Process of making battery separators via spinning

• US 10,243,187 B2
• Filed: 08/09/2016
• Issued: 03/26/2019
• Est. Priority Date: 12/18/2012
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: l'Abee, Roy Martinus Adrianus, Peters, Richard, Teutsch, Erich Otto, Wu, Huiqing, Wang, Yanju, Huang, Qunjian, Rong, Wujun, LaBelle, Jacob Scott
• Primary Examiner(s): Tentoni, Leo B
• Application Number:
  US15/232,290
• Publication Number:
  US 20160348281A1
• Time in Patent Office: 959 Days
• Field of Search: 264 10, 264464, 264465, 264466, 264484
• CPC Class Codes: B29C 48/142 using force fields, e.g. gravity or electrical fields B29C48/9165 takes precedence
• CPC Class Codes: B29C 71/00 After-treatment of articles without altering their shape; Apparatus therefor B29C44/56, B29C73/00 take precedence; surface shaping B29C59/00 ; for joined or sealed parts B29C66/03; after-treatment specially adapted for vulcanising tyres B29D30/0633
• CPC Class Codes: B29C 71/02 Thermal after-treatment B29C71/0063 and B29C71/0072 take precedence
• CPC Class Codes: B29K 2079/085 Thermoplastic polyimides, e.g. polyesterimides, PEI, i.e. polyetherimides, or polyamideimides; Derivatives thereof
• CPC Class Codes: B29K 2995/0058 Inert to chemical degradation
• CPC Class Codes: B29L 2031/3468 Batteries, accumulators or fuel cells battery cases B29L2031/7146
• CPC Class Codes: B29L 2031/755 Membranes, diaphragms
• CPC Class Codes: D01D 5/0007 Electro-spinning non-woven fabrics produced by electro-spinning D04H1/728
• CPC Class Codes: D01D 5/003 the material being a polymer solution or dispersion D01D5/0053 takes precedence
• CPC Class Codes: D01D 5/0038 the fibre formed by solvent evaporation, i.e. dry electro-spinning
• CPC Class Codes: D01D 5/06 Wet spinning methods D01D5/0046 takes precedence
• CPC Class Codes: D01D 5/18 by means of rotating spinnerets
• CPC Class Codes: D01D 5/40 by applying a shearing force to a dispersion or solution of filament formable polymers, e.g. by stirring
• CPC Class Codes: D01F 6/74 from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
• CPC Class Codes: H01M 50/403 Manufacturing processes of separators, membranes or diaphragms
• CPC Class Codes: H01M 50/414 Synthetic resins, e.g. thermoplastics or thermosetting resins
• CPC Class Codes: H01M 50/44 Fibrous material
• CPC Class Codes: H01M 50/489 Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• CPC Class Codes: H01M 50/491 Porosity
• CPC Class Codes: H01M 50/497 Ionic conductivity
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

A method for preparing a high temperature melt integrity separator, the method comprising spinning a polymer by one or more of a mechanical spinning process and an electro-spinning process to produce fine fibers.

Claims

1. A method comprising:

providing a polymer solution comprising a chemical-resistant polymer in a solvent, wherein the chemical-resistant polymer has normalized dry weight of greater than about 90% in 1;

1;

1 EC;

DMC;

EMC and 1 mol/L LiPF₆;

spinning the polymer solution into fine fibers by an electro-spinning method; and

forming a fiber-based structure from the fine fibers, wherein the fiber-based structure does not significantly dissolve in an electrolyte solution comprising 1;

1;

1 EC;

DMC;

EMC and 1 mol/L LiPF₆, and wherein the fiber-based structure has an electrolyte contact angle with the electrolyte solution of equal to or lower than about 30°

,

wherein a viscosity of the polymer solution varies from 100 to 550 centipoise at room temperature; and

wherein a loading of the chemical-resistant polymer in the polymer solution ranges from about 5 to about 20 wt %, based on a total weight of the polymer solution.

