Nitrogen-rich porous carbon in ultra-high yield derived from activation of biomass waste by a novel eutectic salt for high performance Li-ion capacitors
Graphical abstract
Introduction
Due to the expeditious development of potable electronics, electric vehicles, and uninterrupted power supplies, the requirement of high-energy and high-power storage system increasing daily [1]. Lithium-ion batteries (LIBs) and supercapacitors (SCs), which are extensively applied in these field at present, cannot simultaneously meet the high energy and power densities, because LIBs usually possess high energy density but poor power density, and the SCs generally achieve high power density but suffer from low energy density [2,3]. Under these cases, it is very important to open up advanced energy storage apparatuses that combine the complementary characteristics of both LIBs and SCs. Lithium ion capacitors (LICs), originated from the hybrid device of LIBs and SCs, not only provide excellent energy and power density, but also achieve long cycling life [4]. As a result, they have been considered to fill up the gap between the LIBs and ECs and become one of the most promising candidates for meeting the growing demand in energy storage field and also received much more attention in the very recent years [4,5]. In order to improve the electrochemical performance of LICs, many materials possessing unique composition and/or novel structure, such as insertion-type materials (Li4Ti5O12 [6,7], TiO2 [8,9], Nb2O5 [10], TiNb2O7 [11], Li3VO4 [12], and graphite [13,14]) and conversion-type or alloying reaction materials (such as Fe3O4 [15,16], MnFe2O4 [17], MnO [18], Sn/C [19], and Si/C [20]) for anode materials, as well as active carbon (AC) [6,8,10,14,16,21], carbon nanotube (CNT) [19,22], graphene [23,24] and heteroatom-doped porous carbons (HDPCs) [[25], [26], [27], [28], [29]] as cathode materials have been widely explored and successfully utilized for LICs during the past two decades or so. Although great achievements have been achieved in developing high performance LICs, the mismatch of the rate performance between the negative electrode and positive electrode make the full use of the high specific capacity electrode very difficult, resulting in high energy density LICs generally be achieved by sacrificing their power density [30]. As a result, it is still a tremendous challenge to search for idea anode materials with superior rate capability and the cathode materials with higher specific capacities towards constructing high performance LICs [1,30].
In very recent years, LICs with two electrodes using the same materials have just began to attain special interest. Among them, porous carbonaceous materials with novel structure and unique composition are most commonly investigated as both positive and negative materials for the manufacture of high performance LICs, because of their tunable porosity, stable electrochemical property, and rich reserves in nature [[31], [32], [33], [34], [35], [36]]. Among these carbonaceous materials, heteroatom-doped porous carbons (HDPCs), especially for nitrogen-doping porous carbons (NDPCs), with a lot of attractive features (high electronic conductivity, adjustable the interlayer distance, improved wettability of electrolyte and enhanced capacitance performance induced by the rapidly pseudocapacitive reaction and/or rich active sites), exhibited a great potential applications for high performance LICs [[32], [33], [34], [35], [36]]. Thus, the structural design and scalable preparation of NDPCs from a green and low cost route are imperative and necessary.
Biomass and biomass wastes, as cheap and sustainable precursors for the NPCs have been exploited for energy storage apparatuses (such as SCs, LIBs and LICs) in many researchers [[37], [38], [39], [40]]. There are generally two routes for the preparation of NDPCs using the biomass and/or biomass wastes: the first is in-situ direct pyrolysis of the precursor with nitrogen sources and activation agents (such as CaCl2 [41], NaOH [42], KOH [43], K2CO3 [44], and ZnCl2 [41,45]) by one-step, and the other is two-step synthesis method using the pyrolysis procedure firstly to achieve intermediate product and activation of the as-obtained intermediate product secondly [[46], [47], [48]]. For the first route, it is difficult to uniformly disperse the activation agent and nitrogen source in the mixed precursors and also usually cause some highly toxic substances (KOCN and/or KCN) during the activation process [37,44]. For the second route, it is very time-consuming and usually generate NDPCs with low nitrogen level. Meanwhile, low yield (generally less than 25 wt.% based on the biomass) is achieved and tedious washing is required to obtain pure product in both synthesis routes. Although substantial advancement in the preparation of NDPC-based electrode materials, obvious disadvantages such as high energy consumption, tedious procedures and toxic characteristics still hinder their large-scale application in “sustainable and low-cost” energy storages. Thus, a novel route for efficient synthesis of NDPCs for LICs employing eco-friendly and naturally plentiful biomass and/or biomass wastes is worth encouraging.
