IP Library Granted Patent US 9,496,547
Granted Patent B2
US 9,496,547 · App. 13/910,140 · Granted Nov 15, 2016

Composite electrode material of lithium secondary battery and lithium secondary battery

Inventors: Li-Duan Tsai (Hsinchu, TW); Yueh-Wei Lin (Hsinchu, TW); Chia-Chen Fang (Taipei, TW); Wei-Hsin Wu (Kaohsiung, TW); Deng-Tswen Shieh (Hsinchu, TW)
Assignee: Industrial Technology Research Institute
H01M4/366H01M4/38H01M4/505H01M4/525H01M4/583H01M4/5825Y02E60/122
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Quick Facts
Patent No.
US 9,496,547
App. No.
13/910,140
Granted
Nov 15, 2016
Kind
B2
Abstract

A composite electrode material of a lithium secondary battery and a lithium secondary battery are provided. The composite electrode material of the lithium secondary battery at least includes an electrode active powder and a nanoscale coating layer coated on the surface of the electrode active powder, wherein the nanoscale coating layer is composed of a metastable state polymer, a compound A, a compound B, or a combination thereof. The compound A is a monomer having a reactive terminal functional group, and the compound B is a heterocyclic amino aromatic derivative used as an initiator. The weight ratio of the nanoscale coating layer to the composite electrode material of the lithium secondary battery is 0.005% to 10%.

Claims (47)

1. A composite electrode material of a lithium secondary battery, comprising:

an electrode active powder, and

a nanoscale coating layer coated on a surface of the electrode active powder, wherein the nanoscale coating layer is formed from a metastable state polymer, the metastable state polymer is produced from a reaction of a compound A and a compound B, the compound A is a monomer having a reactive terminal functional group, the compound B is a heterocyclic amino aromatic derivative used as an initiator, and a weight ratio of the nanoscale coating layer to the composite electrode material of the lithium secondary battery is 0.005% to 10%,

wherein the compound B is represented by one of Formula (1) to Formula (9):

wherein R 1 is hydrogen, alkyl, alkyl alkenyl, phenyl, dimethylamino, or —NH 2 , and R 2 , R 3 , R 4 , and R 5 are each independently hydrogen, alkyl, alkyl alkenyl, halo, or —NH 2 ,

wherein the compound A is represented by one or a combination of Formula (10) to Formula (13):

wherein n is an integer between 0 and 4:

R 6 is —RCH 2 R′—, —RNHR—, —C(O)CH 2 —, —R′OR″OR′—, —CH 2 OCH 2 —, —C(O)—, —O—, —O—O—, —S—, —S—S—, —S(O)—, —CH 2 S(O)CH 2 —, —(O)S(O)—, —C 6 H 4 —, —CH 2 (C 6 H 4 )CH 2 —, —CH 2 (C 6 H 4 )(O)—, —C 2 H 4 —(NC 2 H 4 )—C 2 H 4 , a siloxane group, biphenylenyl, substituted phenylene, or substituted biphenylenyl, R is C 1-4 alkylene, R′ is C 1-4 alkylene, biphenylenyl, or substituted biphenylenyl, and R″ is C 1-4 alkylene, —C 6 H 4 —C(CF 3 ) 2 —C 6 H 4 —, biphenylenyl, or substituted biphenylenyl:

R 7 is —RCH 2 —, —CH 2 —(O)—, —C(CH 3 ) 2 —, —O—, —O—O—, —S—, —S—S—, —(O)S(O)—, C(CF 3 ) 2 —, or —S(O)—, wherein R is C 1-4 alkylene; and

R 8 is hydrogen, C 1-4 alkyl, phenyl, benzyl, cyclohexyl, sulfonyl hydroxide, —C 6 H 4 CN, N-methoxycarbonyl, —(C 6 H 4 )—O(C 2 H 4 O)—CH 3 , C 2 H 4 —(C 2 H 4 O) 11 —OCH 3 , or —C(O)CH 3 .

