Lithiated polyphosphazene solid polymer electrolyte compositions and methods of manufacture thereof

Patent metadata

Field	Value
Publication number	US-2025167391-A1
Application number	US-202318839612-A
Country	US
Kind code	A1
Filing date	Feb 17, 2023
Priority date	Feb 18, 2022
Publication date	May 22, 2025
Grant date	—

Abstract

Disclosed are polymers and polymer compositions comprising metalized polyphosphazene. Also disclosed are polymer electrolytes comprising the disclosed herein polymers and polymer compositions, and film separators comprising polymers and polymer compositions. Also disclosed are batteries comprising an anode, a cathode and polymer electrolytes. Disclosed are also methods of making polymers, polymer compositions, and batteries.

First claim

1 - 77 . (canceled)

78 . A polymer comprising monomer units of formula (I)

wherein R 1 is independently selected at each occurrence from hydrogen, C 1-12 alkyl, C 1-12 heteroalkyl, —(C 0-5 alkyl)(C 6-14 aryl), —(C 0-5 alkyl)(C 1-13 heteroaryl), —(C 0-5 alkyl)(C 6-14 aryloxy), —(C 0-5 alkyl)(C 3-10 cycloalkyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkyl), —(C 0-5 alkyl-)(C 5-10 cycloalkenyl), C 1-12 haloalkyl, or —(C 0-5 alkyl)(C 3-10 heterocycloalkenyl);
R 2 is independently selected at each occurrence selected from hydrogen, C 1-12 alkyl, C 1-12 heteroalkyl, —(C 0-5 alkyl)(C 6-14 aryl), —(C 0-5 alkyl)(C 1-13 heteroaryl), —(C 0-5 alkyl)(C 6-14 aryloxy), —(C 0-5 alkyl)(C 3-10 cycloalkyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkyl), —(C 0-5 alkyl-)(C 5-10 cycloalkenyl), C 1-12 haloalkyl, or —(C 0-5 alkyl)(C 3-10 heterocycloalkenyl);
R 1 and R 2 each is independently and optionally substituted with one or more of C 1-12 alkyl, C 1-12 alkoxy, C 1-12 heteroalkyl, —(C 0-5 alkyl)(C 6-14 aryl), —(C 0-5 alkyl)(C 1-13 heteroaryl), —(C 0-5 alkyl)(C 6-14 aryloxy), —(C 0-5 alkyl)(C 3-10 cycloalkyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkyl), —(C 0-5 alkyl)(C 5-10 cycloalkenyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ether, dialkyl amines, thio-ethers, halo, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, fluorinated sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl,
X is O, S, or N-M 1 ; and
M 1 is Li, Na, or K.

79 . The polymer of claim 78 , wherein the polymer comprises:
monomer units of formula (Ia), wherein R 1 is different from R 2 ; monomer units of formula (Ib), wherein R 1 is the same as R 2 ; or a combination thereof.

80 . The polymer of claim 78 , wherein the polymer comprises:
monomer units of formula (Ia-N-M 1 ), wherein X is N-M 1 and R 1 is different from R 2 ; monomer units of formula (Ib-N-M 1 ), when X is N-M 1 and R 1 is the same as R 2 ; monomer units of formula (Ia-E), when X is O or S and R 1 is different from R 2 ; monomer units of has formula (Ib-E) when X is O or S and R 1 is the same as R 2 ; or a combination thereof.

81 . The polymer of claim 78 , wherein the polymer further comprises monomer units of formula (II):

wherein R 4 is independently selected at each occurrence from hydrogen, C 1-12 alkyl, C 1-12 heteroalkyl, —(C 0-5 alkyl)(C 6-14 aryl), —(C 0-5 alkyl)(C 1-13 heteroaryl), —(C 0-5 alkyl)(C 6-14 aryloxy), —(C 0-5 alkyl)(C 3-10 cycloalkyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkyl), —(C 0-5 alkyl-)(C 5-10 cycloalkenyl), C 1-12 haloalkyl, or —(C 0-5 alkyl)(C 3-10 heterocycloalkenyl);
R 5 is independently selected at each occurrence from hydrogen, C 1-12 alkyl, C 1-12 heteroalkyl, —(C 0-5 alkyl)(C 6-14 aryl), —(C 0-5 alkyl)(C 1-13 heteroaryl), —(C 0-5 alkyl)(C 6-14 aryloxy), —(C 0-5 alkyl)(C 3-10 cycloalkyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkyl), —(C 0-5 alkyl)(C 5-10 cycloalkenyl), C 1-12 haloalkyl, or —(C 0-5 alkyl)(C 3-10 heterocycloalkenyl);
R 4 and R 5 each is independently and optionally substituted with one or more of C 1-12 alkyl, C 1-12 alkoxy, C 1-12 heteroalkyl, —(C 0-5 alkyl)(C 6-14 aryl), —(C 0-5 alkyl)(C 1-13 heteroaryl), —(C 0-5 alkyl)(C 6-14 aryloxy), —(C 0-5 alkyl)(C 3-10 cycloalkyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkyl), —(C 0-5 alkyl)(C 5-10 cycloalkenyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ether, dialkyl amines, thio-ethers, halo, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, fluorinated sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, and
Y 1 and Y 2 are each independently selected from O or S.

