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Metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode

A metal doping, battery electrode technology, applied in the field of electrochemical batteries, can solve the problems of small capacity and reducing the concentration of mobile ions, etc.

Inactive Publication Date: 2015-12-23
SHARP KK
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The interstitial space of TMHCF occupied by water molecules reduces the concentration of mobile ions in the interstitial space, which leads to the small capacity of TMHCF electrodes during charge / discharge

Method used

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  • Metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode
  • Metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode
  • Metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Example 1: Al 0.05 mn 0.95 -HCF

[0063] Solution 1 is Na 4 Fe(CN) 6 of aqueous solution. Solution 2 contains Mn 2+ and Al 3+ ion. Slowly drop solution 2 into solution 1 to form Al 0.05 mn 0.95 - Precipitation of HCF. After separation, washing and drying, the Al 0.05 mn 0.95 -HCF is used as an electrode in a sodium-ion battery with saturated NaClO 4 Ethylene carbonate / diethyl carbonate (EC / DEC) electrolyte. For comparison, Mn-HCF was synthesized under the same conditions.

[0064] Figure 5A and Figure 5B is Mn-HCF doped with aluminum (Al 0.05 mn 0.95 -HCF) electrode compared with Mn-HCF (undoped) electrode. The capacity was normalized by the maximum capacity of the Mn-HCF electrode during the first discharge. Figure 5A depicts the Mn-HCF and Al 0.05 mn 0.95 - Comparison of charge / discharge curves of HCF electrodes. Using Al 3+ Ion doping increased the capacity of the Mn-HCF electrode by about 15%. The electrodes were then cycled at currents of...

Embodiment 2

[0066] Example 2: NaKMn-HCF

[0067] Solution 1 contains Na 4 Fe(CN) 6 and K 4 Fe(CN) 6 . Solution 2 is Mn 2+The solution. Solution 1 and Solution 2 were mixed together to obtain NaKMn-HCF. For comparison, Mn-HCF was synthesized under the same conditions. NaKMn-HCF was evaluated as an electrode in a Na-ion battery with saturated NaClO 4 Ethylene carbonate / diethyl carbonate (EC / DEC) electrolyte.

[0068] Image 6 is a graph depicting the change in capacity of Mn-HCF and NaKMn-HCF electrodes cycled at different charge / discharge currents. Although the capacity of NaKMn-HCF is lower than that of Mn-HCF during the first cycle, it exhibits better capacity retention. After 100 cycles, the normalized capacity of KNaMn-HCF was 111%, but that of Mn-HCF at 0.1C was 91%. In other words, since K + The doping of ions increases the capacity retention by 20%. K + Ions greater than Na + ions, which support the structure of Mn-HCF and stabilize it during charge / discharge cycles....

Embodiment approach

[0081] US 13 / 897,492 is incorporated herein by reference.

[0082] One with Fe(CN) 6 An additive transition metal hexacyanoferrate (TMHCF) battery electrode comprising: a metal current collector; A covering the current collector x m y Fe z (CN) n .mH 2 O particles; wherein the A cation is selected from alkali metal cations and alkaline earth metal cations; wherein M is a transition metal; wherein x is 0-2; wherein y is 0-2; wherein z is 0.1-2; wherein n is 1-6; Wherein m is 0~7; And Fe(CN) 6 Additive pair A x m y Fe z (CN) n .mH 2 O particles are modified.

[0083] The TMHCF battery electrode, wherein Fe(CN) 6 Additives are selected from ferrocyanide ([Fe(CN) 6 ] 4- ) and ferricyanide ([Fe(CN) 6 ] 3- ).

[0084] The TMHCF battery electrode, wherein the A cation is selected from sodium (Na), potassium (K), calcium (Ca) and magnesium (Mg).

[0085] A kind of synthesis has Fe(CN) 6 A method for additive transition metal hexacyanoferrate (TMHCF) battery electrod...

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Abstract

A method is provided for synthesizing a metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode. The method prepares a first solution of AxFe(CN)6 and Fe(CN)6, where A cations may be alkali or alkaline-earth cations. The method adds the first solution to a second solution containing M-ions and M'-ions. M is a transition metal, and M' is a metal dopant. Subsequent to stirring, the mixture is precipitated to form AxMcM'dFez(CN)n.mH2O particles. The AxMcM'dFez(CN)n.mH2O particles have a framework and interstitial spaces in the framework, where M and M' occupy positions in the framework. Alternatively, the method prepares AaA'bMyFez(CN)n.mH2O particles. A and A' occupy interstitial spaces in the AaA'bMyFez(CN)n.mH2O particle framework. A metal-doped TMHCF electrode is also provided.

Description

technical field [0001] The present invention relates generally to electrochemical cells, and more particularly to a metal-doped transition metal hexacyanoferrate (TMHCF) battery electrode and related methods of manufacture. Background technique [0002] A battery is an electrochemical cell by which chemical energy and electrical energy are converted back and forth. The energy density of a battery is determined by its voltage and charge capacity. Li vs. H 2 / H + Has the most negative potential of -3.04V, and has the highest gravimetric capacity of 3860 milliamp hours per gram (mAh / g). Due to their high energy density, lithium-ion batteries have ushered in a revolution in portable electronic devices. However, the high cost of lithium metal makes the commercialization of lithium batteries as large-scale energy storage devices questionable. Additionally, the demand for lithium and its reserves as a mineral has created the need to construct other types of metal-ion batteries...

Claims

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Application Information

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IPC IPC(8): H01M4/58C01C3/12H01M4/136
CPCC01C3/12H01M4/136H01M4/1397H01M4/364H01M4/5825Y02E60/10
Inventor 鲁宇浩李宗霑大卫·埃文斯
Owner SHARP KK
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