Accepted Manuscript

Resorcinol-formaldehyde based carbon aerogel: Preparation, structure and

applications in energy storage devices

Feng Li, Lijing Xie, Guohua Sun, Qingqiang Kong, Fangyuan Su, Yufang Cao,
Jiacheng Wei, Aziz Ahmad, Xiangyun Guo, Cheng-Meng Chen

PII: S1387-1811(18)30626-7
DOI: https://doi.org/10.1016/j.micromeso.2018.12.007
Reference: MICMAT 9223

To appear in: Microporous and Mesoporous Materials

Received Date: 29 September 2018

Revised Date: 17 November 2018
Accepted Date: 4 December 2018

Please cite this article as: F. Li, L. Xie, G. Sun, Q. Kong, F. Su, Y. Cao, J. Wei, A. Ahmad, X. Guo, C.-
M. Chen, Resorcinol-formaldehyde based carbon aerogel: Preparation, structure and applications in
energy storage devices, Microporous and Mesoporous Materials (2019), doi: https://doi.org/10.1016/
j.micromeso.2018.12.007.

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 ACCEPTED MANUSCRIPT

This review has summarized the recent progress in tailoring RF-CAs toward

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supercapacitors and other advanced energy storage, such as lithium-ion batteries,

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sodium-ion batteries and lithium sulfur batteries. Additionally, we put an emphasis on

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the physico-chemical principles of synthesis strategies and specific illustration of

structure-performance relationship. Finally, some hints on the challenges and

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opportunities for RF-CAs which can provide the further fundamental understanding
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and extend the practical applications in energy storage have been given in this review
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as well.
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1 Resorcinol-formaldehyde based carbon aerogel:

2 preparation, structure and applications in energy storage devices

3 Feng Li a,b, Lijing Xie a, Guohua Sun a, *, Qingqiang Kong a, Fangyuan Su a, Yufang

4 Cao c, Jiacheng Wei a, Aziz Ahmad a, Xiangyun Guo d, Cheng-Meng Chen a, *

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a
5 CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese

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6 Academy of Sciences, Taiyuan 030001, P. R. China.

b
7 University of Chinese Academy of Sciences, Beijing 100049, P. R. China.

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

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9 Suzhou 215000, P. R. China.
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d
10 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese

11 Academy of Sciences, Taiyuan 030001, P. R. China.

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12 * Corresponding author: ccm@sxicc.ac.cn; sunguohua_1@sxicc.ac.cn.

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13
14
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15 Abstract
16 Advanced energy storage devices are becoming more important with the
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17 development of the ever-increasing demand for energy consumption and worse

18 environmental problems. Resorcinol-formaldehyde based carbon aerogels (RF-CAs)

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19 are considered to be a promising candidate for advanced energy storage, owing to

20 their low density, high electrical conductivity, high porosity and chemical inertness,

21 etc. It has been found that numerous researches have focused on the preparations of

22 RF-CAs (such as polymerization process, drying method, carbonization temperature

23 and activation modes, etc.) and their applications in energy storage devices. However,

24 systematic investigations into the surface chemistry, microstructure and applications

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1 of RF-CAs are rarely documented.

2 Herein, this review has summarized the recent progress in tailoring RF-CAs

3 toward supercapacitors and other advanced energy storage, such as lithium-ion

4 batteries, sodium-ion batteries and lithium sulfur batteries. Additionally, we put an

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5 emphasis on the physico-chemical principles of synthesis strategies and specific

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6 illustration of structure-performance relationship. Finally, some hints on the

7 challenges and opportunities for RF-CAs which can provide the further fundamental

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8 understanding and extend the practical applications in energy storage have been given

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9 in this review as well.
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10 Keywords Resorcinol-formaldehyde based carbon aerogel; Synthetic strategies;

11 Supercapacitor; Advanced energy storage.

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12
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13 Contents
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14 1. Introduction……………………………………………………………………3

15 2. Synthetic strategies for RF-CAs………………………………………………5

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16 2.1. Precursors and catalysts during sol-gel process………………………...6

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17 2.2. Drying……………………………………………………………………..9
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18 2.3. Carbonization……………………………………………………………..11

19 2.4. Activation………………………………………………………………….13

20 3. Applications in SCs…………………………………………………………….17

21 3.1. RF-CAs directly used for SCs…………………………….. ……………..18

22 3.1.1. Pore structure…………………………………………………………...18

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1 3.1.2. Electrical conductivity…………………………………………………..22

2 3.1.3. Heteroatoms doping……………………………………………………..27

3 3.2. Composites based on RF-CAs for SCs…………………………………….33

4 4. RF-CAs used for other energy storage devices………………………………39

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5 5. Summery and outlook………………………………………………………...45

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6 Acknowledgements……………………………………………………………47

7 References……………………………………………………………………..48

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8

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9 1. Introduction
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10 With the development of the ever-increasing demand for energy consumption

11 and worse environmental problems, there has been an urgent demand to introduce
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12 alternative energy techniques [1, 2]. Over the past decades, much efforts have been
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13 paid to explore new effective energy storage devices, such as supercapacitors (SCs),
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14 lithium ion batteries (LIBs), lithium sulfur batteries (Li-S batteries), sodium-ion

15 batteries (Na-ion batteries) and fuel cells, etc.) [3-9]. The Ragone plot of various
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16 energy storage systems can be shown in Fig. 1 [10]. On the one hand, SCs possesses
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17 high power density of 196 kW/kg (10–100 times the energy density of electrolytic
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18 capacitors) in just a few seconds and long cycle life of 1 million h (much higher than

19 that of batteries (about 500 h)) [11-15]. On the other hand, the recharge batteries can

20 deliver ultrahigh energy density but at the cost of the charge-discharge rate and cycle

21 life [2]. The electrochemical performance of energy storage devices is mainly depends

22 on the structure of electrodes. It is generally accepted that ideal electrode materials

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1 should have high surface area, proper pore structure and pore size, high electrical

2 conductivity and strong mechanical property [16-18].

3 Carbon materials such as graphene, activated carbon, carbon nanotubes, carbon

4 nanofibers and resorcinol-formaldehyde based carbon aerogels (RF-CAs) are the

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5 popular used electrodes as their non-toxicity, highly accessible channels and high

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6 chemical stability [19-27]. Among them, RF-CAs have many excellent properties for

7 the advanced energy storage applications: (1) the high surface area provides more ion

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8 adsorption for the formation of electrical double-layer as well as achieve the high

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9 mass loading of sulfur for Li-S batteries, resulting in the enhanced energy storage; (2)
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10 the 3D interconnected porous structure can provide continuous unobstructed

11 transportation channels for electrolyte ions and accordingly improve the effective
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12 electrochemical utilization of carbon aerogels; (3) the high electrical conductivity can
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13 promote fast transportation of charges, which is essential for high power performances.
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14 In addition, compare with 1D and 2D structures (carbon nanotube, carbon fiber and

15 graphene, etc.), the hierarchical 3D architecture of RF-CAs can be considered as

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16 effectively building blocks to achieve the high mass loading of active materials
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17 (conductive polymers, transition metal oxides/hydroxides, sulfur, etc.), which can

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18 achieve ultrahigh energy density for rechargeable batteries. Moreover, benefiting from

19 the high mechanical strength, RF-CAs can also be consider as a good robust

20 supporting body to assemble active materials (metal oxides, conductive polymers and

21 sulfur, etc.) for developing high performance energy storage devices such as LIBs and

22 Li-S batteries and Na-ion batteries. Based on the above mentioned characteristics,

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1 RF-CAs have been considered as an extremely promising candidate for energy

2 storage applications. Since Pekala’s research in 1989 [28], researchers have spent a

3 great efforts on the preparations of RF-CAs and their applications in SCs, LIBs, Li-S

4 batteries and Na-ion batteries, etc. [29-35]. However, the relationship between

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5 structure and property is still not fully understood.

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6 Thus, this article provides an overview on the recent progress on RF-CAs for

7 advanced energy storage devices, particularly discussed the effects of related synthetic

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8 parameters (eg. precursor, catalyst, drying, carbonization and activation) on the

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9 morphology and surface chemistry of RF-CAs. The relationship between structure
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10 (pore structure, conductivity and heteroatoms doping) and electrochemical

11 capacitance is built, which is advantageous for designing advanced carbon aerogels

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12 with maximized electrochemical performance. In addition, the electrode fabrication of

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13 RF-CAs with metal oxide or conductive polymers to achieve excellent performances

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14 is proposed. Furthermore, the RF-CAs’ applications towards other advanced energy

15 storage devices, such as LIBs, Na-ion batteries and Li-S batteries are also mentioned.
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16 And lastly, the structure optimization for the next generation of RF-CAs has been
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17 given in this review as well.

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18 2. Synthetic strategies for RF-CAs

19 As shown in Fig. 2, the traditional synthesis route of RF-CAs can be divided into

20 three steps (sol-gel, drying and carbonization).

21 During the sol-gel process, a resorcinol-formaldehyde organic gel is prepared by

22 the polymerization of resorcinol and formaldehyde under the existence of catalyst.

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1 Ascribed to the phase separation caused by drying method (eg. drying at room

2 temperature [36], solvent exchange [37], freeze-drying or supercritical drying [38],

3 [39], [40] etc.), a fluffy aerogel is obtained. At the final stage, a carbon aerogel with

4 three-dimensional structure is obtained by carbonization with different heat-treatment

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5 temperatures in an inert atmosphere (N2 or Ar) [35, 41-43]. In addition, the pore

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6 structure of RF-CAs can be further improved by activation [25, 44, 45]. During the

7 above-mentioned process, the textural features of RF-CAs (e.g. morphology, porosity,

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8 conductivity and surface chemistry) greatly depend on the preparation conditions (eg.

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9 precursor, catalyst, drying method, carbonization and activation etc.). In this section,
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10 we will systematically discuss the effects of preparation parameters on the pore

11 structure and build the relationship between structure and factors, which can be
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12 referred for designing advanced carbon aerogels with desired performance.

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13 2.1. Precursors and catalysts during sol-gel process

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14 The traditional organic aerogels are prepared using phenols and formaldehydes

15 as raw materials. Pekala et al. firstly designed a novel organic aerogel by the sol-gel
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16 polymerization of resorcinol with formaldehyde under alkaline conditions [28]. The

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17 obtained materials comprised of interconnected pores with diameters of 7-10 nm and

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18 cell sizes less than 100 nm. Phenol can also be adopted as precursor under acid

19 conditions. Compared with resorcinol, only one hydroxyl on phenol can take part in

20 the polymerization of formaldehyde, resulting in the longer sol-gel time [46, 47]. The

21 carbon aerogels can be successfully prepared by melamine. The melamine-resorcinol

22 (MF) aerogels have more stable and robust networks than RF aerogels because of

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1 multistep reactions in the MF system [48, 49]. In addition, the MF carbon aerogel

2 contains large numbers of nitrogenous functional groups (～11 wt%) [50]. The

3 nitrogen in melamine can make a positive effect on the electrochemical performance

4 of SCs, which can provide pseudocapacitance caused by reversible

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5 oxidation-reduction reactions and long cyclic stability contributing from the improved

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6 wettability and electronic conductivity [51-53]. As gel obtained in RF system needs a

7 time-consuming solvent exchange step because of the existence of water in the gel

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8 matrix, which is not being suitable for supercritical or freeze drying. Phloroglucinol

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9 can be a promising candidate as a carbon precursor because of its alcohol-soluble
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10 characteristic [54]. The drying procedure thus can be simplified. In addition, the

11 material obtained in phloroglucinol-formaldehyde exhibited a shorter sol-gel time

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12 than that of achieved in phenol and resorcinol system, which is caused by the faster
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13 reacts due to the higher electron density in the 1,3,5 position of benzene ring [55].
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14 When phloroglucinol was used as carbon monomers, the gel was formed at room

15 temperature within tens of minutes [56]. Nowadays, the selection of RF-CAs’ raw
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16 materials is prone to be low price, nontoxic and environment-friendly.

