Surface-modified cyanide-based transition metal compounds

Patent metadata

Field	Value
Publication number	US-10414666-B2
Application number	US-201715859160-A
Country	US
Kind code	B2
Filing date	Dec 29, 2017
Priority date	Jun 30, 2015
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

A system, method, and articles of manufacture for a surface-modified transition metal cyanide coordination compound (TMCCC) composition, an improved electrode including the composition, and a manufacturing method for the composition which may include multiple chelation species (Che_x). The composition, compound, device, and uses thereof according to AxMn(y-k)Mjk[Mnm(CN)(6-p-q)(NC)p(Che_I)rq]z. CHE_GROUP (Vac)(1-z).nH2O, wherein CHE_GROUP includes one or more chelation materials selected from the group consisting of (Che_I)rw, (Che_II)sv, and combinations thereof, and wherein 0<j≤4, 0≤k≤0.1, 0≤(p+q)≤6, 0<x≤4, 0<y≤1, 0<z≤1, 0<w≤0.2; −3≤r≤3; 0<v≤0.2; −3≤s≤3; and 0≤n≤6; wherein x+2(y−k)+jk+(m+(r+1)q−6)z+wr+vs=0.

First claim

What is claimed as new and desired to be protected by Letters Patent of the United States is:

1. A method for manufacturing an environment-stabilized TMCCC material, comprising:
a) synthesizing a particulated TMCCC material from a precursor salt, said precursor salt including a transition metal and a first chelation species (Che_I); and thereafter
b) combining the particulated TMCCC material with a solution including a second chelation species (Che_II) to produce a stabilized TMCCC, said second chelation species including one or more chemical species selected from the group including a first material including said first chelation species, a second material excluding said first chelation species, and combinations thereof;
wherein said stabilized TMCCC material includes:
at least one composition represented by Formula II:
A x Mn (y-k) M j k [Mn m (CN) (6-p-q) (NC) p (Che_I) r q ] z . CHE_GROUP (Vac) (1-z) .nH 2 O, wherein CHE_GROUP includes one or more chelation materials selected from the group consisting of (Che_I) r w , (Che_II) s v , and combinations thereof:
wherein, in Formula II, each A is an independently selected alkali metal Li, Na, or K;
and each dopant M may optionally be at least one independently selected alkaline earth metal Mg or Ca, post-transition metal Al, Ga, In, Sn, or Pb, or transition metal Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Pd, Ag, or Cd having an average valence j; and Che represents an acid chelating agent which includes ligand binding atoms that form one or more covalent linkages with Mn or with Mn and M; and
wherein 0<j≤4, 0≤k≤0.1, 0≤(p+q)≤6, 0<x≤4, 0<y≤1, 0<z≤1, 0<w≤0.2; −3≤r≤3; 0<v≤0.2; −3≤s≤3; and 0≤n≤6;
wherein x+2(y−k)+jk+(m+(r+1)q−6)z+wr+vs=0; and
wherein Formula II includes one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes each including an Mn atom, and wherein p is an average number of NC groups found in said one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes; and wherein q is an average number of Che_I groups found in said one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes; and
wherein m is an average valence of said Mn atoms found in said one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes;
wherein (Vac) identifies a Mn(CN) (6-p-q) (NC) p (Che_I) r q vacancy;
wherein CN identifies a cyano group; and
wherein NC identifies an isocyano group.

2. The method of claim 1 further comprising:
c) isolating said stabilized TMCCC.

3. The method of claim 1 wherein one or both of said first chelation species and said second chelation species comprises an organic acid.

4. The method of claim 3 wherein said organic acid comprises a compound containing a carboxylate group.

5. The method of claim 4 wherein said compound comprises one or more of acetic acid, formic acid, oxalic acid, gluconic acid, succinic acid, lactic acid, citric acid, sodium glycinate, or sodium oxalate.