2. The composite electrode material of the lithium secondary battery of claim 1 , wherein a molar ratio of the compound A to the compound B is 10:1 to 1:10.

3. The composite electrode material of the lithium secondary battery of claim 2 , wherein the compound B is selected from the group consisting of imidazole, imidazole derivative, pyrrole, pyrrole derivative, pyridine, 4-tert-butylpyridine, 3-butylpyridine, 4-dimethylaminopyridine, 2,4,6-triamino-1,3,5-triazine, 2,4-bimethyl-2-imidazoline, pyridazine, pyrimidine, and pyrazine.

4. The composite electrode material of the lithium secondary battery of claim 1 , wherein the electrode active powder comprises a cathode material.

5. The composite electrode material of the lithium secondary battery of claim 4 , wherein a thickness of the nanoscale coating layer is between 1 nm and 30 nm.

6. The composite electrode material of the lithium secondary battery of claim 4 , wherein the cathode material is selected from the group consisting of lithiated oxide, lithiated sulfide, lithiated selenide, lithiated telluride of vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt, and manganese, and a combination thereof.

7. The composite electrode material of the lithium secondary battery of claim 4 , wherein the cathode material comprises LiMn 2 O 4 , LiNi x Co y O 2 , LiCoO 2 , LiFePO 4 , LiNi x Co y MnO 2 , or LiNi x Mn y O 2 .

8. The composite electrode material of the lithium secondary battery of claim 1 , wherein the electrode active powder comprises an anode material.

9. The composite electrode material of the lithium secondary battery of claim 8 , wherein a thickness of the nanoscale coating layer is between 1 nm and 30 nm.

10. The composite electrode material of the lithium secondary battery of claim 8 , wherein the anode material is selected from the group consisting of mesocarbon microbeads (MCMB), mesophase graphite powder (MGP), vapor-grown carbon fiber (VGCF), carbon nanotube (CNT), coke, carbon black, natural graphite, artificial graphite, acetylene black, carbon fiber, glassy carbon, a lithium alloy, and a combination thereof.

11. A lithium secondary battery, at least comprising:

at least one electrode material, wherein the electrode material is the composite electrode material of the lithium secondary battery of claim 1 ;

a non-aqueous electrolyte solution, in contact with the electrode material, wherein the non-aqueous electrolyte solution comprises a non-aqueous solvent and lithium salt; and

a separator, located in the non-aqueous electrolyte solution.

12. A composite electrode material of a lithium secondary battery, comprising:

an electrode plate, composed of an electrode active powder; and

a first nanoscale coating layer, coated on a surface of the electrode plate, wherein the first nanoscale coating layer is formed from a first metastable state polymer, the first metastable state polymer is produced from a reaction of a compound A and a compound B, the compound A is a monomer having a reactive terminal functional group, the compound B is a heterocyclic amino aromatic derivative used as an initiator, and a weight ratio of the first nanoscale coating layer to the composite electrode material of the lithium secondary battery is 0.005% to 10%,

wherein the compound B is represented by one of Formula (1) to Formula (9):

wherein R 1 is hydrogen, alkyl, alkyl alkenyl, phenyl, dimethylamino, or —NH 2 , and R 2 , R 3 , R 4 , and R 5 are each independently hydrogen, alkyl, alkyl alkenyl, halo, or —NH 2 ,

wherein the compound A is represented by one or a combination of Formula (10) to Formula (13):

wherein n is an integer between 0 and 4;

R is —RCH 2 R′—, —RNHR—, —C(O)CH 2 —, —R′OR″OR′—, —CH 2 OCH 2 —, —C(O)—, —O—, —O—O—, —S—, —S—S—, —S(O)—, —CH 2 S(O)CH 2 —, —(O)S(O)—, —C 6 H 4 —, —CH 2 (C 6 H 4 )CH 2 —, —CH 2 (C 6 H 4 )(O)—, —C 2 H 4 —(NC 2 H 4 )—C 2 H 4 , a siloxane group, biphenylenyl, substituted phenylene, or substituted biphenylenyl, R is C 1-4 alkylene, R′ is C 1-4 alkylene, biphenylenyl, or substituted biphenylenyl, and R″ is C 1-4 alkylene, —C 6 H 4 —C(CF 3 ) 2 —C 6 H 4 —, biphenylenyl, or substituted biphenylenyl:

