Abstract
In recent years, carbon-based flexible anodes for potassium-ion batteries are increasingly investigated owing to the low reduction potential and abundant reserve of K and the simple preparation process of flexible electrodes. In this review, three main problems on pristine carbon-based flexible anodes are summarized: excessive volume change, repeated SEI growth, and low affinity with K+, which thus leads to severe capacity fade, sluggish K+ diffusion dynamics, and limited active sites. In this regard, the recent progress on the various modification strategies is introduced in detail, which are categorized as heteroatom-doping, coupling with metal and chalcogenide nanoparticles, and coupling with other carbonaceous materials. It is found that the doping of heteroatoms can bring the five enhancement effects of increasing active sites, improving electrical conductivity, expediting K+ diffusion, strengthening structural stability, and enlarging interlayer spacing. The coupling of metal and chalcogenide nanoparticles can largely offset the weakness of the scarcity of K+ storage sites and the poor wettability of pristine carbon-based flexible electrodes. The alloy nanoparticles consisting of the electrochemically active and inactive metals can concurrently gain a stable structure and high capacity in comparison to mono-metal nanoparticles. The coupling of the carbonaceous materials with different characteristics can coordinate the advantages of the nanostructure from graphite carbon, the defects and vacancies from amorphous carbon, and the independent structure from support carbon. Finally, the emerging challenges and opportunities for the development of carbon-based flexible anodes are presented.
Introduction
At present, the increasing energy demand leads to the depletion of fossil fuels, deterioration of the environment, and pollution, which puts forward higher requirements for the efficient use of renewable clean energy, such as solar energy, wave energy, wind energy, and other renewable energy (). However, the intermittent characteristics and geographic selectivity limit their stable output. Developing low-cost and high-performance energy-storage systems is a feasible solution, where rechargeable batteries have attracted much attention due to their low pollution, high efficiency, and long life cycle (; ). As the mature and most widely used rechargeable battery, lithium-ion batteries (LIBs) have gained popular application in daily electronic products, electric vehicles, and energy-storage systems (). However, the shortage of commercially available Li resources on Earth makes it difficult to meet the rapidly growing demand of the market, and the cost of lithium salt rapidly increases year by year, which greatly influences the development prospects of LIBs (; (Yang et al., 2021b). As a result, concerns about the price and depletion of lithium have accelerated the search for alternatives to LIBs in recent years (Yao and Zhu, 2020).
Potassium (K) possesses a lower reduction potential than lithium, which allows the potassium-ion batteries (PIBs) to operate at a higher potential, bringing a higher energy density (). At the same time, elements of potassium are abundant on Earth and have similar chemical properties to lithium. Therefore, PIBs have received widespread attention in recent years and are regarded as a more likely alternative to LIBs (; (). Generally, in a full-battery system, the anode is a key configuration that determines the electrochemical performance of the battery. The preparation process of a powder electrode for PIBs is mainly based on the slurry coating method, where the slurry mixed with the active material, conductive carbon, and adhesive in different proportions is coated on copper or aluminum foil (). On the one hand, during the repeated insertion and extraction of bulky K+ by conversion or alloying reactions, the anode material would undergo excessive volume change, thus producing severe pulverization (), especially, the weak contact of the powder electrode material with the current collector would further result in the exfoliation of pulverized active materials, eventually leading to rapid capacity decline (). On the other hand, the addition of a binder and conductive carbon restricts the loading of active materials, and hence, affects the energy density of the battery. Meanwhile, the degradation of binders and the generation of side reactions through the interaction of binders and electrolytes lead to worse capacity stability during the long cycle process. In response to the aforementioned two issues of powder electrodes, the traditional slurry casting method needs to be improved or even replaced; in other words, it is necessary to search for a new type of electrode (; ().