82 . The polymer of claim 81 , wherein Y 1 and Y 2 are both O.

83 . The polymer of claim 81 , wherein the polymer comprises:
monomer units of formula (IIa), wherein R 4 is different from R 5 ; monomer units of formula (IIb), wherein R 4 is the same as R 4 ; or a combination thereof.

84 . The polymer of claim 81 , wherein R 2 is the same as R 4 , or R 2 is the same R 5 , or
R 2 is the same as both R 4 and R 5 .

85 . The polymer of claim 78 , further comprising monomer units of formula (III):

wherein the wavy line represents a bond to a phosphorus atom in a polymer chain;
G is R 1 —N—, R 2 —X—, R 4 —Y—, or R 5 —Y—;
D is O, S, N; and
R 3 is a linking group.

86 . The polymer of claim 85 , where R 3 is selected from alkenylene, alkylene, or arylene, each optionally substituted by with one or more of C 1-12 alkyl, C 1-12 alkoxy, C 1-12 heteroalkyl, —(C 0-5 alkyl)(C 6-14 aryl), —(C 0-5 alkyl)(C 1-13 heteroaryl), —(C 0-5 alkyl)(C 6-14 aryloxy), —(C 0-5 alkyl)(C 3-10 cycloalkyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkyl), —(C 0-5 alkyl-)(C 5-10 cycloalkenyl), —(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ether, dialkyl amines, thio-ethers, halo, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, fluorinated sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl.

87 . The polymer of claim 78 , wherein M 1 is Li.

88 . The polymer of claim 78 , wherein X is independently selected from 0 and N-M 1 .

89 . The polymer of claim 78 , wherein R 1 , R 2 , R 4 , and R 5 are independently selected from C 1-12 alkyl and C 1-12 heteroalkyl, each optionally substituted one or more times by, independently halo or C 1-12 alkoxy.

90 . The polymer of claim 78 , wherein R 1 and R 2 are independently selected from (CH 2 ) x O-alkyl, (CH 2 ) x O(CH 2 ) x (O)alkyl, and (CH 2 ) q —CF 3 , wherein x is 2-4 and q is 1-4,

91 . A method of making the polymer of claim 78 , comprising combining a polymer of Formula (IV):

wherein
L is a leaving group selected from halo or OSO 3 R,
R is —CH 3 , —CF 3 , —CH 2 CH 3 , aryl, alkyl, haloalkyl, wherein R is optionally substituted; and
n is greater or equal to 2,
with a compound having formula R 1 —NH-M a to form a polymer of formula (V):

wherein
L* is L or R 1 —N-M a ;
M a is H or Li, Na, or K, and
n is greater or equal to 2; and
combining the polymer of formula (V) with a compound having formula M b -X′—R 2 to provide a polymer comprising monomer units of formula (VI):

wherein X′ is O, S, or N-M b , and M b is H or Li, Na, or K.

92 . A composition comprising the polymer of claim 78 , and an organic solvent, a metal salt, a ceramic additive, or a combination thereof.

93 . The composition of claim 92 , where the organic solvent comprises ethyl carbonate, propylene carbonate, polyethylene glycol dimethyl ether, tetraglyme, dibutyl phthalate, modified carbonate, polyethylene glycol, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, cyclic phosphates, succinonitrile, ethyl propionate, ethyl acetate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbon

Assignees

• Georgia Tech Res Inst

Inventors

• Yushin Gleb
• Jhulki Samik
• Johnson Billy
• Raman Ashwin Sankara
• Turcheniuk Kostiantin

Classifications

• H01M10/052

  Li-accumulators · CPC title

• C08G79/025

  Polyphosphazenes · CPC title

• H01M50/46

  Separators, membranes or diaphragms characterised by their combination with electrodes · CPC title

• H01M50/446

  Composite material consisting of a mixture of organic and inorganic materials · CPC title

• H01M50/431

  Inorganic material · CPC title