Thermodynamics of mixed-valence intercalation reactions: the electrochemical reduction of Prussian blue

McCargar, James W.; Neff, Vernon D.

doi:10.1021/j100323a055

Cited by 89 publications

(83 citation statements)

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“…2b ). Th e sloping, S-shaped potential profi le indicates a solid solution reaction proceeding by intercalation, which is also consistent with previous measurements of Prussian Blue analogues 13,14,16,22,23 . During cycling at a rate of 0.83C, a capacity of 59.14 mAh g − 1 was observed, and 67 % of this capacity, 40.1 mAh g − 1 , was retained during cycling at a rate 100 times greater, 83C ( Fig.…”

Section: Resultssupporting

confidence: 90%

“…Although the position of each diff raction peak shift ed with charge state, no new peaks appeared during charging. Th is confi rms that the electrochemical cycling of CuHCF is a single-phase reaction, in agreement with the observed potential profi les and previous discussions of Prussian Blue analogues 13,14,23 . Th e 0.9 % increase in lattice parameter ( Fig.…”

Section: Resultssupporting

confidence: 90%

“…Electrodeposited thin fi lms with this structure are known to reversibly intercalate potassium and other hydrated ions in aqueous electrolytes 13,14 . Th e general formula for these materials is A x PR(CN) 6 , and their crystal structure is analogous to that of the ABX 3 perovskites, with P m + and R n + ions in an ordered arrangement on the B sites 10 -12 .…”

mentioning

confidence: 99%

“…Prussian Blue, nominally KFe 3 + Fe 2 + (CN) 6 , but which also contains zeolitic water, is the prototype material for this open framework structure, and its physical and thermodynamic properties are now well established 14,15 . With this composition only half of the A sites are occupied, the Fe 3 + ions are octahedrally coordinated to the nitrogen ends of the CN − groups, and the Fe 2 + ions to their carbon ends.…”

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confidence: 99%

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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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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 90%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Copper hexacyanoferrate battery electrodes with long cycle life and high power

2011

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“…In addition, a useful anode must have a very long cycle life and high-rate capability to match the remarkable properties of the CuHCF cathode. In addition to K + , CuHCF can also react with alkali ions, such as Li + and Na + , so an anode capable of reacting with any of these ions could be used 17 . An intuitive choice would be another Prussian Blue analogue with a reaction potential near the SHE.…”

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confidence: 99%

A high-rate and long cycle life aqueous electrolyte battery for grid-scale energy storage

et al. 2012

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new types of energy storage are needed in conjunction with the deployment of solar, wind and other volatile renewable energy sources and their integration with the electric grid. no existing energy storage technology can economically provide the power, cycle life and energy efficiency needed to respond to the costly short-term transients that arise from renewables and other aspects of grid operation. Here we demonstrate a new type of safe, fast, inexpensive, long-life aqueous electrolyte battery, which relies on the insertion of potassium ions into a copper hexacyanoferrate cathode and a novel activated carbon/polypyrrole hybrid anode. The cathode reacts rapidly with very little hysteresis. The hybrid anode uses an electrochemically active additive to tune its potential. This high-rate, high-efficiency cell has a 95% round-trip energy efficiency when cycled at a 5C rate, and a 79% energy efficiency at 50C. It also has zero-capacity loss after 1,000 deep-discharge cycles.

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