In recent years, with the increasing demand for flexible devices such as wearable devices, roll-up displays, and soft portable electronic products, there are more studies on flexible and environmentally friendly electrochemical energy-storage devices. Flexible electrodes have been raised and developed to improve the electrochemical performance of PIBs and avoid the complicated preparation process of powder electrodes (). The independent electrode structure provides flexible properties, possesses the characteristics of non-binder and solvent-free electrode preparation, and eliminates the use of a collector during battery assembly. Meanwhile, a tightly bind of support and active electrode materials are thought to accommodate the volumetric change and the decomposition of electrode materials during battery applications. In flexible electrodes, the supports usually include the commercial carbon fiber cloth with three-dimensional structures, good flexibility, and good conductivity (), carbon nanotubes with excellent physical, chemical, and mechanical properties (Zhao et al., 2017), nickel foam with three-dimensional uniform network structures (), and graphene with a large surface area, high conductivity (), and so on.
To the best of our knowledge, there have already been several excellent reviews devoted to PIBs or flexible energy-storage devices, whereas, a comprehensive review focusing on flexible anodes for PIBs has not been reported up to now, because the application of self-supporting materials in PIBs is in its infancy. Considering this, in this review, our main contribution is to summarize and briefly discuss the recent development of flexible anodes for PIBs. Especially, the modification method of self-supporting carbon-based materials and the electrochemical enhancement mechanism of carbon-based flexible electrodes are introduced in detail. In conclusion, through this review, we aim to better understand the flexible anode materials for PIBs and provide guidance for the infancy design of non-binder potassium-based energy-storage devices in the future (; ().
Carbon-based flexible anodes for PIBS
Carbonaceous materials usually possess superior conductivity, excellent structural stability, and unique mechanics (Yang et al., 2020). Thus, abundant reported flexible electrodes are developed based on carbon-based materials (graphene films, carbon cloth, carbon nanofibers, carbon foams, etc.). When applied in PIBs, the flexible carbonaceous material can not only serve as an active material by itself but also support other active materials (). As a result, highly flexible carbon-based materials have been extensively studied as anodes for PIBs.
reported for the first time that K+ can electrochemically intercalate into carbonaceous materials at ambient temperature and pressure. The local K+ insertion phenomenon between graphite layers is indicated in Figure 1A, where graphite can be reversibly intercalated by K+, showing a reversible capacity of 273 mAh g−1 at low current density. However, as the current density rises, the reversible capacity of graphite decreases sharply (Figure 1B), which may be related to the severe volume expansion of the dense graphite structure. Thereafter, carbon-based materials as the flexible materials for K+ storage have also been applied. first synthesized an rGO film using the modified Hummer’s method and directly employed it as the PIB anode without utilizing any binder, carbon additives, and current collector (Figure 1C) (). The self-supporting electrode exhibits excellent electrochemical performance with a charge capacity of 222 mAh g−1 at 5 mA g−1, and a capacity of 150 mAh g−1 after 175 cycles at 10 mA g−1 (Figure 1D). This work presents a broader application foreground of carbonaceous materials as a PIB free-standing electrode ().