6. The method of claim 3 wherein said organic acid comprises a compound containing an acid of an amine.

7. The method of claim 6 wherein said compound comprises EDTA.

8. The method of claim 3 wherein said organic acid comprises a compound containing a phosphonic acid group.

9. The method of claim 8 wherein said compound comprises HEDP.

10. The method of claim 1 wherein one or both of said first chelation species and said second chelation species comprises one or more components selected from the group consisting of formic acid, acetic acid, gluconic acid, malic acid, citric acid, homo citric acid, succinic acid, lactic acid, malonic acid, aspartic acid, 3,4-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, tartaric acid, salicylic acid, glutamic acid, oxalic acid, 2,3-Di mercapto-1-propane sulfonic acid, meso-2,3-di mercapto succinic acid, glycine, alanine, imino di acetic acid, EDTA (ethylene diamine tetra-acetic acid), EGTA ethylene glycol-bis(2-amino ethyl ether)-N,N,N′,N′-tetra acetic acid), EDDS (ethylene di amine-N,N′-di succinic acid), NTA (nitrilo-tri-acetic acid), DTPA (diethyl triamine penta-acetic acid), PDTA (1,3-propylene diamine penta-acetic acid), MGDA (methyl glycine diacetic acid), β-ADA (β-alanine diacetic acid), HEIDA (N-(2-hydroxyethyl)imino diacetic acid), DHEG (N,N-bis(2-hydroxyethyl)glycine), HEDTA (hydroxy ethyl-ethylene diamine tri-acetic acid), quadrol (N,N,N′,N′-tetrakis-2-hydroxyisopropyl-ethylendiamine), DTPMP (diethylene triaminopenta (methylene phosphonic acid)), EDTMP (ethylene diaminotetra(methylene phosphonic acid)), HDTMP (hexamethylene diaminotetra (methylene phosphonic acid)), ATMP (aminotrimethylene phosphonic acid), HEDP (hydroxyethane dimethylene phosphonic acid) and PBTC (2-butane phosphate 1,2,4-tricarboxylic acid), phosphoric acid, pyrophosphoric acid, and combinations thereof.

11. A material, comprising:
at least one composition represented by Formula II:
A x Mn (y-k) M j k [Mn m (CN) (6-p-q) (NC) p (Che_I) r q ] z . CHE_GROUP (Vac) (1-z) .nH 2 O, wherein CHE_GROUP includes one or more chelation materials selected from the group consisting of (Che_I) r w , (Che_II) s v , and combinations thereof:
wherein, in Formula II, each A is an independently selected alkali metal Li, Na, or K;
and each dopant M may optionally be at least one independently selected alkaline earth metal Mg or Ca, post-transition metal Al, Ga, In, Sn, or Pb, or transition metal Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Pd, Ag, or Cd having an average valence j; and Che represents an acid chelating agent which includes ligand binding atoms that form one or more covalent linkages with Mn or with Mn and M; and
wherein 0<j≤4, 0≤k≤0.1, 0≤(p+q)≤6, 0<x≤4, 0<y≤1, 0<z≤1, 0<w≤0.2; −3≤r≤3; 0<v≤0.2; −3≤s≤3; and 0≤n≤6;
wherein x+2(y−k)+jk+(m+(r+1)q−6)z+wr+vs=0; and
wherein Formula II includes one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes each including an Mn atom, and wherein p is an average number of NC groups found in said one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes; and wherein q is an average number of Che_I groups found in said one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes; and
wherein m is an average valence of said Mn atoms found in said one or more Mn(CN) (6-p-q) (NC) p (Che_I) r q complexes;
wherein (Vac) identifies a Mn(CN) (6-p-q) (NC) p (Che_I) r q vacancy;
wherein CN identifies a cyano group; and
wherein NC identifies an isocyano group.

12. The material of claim 11 wherein one or both of said first chelation species and said second chelation species comprises an organic acid.

13. The material of claim 12 wherein said organic acid comprises a compound containing a carboxylate group.

14. The material of claim 13 wherein said compound comprises one or more of acetic acid, formic acid, oxalic acid, gluconic acid, succinic acid, lactic acid, citric acid, sodium glycinate, or sodium oxalate.

15. The material of claim 11 wherein said organic acid comprises a compound containing an acid of an amine.

16. The material of claim 15 wherein said compound comprises EDTA.

17. The material of claim 11 wherein said organic acid comprises a compound containing a phosphonic acid group.

18. The material of claim 17 wherein said compound comprises HEDP.

19. An electrode, comprising:
a current collector having a surface; and
a composite coupled to said surface, said composite including an electrochemically active material having a composition, a binder, and an electrically conductive material, wherein said composition comprises at least one composition represented by Formula II:
A x Mn (y-k) M j k [Me(CN) (6-p-q) (NC) p (

Assignees

• Natron Energy Inc

Inventors

• Motallebi Shahrokh
• Wessells Colin Deane

Classifications

• H01M10/05

  Accumulators with non-aqueous electrolyte (H01M10/39 takes precedence) · CPC title

• H01M4/60

  of organic compounds · CPC title

• H01M10/36

  Accumulators not provided for in groups H01M10/05-H01M10/34 · CPC title

• C01C3/11 Primary

  Complex cyanides · CPC title

• C01C3/12

  Simple or complex iron cyanides · CPC title