Structure and Properties of Prussian Blue Analogues in Energy Storage and Conversion Applications

Yi, Haiqiong; Qin, Runzhi; Shihua, Ding; Wang, Yuetao; Li, Shunning; Zhao, Qinghe; Pan, Feng

doi:10.1002/adfm.202006970

Cited by 295 publications

(227 citation statements)

References 123 publications

(162 reference statements)

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“…They have also been proposed as insertion cathodes for next-generation batteries, especially SIBs. [27][28][29][30][31] PBAs can be described using the chemical formula…”

Section: Introductionmentioning

confidence: 99%

“…Recently, it has been reported that the M position in this system can be substituted by other redox-active transition metals, such as Mn, Ni, Cu, Co, V, and Cr, thus allowing modification of the electrochemical behavior. [27][28][29][30][31] In this study, the high-entropy approach is applied to the Prussian blue (PB) structure, utilizing metal cations previously reported in conventional single-or dual-metal PBAs. The HE-PBA material Na x (FeMnNiCuCo)[Fe(CN) 6 ], where the different transition metals have been introduced to the M site in equimolarity, is presented.…”

Section: Introductionmentioning

confidence: 99%

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High‐Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage

et al. 2021

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Prussian blue analogues (PBAs) are reported to be efficient sodium storage materials because of the unique advantages of their metal–organic framework structure. However, the issues of low specific capacity and poor reversibility, caused by phase transitions during charge/discharge cycling, have thus far limited the applicability of these materials. Herein, a new approach is presented to substantially improve the electrochemical properties of PBAs by introducing high entropy into the crystal structure. To achieve this, five different metal species are introduced, sharing the same nitrogen‐coordinated site, thereby increasing the configurational entropy of the system beyond 1.5R. By careful selection of the elements, high‐entropy PBA (HE‐PBA) presents a quasi‐zero‐strain reaction mechanism, resulting in increased cycling stability and rate capability. The key to such improvement lies in the high entropy and associated effects as well as the presence of several active redox centers. The gassing behavior of PBAs is also reported. Evolution of dimeric cyanogen due to oxidation of the cyanide ligands is detected, which can be attributed to the structural degradation of HE‐PBA during battery operation. By optimizing the electrochemical window, a Coulombic efficiency of nearly 100% is retained after cycling for more than 3000 cycles.

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“…They have also been proposed as insertion cathodes for next-generation batteries, especially SIBs. [27][28][29][30][31] PBAs can be described using the chemical formula…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

High‐Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage

et al. 2021

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“…PBAs are regarded as one of most promising hosts for metal ion intercalation due to high capacity stemming from multi-electron reaction and its 3D open framework with large ionic channels for rapid ion conduction. [153][154][155] Generally, it can be described as…”

Section: Prussian Blue Analogsmentioning

confidence: 99%

Manganese‐Based Materials for Rechargeable Batteries beyond Lithium‐Ion

Zhang

Sun

et al. 2021

Advanced Energy Materials

108

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etc., is essentially crucial to help combat these hazards and build a sustainable society. Among them, rechargeable battery has been regarded as a key technology. In the past decade, we have witnessed that the prevailing lithium-ion batteries (LIBs) made our society more portable, intelligent, and cleaner. [17][18][19] Nevertheless, the limited lithium resources and rising cost hinder their applications in the long run, especially in the field of large-scale stationary energy storage for renewable energy resources (e.g., solar, tide, and wind power). Thus, it is a huge stimulus for researchers to explore more sustainable rechargeable battery systems, which are expected to involve abundant and nontoxic metals to reduce the cost and impacts on environment.Diversified rechargeable batteries such as, the monovalent sodium-ion batteries (SIBs), [20][21][22][23][24] potassium-ion batteries (PIBs), [25][26][27] bivalent zinc-ion batteries (ZIBs), [28][29][30][31] magnesium-ion batteries (MIBs), [32][33][34][35] calcium-ion batteries (CIBs), [36][37][38][39] and trivalent aluminum-ion batteries (AIBs), [40][41][42] have emerged and shown great energy storage promise. As depicted in Figure 1a, those nonlithium metals are much more abundant than Li, especially Al, Ca, Na, K, and Mg, all of which rank the top-8 abundant elements in earth crust. For SIBs and PIBs, since Al would not form alloys with Na and K, Al foil can be used as anode collector, which further lowers the prices of SIBs and PIBs. On the other hand, the higher standard potential of Na/Na + (−2.71 V vs standard hydrogen electrode, SHE) and K/K + (−2.93 V) and their heavier atomic weights make energy densities of SIBs and PIBs intrinsically lower than that of LIBs. For multivalent-ion batteries, the multielectron transfer enables their volumetric capacities (e.g., 5857 and 8056 mA h cm −3 for Zn and Al, respectively) higher than that of Li (2042 mA h cm −3 ). [43,44] Additionally, the small cation radius of Zn 2+ (0.74 Å), Mg 2+ (0.72 Å), and Al 3+ (0.54 Å) indicate that many intercalation electrode materials typical in LIBs may be also potential hosts for reversible intercalation of these multivalent ions. Combining all the above merits, one can anticipate that these emerging rechargeable batteries would be considered as promising alternatives to LIBs.In quest of safe, cost-effective, and high-performance rechargeable batteries, two technical routes have been

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“…Due to their open framework of PBAs with enough space for Na + ion accommodation and the advantage of SIBs, the research interest of PBAs as electrode materials in SIBs has been particularly increasing. [ 52 ] KM II Fe III (CN) 6 (M = Mn, Fe, Co, Ni, and Zn) compounds were first examined by Goodenough and co‐workers as cathodes for nonaqueous SIBs. [ 53 ] A reversible capacity less than 70 mAh g −1 was delivered in KM II Fe III (CN) 6 (M = Mn, Co, Ni, and Zn) electrodes originating from the Fe 3+ /Fe 2+ redox couple with single ≈3.0 V plateau.…”

Section: Applications Of Nano‐pbas Themselves For Energy Storagementioning

confidence: 99%

Prussian Blue Analogs and Their Derived Nanomaterials for Electrochemical Energy Storage and Electrocatalysis

Song

Wang

et al. 2021

Small Methods

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Prussian blue analogs (PBAs), the oldest artificial cyanide‐based coordination polymers, possess open framework structures, large specific surface areas, uniform metal active sites, and tunable composition, showing significant perspective in electrochemical energy storage. These electrochemically active materials have also been converted to various functional metal containing nanomaterials, including carbon encapsulated metals/metal alloys, metal oxides, metal sulfides, metal phosphides, etc. originating from the multi‐element compositions as well as elaborate structure design. In this paper, a comprehensive review will be presented on the recent progresses in the development of PBA frameworks and their derivatives based electrode materials and electrocatalysts for electrochemical energy storage and conversion. In particular, it will focus on the synthesis of representative nanostructures, the structure design, and figure out the correlation between nanomaterials structure and electrochemical performance. Lastly, critical scientific challenges in this research area are also discussed and perspective directions for the future research in this field are provided, in order to provide a brand new vision into the further development of novel active materials for the next‐generation advanced electrochemical devices.

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Structure and Properties of Prussian Blue Analogues in Energy Storage and Conversion Applications

Cited by 295 publications

References 123 publications

High‐Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage

High‐Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage

Manganese‐Based Materials for Rechargeable Batteries beyond Lithium‐Ion

Prussian Blue Analogs and Their Derived Nanomaterials for Electrochemical Energy Storage and Electrocatalysis

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