Non-woven polymer fiber mat for use in a lithium ion battery electrochemical cell

• US 9,346,066 B2
• Filed: 06/05/2012
• Issued: 05/24/2016
• Est. Priority Date: 06/05/2012
• Status: Active Grant

• Current Assignee: GM Global Technology Operations LLC (General Motors Company)
• Original Assignee: GM Global Technology Operations LLC (General Motors Company)
• Inventors: Huang, Xiaosong
• Primary Examiner(s): Ruddock, Ula C
• Assistant Examiner(s): AMPONSAH, OSEI K
• Application Number:
  US13/488,691
• Publication Number:
  US 20130319599A1
• Time in Patent Office: 1,449 Days
• Field of Search: 427402-4211, 264/115
• US Class Current: 1/1
• CPC Class Codes: B05B 5/025 Discharge apparatus, e.g. electrostatic spray guns
• CPC Class Codes: D01D 5/0069 characterised by the spinning section, e.g. capillary tube, protrusion or pin
• CPC Class Codes: D04H 1/413 containing granules other than absorbent substances
• CPC Class Codes: D04H 1/728 by electro-spinning electro-spinning methods and apparatus D01D5/0007
• CPC Class Codes: D04H 3/03 at random
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 50/417 Polyolefins
• CPC Class Codes: H01M 50/42 Acrylic resins
• CPC Class Codes: H01M 50/423 Polyamide resins
• CPC Class Codes: H01M 50/426 Fluorocarbon polymers
• 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: Y02E 60/10 Energy storage using batteries

Abstract

A method of making a non-woven polymer fiber mat that includes one or more polymer fibers and particles intermingled with the one or more polymer fibers is disclosed. The method, more specifically, includes simultaneously electrospinning the one or more polymer fibers and spraying the particles onto a collection face of a collector substrate. Once formed, the non-woven polymer fiber mat may be incorporated into an electrochemical battery cell of a lithium ion battery.

Claims

1. A method comprising:

(a) providing a collector substrate that includes a collection face;

(b) positioning the collection face of the collector substrate into deposition alignment with both an electrospinning apparatus and an electrospraying apparatus; and

(c) forming a non-woven polymer fiber mat onto the collection face of the collector substrate, the non-woven polymer fiber mat comprising a fibrous web of one or more polymer fibers and particles dispersed throughout the fibrous web, the non-woven polymer fiber mat being formed by at least the steps of;

(c1) electrospinning the fibrous web of one or more polymer fibers onto the collection face; and

, simultaneously;

(c2) electrospraying the particles towards the same portion of the collection face of the collector substrate so that the particles become intermingled with the polymer fiber(s) as the particles and the polymer fiber(s) travel towards the collection face of the collector substrate;

(d) removing the non-woven polmer fiber mat from the collection face of the collector substrate; and

(e) calculating the non-woven polymer fiber mat by passing the non-woven polymer fiber mat between a pair of counter-rotating rollers to compress the mat.

2. The method set forth claim 1, wherein the polymer fiber(s) are comprised of a polyolefin, a polyamic acid, a polyimide, a polyamide, a polysulfone, a polyester, a fluoropolymer, a polyacrylate, a polycarbonate, a polyurethane, or mixtures thereof.

3. The method set forth in claim 1, wherein the polymer fiber(s) are comprised of polypropylene, polyethylene, polyetherimide, polyhexamethylene adipamide, polycaprolactam, polyparaphenylene terephthalamide, standard polysulfone, polyarylsulfone, polyethersulfone, polyphenylsulfone, polyethylene terephthalate, polyvinylidene fluoride, poly(methyl methacrylate), polyacrylonitrile, poly(bisphenol A-carbonate), or mixtures thereof.

4. The method set forth in claim 1, wherein the polymer fiber(s) are comprised of polyethylene terephthalate, polyvinylidene fluoride, polyacrylonitrile, polyetherimide, an aromatic polyamide, a liquid crystal polymer, or mixtures thereof.

5. The method set forth in claim 1, wherein the particles are comprised of a ceramic material, a polymer material, or a mixture thereof.

6. The method set forth in claim 1, wherein the non-woven polymer fiber mat has a thickness that ranges from about 5 μ

m to about 50 μ

m.

7. The method set forth in claim 1, wherein the polymer fiber(s) have a diameter in the range of about 10 nm to about 10 μ

m and the particles have diameters in the range of about 50 nm to about 5 μ

m.

9. The method set forth in claim 1, wherein the collector substrate comprises an electrode composed as either a negative electrode or a positive electrode for a lithium ion battery cell, and further comprising:

pressing the collector substrate and the non-woven polymer fiber mat retained on the substrate together with another electrode complimentary to the electrode included in the collector substrate, and wherein the non-woven polymer fiber mat is situated between the electrodes.

8. The method set forth in 1 further comprising:

incorporating the non-woven polymer fiber mat into an electrochemical battery cell of a lithium ion battery.

