Anion-coordinating polymer electrolytes and related compositions, methods and systems

Patent metadata

Field	Value
Publication number	US-10118976-B2
Application number	US-201715398682-A
Country	US
Kind code	B2
Filing date	Jan 4, 2017
Priority date	Jan 4, 2016
Publication date	Nov 6, 2018
Grant date	Nov 6, 2018

Abstract

Anion-coordinating polymers comprising one or more anion-coordinating unit of Formula (I), optionally in combination with one or more cation-coordinating unit of Formula (II) and/or a linking unit of Formula (III) and related electrolytes, batteries, methods and system.

First claim

The invention claimed is:

1. An anion-coordinating polymer comprising a plurality of one or more anion-coordinating units of Formula (I)

wherein
X 1 , is B, Al or Ga,
X 2 , X 3 , X 4 and X 5 are atoms other than H each optionally bound to one to three hydrogen atoms,
R 1 and R 2 are independently a C1 to C5 linear alkyl group optionally substituted with one or more C1 to C4 alkyl groups, the one or more C1 to C4 groups being optionally substituted with a BF2 group,
x 1 =1, and x 2 , x 3 , x 4 , and x 5 are independently 0 or 1, so that x 1+ x 2+ x 3+ x 4+ x 5 =1 to 4, and
r 1 and r 2 are independently 0 or 1,
and wherein
X 1 , forms together with any optionally bound H atoms, a united atom having a positive partial charge with a magnitude |δ1|=0.25 to 1.15±0.1, and
each of X 2 , X 3 X 4 and X 5 is an atom independently forming, together with any optionally bound H atoms, a united atom having a negative partial charge, with negative partial charges of X 2 , X 3 X 4 and X 5 united atoms having a magnitude |δ2| equal to or less than |δ1|;
optionally in combination with one or more cation coordinating units of Formula (II)

wherein
Q is a group of one to 5 atoms other than H each optionally bound to one to three hydrogen atoms, in which
at least one atom other than C forms together with any optionally bound H atoms, a united atom having has a negative partial charges with a magnitude |δ5|,
and each of the remaining atoms form together with any optionally bound H atoms a united atom, with the remaining united atoms having a positive partial charges with a magnitude |δ6|≤|δ5|,
R 3 and R 4 are independently a C1 to C5 linear alkyl group optionally substituted with one or more C1 to C4 alkyl groups, and
r 3 and r 4 are independently 0 or 1
wherein
the anion-coordinating units of Formula (I) are independently selected to provide in the anion-coordinating polymer a total number of anion-coordinating units u, and
the cation-coordinating units of Formula (II) are independently selected to provide in the anion-coordinating polymer a total number of cation-coordinating units v, and wherein u≥v.

2. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more anion coordinating units of Formula (Ia)

wherein X 1 is B, Al, or Ga, x 2 , x 3 , and x 5 are independently 0 or 1,
R 1 is a C1 to C5 linear alkyl group optionally substituted with one or more C1 to C4 alkyl groups, and
R4 is H or a C1 to C4 alkyl group.

3. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more anion coordinating unit of Formula (Ib)

wherein X1 is B, Al, or Ga,
X 2 is a C1 to C4 alkyl group, and
x 2 , is independently 0 or 1.

4. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more anion coordinating unit of Formulas (Ic) to (If)

5. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more anion coordinating units of Formulas (Ic) or (Id)

6. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more anion coordinating units of Formulas (Ig) to (Iv)

7. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more cation-coordinating units of Formula (IIa):

wherein
Q 1 , Q 2 , Q 3 Q 4 and Q 5 are atoms other than H, each optionally bound to one to three hydrogen atoms,
R 3 and R 4 are independently selected from a C1 to C5 linear alkyl group optionally substituted with one or more C1 to C4 alkyl groups,
q 1 =1, and q 2 q 3 , q 4 , and q 5 are independently 0 or 1, so that q 1+ q 2+ q 3+ q 4+ q 5 =1 to 4, and
r 3 is 0 or 1
and wherein
Q 1 , is an atom forming, together with any optionally bound H atoms, a united atom having a negative partial charge with a magnitude |δ5|=0.25 to 1.15±0.1, and
each of Q 2 , Q 3 Q 4 and Q 5 is an atom independently forming, together with any optionally bound H atoms, a united atom having a positive partial charge, with positive partial charges of Q 2 , Q 3 Q 4 and Q 5 united atoms having a magnitude |δ6| equal to or less than |δ5|.

8. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more cation-coordinating units of Formula (IIb):

wherein Q 1 is N, S or O,
Q 2 , Q 3 and Q 5 are independently a C1 to C4 alkyl group
q 2 , q 3 , and q 5 are independently 0 or 1, and wherein when Q 1 is O q 2 is 0, and
R3 is a C1 to C5 linear alkyl group optionally substituted with one or more C1 to C4 alkyl groups, and
wherein when Q1 is N q2 is 1 and when Q1 is S or O, q2 is 0.

9. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises one or more linking units of formula (III),

wherein L is a moiety of formula (IIIa) to (IIIh)

wherein k 1 to k 8 are independently selected from 1 to 100.

10. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises an unspecified, statistical random alternative block and/or graft copolymer.

11. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises a dendritic polymer of formula (XVI)

wherein T is independently B, Al or Ga, and wherein
E is independently a moiety of Formula (IIIa) to (IIIh)

wherein k 1 to k 8 are independently 1-100.

12. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises a homopolymer of monomers formed by an anion coordinating unit of Formula (Ic), (Id), (Ie) or (If)

13. The anion-coordinating polymer of claim 1 , wherein the anion-coordinating polymer comprises a homopolymer of monomers formed by an anion coordinatin

Assignees

• California Inst Of Techn
• Univ Cornell

Inventors

• Savoie Brett M
• Webb Michael A
• Grubbs Robert H
• Miller Iii Thomas F
• Coates Geoffrey W
• Zheng Qi

Classifications

• C08L87/00

  Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• H01M10/052

  Li-accumulators · CPC title

• C08F30/06 Primary

  containing boron · CPC title

• C08L43/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers (of metal salts, e.g. phenolates, alcoholates, see the parent compounds) · CPC title

• C08K3/10

  Metal compounds · CPC title