Polymeric ion traps for suppressing or minimizing transition metal ions and dendrite formation or growth in lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-10581119-B2
Application number	US-201715644422-A
Country	US
Kind code	B2
Filing date	Jul 7, 2017
Priority date	Jul 7, 2017
Publication date	Mar 3, 2020
Grant date	Mar 3, 2020

Abstract

Electrochemical cells that cycle lithium ions and methods for suppressing or minimizing dendrite formation are provided. The electrochemical cells include a positive electrode, a negative electrode, and a separator disposed therebetween. At least one transition metal ion-trapping moiety, including one or more polymers functionalized with one or more trapping groups, may be included within the electrochemical cell as a coating, pore filler, substitute pendant group, or binder. The one or more trapping groups may be selected from the group consisting of: crown ethers, siderophores, bactins, ortho-phenanthroline, iminodiacetic acid dilithium salt, oxalates malonates, fumarates, succinates, itaconates, phosphonates, and combinations thereof, and may bind to metal ions found within the electrochemical cell to minimize or suppress formation of dendrite protrusions on the negative electrode.

First claim

What is claimed is:

1. An electrochemical cell that cycles lithium ions having improved capacity retention comprising:
a positive electrode comprising a positive lithium-based electroactive material and one or more polymeric binder materials;
a negative electrode comprising a negative electroactive material;
a microporous polymeric separator disposed therebetween; and
at least one transition metal ion-trapping moiety comprising one or more polymers functionalized with one or more trapping groups selected from the group consisting of: ortho-phenanthroline, malonates, fumarates, succinates, and combinations thereof, wherein the one or more trapping groups bind to at least one transition metal ion within the electrochemical cell to minimize or suppress formation of dendrite protrusions on the negative electrode.

2. The electrochemical cell of claim 1 , wherein the at least one transition metal ion-trapping moiety is included in one or more of the following:
a) coated on a surface of the positive electrode;
b) coated on a surface of the negative electrode;
c) coated on a surface of the separator;
d) disposed in pores of the positive electrode as a pore filler;
e) mixed with the polymeric binder materials of the positive electrode;
f) disposed in pores of the separator as a pore filler; or
g) grafted as a substitute pendant group onto one or more polymers forming the microporous polymeric separator.

3. The electrochemical cell of claim 1 , further comprising an electrolyte system, wherein the electrolyte system comprises the at least one transition metal ion-trapping moiety and conducts lithium ions and the electrolyte system is soaked into at least one of the positive electrode, the negative electrode, or the separator.

4. The electrochemical cell of claim 3 , wherein the electrolyte system further comprises:
one or more lithium salts selected from the group consisting of: lithium hexafluorophosphate (LiPF 6 ); lithium perchlorate (LiClO 4 ); lithium tetrachloroaluminate (LiAlCl 4 ); lithium iodide (LiI); lithium bromide (LiBr); lithium thiocyanate (LiSCN); lithium tetrafluoroborate (LiBF 4 ); lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ); lithium bis-(oxalate)borate (LiB(C 2 O 4 ) 2 ) (LiBOB); lithium hexafluoroarsenate (LiAsF 6 ); lithium trifluoromethanesulfonate (LiCF 3 SO 3 ); bis(trifluoromethanesulfonimide) (LiN(CF 3 SO 2 ) 2 ); lithium fluorosulfonylimide (LiN(FSO 2 ) 2 ); and combinations thereof; and
one or more solvents selected from the group consisting of: cyclic carbonates, acyclic carbonates, aliphatic carboxylic esters, γ-lactones, chain structure ethers, cyclic ethers, and combinations thereof.

5. The electrochemical cell of claim 1 , wherein the negative electroactive material of the negative electrode includes one or more of the following: graphite, lithium titanate, silicon, silicon-carbon composites, silicon oxides, or tin oxides; and
the positive lithium-based electroactive material of the positive electrode includes one or more of the following: spinel lithium manganese oxide; lithium cobalt oxide; lithium iron phosphate; lithium manganese phosphate; lithium vanadium phosphate; binary combinations of lithium iron phosphate, lithium manganese phosphate, or lithium vanadium phosphate; a lithium binary oxide of two elements selected from manganese (Mn), nickel (Ni), and cobalt (Co); or a lithiated ternary oxide of manganese (Mn), nickel (Ni), and cobalt (Co).

