High temperature melt integrity battery separators via spinning

• US 9,577,235 B2
• Filed: 12/18/2013
• Issued: 02/21/2017
• Est. Priority Date: 12/18/2012
• Status: Expired due to Fees

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• 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:
  US14/132,718
• Publication Number:
  US 20140167329A1
• Time in Patent Office: 1,161 Days
• Field of Search: 264/10, 264/178.F, 264/178.R, 264/183, 264/184, 264/203, 264/205, 264/211.1, 264/211.12, 264/464, 264/465, 264/466, 264/484
• US Class Current: 1/1
• 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:

dissolving a polymer in a solvent to provide a polymer solution, wherein the polymer comprises one or more of polyetherimide, poly(amic acid), aromatic polyamide, poly(amide-imide), and polyphenylene oxide; and

spinning the polymer solution into fine fibers by a shear solution spinning method, wherein the shear solution spinning method comprises injecting the polymer solution into an anti-solvent medium, and wherein flow rate and viscosity of the anti-solvent medium are configured to generate shear forces on the injected polymer solution to form fine fibers.

2. The method of claim 1, wherein the solvent comprises acetone, chloroform, ethanol, isopropanol, methanol, butanol, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, ethyl acetate, methyl acetate, dimethyl acetate, water, benzene, styrene, ethyl benzene, benzyl alcohol, 1,4-dioxane, propanol, carbon tetrachloride, tetrachloroethylene, cyclohexane, hexane, pentane, cyclohexanone, cyclopentane, methylene chloride, a phenolic solvent, pyridine, trichloroethane, trichloroethylene, N,N-dimethyl formamide, ethylene dichloride, dimethyl sulfoxide, N,N-dimethylacetamide, a pyrrolidone-based solvent, ethylene carbonate, propylene carbonate, dimethyl carbonate, acetonitrile, N-methylmorpholine-N-oxide, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, diethylether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolane, ethyl methyl carbonate, methyl formate, 3-methyloxazolidin-2-on, methyl propionate, 2-methyletetrahydrofurane, sulpholane, anisole, isophorone, xylene, carbon disulfide, chlorobenzene, dichlorobenzene, sulfuric acid, or dichloroethane, or a combination thereof.

3. The method of claim 1, wherein the anti-solvent medium comprises water, ethylene glycol, glycerol, acetone, chloroform, ethanol, isopropanol, methanol, butanol, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, ethyl acetate, methyl acetate, dimethyl acetate, water, benzene, styrene, ethyl benzene, benzyl alcohol, 1,4-dioxane, propanol, carbon tetrachloride, tetrachloroethylene, cyclohexane, hexane, pentane, cyclohexanone, cyclopentane, methylene chloride, a phenolic solvent, pyridine, trichloroethane, trichloroethylene, N,N-dimethyl formamide, ethylene dichloride, dimethyl sulfoxide, N,N-dimethylacetamide, a pyrrolidone-based solvent, ethylene carbonate, propylene carbonate, dimethyl carbonate, acetonitrile, N-methylmorpholine-N-oxide, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, diethylether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolane, ethyl methyl carbonate, methyl formate, 3-methyloxazolidin-2-on, methyl propionate, 2-methyletetrahydrofurane, sulpholane, anisole, isophorone, xylene, carbon disulfide, chlorobenzene, or dichlorobenzene, or a combination thereof.

4. The method of claim 1, wherein the polymer solution during the shear solution spinning method has a temperature from about 23°

C. to about the boiling point of the solvent.

5. The method of claim 1, wherein the polymer solution comprises about 2.5 wt % to about 35 wt % of the polymer based on the total weight of the polymer solution.

6. The method of claim 1, wherein the polymer solution has a viscosity of about 14 cP to about 290,000 cP.

7. The method of claim 1, further comprising collecting the fine fibers in a solvent or an anti-solvent medium as a slurry.

8. The method of claim 7, further comprising forming a fiber-based structure, wherein the forming the fiber-based structure comprises subjecting the slurry to a wet-laid non-woven fabrication process.

9. The method of claim 7, further comprising forming a fiber-based structure, wherein the forming the fiber-based structure comprises subjecting the slurry to a dry-laid fabrication process.

10. The method of claim 1, further comprising forming a fiber-based structure by collecting the fine fibers onto a collector.

11. The method of claim 10, wherein the collector comprises a woven polymer, nonwoven substrate, a porous polymer substrate, a polyethylene micro-porous substrate, a battery electrode or a capacitor electrode, or a combination thereof.

12. The method of claim 1, wherein the formed fibers are used to prepare a fiber-based structure by a drying step, a dispersion step into a solvent, a dry laid process, a wet laid process, a paper-making process, a dry spraying method, a wet spraying method, a thermal treatment, a pressure treatment, or combinations thereof.

13. The method of claim 1, further comprising forming a fiber-based structure, wherein the porosity of the fiber-based structure is in the range of about 10% to about 90%.

14. The method of claim 1, further comprising forming a fiber-based structure, wherein the fiber-based structure has a thickness of about 10 μ

m to about 200 μ

m.

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

m.

16. The method of claim 1, further comprising forming a fiber-based structure, wherein the fiber-based structure shows less than about 5% deformation at a temperature of about 150°

C.

17. A method comprising:

dissolving a polymer in a solvent to provide a polymer solution, wherein the polymer comprises one or more of polyetherimide, poly(amic acid), aromatic polyamide, poly(amide-imide) and polyphenylene oxide; and

spinning the polymer solution into fine fibers by a centrifugal force spinning method, wherein the centrifugal force spinning method comprises spinning the polymer solution through a spinneret with an array of fine gauge capillaries, wherein the polymer solution exits the fine gauge capillaries in a radially outward direction under the centrifugal force to form the fine fibers.

