Microporous membranes, separators, lithium batteries, and related methods

Patent metadata

Field	Value
Publication number	US-12573717-B2
Application number	US-202117531929-A
Country	US
Kind code	B2
Filing date	Nov 22, 2021
Priority date	Apr 10, 2015
Publication date	Mar 10, 2026
Grant date	Mar 10, 2026

Abstract

In accordance with at least selected embodiments, novel or improved separator membranes, separators, batteries including such separators, methods of making such membranes and/or separators, and/or methods of using such membranes and/or separators are disclosed or provided. In accordance with at least certain embodiments, an ionized radiation treated microporous polyolefin, polyethylene (PE), copolymer, and/or polymer blend (e.g., a copolymer or blend comprising PE and another polymer, such as polypropylene (PP)) battery separator for a secondary or rechargeable lithium battery and/or a method of making an ionized radiation treated microporous battery separator is disclosed. The ionized radiation treatment may provide a microporous membrane or battery separator having a lower onset temperature of thermal shutdown, an extended thermal shutdown window, physical, dimensional, and/or mechanical integrity maintained at higher temperatures, improved battery safety performance in a rechargeable lithium battery, a treated polyethylene separator membrane with the high temperature performance of a polypropylene membrane or separator membrane, or polypropylene-based trilayer product (by way of example only, a trilayer membrane made of two polypropylene layers with a polyethylene layer in between), reduced thermal shrinkage resulting in both improved thermal stability and high temperature physical integrity, which maintains the separation of cathode and anode in a battery system and avoids thermal runaway in a rechargeable or secondary lithium battery, and/or combinations thereof.

First claim

What is claimed is:

1 . A microporous battery separator membrane, comprising:
a microporous polyolefin separator membrane having a thickness less than about 14 μm and wherein: said microporous polyolefin separator membrane has an onset of thermal shutdown occurring at a temperature ≤138° C.; said microporous polyolefin separator membrane has % machine direction thermal shrinkage at 120° C. for one hour of ≤7.5%; said microporous polyolefin separator membrane has % transverse direction thermal shrinkage at 120° C. for one hour ≤1%; and/or said microporous polyolefin separator membrane has been improved and/or modified using ionized radiation energy at an energy from 100 to 120 kGy.

2 . The battery separator membrane of claim 1 wherein said microporous polyolefin separator membrane has been improved and modified using low energy electron beam radiation.

3 . The battery separator membrane of claim 2 wherein said low energy electron beam radiation is applied using a single dosage application step.

4 . The battery separator membrane of claim 2 wherein said microporous polyolefin separator membrane is a single layer membrane, a multiple layer membrane, a single ply structure, or a multi-ply structure.

5 . The battery separator membrane of claim 2 wherein said microporous polyolefin separator membrane comprises polyethylene.

6 . The battery separator membrane of claim 1 wherein the polyolefin is a semi-crystalline polymer.

7 . The battery separator membrane of claim 1 wherein the polyolefin is polyethylene or polypropylene.

8 . The battery separator membrane of claim 7 wherein the polyolefin is polyethylene having a molecular weight less than 800,000.

9 . The battery separator membrane of claim 7 wherein the polyolefin is polyethylene and the polyethylene microporous separator membrane is manufactured using a wet process.

10 . The battery separator membrane of claim 1 wherein said microporous polyolefin separator membrane has a thermal shutdown window extended from ≤138° C. to ≥155° C., extended from ≤138° C. to ≥160° C., or extended from ≤138° C. to ≥170° C. at an Electrical Resistance ≥1000 ohm-cm 2 .

11 . A rechargeable lithium-ion battery comprising the microporous battery separator membrane of claim 1 .

12 . A method of producing a more wettable polyethylene battery separator, wherein said method comprises providing the battery separator membrane of claim 1 , wherein the polyolefin comprises polyethylene; and treating said battery separator with low energy electron beam radiation.

13 . The method of claim 12 , wherein said treatment with said low energy electron beam radiation includes a dose ranging from about 50 to about 150 kGy.

