Organic sulfur material, electrode, and lithium-ion secondary batteries, and producing method

Patent metadata

Field	Value
Publication number	US-11876228-B2
Application number	US-202117234149-A
Country	US
Kind code	B2
Filing date	Apr 19, 2021
Priority date	Apr 20, 2020
Publication date	Jan 16, 2024
Grant date	Jan 16, 2024

Abstract

Provided is an organic sulfur material comprising a sulfur-modified acrylic resin, wherein an acrylic resin is at least one polymer selected from the group consisting of (a) a polymer of at least one selected from the group consisting of acrylate compounds represented by CH 2 ═C(R 11 )COOR 12 , wherein R 11 is a hydrogen atom or a methyl group and R 12 is an alkyl group, and (b) a polymer of at least one selected from the group consisting of acrylate compounds above and at least one selected from the group consisting of diacrylate compounds represented by CH 2 ═C(R 21 )COO—Y—OCO(R 22 )C═CH 2 , wherein each of R 21 and R 22 is the same or different and is a methyl group, etc., Y is a hydrocarbylene group, etc., wherein the hydrocarbylene group may have a substituent selected from a hydroxyl group and an alkyl group.

First claim

What is claimed is:

1. An organic sulfur material comprising:
a sulfur-modified acrylic resin formed by calcination of sulfur and an acrylic resin wherein the amount of sulfur in the organic sulfur material is 50.0% by mass or more, and
wherein the acrylic resin is a copolymer formed from a monomer of at least one selected from the group consisting of acrylate compounds represented by the following formula (1) and a monomer of at least one selected from the group consisting of diacrylate compounds represented by the following formula (2),
CH 2 ═C(R 11 )COOR 12   (1)

wherein R 11 is a hydrogen atom or a methyl group, and R 12 is an alkyl group,
CH 2 ═C(R 21 )COO—Y—OCO(R 22 )C═CH 2   (2)

wherein
each of R 21 and R 22 is the same or different and is a hydrogen atom or a methyl group,
Y is a hydrocarbylene group, wherein the hydrocarbylene group may have at least one substituent selected from the group consisting of a hydroxyl group and an alkyl group,
a carbon skeleton constituting the hydrocarbylene group may have an ether bond with an oxygen atom, and
when there are two or more ether bonds, two or more carbon atoms always intervene between the adjacent oxygen atoms.

2. The organic sulfur material of claim 1 , wherein the modification is performed by calcination under a non-oxidizing atmosphere.

3. The organic sulfur material of claim 1 , wherein R 12 is an alkyl group having 1 to 6 carbon atoms, wherein Y is a hydrocarbylene group having 2 to 6 carbon atoms, wherein the hydrocarbylene group has 1 to 4 substituents, wherein the alkyl group, which is a substituent, has 1 to 4 carbon atoms, and wherein the carbon skeleton constituting the hydrocarbylene group has 1 or 2 ether bonds.

4. The organic sulfur material of claim 1 , wherein a particle size of the acrylic resin is 0.1 to 300.0 μm.

5. The organic sulfur material of claim 1 , wherein the acrylic resin has a porous structure.

6. The organic sulfur material of claim 1 , wherein, in a Raman spectrum detected by Raman spectroscopy, there exists a main peak around 1450 cm −1 , and there exists other peaks around 485 cm −1 , around 1250 cm −1 , and around 1540 cm −1 in a range of 200 to 1800 cm −1 .

7. The organic sulfur material of claim 6 , wherein, in the Raman spectrum, with a straight line connecting an intensity of 1000 cm −1 and an intensity of 1800 cm −1 being as a baseline, when a difference (I 1450 ) between a peak intensity around 1450 cm −1 and a corresponding baseline intensity and a difference (I 1540 ) between a peak intensity around 1540 cm −1 and a corresponding baseline intensity are calculated, a value of I 1450 /I 1540 is in a range of 1 to 4.

8. The organic sulfur material of claim 1 , wherein the acrylic resin is at least one polymer selected from the group consisting of a polymer of at least one selected from the group consisting of acrylate compounds represented by the formula (1).

9. An electrode comprising the organic sulfur material of claim 1 .

10. A lithium-ion secondary battery comprising the electrode of claim 9 .

11. A method of producing an organic sulfur material, the method comprising steps of:
(1) preparing an acrylic resin, and
(2) modifying the acrylic resin with sulfur by calcination of the acrylic resin and sulfur,
wherein the acrylic resin is a copolymer formed from a monomer of at least one selected from the group consisting of acrylate compounds represented by the following formula (1) and a monomer of at least one selected from the group consisting of diacrylate compounds represented by the following formula (2),
CH 2 ═C(R 11 )COOR 12   (1)

wherein R 11 is a hydrogen atom or a methyl group, and R 12 is an alkyl group,
CH 2 ═C(R 21 )COO—Y—OCO(R 22 )C═CH 2   (2)

wherein
each of R 21 and R 22 is the same or different and is a hydrogen atom or a methyl group,
Y is a hydrocarbylene group, wherein the hydrocarbylene group may have at least one substituent selected from the group consisting of a hydroxyl group and an alkyl group,
a carbon skeleton constituting the hydrocarbylene group may have an ether bond with an oxygen atom, and
when there are two or more ether bonds, two or more carbon atoms always intervene between the adjacent oxygen atoms, and
wherein the amount of sulfur in the organic sulfur material is 50.0% by mass or more.

12. The method of claim 11 , wherein the modification is performed by calcination under a non-oxidizing atmosphere.

13. The method of claim 11 , wherein an amount of the sulfur with respect to the acrylic resin is 50 to 1000 parts by mass based on 100 parts by mass of the acrylic resin.

14. The method of claim 12 , wherein a temperature of the calcination is 250 to 550° C.

15. The method of claim 11 , wherein a particle size of the acrylic resin is 0.1 to 300.0 μm.

16. The method of claim 11 , wherein the acrylic resin has a porous structure.

17. A method of producing an electrode, the method further comprising, after producing the organic sulfur material by the method of claim 11 , a step of:
(3) preparing an electrode by incorporating the organic sulfur material.

18. A method of producing a lithium-ion secondary battery, the method further comprising, after producing the electrode by the method of claim 17 , a step of:
(4) preparing a lithium-ion secondary battery by incorporating the electrode.

Assignees

• Sumitomo Rubber Ind

Inventors

• Chujo Fumiya
• Kubo Tatsuya

Classifications

• H01M4/604 Primary

  containing aliphatic main chain polymers · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M10/0525

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

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M4/60 Primary

  of organic compounds · CPC title