18. The method of claim 17, the polymer solution comprises about 2.5 wt % to about 35 wt % of the polymer based on the total weight of the polymer solution.

19. The method of claim 17, wherein the polymer solution has a viscosity of about 14 cP to about 290,000 cP.

20. A method comprising:

dissolving a polymer in a solvent to provide a polymer solution, wherein the polymer comprises thermoplastic polymers having a glass transition temperature higher than about 180°

C.; and

spinning the polymer solution into fine fibers by a shear solution spinning method, wherein the shear solution method comprises injecting the polymer solution into an anti-solvent medium, and wherein flow rate and viscosity of the anti-solvent medium are configured to generate shear forces on the injected polymer solution to form fine fibers.

21. The method of claim 20, wherein the polymer comprises one or more of polyetherimide, poly(amic acid), aromatic polyamide, poly(amide-imide), polysulfone, polyethersulfone, polyphenylsulfone, polybenzoxazole, polybenzimidazole, and polyphenylene oxide.

22. The method of claim 20, wherein the solvent comprises acetone, chloroform, ethanol, isopropanol, methanol, butanol, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, ethyl acetate, methyl acetate, dimethyl acetate, water, benzene, styrene, ethyl benzene, benzyl alcohol, 1,4-dioxane, propanol, carbon tetrachloride, tetrachloroethylene, cyclohexane, hexane, pentane, cyclohexanone, cyclopentane, methylene chloride, a phenolic solvent, pyridine, trichloroethane, trichloroethylene, N,N-dimethyl formamide, ethylene dichloride, dimethyl sulfoxide, N,N-dimethylacetamide, a pyrrolidone-based solvent, ethylene carbonate, propylene carbonate, dimethyl carbonate, acetonitrile, N-methylmorpholine-N-oxide, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, diethylether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolane, ethyl methyl carbonate, methyl formate, 3-methyloxazolidin-2-on, methyl propionate, 2-methyletetrahydrofurane, sulpholane, anisole, isophorone, xylene, carbon disulfide, chlorobenzene, dichlorobenzene, sulfuric acid, or dichloroethane, or a combination thereof.

23. The method of claim 20, wherein the polymer solution during the shear solution spinning method has a temperature from about 23°

C. to about the boiling point of the solvent.

24. The method of claim 20, the polymer solution comprises about 2.5 wt % to about 35 wt % of the polymer based on the total weight of the polymer solution.

25. The method of claim 20, wherein the polymer solution has a viscosity of about 14 cP to about 290,000 cP.

26. A method comprising:

melting a polymer comprising, poly(4-methylpentene), poly(amide-imide), polyoxymethylene, polyphthalamide, polysulfone, polyethersulfone, polyphenylsulfone, polyetherimide, polyketone, polyetherketone, polyetheretherketone, polyphenylene sulfide, or a copolymer or blend thereof; and

spinning the polymer melt into fine fibers by a centrifugal force spinning method, wherein the centrifugal force spinning method comprises spinning the polymer melt through a spinneret with an array of fine gauge capillaries, creating a centrifugal force, and applying heat to the polymer melt at a temperature of equal to or higher than about 450°

C., wherein the centrifugal force facilitates formation of the fine fibers.

27. A method comprising:

dissolving a polymer in a solvent to provide a polymer solution, wherein the polymer comprises thermoplastic polymers having a glass transition temperature higher than about 180°

C.; and

spinning the polymer solution into fine fibers by a centrifugal force spinning method, wherein the centrifugal force spinning method comprises spinning the polymer solution through a spinneret with an array of fine gauge capillaries, wherein the polymer solution exits the fine gauge capillaries in a radially outward direction under the centrifugal force to form the fine fibers.

28. The method of claim 27, wherein the polymer comprises one or more of polyetherimide, poly(amic acid), aromatic polyamide, poly(amide-imide), polysulfone, polyethersulfone, polyphenylsulfone, polybenzoxazole, polybenzimidazole, and polyphenylene oxide.

29. The method of claim 27, wherein the solvent comprises acetone, chloroform, ethanol, isopropanol, methanol, butanol, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, ethyl acetate, methyl acetate, dimethyl acetate, water, benzene, styrene, ethyl benzene, benzyl alcohol, 1,4-dioxane, propanol, carbon tetrachloride, tetrachloroethylene, cyclohexane, hexane, pentane, cyclohexanone, cyclopentane, methylene chloride, a phenolic solvent, pyridine, trichloroethane, trichloroethylene, N,N-dimethyl formamide, ethylene dichloride, dimethyl sulfoxide, N,N-dimethylacetamide, a pyrrolidone-based solvent, ethylene carbonate, propylene carbonate, dimethyl carbonate, acetonitrile, N-methylmorpholine-N-oxide, butylene carbonate, 1,4-butyrolactone, diethyl carbonate, diethylether, 1,2-dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dioxolane, ethyl methyl carbonate, methyl formate, 3-methyloxazolidin-2-on, methyl propionate, 2-methyletetrahydrofurane, sulpholane, anisole, isophorone, xylene, carbon disulfide, chlorobenzene, dichlorobenzene, sulfuric acid, or dichloroethane, or a combination thereof.

30. The method of claim 27, wherein the polymer solution during the centrifugal force spinning method has a temperature from about 23°

C. to about the boiling point of the solvent.

31. The method of claim 27, wherein the polymer solution comprises about 2.5 wt % to about 35 wt % of the polymer based on the total weight of the polymer solution.

32. The method of claim 27, wherein the polymer solution has a viscosity of about 14 cP to about 290,000 cP.