Cathode composite material, lithium ion battery, and method for making the same

Patent metadata

Field	Value
Publication number	US-2017271658-A1
Application number	US-201715612208-A
Country	US
Kind code	A1
Filing date	Jun 2, 2017
Priority date	Dec 5, 2014
Publication date	Sep 21, 2017
Grant date	—

Abstract

A method for making a cathode composite material is disclosed. In the method, a maleimide-based material is provided. The maleimide-based material is a maleimide monomer, a maleimide polymer formed from the maleimide monomer, or combinations thereof. The maleimide-based material, an inorganic electrical conductive carbonaceous material, and a cathode active material are mixed to form a mixture. The mixture is heated to a temperature of about 200° C. to about 280° C. in a protective gas to obtain the cathode composite material. A cathode composite material and a lithium ion battery are also disclosed.

First claim

What is claimed is:

1 . A method for making a cathode composite material comprising:
providing a maleimide-based material selected from the group consisting of a maleimide monomer, a maleimide polymer formed from the maleimide monomer, and combinations thereof; mixing the maleimide-based material, an inorganic electrical conductive carbonaceous material, and a cathode active material to form a mixture; and heating the mixture to a temperature of about 200° C. to about 280° C. in a protective gas.

2 . The method of claim 1 , wherein the inorganic electrical conductive carbonaceous material is selected from the group consisting of acetylene black, carbon black, carbon nanotubes, graphene, and combinations thereof.

3 . The method of claim 1 , wherein the maleimide monomer is selected from the group consisting of a monomaleimide monomer, a bismaleimide monomer, a polymaleimide monomer, a maleimide derivative monomer, and combinations thereof.

4 . The method of claim 3 , wherein the monomaleimide monomer is represented by a general formula I, and the bismaleimide monomer is represented by formulas II or III:

5 . The method of claim 4 , wherein
R 1 is —R, —RNH 2 R, —C(O)CH 3 , —CH 2 OCH 3 , —CH 2 S(O)CH 3 , a monovalent alicyclic group, a monovalent substituted aromatic group, or a monovalent unsubstituted aromatic group; R 2 is —R—, —RNH 2 R—, —C(O)CH 2 —, —CH 2 OCH 2 —, —C(O)—, —O—, —O—O—, —S—, —S—S—, —S(O)—, —CH 2 S(O)CH 2 —, —(O)S(O)—, —R—Si(CH 3 ) 2 —O—Si(CH 3 ) 2 —R—, a bivalent alicyclic group, a bivalent substituted aromatic group, or a bivalent unsubstituted aromatic group; R 3 is —CH 2 —, —C(O)—, —C(CH 3 ) 2 —, —O—, —O—O—, —S—, —S—S—, —S(O)—, or —(O)S(O)—; and R is a hydrocarbyl with 1 to 6 carbon atoms.

6 . The method of claim 1 , wherein the maleimide monomer is selected from the group consisting of N-phenyl-maleimide, N-(p-tolyl)-maleimide, N-(m-tolyl)-maleimide, N-(o-tolyl)-maleimide, N-cyclohexyl-maleimide, monomaleimide, maleimidephenol, maleimidebenzocyclobutene, dimethylphenyl-maleimide, N-methyl-maleimide, ethenyl-maleimide, thio-maleimide, ketone-maleimide, methylene-maleimide, maleimide-methyl-ether, maleimide-ethanediol, 4-maleimide-phenyl sulfone, and combinations thereof; and
the bismaleimide monomer selected from the group consisting of N,N′-bismaleimide-4,4′-diphenyl-methane, 1,1′-(methylene-di-4,1-phenylene)-bismaleimide, N,N′-(1,1′-diphenyl-4,4′-dimethylene)-bismaleimide, N,N′-(4-methyl-1,3-phenylene)-bismaleimide, 1,1′-(3,3′-dimethyl-1,1′-diphenyl-4,4′-dimethylene)-bismaleimide, N,N′-ethenyl-bismaleimide, N,N′-butenyl-bismaleimide, N,N′-(1,2-phenylene)-bismaleimide, N,N′-(1,3-phenylene)-bismaleimide, N,N′-thiodimaleimide, N,N′-dithiodimaleimide, N,N′-ketonedimaleimide, N,N′-methylene-bismaleimide, bismaleimidomethyl-ether, 1,2-bismaleimido-1,2-ethandiol, N,N′-4,4′-diphenyl-ether-bismaleimide, 4,4′-bismaleimido-diphenylsulfone, and combinations thereof.