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17 During the sol-gel process, the size of colloid particles is affected by the amount
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18 and type of catalyst. A higher amount of catalyst can form more primary clusters due

19 to the enhanced addition reaction rate between formaldehyde and resorcinol. At the

20 same time, the cross-linking processes are facilitated under the low R/C condition

21 (high amount of catalyst), leading to smaller pore sizes in the carbon aerogel.

22 Particularly noteworthy is that the average pore size and total pore volume showed a

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1 tendency to increase with an increase in the R/C ratio [57].

2 Catalysts in synthesis of RF-CAs can be mainly divided into acidic (HCl, H3BO3

3 and C6H5B(OH)2, etc.) [25, 58], basic groups (NaOH, KOH, NH3, LiOH, Ca(OH)2

4 and Mg(OH)2, etc.) [59, 60] and metal salts (Na2CO3, K2CO3, Zn(CH3COO)2, etc.)

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5 [61, 62]. The catalyst is mainly used to maintain a suitable pH value which is the rate

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6 determining step of creating an intermediate chelated form [63]. It was found that

7 metal valence and cation radius of catalysts are key factors to the sol-gel time and the

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8 structure of RF-CAs. Divalent cations are responsible for faster formaldehyde

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9 consumption than monovalent [60]. Meanwhile, the oligomers are less soluble when
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10 catalyst with larger cations, leading to large clusters and increased pore sizes, such as

11 the as-obtained samples using Ce and Mg cations as catalyst results in a larger pore
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12 size compared with Li+ and Na+ catalyzed aerogel [64, 65]. In addition, some novel
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13 catalysts have also been adopted to obtain RF-CAs. Chang et al. used nano γ-Fe2O3
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14 served as a template and graphitized catalyst precursor as well as activation promoting

15 agent to prepare porous aerogels. The obtained carbon materials possessed a highly
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16 graphitized carbon framework and a superior hierarchical porous structure (SBET=

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17 2235.1 m2/g) [66]. Graphene Oxide (GO) sheet can be used as catalyst as it contains
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18 large amounts of hydroxyl, carboxyl, carbonyl and other hydrophilic functional

19 groups, which can be crosslinked with resorcinol-formaldehyde clusters to form a

20 network structure [67]. Guo et al. incorporated graphene oxide (GO) into the RF

21 matrix to prepare aerogels. GO can obviously reduce the gelation time of the RF

22 solution and prevent aerogel shrinkage during the drying process. When the GO

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1 content arrived at 1 wt%, the gelation time decreased from 164 to 93 min (Fig. 3a).

2 When the GO content increased from 0 to 2 wt%, both the linear shrinkage and

3 density of aerogels decreased from 28.3% to 2.0% and 506 to 195 kg/m3, respectively

4 (Fig. 3b) [68]. At present, Zhao et al. developed a facile synthesis of highly

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5 monodisperse carbon aerogel spheres prepared by the polymerization of

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6 3-aminophenol and formaldehyde without using any catalyst. The raw material

7 (3-amoniaphenol) can not only to participate in the polymerization to form the

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8 structure of polybenzoxazine but also to catalyze the polymerization [69]. This

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9 method was low cost, environmentally friendly and suitable to the large-scale
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10 production of RF-CAS.

11 2.2. Drying
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12 Drying process is a crucial step to make a fluffy aerogel because it determines

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13 the micro-structure of the final product. In 2002, Lee et al. explored atmospheric
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14 drying process [36]. However, the network usually shrinks and even collapses because

15 of the strong capillary forces between the interface of the internal solvent and the
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16 network. To address this problem, some researchers replace initial solvent by low
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17 surface tension organic solvents, such as ethanol, acetone, and isopropanol, etc. [70].
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18 However, the long period and toxic organic solvents limit their amplification

19 production. Freeze-drying can effectively eliminate the influence of capillary force

20 where the solvent in the gel will be frozen and removed from the network by

21 sublimation, resulting in a well retained structure. However, the formation of solvent

22 crystal will cause damage to the network of gel. As the elimination of capillary or

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1 crystallization forces by CO2 supercritical drying, a well-defined network can be

2 obtained (Fig. 4) [71].

3 The removal of water from gels will cause the shrinkage of the structure, which

4 limits their large-scale industrial setting. To produce RF-CAs with the desired

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5 mechanical properties, some researchers attempted to combine the aerogel with some

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6 flexible carbons, such as carbon nanotube (CNT) [72], graphene [73] and carbon fiber

7 [74] etc. By mixing CNT with resorcinol-formaldehyde precursor, the polymerization

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8 occurs on the walls of the CNT bundles and an organic binder forms at the junctions

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9 between adjacent bundles. The obtained materials are approximately twelve and three
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10 times stiffer than conventional silica and CAs, respectively [75]. Graphene oxide (GO)

11 is an effective additive for strengthening the nanostructure and suppressing the

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12 collapse of nanopores during the drying process. During the sol-gel process, GO can
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13 obviously accelerate the gelation of the precursor solution and reduce the drying
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14 shrinkage and aerogel density [68]. Carbon fiber could be used as the structural

15 support and 3D reinforcement because of its high porosity, low thermal conductivity
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16 and high temperature capability. Wang et al. prepared a lightweight organic

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17 aerogel-impregnated low-density carbon/carbon composite (RF-C/C) with carbon

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18 fiber as substrate and resorcinol-furfural aerogel as infiltrant. The as prepared RF-C/C

19 possessed low densities of 0.26-0.37 g/cm3, relatively high compressive strength,

20 ranging from 0.45 to 3.27 MPa at room temperature [76]. Feng et al. used oxidized

21 polyacrylonitrile (PAN) fibers as soft reinforcements to prepare an organic

22 fiber-reinforced organic aerogel composite. The three point bend strength of the

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1 C/CAs is 7.1 +1.7 MPa [77]. Metal ions (such as Co2+, Ni2+ and Mo6+ , etc.) are also

2 effective additives for enhancing the strength of RF-CAs’ structure [78-81]. They can

3 act as cross-linkers for assembling clusters into 3D porous gels and substitute the

4 traditional catalysts (Na2CO3) used for the polymerization of resorcinol and

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5 formaldehyde. Yu et al. prepared a resorcinol–formaldehyde/graphene oxide

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6 composite aerogels with CoCl2·6H2O as additive. The aerogels can tolerate a strain as

7 high as 80% and quickly recover their original morphology after the released

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8 compression. The maximum degradation under compressive stress is smaller than 10%

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9 after 100 cycles, and the plastic deformation is only approximately 11.4% after
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10 fatigue testing (Fig. 5) [82]. As seen in the above examples, the additive-to-aerogel

11 can be linked by covalent or noncovalent. These methods can effectively enhance the
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12 strength of RF-CAs, which is beneficial for rigors applications.

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13 2.3. Carbonization
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14 As aerogel contains a large amount of moisture and organic components, the

15 as-obtained material possesses low SSA and high electrical resistivity, which limits
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16 their application in supercapacitor. The pyrolysis process eliminates volatile materials

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17 and promotes the formation of conjugated sp2-carbon atoms, which can be a

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18 promising method to increase surface area and improve electrical conductivity. When

19 aerogel is decomposed under inert gas, the thermal decomposition behavior can be

20 divided into four stages. The first step (25 to 200 oC) relates to endothermic

21 evaporation of water in the composites [83]. When the temperature increases from

22 200 to 1000 oC, the decomposition corresponds to the pyrolysis of phenolic hydroxyl

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1 group, methylene, diphenyl ether, and other oxygen-containing functional groups

2 [84-86]. With the continuously increasing of temperature from 600 to 1000 oC, the

3 pyrolysis behavior attributes to the carbonization stage which mainly involves the

4 decomposition of amino and hydroxyl groups and the dehydrogenation. Above 1000

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5 C, the small weight loss is ascribed to the arrangements of carbon structure

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6 accompanied by minute quantities of volatile components escaping from carbon

7 skeletons [87]. The textural features (e.g. morphology, porosity, conductivity and

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8 surface chemistry) are closely determined by the carbonization conditions (e.g.

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9 carbonization temperature, heating rate, constant time, and finishing temperature). For
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10 example, the material carbonized under 500 oC exhibits a low SSA of 649 m2/g, while

11 the SSA increases to 1344 m2/g at the pyrolysis temperature of 900 oC [88]. Currently,
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12 Hasegawa et al. find that disordered graphene fragments smaller than 1-2 nm
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13 distributed on aerogel treated at low carbonized temperature. After the temperature

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14 elevated to 2000 oC, the layered structure evolved into embowed layers composed of

15 5 graphene stacking [89]. The produced sp2 carbons can effectively boost
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16 ion/electrons quickly transfer the interfaces between the electrodes and electrolyte. In
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17 terms of heating rate, a lower heating rate leads to a high SSA, while higher heating
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18 rates results in a lower variability of pore textures. For example, with the heating rate

19 increasing from 2.5 to 5 oC/min during carbonization, the SSA of the carbon aerogels

20 decreases from 1292 to 974 m2/g and the bulk densities of samples increase from 0.15

21 ~ 0.22 g/cm3 to 0.17 ~ 0.31g/cm3 [90]. However, one-step carbonization usually has a

22 low SSA of about 1000 m2/g. Currently, activation can be an efficient approach to

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1 enhance the SSA and adjust pore size distributions by mixing carbon or carbon

2 precursors with activators (CO2, KOH, K2CO3, ZnCl2 and H3PO4, etc.) under elevated

3 temperature.

4 2.4. Activation

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5 Activation, including chemical and physical activations, is an effective method to

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6 improve the texture of RF-CAs [91]. Physical activation is generally divided into two

7 steps. The raw material is firstly carbonized under proper temperature (below 1000

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8 C), then activated by gas (steam and CO2, etc.) under elevated temperature. At higher

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9 temperature, C atoms in the carbon skeleton can react with activators and release CO,
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10 H2 or CO2, forming a mico/meso/macroporous structure. The carbonized material

11 possesses a low SSA of 857 m2/g and pore volume of 0.53 cm3/g. Due to the presence
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12 of abundant macropores and robust skeleton, the CO2 can easily get access to the
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13 inner pore channels without the collapse of the network. After CO2 activation, both of
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14 the SSA and pore volume dramatically increase up to 1801 m2/g and 1.30 cm3/g,

15 which is 2 times higher than that of unactivated carbon aerogel. Usually, CO2
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16 activated samples have pore size predominantly ranging from 0.6 to 2 nm

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17 significantly wider than that of un-activated samples (mainly in 0.6 nm) [41].
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18 Christine et al. also designed carbon aerogel with a high SSA of 2213 m2/g and a high

19 pore volume of 2.21 cm3/g by CO2 activation, which is higher than those of carbon

20 aerogel obtained by one-step carbonization [92]. M. Godino-Ojer et al. prepared a

21 series of metal-doped monolithic organic aerogels after carbonized under 1000 oC.

22 Because carbon dioxide is a mild activator, the coral-like structure is preserved along

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1 the activation processes [78]. The physical activation temperature and activation time

2 are higher and longer than that of chemical activation, resulting in the higher energy

3 consumption and cost.

4 The chemical activation process is composed of contacting a carbonaceous

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5 precursor with chemical reagents, followed by a heat treatment stage [93-95].

