Cl, Lys-KOH and Lys-K2CO3. Characterization The scanning electron microscopy (SEM) and mapping were taken on JEOL JSM-7610F. X-ray diffraction (XRD) was conducted through Bruker D8 Advance and Raman scattering spectra was taken on Renishaw inVia, UK. X-ray photoelectron spectra (XPS, Thermo ESCALAB 250XI, USA) were used for analyzing the chemical composition. Nitrogen adsorption isotherms were carried out at –196 °C (77 K) on a Micromeritics ASAP 2020. The specific surface area (SSA) was calculated by the Brunauer–Emmett–Teller (BET) method while the pore size distribution was computed on the basis of density functional theory (DFT) method. Transmission electron microscope (TEM) was performed on JEM-2100 at 200 kV. Thermogravimetric analysis (TG) curve was carried out by STA7200 ( heating rate: 5 ℃/min, nitrogen flow: 50 mL/min).


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Electrochemical measurements The working electrodes were prepared by mixing the active material, acetylene black and polytetrafluoroethylene in a mass ration of 8 : 1 : 1 in ethanol, then dried in the oven at 80℃. The obtained mixture was pressed into Ni foam in alkaline and neutral electrolyte and stainless steel grid in acid electrolyte (8.0 mg of electroactive material, 1 cm2). The electrochemical tests were conducted on CHI660E electrochemical workstation and CT2001A cycling test system. The electrochemical performance of all the samples was investigated in 2 M Na2SO4 with the reference electrode by Ag/AgCl in the potential window of -0.8-0.4 V and in 1 M H2SO4 with Hg/Hg2SO4 as the reference electrode from -0.2 to 0.8 V by three-electrode system. And then the cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS) were tested in the potential window of -1.0-0 V in 6 M KOH with the reference electrode of Hg/HgO by three-electrode system and two-electrode system in detail. The EIS was performed with the frequency of 10-2 to 105 Hz. The specific capacitance (C, F g-1) was tested by GCD process using the equation (1): 43 C = I Δt / m ΔV

(1)

Where I (A), was the discharge current, Δt (s) represents the discharge time, m (g) was the mass of active material, respectively. C = 4IΔt/mΔv E = C ΔV2 / 8 × 3.6 P = 3600 E /Δ t

(2) (3) (4)


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The samples were further measured by a two-electrode symmetric supercapacitors, in which two symmetric weight electrode separated by glassy KOH soaked-paper using 6 M KOH electrolyte, the specific capacitance (C, F g-1) of single electrode, energy density (E, Wh kg-1) and power density (P, W kg-1) were calculated according to the equations as follows: 44

Scheme 1. Schematic illustration of the synthesis of porous carbon materials. RESULT AND DISCUSSION The carbon yield of AA-PILs and the electrochemical performance The investigated 21 AA-PILs were divided into three groups depending on the R group of amino acid (R-CHNH2COOH), which can has an effect on the carbon yield of AA-PILs.45 They were aromatic amino acid, heterocyclic amino acid and aliphatic amino acid as shown in Table 1. It can be seen from Figure 1 that the aromatic AA-PILs gave a higher carbon yield than the heterocyclic and aliphatic AA-PILs, which was attributed that the activation energy for the initiation step with benzene was higher than pyridine and aliphatic chains.46 The carbon yield of aliphatic group was close to the heterocyclic group, in which Lys exhibited a higher carbon yield


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than others due to its highest bond energy among the aliphatic group. The carbonization of Lys was typically investigated by TG as shown in Figure S2. It can be seen that the first step was the loss of H2O below 200 ℃. When the temperature increased 300 ℃, the second step was the loss of NH3 and SO2. The weight was maintained at 900 ℃ , suggesting the produce of carbon. In addition, the carbon yield of Trp was much higher than Phe and Try, due to the large conjugation with benzene and pyrrole.47 Meanwhile, the electrochemical performances of the carbon materials were investigated by GCD at various current density, with the highest specific capacitance up to 240 F g-1 at 1 A g-1 (as depicted in Figure 1). The carbon materials exhibited various specific capacitance as expected, and then Lys and Trp were further researched considering the carbon yield.

Figure 1. The carbon yield and specific capacitance (current of 1 A g-1) of carbon materials obtained from AA-PILs.