FIGURE 1
However, there are three problems with the pristine carbon-based materials directly employed as the flexible anode for PIBs: excessive volume change, repeated SEI growth and low affinity with K+, which thus leads to severe capacity degradation, sluggish K+ diffusion dynamics, and limited active sites (
Modification strategies of carbon-based flexible anodes for PIBS
Heteroatom-doping
Monoatom-doping
Recently, related research studies have indicated that the electrochemical performances of carbonaceous materials could be regulated and ameliorated via heteroatom doping, which has almost no influence on the intrinsic electrode structure (
FIGURE 2

(A) Schematic representation of the preparation process of a flexible CS-derived carbon membrane. (B,C) Illustration of the storage mechanism of K+ in the porous CS-derived carbon membrane. Reproduced with permission (
The characterization of graphene could be changed when a single element is doped into graphene sheets, which thus exhibits enhanced electronic conductivity (
Dual-doping
To overcome the weaknesses of monoatom-doping, a dual-doping strategy is developed to synergize the effect of each specie in boosting the electrochemical performances of carbonaceous materials (
FIGURE 3

(A) Theoretical simulations of K-atom adsorption and diffusion. (B) Cycling performances at 1 A g−1 and (C) rate performances at the current densities from 0.1 to 5 A g−1 for NOC@GF and the NOC-F anode. Reproduced with permission (Zeng et al., 2020). Copyright 2021 Elsevier Ltd. (D) Preparation diagram and (E) cycling performances at various current densities for the N, P-VG@CC anode. Reproduced with permission (
Coupling with metal and chalcogenide nanoparticles
According to the theoretical calculation, the metal nanoparticles composed of group IVA and VA elements, such as Co (Yang et al., 2021a), Sb (
Coupling with mono-metal nanoparticles
Metallic Sb possessing high theoretical capacity (K3Sb, 660 mAh g−1), small electrochemical polarization (0.2 V), and low operating voltage has been broadly investigated as one of the potential PIB anode materials (
FIGURE 4

(A) Preparation diagram of the u-Sb@CNF free-standing electrode. (B) Rate properties of u-Sb@CNFs and Sb@s-CNFs. Reproduced with permission (
Subsequently,
Coupling with alloy nanoparticles
In addition to mono-metal nanoparticles, many research studies have also shown that alloy nanoparticles have more K+ storage sites than the intercalated anode (
FIGURE 5

(A) Schematic diagram of the electrochemical enhancement mechanism of CoSb@C nanofibers. (B–D) SEM images of CoSb@C nanofibers during the initial cycle process. (E) Rate performance and (F) long-term K+ storage performance of CoSb@C nanofibers’ electrode at 1 A g−1. Reproduced with permission (
The structural evolution of N-doped CoSb@C nanofibers at different voltages demonstrates that the surface of nanofibers becomes smooth after initially discharging to 0.01 V (Figure 5C), which is caused by the thorough conversion of Sb to K3Sb. When the voltage is returned to 3.0 V, CoSb nanoparticles are regenerated (Figure 5D), suggesting the structure stability and the reversibility of the electrochemical reaction. Thus, the bimetallic CoSb alloys can be applied as a high-capacity flexible anode for PIBs, where a large cycling capacity of 250 mAh g−1 at 1 A g−1 after 500 cycles is gained and a superior rate capacity of 160 mA h g−1 at 2 A g−1 is realized (Figures 5E,F). After that, the work of bimetallic compatible flexible anodes has also been reported by
FIGURE 6

(A) TEM image, (B) HRTEM image, and (C) SAED pattern of CoSn(OH)6 nanoboxes. (D) TEM image, (E) HRTEM image, and (F) SAED pattern of CoSn@N-C nanotubes. (G) Synthesis diagram of CoSn@N-C nanotubes. Reproduced with permission (
When employed as the flexible anode for PIBs, CoSn@N-C nanotubes have three advantages. First, the inactive metal Co matrix and the holes in the nanoboxes ensure the effective mitigation of the stress caused by excessive Sn volume expansion. Second, the encapsulation layer of nanotubes prevents the fracture of nanoboxes during the repeated insertion/extraction of K+ and accelerates the infiltration of the electrolyte into the electrode material and hence promotes the electrochemical dynamics. Third, the CoSn@N-C membrane can be directly employed as a flexible PIB anode in the premise of no binder and current collector, which contributes to obtaining great energy density. Benefitting from the aforementioned three advantages, the CoSn@N-C flexible anode delivers a large capacity of 178 mAh g−1 after 2,000 cycles at 0.5 A g−1 and superior rate capacity of 134.8 mAh g−1 at 10 A g−1.
Alloy nanoparticles’ anode materials often exhibit higher theoretical specific capacity. Especially, when two kinds of metal with electrochemical activity form alloys, they can exploit their respective advantages for potassium storage. When the carbon-based self-supporting materials are combined with the aforementioned alloy nanoparticles, the cycle stability can be improved to a certain extent, but it is still necessary to cooperate with the regulation of the structure and specific surface area to further enhance the electrochemical performance.