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6 Chemical activation offers well-known advantages over physical activation, such as

7 low activation temperature, high activation yield and ultrahigh SSA. The use of

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8 activating reagents, including KOH [96], K2CO3 [97], and H3PO4 [98] etc., has been

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9 reported previously. It is well-known that strong alkali reagents are effective chemical
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10 activators owing to its strong etching reactions and a well-defined microporous

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11 distribution. When the activation temperature is higher than 750 C, the
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12 decomposition of alkali reagents produces CO2 and K2O [97]. With the chemical
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13 reactions between K2O and carbon and the continuous etching of CO2, micropores can
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14 be introduced. And, another parts of alkali reagents can directly react with carbon to

15 produce K2CO3, H2 and other complex compounds [99]. The carbon skeleton is
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16 continuously etched by these reaction products, making contributions to the total

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17 surface area. Recently, Li et al. synthesized graphene/resin-derived carbon composite

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18 (GRDC) by polymerization of 2, 4-dihydroxy benzoic acid and formaldehyde in the

19 presence of KOH, followed by carbonization in N2 atmosphere. During the

20 preparation, K+ ion can exchange with H+ in the carboxyl groups, leading to atomic

21 dispersion of K+ ions in the bulk of GO/phenolic resin composite. During the

22 following carbonization step, the high dispersion of K+ ions results in homogeneous

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1 and efficient chemical activation. The as-prepared aerogel possesses a humble surface

2 area of 2034 m2/g and a total pore volume of 1.78 cm3/g (Fig. 6) [96].

3 Moreover, alkali activator usually contains high oxygen content, which leads to

4 large numbers of oxygen exist in products. Oxygen retards the transition from

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5 amorphous to graphitized structure and is considered as the electrochemically

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6 unstable surface oxygen groups due to the occurrence of irreversible redox reactions

7 during the long-term cycle [100, 101]. NH3 activation can be a promising method

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8 because of large SSA for amounts of accessible active sites, highly graphitization for

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9 excellent electrical conductivity [102-104]. A prolonged NH3 activation process
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10 results in carbon aerogel with a high surface area of 1458 m2/g, which is 2 times of

11 unactivated carbon (724 m2/g). The activated sample shows the micropore volume of
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12 0.76 cm3/g [105].

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13 During activation process, ZnCl2 has double effects: (i) ZnCl2 can serve as a
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14 dehydration agent under the heat treatment process. A porous structure can be

15 obtained as the removal of hydrogen and oxygen in the form of water vapor. (ii) ZnCl2
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16 can serve as a salt template. ZnCl2 can be added into carbon precursors during sol-gel
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17 process. Large numbers of mesopores are produced after the removal of ZnCl2 by
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18 evaporation under temperature and acid washing. Ling et al. prepared hierarchical

19 porous carbons through a sol–gel polymerization process followed in-situ chemical

20 activation during carbonization. ZnCl2 could also act as an in-situ activation agent

21 during the carbonization process to generate large SSA of 1106 m2/g and pore volume

22 of 1.2 cm3/g. In addition, the proportion of mesorpore is up to 66%. Large amounts of

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1 appropriate pores are produced by the homogeneous and continuous in-situ activation

2 in the polymer frameworks during carbonization process [106]. However, ZnCl2

3 mainly enables the generation of abundant mesopores during carbonization process,

4 causing a lower SSA than that of samples activated by KOH and CO2. Some chemical

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5 activators are corrosive to the equipment and detrimental to the ecological

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6 environment. In addition, the residual chemical activator is difficult removed, which

7 seriously affects the electrochemical performance of prepared materials. As H3PO4

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8 can form a large number of soluble phosphates, H3PO4 hence can be used as an ideal

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9 chemical activator compared with ZnCl2 and KOH. Currently, Yang et al. proposed a
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10 method to prepare a kind of mesoporous activated carbon aerogel (MACA) based on

11 the pore formation and widening effect of H3PO4. H3PO4 not only acts as a porogen to
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12 introduce micropores onto the nano-framework, but also produces mesopores by

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13 continuously etching the as-obtained micropores, resulting in a high meso-porosity.

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14 The as-prepared MACA demonstrates a high SSA of 2161 m2/g with an extremely

15 high mesopore ratio of 92 % [107]. Zhou et al. reported a process for the preparation
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16 of spherical activated carbons (SACs) with much improved textural properties using
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17 H3PO4 activation. SACs possess a high surface area of 2729 m2/g and a large total
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18 pore volume of 1.529 cm3/ g [108].

19 Activator with multiple functions should be focused during the preparation

20 process. For example, carbon aerogel has been developed via a polymerization of

21 phenol and formaldehyde under the existence of ZnCl2 salt by Yu et al. [109]. ZnCl2

22 serves as dehydration agent, foaming agent, as well as porogen, which obviously

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1 simplifies activation process and realizes in-situ activation. The obtained carbon

2 aerogels exhibit very low density (25 mg/cm3), high SSA (1340 m2/g) and a large

3 micro/mesopore volume (0.75 cm3/g). Besides, K2CO3 shows triple functionalities:

4 catalyst, shape-directing agent and in-situ activator during the preparation process.

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5 Through adjusting the salt amount, the microstructure of the carbon aerogel is tuned

from micro- to mesoporous material with apparent SSA up to 4568.9 m2/g and pore

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6

7 volume up to 4.92 cm3/g, respectively (Fig. 7) [97]. In addition, NH3 [110, 111],

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8 H3PO4 can serve as both activators and doping agents (N, P). For example, Yi et al.

U
9 prepared a modified carbon aerogel with NH3 as the activating agent. The obtained
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10 structure has a large SSA (2600 m2/g) and high content of N dopants (3.12 at.%) [111].

11 The multiple functions of activator can not only simplify the preparation process but
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12 also improve the electrochemical performance.

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13 3. Applications in SCs
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14 The energy storage mechanisms of SCs can be divided into two categories:

15 electrochemical double layer capacitors (EDLCs) and psedocapacitors (Fig. 8) [112].

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16 For EDLCs, capacitance derives from the electrostatic charge accumulated at the
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17 interface between the electrode and electrolyte, which strongly relies on the SSA and
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18 conductivity of electrodes [113]. With high SSA and electrical conductivity, RF-CAs

19 can be directly assembled as electrodes for SCs. The specific capacitance of carbon

20 aerogels is various from 120–240 F/g [114-116]. For pseudocapacitors, the

21 pseudocapacitance is generated from the quick and reversible Faradic redox reactions

22 on the surface of electrode. Compared with conventional activated carbons, carbon

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1 aerogels usually contain certain of heteroatoms-containing functional groups (oxygen,

2 nitrogen and sulfur, etc.), which can increase the specific capacitance by the

3 additional pseudo-capacitance and improved wettability [51, 117-119]. Conductive

4 polymers and transition metal oxides/hydroxides are widely used as the electrodes of

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5 pseudocapacitor. The mechanical degradation and poor cycling stability resulting from

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6 faradaic process still hinder their further applications as electrodes [120-122].

7 Benefiting from the high mechanical strength, carbon aerogels can be consider as a

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8 good robust supporting body, which can directly serve as conductive supports to

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9 assemble metal oxides or conductive polymers for developing high performance
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10 pseudocapacitor. The pseudocapacitance can arrive at 1010 F/g with excellent cyclic

11 stability [123].
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12 3.1. RF-CAs directly used for SCs

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13 A detailed discussion about the effect of structure (pore structure, conductivity

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14 and heteroatom doping) on electrochemical property is elaborated below.

15 3.1.1. Pore structure

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16 Table 1 shows the SSA (285-1454 m2/g) and the specific capacitance (35-269 F/g
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17 in three-electrode system and 9.1-151.85 F/g in two-electrode system) of the RF-CAs

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18 synthesized by one step carbonization. Micropores (pore diameter < 2 nm) are critical

19 for the maxiumization of cappacitance due to large numbers of desolvated electrolyte

20 ions entering the micropores [124]. For example, carbon aerogel microsphere

21 carbonized at 1000 °C possesses a homogeneous particle size of 1 um, a SSA of 1454

22 m2/g, a large microporous content of 63%, and a relatively narrow microporous size

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1 distribution mainly located below 1.0 nm. The well-developed porous structure and

2 the short ion diffusion path inside microspheres are conductive to forming the

3 efficient electric double layer and achieving fast charge/discharge. They delivered a

4 higher energy density of 38.4 Wh/kg at a power density of 0.17 kW/kg, a good rate

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5 capability ( the energy density can retain 25.5 Wh/kg even at a high power density of

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6 10.2 kW/kg), and excellent cycling stability (the capacitance loss of 16% can be

7 achieved after 10,000 cycles) [87]. Activation is an effective method to improve the

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8 pore structure and electrochemical property of RF-CAs (Table 2) [125]. An organic

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9 polymer microsphere is developed based on the copolymerization of resorcinol and
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10 formaldehyde. KOH activation is further employed to develop the porous texture of

11 carbon microspheres without sacrificing the spherical morphology. The activated

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12 sample exhibits homogeneous particle size of 80 nm, and high SSA of 1528 m2/g,
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13 with pore size predominantly ranging from 0.7-2 nm. When used as the electrode
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14 materials for SCs, the activated carbon microsphere shows a high capacitance up to

15 186 F/g, without much degradation even with 200 time increase of the current density
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16 [114]. The CO2 activated carbon aerogels obtained by Liu et al. have a high SSA of
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17 3431 m2/g with the micropores proportion of 79% and the average pore diameter of
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18 2.08 nm. And, specific capacitances are three times higher than that of the raw carbon

19 aerogels [126]. In addition, carbon aerogel fabricated by Chang et al. shows a surface

20 area of 3419 m2 /g and a SMicro of 1987 m2/g. The specific capacitance can be up to

21 324.8 F/g in 0.5 M H2SO4 aqueous solution at 1 A/g for potential window of 0-1 V. In

22 comparsion, sample without CO2 activation displays a similar morphology. However,

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1 its SSA and specific capacitance are reduced considerably to 449 m2/g and 34.7 F/g,

2 respectively [25]. However, the materials with high SSA do not always show good

3 capacitance. Ultrahigh specific surface area will produce a large number of void holes

4 (dead holes) and ultra-micropore (pore diameter <0.7 nm). These pores fail in the

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5 formation of the electrical double-layer and hinder ion transfer into the interface of

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6 electrode and electrolyte, which increase ion diffusion resistance, leading to poor

7 power performance at high discharge rate. For example, with the a SSA of 2796 m2/g,

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8 the specific capacitance of carbon xerogels is 181 F/g at 10 mV/s. However, the

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9 carbon xerogel with the specific surface area of 1139 m2/g has a larger specific
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10 capacitance of 211 F/g at the same scan rate [127].

11 Besides micropres, mesopores (pore diameter 2-50 nm) can offer ample
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12 accessible channels to facilitate the diffusion of ions, leading to a long cycle stability
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13 [72]. Currently, a mesopore dominant activated carbon aerogel (ACA-P) was obtained
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14 by Li et al. using H3PO4 as the porogen. The obtained aerogel presents a much larger

15 SSA of 2477 m2/ g than that of raw material (635 m2/g), while simultaneously keeping
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16 an extremely developed Vmes% of 99%. Compared with commercial AC-YP (161 F/g
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17 and 74%)，ACA-P shows much higher capacitance of 201 F/g with capacitance
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18 retention of 90% when the current density expands 50 times [128]. Utilizing

19 templates to introduce well-defined micro/mesopores to carbon aerogel is very

20 meaningful for the precise control on pore structure of RF-CAs. The micro/mesopores

21 can efficiently increase the charge storage and enhance the penetration of electrolyte

22 [72]. In 2009, monolithic carbon aerogels were prepared through a PPO-PEO-PPO

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1 block copolymer assisted route by Gutierrez et al. With PPO15-PEO22-PPO15 as

2 templates, carbon aerogel monoliths have a 3D continuous macroporous network built

3 of sintered microporous carbon colloids at nanometer dimensions (ca. 100–200 nm).