Herein, we reported a novel route for the preparation of NDPC in high yield (>40 wt% based on the mass of bagasse), making use of sugar cane bagasse as the carbon precursor and a new eutectic salt as both the activation agent and nitrogen sources. We choose bagasse as the carbon precursor herein because of its abundance, sustainability and low cost, which has also been successfully applied as the carbon precursor for the fabrication of porous carbon-based materials for energy storage devices [41,43,49]. The new eutectic salt, directly prepared via the mixing of ZnCl2, urea and KCl in a mass ratio of 3:2:0.5 at 110 °C, is also environment friendly and low cost. The as-prepared NDPC sample (labelled as NDPC-0.5) with high specific surface area (SSA, 1505.9 m2 g−1), moderate total pore volume (Vt = 0.88 cm3 g−1), rich nitrogen-doping content (up to 9.5 at.%) and hierarchical porous structure shows obviously enhanced electrochemical performance as both positive and negative materials for LICs. Based on these unique features, thus, a LIC (NDPC-0.5//NDPC-0.5) assembled by the NPDC-0.5-based cathode and anode exhibits superior electrochemical properties, delivering a high energy density of 87.7 Wh kg−1 at a high power density of 10,000 W kg−1.
Section snippets
Preparation of nitrogen-doping porous carbons (NDPC)
In a representative experiment, ZnCl2 (6.0 g), urea (4.0 g) and KCl (1.0 g) were firstly mixed in a bake and then heated at 110 °C for 1 h to generate a deep eutectic salt (DES), after that, sugar cane bagasse (2.0 g) was immersed into the DES liquid and stirred for another 30 min, then the mixture was transferred into a tube furnace, heated up to 800 °C under N2 atmosphere with a ramp rate of 5 °C min−1 and maintained this temperature for additional 2.0 h to carbonize and activate the mixed
Synthesis process
Previous investigation suggested that different mass ratios of ZnCl2 and urea can form deep eutectic solvents (salts) at low temperature [51,52], which allows them possible to act as solvents for uniformly mixing the raw materials firstly and then act as activators for generating porous structure during the preparation of NPCs materials. Furthermore, it can act as an efficient nitrogen source for the preparation of NPCs. After a series of comparative experiments via the change of the chemical
Conclusions
In summary, we have developed a cheap and high efficient route for the synthesis high performance NDPCs in high yields with rich N-doping level and adjustable SSAs and pours structure, using novel DESs as activation agents. By optimized the chemical compositions of the DESs, the as-prepared NDPC-0.5 material, with rich N-doping level, high SSA, moderate Vt and hierarchically porous structure, exhibits high specific capacity, superior rate performance and excellent cycle capability as both
CRediT authorship contribution statement
Kaixiang Zou: Conceptualization, Formal analysis, Investigation, Writing - original draft. Zixing Guan: Resources, Validation. Yuanfu Deng: Conceptualization, Writing - review & editing, Supervision, Funding acquisition. Guohua Chen: Supervision, Project administration.
Declaration of competing interest
We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in. In word, the manuscript entitled “Nitrogen-rich porous carbon in ultra-high yield derived from activation of biomass waste by a novel eutectic salt for high performance Li-ion
Acknowledgements
This work was supported by the National Natural Science Foundation of China, China (Grant No. 21875071), the National Natural Science Foundation of China-Hong Kong Research Grant Council (NSFC-RGC) Joint Research Scheme (Grant No. 21661162002 and N_HKUST601/16).
References (60)
- et al.
Hybird energy storage devices: Advanced electrode materials and matching principles
Energy Storage Mater.
(2019) - et al.
Three-dimensional graphene and their integrated electrodes
Nano Today
(2014) - et al.
Toward ultrafast lithium ion capacitors: a novel atomic layer deposition seeded preparation of Li4Ti5O12/graphene anode
Nano Energy
(2017) - et al.