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Group

Cations of AA-PILs

Aromatic amino acid Tryptophan

Tyrosine

Phenylalanine

Hydroxyproline

Proline

Histidine

Heterocyclic amino acid

Threonine

Alanine

Methionine

Glycine

Cystine

Lysine

Asparagine

Serine

Aspartic

Glutamate

Arginine

Valine

Leucine

Cysteine

Glutamine

Aliphatic amino acid

Table 1. The cations structure of AA-PILs, and the anion was [HSO4]-. Morphology and structure On the basis, Lys and Trp were activated by NH4Cl, KOH and K2CO3, respectively. And the morphology formation of the Lys, Lys-NH4Cl, Lys-KOH and Lys-K2CO3 were clarified by


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SEM imaging, as depicted in Figure 2a-e. The loose laminated structure of Lys can be observed from Figure 2a. Figure 2b-e clearly demonstrated the interconnected porous carbons with large amount interface for charge storage obtained by activation. The abundant interconnected pores network frameworks can be seen in Figure 2b, indicating the successful “gas escaping channels” induced by NH4Cl.48-50 The microstructure of Lys-KOH and Lys-K2CO3 possessed numerous channels from several micrometer to hundred nanometers owing to the drastic redox reactions between carbon and potassium compounds, providing the electrolyte ion-buffering reservoir and fast transportation path.51-52 The corresponding EDX element mapping of Lys-K2CO3 were depicted in Figure 2 f-h, O, N and S elements are uniformly distributed throughout the materials, implied the successful preparation of in-situ heteroatoms co-doping from AA-PILs. In addition, the disordered interconnect wormlike pores with different size were translucent in Figure S3 a-c, suggesting the effects of activator on the carbon materials. Meanwhile, the microstructure of Trp, Trp-NH4Cl, Trp-KOH, Trp-K2CO3 was also investigated as showed in Figure S4. The large sheet materials seen in Figure S4a indicated that the thermally stable benzene moieties compared with Lys. After activation, the Trp-NH4Cl showed three-dimensional inter-penetrating nanostructure compared with the large monolithic of Trp as illustrated in Figure S4b. The Trp-KOH and TrpK2CO3 displayed a hierarchically porous network containing numerous small-sized mesopores and hundreds of nanometers macropores, indicating the relatively excellent pore structure.53 As a consequence, the carbon materials hold a hierarchical nanostructure with good pore connectivity.


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Figure 2. SEM images: a) Lys, b) Lys-NH4Cl, c) Lys-KOH, d-e) Lys-K2CO3, f-h) EDX mapping of Lys-K2CO3. To obtain further insights into the structure of the Lys, Lys-NH4Cl Lys-KOH and LysK2CO3, the XRD patterns (Figure 3a) showed two broad peaks centered at 23.8° and 44.2° corresponding to the graphitic (002) and (101) plane of amorphous carbon.54 Raman spectroscopy, an effective strategy of the graphitization degree for carbon materials, were employed and shown in Figure 3b. All the samples exhibited two distinct peaks at 1340 (D-band, disordered sp2 carbon) and 1595 cm-1 (G-band, graphitic sp2 carbons), and the ration of ID/IG reflects the degree of disorder of the materials.55 Compared with Lys (0.96), the ration of ID/IG of Lys-NH4Cl (0.98), Lys-KOH (0.99) and Lys-K2CO3 (1.03) all increased after activation, indicating the disorder and defection during the high temperature process activation. The XRD and Raman spectroscopy of Trp, Trp-NH4Cl, Trp-KOH and Trp-K2CO3 are similar to that of Lys, Lys-NH4Cl, Lys-KOH and Lys-K2CO3 except the ration of ID/IG, as illustrated in Figure S5a-b. The specific surface area and pore size distribution of Lys, Lys-NH4Cl, Lys-KOH and Lys-


