A Metal–Organic Compound as Cathode Material with Superhigh Capacity Achieved by Reversible Cationic and Anionic Redox Chemistry for High‐Energy Sodium‐Ion Batteries

Fang, Chun; Huang, Ying; Yuan, Lixia; Liu, Yaojun; Chen, Wei‐Lun; Huang, Yangyang; Chen, Kongyao; Han, Jiantao; Liu, Qingju; Huang, Yunhui

doi:10.1002/anie.201701213

Cited by 90 publications

(65 citation statements)

References 25 publications

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“…Moreover, the transition metal ions participate in the electrochemical reaction at high potentials, which is helpful to raise the battery voltage. In our previous work, we demonstrated a metal–organic compound of CuTCNQ as SIB cathode material showing a very high specific capacity. We found that the cationic Cu + and anionic TCNQ − could simultaneously participate in the redox reaction with a three‐electron transfer process.…”

Section: Figurementioning

confidence: 99%

In Situ‐Formed Hierarchical Metal–Organic Flexible Cathode for High‐Energy Sodium‐Ion Batteries

et al. 2017

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Metal-organic compounds are a family of electrode materials with structural diversity and excellent thermal stability for rechargeable batteries. Here, we fabricated a hierarchical nanocomposite with metal-organic cuprous tetracyanoquinodimethane (CuTCNQ) in a 3 D conductive carbon nanofibers (CNFs) network by in situ growth, and evaluated it as flexible cathode for sodium-ion batteries (SIBs). CuTCNQ in such flexible composite electrode is able to exhibit a high capacity of 252 mAh g at 0.1 C and highly reversible stability for 1200 cycles within the voltage range of 2.5-4.1 V (vs. Na /Na). A high specific energy of 762 Wh kg was obtained with high average potential of 3.2 V (vs. Na /Na). The in situ-formed electroactive metal-organic composites with tailored nanoarchitecture provide a promising alternative choice for high-performance cathode materials in SIBs with high energy.

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Section: Figurementioning

confidence: 99%

In Situ‐Formed Hierarchical Metal–Organic Flexible Cathode for High‐Energy Sodium‐Ion Batteries

et al. 2017

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“…[1][2][3][4][5][6][7][8][9][10][11] Hitherto, the commercialization of SIBs has been held back, however, by their low energy density and unsatisfactory cycle life. [1][2][3][4][5][6][7][8][9][10][11] Hitherto, the commercialization of SIBs has been held back, however, by their low energy density and unsatisfactory cycle life.…”

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confidence: 99%

Stress Distortion Restraint to Boost the Sodium Ion Storage Performance of a Novel Binary Hexacyanoferrate

Han

Wang

et al. 2019

Advanced Energy Materials

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and are considered as a new generation of energy storage devices to replace lithium ion batteries (LIBs) in certain applications. [1][2][3][4][5][6][7][8][9][10][11] Hitherto, the commercialization of SIBs has been held back, however, by their low energy density and unsatisfactory cycle life. The cathode, as much as the anode, also plays an important role in the final performance of the battery. Thus, it is crucial to develop cathode candidates with both high energy density and stable cycle life for sodium ion storage.It is accepted that the energy density is determined by the specific capacity and the voltage plateau of an electrode. The commercial cathode materials for LIBs can deliver 510-700 Wh kg −1 energy density with a potential plateau of 3.4-4.1 V (3.4 V for LiFePO 4 and 4.1 V for spinel LiMn 2 O 4 ) and high specific capacity of over 150 mAh g −1 . In comparison, most of the cathode candidates reported for SIBs show a potential plateau below 3.2 V and a capacity below 110 mAh g −1 , delivering energy density lower than 350 Wh kg −1 . [12][13][14][15][16][17] Exceptionally, the sodium superionic conductor Na 3 V 2 (PO 4 ) 3 presented a 3.4 V potential plateau and 115 mAh g −1 capacity; Na 3 (VO 1−x PO 4 ) 2 F 1+2x (0 < x < 1) showed 3.8-3.9 V average voltage and 120-130 mAh g −1 capacity. [18][19][20][21][22] Honeycomb-layered Na 3 Ni 2 SbO 6 provided an average working potential at 3.3 V and a high capacity of ≈120 mAh g −1 . Moreover, Na 3 Ni 2 SbO 6 showed superior rate capability and excellent cycling performance. [23,24] In the long run, however, these cathode materials containing toxic elements (V and Sb) are not suitable for commercial SIBs because commercialization also requires electrode materials to possess the properties of environmental friendliness and low cost in addition to excellent electrochemical performance.Recently, Prussian blue analogues (PBAs) have attracted much attention owing to their low cost and environmentalfriendliness. [6,[25][26][27][28] The PBAs utilized for electrode materials can be classified into three groups, that is, hexacyanoferrates (ATFe(CN) 6 ), hexacyanomanganates (ATMn(CN) 6 ), and hexacyanocobaltates (ATCo(CN) 6 , where A = K, Na; T = Fe, Mn, Ni, Co). Among them, hexacyanoferrates, in particular, have been put under the spotlight due to their nonpoisonous raw material ferrocyanide (Na 4 Fe(CN) 6 or K 3 Fe(CN) 6 ), while the raw materials K 3 Mn(CN) 6 for hexacyanomanganate and K 3 Co(CN) 6 for hexacyanocobaltate are harmful and toxic. In the case of Mn-based hexacyanoferrate Na x MnFe(CN) 6 (NMHFC) has been attracting more attention as a promising cathode material for sodium ion storage owing to its low cost, environmental friendliness, and its high voltage plateau of 3.6 V, which comes from the Mn 2+ /Mn 3+ redox couple. In particular, the Na-rich NMHFC (x > 1.40) with trigonal phase is considered an attractive candidate due to its large capacity of ≈130 mAh g −1 , delivering high energy density. Its unstable cycle life, however, is holding back its practica...

