鉀離子電池的研究進展及展望

廖樹青; 董廣生; 趙贏營; 陳玉金; 曹殿學; 朱凱

doi:10.13374/j.issn2095-9389.2021.08.17.004

鉀離子電池的研究進展及展望

doi: 10.13374/j.issn2095-9389.2021.08.17.004

廖樹青¹,
董廣生¹,
趙贏營^{1, 2, ,},
陳玉金^{1, 2},
曹殿學¹,
朱凱^1, ,

1.
哈爾濱工程大學材料科學與化學工程學院，哈爾濱 150001
2.
哈爾濱工程大學物理與光電工程學院，哈爾濱 150001

基金項目: 國家自然科學基金資助項目（51702063）

詳細信息

通訊作者:
趙贏營, E-mail: zhaoyy@hrbeu.edu.cn

朱凱, E-mail: kzhu@hrbeu.edu.cn

中圖分類號: TG142.71
計量
- 文章訪問數: 978
- HTML全文瀏覽量: 1129
- PDF下載量: 244
- 被引次數: 0
出版歷程
- 收稿日期: 2021-08-17
- 網絡出版日期: 2021-10-08
- 刊出日期: 2023-07-25

Research progress and prospect of potassium-ion batteries

1.
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
2.
College of Physics and Optoelectronic Engineering, Harbin Engineering University, Harbin 150001, China

More Information

Corresponding author: ZHAO Ying-ying, E-mail: zhaoyy@hrbeu.edu.cn;; ZHU Kai, E-mail: kzhu@hrbeu.edu.cn

摘要

摘要: 鋰離子電池（LIBS）已經廣泛應用到便攜式電子產品和電動汽車上。然而，隨著鋰資源的開采使用，鋰離子電池的成本也在逐漸增加。相比之下，地殼中較高的鉀含量使得鉀離子電池（KIB）成本相對較低。進而，鉀離子電池作為一種新型低成本儲能器件受到了廣泛關注。但鉀離子的半徑較大，導致充放電過程中，離子嵌入/脫出的動力學性能較差。因此，電池電極材料的選擇面臨著新的挑戰。在對鉀離子電池電極材料進行分類和總結的基礎之上，重點介紹了石墨及各種形式的碳材料、過渡金屬氧化物、合金類等負極材料以及普魯士藍、層狀金屬氧化物、聚陰離子型化合物等正極材料的研究進展，并對鉀離子電池的發展進行了展望，以期對高性能鉀離子電池的發展提供新思路。
- 鉀離子電池 /
- 負極材料 /
- 正極材料 /
- 研究進展 /
- 高性能
Abstract: Development and utilization of renewable energy sources have gain great progress in recent years, which lead to increasing demands for large scale energy storage systems. Lithium-ion batteries have been widely used in portable electronic devices and electric vehicles. However, with the exploitation of the Earth’s lithium resources, the cost of lithium-ion batteries is gradually increasing. In contrast, the higher terrestrial potassium content promises inexpensive potassium-ion batteries, and the chemical properties of potassium and lithium ions are similar. Meanwhile, the low redox potential of K promises a high working voltage of potassium ion batteries. Thus, potassium-ion batteries have attracted considerable attention as a capable battery technology. However, the large radius of the potassium ion leads to unsatisfactory ion intercalation and extraction behavior during charging and discharging processes, resulting in poor cycling performance, unsatisfactory rate ability, and low capacity. The challenge remains to explore capable electrode materials for potassium-ion batteries to achieve a high energy density and power density. This review summarizes the anode and cathode materials of potassium-ion batteries in recent reports, including the research progress of graphite and other carbon materials, transition metal oxides/sulfides, alloys, and other anode materials, as well as Prussian blue, layered metal oxides, and polyanionic compound cathode materials, which will provide new ideas for developing high-performance potassium-ion batteries. We also discuss the potassium ion storage mechanism in these electrode materials. This review also demonstrates the approaches (nanotechnology, heteroatom doping, carbon coating, composite fabrication) to further improve the electrochemical performance of the cathode and anode. In addition, we point out the key factors for potassium ion batteries performance, such as the design of anode materials, exploitation of novel cathode materials, and optimization of full potassium ion cells fabrication, which would provide new thought for the development of potassium ion batteries with high performances.
- potassium-ion battery /
- anode materials /
- cathode materials /
- research progress /
- high performance

HTML全文

圖 1 鉀離子嵌入石墨的過程階段研究. （a）在27.9 mA·g^?1電流密度下的第一圈恒流充放電曲線; （b）非原位XRD表征; （c）反應結構示意圖^[13]