6. The electrochemical cell of claim 1 , wherein the one or more polymer binder materials is selected from the group consisting of: vinylbenzene-styrene copolymer, polyvinylidene fluoride (PVdF), ethylene polypropylene diene monomer rubber (EPDM), carboxymethyl cellulose (CMC), lithium salt of polyacrylic acid (LiPAA), lithium salt of sodium alginate, lithium salt of lithium alginate, and combinations thereof.

7. The electrochemical cell of claim 1 , wherein the malonates are polymer-bound sodium (Na) or lithium (Li) salts of malonic acid; the fumarates are polymer-bound sodium (Na) or lithium (Li) salts of fumaric acid; and the succinates are polymer-bound sodium (Na) or lithium (Li) salts of succinic acid.

8. The electrochemical cell of claim 1 , wherein the electrochemical cell includes the at least one transition metal ion-trapping moiety in an amount greater than or equal to about 5 weight % of a weight of the separator to less than or equal to about 50 weight % of the weight of the separator.

9. The electrochemical cell of claim 1 , wherein the at least one transition metal ion includes iron (Fe) ions, nickel (Ni) ions, cobalt (Co) ions, chromium (Cr) ions, copper (Cu) ions, zinc (Zn) ions, tin (Sn), or combinations thereof.

10. An electrochemical cell that cycles lithium ions having improved capacity retention comprising:
a positive electrode comprising a positive lithium-based electroactive material and one or more polymeric binder materials;
a negative electrode comprising a negative electroactive material;
a microporous polymeric separator disposed therebetween
an electrolyte system disposed within at least one of the positive electrode, negative electrode, and separator; and
at least one transition metal ion-trapping moiety comprising one or more polymers functionalized with one or more trapping groups selected from the group consisting of: ortho-phenanthroline, malonates, fumarates, succinates, and combinations thereof, wherein the one or more trapping groups bind to iron (Fe) ions within the electrochemical cell to minimize or suppress aggregation of the iron (Fe) ions and a surface of the negative electrode is substantially free of protruding dendrites.

11. The electrochemical cell of claim 10 , wherein the at least one transition metal ion-trapping moiety is included in one or more of the following:
a) coated on a surface of the positive electrode;
b) coated on a surface of the negative electrode;
c) coated on a surface of the separator;
d) disposed in pores of the positive electrode as a pore filler;
e) mixed with the polymeric binder material of the positive electrode;
f) disposed in pores of the separator as a pore filler; or
g) grafted as a substitute pendant group onto one or more polymers forming the microporous polymeric separator.

12. The electrochemical cell of claim 10 , wherein the electrochemical cell includes the at least one transition metal ion-trapping moiety in an amount greater than or equal to about 5 weight % of a weight of the separator to less than or equal to about 50 weight % of the weight of the separator.

13. The electrochemical cell of claim 10 , wherein the malonates are polymer-bound sodium (Na) or lithium (Li) salts of malonic acid; the fumarates are polymer-bound sodium (Na) or lithium (Li) salts of fumaric acid; and the succinates are polymer-bound sodium (Na) or lithium (Li) salts of succinic acid.

14. A method of suppressing or minimizing dendrite formation and improving cycling performance and capacity retention in an electrochemical cell that cycles lithium ions, the method comprising:
introducing at least one transition metal ion-trapping moiety into the electrochemical cell, wherein the at least one transition metal ion-trapping moiety comprises one or more polymers functionalized with one or more trapping groups selected from the group consisting of: 1,7-dialkyldiaza-12-crown-4; 1,4,13-trioxa-7,10-dialkyl-7,10-diazacyclopentadecane; 1,4,10,13-tetraoxa-7,16-dialkyl-7,16-diazacyclooctadecane; 7,16-di(alkylbenzyl)-1,4,10,13-tetra-7,16-diazacyclooctadecane; 3,11-dialkyl-3,11-diaza-1,5,9,13-tetrathiacyclohexadecane; 3,11,19-trialkyl-3,11,19-triaza-1,5,9,13,17,21-hexathiacyclotetracosane; 1,4,7

Assignees

• Gm Global Tech Operations Llc

Inventors

• Halalay Ion C
• Li Zicheng
• Fuller Timothy J
• Powell Jr Bob R

Classifications

• B01J39/18

  Macromolecular compounds (B01J39/17 takes precedence) · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M4/13

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title

• H01M4/628

  Inhibitors, e.g. gassing inhibitors, corrosion inhibitors · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title