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K2CO3 were further investigated by nitrogen adsorption and desorption measurements (Figure 4a， b), which was highly related to their electrochemical properties. The N2-adsoption isotherms of the Lys and Lys-NH4Cl showed a typical Type-I curve according to the IUPAC classification, suggesting the micropores structure (< 2 nm). While Lys-KOH and Lys-K2CO3 showed hybrid I/IV type isotherms, corresponds to the abundant micropores and highly developed mesopores, which facilitate the electrolyte transmission and storage.56-58 The specific surface area of LysKOH (as shown in Table 2) was measured 2370 m2 g-1, including micropore surface area (1546 m2 g-1), pore volume (1.475 m2 g-1), micropore volume (0.700 cm3 g-1). Lys- K2CO3 exhibited a higher SSA of 2959 m2 g-1, with a micropore surface area (1219 m2 g-1), pore volume (1.99 cm3 g-1) and micropore volume (0.55 cm3 g-1). Therefore, such hierarchically porous materials with micropores and developed mesopores would provide sufficient electrode ions transports and storage, suggesting a better capacitive performance for supercapacitors. Moreover, XPS analysis were employed to investigated functional groups and compositions of Lys, Lys-NH4Cl, LysKOH and Lys-K2CO3 ( Figure 4c), displaying four peaks corresponding to C1s, N 1s, S 2p, and O 1s.59 Moreover, the N 1s, O 1s, and S 2p spectra of Lys, Lys-NH4Cl, Lys-KOH were similar with Lys-K2CO3 as shown in Figure S6. The peaks of N 1s spectra towards Lys- K2CO3 (Figure 4d) displayed the concentrated four peaks at 397.97 eV (N-6, pyridinic nitrogen), 399.27 eV (N5, pyrrolic nitrogen), 400.77 eV (N-Q, N substituted aromatic graphite structure), and 403.57 eV (pyridine-N oxides). The N-6 can offer one pair of electrons to conjugate with the π-conjugated system, introducing the electron donor into the carbon materials with a significant impact on the enhanced capacitance. The N-5 improved excellent electron donor feature and higher charge transfer, enhancing electrochemical active sites during electron shift process. A certain amount of remarkable electron-donor N groups situated at the disabled graphite lattice center will


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strongly increase specific conductivity and transport paths.60, 61 The O1s spectra in Figure 4e was deconvoluted into four peaks at 532.7 eV (C=O), 533.3 eV (C-O), 534.2 eV (O=C-O-C=O), and 535.4 eV (O=C-O), which was essential to the good wettability of carbon materials.62 The S 2p spectrum depicted in Figure 4f illustrated three distinct peaks of about 168.5 (C-SOx-C), 165.0 (C-S-C 2p 1/2), and 163.5 (C-S-C 2p 3/2) eV.63-65 It can be considered that sulfur atoms are successfully incorporated into the carbon skeleton contributing for pseudocapacitance. The doping of N, O and S heteroatoms can enhance the wettability of electrode materials, leading to significant increases in the accessible surface area for electrolyte. The contents of oxygencontaining functional groups have changed due to the various activators as shown in Table S2. The electrochemical properties are not only related to the heteroatoms, but also to the pore size distribution. Therefore, these properties combine to give samples high-performance electrode materials for supercapacitors and other energy storage devices.

Figure 3. a), b) XRD patterns and Raman spectra of Lys, Lys-NH4Cl, Lys-KOH, Lys-K2CO3.


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Figure 4. a) N2 adsorption/desorption isotherms and b) the pore size distribution of the Lys, LysNH4Cl, Lys-KOH and Lys-K2CO3, c) the full XPS spectrum of Lys, Lys-NH4Cl, Lys-KOH and Lys-K2CO3, high-resolution XPS spectra of the Lys-K2CO3 d), N 1s, e) O 1s, and f) S 2p.

Chemical Composition (at%)

SBET

Smic

Vtot

Vmic

(m2 g-1)

(m2 g-1)

(cm3 g-1)

(cm3 g-1)

C

O

N

S

Lys

900

859

0.378

0.342

78.54

16.52

3.82

1.12

Lys-NH4Cl

1109

1046

0.504

0.431

84.3

7.71

4.8

1.51

Lys-KOH

2370

1546

1.475

0.700

85.09

11.05

2.77

1.09

Lys-K2CO3

2959

1219

1.999

0.550

88.9

9.01

1.07

0.99

Samples

Table 2. Specific surface areas and total pore volumes of Lys, Lys-NH4Cl, Lys-KOH, LysK2CO3. Supercapacitor performance