Figure 1. Study on the process stage of potassium ion intercalate into graphite: (a) first-cycle galvanostatic charge and discharge profiles at 27.9 mA·g^?1; (b) ex situ XRD; (c) structure diagrams^[13]

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圖 2 大規模制備分層多孔氮摻雜碳微球作為鉀離子電池負極材料的示意圖^[40]

Figure 2. Schematic of the large-scale fabrication of hierarchically porous nitrogen-doped carbon microspheres as anode material in KIBs^[40]

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圖 3 SNHC和高溫碳化聚苯胺（CPAN）的儲鉀性能. （a）用于鉀離子電池的SNHC中大容量存儲的示意圖; （b）不同倍率下的倍率性能;（c）SNHC電極在3 A·g^?1下超過1200次的循環性能^[44]

Figure 3. Potassium storage properties of SNHC and CPAN: (a) schematic of bulk storage in SNHC for KIBs; (b) rate performance at different rates; (c) cycling performance of the SNHC electrodes at 3 A·g^?1 over 1200 cycles^[44]

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圖 4 電弧放電示意圖和NPG在鉀離子電池中的電化學性能. （a）電弧放電過程示意圖; （b）電弧放電系統圖; （c）電弧等離子區; （d）NPG電極在鉀離子電池中不同電流密度下的倍率; （e）電流密度為500 mA·g^?1時NPG電極的循環和庫侖效率圖^[80]

Figure 4. Schematic of discharge process and electrochemical performances of NPG at PIB: (a) schematic of the arc discharge process; (b) digital image of the arc discharge system; (c) typical photograph of the arc plasma; (d) rate capabilities of NPG electrodes in the potassium battery; (e) graph of the cycle and coulombic efficiency of NPG electrodes at a current density of 500 mA·g^?1[80]

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圖 5 TiO₂/RGO合成示意圖和電化學性能. (a)合成示意圖；（b）在鋰離子電池中的充放電曲線; （c）循環伏安曲線; （d）贗電容貢獻; （e）鉀離子電池中的倍率性能; （f）長循環性能^[89]

Figure 5. Formation schematic and electrochemical performances of TiO₂/RGO: (a) formation schematic; (b) charge-discharge curves in Li ion battery; (c) CV curves; (d) pseudocapacitance contributions; (e) rate capability in K-ion battery; (f) long cycling performance ^[89]

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圖 6 KMO/NTS?30和CuO納米片的形貌和電化學性能. （a）KMO/NTS?30材料的SEM圖^[90]；（b）所制備的KMO/CNT?30電極和對照KMO電極的循環性能^[90]；（c）CuO納米片的SEM圖;（d）在100 mA·g^?1時的循環性能^[91]

Figure 6. Morphology and electrochemical properties of KMO/NTS?30 and CuO nanosheets: (a) SEM image of KMO/NTS?30 material^[90]; (b) cycling performance of the as-prepared KMO/CNT?30 electrode and the control KMO electrode^[90]; (c) SEM image of CuO nanosheets; (d) cycling performance at 100 mA·g^{?1 [91]}

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圖 7 CoP?NPPCS的合成過程和電化學性能. （a）合成過程示意圖; （b）倍率性能; （c）循環性能^[99]

Figure 7. Febrication schematic and electrochemical performances of CoP?NPPCS: (a) schematic of the synthesis process; (b) rate performance; (c) cycling performance^[99]

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圖 8 Sb@CSN材料的合成示意圖和電化學性能與機制.（a）Sb@CSN材料的合成示意圖；（b）K的晶體結構和鉀化過程中從Sb到K₃Sb的結構演變；（c）不同鉀化過程的DFT計算的平衡電壓；（d）Sb@CSN電極在0.05 mV?s^?1掃描速率下的初始CV曲線；（e）從具有不同放電電壓的EDS結果獲得的K和Sb的相對原子百分比；（f）放電截止電壓為0.01V時K₃Sb的EDS元素分析^[111]

Figure 8. Synthetic schematic, electrochemical properties and mechanisms of Sb@CSN material: (a) synthetic schematic; (b) crystal structure of K and the structure evolution from Sb to K₃Sb during the potassiation process; (c) equilibrium voltages calculated by DFT of different potassiation processes; (d) initial CV curves of the Sb@CSN electrode at a scan rate of 0.05 mV?s^?1; (e) relative atomic percent of K and Sb obtained from EDS results with different discharge voltages; (f) EDS element analysis for K₃Sb with a discharge cut-off voltage of 0.01 V ^[111]

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