Coupling with metal chalcogenide nanoparticles
During the latest decade, metal chalcogenides have attracted increasing attention and developed rapidly as a kind of hot research material in the energy storage and conversion field. In the as-reported PIBs, metal chalcogenides are commonly composed of metals such as Mo, Fe, Sb, Co, and V and chalcogens O, S, and Se. However, in the K+ storage process, these electrodes manifest poor cycling performance and weak rate capability due to their serious volume fluctuations, low electron and ionic conductivity, and big K+ radius. Among various solution strategies, it is an effective strategy to introduce flexible carbon-based materials to restrain the excessive volume expansion and quicken e− transfer.
FIGURE 7

(A) SEM and (B) elemental mapping images of v-MoSSe@CM. (C) Second, 10th, and 200th charge/discharge profiles at 0.5 A g−1 for v-MoSSe@CM. Reproduced with permission (
In addition, the precise control of the material microstructure at the molecular and nanoscale is also pivotal to enhancing the electrochemical performance and discovering differentiated energy storage mechanisms. For example,
For Sb-based metal chalcogenides, the alloying reaction provides the main capacity. However, the shortcomings of the large radius of K+ and the sluggish reaction kinetics in the alloying process affect the cyclic stability. In this regard, we used vacuum filtration and a subsequent annealing process to construct the Sb2Se3 nanorods on the surface of graphene (Sb2Se3@h-rGO) with the formation of Sb-O-C chemical bonds in their interfaces in the previous work (Figures 8A,B) (Yang et al., 2022). These as-constructed chemical bonds can effectively reduce the diffusion energy barrier of K+ in the de-alloying reaction, promoting the formation/breaking of K-Sb bonds in the discharge alloy product of K3Sb. Therefore, Sb2Se3@h-rGO shows excellent electrochemical performance when used as a free-standing anode for PIBs.
FIGURE 8

K diffusion paths in (A) K3Sb@graphene and (B) K3Sb model. (C) Rate capability for free-standing Sb2Se3@h-rGO electrodes. SEM images of (D) free-standing Sb2Se3@h-rGO electrode and (E) Sb2Se3 powder electrode after 50 repeated cycles. (F) Cycling performances of the free-standing Sb2Se3@h-rGO electrode at 0.1 A g−1 for 500 cycles. Reproduced with permission (Yang et al., 2022). Copyright 2021 Elsevier Ltd.
The specific capacity of Sb2Se3@h-rGO arrives at 73 mAh g−1 at the current density of 2 A g−1 (Figure 8C). After 50 cycles at 0.1 A g−1, the nanorod morphology is well maintained (Figures 8D,E), suggesting its outstanding microstructure reversibility. After 500 cycles, the free-standing electrode can still deliver the specific capacity of 382 mAh g−1 at 0.1 A g−1 (Figure 8F). In addition to the aforementioned reports, many other free-standing electrodes composed of metal chalcogenide such as SnO2 (
Coupling with other carbonaceous materials
Carbonaceous materials with narrow interlayer spacing frequently show poor circulation ability as PIB anodes on account of the large volume change and further structure collapse induced by the repeated insertion of K+. The coupling of the carbonaceous materials with different characteristics is conducive to gathering the preponderances of the nanostructure from graphite carbon, the defects and vacancies from amorphous carbon, and the independent structure from matrix carbon (
Thus, the abundant K+ storage sites, stable cycle structure, and fast charge transfer can be realized simultaneously for the flexible carbon-based composite electrode. For example,
FIGURE 9

(A) HRTEM image of graphitic. (B) Digital photograph of folded HG-CNFs. (C) Rate capabilities from 0.1 to 35 C for LG-CNFs and HG-CNFs. (D) Long-term cycle stability and corresponding Coulombic efficiency of HG-CNFs at 0.2 C. Reproduced with permission (
FIGURE 10

(A) TEM image of SMCF@CNTs. (B) Rate performance from 0.1 to 5 C. (C) Cycling performance at 1 C. Reproduced with permission (
Conclusion and perspectives
Conclusion
In most cases, binder-free electrode materials often show excellent electrochemical performance such as high capacity, rate capability, and cycling stability. The electrochemical properties of the materials involved in this work are shown in Table 1. However, there are three problems with the pristine carbon-based materials directly employed as the flexible anode for PIBs: excessive volume change, rrepeated SEI growth and low affinity with K+, which thus leads to severe capacity fade, sluggish K+ diffusion dynamics and limited active sites.