10. A method comprising:

(a) providing a collector substrate that includes a collection face;

(b) electrospinning a fibrous web of one or more polymer fibers onto the collection face of the collector substrate; and

(c) spraying particles towards the collection face of the collector substrate, the spraying of particles being a separate operation than the electrospinning of the one or more polymer fibers and being performed such that the sprayed particles become intermingled with the one or more polymer fibers as the particles and the one or more polymer fibers travel towards the same portion of the collection face of the collector substrate;

wherein step (b) and step (c) are performed simultaneously to fabricate the non-woven polymer fiber mat includes the fibrous web of the polymer fiber(s) and the particles dispersed throughout the fibrous web, the non-woven polymer fiber mat having a first major face and a second major face that together define a thickness of the mat, the first and second major faces being oriented so than one of the first or second major faces confronts the negative electrode and the other of the first or second major faces confronts the positive electrode when the non-woven polymer fiber mat is situated between spaced apart and confronting surfaces of the negative electrode and the positive electrode within the electrochemical battery cell of a lithium ion battery, the non-woven polymer fiber mat further having a thickness that ranges anywhere from about 5 μ

m to about 50 μ

m and a porosity that ranges anywhere from about 30% to about 90%.

11. The method set forth in claim 10, wherein step (b) comprises deriving the polymer fiber(s) from an electrified jet of a polymer liquid conducive to electrospinning, and wherein step (c) comprises deriving the particles from an electrified spray of a liquid conducive to electrospraying.

12. The method set forth in claim 11, wherein the polymer liquid conducive to electrospinning comprises a polyolefin, a polyamic acid, a polyimide, a polyamide, a polysulfone, a polyester, a fluoropolymer, a polyacrylate, a polycarbonate, a polyurethane, or mixtures thereof, and wherein the liquid conducive to electrospraying comprises a ceramic material, a polymer material, or mixtures thereof.

13. The method set forth in claim 10, wherein the collector substrate comprises a metal layer.

14. The method set forth in claim 10, wherein the collector substrate comprises an electrode composed as either a positive electrode or a negative electrode for an electrochemical battery cell of a lithium ion battery, and wherein either the electrode or a ceramic particle layer overlying the electrode is exposed at the collection face.

15. The method set forth in claim 10, wherein the polymer fiber(s) have a diameter in the range of about 10 nm to about 10 μ

m and the particles have diameters in the range of about 50 nm to about 5 μ

m.

16. The method set forth in claim 10, further comprising:

(d) incorporating the non-woven polymer fiber mat into an electrochemical battery cell of a lithium ion battery such that that the non-woven polymer fiber mat functions as all or part of a separator that physically separates and electrically insulates a negative electrode and the positive electrode.

17. A method comprising:

(a) positioning a collection face of a collector substrate in deposition alignment with both an electrospinning apparatus and an electrospraying apparatus;

(b) generating an electric field between the collector substrate and each of the electrospinning apparatus and the electrospraying apparatus, the electric field being such that an electrical potential difference of the same polarity exists (1) between the electrospinning apparatus and the collector substrate and (2) between the electrospraying apparatus and the collector substrate;

(c) pushing a polymer liquid conducive to electrospinning through an orifice of the electrospinning apparatus so that an electrically charged jet of the polymer liquid is ejected towards the collection face of the collector substrate, the electrically charged jet of the polymer liquid solidifying into one or more polymer fibers when traveling towards the collection face of the collector substrate;

(d) pushing a liquid conducive to electrospraying through an orifice of the electrospraying apparatus so that an electrically charged spray of the liquid is ejected towards the collection face of the collector substrate at the same time that the electrically charged jet of the polymer liquid is being ejected from the electrospinning apparatus, the electrically charged spray providing particles that intermingle with the one or more polymer fibers produced by the electrospinning apparatus as the particles and the one or more polymer fibers travel towards the same portion of the collection face of the collector substrate; and

(e) collecting a non-woven polymer fiber mat on the collection face of the collector substrate, the non-woven polymer fiber mat comprising (1) a fibrous web of the one or more polymer fibers derived from the electrified jet of the polymer liquid conducive to electrospinning and (2) particles derived from the electrified spray of the liquid conducive to electrospraying which are dispersed throughout the fibrous web of the polymer fiber(s), the polymer fiber(s) having a diameter in the range of about 10 nm to about 10 μ

m and the particles having diameters in the range of about 50 nm to about 5 μ

m.

18. The method set forth in claim 17, wherein step (b) comprises applying an electrical potential to the electrospinning apparatus and the electrospraying apparatus so that the electrical potential difference between each of (1) the electrospinning apparatus and the collector substrate and (2) the electrospraying apparatus and the collector substrate ranges from about 5 kV to about 50 kV.

19. The method set forth in claim 17, wherein the non-woven polymer fiber mat comprises about 20 vol. % to about 80 vol. % of the polymer fiber(s) and about 20 vol. % to about 80 vol. % of the particles, each based on the total volume of the polymer fiber(s) and the particles.

20. The method set forth in claim 17, further comprising:

(f) calendering the non-woven polymer fiber mat; and

(g) incorporating the non-woven polymer fiber mat into an electrochemical battery cell of a lithium ion battery such that that the non-woven polymer fiber mat functions as all or part of a separator that physically separates and electrically insulates a negative electrode and a positive electrode.