The crystal structure of Prussian Blue:  Fe4[Fe(CN)6]3.xH2O

Buser, H. J.; Schwarzenbach, D.; Petter, W.; Lüdi, A.

doi:10.1021/ic50177a008

Cited by 951 publications

(755 citation statements)

References 6 publications

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“…3.33 for x = 1.0. The water content is found to increase with increasing x for x B 0.8, which is not what is expected and it is contrary to what has been reported in other studies, where alkali-rich compounds have been found to have lower water contents than alkali-free ones [13,14]. The observed variation with x can qualitatively be attributed to the fact that the incorporated K ?…”

Section: Degree Of Hydrationcontrasting

confidence: 96%

“…alkali-free, with formula Fe III [Fe II (CN) 6 ] 3/4 Á3.5-4H 2 O. The two terms soluble and insoluble refer to the ease of peptization rather than true solubility, as both compounds are highly insoluble in water [13,14]. PBAs have a general formula A x M[M 0 (CN) 6 ] z ÁnH 2 O, where M and M 0 are transition metal ions, A is a monovalent cation, and z B 1.…”

Section: Introductionmentioning

confidence: 99%

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A thermogravimetric study of thermal dehydration of copper hexacyanoferrate by means of model-free kinetic analysis

Åkerblom

Ojwang

Grîns

et al. 2017

J Therm Anal Calorim

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The kinetics of thermal dehydration of K 2x/3 Cu [Fe(CN) 6 ] 2/3 ÁnH 2 O was studied using thermogravimetry for x = 0.0 and 1.0. Data from both non-isothermal and isothermal measurements were used for model-free kinetic analysis by the Friedman and KAS methods. The water content was determined to be n = 2.9-3.9, plus an additional *10% of water, likely surface adsorbed, that leaves very fast when samples are exposed to a dry atmosphere. The determined average activation energy for 0.2 B a B 0.8 is 56 kJ mol -1 . The dehydration is adequately described as a diffusion-controlled single-step reaction following the D3 Jander model. The determined dehydration enthalpy is 11 kJ (mol H 2 O) -1 for x = 0.0 and 27 kJ (mol H 2 O) -1 for x = 1.0, relative to that of water. The increase with increasing x is evidence that the H 2 O molecules form bonds to the incorporated K ? ions.

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Section: Degree Of Hydrationcontrasting

confidence: 96%

Section: Introductionmentioning

confidence: 99%

A thermogravimetric study of thermal dehydration of copper hexacyanoferrate by means of model-free kinetic analysis

Åkerblom

Ojwang

Grîns

et al. 2017

J Therm Anal Calorim

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“…For these reasons, Mn II -N CMn III/II was selected as the anode to be used in full cells with the Cu II -N C-Fe III/II cathode. X-ray diffraction of the fresh powders of both Cu II -N CFe III and Mn II -N C-Mn III revealed that they both have the FCC Prussian Blue crystal structure 27 . Their fully indexed diffraction spectra are shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…This structure is composed of a face-centred cubic framework of transition metal cations where each cation is octahedrally coordinated to hexacyanometallate groups ( Fig. 1) [25][26][27] . For instance, in the copper hexacyanoferrate cathode, sixfold carboncoordinated iron and sixfold nitrogen-coordinated copper are linked by CN ligands.…”

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confidence: 99%

Full open-framework batteries for stationary energy storage

et al. 2014

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New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.

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“…Th e previously described Prussian Blue batteries and electrochromics used electrodeposited thin fi lm electrodes that were less than 300 nm thick, and that had mass loadings too low ( μ g cm − 2 ) to be relevant for large-scale energy storage 16 . Th e extreme insolubility of Prussian Blue makes the control of bulk precipitation syntheses diffi cult, and they oft en result in products with poor crystallinity and K + and Fe 3 + impurities 11,12 . Here we replace the nitrogen-coordinated Fe 3 + with Cu 2 + , and use a controlled co-precipitation synthesis to produce highly crystalline nanoparticles of CuHCF with the Prussian Blue open framework structure.…”

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confidence: 99%

Copper hexacyanoferrate battery electrodes with long cycle life and high power

2011

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Short-term transients, including those related to wind and solar sources, present challenges to the electrical grid. Stationary energy storage systems that can operate for many cycles, at high power, with high round-trip energy effi ciency, and at low cost are required. Existing energy storage technologies cannot satisfy these requirements. Here we show that crystalline nanoparticles of copper hexacyanoferrate, which has an ultra-low strain open framework structure, can be operated as a battery electrode in inexpensive aqueous electrolytes. After 40,000 deep discharge cycles at a 17 C rate, 83 % of the original capacity of copper hexacyanoferrate is retained. Even at a very high cycling rate of 83 C, two thirds of its maximum discharge capacity is observed. At modest current densities, round-trip energy effi ciencies of 99 % can be achieved. The low-cost, scalable, room-temperature co-precipitation synthesis and excellent electrode performance of copper hexacyanoferrate make it attractive for largescale energy storage systems.

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The crystal structure of Prussian Blue: Fe4[Fe(CN)6]3.xH2O

Abstract: During this period final calculations were performed and the manuscript was prepared.Registry No. [Te(etu)4]Cl2-2H20, 63848-47-5.

Cited by 951 publications

References 6 publications

A thermogravimetric study of thermal dehydration of copper hexacyanoferrate by means of model-free kinetic analysis

A thermogravimetric study of thermal dehydration of copper hexacyanoferrate by means of model-free kinetic analysis

Full open-framework batteries for stationary energy storage

Copper hexacyanoferrate battery electrodes with long cycle life and high power

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