7 . The method of claim 1 , wherein the maleimide polymer is a low-molecular weight polymer having an average molecular weight in a range from about 200 to about 2999.

8 . The method of claim 1 , wherein the maleimide polymer is formed by dissolving and mixing a barbituric acid compound and the maleimide monomer in an organic solvent to form a solution; and heating and stirring the solution at a temperature of about 100° C. to about 150° C. to form the maleimide polymer.

9 . The method of claim 1 , wherein a mass ratio of the inorganic electrical conductive carbonaceous material to the maleimide-based material is in a range from about 1:10 to about 1:1.

10 . The method of claim 1 , wherein a ratio of a total mass of the inorganic electrical conductive carbonaceous material and the maleimide-based material to a mass of the cathode active material is in a range from about 1:9999 to about 5:95.

11 . The method of claim 1 , wherein the heating the mixture to a temperature of about 200° C. to about 280° C. in a protective gas forms a high-molecular weight crosslinked polymer, and an average molecular weight of the high-molecular weight crosslinked polymer is in a range from about 5000 to about 50000.

12 . A cathode composite material comprising a cathode active material and an inorganic-organic composite material composited with the cathode active material, wherein the inorganic-organic composite material comprises an inorganic electrical conductive carbonaceous material and a crosslinked polymer, and the crosslinked polymer is formed by heating a maleimide-based material to a temperature of about 200° C. to about 280° C. in the protective gas.

13 . The cathode composite material of claim 12 , wherein the maleimide-based material is selected from the group consisting of a maleimide monomer, a maleimide polymer formed from the maleimide monomer, and combinations thereof.

14 . The cathode composite material of claim 12 , wherein a mass percentage of the inorganic-organic composite material in the cathode composite material is in a range from about 0.01% to about 10%.

15 . The cathode composite material of claim 12 , wherein the inorganic electrical conductive carbonaceous material is selected from the group consisting of acetylene black, carbon black, carbon nanotubes, graphene, and combinations thereof.

16 . The cathode composite material of claim 13 , wherein the maleimide monomer is selected from the group consisting of a monomaleimide monomer, a bismaleimide monomer, a polymaleimide monomer, a maleimide derivative monomer, and combinations thereof.

17 . The cathode composite material of claim 16 , wherein the monomaleimide monomer is represented by a general formula I, and the bismaleimide monomer is represented by formulas II or III:

18 . The cathode composite material of claim 17 , wherein
R 1 is —R, —RNH 2 R, —C(O)CH 3 , —CH 2 OCH 3 , —CH 2 S(O)CH 3 , a monovalent alicyclic group, a monovalent substituted aromatic group, or a monovalent unsubstituted aromatic group; R 2 is —R—, —RNH 2 R—, —C(O)CH 2 —, —CH 2 OCH 2 —, —C(O)—, —O—, —O—O—, —S—, —S—S—, —S(O)—, —CH 2 S(O)CH 2 —, —(O)S(O)—, —R—Si(CH 3 ) 2 —O—Si(CH 3 ) 2 —R—, a bivalent alicyclic group, a bivalent substituted aromatic group, or a bivalent unsubstituted aromatic group; R 3 is —CH 2 —, —C(O)—, —C(CH 3 ) 2 —, —O—, —O—O—, —S—, —S—S—, —S(O)—, or —(O)S(O)—; and R is a hydrocarbyl with 1 to 6 carbon atoms.

19 . The cathode composite material of claim 12 , wherein an average molecular weight of the crosslinked polymer is in a range from about 5000 to about 50000.

20 . A lithium ion battery comprising:
a cathode comprising a cathode composite material; a separator; an anode separated from the cathode by the separator; and an electrolyte solution; wherein the cathode composite material comprises a cathode active material and an inorganic-organic composite material composited with the cathode active material, the inorganic-organic composite material comprises an inorganic electrical conductive carbonaceous material and a crosslinked polymer, and the crosslinked polymer is formed by heating a maleimide-based material to a temperature of about 200° C. to about 280° C. in the protective gas.

Assignees

• Jiangsu Huadong Inst Of Li-Ion Battery Co Ltd
• Univ Tsinghua

Inventors

• Qian guan-nan
• He xiang-ming
• Wang Li
• Shang yu-ming
• Li Jian-Jun
• Luo Jing
• Xu cheng-hao
• Gao Jian
• Wang yao-wu

Classifications

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M10/0525

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

• H01M4/60

  of organic compounds · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title