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The electrochemical behaviors of all the samples were investigated in 6 M KOH, 2 M Na2SO4 and 1 M H2SO4. The samples all showed better electrochemical properties in alkaline electrolyte compared with other aqueous electrolyte (shown in Figure S7). As a result, cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) tests were carried out in 6 M KOH in details. Figure 5a shows the CV curves of Lys, Lys-NH4Cl, Lys-KOH and Lys-K2CO3 electrode at the scan rate of 100 mV s-1 , which were measured in a potential window of -1-0 V. It worth noted that Lys-K2CO3 exhibited the largest rectangular-shaped area among the electrodes, indicating the ideal electric capacitance due to the highest SBET with micropores and mesopores. On the contrary, Lys displayed the smallest double-layer capacitance attributed to the small specific area only with little micropores. The typical GCD profiles of the samples at 1 A g-1 were described in Figure 5b, revealing isosceles triangle shape although imperfect symmetry. The linear symmetric GCD profiles showed that the capacitive behavior was fully reversible in the initial cycle, demonstrating the fast charge transfer. The calculated specific capacitance of the four electrodes in terms of the charge-discharge curves based on equation (1) were presented in Figure 5c, which showed higher specific capacitance compared with other carbon materials ever reported as illustrated in Table S3. Lys-K2CO3 showed the highest specific capacitance of 350 F g-1, which can be attributed to the highly interconnected hierarchically pore structure for the efficient electrolyte ions diffusion and transport.66 A higher rate capability of 77 % retention was observed in the range of current density from 1 A g-1 to 20 A g-1. Moreover, the electrochemical performance of Lys-K2CO3 was investigated deeply in Figure 5d-f. The rectangular shape of CV curves at different scan rate (Figure 5d) confirms that the materials possess an ideal electrochemical capacitor. Figure 5e depicted the symmetrical triangular GCD profiles over a wide range from 1 to 20 A g-1 without


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significant drop. Besides, the long-life GCD at a current density of 5 A g-1 was tested and showed excellent cycling stability with almost 100 % after 5000 cycles (Figure 5f), indicating the excellent electrochemical stability. In addition, the electrochemical properties of Trp, TrpNH4Cl, Trp-KOH and Trp-K2CO3 were illustrated in Figure S8. The CV and GCD curves exhibited a quintessential electric double layer behavior due to the unique porous structure. The highest specific capacitance of the four samples was Trp-K2CO3 (270 F g-1 at 1 A g-1), with 67% retention in the range of current density from 1 to 10 A g-1. These results further suggest that it was feasible to prepare high performance capacitors from the AA-PILs.

Figure 5. Electrochemical performance of the Lys, Lys-NH4Cl, Lys-KOH and Lys-K2CO3: a) CV curves at 100 mV s–1; b) GCD curves under 1 A g–1; c) variation of the specific capacitances at different current densities; Electrochemical performance of the Lys-K2CO3: d) CV curves versus different scan rates; e) GCD curves versus different current densities; f) cycling performance by repeating GCD at 5 A g–1.


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The Nyquist plots of the EIS examination were carried out from 10-2 to 105 Hz in Figure 6ab. All the electrodes displayed a near-vertical curve in the low-frequency region, demonstrating the good capacitive behavior with fast ion diffusion and transport.67 Besides, semicircles in the high-frequency region were observed because of the charge-discharge resistance of the faradic reactions.27 In addition, the Lys-K2CO3 exhibited the lowest equivalent series resistance of 0.54 Ω (calculated according to the intercept in the Z’ axis) and the smallest diameter of the semicircle among the four electrodes, illustrating the fast electron-transfer kinetics by the heteroatom-doped and the developed hierarchical porous framework. The equivalent series resistance of other electrodes was all smaller than 1 Ω, indicating the good conductivity of the N/S so-doped carbon electrodes. The Bode phase plot (dependence of the phase angle on frequency) for Lys and Lys-K2CO3 were shown in Figure 6c. The corresponding time constant τ0 ( = 1/f0) of Lys-K2CO3 was calculated to be 0.7 s, compared with 2.6 s of Lys, suggesting that Lys-K2CO3 possess enormous potential for the instantaneous delivery of ultrahigh power and energy.68 The Nyquist plot of Trp, Trp-NH4Cl, Trp-KOH and Trp-K2CO3 were also investigated. Figure S5 d-e showed a vertically straight line almost 90° angle at the low frequency, and the expanded view of the high frequency exhibited the equivalent series resistance was 0.53 Ω, showing excellent electric conductivity. Compare the response of Trp and Trp-K2CO3 in the Bode plots of impendence phase angle against frequency. The capacitor response frequency f0 for Trp-K2CO3 at a phase angle of 45°, the corresponding relaxation time constant τ0 was 2.1 s (Figure S5 f), indicating a fast charge and discharge rate of in 6 M KOH electrolyte.


