# US 2014/0193716 A1 · Laser-perforated porous solid-state films and applications thereof

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- Number: US 2014/0193716 A1
- Document ID: US20140193716A1
- Status: Published application
- Kind: A1
- Application number: 14/150,846
- Filed: 2014-01-09
- Published: 2014-07-10
- Earliest claimed: 2013-01-10
- Assignees: Sabic Global Technologies B.V.
- Applicants: SABIC Innovative Plastics IP B.V.
- Inventors: Roy Martinus Adrianus L'Abee; Tony Farrell
- Web page: https://patentgrep.com/patent/US20140193716A1

## CPC

- C08F 110/02: Ethene
- B23K 26/38: by boring or cutting
- B23K 26/382: by boring
- B23K 26/386: of blind holes
- B23K 26/389: {of fluid openings, e.g. nozzles, jets}
- B23K 26/402: involving non-metallic material, e.g. isolators
- H01G 11/52: Separators
- H01M 8/1067: characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
- H01M 8/1069: characterised by the manufacturing processes
- H01M 8/1079: {Inducing porosity into non porous precursors membranes, e.g. leaching, pore stretching}
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/414: Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M 50/44: Fibrous material
- H01M 50/449: having a layered structure
- 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
- H01M 50/491: Porosity
- B23K 2103/42: {Plastics other than composite materials}
- B23K 2103/50: {Inorganic materials other than metals or composite materials}
- H01G 9/02: Diaphragms; Separators
- Y02E 60/10: Energy storage using batteries
- Y02E 60/13: Energy storage using capacitors
- Y02E 60/50: Fuel cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- Y10T 428/24273: including aperture
- Y10T 428/24322: Composite web or sheet
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B23K: SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The disclosure relates, in one aspect, to porous solid-state films with controlled pore structures obtained by laser perforation. A thin laser-perforated film can comprise a slab defining a plurality of pores distributed in a predetermined arrangement, the plurality of pores having a distribution of sizes bound by a predetermined magnitude. In an aspect, the plurality of pores are formed in the slab with a laser having a wavelength less than about 400 nm and the slab has a transmission of the laser light of equal to or less than about 70% measured at a thickness of the slab of 100 micrometer or less.

## Claims

### Claim 1

A perforated film comprising:
a slab defining a plurality of pores distributed in a predetermined arrangement, the plurality of pores having a mean diameter less than about 50 μm;
wherein the plurality of pores are formed in the slab with a laser having a wavelength less than about 400 nm and the slab has a transmission of the laser light of equal to or less than about 70% measured at a thickness of the slab of 100 micrometer or less; and
wherein the slab has a high temperature melt integrity (HTMI) equal to or exceeding about 180° C.

### Claim 2 (depends on 1)

The perforated film of claim 1, wherein the transmission of the laser light is measured according to ASTM D1003-00, Procedure A, using D65 illumination, 10 degrees observer.

### Claim 3 (depends on 1)

The perforated film of claim 1, wherein the slab is formed from a polymer comprising one or more of polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polycarbonate, poly(4-methylpentene), cyclic olefin copolymers, polyamide, aromatic polyamide, poly(amide-imide), polyoxymethylene, polyphthalamide, polysulfone, polyethersulfone, polyphenylsulfone, liquid crystalline polymers, polyetherimide, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyphenylene oxide, polyimide, polyketone, polyetherketone, polyetheretherketone, polyphenylene sulfide, or a copolymer and/or blend thereof.

### Claim 4 (depends on 3)

The perforated film of claim 3, wherein the polymer comprises an ultraviolet absorbing additive selected from hydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines, cyanoacrylates, oxanilides, benzoxazinones, benzylidene malonates, hindered amine light stabilizers, nano-scale inorganics, or combinations comprising at least one of the foregoing.

### Claim 5 (depends on 1)

The perforated film of claim 1, wherein each of the plurality of pores is formed via laser perforation or laser drilling.

### Claim 6 (depends on 1)

The perforated film of claim 1, wherein each of the plurality of pores is formed via laser perforation of the slab or laser drilling of the slab, a surface of the slab being coupled to a mask, where the mask is locally transparent to electromagnetic radiation emitted from a laser in a pre-defined manner that enables laser perforation of the slab through the areas of the mask that are substantially transparent to the electromagnetic radiation.

