POROUS ETCHED ION-TRACK POLYMER MEMBRANE AS A SEPARATOR FOR A BATTERY

• US 20200136115A1
• Filed: 06/14/2018
• Published: 04/30/2020
• Est. Priority Date: 06/14/2017
• Status: Active Application

• Current Assignee: Centre National De La Recherche Scientifique, GSI Helmholtzzentrum FüR Schwerionenforschung GmbH (Government of Germany), Technische Universitã¤T Darmstadt, University of Picardie Jules Verne
• Original Assignee: Centre National De La Recherche Scientifique
• Inventors: TOIMIL MOLARES, Maria Eugenia, TRAUTMAN, Christina, LEE, Pui Lap Jacob, MORCRETTE, Mathieu
• Application Number:
  US16/622,102
• Publication Number:
  US 20200136115A1
• Time in Patent Office: Days
• CPC Class Codes: B01D 2325/021 Pore shapes
• CPC Class Codes: B01D 2325/02832 1-10 nm
• CPC Class Codes: B01D 2325/02833 more than 10 and up to 100 nm
• CPC Class Codes: B01D 67/0032 by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B01D 71/48 Polyesters
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• 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 50/451 comprising layers of only organic material and layers containing inorganic 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: Y02E 60/10 Energy storage using batteries

Abstract

The present invention relates to the use of a porous polymer etched ion-track membrane as separator for batteries comprising a positive electrode, a negative electrode and a liquid electrolyte comprising at least one salt of a cationic ion in solution in a solvent, and to batteries comprising such a membrane as porous separator.

Claims

1. A method to suppress or at least reduce the redox shuttle phenomenon in batteries comprising the use of a porous polymer etched ion-track membrane as a separator in a lithium-sulfur battery comprising at least one positive electrode, at least one negative electrode and at least one liquid electrolyte comprising at least one salt of a cationic ion selected in the group consisting of lithium, sodium, potassium and calcium in solution in at least one solvent, wherein:

said polymer is selected from the group comprising polyethyleneterephtalate (PET), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyimide (PI) polytetrafluoroethylene (PTFE), and polyvinilidene fluorure (PVdF),

said membrane has a frontside, a backside, and a thickness,

the frontside of said membrane is designed to face the positive electrode,

the backside of said membrane is designed to face the negative electrode,

the thickness of said membrane between said frontside and said backside is ranging from about 5 to 60 μ

m,

said membrane comprises a plurality of nanochannels,

the majority in number of said nanochannels is continuous and has an opening tip at the frontside and an opening tip at the backside of said membrane,

the opening tip diameter of each of said nanochannels at the frontside of said membrane (D_FS) ranges from about 10 to 200 nm,

the opening tip diameter distribution of the nanochannels at the front side and at the back side is narrow.

2. The method according to claim 1, wherein:

thickness of said membrane preferably ranges from 5 to 30 and/or

the opening tip diameter of each of said nanochannels at the frontside of the membrane ranges from 50 nm to 150; and

/or

the opening tip diameter of each of said nanochannels at the backside of the membrane (D_BS) ranges from 10 nm to 600 nm.

5. The method according to claim 1, wherein the opening tip diameter of each of said nanochannels at the backside of the membrane (D_BS) is substantially identical to the opening tip diameter of each of said nanochannels at the frontside of the membrane (D_FS) and ranges from 50 to 150 nm.

6. The method according to claim 5, wherein said nanochannels have a cylindric shape and their longitudinal axis are substantially parallel oriented to one another.

7. The method according to claim 5, wherein said nanochannels are interconnected.

8. The method according to claim 1, wherein the opening tip diameter of each of said nanochannels at the backside of the membrane (D_BS) is greater or smaller than the opening tip diameter of each of said nanochannels at the frontside of the membrane (D_FS) and ranges from 10 to 600 nm.

9. The method according to claim 8, wherein said nanochannels have a conical shape and their longitudinal axis are substantially parallel oriented to one another.

10. The method according to claim 1, wherein the said polymer is polyethyleneterephtalate.

11. The method according to claim 1, wherein the ratio of the total volume of the nanochannels/total volume of the membrane ranges from 2 to 50%.

12. The method according to claim 1, wherein the nanochannels density in said membrane ranges from to 10⁶ to 10¹² nanochannels/cm².

13. The method according to claim 1, wherein at least one of the surfaces of the porous membrane comprises a coating of at least one layer of oxide of a metal or of a metalloid.

14. The method according to claim 13, wherein said at least one surface is the surface designed to face the positive electrode.

15. The method according to claim 13, wherein said layer is a layer of TiO₂, SiO₂ or Al₂O₃.

16. A separator for a battery comprising at least one positive electrode, at least one negative electrode and at least one separator impregnated by a liquid electrolyte comprising at least one salt of a cationic ion selected in the group consisting of lithium, sodium, potassium and calcium in solution in at least one solvent, wherein said separator is a porous polymer etched ion-track membrane such as used in claim 1.

17. The separator of claim 16, wherein said membrane is inserted between two microporous polymer supports.

18. A lithium-sulfur battery comprising at least a negative electrode, a positive electrode, a liquid electrolyte comprising at least one salt of a cationic ion selected in the group consisting of lithium, sodium, potassium and calcium in solution in at least one solvent, and a porous separator, wherein said porous separator is a separator according to claim 1.

3. (canceled)

4. (canceled)

20. The method according to claim 19, wherein the membrane, the nanochannel and the polymer are as described in claim 4.

17-1. Method to suppress or at least reduce the redox shuttle phenomenon in batteries comprising the use of a porous polymer etched ion-track membrane as a separator in battery comprising at least one positive electrode, at least one negative electrode and at least one liquid electrolyte comprising at least one salt of a cationic ion selected in the group consisting of lithium, sodium, potassium and calcium in solution in at least one solvent, wherein:

said polymer is selected from the group comprising polyethyleneterephtalate (PET), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyimide (PI) polytetrafluoroethylene (PTFE), and polyvinilidene fluorure (PVdF),

said membrane has a frontside, a backside, and a thickness,

the frontside of said membrane is designed to face the positive electrode,

the backside of said membrane is designed to face the negative electrode,

the thickness of said membrane between said frontside and said backside is ranging from about 5 to 60 μ

m,

said membrane comprises a plurality of nanochannels,

the majority in number of said nanochannels is continuous and has an opening tip at the frontside and an opening tip at the backside of said membrane,

the opening tip diameter of each of said nanochannels at the frontside of said membrane (D_FS) ranges from about 10 to 200 nm,

the opening tip diameter distribution of the nanochannels at the front side and at the back side is narrow,

at least one of the surfaces of the porous membrane comprises a coating of at least one layer of oxide of a metal or of a metalloid.

21-32. -32. (canceled)