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Figure 6. a, b) Nyquist plots in 6 M KOH solution, c) Bode plots of phase angle versus frequency. Herein, the electrode performance of Lys-K2CO3 and Trp-K2CO3 were further examined by a two-electrode symmetrical supercapacitors in 6 M KOH electrolyte. As shown in Figure 7a, the CV curves of Lys-K2CO3 at different scan rate from 10 to 100 mV s-1 present a quasi-rectangular shape of ideal double-layer capacitor behaviors. The GCD voltage profiles (in Figure 7b) of the supercapacitors exhibited symmetrically linear forms without distinct voltage drop from 1 to 20 A g-1. Similar to Lys-K2CO3, the CV and GCD curves of Trp-K2CO3 were displayed in Figure. 7c-d, showing the quasi-rectangular and typical triangular shapes. The calculated specific capacitance of the device by equation (2) as illustrated in Figure 7e was 200 and 170 F g-1 at 1 A g-1, demonstrating the outstanding capacitance performance. Meanwhile, the energy and power densities of the symmetric supercapacitor were calculated according to equation (3) (4). Figure 7f depicted the Ragone plots of the energy density (6.9 Wh kg-1) and power density (248 W kg-1) for the device in a voltage window of 0-1 V based on Lys-K2CO3. In addition, the energy density and power density for the capacitor based on Trp-K2CO3 were 5.9 Wh kg-1 and 250 W kg-1, suggesting the excellent electrochemistry reversibility and Columbic efficiency for supercapacitors. Notably, the Lys-K2CO3 symmetric supercapacitors could drive a commercial


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red LED bulb brightly more than 3 min being fully charged at 1 A g-1 (insert Figure. 7f), revealing the potential for application as energy storage device.

Figure 7. Electrochemical performance of the Lys-K2CO3 and Trp-K2CO3: a, c) CV curves versus different scan rates; b, d) GCD curves under different current densities; e) the specific capacitances at different current densities; f) Ragone plots, the insert was the images of lighting a red LED bulb by three symmetrical supercapacitors in series.. CONCLUSIONS In summary, N/S co-doped micro-mesopores porous carbon materials have been prepared by AA-PILs derived from low cost and abundant amino acid, which serves as single carbon source and heteroatom donor. The influence induced by R group of AA-PILs towards carbon yield and electrochemical performance have been discussed in details. In addition, the effect of different activators on the pore structure of carbon materials were investigated, and the derived


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carbon materials of Lys-K2CO3 exhibited outstanding rate capability and long cycling life. These results have been proved the successful attempt to produce advanced hierarchically porous carbon materials from AA-PILs, which provided strategy for the efficient utilization and transformation of waste biomass protein. ASSOCIATED CONTENT Supporting Information. The characterization, SEM images, TEM images, TG curve, XRD patterns, Raman spectra, XPS spectra, the specific capacitances of Trp, Trp-NH4Cl, Trp-KOH and Trp-K2CO3 were supplied in Supporting Information. AUTHOR INFORMATION Corresponding Author *E-mail address: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT The authors thank the National Natural Science Foundation of China (21776061, 21576071, U1504215 and 41807128), the program for Science & Technology Innovation Team in Universities of Henan Province (19IRTSTHN029), the program for Science & Technology Innovation Talents in Universities of Henan Province (19HASTIT037).


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doped

ultrathin

porous

carbon

nanosheets

for

high

performance

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For Table of Contents Use Only

Synopsis N/S co-doped hierarchical porous carbon materials were prepared from the multifunctional carbon precursor of amino acids protic ionic liquids for high-performance supercapacitors.


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Amino Acid Protic Ionic Liquids: Multifunctional Carbon Precursor for N

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