4 As the macropores allow the electrolyte easily transport to carbon colloids and the

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5 nanometer dimensions of the colloids favor the electrolyte accessibility to the whole

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6 micropore area, the resulting carbon aerogel monoliths exhibits a remarkably high

7 specific capacitance of 180 and 225 F/g in the electrolyte KOH and H2SO4,

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8 respectively [129]. In addition, a commercial triblock copolymer F127 (PEO106–

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9 PPO70–PEO106) was adopted as template to prepare aerogels. The block copolymer
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10 surfactant will form hydrogen-bonding networks with polymeric precursors

11 containing hydroxyl groups. The Vtot (0.29 cm3/g), Vmeso (0.02 cm3/g) and D
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12 (average pore diameter, 1.9 nm) of raw aerogel are smaller than that of samples with
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13 F127. When the content of F127 is 0.6 wt%, the Vtot (0.90 cm3/g), Vmeso (0.77
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14 cm3/g) and D (average pore diameter, 6.1 nm) are achieved. Its mesoporosity is up to

15 about 86% in total volume, which is an order of magnitude over that of raw aerogel.
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16 The specific capacitance of CA with 0.6% F127 electrode is approximately 130.8 F/g
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17 in 4 M KOH, which is 45% higher than that of aerogel solely catalyzed by Mg(OH)2.
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18 The high specific capacitance is associated with its enhanced mesoporosity as well as

19 the high pore volume [130]. Currently, Liu et al. reported an ordered mesoporous

20 carbon and graphene aerogel (OMC/GA). During the self-assembly process, GA is

21 used as a macroporous substrate, resol as a carbon precursor, pre-hydrolyzed TEOS as

22 an inorganic precursor, and tri-block copolymer F127 as a soft template. The

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1 monolithic OMC/GA possesses 3D interconnected macropores, ordered mesopores

2 with the size of 5 nm, a surface area of 715 m2/g and pore volume of 0.99 cm3/g.

3 When used as electrodes, OMC/GA shows outstanding specific capacitance (177 F/g

4 at 5 mV/s) and excellent cycling stability (only 7% capacitance loss after 10 000

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5 cycles). Such excellent electrochemical performance can be ascribed to a synergistic

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6 effect of highly conductive macroporous aerogel and mesoporous carbons with high

7 surface area (Fig. 9) [131]. Table 2 summarized some works on the regulating

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8 porosity of RF-CAs with activation method. The electrochemical properties are

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9 obviously enhanced due to the improvment of SSA and pore volume.
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10 3.1.2. Electrical conductivity

11 The electronic conductivity of RF-CAs plays a key role in their electrochemical

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12 performances, such as energy density, charge transfer resistance, cyclic stability, and
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13 energy efficiency. The electronic conductivity is closely related to their synthesis

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14 parameters, defect sites and edge sites, etc. Some researchers found that the electrical

15 conductivity increases with the increasing of density of samples [132][133]. With

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16 increasing mass density, the particle size maintains constant, but the packing ratio of
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17 these particles increases while the mesopores that scaffold the distance between
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18 chains of interconnected particles decreases. Therefore, the more closely packing the

19 conducting grains, the higher the electronic conductivity of carbon aerogels. The

20 improved electronic conductivity brings a better cyclic performance. During the

21 heat-treatment stage, the carbon aerogel carbonized under low temperature (～600 oC)

22 is an type of amorphous carbon with sp3 hybridization configuration, which exists

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1 large numbers of disorder and defects in the carbon [134]. The disorder and defects in

2 the carbon skeleton hinder the electron transfer, leading to a low electronic

3 conductivity. Moreover, the defects and a large degree of disorder do a severe damage

4 to the rate performance of RF-CAs. The thermal annealing of carbon aerogels at

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5 elevated temperature is an effective post-treatment approach to control defect

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6 reconstruction in carbon skeleton. For example, the carbon aerogel carbonized below

7 650 oC was almost electrically non-conductive, while the electrical conductivity

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8 increased to 50 S/cm when the pyrolysis temperature reached 1200 oC [135]. This is

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9 due to the removal of residual organic materials and the decrease of the disorder and
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10 defects through the boundary between particles. The RF-CAs carbonized under 600

o
11 C shows a low conductivity of 0.031 S/cm. As the heat-treatment temperature
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12 increases from 600 to 1600 °C, the value of ID/IG decreased from 1.25 to 1.45 along
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13 with the emergence of an ordered structure with uniform orientation and a lattice
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14 spacing of 0.333 nm, indicating the elimination of dislocations and defects. Thus, the

15 conductivity of carbon aerogel sharply increases to 250 S/cm. The good conductivity
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16 is beneficial to facilitate the electron transfer in electrolytes. The aerogel carbonized

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17 under 1600 oC has the lower relaxation time of 0.38 s (the minimum time needed to
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18 discharge all the energy from the device with an efficiency of more than 50% [136])

19 than that of PR-0.1-600 (0.69 s) [87]. However, this method needs higher elevated

20 temperature, leading to high energy consumption. Moreover, the issues such as

21 smaller surface area and lower yield can’t be ignored.

22 Some additives (e.g. Fe, Co, Ni, and TiO2 etc.) can decrease the disorder and

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1 defects and accelerate the transformation of hydrocarbons into graphitic

2 nanostructures at low temperature [137]. This method, named catalytic graphitization,

3 not only reduces energy loss but increase the charge transfer capability. In the

4 presence of Co or Ni particles, the growth of graphitic nanoribbons with variable

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5 curvature was observed when carbon aerogels were pyrolyzed at 1050 oC [138].

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6 Huang et al. reported porous carbons with graphitic structures using Ni as

7 graphitization catalyst. The graphitic structures in materials can be obtained at low

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8 pyrolysis temperature of 800 oC, which is much lower than the high graphitization

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9 temperature of 2000 oC [139].Thereafter, carbon aerogels with a graphitic framework
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10 have been observed by the carbonization of polymeric monoliths of

11 poly(benzoxazine-co-resol) using Fe, Ni or Co as catalyst. The resulting carbon

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12 monoliths contain a large proportion of graphitic carbon (> 50 wt %), which

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13 considerably improves their electrical conductivity (from 1.5 S/cm for the carbon
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14 monolith up to 6.4 S/cm for the Ni-graphitized carbon monolith). Those material, as

15 supercapacitor electrodes in organic electrolyte (1 M TEABF4/AC), shows a good

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16 capacitance retention combined with a lower IR drop [140]. Based on that, Karthik
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17 and co-workers et al. prepared graphitized macro-mesoporous carbon (GMMC) foam

AC

18 using iron as catalyst at low heat-treatment temperature. A sharp diffraction peak of

19 (002) in XRD pattern and strong Raman intensities of G and G0 bands indicates a high

20 graphitic character. The conductivity of GMMC at room temperature is 11 S/cm,

21 which is 30 times higher than that of amorphous macro-mesoporous carbon [134] (Fig.

22 10). TiO2 particles were able to catalyze the partial graphitization structure of the

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1 RF-CAs. TiO2-mounted carbon aerogels were synthesized via the sol–gel

2 polymerization of a mixture of resorcinol, formaldehyde and TiO2, followed by

3 carbonization in N2 atmosphere. Compared with sample without TiO2 (CA0), the

4 mesopore volume, total pore volume and average pore size of the prepared sample are

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5 increased by 95, 188, and 176 %, respectively. TiO2 mounted aerogels have more

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6 stable electrochemical properties and less internal resistance in 30 % KOH aqueous

7 solution than CA0. Moreover, the TiO2 in the structure does not take part in the redox

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8 reaction [141].

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9 Different from 0 D and 2 D materials (carbon nanotubes, graphene and graphene
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10 oxide) with simple structure and abundant body and edge defects，there are few

11 related defects on the carbon skeleton of RF-CAs. In addition, the 3 D structure of

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12 RF-CAs formed by the polymer polymerization of resorcinol and formaldehyde is

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13 rather complicated, which takes a great quantity time to build the corresponding
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14 models to interpret the affection of defects on the electrochemical performance. Thus,

15 the way of the defects on the carbon aerogel skeleton affecting the electrical
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16 conductivity of materials is still unclear.

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17 As previous works report that defects in carbons can also bring the different
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18 number of occupied electrons of the majority and minority-spin; those spin electrons

19 contributes high activity in chemical reactions [142]. In addition, the edge sites in the

20 carbons resembling a linked row of vacancy defects could generate a large variety of

21 localized spin electrons, which can promote the chemical reactivity. Thus, researchers

22 introduce defects into the carbon skeleton to improve the electronic structure of

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1 carbon nanomaterials and modify the chemisorption of the key intermediates, which

2 could effectively enhance kinetics for an improved performance. Heteroatom doping

3 can be considered as one of the most widely used methods, which will be further

4 discussed in details in 3. 1. 3.

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5 In addition, carbon materials with good electrical conductivity (such as graphene,

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6 carbon nanotubes, and carbon paper, etc.) can be used as additives to connect with the

7 framework of RF-CAs to form macroscopic blocks, which can greatly enhance the

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8 overall electron mobility. Wang and co-workers et al. prepared carbon cloth reinforced

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9 RF aerogel films with no catalyst. The electrical in plane conductivity for the carbon
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10 cloth reinforced aerogel films is 21 S/cm, which is about 50% larger than that of pure

11 aerogel film [143]. Then, Tao et al. fabricated a series of conductive and mesoporous
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12 single-wall carbon nanohorn/resorcinol-formaldehyde aerogel composites

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13 (SWCNH/RFA) by embedding organic resorcinol-formaldehyde aerogels with

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14 single-wall carbon nanohorns. The SWCNH/RFA shows a sharp increase of the

15 conductivity from 2.0 × 10-11 S/m for pure RF to 5.0 × 10-4 S/m for SWCNH/RFA
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16 [144]. Carbon nanotubes (CNT) possess a unique 1D carbon allotrope with structural,
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17 electrical, and thermal properties that enable efficient energy conversion [145].
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18 Worsley et al. present robust and electrical conductive CNT-based foams utilizing

19 carbon aerogel nanoparticles as the conductive binder for networks of single-walled

20 carbon nanotubes. Benefiting the ultrahigh CNT content of 50 wt.%, the SWNT-CA-2

21 shows electrical conductivity of 1.12 S/cm, which is five times more than that of pure

22 CA (0.23 S/cm) [146]. The improved electrical conductivity contributes into low

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1 resistance and small leakage current in supercapacitor. Graphene oxide (GO) has

2 functional groups in the sheet basal plane and at the edges, which could facilitate their

3 dispersion in aqueous media. Recently, Gloria et al. synthesized resorcinol

4 formaldehyde based carbon aerogels with different graphene oxide loadings from 1.2

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5 to 2.5%. Benefiting from the improved electrical conductivity, the fabricated electrode

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6 shows a specific capacitance of 120 F/g at very high scan rate of 500 mV/s as well as

7 power densities above 30 kW/kg, which is a significant improvement of 180% with

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8 respect to the pristine xerogels [147].

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9 3.1.3. Heteroatoms doping
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10 Doping chemistry of heteroatoms, such as nitrogen (N), phosphorus (P), boron

11 (B) and sulfur (S) is attractive for improving the capacitive performance by
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12 enhancement of conductivity and the additional pseudo-capacitance arising from

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13 electrochemical active sites [148].

