ChemInform Abstract: Anomalous Non‐Prussian Blue Structures and Magnetic Ordering of K2MnII[MnII(CN)6] and Rb2MnII[MnII(CN)6].

Her, Jae‐Hyuk; Stephens, Peter W.; Kareis, Christopher M.; Moore, Joshua G.; Min, Kil Sik; Park, Jong-Won; Bali, Garima; Kennon, Bretni S.; Miller, Joel S.

doi:10.1002/chin.201026017

Cited by 14 publications

(44 citation statements)

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“…These values deviate significantly from linearity (i.e., 180°). Similar values have also been reported previously for A 2 Mn[Mn(CN) 6 ] (A = K, Rb) . The linearity of the PBAs framework arrangement is dependent on the ionicity of the M′–CN and M–NC bonding; viz., if they are covalent, then the M′–CN–M angles should be linear.…”

Section: Resultssupporting

confidence: 88%

“…The difference in bond lengths for both the low-spin and high-spin Mn 2+ ions is ∼0.1 Å. This value is of the same magnitude as those reported in literature and may well be credited to slightly distorted MnC 6 and MnN 6 octahedra. , The average Mn–C–N and Mn–N–C bond angles are 165.37(5)° and 143.65(5)°, respectively. These values deviate significantly from linearity (i.e., 180°).…”

Section: Resultssupporting

confidence: 78%

“…The CN stretching frequency can be used to determine the oxidation state, coordination number, and electronegativity of the metals bound to the CN ligands . The ν(CN) stretching mode of [Mn II (CN) 6 ] 4– in PBAs was previously reported to occur in a wavenumber range of <2100 cm –1 with characteristic values around 2055 cm –1 for K 2 Mn[Mn(CN) 6 ]. , The IR spectrum of K 2 Mn[Mn(CN) 6 ]·0.1H 2 O in Figure a exhibits a single ν(CN) band at 2048 cm –1 ( F 1u mode) accompanied by a small shoulder at ∼2023 cm –1 , which is in accord with previous observations . This sharp absorption feature is attributable to Mn II –CN–Mn II , and agrees well with previous reports for this distinctive band. , Antisymmetric stretching vibrations of the main CN stretching band can contribute to the weak shoulder at ∼2023 cm –1 (see also Figure S1 in Supporting Information).…”

Section: Resultsmentioning

confidence: 94%

“…The crystal structure of K 2 Mn[Mn(CN) 6 ] was refined according to the Rietveld method . A monoclinic structural model provided by Her et al (S. G. P 2 1 /n ) resulted in a good refinement fit without considerable modification. The refined cell parameters and volume are a = 10.1660(37) Å, b = 7.3879(22) Å, c = 6.9832(26) Å, β = 90.1685(48)°, and V = 524.473(31) Å 3 .…”

Section: Resultsmentioning

confidence: 99%

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Manganese Hexacyanomanganate as a Positive Electrode for Nonaqueous Li-, Na-, and K-Ion Batteries

et al. 2019

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K2Mn[Mn(CN)6] is synthesized, characterized, and evaluated as possible positive electrode material in nonaqueous Li-, Na-, and K-ion batteries. This compound belongs to the rich and versatile family of hexacyanometallates displaying distinctive structural properties, which makes it interesting for ion insertion purposes. It can be viewed as a perovskite-like compound in which CN-bridged Mn(CN)6 octahedra form an open framework structure with sufficiently large diffusion channels able to accommodate a variety of insertion cations. By means of galvanostatic cycling and cyclic voltammetry tests in nonaqueous alkali metal half-cells, it is demonstrated that this material is able to reversibly host Li+, Na+, and K+ ions via electrochemical insertion/deinsertion within a wide voltage range. The general electrochemical features are similar for all of these three ion insertion chemistries. An in operando X-ray diffraction investigation indicates that the original monoclinic structure is transformed into a cubic one during charging (i.e., removal of cations from the host framework) and that such a process is reversible upon subsequent cell discharge and cation reuptake.

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Section: Resultssupporting

confidence: 88%

Section: Resultssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

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Manganese Hexacyanomanganate as a Positive Electrode for Nonaqueous Li-, Na-, and K-Ion Batteries

et al. 2019

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“…K 2 FeFe(CN) 6 is isostructural to monoclinic K 2 MnMn(CN) 6 Figure a illustrates that the iron is either bound to six carbon atoms of the CN ligands to form FeC 6 octahedra, or bound to six nitrogen atoms of the CN ligands to form FeN 6 octahedra.…”

mentioning

confidence: 99%

Crystallite Size Control of Prussian White Analogues for Nonaqueous Potassium-Ion Batteries

2017

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Nonaqueous potassium-ion batteries have emerged as possible lowcost alternatives to Li-ion batteries for large-scale energy storage, owing to their ability to use graphitic carbon as the negative electrode. Positive electrode materials remain a challenge. Here, we report control of the crystal dimensions of the Prussian white hexacyanoferrate (HCF), K 1.7 Fe[Fe(CN) 6 ] 0.9 , using solution chemistry to obtain either nano, submicron, or micron crystallites. We observe a very strong effect of crystallite size on electrochemical behavior. The optimal cathode material comprised of 20 nm crystallites delivers a close-to-theoretical reversible capacity of 140 mAh g −1 with two well-defined plateaus at 4.0 and 3.2 V vs K/K + upon discharge. Slightly inferior electrochemical behavior is observed for crystallites up to ∼160−200 nm in diameter, but unlike the analogous Na HCFs, micron-sized crystals show very limited capacity. For the nanosized crystallites, however, the energy density of ∼500 Wh kg −1 is comparable to that of the best Na HCF cathode materials. At a relatively high current density of 100 mA g −1 , half-cells cycled with ethylene carbonate/diethyl carbonate (EC/DEC) and 5% fluoroethylene carbonate (FEC) demonstrate an initial discharge capacity of 120 mAh g −1 with a capacity retention of 85% after 100 cycles and 65% after 300 cycles.

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Tuning the Particle Size of Prussian Blue by a Dual Anion Source Method

Wang

Zhu

et al. 2018

Crystal Growth & Design

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The preparation of coordination polymer nanoparticles with different sizes has been currently the focus of research attention in many fields such as gas storage, batteries, drug delivery, magnetic resonance imaging, etc. In this paper, we reported a facile dual anion source (DAS) method to prepare Prussian blue (PB) nanoparticles with different particle sizes. With the increasing of FeII(CN)6 4– reactant usage proportions, the mean size of PB particles increased from 100 nm to 1.6 μm. Such a wide size range was found closely related to the different nucleation processes with varied chemical compositions (proportions of Fe(II) and Fe(III)) of the products. With increasing Fe(II) content in both ends of the cyanide bridge, the PB nucleus generation rate would descend in the product nucleation period. The reported DAS method exploited a new synthetic strategy for controlling the particle size of PB particles. The results would contribute to the research on other coordination polymers in the future.

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ChemInform Abstract: Anomalous Non‐Prussian Blue Structures and Magnetic Ordering of K₂Mn^II[Mn^II(CN)₆] and Rb₂Mn^II[Mn^II(CN)₆].

Cited by 14 publications

References 1 publication

Manganese Hexacyanomanganate as a Positive Electrode for Nonaqueous Li-, Na-, and K-Ion Batteries

Manganese Hexacyanomanganate as a Positive Electrode for Nonaqueous Li-, Na-, and K-Ion Batteries

Crystallite Size Control of Prussian White Analogues for Nonaqueous Potassium-Ion Batteries

Tuning the Particle Size of Prussian Blue by a Dual Anion Source Method

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