TABLE 1
| Flexible materials | Material varieties | Templates | Rate capability (mAh g−1) | Cyclability (mAh g−1) | Reference |
|---|---|---|---|---|---|
| Graphite | - | Free | 80 at 279 mA g−1 | 100 at 0.14 A g−1 after 50 cycles | |
| rGO film | - | Free | 222 at 5 mA g−1 | 150 at 0.01 A g−1 after 175 | |
| CNF | Porous carbon nanofiber | Carbon nanofiber paper | 100 at 7.7 A g−1 | 270 at 0.2 A g−1 after 1,200 | Zhao et al. (2017) |
| CS | N-doped carbon | Free | - | 146 at 2 A g−1 after 500 | |
| S-RGO | S-doped carbon | Free | 361 at 50 mA g−1 | 229 at 1 A g−1 after 500 | |
| NOC@GF | N, O dual-doped | Graphene foam | 123 at 5 A g−1 | 281 at 1 A g−1 after 5,500 | Zeng et al. (2020) |
| NO/CNFs | N, O dual-doped | Free | 110 at 2.7 A g−1 | 170 at 0.27 A g−1 after 1,900 | |
| N, P-VG@CC | N, P dual-doped | Carbon clothes | 156.1 at 2 A g−1 | 142.4 at 1 A g−1 after 1,000 | |
| BNCS | N, O dual-doped | Carbon scaffold | 118 at 10 A g−1 | 184 at 1 A g−1after 5,000 | |
| u-Sb@CNFs | Sb-embedded CNFs | Free | 184 at 2 A g−1 | 188 at 2 A g−1 after 3,000 | |
| Sb-G-C | Sb-graphene-carbon | Free | 120.83 at 1 A g−1 | 204.95 at 0.1 A g−1 after 100 | |
| CoSb@C | Co, Sb-embedded CNFs | Free | 160 at 2 A g−1 | 250 at 1 A g−1 after 500 | |
| CoSn@N-C | CoSn alloy-embedded CNFs | Free | 134.8 at 10 A g−1 | 178 at 0.5 A g−1 after 2,000 | |
| SnO2@CF | SnO2 grown on GF | Graphene foam | 143.5 at 5 A g−1 | 231.7 at 1 A g−1 after 400 | |
| V2O3@PNCNFs | V2O3-embedded CNFs | Free | 134 at 1 A g−1 | 240 at 0.5 A g−1 after 500 | |
| v-MoSSe@CM | MoSSe grown on carbon | Free | 202 at 5 A g−1 | 220.5 at 0.5 A g−1 after 1,000 | |
| OM-G | Fe2O3 bonds with graphene | Free | 306.6 at 10 A g−1 | 384.8 at 1 A g−1 after 2,000 | |
| Sb2Se3@h-rGO | Sb2Se3 bonds with graphene | Free | 73 at 2 A g−1 | 382 at 0.1 A g−1 after 500 | Yang et al. (2022) |
| CDs@rGO | Carbon dots and graphene | Free | 185 at 0.5 A g−1 | 244 at 0.2 A g−1 after 840 | |
| HG-CNFs | Highly graphitized carbon | Carbon scaffold | 225.7 at 9.7 A g−1 | 162.5 at 0.05 A g−1 after 500 | |
| SMCF@CNTs | Carbon nanotubes and fiber | Free | 108 at 136 mA g−1 | 193 at 0.279 A g−1 after 300 | |
| CNTs/GCF | Carbon nanotubes and GCF | Graphene foam | 74 at 1 A g−1 | 127 at 0.5 A g−1 after 2,000 | Zeng et al. (2019) |
Electrochemical performance of the various carbon-based flexible anodes in the study for PIBs.