Highly porous Li4Ti5O12/C nanofibers for ultrafast electrochemical energy storage
Nano Energy
(2014) - et al.
TiNb2O7 hollow nanofiber anode with superior electrochemical performance in rechargeable lithium ion batteries
Nano Energy
(2017) - et al.
Rational design of stable 4 V lithium ion capacitor
Nano Energy
(2016) - et al.
All nanocarbon Li-ion capacitor with high energy and high power density
Mater. Today Energy
(2018) - et al.
Synthesis and supercapacitor performance studies of N-doped graphene materials using o-phenylenediamine as the double-N precursor
Carbon
(2013) - et al.
Nitrogen and oxygen co-doped porous carbon nanosheets as high-rate and long-lifetime anode materials for high-performance Li-ion capacitors
Carbon
(2019) - et al.
One-step synthesis of ultra-high surface area nanoporous carbons and their application for electrochemical energy storage
Carbon
(2018)
Hierarchically porous nitrogen-doped carbon derived from the activation of agriculture waste by potassium hydroxide and urea for high-performance supercapacitors
J. Power Sources
Insight to the synergistic effect of N-doping level and pore structure on improving the electrochemical performance of sulfur/N-doped porous carbon cathode for Li-S batteries
Carbon
Porous activated carbon derived from Chinese-chive for high energy hybrid lithium-ion capacitor
J. Power Sources
Biomass waste-derived nitrogen-rich hierarchical porous carbon offering superior capacitive behavior in an environmentally friendly aqueous MgSO4 electrolyte
J. Colloid Interface Sci.
Mesoporous activated carbon materials with ultrahigh mesopore volume and effective specific surface area for high performance supercapacitors
Carbon
Outstanding performance of activated graphene based supercapacitors in ionic liquid electrolyte from −50 to 80 °C
Nano Energy
High-energy Li-ion hybrid supercapacitor enabled by a long life N-rich carbon based anode
Electrochim. Acta
Synthesis and supercapacitor performance studies of N-doped graphene materials using o-phenylenediamine as the double-N precursor
Carbon
Effect of pre-lithiation degrees of mesocarbon microbeads anode on the electrochemical performance of lithium-ion capacitors
Electrochim. Acta
Electrode materials, electrolytes, and challenges in nonaqueous lithium-ion capacitors
Adv. Mater.
Review of hybrid ion capacitors: from aqueous to lithium to sodium
Chem. Rev.
Lithium ion capacitors in organic electrolyte system: scientific problems, material development, and key technologies
Adv. Energy Mater.
A novel high-energy hybrid supercapacitor with an anatase TiO2-reduced graphene oxide anode and an activated carbon cathode
Adv. Energy Mater.
Rapid and facile synthesis of hierarchically mesoporous TiO2–B with enhanced reversible capacity and rate capability
J. Mater. Chem. A
In-plane assembled orthorhombic Nb2O5 nanorod films with high-rate Li+ intercalation for high-performance flexible Li-ion capacitors
Adv. Funct. Mater.
Peapod-like Li3VO4/N-doped carbon nanowires with pseudocapacitive properties as advanced materials for high-energy lithium-ion capacitors
Adv. Mater.
Graphitic carbon balanced between high plateau capacity and high rate capability for lithium ion capacitors
J. Mater. Chem. A
Metalorganic quantum dots and their graphene-like derivative porous graphitic carbon for advanced lithium-ion hybrid supercapacitor
Adv. Energy Mater.
High performance lithium-ion hybrid capacitors employing Fe3O4–graphene composite anode and activated carbon cathode
ACS Appl. Mater. Interfaces
NaCl-templated synthesis of hierarchical porous carbon with extremely large specific surface area and improved graphitization degree for high energy density lithium ion capacitors
J. Mater. Chem. A
Cited by (80)
N/B co-doped porous carbon with superior specific surface area derived from activation of biomass waste by novel deep eutectic solvents for Zn-ion hybrid supercapacitors
2024, Journal of Materials Science and TechnologyHierarchical porous activated carbon anode for dual carbon lithium-ion capacitors: Energy storage mechanisms and electrochemical performances
2024, Journal of the Taiwan Institute of Chemical Engineers