High rate, long cycle life battery electrode materials with an open framework structure

A technology of electrode materials and anode materials, applied in battery electrodes, structural parts, primary batteries, etc., can solve problems such as reducing round-trip energy efficiency

Inactive Publication Date: 2014-03-05
THE BOARD OF TRUSTEES OF THE LELAND STANFORD JUNIOR UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Additionally, these battery technologies typically exhibit a significant amount of voltage hysteresis and thus have reduced round-trip energy efficiency when operating at high rates

Method used

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  • High rate, long cycle life battery electrode materials with an open framework structure
  • High rate, long cycle life battery electrode materials with an open framework structure
  • High rate, long cycle life battery electrode materials with an open framework structure

Examples

Experimental program
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Embodiment 1

[0099] copper hexacyanoferrate

[0100] This example describes copper hexacyanoferrate ("CuHCF"), whose electrochemical reaction can be expressed as KCuFe III (CN) 6 +xK + +xe - =K 1+x Cu[Fe II (EN) 6 ] x [Fe III (EN) 6 ] 1-x . Anhydrous KCuFe(CN) 6 The theoretical specific capacity for some embodiments is about 85 mAh / g. In practice and for some embodiments, capacities of about 60 mAh / g and lower are typically observed because the framework structure contains zeolite water. Inductively coupled plasma mass spectrometry of CuHCF synthesized by the bulk precipitation reaction found a K:Cu:Fe ratio of approximately 0.71:1:0.72. Following the previous convention for hydration of crystal structures, the formula for copper-based materials is K 0.71 Cu[Fe(CN) 6 ] 0.72 3.7H 2 O. The theoretical specific capacity of the material with this formula is about 62 mAh / g, which is consistent with the observed specific capacity. Because the exact water content varies with te...

Embodiment 2

[0112] Nickel hexacyanoferrate

[0113] This example describes nickel hexacyanoferrate ("NiHCF"), whose electrochemical reaction can be expressed as ANiFe III (EN) 6 +A + +e – =A 2 NiFe II (EN) 6 , where A + is a cation such as sodium or potassium. The following describes the unique behavior of high-capacity battery electrodes comprising bulk NiHCF powders prepared by the chemical precipitation method.

[0114] NiHCF has a Prussian blue crystal structure in which transition metal cations such as Fe and Ni are bound by bridging CN ligands to form a face-centered cubic structure (see Image 6 ). In the case of NiHCF, Fe is sixfold carbon coordinated, while Ni (e.g., Ni 2+ ) is six heavy nitrogen coordination. The resulting framework has large channels oriented in the direction, and hydrated cations such as K + and Na + can diffuse through it. These cations occupy interstitial "A" sites on the center of each of the eight subcells of the unit cell. When the materia...

Embodiment 3

[0125] Copper hexacyanoferrate and nickel hexacyanoferrate

[0126] This example describes additional measurements of CuHCF and NiHCF of some embodiments. To investigate the effect of intercalation species on the electrochemical properties of bulk CuHCF and NiHCF, these materials were cycled in aqueous electrolytes containing lithium, sodium, potassium, or ammonium ions.

[0127] The synthesis of CuHCF and NiHCF nanopowders was carried out by co-precipitation method. Simultaneous dropwise addition of approximately 40 mM copper or nickel nitrate and approximately 20 mM potassium hexacyanoferrate to deionized water allowed controlled co-precipitation of solid CuHCF or NiHCF product. The synthesis of CuHCF is carried out at room temperature, while the synthesis of NiHCF is carried out at about 70°C. These solid products were filtered, washed with water, and dried under vacuum at room temperature. Up to about 3 g of product are produced during each synthesis, and these synthese...

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Abstract

A battery includes a cathode, an anode, and an aqueous electrolyte disposed between the cathode and the anode and including a cation A. At least one of the cathode and the anode includes an electrode material having an open framework crystal structure into which the cation A is reversibly inserted during operation of the battery. The battery has a reference specific capacity when cycled at a reference rate, and at least 75% of the reference specific capacity is retained when the battery is cycled at 10 times the reference rate.

Description

[0001] Cross References to Related Applications [0002] This application claims the benefit of U.S. Provisional Application Nos. 61 / 499,877 and 61 / 529,766, filed June 22, 2011 and August 31, 2011, respectively, and U.S. Application Nos. 13 / 482,793 and 13 / 482,796, both Both were filed on May 29, 2012, the disclosures of which are hereby incorporated by reference in their entirety. technical field [0003] The present invention relates generally to batteries, and more particularly to electrode materials for aqueous electrolyte batteries. Background technique [0004] To a large extent, recent research and development in battery technology has involved work on various forms of lithium-ion systems and has focused on small to medium scale applications such as portable electronics and vehicle propulsion. Despite the costly short outage periods, the rapidly growing need for frequency regulation, and the need for load balancing corresponding to the integration of intermittent ener...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M10/04H01M6/04
CPCH01M4/505H01M10/0568H01M4/58H01M10/0525H01M2300/0005H01M4/02H01M6/045H01M10/054Y02E60/122H01M10/36H01M2300/0091H01M4/366Y02P70/50Y02E60/10H01M4/62
Inventor R·A·胡金斯Y·崔M·帕斯塔C·维塞尔斯
Owner THE BOARD OF TRUSTEES OF THE LELAND STANFORD JUNIOR UNIV
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