2. The method of claim 1, wherein the polymer solution comprises a polyetherimide comprising structural units based on para-phenylene diamines.

3. The method of claim 1, wherein the solvent comprises a phenolic solvent, hexafluoroisopropanol, dichloromethane, trifluoroacetic acid, chloroform, tetrachloroethane, 1,3-dimethyl-2-imidazolidinone, a pyrrolidone-based solvent, or a combination thereof.

4. The method of claim 1, where the chemical resistant polymer has a weight to volume concentration of about 1% to about 20% in the solvent.

5. The method of claim 1, wherein forming the fiber-based structure comprises a drying step, a dry laid process, a thermal treatment, a pressure treatment, or combinations thereof.

6. The method of claim 1, wherein the fiber-based structure has a porosity in the range of about 10% to about 90%.

7. The method of claim 1, wherein the fiber-based structure has a MacMullin number equal to or lower than 10.

8. The method of claim 1, wherein the fiber-based structure has an average pore size in the range of about 0.01 μ

m to about 20 μ

m.

9. The method of claim 1, wherein the fiber-based structure has a thickness of about 10 μ

m to about 200 μ

m.

10. The method of claim 1, wherein the fiber-based structure comprises fibers with an individual average diameter of about 10 nm to about 50 μ

m.

11. The method of claim 1, wherein the fiber-based structure shows about 5% deformation at a temperature of equal to or exceeding about 150°

C.

20. The method of claim 1, wherein the electro-spinning method comprises:

a voltage in a range of 10-30 kilovolts;

use of a spinneret and a collector;

a distance between the spinneret and the collector of about 10 to about 30 centimeters;

rotating the spinneret at a speed varying from 0-1300 revolutions per minute; and

a humidity varying from about 30 to about 75%.

12. A method comprising:

providing a polymer solution comprising a chemical-resistant polymer in a solvent, wherein the chemical-resistant polymer has normalized dry weight of greater than about 90% in 1;

1;

1 EC;

DMC;

EMC and 1 mol/L LiPF₆; and

spinning the polymer solution into fine fibers by an electro-spinning method,

wherein a viscosity of the polymer solution varies from 100 to 550 centipoise at room temperature; and

wherein a loading of the chemical-resistant polymer in the polymer solution ranges from about 5 to about 20 wt %, based on a total weight of the polymer solution.

13. The method of claim 12, wherein the polymer solution comprises a polyetherimide having structural units based on para-phenylene diamines.

14. The method of claim 12, wherein the solvent comprises a phenolic solvent, hexafluoroisopropanol, dichloromethane, trifluoroacetic acid, chloroform, tetrachloroethane, 1,3-dimethyl-2-imidazolidinone, a pyrrolidone-based solvent, or a combination thereof.

15. The method of claim 12, where the chemical resistant polymer has a weight to volume concentration of about 1% to about 20% in the solvent.

16. The method of claim 12, further comprising forming a fiber-based structure from the fine fibers, wherein the fiber-based structure has a porosity in the range of about 10% to about 90% or the fiber-based structure has a MacMullin number equal to or lower than 10.

17. The method of claim 12, further comprising forming a fiber-based structure from the fine fibers, wherein the fiber-based structure shows about 5% deformation at temperatures equal to or exceeding about 150°

C.

18. The method of claim 12, further comprising forming a fiber-based structure from the fine fibers, wherein the fiber-based structure has an electrolyte contact angle of equal to or lower than about 30°

in 1;

1;

1 EC;

DMC;

EMC and 1 mol/L LiPF₆.

19. The method of claim 12, wherein the electro-spinning method comprises:

a voltage in a range of 10-30 kilovolts;

use of a spinneret and a collector;

a distance between the spinneret and the collector of about 10 to about 30 centimeters;

rotating the spinneret at a speed varying from 0-1300 revolutions per minute; and

a humidity varying from about 30 to about 75%.