14 . A microporous polyolefin battery separator membrane, comprising:
a microporous separator membrane having a thickness less than about 14 μm and wherein: said microporous separator membrane has at least one of:
an onset of thermal shutdown occurring at a temperature ≤138° C.;
% machine direction thermal shrinkage at 120° C. for one hour of ≤7.5%; and,
% transverse direction thermal shrinkage at 120° C. for one hour ≤1%;
and wherein said microporous separator membrane has been improved and/or modified by cross-linking using ionized radiation at a power between 100 and 120 kGy.

15 . In a separator, battery, device, product, or vehicle, the improvement comprising the membrane of claim 14 .

16 . In a separator, battery, device, product, or vehicle, the improvement comprising the membrane of claim 1 .

17 . A microporous battery separator membrane comprising:
a microporous polyolefin separator membrane modified with low energy electron beam radiation from 100 to 120 kGy, and having a thickness of 20 microns or less and wherein: said microporous polyolefin separator membrane has an onset of thermal shutdown occurring at a temperature ≤138° C.; said microporous polyolefin separator membrane has % machine direction thermal shrinkage at 120° C. for one hour of ≤7.5%; and/or said microporous polyolefin separator membrane has % transverse direction thermal shrinkage at 120° C. for one hour ≤1%.

18 . The battery separator membrane of claim 17 wherein said low energy electron beam radiation is applied using a single dosage application step.

19 . The battery separator membrane of claim 17 wherein said microporous polyolefin separator membrane is a single layer membrane, a multiple layer membrane, a single ply structure, or a multi-ply structure.

20 . The battery separator membrane of claim 17 wherein said microporous polyolefin separator membrane comprises polyethylene.

21 . The battery separator membrane of claim 17 wherein the polyolefin is a semi-crystalline polymer.

22 . The battery separator membrane of claim 17 wherein the polyolefin is polyethylene or polypropylene.

23 . The battery separator membrane of claim 22 wherein the polyolefin is polyethylene having a molecular weight less than 800,000.

24 . The battery separator membrane of claim 22 wherein the polyolefin is polyethylene and the polyethylene microporous separator membrane is a wet process membrane.

25 . The battery separator membrane of claim 17 wherein said microporous polyolefin separator membrane has a thermal shutdown window extended from ≤138° C. to ≥155° C., extended from ≤138° C. to ≥160° C., or extended from ≤138° C. to ≥170° C. at an Electrical Resistance ≥1000 ohm-cm 2 .

26 . A rechargeable lithium-ion battery comprising the microporous battery separator membrane of claim 17 .

27 . A microporous polyolefin battery separator membrane comprising:
a microporous separator membrane having a thickness of 20 microns or less, the polyolefin is cross-linked with low energy electron beam radiation in a dosage ≥100 kGy and ≤120 kGy, and wherein: said microporous separator membrane has at least one of:
an onset of thermal shutdown occurring at a temperature ≤138° C.;
% machine direction thermal shrinkage at 120° C. for one hour of ≤7.5%; and/or
% transverse direction thermal shrinkage at 120° C. for one hour ≤1%.

28 . A separator, battery, device, product, or vehicle comprising the membrane of claim 27 .

29 . A separator, battery, device, product, or vehicle comprising the membrane of claim 17 .

30 . The microporous battery separator membrane of claim 25 , wherein said microporous polyolefin separator membrane has a thermal shutdown window extended from ≤138° C. to ≥160° C. at an Electrical Resistance ≥1000 ohm-cm 2 .

31 . The microporous battery separator membrane of claim 25 , wherein said microporous polyolefin separator membrane has a thermal shutdown window extended from ≤138° C. to ≥170° C. at an Electrical Resistance ≥1000 ohm-cm 2 .

Assignees

• Celgard Llc

Inventors

• Adams Changqing Wang
• Bielmann Michael
• Zhang Zhengming

Classifications

• H01M50/457

  comprising three or more layers · CPC title

• H01M50/417

  Polyolefins · CPC title

• H01M50/489

  Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• B32B27/08

  of synthetic resin · CPC title