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14 Nitrogen atoms in RF-CAs usually exhibit four types: pyridine nitrogen

15 (hydroxyl-pyridine nitrogen), pyrrolic nitrogen, quaternary nitrogen and oxide

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16 pyridine nitrogen (Fig. 11a) [149]. The contributions of nitrogen atoms to the
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17 electrochemical performance of CAs are as follows:

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18 1) The reversible redox reactions of pyridine nitrogen, hydroxyl-pyridine nitrogen

19 and pyrrolic nitrogen during the charge-discharge process provide

20 pseudo-capacitance.

21 2) The nitrogenous functional groups have good hydrophilicity, which can promote

22 the diffusion of electrolyte ions between the interface of electrode and electrolyte,

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1 and decrease the migration resistance.

2 3) Quaternary nitrogen in the carbon lattice can improve the conductivity of RF-CAs,

3 which is conducive to reducing the charge transfer resistance (Fig. 11 b) [150].

4 There are usually two ways to introduce nitrogen elements to the surface of the

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5 material: post-treatment method and in-situ method. A certain amount of nitrogen

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6 atoms can be introduced to the surface of the material by placing carbon aerogel in a

7 nitrogen rich environment for heat treatment. ZnCl2-impregnated RF resin spheres

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8 were directly carbonized in a NH3 atmosphere by Chang et al. During the one-step

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9 heat-treatment process, nitrogen atom can be efficiently incorporated into the carbon
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10 skeleton and the mount is up to 3.66%. For supercapacitor application, the N

11 functionality can improve the wettability of the carbon surface, enhance the
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12 accessibility of active surface area to the electrolyte solution and generate an

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13 additional pseudocapacitance for EDLCs. The resultant nitrogen-doped hierarchical

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14 porous carbon sphere materials exhibits a satisfactory charge storage capacity with a

15 specific capacitance of 273.8 F/g at a current density of 0.5 A /g and still maintains
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16 209.4 F/g even at a high current density of 10 A/g (Fig. 12) [110]. The unique porous
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17 structure and nitrogen-doping characteristic endue the electrode material with a

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18 potential application for high-performance SCs.

19 Given the cost and safety of post treament method, extensive reaserches have

20 focused on choosing the nitrogen-rich precursors (melamine [151], tripolycyanamide

21 [152], hexamethylenetetramine [153] ) to experience one-step carbonization process,

22 named in-situ method. Melamine is a promising candidate due to its high

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1 nitrogen contains (67% by mass). For example, Lee et al. prepared a series of

2 nitrogen-enriched carbon aerogels by a sol–gel polymerization of MRF

3 (melamine-resorcinol-formaldehyde). The aerogel shows a high specific capacitance

4 (121 F/g), due to high nitrogen contents of 5.35% and the largest amount of pyridinic

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5 nitrogen of 38.7% [154]. Recently, Zhang et al. prepared a N-doped 3D carbon

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6 aerogel utilizing bamboo cellulose nanofibers/graphene oxide hybrid aerogel as the

7 carbon precursor and melamine as the N doping agents, respectively. A nitrogen

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8 content of 6.22 atom.% is higher than that of post-treatment. The types of N could be

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9 divided into graphitic N and pyridinic N, both of which have been proven to facilitate
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10 the electron transfer in the carbon skeleton and give highly active sites in the porous

11 networks [155, 156]. Due to N-doping, the N-doped carbon aerogel exhibits excellent
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12 wettability with a water contact angle of 00. Whereas the neat CNF-derived carbon
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13 aerogel shows obvious hydrophobic characteristics with a water contact angle of

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14 about 1320. The high hydrophilicity can accelerate the infiltration of electrolytes,

15 giving rise to improved electrochemical performance. The prepared sample exhibits

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16 an excellent specific capacitance of 225 F/g at current density of 0.25 A/g as well as
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17 high energy and power densities of 31.25 Wh/kg and 12.9 kW/kg, respectively.
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18 Furthermore, after 100 compression-release cycles, the fully recovered carbon aerogel

19 still maintains great capacitive performances, indicating its superior mechanical

20 durability and electrochemical stability (Fig. 13) [31]. In comparison with the

21 post-treatment method, the in-situ method can efficiently introduce nitrogen atoms to

22 carbon skelotons by one-step carbonization, which is easy to enlarge the production

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1 for commercial supply.

2 Boron (B) is widely used as a doping element in carbon materials. It can

3 substitute carbon atoms at the trigonal sites, thereby lowers the Fermi level of the

4 solid and modifies its electronic properties [157]. B can also be present in the form of

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5 oxides, oxycarbides, and carbides, which can alter the physicochemical properties of

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6 the solids [58, 158]. These modifications can enhance the electric double layer

7 capacitance and pseudocapacitance of B doped carbon electrodes. Carbon aerogels

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8 were prepared by the carbonization of polymers formed by the polymerization of

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9 resorcinol, pyrocatechol and formaldehyde, where boric acid is used as
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10 polymerization catalysts. Carbon aerogels with heat-treated at 900 oC shows an

11 interfacial capacitance 146 F/g. Usually, the introduce of B is companied by the

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12 O-doping, which can provide the pseudo-faradaic capacitance [159]. B-doped carbon
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13 gels were prepared by the polymerization of resorcinol and formaldehyde using either
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14 boric acid or phenyl boronic acid as dopants. The hydrophobicity of the samples

15 decreased linearly with a higher B content, which is beneficial for ion transfer in the
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16 interface of electrolyte. The cryogel and vacuum-dried xerogel obtained from boric
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17 acid show high gravimetric and volumetric capacitances of around 140 F/g and 95
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18 F/cm3, respectively [58].

19 Similar to nitrogen, phosphorus (P) also has the valance electrons. Importantly,

20 phosphorus has stronger n-type behavior and electron-donating ability than nitrogen,

21 leading to a promising dopant for carbon materials. It was reported that P-doped

22 carbon shows highly stable capacitive performance because P doping in the carbon

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1 scaffold can effectively suppress the formation of electrophilic oxygen species and

2 inhibit the combustion of oxygen species (Fig. 14) [101]. Zhao et al. reported the

3 synthesis of P-incorporated ordered mesoporous carbons (P-OMCs) via a one-pot

4 aqueous self-assembly strategy. P doping suggests that a high content of P

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5 introduction may induce a deterioration of the long-range structural order. The P

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6 contents vary from 0.90 to 2.12 wt % when the atomic ratio of phosphoric to

7 resorcinol changes from 0.3 to 0.7. Incorporation of P leads to a large increase in

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8 specific capacitance, from 0.16 F/m2 to 0.28 F/m2. When the scan rate was increased

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9 from 2 to 100 mV/s, the capacitance retention of Norit carbon was only 49%, which is
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10 significantly lower than P incorporated carbons (73%) [160]. Thereafter, Daniel

11 Carriazo et al. prepared phosphate-functionalized carbon monoliths (PfCMs) using

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12 phosphoric acid as doping agent. The binding energy shown in the XPS spectrum of
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13 the PfCM exhibits the P percentage of 8 % and allowed the identification of the
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14 phosphorous species as tetra-coordinated phosphorous (V) (e.g., PO43-). The

15 voltammograms exhibit a rectangular shape and are still maintained when the voltages
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16 up to 1.4 V, which is well beyond the theoretical decomposition potential of water

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17 (1.23 V). The PfCM exhibits a lower equivalent series resistance (ESR) than the
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18 non-doping material with identical height (e.g., 2.6 versus 4.7 Ω at 63.7 mA/cm2 for

19 PfCM and non-doping material, respectively). Moreover, it is worth noting that the

20 stable cycling capacitance of PfCMs of 90% is retained over more than 10000 cycles

21 at harsh conditions (0–1.4 V and 63.7 mA/cm2) [98]. This is mainly ascribed to the

22 blockage of non-stable but electrochemically active oxidation sites (e.g., quinone

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1 groups) by phosphate groups and the minimized capacitance deterioration associated

2 with free oxygen atoms. Usually, sulfur (S) doping is preferential in polarizing

3 electron pairs and improving graphitization degree of carbons as well as introduction

4 of redox reactions, due to its large size and high chemical activity [161]. Su et al.

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5 prepared mesoporous carbon with resorcinol and thiol diphenol as the carbon and

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6 sulfur precursors. The S-doped material shows the S content of 1.49% with four types:

7 aromatic sulfide (mainly exist), sulfoxide and sulfone. S-doped sample possesses a

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8 capacitance of 24.8 uF/cm2, which is 39% higher than that of sample without sulfur.

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9 After further H2O2 treatment, the capacitance achieves a further 25% higher than
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10 S-doped carbons, which is attributed to the pseudo-capacitive properties of oxidized

11 sulfur species introduced into the carbon skeleton [162]. However, compared with
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12 nitrogen and boron doping method, there are few reports on P and S-doped carbon
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13 aerogels for SCs, which is highly desired in the future.

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14 Dual heteroatoms doping is also attractive for researchers. The co-doping of B

15 and P was investigated by Zhao et al. The simultaneous incorporation of B and P can
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16 increase the actual concentration of B and P in the materials and facilitate the
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17 formation of mesoporous structure with suppressing the framework shrinkage of

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18 carbons during pyrolysis. The obtained materials exhibits a high specific capacitance

19 of 172 F/g (approximately 1.60 and 1.94 times that of blank sample at a scan rate of 2

20 and 100 mV/s, respectively) [160]. Zhou et al. prepared a P/S co-doped porous carbon

21 derived from resorcinol and furaldehyde as precursor with the addition of phosphorus

22 pentasulfide as P and S source. The mixture experienced one-step sol-gel process

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1 followed with freeze-drying and carbonization in N2. The P/S co-doping strategy

2 could facilitate the pore size widening both in micropore and mesopore regions, and

3 also enhance the degree of graphitization of porous carbon by elimination of

4 amorphous carbon through the formation and evaporation of carbon disulfide. In

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5 terms of the single electrode, the specific capacitance of P/S co-doped porous carbon

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6 is higher 43.5% than that of pristine porous carbon. P contributed complementary

7 pseudocapacitance in organic electrolyte while S content was lower than the limit

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8 sensitivity of detectable pseudocapcitance [163].

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9 3.2. Composites based on RF-CAs for SCs
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10 Metal oxides and conductive polymers can provide ultrahigh energy density

11 through reversible faradaic reactions. However, the mechanical degradation and poor
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12 cycling stability resulting from faradaic process hinder their further applications as
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13 electrodes. It is a promising method to achieve ultrahigh energy density and long

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14 cycle life by combining metallic oxides or conductive polymers with RF-CAs. Up to

15 now, different type of materials (polymers and transition metal oxides) combined with
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16 RF-CAs, such as RuO2 [164], WO3 [32], ZnO [165], MoSe2 [166] and polyaniline
C

17 (PANI) [167] have been reported as electrode materials for supercapacitor

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18 applications (Table 3). These composites show higher specific capacitance (350-1700

19 F/g) than EDLCs.

20 For metal oxide, RuO2 is a preferred choice due to the accessibility of three

21 distinct oxidation states of ruthenium within narrow voltage range. The specific

22 capacitance of carbon aerogel was 153 F/g, RuO2 loading significantly enhanced the

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1 specific capacitance to 308 F/g for the obtained sample [164]. However, the

2 RuO2-based SCs is limited by the high cost and rareness of Ru. MnOx as promising

3 candidates for electrochemical SCs have attracted much attentions because of their

4 superior electrochemical performance, low cost, and environmentally benign nature.