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“…The cathodic peaks at 2.35 and 2.15 Vs hift to higherp otential and the integral areas of these peaks along with anodic peak at 3.0 Vs hrink, caused by the dissolution of TCNQ xÀ ,asreported previously. [22,23] An unnoticeable anodicp eak at 1.6 Vi nt he first three scans remains after 100 cycles,w hichm ight be caused by pesudocapacitance similar to Cu-vacancy formed in Cu 2 Ou ltra-small nanocrystals. [34] The cycling performance of Cu-TCNQ/Cu was measured in a voltager ange of 0.01-3.0 Va nd compared with Cu-TCNQ powder ( Figure 3b).…”

Section: Resultsmentioning

confidence: 99%

“…[19][20][21] Recently,asamember of MOFs,Cu-TCNQ has been investigated as ap romising high-capacity cathode materialf or both sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). [22][23][24][25] Elaborately designed experimentsr eveal that the super high capacity of Cu-TCNQ as cathode materialf or SIBs is contributed by at hree-electron redoxc hemistry in each charge/discharge process between 2.0-4.1 V. Both copper and TCNQ species take parti nt he electrochemical conversion reactions for sodium storage. [23] Although LIBs and SIBs are similar in the redox reactionm echanism, smaller diameterso fL i + ions make LIBs perform distinctively.…”

Section: Introductionmentioning

confidence: 99%

“…[22][23][24][25] Elaborately designed experimentsr eveal that the super high capacity of Cu-TCNQ as cathode materialf or SIBs is contributed by at hree-electron redoxc hemistry in each charge/discharge process between 2.0-4.1 V. Both copper and TCNQ species take parti nt he electrochemical conversion reactions for sodium storage. [23] Although LIBs and SIBs are similar in the redox reactionm echanism, smaller diameterso fL i + ions make LIBs perform distinctively. [26] To date, Cu-TCNQ has not been investigated as an anode materialf or LIBs in the lower voltage range.…”

Section: Introductionmentioning

confidence: 99%

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Multiple Active Sites: Lithium Storage Mechanism of Cu‐TCNQ as an Anode Material for Lithium‐Ion Batteries

Meng

Chen

Fang

et al. 2019

Chemistry An Asian Journal

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Recently, carboxylate metal‐organic framework (MOF) materials were reported to perform well as anode materials for lithium‐ion batteries (LIBs); however, the presumed lithium storage mechanism of MOFs is controversial. To gain insight into the mechanism of MOFs as anode materials for LIBs, a self‐supported Cu‐TCNQ (TCNQ: 7,7,8,8‐tetracyanoquinodimethane) film was fabricated via an in situ redox routine, and directly used as electrode for LIBs. The first discharge and charge specific capacities of the self‐supported Cu‐TCNQ electrode are 373.4 and 219.4 mAh g−1, respectively. After 500 cycles, the reversible specific capacity of Cu‐TCNQ reaches 280.9 mAh g−1 at a current density of 100 mA g−1. Mutually validated data reveal that the high capacity is ascribed to the multiple‐electron redox conversion of both metal ions and ligands, as well as the reversible insertion and desertion of Li+ ions into the benzene rings of ligands. This work raises the expectation for MOFs as electrode materials of LIBs by utilizing multiple active sites and provides new clues for designing improved electrode materials for LIBs.

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A Metal–Organic Compound as Cathode Material with Superhigh Capacity Achieved by Reversible Cationic and Anionic Redox Chemistry for High‐Energy Sodium‐Ion Batteries

Cited by 90 publications

References 25 publications

In Situ‐Formed Hierarchical Metal–Organic Flexible Cathode for High‐Energy Sodium‐Ion Batteries

In Situ‐Formed Hierarchical Metal–Organic Flexible Cathode for High‐Energy Sodium‐Ion Batteries

Stress Distortion Restraint to Boost the Sodium Ion Storage Performance of a Novel Binary Hexacyanoferrate

Multiple Active Sites: Lithium Storage Mechanism of Cu‐TCNQ as an Anode Material for Lithium‐Ion Batteries

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