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摘要: 钾离子电容器（PICs）是与锂离子电容器和钠离子电容器相比极具竞争力和发展前景的一种储能设备。PICs结合了电池式阳极和电容式阴极的优点，具有成本低、能量密度高、功率密度高、循环寿命长等优点。然而，在PICs中一直存在正负极比容量和动力学不匹配的问题。前期研究证明，合理选择电极材料并对其进行优化是解决这一问题的有效手段之一。本文对PICs阳极材料的研究进展进行了综述，主要包括插入型负极材料和转换型负极材料。主要讨论了炭材料(石墨、软炭、硬炭等)、KTO、MXenes、K2TP等插入型材料和金属硫化物/硒化物、金属磷化物、NASICON型磷酸盐等转化型材料。对半电池和PICs中不同电极的制备方法、结构特点和电化学性能进行总结，并进一步展望了PICs未来的发展机遇和挑战。Abstract: Potassium-ion capacitors (PICs) are promising energy storage devices, which are competitive with lithium-ion and sodium ion capacitors. PICs combine the advantages of a battery-type anode and a capacitive cathode, resulting in a low cost, high energy density, high power density and long cycle life. However, there is still a mismatch between the anode and cathode materials for achieving the optimum specific capacity and kinetics in PICs. Early studies have shown that the careful selection of electrode materials and their optimization is an effective way to solve this problem. We focus on the development of PIC anode materials including insertion-type and conversion-type materials. The insertion-type materials include carbon materials (graphite, soft carbons, hard carbons, etc.), K-based titanates, MXenes, and dipotassium terephthalate. The conversion-type materials include metal sulfides/selenides, metal phosphides and sodium super ionic conductor-type phosphates (NASICON). Their preparation, structural characteristics, electrochemical performance as anode materials in half-cell and PIC devices are summarized and discussed. The future prospects and challenges of PICs are also considered.
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Key words:
- Potassium-ion capacitors /
- Carbon materials /
- Anode /
- Energy storage devices
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Figure 1. Development of metal-ion capacitors. The hybrid capacitors included in the picture: LIC: Li4Ti5O12//AC[7], graphite//AC[8], SIC: V2O5/CNT//AC[9] (Reprinted with permission by John Wiley and Sons), NTO/CT//GF[10], PIC: graphite//AC[11] (Reprinted with permission by Elsevier), K2TP//AC[12], MoSe2/C//AC[13], S-KTO@C//AC[14] , MDPC//PDPC[15], and BN-PC//BN-PC[16] (Reprinted with permission by John Wiley and Sons).
Figure 2. (a) TEM image of SC and (b) schematic illustration of discharging mechanism of SC//AC PICs[38] (Reprinted with permission by John Wiley and Sons).
Figure 3. (a) SEM image of WPCS, (b) active mass normalized Ragone plots based on total mass of both the cathode and anode compared with previously reported WPCS-based PICs, (c) rate capability profiles for WPCS electrode[46] (Reprinted with permission by American Chemical Society).
Figure 4. (a) The schematic image of the BPCS structure made by the “tree crown-stem” model, (b) cycling performance of the PIC tested at 2 A g−1[47] (Reprinted with permission by American Chemical Society), (c) TEM image of MDPC, d) long‐term cycling performance at 2 A g−1[15] (Reprinted with permission by John Wiley and Sons), (e) SEM image of OLC, (f) cycling performance of the assembled OLC//AC PICs with different mass ratios (1∶2, 1∶1 and 2∶1) at the current density of 2 A g−1[74] (Reprinted with permission by Royal Society of Chemistry).
Figure 5. (a) SEM image of 3DNFC, (b) cycling stability of the optimal 3DNFC//3DNFAC device tested at 2 A g−1 for 10000 cycles within the voltage window of 0−4.2 V[80] (Reprinted with permission by Elsevier), (c) SEM images of BN-PC, and (d) cycling performance of PIC-1∶1 tested at a current density of 2 A g−1[16] (Reprinted with permission by John Wiley and Sons).