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5 MnO2 with a high SSA (120 m2/g) and uniform pore-size distribution (around 5 nm)

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6 was used as an additive to prepare mesoporous MnO2/carbon aerogel composites by

7 Li et al. The mesoporous structure will optimize the electronic and ionic conductivity

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8 to minimize the total resistance. Compared with the specific capacitance of bare

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9 carbon aerogel (182 F/g), bulk MnO2/carbon aerogel exihibits much higher specific
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10 capacitance (515.5 F/g) and outstanding cyclic stability (about 97% of the first cycle

11 after 1000 cycles), indicating the potentially promising applications as

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12 high-performance supercapacitor electrode materials [168]. Different from

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13 MnO2/carbon aerogel, Mn3O4/carbon aerogel composite electrodes were prepared by

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14 a self-limiting anodic-electrochemical deposition of manganese oxide into a binder

15 enriched carbon aerogel layer and drop-cast on a graphite substrate. The specific
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16 capacitance, as measured in 0.5 M Na2SO4 shows a maximum value of 503 F/g at 25

C

17 mV/s with a negligible decay of less than 1% after 6000th cycle, implying an
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18 extraordinary cycling stability [27]. Mn3O4, growing in the form of thin nanofibers

19 along the backbone of aerogel, leaves adequate working space for electrolyte, which

20 enables a full extent of Mn3O4 utilization. Nickel cobaltite (NiCo2O4), a low-cost,

21 relatively earth-abundant and environmentally friendly transition metal oxide,

22 possesses excellent capacitive properties. NiCo2O4 with a thin nanostructure of 3–5

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1 nm nanocrystals has been deposited into carbon aerogels by Chien et al. This

2 NiCo2O4/carbon aerogel composite shows ultrahigh specific capacitances of around

3 1700 F/g at 25 mV/s within a potential window of -0.05 to 0.5 V in 1 M NaOH

4 solutions. The composite also still maintains the specific capacitances above 800 F/g

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5 at a high scan rate of 500 mV/s, and an outstanding cycling stability of a negligible

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6 2.4% decay in specific capacitances after 2000 cycles [169]. The thin nanostructure of

7 the prepared material exposed its large surface area to the electrolyte and shortened

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8 the travel distance for the charge transport. The highly porous hiarchical matrix

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9 facilites the mass transfer of the electrolyte. Esfahani et al. prepared hybrid
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10 nanostructures composed of porous Co3O4 nanoballs anchored in carbon aerogel

11 matrix. The three-dimensional structure of the carbon aerogel exhibits a high SSA of
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12 907 m2/g and mesopore volume of 4.86 cm3/g. This Co3O4 nanoball/carbon aerogel
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13 hybrid nanostructure exhibits a large specific capacitance of 350 F/g at the current
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14 density of 1 A/g in 6 M KOH electrolyte. These prominent performance

15 characteristics demonstrate the promising supercapacitor applications of the prepared

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16 hybrid nanostructure (Fig. 15) [170].

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17 Metal oxides coated on the surface of RF-CAs can be corrosion and accumulated
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18 during repeatedly charge-discharge processes, resulting in inferior cycling stability.

19 Based on this issue, reseachers choose supports to make metal oxide nanoparticles

20 encapsulated in mutiporous aerogels. Jayaseelan et al. reported mesoporous 3D

21 NiCo2O4/MWCNT nanocomposite aerogels via a supercritical CO2 drying method.

22 The NiCo2O4 nanoparticles are well connected with MWCNTs in the aerogel matrix

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1 to produce the mesoporous network-like structure, which not only reduces the

2 agglomeration of metal nanoparticles but also effectively improves the diffusion of

3 electrolyte ions into the electrode surface. The prepared mesoporous 3D

4 NiCo2O4-MWCNT nanocomposite aerogel shows an outstanding specific capacitance

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5 of 1010 F/g at 0.1 A/g in alkaline medium. The assembled asymmetric supercapacitor

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6 demonstrates a high stability with capacitance retention of 83.4% after 2000

7 charge-discharge cycles [123].

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8 For conductive polymers, the nitrogen-rich carbon spheres were prepared by

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9 one-pot hydrothermal synthesis in the presence of resorcinol/formaldehyde as carbon
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10 precursors and ethylenediamine (EDA) as both a base catalyst and a nitrogen

11 precursor, followed by carbonization in N2 and activation in CO2. The maximum

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12 nitrogen doping level (7.2 wt %) in carbon spheres can be achieved without

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13 sacrificing the spherical morphology. The diameter of these carbon spheres (CS)
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14 ranging from 50 to 1200 nm can be tuned by varying the EDA amount. The

15 aforementioned activated carbon spheres exhibits high SSA up to 1224 m2/g. When
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16 fabricated as supercpapacitor, the carbon sphere shows very high capacitance of 388
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17 F/g at 1.0 A/g and unprecedented cycling stability with capacitance retention of 98%
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18 after 8000 cycles in 1 M H2SO4 electrolyte solution [171]. On the other hand,

19 polyaniline (PANI) can be used as a good electrode material due to its facile synthesis,

20 environmental stability, high redox reversibility, and low cost. Christine et al.

21 fabricated polyaniline coated carbon aerogels. Here, PANI plays a critical role as an

22 electroactive cross-linker, which not only reinforces the aerogel structure, rendering it

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1 compressible up to ~50%, but also contributes to pseudocapacitance, leading to an

2 increase in overall capacitance. When the PANI content arrived 57.0 wt%, the sample

3 achieves a high specific capacitance of 420 F/g at 1 mV/s, which is three times more

4 than that of bare sample (137 F/g) [167]. In addtion, carbon aerogel spheres were

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5 prepared by an emulsion polymerization of resorcinol, pyrocatechol, or

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6 3-hydroxypyridine with formaldehyde under basic conditions. The use of

7 3-hydroxypyridine can introduce the N functionalities into the final carbons, which

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8 can significantly alter electrochemical performance of the electrodes due to the

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9 pseudocapacitance effects and the enhanced electronic conductivity and surface
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10 wettability. The obtained material shows a high capacitance of 200 F/g or 17.3 F/cm2

11 at 1 A/g in 1M H2SO4 [172]. Recently, Zhu et al. introduced resorcinol/formaldehyde

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12 resol and zinc tartrate into the inter space of sodium polyacrylate (PAAS) to form
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13 interpenetrating polymer networks. Hierarchical porous carbons (HPCs) with

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14 foam-like macropores, uniform mesopores (~3.8 nm) and abundant micropores were

15 obtained by direct carbonization of the interpenetrating polymer networks. The

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16 macropores and uniform mesopores are ascribed to the synergistic effect of PAAS and
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17 zinc tartrate, while the abundant micropores come from the decomposition of
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18 interpenetrating polymer networks and zinc tartrate as well as the carbothermal

19 reduction process. The resultant sample shows a high specific surface area of 1371

20 m2/g and pore volume of 1.23 cm3/g. And, The supercapacitor electrode exhibits a

21 high specific capacitance of 283 F/g at 1.0 A/g and an excellent electrochemical

22 stability with 95.86% retention after 10000 cycles at 2.0 A/g (Fig. 16) [173]. The

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1 number of works focused on organic polymers-based supercapacitor is increasing year

2 by year, which is very meaningful for RF-CAs applicated in supercapacitor.

3 All-solid state asymmetric supercapacitor is a good choice for RF-CAs based

4 composite electrode. On the one hand, they extend the cell potential window with

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5 both Faradic electrode as energy source and capacitive electrode as power source. On

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6 the other hand, solid-state electrolyte is more promising in supercapacitor for its

7 advantage of leak-free and easy transportation [174, 175]. For example, Zhao et al.

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8 assembled quasi-solid-state full sodium-ion capacitors with N-doped carbon hollow

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9 microspheres as matrix. The assembled devices exhibit a comprehensive and superior
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10 electrochemical performance in terms of ultrahigh operating voltage of 4.4 V, high

11 energy density of 157 Wh/kg at 620 W/kg and prolonged cycling stability over 1000
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12 cycles with ~70% of capacitance retention (Fig. 17) [176]. Liu et al. fabricated a
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13 asymmetric supercapacitor using carbon aerogel microspheres as the negative

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14 electrode and Co3O4 nanowires on nickel foam (Co3O4-NF) as the positive electrode

15 separated by PVA-KOH membrane as the electrolyte. The as-prepared carbon

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16 materials show perfectly spherical shape in uniform size. Homogeneous pores on the
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17 carbon microspheres are formed when the RF condensation occurs. The formation of
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18 pass-through channels ensures the access of electrolyte ions into the electrode

19 material, resulting in a low electrode resistance. Resulting from 3D interconnected

20 caron aerogel microspheres, uniformly aligned Co3O4 nanowires with abundant pores,

21 and the robust contact between Co3O4 and nickel foam, the asymmetric supercapacitor

22 delivers a prominent energy density of 17.9 Wh/kg at a power density of 750 W/kg

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1 with stable cycling performance. Besides, it can also operates at a high power density

2 of 7.5 kW/kg with an energy density of 10.44 Wh/kg [177]. Such all solid state

3 asymmetric supercapacitor offers a great promising for further electrochemical

4 applications in the energy storage systems.

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5 4. RF-CAs used for other energy storage devices

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6 Fig. 18 shows the Ragone plot of the recharge batteries including lead acid

7 batteries, Ni-Cd batteries, Ni-MH batteries and LIBs [178]. Due to its higher energy

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8 density than other rechargeable batteries, LIBs have been considered one of the most

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9 promising electrochemical energy storage devices for a variety of applications such as
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10 portable electronics, emerging electric vehicles, hybrid electric vehicles, and energy

11 storage system [179, 180]. For the aim of lighter, thinner and higher capacity, much
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12 effort has been paid to find novel electrode materials. Owing to its high electrical
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13 conductivity, high porosity and good mechanical stability, RF-CA can be a good
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14 electrode material for LIBs. On the one hand, RF-CAs can be used as conductive

15 additives added into conventional carbons such as carbon black, carbon nanotube, and
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16 graphene, to construct a conductive network, promoting the ion kinetics for enhancing
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17 the high-rate capability. Ning et al. prepared interconnected N-doped porous carbons
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18 derived from melamine anchored with MoS2 composite. In the work, the N-doped

19 porous carbons are entwined and interconnected with each other, can be effectively

20 used a reinforced concrete structure to form a robust skeleton and an excellent 3D

21 conductive network. Moreover, MoS2 nanoflowers consisting of several nanosheets

22 are closely incorporated with the composites. Benefiting from the above-mentioned

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1 characteristics, the assembled LIB shows excellent electrochemical performance, for

2 example, a high specific capacity of 1218.7 mA h/g at 200 mA/g, a superior rate

3 capability of 452.2 mA h/g at 4000 mA/g and an good cycle performance of 526.1 mA

4 h/g after 400 cycles at a high current rate of 1000 mA/g [181]. Recently,

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5 FePO4@C/reduced graphene oxide (rGO) hierarchical microspheres was obtained

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6 through the three-component precursor of LiFePO4OH@RF/GO (RF=resorcinol–

7 formaldehyde, GO=graphene oxide) direct calcination at high temperature. The

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8 RF/GO layer provides a highly conductive skeleton and improves ionic kinetics for

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9 fast electron and Li+ ion transport. The composites deliver good electrochemical
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10 performance for LIB, for example, 157.2 mA h/g at a rate of 0.2 C, the reversible

11 capacities almost reaches to the initial values of 109.3 mA h/g at a rate of 60C, and a
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12 relatively flat voltage plateau at all rates [182]. On the other hand, owing to its good
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13 mechanical behavior, RF-CAs can be assembled into free-standing electrodes for

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14 lithium storage or as a good physical support to load active materials (LiFePO4,

15 LixCoO2, LixNiO2 and LixMnO4, etc.). Kakunuri et al obtained carbon aerogel

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16 nanoparticles by using repeated inverse emulsion polymerization of resorcinol and

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17 formaldehyde, followed by subcritical drying and pyrolysis at 1173 K. The fabricated

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18 battery composed of carbon xerogel nanoparticles as a working electrode

19 and lithium metal as a reference electrode. The lithium-ion intercalation capacity for

20 RF-CAs shows a reversible capacity of 400 mA h/g, which is higher than that of

21 graphite (theoretical lithium-ion intercalation capacity is 372 mA h/g) [33]. Then,

22 Yang et al. prepared mesoporous activated carbon aerogel (MACA) from the pore

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1 formation and widening effect of H3PO4. The as-obtained MACA exhibits a high SSA

2 of 2161 m2/g with a large mesopore ratio of 92 %. This hierarchical porous

3 nanostructure can offer large ion-accessible channels for Li storage reactions as well

4 as promote better mass transfer capability. After electrochemical test, MACA shows a

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5 much higher specific capacity of 610 mA h/g at 0.1 A/g and an extraordinary high-rate

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6 performance in contrast to that of amorphous carbons and commercial graphite [107].

