Iron Borophosphate as a Potential Cathode for Lithium- and Sodium-Ion Batteries

Asl, Hooman Yaghoobnejad; Stanley, Patrick; Ghosh, K.; Choudhury, Amitava

doi:10.1021/acs.chemmater.5b02642

Cited by 20 publications

(7 citation statements)

References 53 publications

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“…e) Demonstration of Li 0.8 Fe(H 2 O) 2 [BP 2 O 8 ]·H 2 O crystal structure and f) its first three galvanostatic charge–discharge curves. Reproduced with permission . Copyright 2015, American Chemical Society.…”

Section: Iron/manganese‐based Polyanionic‐type Cathode Materialsmentioning

confidence: 99%

“…Other researchers investigated the potential of iron borophosphate as the sodium host for SIBs. Choudhury's group first synthesized the elusive Li‐containing iron borophosphate Li 0.8 Fe(H 2 O) 2 [BP 2 O 8 ]·H 2 O by a hydrothermal approach (Figure e) . This hexagonal structured (space group P 6 5 22) material showed an average voltage of 2.76 V with a discharge capacity of 60 mAh g −1 in half cells (Figure f).…”

Section: Iron/manganese‐based Polyanionic‐type Cathode Materialsmentioning

confidence: 99%

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High‐Abundance and Low‐Cost Metal‐Based Cathode Materials for Sodium‐Ion Batteries: Problems, Progress, and Key Technologies

Chen

Liu

Wang

et al. 2019

Advanced Energy Materials

195

149

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Recently, room-temperature stationary sodium-ion batteries (SIBs) have received extensive investigations for large-scale energy storage systems (EESs) and smart grids due to the huge natural abundance and low cost of sodium. The SIBs share a similar "rocking-chair" sodium storage mechanism with lithium-ion batteries; thus, selecting appropriate electrodes with a low cost, satisfactory electrochemical performance, and high reliability is the key point for the development for SIBs. On the other hand, the carefully chosen elements in the electrodes also largely determine the cost of SIBs. Therefore, earth-abundantmetal-based compounds are ideal candidates for reducing the cost of electrodes. Among all the high-abundance and low-cost metal elements, cathodes containing iron and/or manganese are the most representative ones that have attracted numerous studies up till now. Herein, recent advances on both ironand manganese-based cathodes of various types, such as polyanionic, layered oxide, MXene, and spinel, are highlighted. The structure-function property for the iron-and manganese-based compounds is summarized and analyzed in detail. With the participation of iron and manganese in sodium-based cathode materials, real applications of room-temperature SIBs in large-scale EESs will be greatly promoted and accelerated in the near future.

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Section: Iron/manganese‐based Polyanionic‐type Cathode Materialsmentioning

confidence: 99%

Section: Iron/manganese‐based Polyanionic‐type Cathode Materialsmentioning

confidence: 99%

High‐Abundance and Low‐Cost Metal‐Based Cathode Materials for Sodium‐Ion Batteries: Problems, Progress, and Key Technologies

Chen

Liu

Wang

et al. 2019

Advanced Energy Materials

195

149

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“…Most of the known structures of iron phosphates have been tested as electrodes for Li or Na ion batteries. These include NASICON-type Li 3 Fe 2 (PO 4 ) 3 , lipscombite-type Fe 1.18 (PO 4 )(OH), , other hydroxy-phosphate phases (Fe 5 (PO 4 ) 4 (OH) 3 ·2H 2 O), tavorite-type LiFePO 4 (OH) 1– x F x , − fluoro-phosphates (Na 2 FePO 4 F and LiNaFePO 4 F), , various hydrated phosphates, − pyro-phosphates (LiFeP 2 O 7 , Li 2 FeP 2 O 7 , Na 2 FeP 2 O 7 ), and some mixed polyanions consisting of phosphate and another polyanion: for example, phosphate-pyrophosphate (Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )), phosphate-carbonates, phosphate-nitrate, and boro-phosphates. , In addition to these, a large number of phosphates and mixed polyanions in combination with phosphates in known structure types have been theoretically predicted as potential cathodes for Li ion batteries. − Further development of a low-cost nontoxic electrode has been thwarted due to the lack of known materials in iron phosphate families. A large number of iron phosphates have been discovered in recent years using organo-ammonium cations, but they are not very useful for battery applications since the organic cation occupies a large volume of space in the crystal structure and forms strong hydrogen bonds with the framework oxygen, making it impossible to exchange with smaller alkali ions. − Therefore, synthesis in the presence of alkali ions remains a viable option to discover new iron phosphates.…”