### Claim 7 (depends on 1)

The perforated film of claim 1, wherein the slab is formed from a material containing at least one polymeric component that absorbs electromagnetic radiation having wavelengths below about 400 nm.

### Claim 8 (depends on 1)

The perforated film of claim 1, wherein the slab is formed from a material containing at least one component that absorbs electromagnetic radiation having wavelengths below about 400 nm.

### Claim 9 (depends on 1)

The perforated film of claim 1, wherein the slab has a total hole area of 10 to 80%.

### Claim 10 (depends on 1)

The perforated film of claim 1, wherein the slab comprises a plurality of material layers.

### Claim 11 (depends on 1)

The perforated film of claim 1, wherein the slab is integrated as high temperature separator for lithium ion battery or a separator for an electrolytic supercapacitor or a support membrane for a fuel cell membrane.

### Claim 12

A method, comprising:
providing a slab having a high temperature melt integrity (HTMI) equal to or exceeding about 180° C.; and
removing material from the slab by exposing the slab to a laser having a wavelength less than about 400 nm to produce a plurality of pores in the slab, the plurality of pores having a mean diameter less than about 50 μm and the slab having a transmission of the laser of equal to or less than about 70% measured at a thickness of the slab of 100 micrometer or less.

### Claim 13 (depends on 12)

The method of claim 12, wherein the transmission of the laser light is measured according to ASTM D1003-00, Procedure A, using D65 illumination, 10 degrees observer.

### Claim 14 (depends on 12)

The method of claim 12, further comprising arranging the slab in proximity of a porous thin film.

### Claim 15 (depends on 14)

The method of claim 14, wherein the porous thin film if formed from a process that is different from the process used to form the porous slab.

### Claim 16 (depends on 14)

The method of claim 14, wherein the porous thin film comprises a polymer selected from polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polycarbonate, poly(4-methylpentene), cyclic olefin copolymers, polyamide, aromatic polyamide, poly(amide-imide), polyoxymethylene, polyphthalamide, polysulfone, polyethersulfone, polyphenylsulfone, liquid crystalline polymers, polyetherimide, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyphenylene oxide, polyimide, polyketone, polyetherketone, polyetheretherketone, polyphenylene sulfide, or a copolymer and/or blend thereof.

### Claim 17 (depends on 16)

The method of claim 16, wherein the polymer comprises one or more ultraviolet absorbing additives selected from hydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines, cyanoacrylates, oxanilides, benzoxazinones, benzylidene malonates, hindered amine light stabilizers, nano-scale inorganics, or combinations comprising at least one of the foregoing.

### Claim 18

A composite film comprising:
a porous thin film; and
a slab arranged in proximity of the porous thin film and defining a plurality of pores distributed in a predetermined arrangement, the plurality of pores having a mean diameter less than about 50 μm;
wherein the slab has a high temperature melt integrity (HTMI) equal to or exceeding about 180° C. and the slab having a transmission of the laser of equal to or less than about 70% measured at a thickness of the slab of about 100 micrometer or less.

### Claim 19 (depends on 18)

The composite film of claim 18, wherein the transmission of the laser light is measured according to ASTM D1003-00, Procedure A, using D65 illumination, 10 degrees observer.

### Claim 20 (depends on 18)

The composite film of claim 18, wherein the porous thin film is based on polyethylene and melts at temperatures ranging from about 100° C. to about 130° C., thereby providing a shutdown mechanism.

### Claim 21 (depends on 18)

The composite film of claim 18, wherein the polyethylene porous thin film has a thickness of at least 5 microns.

### Claim 22 (depends on 18)

The composite film of claim 18, wherein the composite film is contained in a battery, thereby forming an HTMI battery separator.

### Claim 23 (depends on 18)

The composite film of claim 18, wherein the composite film is contained in an electrolytic capacitor as a separator.

### Claim 24 (depends on 18)

The composite film of claim 18, wherein the composite film is contained in a fuel cell as a support membrane.