7 Hierarchical porous RF-CAs with a highly interconnected three-dimensional network

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8 can be prepared by the evaporation induced co-assembly method from sol-gel

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9 polymerization of resorcinol-formaldehyde. The RF-CAs shows a high SSA of 2600
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10 m2/g with a distribution of micro-, meso- and macroporous domains. The 3D

11 interconnected structure not only provides enough space for lithium storage but
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12 promote charge transfer reaction. Thus, the assembled electrode delivers a high
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13 capacitance of 890 mAh/g after 100 cycles and coulombic efficiency of ～99% at a
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14 current density of 50 mA/g [183]. These works can provide an alternative material to

15 graphite as commercial lithium-ion battery anode material. Recently, Xu et al.

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16 successfully adopted a three-dimensionally ordered macro/mesoporous carbon

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17 aerogels as the ZnO nanoparticles support used for the anode material in LIBs. In the
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18 design, the ordered mesopores could offer the rapid diffusion for Li ions and

19 electrolytes; the interconnected macropores can provide sufficient space for the

20 volume expansion of ZnO during the repeated extraction-insertion process of lithium

21 ions. The ZnO nanoparticles (~4.5 nm) can be homogenously dispersed on the

22 macropore walls of carbon aerogels. In addition, the fabricated electrode shows a high

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1 content of 40 wt% ZnO, which can provide enough reversible lithium storage capacity

2 [184].

3 Recently, Na-ion batteries can be considered as a promising alternative to LIBs

4 due to their low cost and abundant sodium resources [185, 186]. However, as the

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5 radius of Na+ (∼0.102 nm) is much larger than that of Li+ (∼0.076 nm), the majority

materials used for LIBs are difficult to host Na+ [187, 188]. Thus, it is important to

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6

7 find suitable host materials to accommodate the larger Na+. Liu et al adopted carbon

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8 aerogel nanospheres as anode for Na-ion batteries. The obtained material possesses a

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9 large SSA of 428 m2/g, a total pore volume of 0.50 cm3/g and with particle size
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10 around 50 nm. After test, the initial discharge/charge specific capacity reaches 411

11 mAh/g at a current rate of 100 mA/g [189]. Nitrogen-doped hollow carbon

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12 microspheres (NHCSs) were synthesized in the present of resorcinol/formaldehyde as

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13 carbon precursors and ethylenediamine (EDA) as both a base catalyst and nitrogen
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14 precursor. The NHCS shows a micro/ mesoporous structures with a SSA of 182.6

15 m2/g and nitrogen content of 12.40 wt%, which can serve as accessible channels for
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16 sodium ions and promote ions transfer capabilities during electrochemical cycling.
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17 The obtained sample shows a reversible discharge capacity of 334 mA h/g after 100
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18 cycles at a current of 50 mA/g [34]. After that, the author prepared a type of

19 core-double shell polyhedron structure for sodium anode electrode through a

20 sulfidation reaction with thioacetamide and a cation exchange process by introducing

21 the protective RF layer. The architecture was consistent of ZnS as inner core and a

22 complex Sb2S3/C as shell. On the one hand, the unique structure not only promotes

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1 the electrolyte infiltration to reduce the Na-ion diffusion length, leading to the

2 improvement of the electrochemical reaction kinetics. On the other hand, the carbon

3 shell can act as a protective layer to prevent the structure pulverization caused by

4 Na-ion insertion/extraction, optimizing the stable cycle performance. The electrode

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5 exhibits excellent electrochemical performance with a high reversible capacity of 630

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6 mAh/g at 100 mA/g after 120 cycles [190]. Currently, a carbon nanotube-backboned

7 mesoporous carbon (TBMC) material for the impregnation of red phosphorus was

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8 adopted for the electrode of Na-ion batteries. In the design, multi-walled carbon

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9 nanotubes can facilitate the electron transfer owing to the high content of sp2 carbon,
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10 while the mesoporous carbon layers provides adequate space to load appropriate

11 amounts of phosphorus but leave enough space to alleviate the huge volume change
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12 of the phosphorus during sodiation/desodiation process. The composite shows a high

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13 reversible desodiation capacity (~ 1000 mA h/g at 0.05 A/g), excellent rate

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14 performance (~ 430 mA h/g retained at 8 A/g), and superior cycle life (no capacity

15 decay for 800 cycles at 2.5 A/g) [7].

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16 Li-S batteries, one of next-generation advanced energy storage devices, have

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17 attracted a great deal of attention as promising alternatives to LIBs and Na-ion

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18 batteries in the large-scale energy storage systems, due to its ultrahigh energy density

19 (1675 mA h/g) [6, 161]. Despite these promising advantages, the insulation of both

20 sulfur (5×10-30 S cm-1 at 25 oC) and the continue soluble of long chain lithium

21 polysulfides (Li2Sn, 4≤n≤8) during the repeated electrochemical process could bring a

22 high ion transfer resistance and the serious loss of the active material loading on the

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1 sulfur electrode, leading to a low capacity and poor cyclic stability. Li et al. report

2 sulfur loaded in micropore-rich carbon aerogel used as cathode of lithium-sulfur

3 battery. Benefiting from the high electronic conductivity and micropore volume over

4 66% of total pore volume, the small S2-4 allotropes can be well immobilized and the

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5 solution amounts of Li2S4-8 can be effectively reduced, leading to the improved cyclic

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6 stability [47]. Li et al. successfully decorated Sm2O3 into carbon aerogel through a

7 sol-gel of resorcinol, phloroglucinol, formaldehyde and doping compound with

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8 Sm2O3. The obtained carbon aerogel shows an interconnected porous structure and

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9 high SSA. The interconnected porous structure not only provides more space to
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10 transport ions but also accommodate available volumetric expansion for sulfur during

11 the charge/discharge process. The fabricated electrode delivers initial discharge

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12 capacities of 1347, 1223, 1119 and 976 mA h/g at current densities of 0.2, 0.5, 1 and 2
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13 C, respectively. Moreover, it still maintains 889 mA h/g after 300 cycles with a
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14 capacity decay of 0.091% per cycle (Fig. 19) [35]. Recently, MoS2-decorated carbon

15 aerogel was synthesized by phenol-aldehyde reaction on the substrate of multi-walled

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16 carbon nanotube followed infiltration process with sulfur. The obtained sample
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17 possesses a large SSA of 894 m2/g and pore volume of 1.32 cm3/g. The fabricated
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18 electrode shows a large sulfur loading of 3.8 mg/cm2 and high sulfur content of 64%,

19 which can bring quantity of reversible capacities. After test, the fabricated electrode

20 delivers a discharge capacity of 1343 mA h/g at 0.2 C with the capacity retention of

21 81% after 200 cycles. Even at 5 C, the electrode still maintains high a capacity of 723

22 mA h/g [191]. This excellent electrochemical performance contributes from multiple

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1 positive factors including coaxial nano-cable structure, large SSA, suitable pore size

2 and improved electronic conductivity. Although the electrochemical properties such as

3 the initial reversible capacity and cyclic stability of lithium ion/sulfur batteries can be

4 effectively improved, it still exist some challenges for the next generations, for

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5 example, the safe operation in wide rage temperature (-20～100 oC) and standard

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6 preparation process for large-scale production.

7 5. Summary and outlook

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8 RF-CAs have been explored since Pekala’s work in 1990s. The unique structures

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9 of RF-CAs make them a promising candidate for energy storage applications. In this
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10 review, the effects of preparation parameters (eg. precursor, catalyst, drying method,

11 carbonization and activation) on the final structures (e.g. morphology, pore structure,
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12 conductivity, and surface chemistry etc.) are discussed in detail. The relationship
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13 among surface property, structure characteristics (pore structure, electrical

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14 conductivity and heteratoms doping) and electrochemical performance of RF-CAs is

15 proposed. RF-CAs combined with conductive polymers (e.g. EDA, PANI and PAAS,
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16 etc.) or metal oxides (e.g. MnO2, Co3O4, and NiCo2O4, etc.) show outstanding
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17 electrochemical performance because of the synergistic effects of large surface area,

AC

18 high electrical conductivity and additional pseudocapacitance. In addition, RF-CAs

19 also exhibit great potential in advanced energy storage devices, such as LIBs, Na-ion

20 batteries and Li-S batteries. However, tremendous efforts should be made to solve the

21 following challenges：

22 (1) The precise control of polymerization of different raw materials should be

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1 mastered to realize the oriented synthesis, which is related to the interdisciplinary

2 of macromolecules and materials science.

3 (2) Reagents with multiple functions should be focused during the preparation process.

4 For example, HBO3 [58, 159] and H3PO4 [98] can serve as catalysts and doping

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5 agents (B,P). NH3 [110, 111], H3PO4 [205] can serve as both activators and doping

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6 agents (N, P). K2CO3 [97] and ZnCl2 [109] can serve as catalysts, templates, and

7 activators. By appling these methods, not only the preparation process can be

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8 simplied but also the supercapacitor performance can be improved.

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9 (3) The high cost of preparation resulted from the expensive drying equipment is still
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10 a key issue for industrilization. For instance, one set of supercritical drying

11 equipment with the volume of 1 m3 costs 30~40 million RMB. Therefore, it is of

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12 great importance to develop a economical drying equipment to decrease the initial

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13 investment.
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14 (4) During supercapacitor assembling process, it is inevitable to adopt binder (eg.

15 polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and Nafion, etc.)

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16 and current collectors (eg. aluminum foil, copper foil, and nickle foil, etc.), which
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17 can increase the charge transfer resistance during a charge-discharge cycle, and
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18 thus leads to a low capacity. So developing novel free-standing electrode is

19 necessary for the next generation of energy storage materials.

20 (5) More efforts are still needed to find the full potentials of RF-CAs electrode for

21 high energy density and power density energy storage systems.

22 (Ⅰ) The effects of pore structure and surface chemistry of RF-CAs on the

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1 electrochemical properties in different electrolytes and potentials should be further

2 studied.

3 (Ⅰ) The SCs fabricated with multi-units (RF-CAs/NiCo2O4,

4 Mn3O4/graphene/RF-CAs and NiCo2O4/MWCNT/RF-CAs, etc.) still hold great

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5 promise, which can achieve both high power and energy density by combine

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6 EDLC and pseudocapacitance together.