The modification strategies are categorized as heteroatom-doping (monoatom-doping and dual-doping), coupling with metal (mono-metal and alloy nanoparticles) and chalcogenide nanoparticles, and coupling with other carbonaceous materials. The doping of the heteroatom can bring the five enhancement effects of increasing active sites, improving electrical conductivity, expediting K+ diffusion, strengthening structural stability, and enlarging interlayer spacing. The coupling of metal and chalcogenide nanoparticles can largely offset the weakness of the scarcity of K+ storage sites and the poor wettability of pristine carbon-based flexible electrode. The alloy nanoparticles consisting of electrochemically active and inactive metals can concurrently attain a stable structure and high capacity in comparison to mono-metal nanoparticles. The coupling of the carbonaceous materials with different characteristics can coordinate the advantages of the nanostructure from graphite carbon, the defects and vacancies from amorphous carbon, and the independent structure from the support carbon.
Perspectives
Although some investigates have been performed in the past decade, some problems and challenges still need to be solved in the practical application of carbon-based flexible anodes for PIBs:
1) More varieties of non-metallic elements, such as I, B, and Br, can be introduced, and accurately adjusting the doping element content can be carried out to further improve the K+ storage properties of carbon-based flexible electrodes.
2) More varieties of metal and inorganic nanoparticles with more K+ storage sites and better electrochemical reversibility can be coupled, and accurately adjusting the proportion of nanoparticles in the carbon-based flexible electrodes can be further explored. Especially, the hetero-interfaces between carbonaceous materials and nanoparticles need to be emphatically concerned.
3) The carbon-based substrates concurrently possessing strong mechanical properties (flexibility, tensility, and compressibility) need to be developed to further promote the application of carbon-based flexible PIB electrodes in the field of wearable devices, roll-up displays, and soft portable electronic products.
Statements
Author contributions
ZY, conceptualization, roles/writing—original draft; WL, conceptualization, roles/writing—original draft, formal analysis; JZ, visualization, investigation; JW, investigation; XL, conceptualization, funding acquisition, resources, supervision, writing—review and editing.
Funding
This work was supported by the National Natural Science Foundation of China (5210130199 and 52072298), China Postdoctoral Science Foundation (2021M692596), Innovation Ability Strengthening Foundation Plan of Xi’an (21XJZZ0043), the Local Special Service Program Funded by Education Department of Shaanxi Provincial Government (Program No.19JC031), Young Talent Fund of University Association for Science and Technology in Shaanxi of China (20200418), and the Open Foundation of Key Laboratory of Green Preparation and Functionalization for Inorganic Materials (202002).
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Publisher’s note
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Summary
Keywords
flexible electrodes, potassium-ion battery, carbon-based substrates, heteroatom doping, metal nanoparticles
Citation
Li W, Yang Z, Zuo J, Wang J and Li X (2022) Emerging carbon-based flexible anodes for potassium-ion batteries: Progress and opportunities. Front. Chem. 10:1002540. doi: 10.3389/fchem.2022.1002540
Received
25 July 2022
Accepted
22 August 2022
Published
08 September 2022
Volume
10 - 2022
Edited by
Tao Wei, Jiangsu University of Science and Technology, China
Reviewed by
Weiling Liu, Nanyang Technological University, Singapore
Xianhong Rui, Guangdong University of Technology, China
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© 2022 Li, Yang, Zuo, Wang and Li.
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*Correspondence: Xifei Li, xfli2011@hotmail.com
† These authors have contributed equally to this work
This article was submitted to Electrochemistry, a section of the journal Frontiers in Chemistry
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