Figure 6. (a) Schematic illustration for preparation of S-N-PCNs, (b) rate capabilities of the S-N-PCNs, N-PCNs and PCNs electrodes, (c) long-term cycle performance of the AC//S-N-PCNs at a current density of 1 A g−1[83] (Reprinted with permission by John Wiley and Sons).
Figure 7. (a) Schematic illustration showing the structural characteristics of the TiO2/C@NPSC material, (b) the cycling stability and CE of TiO2/C@NPSC at 1 A g−1, (c) the long cycle stability and CE of the as-assembled TiO2/C@NPSC//ZDPC PIC[84] (Reprinted with permission by Royal Society of Chemistry). (d) TEM images of NPG nanosheets, (e) CV curves at scan rates of 5, 10, and 20 mV s−1 and (f) galvanostatic charge–discharge curves at current densities of 0.5−10 A g−1[88] (Reprinted with permission by Springer Nature).
Figure 8. (a) SEM images of K2Ti6O13 (KTO), (b) long-term cycling stability at the current density of 1 A g−1[93] (Reprinted with permission by American Chemical Society), (c) SEM images of S-KTO@C and (d) long-term cycling stability of the PIC device at 5 A g−1 for 3000 cycles[14] (Reprinted with permission by John Wiley and Sons).
Figure 9. (a) Morphology and structure characters of the 3D-Ti3C2 , (b) electrochemical performance of PICs (3D-Ti3C2//HPAC)[97] (Reprinted with permission by John Wiley and Sons), (c) schematic illustration of the PIC with the configuration K2TP//DME-based electrolyte//AC, (d) ragone plots of the PIC of K2TP//AC, and other reported PICs and (e) cycling performance of the PIC at 100 mA g−1 for 500 cycles[12] (Reprinted with permission by Royal Society of Chemistry).
Figure 10. (a) SEM images of N-MoSe2/G, (b) long-term cyclic performance at 1 A g−1[13] (Reprinted with permission by John Wiley and Sons), (c) SEM images of MoSe2/C-700, (d) cycling performance of MoSe2/C-700, (e) cycling performance of the PIC at 1.0 A g−1[105] (Reprinted with permission by Royal Society of Chemistry), (f) SEM images of FeSe2 and (g) the cycle stability of the PIC at 500 mA g−1[106] (Reprinted with permission by John Wiley and Sons).
Figure 11. (a) SEM images of ED-MoS2@CT, (b) cycling performance for ED-MoS2@CT//PC PIC with an optimal mass ratio tested at 10 A g−1 between 0 and 4.0V[35] (Reprinted with permission by John Wiley and Sons, (c) low magnification TEM image of MoS2/3Se4/3/CHNTs, (d) cycling performance of MoS2/3Se4/3/C-HNTs and pure MoS2/C-HNTs at 0.2 A g−1, (e) cycling stability of PIC based on the MoS2/3Se4/3/C-HNT anode and AC cathode at 2.0 A g−1[115] (Reprinted with permission by Royal Society of Chemistry), (f) SEM image of NbSe2/NSeCNFs composite and (g) the cycling stability of the NbSe2/NSeCNFs//AC PICs at 2 A g−1[120] (Reprinted with permission by John Wiley and Sons).
Figure 12. (a) Low-magnification TEM images of the U-Co2P@rGO-14 nanocomposite, (b) long-cycle performance of the AC//U-Co2P@rGO-14 PIC device[124] (Reprinted with permission by Royal Society of Chemistry, (c) SEM images of CTP@C and (d) long-cycle performance and the charge–discharge curves (inset) of PIC[127] (Reprinted with permission by John Wiley and Sons).
Table 1. A comparison of the physical properties of Li, Na and K.
Li Na K Atomic number 3 11 19 Melting point (°C) 180 97.72 63.25 Density (g/cm3) 0.534 0.968 0.86 Atomic radius (pm) 123 154 203 Voltage vs S.H.E (V) −3.04 −2.71 −2.93 Price (USD/Ton) 13900 152 790 Element content in the crust (%） 0.0017 2.36 2.09 
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