7 (Ⅰ) Volumetric energy density is also a key factor for the miniaturization of

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8 electronic devices. Researchers are trying to exploit high dense aerogels, such as

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9 carbon aerogel microspheres [87, 206].
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(6)
10 (6) Owing to the unique structure, RF-CAs can be a good candidate in other fields as

11 well, such as electronics (asymmetrical electrochemical capacitors), environmental

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(7)
12 remedition (adsorption and capacitive deionization), and catalysis.
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13 Acknowlegements: This work was supported by the National Natural Science

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14 Foundation of China (51402325, 51002166), National Defense Technology

15 Research Project (17-163-13-ZT-009-077-001), Scientific Research Foundation for

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16 Young Scientists of Shanxi Province (201601D021061) and Youth Innovation

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17 Promotion Association of CAS.

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18

19

20

21

22

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1 Figure caption
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Fig. 1. Ragone plot of various chemical energy storage systems. Reprinted with
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2 picture of GO–RF composite aerogels. Reprinted with permission from Ref. [68].

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6 Fig. 10. Schematic process of the graphitized carbon aerogel. Reprinted with

7 permission from Ref. [134].

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a b

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1

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2 Fig. 11. (a) Distribution of nitrogen atoms in carbon structure. Reprinted with

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3 permission from Ref. [149]. (b) Possible redox reactions associated involving

4 pyridinic, pyrrolic, and pyridone-type nitrogen species. Reprinted with permission

5 from Ref. [150].

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7 Fig. 12. Schematic illustrations of the preparation of NHPCS materials. (a) GCD

8 curves of all NHPCS electrode materials at current density of 1 A/g−1 measured in a

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1 three-electrode system; (b) CV curves of NHPCS-2-8 electrode material at different

2 scan rates measured in a three-electrode system; (c) GCD curves of NHPCS-2-8

3 electrode at different current density measured in a three-electrode system; (d)

4 specific capacitances of all NHPCS electrode materials at different current density in

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5 a three-electrode system. Reprinted with permission from Ref. [110].

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7 Fig. 13. Schematic illustrations of the preparation of NCA materials. Reprinted with
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8 permission from Ref. [31].

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1 Fig. 14. Possible schematic illustration for the binding conditions of carbon, oxygen

2 and phosphorus in CK-P-xs during H3PO4 post-activation. Reprinted with permission

3 from Ref. [101].

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5 Fig. 15. A schematic of the formation of the porous Co3O4 nanoball/carbon aerogel

6 hybrid. Reprinted with permission from Ref. [170].

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8 Fig. 16. Synthesis of hierarchical porous carbons. Reprinted with permission from Ref.

9 [173].

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2 Fig. 17. Schematic illustration of N-doped carbon hollow microspheres for metal-free
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3 quasi-solid-state full sodium-ion capacitors. Reprinted with permission from

4 Ref.[176].
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2 Fig. 18. Ragone plot of the recharge batteries as a function of volumetric and specific

3 energy densities. Reprinted with permission from Ref. [178].

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5 Figure 19. Schematic illustration of the formation for CA/S-Sm composite. Reprinted
6 with permission from Ref [35].
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1 Table 1 Maximum capacitance values of pyrolysis carbon aerogels.

Sample Pyrolysis SBET Cma Measure Electrolyte SCb Ref.

temperature (m2/g) (F/g) conditions
(oC)

CA 800 681 93 1 A/g 1M H2SO4 2c [154]

CMS-3 800 485 129 0.1 A/g 3M H2SO4 2 [114]

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CA 500 706 90 1A/g 6M KOH 3d [192]
RF 800 733 75.8 0.5 mV/s 0.1M NaCl 3 [193]
RF 800 733 78.3 0.5 mV/s 0.1M NaNO3 3 [193]

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RF 800 733 61.2 0.5 mV/s 0.1M 3 [193]
Na2HPO4/NaH2

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PO4
GD 950 449 56.9 5 mV/s 0.5M H2SO4 3 [25]
CA 900 504 67.5 1 A/g 6M KOH 3 [194]

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Bv 900 568 159 0.125 A/g 1M H2SO4 3 [58]
Pmw 900 149 149 0.125 A/g 1M H2SO4 3 [58]
AN
PR-0.1-1000 1000 1454 174.4 0.5 A/g 6M KOH 3 [87]
PR-0.1-1600 1600 954 80.7 0.5 A/g 6M KOH 3 [87]
CA 900 635 87 0.1 A/g 6M KOH 3 [128]
M

CA-500 800 731 14.4 5 mV/s 1M 2 [57]

TEABF4/ACN
D

CA-2000 800 847 17.6 5 mV/s 1M 2 [57]

TEABF4/ACN
TE

PR-0.1-1000 1000 1454 151.9 0.5 A/g 1M TEA/BF4 2 [87]

PR-0.1-1600 1600 954 106.3 0.5 A/g 1M TEA/BF4 2 [87]
PC 1000 314 14.7 0.5 mA 1M 2 [163]
EP

TEATFB/PC-D
MC
N-UCN 850 1439 269 1.0 A/g 6 M KOH 3 [153]
C

CA//CA 800 - 180.8 1.0 A/g KOH gel 2 [177]

CQD-free 1050 755 14.6 0.05 A/g 1M LiClO4 2 [195]
AC

OMC 700 1030 123 0.5A/g 6M KOH 3 [196]

RFSL 1100 1670 150 1 A/g 6M KOH 2 [197]
RF 800 725 210 1 mV/s 1M H2SO4 3 [198]
RF 800 725 110 1 mV/s 1MKNO3 3 [198]
R-C 800 - 110.6 1 mV/s 6M KOH 3 [199]
R-C 800 - 87.2 1 mV/s 1M H2SO4 3 [199]
R-C 800 - 69.9 1 mV/s 2M (NH4)2SO4 3 [199]
POX-900 900 519 167 1 mV/s 1M H2SO4 3 [159]
POX-1500 1500 285 35 1 mV/s 1M H2SO4 3 [159]
CA/F-06 800 522 131 1mV/s 4M KOH 3 [130]
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CA 1100 738 113 1 mV/s 1MH2SO4 3 [167]
CA 800 679 95 10 mV/s 1 MH2SO4 3 [164]
1 *Cma-maximum capacitance; SCb-system conditions; 3c-three electrode; 2d-two-electrode.
2
3 Table 2 Maximum capacitance values of activated carbon aerogels.
Sample Activation SBET Cma Measurement Electrolyte SCb Ref.
method (m2/g) (F/g) conditions
253.2 0.1 A/g 1M H2SO4 3c

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CR3 K2CO3 4569 233.4 0.1 A/g 6M KOH 3 [97]
C-200-20-T CO2 1139 211 10 mV/s 6M KOH 3 [127]
ACA-H3PO4 H3PO4 899 120 1 A/g 6M KOH 3 [192]

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ACA-P H3PO4 2477 201 0.1 A/g 6M KOH 3 [128]

ACA-K2CO3 K2CO3 1166 152 1 A/g 6M KOH 3 [192]

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ACA-KOH KOH 1447 136 1 A/g 6M KOH 3 [192]
ACMS-3-3 KOH 1980 241 0.1A/g 3M H2SO4 2 [114]
ACA-ZnCl2 ZnCl2 897 104 1 A/g 6M KOH 3 [192]

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ACA K2CO3 1384 271 1 A/g 6M KOH 3 [125]
A-RF CO2 1069 120.3 0.5 mV/s 0.1M NaCl 3 [193]
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A-RF CO2 1069 100.5 0.5 mV/s 0.1M NaNO3 3 [193]
A-RF CO2 1069 89.6 0.5 mV/s 0.1M 3
Na2HPO4/Na [193]
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H2PO4
GC CO2 3418 312.3 5 mV/s 0.5M H2SO4 3 [25]
D

ACRF-25 CO2 3431 152 0.3 A/g 1M 2d [126]

Et4NBF4–
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AN
ACRF200 CO2 1025 210 2 mA/cm2 EMImBF4 2 [124]
RFMC750-10 Mg(OH)2 1138 187 0.2 A/g 6M KOH 3 [59]
EP

NHPCS-0-8 NH3 1197 182.9 1 A/g 6M KOH 3 [110]

NHPCS-2-8 ZnCl2-NH3 1291 261.2 1A/g 6M KOH 3 [110]
CR3 K2CO3 4568 173.6 3 A/g EMIMBF4 2 [97]
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ACA KOH 1645 23.3 1 A/g 1MTEABF4/ 2 [200]

ACN
AC

NHPCS-2-8 ZnCl2-NH3 1291 19.1 0.1 A/g 0.5 M 2 [110]

Na2SO4
APS-PC air 953.2 103.5 0.5 mA 1M 2 [163]
TEATFB/PC-
DMC
ACA air - 40 5 mA/cm3 6M KOH 2 [201]
ACA air - 35 5 mA/cm3 1M H2SO4 2 [201]
ANC KOH 2125 67.7 7.5 mA/cm3 6M KOH 2 [151]
ANC/ACA KOH 1848 110.6 7.5 mA/cm3 6M KOH 2 [151]
ACA CO2 1987 153 10 mV/s 1 MH2SO4 3 [164]
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1 *Cma-maximum capacitance; SCb-system conditions; 3c-three electrode; 2d-two-electrode.
2
3 Table 3 Maximum capacitance values of composites based on RF-CAs for SCs.
Sample Additive SBET Cma Measurement Electrolyte SCb Ref.
(m2/g) (F/g) conditions
ACAG GO 1158 300 1 A/g 6M KOH 3 [125]
NCG GO - 225 0.25 A/g 2M H2SO4 3 [31]
OMC/GA-2 GO 254 197 0.5 A/g 6M KOH 3 [196]

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OMC/GA GO 715 177 5 mV/s 6M KOH 3 [131]
CQD GO 1027 294.7 0.5 A/g 1M LiClO4 2 [195]
4G/CX graphene 761 230 0.1 A/g 6M KOH 3 [202]

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CAG Carbon Fiber 163.1 64.7 5 mV/s 3M KCl 3 [203]
Ni-CA Ni 584 126 1 A/g 6M KOH 3 [194]
2d

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PS-PC P 2S 5 268 21.1 0.5 mA 1M [163]
TEATFB/P
C-DMC
BNC ammonia 621 75 - TEATFB 2 [204]

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RuO2/ACA RuO2 1748 308 10 mV/s 1 MH2SO4 3 [164]
Co3O4-NF// Co3O4 - 278 1 A/g KOH gel 2 [177]
Co3O4-NF
0.1 A/cm2
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ZnO/CA ZnO - 500 6M KOH 3 [165]

Co3O4 Co3O4 907 350 1 A/g 6MKOH 3 [170]
nanoball/CA
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MoSe2-CA MoSe2 47.3 775 1 A/g 6MKOH 3 [166]

MnO2/CA MnO2 120 515 2 mV/s 1M Na2SO4 3 [168]
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Mn3O4/CA Mn3O4 - 503 25 mV/s 0.5MNa2SO 3 [27]

4

NiCo2O4/CA NiCo2O4 206 1700 25 mV/s 1M NaOH 3 [169]

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WO3/CA WO3 710 700 25 mV/s 0.5MH2SO4 3 [32]

NiCo2O4/MW NiCo2O4/ - 1010 0.1 A/g 2MKOH 3 [123]
CNT/N-doped MWCNT
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carbon aerogel
PANI@AGCA PANI 2213 420 1 mV/s 1MH2SO4 3 [167]
AC

CS2-O 3-hydroxypyrid 1156 200 1 A/g 1MH2SO4 3 [172]

ine
HPCs sodium 1371 283 1 A/g 6M KOH 3 [173]
polyacrylate
4 *Cma-maximum capacitance; SCb-system conditions; 3c-three electrode; 2d-two-electrode.

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(1) Discuss the physico-chemical principles of synthesis strategies on the

structure of RF-CAs.

(2) Build the relationship between structure and performance in energy storage

devices.

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(3) Propose the structure optimization for the next generation of RF-CAs.

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