Section: Introductionmentioning

confidence: 99%

Soft chemical routes to electrochemically active iron phosphates

et al. 2019

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New iron phosphates with related structures have been synthesized using hydrothermal and ion-exchange routes, and their electrochemical properties were investigated. First, NaFe(HPO 4 ) 2 was synthesized employing a hydrothermal route and its structure was determined from singlecrystal X-ray diffraction data. Subsequent Na + and partial proton ion exchange with Li + ion produced a known phase, Li 2 Fe(H 0.5 PO 4 ) 2 , and complete deprotonation of Li 2 Fe-(H 0.5 PO 4 ) 2 with Li + by employing a solid-state ion-exchange route produced the new phase Li 3 Fe(PO 4 ) 2 . The structure of the latter was solved from synchrotron powder X-ray data by employing ab initio methods. All of these phases are highly crystalline, built up of similar connectivities between FeO 6 octahedra and PO 4 tetrahedral units. Magnetic susceptibility measurements and room-temperature 57 Fe Mossbauer spectroscopic studies confirm the 3+ oxidation state of the compounds and their antiferromagnetic ordering with Li 2 Fe(H 0.5 PO 4 ) 2 showing some interesting metamagnetic behavior. The compounds are stable up to 400 °C and undergo facile electrochemical lithium/sodium insertion through the reduction of Fe 3+ to Fe 2+ . Galvanostatic charge−discharge studies indicate that up to 0.6 lithium ion and 0.5 sodium ion per formula unit can be inserted at average voltages of 3.0 and 2.75 V for lithium and sodium ion batteries, respectively, for NaFe(HPO 4 ) 2 . The partially Li ion exchanged compound Li 2 Fe(H 0.5 PO 4 ) 2 showed better cycle life and experimentally achievable capacities up to 0.9 Li insertion with strong dependence on particle size. The electrochemical Li insertion in Li 3 Fe(PO 4 ) 2 was also investigated. The electrochemistry of these three related phases were compared with each other, and their mechanism of Li insertion was investigated by ex situ PXRD.

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“…The structural diversity of BPOs also brings along a variety of different functionalities. Examples include nonlinear-optical, − luminescent, , magnetic, − and lithium- and sodium-ion-battery materials. , …”

Section: Introductionmentioning

confidence: 99%

Open-Framework Manganese(II) and Cobalt(II) Borophosphates with Helical Chains: Structures, Magnetic, and Luminescent Properties

et al. 2017

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Two borophosphates, (NH)M(HO)(BPO)·yHO with M = Mn (I) and Co (II), synthesized hydrothermally crystallize in enantiomorphous space groups P622 and P622 with a = 9.6559(3) and 9.501(3) Å, c = 15.7939(6) and 15.582(4) Å, and V = 1275.3(1) and 1218.2(8) Å for I and II, respectively. Both compounds feature helical chains composed of vertex-sharing tetrahedral PO and BO groups that are connected through O atoms to transition-metal cations, Mn and Co, respectively. For the two crystallographically distinct transition-metal cation sites present in the structure, this results in octahedral coordination with different degrees of distortion from the ideal symmetry. The crystal-field parameters, calculated from the corresponding absorption spectra, indicate that Mn and Co ions are located in a weak octahedral-like crystal field and suggest that the Co-ligand interactions are more covalent than the Mn-ligand ones. Luminescence measurements at room temperature reveal an orange emission that red-shifts upon lowering of the temperature to 77 K for I, while II is not luminescent. The luminescence lifetimes of I are 33.4 μs at room temperature and 1.87 ms at 77 K. Both compounds are Curie-Weiss paramagnets with negative Weiss constants and effective magnetic moments expected for noninteracting Mn and Co cations but no clear long-range magnetic order above 2 K.

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Iron Borophosphate as a Potential Cathode for Lithium- and Sodium-Ion Batteries

Abstract: Figure S1. Acquired and calculated powder XRD patterns of Li 0.8 Fe(H 2 O) 2 [BP 2 O 8 ]•H 2 O.Figure S2. FT-IR spectra of Li 0.8 Fe(H 2 O) 2 [BP 2 O 8 ]•H 2 O and its chemically oxidized phase.

Cited by 20 publications

References 53 publications

High‐Abundance and Low‐Cost Metal‐Based Cathode Materials for Sodium‐Ion Batteries: Problems, Progress, and Key Technologies

High‐Abundance and Low‐Cost Metal‐Based Cathode Materials for Sodium‐Ion Batteries: Problems, Progress, and Key Technologies

Soft chemical routes to electrochemically active iron phosphates

Open-Framework Manganese(II) and Cobalt(II) Borophosphates with Helical Chains: Structures, Magnetic, and Luminescent Properties

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