Li-ion and Na-ion insertion into size-controlled nickel hexacyanoferrate nanoparticles

Abstract

The influence of particle size on the electrochemical properties of guest-ion storage materials has attracted much attention because of the extensive need for long cycle-life, high energy density, and high power batteries. The present work describes a systematic study of the effect of particle size on the guest-ion storage capabilities of a cyanide-bridged coordination polymer. A series of nickel hexacyanoferrate particles ranging from approximately 40 to 400 nm were synthesized by a co-precipitation method and were used as the cathode material for both Li-ion and Na-ion insertion/extraction experiments using organic electrolyte. A large polarization was observed for the largest particles during Li-ion cycling, indicating a heterogeneous ion concentration within the lattice. As a consequence, the available capacity of Li-ion intercalation at high rates is significantly improved by reducing the particle size. On the other hand, Na-ion intercalation shows excellent rate capability regardless of the particle size.Scheme 1 Schematic depiction of alkali ion insertion mechanism in the cubic Prussian blue analogue structure. The cyanometallate vacancies and coordinated and zeolitic water molecules are omitted for clarity.

A High‐Energy Aqueous Sodium‐Ion Capacitor with Nickel Hexacyanoferrate and Graphene Electrodes

“…The nickel hexacyanoferrate (Ni‐HCF) nanostructures were prepared by a rapid sonochemical reaction using nickel chloride, and potassium ferricyanide precursors . Briefly, aqueous solution containing 1 M nickel chloride and 0.5 M potassium ferricyanide were prepared separately in two beakers.…”

Nickel hexacyanoferrate, a versatile intercalation host for divalent ions from nonaqueous electrolytes

“…The capacities in all three electrolytes are similar to the capacities seen in Na and aqueous batteries (50 mAh/g). [7,15,18] The capacity and voltage behavior variations with cycling are dependent on the chemistry. In particular, the response of the Mg and Ca systems investigated are opposite with respect to capacity retention upon cycling.…”

“…In the example of V 2 O 5 , only low intercalation capacity can be obtained unless substantial amounts of water are present in the electrolyte. [14] Prussian blue type complexes have been explored extensively for use in Na and Li based nonaqueous batteries, [15][16][17][18][19] making them a promising candidate for use with multivalent ions.…”

Comparison of Charge Storage Properties of Prussian Blue Analogues Containing Cobalt and Copper

“…Prussian blue analogues (PBAs) and other open framework intercalation compounds have been the subject of increasing interest as promising battery materials [1][2][3][4][5][6]. The general formula for PBAs can be written as A j M k [M (CN) 6 ] l , where M and M are transition metals, A is a counter cation, and the stoichiometry depends on the identities of M, M , and A, as well as the number of cyanometalate vacancies incorporated into the structure [7]. Supercapacitive behavior occurs in these materials when the metal centers change oxidation state, accompanied by the intercalation or deintercalation of counter cations.…”

“…Supercapacitive behavior occurs in these materials when the metal centers change oxidation state, accompanied by the intercalation or deintercalation of counter cations. For example, in the subset of PBAs known as hexacyanoferrates (HCFs), where M = Fe, one possible redox reaction is [7,8] AM II Fe III (CN) 6…”