Negative electrode for metal battery, metal battery comprising the same, and method of preparing the negative electrode for metal battery

Patent metadata

Field	Value
Publication number	US-10818913-B2
Application number	US-201816102162-A
Country	US
Kind code	B2
Filing date	Aug 13, 2018
Priority date	Dec 18, 2017
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

A negative electrode for a metal battery, the negative electrode a metal substrate; and a protective layer disposed directly on at least a portion of the metal substrate, wherein the protective layer comprises an ion-conductive oligomer, wherein the ion-conductive oligomer comprises an ion-conductive structural unit in at least one of a main chain and a side chain of the an ion-conductive oligomer, and at least two hydrogen-bond-forming functional groups at different ends of the ion-conductive oligomer, and wherein the protective layer has a thickness of 5 micrometers or less.

First claim

What is claimed is:

1. A negative electrode for a metal battery, the negative electrode comprising:
a metal substrate; and
a protective layer disposed directly on at least a portion of the metal substrate,
wherein the protective layer comprises an ion-conductive oligomer,
wherein the ion-conductive oligomer comprises an ion-conductive structural unit in at least one of a main chain and a side chain of the ion-conductive oligomer, and at least two hydrogen-bond-forming functional groups at different ends of the ion-conductive oligomer,
wherein the ion-conductive oligomer is represented by Formula 1 below and has a weight average molecular weight of about 100 grams per mole to about 5000 grams per mole:

wherein in Formula 1,
CY1 and CY2 are each independently a substituted or unsubstituted pyrimidinone, a substituted or unsubstituted pyrimidinol, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted purinone, or a combination thereof,
A is a C1-C30 alkylene oxide group, —{Si(R)(R 1 )—O-} b —, or —(CH 2 CH 2 O) a -{Si(R)(R 1 )—O-} b —, wherein R and R 1 are each independently a hydrogen atom or a C1-C10 alkyl group and a and b are each independently an integer from 1 to 10,
L 1 and L 2 are each independently a single bond, —CO—, —C(O)O—, —CO—(R′)—CO—, —C(O)O—(R′ 1 )—C(O)O—, —CO—(R′ 2 )—C(O)O—, —C(O)O—(R′ 3 )—CO—, —(R′ 4 )—NHCO—, —(R′ 5 )—NHC(O)O—, —(R′ 6 )—NHC(O)O—(R′ 7 ), —NCO—(R′ 8 )—NCO—, —NCO—(R′ 9 )—CO—, —NCO—(R′ 10 )—C(O)O—, —CO—(R′ 11 )—NCO—, —C(O)O—(R′ 12 )—NCO—, or a combination thereof, wherein R′, R′ 1 , R′ 2 , R′ 3 , R′ 4 , R′ 5 , R′ 6 , R′ 7 , R′ 8 , R′ 9 , R′ 10 , R′ 11 , and R′ 12 are each independently a C1-C10 alkylene group, an amino group, or a C1-C10 aminoalkylene group,
L 1 is linked to a substituent of CY1,
L 2 is linked to a substituent of CY2, and
wherein the protective layer has a thickness of 5 micrometers or less.

2. The negative electrode of claim 1 , wherein the protective layer is a solid protective layer.

3. The negative electrode of claim 1 , wherein a Young's modulus of the protective layer is 50 megapascals or greater.

4. The negative electrode of claim 1 , wherein a melting point of the protective layer is greater than 60° C.

5. The negative electrode of claim 1 , wherein the main chain or the side chain of the ion-conductive oligomer is a C1-C30 alkylene oxide group, —{Si(R)(R 1 )—O-}—, —(CH 2 CH 2 O)—{Si(R)(R 1 )—O—}—, or —{CH(R 2 )C(R 3 )C(O)O(R 4 )}—,
wherein R, R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom or a C1-C10 alkyl group.

6. The negative electrode of claim 1 , wherein the ion-conductive structural unit is a C1-C20 alkylene oxide group, —{Si(R)(R 1 )—O-}—, or —(CH 2 CH 2 O)—{Si(R)(R 1 )—O-}—,
wherein R and R 1 are each independently a hydrogen atom or a C1-C10 alkyl group.

7. The negative electrode of claim 1 , wherein the hydrogen-bond-forming functional group is a substituted or unsubstituted pyrimidinone, a substituted or unsubstituted pyrimidinol, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted triazine, a substituted or unsubstituted pyridyl, a substituted or unsubstituted benzimidazole, a substituted or unsubstituted naphthyridine, a substituted or unsubstituted purinone, or a combination thereof.

8. The negative electrode of claim 1 ,
wherein CY1 and CY2 are each substituted with a —NH 2 group,
wherein L 1 and L 2 are each independently linked to an —NH 2 substituent of CY1 and CY2.

9. The negative electrode of claim 1 , wherein CY1 and CY2 are each independently represented by Formula 2, Formula 3, or Formula 4:

wherein, in Formula 2,
R a , R b , R c , and R d are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —NH 2 , —C(O)R″, —C(O)OR″, —OCO(OR″), —C═N(R″), a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a C2-C10 alkylene oxide group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C6-C20 heteroaryl group, or a combination thereof, wherein R″ is a hydrogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group, and
at least one of R a , R b , R c , and R d is —NH 2 ,

wherein, Formula 3,
R e , R f , R g , and R i are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —NH 2 , —C(O)R″, —C(O)OR″, —OCO(OR″), —C═N(R″), a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a C2-C10 alkylene oxide group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C6-C20 heteroaryl group, or a combination thereof, wherein R″ is a hydrogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group, and
at least one of R e , R f , R g , and R i is —NH 2 ,

wherein, in Formula 4,
R j , R k , R l , R m , R n , R o , R p , and R q are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —NH 2 , —C(O)R″, —C(O)OR″, —OCO(OR″), —C═N(R″), a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a C2-C10 alkylene oxide group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C6-C20 heteroaryl group, or a combination thereof, wherein R″ is a hydrogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group, and
at least one of R j , R k , R l , R m , R n , R o , R p , and R q is —NH 2 .

10. The negative electrode of claim 1 , wherein a radius of gyration of the ion-conductive oligomer is 3 nanometers or less.

11. The negative electrode of claim 1 , wherein the protective layer further comprises a lithium salt.

12. The negative electrode of claim 11 , wherein the lithium salt comprises LiSCN, LiN(CN) 2 , LiClO 4 , LiI, LiBF 4 , LiAsF 6 , LiPF 6 , LiCF 3 SO 3 , LiC(CF 3 SO 2 ) 3 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , LiSbF 6 , LiPF 3 (CF 2 CF 3 ) 3 , LiPF 3 (CF 3 ) 3 , LiB(C 2 O 4 ) 2 , or a combination thereof.

13. The negative electrode of claim 1 , wherein the protective layer further comprises an organic particle, an inorganic particle, an organic-inorganic particle, or combination thereof, each having a particle diameter greater than 1 micrometer and equal to or less than 100 micrometers.

14. The negative electrode of claim 13 , wherein the particle comprises polystyrene, a copolymer comprising a styrene repeating unit, a copolymer comprising a repeating unit having a crosslinkable functional grou

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Lee Yonggun
• Ryu Saebom
• Sugimoto Toshinori
• Im Dongmin
• Chang Wonseok

Classifications

• H01M50/491

  Porosity · CPC title

• H01M50/409

  Separators, membranes or diaphragms characterised by the material · CPC title

• H01M4/1395

  of electrodes based on metals, Si or alloys · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M4/134 Primary

  Electrodes based on metals, Si or alloys · CPC title