R 7 is —RCH 2 —, —CH 2 —(O)—, —C(CH 3 ) 2 —, —O—, —O—O—, —S—, —S—S—, —(O)S(O)—, C(CF 3 ) 2 —, or —S(O)—, wherein R is C 1-4 alkylene; and

R 8 is hydrogen, C 1-4 alkyl, phenyl, benzyl, cyclohexyl, sulfonyl hydroxide, —C 6 H 4 CN, N-methoxycarbonyl, —(C 6 H 4 )—O(C 2 H 4 O)—CH 3 , C 2 H 4 —(C 2 H 4 O) 11 —OCH 3 , or —C(O)CH 3 .

13. The composite electrode material of the lithium secondary battery of claim 12 , wherein the electrode active powder is a powder coated with a second nanoscale coating layer, wherein the second nanoscale coating layer is formed from a second metastable state polymer, the second metastable state polymer is produced from a reaction of the compound A and the compound B, and a weight ratio of the second nanoscale coating layer to the composite electrode material of the lithium secondary battery is 0.005% to 10%.

14. The composite electrode material of the lithium secondary battery of claim 13 , wherein a molar ratio of the compound A to the compound B is 10:1 to 1:10.

15. The composite electrode material of the lithium secondary battery of claim 14 , wherein the compound B is selected from the group consisting of imidazole, imidazole derivative, pyrrole, pyrrole derivative, pyridine, 4-tert-butylpyridine, 3-butylpyridine, 4-dimethylaminopyridine, 2,4,6-triamino-1,3,5-triazine, 2,4-bimethyl-2-imidazoline, pyridazine, pyrimidine, and pyrazine.

16. The composite electrode material of the lithium secondary battery of claim 12 , wherein the electrode active powder comprises a cathode material.

17. The composite electrode material of the lithium secondary battery of claim 16 , wherein a thickness of the first nanoscale coating layer is between 1 nm and 30 nm.

18. The composite electrode material of the lithium secondary battery of claim 16 , wherein the cathode material is selected from the group consisting of lithiated oxide, lithiated sulfide, lithiated selenide, lithiated telluride of vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt, and manganese, and a combination thereof.

19. The composite electrode material of the lithium secondary battery of claim 16 , wherein the cathode material comprises LiMn 2 O 4 , LiNi x Co y O 2 , LiCoO 2 , LiFePO 4 , LiNi x Co y Mn z O 2 , or LiNi x Mn y O 2 .

20. The composite electrode material of the lithium secondary battery of claim 12 , wherein the electrode active powder comprises an anode material.

21. The composite electrode material of the lithium secondary battery of claim 20 , wherein a thickness of the first nanoscale coating layer is between 1 nm and 30 nm.

22. The composite electrode material of the lithium secondary battery of claim 20 , wherein the anode material is selected from the group consisting of MCMB, VGCF, CNT, coke, carbon black, natural graphite, artificial graphite, acetylene black, carbon fiber, glassy carbon, a lithium alloy, and a combination thereof.

23. A lithium secondary battery, at least comprising:

at least one electrode material, wherein the electrode material is the composite electrode material of the lithium secondary battery of claim 12 ;

a non-aqueous electrolyte solution, in contact with the electrode material, wherein the non-aqueous electrolyte solution comprises a non-aqueous solvent and lithium salt; and

a separator, located in the non-aqueous electrolyte solution.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 7, 2013
From: TSAI, LI-DUAN; LIN, YUEH-WEI; FANG, CHIA-CHEN; WU, WEI-HSIN; SHIEH, DENG-TSWEN
To: INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE
Reel/Frame 030563/0763 →
Priority Claims (1)
TW 101149882 A · Dec 25, 2012 · national
Continuity (1)
Related Publication 20140178747A1 · Jun 26, 2014