Lithium ion batteries comprising nanofibers

Patent metadata

Field	Value
Publication number	US-11728545-B2
Application number	US-202117360659-A
Country	US
Kind code	B2
Filing date	Jun 28, 2021
Priority date	Mar 2, 2012
Publication date	Aug 15, 2023
Grant date	Aug 15, 2023

Abstract

Lithium ion batteries, electrodes, nanofibers, and methods for producing same are disclosed herein. Provided herein are batteries having (a) increased energy density; (b) decreased pulverization (structural disruption due to volume expansion during lithiation/de-lithiation processes); and/or (c) increased lifetime. In some embodiments described herein, using high throughput, water-based electrospinning process produces nanofibers of high energy capacity materials (e.g., ceramic) with nanostructures such as discrete crystal domains, mesopores, hollow cores, and the like; and such nanofibers providing reduced pulverization and increased charging rates when they are used in anodic or cathodic materials.

First claim

The invention claimed is:

1. A polymer nanocomposite nanofiber produced by coaxially gas assisted electrospinning, comprising:
(i) a plurality of nanostructures comprising a clay, a ceramic, a ceramic precursor, or any combination thereof; and
(ii) a polymer portion comprising one or more polymers;
wherein the polymer portion is a continuous polymer matrix;
wherein the plurality of nanostructures comprises non-aggregated ceramic and/or clay nanostructures embedded within the polymer matrix; and
wherein the polymer nanocomposite nanofiber comprises 0.5 to 50 wt % ceramic and/or clay.

2. The polymer nanocomposite nanofiber of claim 1 , wherein the polymer matrix comprises PE, UHMWPE, PP, PVA, PAN, PEO, PVP, PVDF, PMMA, PI, nylon, aramid, or a combination thereof.

3. The polymer nanocomposite nanofiber of claim 1 , wherein the polymer nanocomposite nanofiber comprises 1-15 wt % clay, 1-15 wt % ceramic, or 1-15 wt % of ceramic and clay combined.

4. The polymer nanocomposite nanofiber of claim 1 , wherein the nanostructures comprises ceramic, wherein the ceramic is generated by one or more ceramic precursors.

5. The polymer nanocomposite nanofiber of claim 1 , wherein the nanostructures comprise clay, which clay is bentonite, aluminum phyllosilicate, montmorillonite, kaolinite, illite, vermiculite, smectite, chlorite, silicate clay, sesquioxide clay, allophane, imogolite, fluorohectorate, laponite, bentonite, beidellite, hectorite, saponite, nontronite, sauconite, ledikite, magadiite, kenyaite, stevensite, or combinations thereof.

6. The polymer nanocomposite nanofiber of claim 1 , wherein the nanostructures are dispersed in a substantially uniform manner along the length of the nanofiber.

7. The polymer nanocomposite nanofiber of claim 1 , further comprising a lithium metal oxide having a formula of:
Li a M b X c ,
wherein M comprises one or more metal element selected from Fe, Ni, Co, Mn, V, Ti, Zr, Ru, Re, Pt, Bi, Pb, Cu, Al, Li, or a combination thereof;
wherein X comprises one or more non-metals selected from C, N, O, P, S, SO 4 , PO 4 , Se, halide, F, CF, SO 2 , SO 2 Cl 2 , I, Br, SiO 4 , BO 3 , or a combination thereof; and
wherein a is in a range of 1-5, b is in a range of 0-2, and c is in a range of 0-10.

8. The polymer nanocomposite nanofiber of claim 1 , wherein the nanofiber comprises a hollow core surrounded by a continuous tube of matrix material.

9. The polymer nanocomposite nanofiber of claim 1 , wherein the nanofiber is porous and comprises one or more of:
(a) a plurality of pores with an average diameter of at least 1 nm;
(b) a specific surface area of at least 100 m 2 /g;
(c) a porosity of at least 20%;
(d) a plurality of pores having a substantially uniform shape, substantially uniform size and/or substantially uniform distribution across the nanofiber; and
wherein the porous nanofiber is produced by heating to carbonize or selectively remove a polymer and/or polymer phase or by chemically treating to remove carbon.

10. The polymer nanocomposite nanofiber of claim 1 , wherein:
the non-aggregated ceramic and/or clay nanostructures comprise at least one high energy capacity material selected from Si, Sn, Ge, Al, Co, Cu, Fe, an oxide thereof, a carbide thereof, an alloy thereof, or a combination thereof; and
the high energy capacity material is capable of intercalating and deintercalating lithium ions.

11. The polymer nanocomposite nanofiber of claim 10 , wherein domains of the high energy material comprise substantially uniform shapes and/or substantially uniform size.

12. A battery comprising:
an anode;
a cathode; and
a separator;
wherein at least one of the anode, the cathode, and the separator comprises one or more polymer nanocomposite nanofibers according to claim 1 .

13. The battery of claim 12 , wherein the polymer matrix of the one or more polymer nanocomposite nanofibers comprises PE, UHMWPE, PP, PVA, PAN, PEO, PVP, PVDF, PMMA, PI, nylon, aramid, or a combination thereof.

14. The battery of claim 12 , wherein the one or more polymer nanocomposite nanofibers comprises 1-15 wt % clay, 1-15 wt % ceramic, or 1-15 wt % of ceramic and clay combined.

15. The battery of claim 12 , wherein the nanostructures of the one or more polymer nanocomposite nanofibers comprises ceramic, wherein the ceramic is generated by one or more ceramic precursors.

16. The battery of claim 12 , wherein the nanostructures of the one or more polymer nanocomposite nanofibers comprise clay, which clay is bentonite, aluminum phyllosilicate, montmorillonite, kaolinite, illite, vermiculite, smectite, chlorite, silicate clay, sesquioxide clay, allophane, imogolite, fluorohectorate, laponite, bentonite, beidellite, hectorite, saponite, nontronite, sauconite, ledikite, magadiite, kenyaite, stevensite, or combinations thereof.

17. The battery of claim 12 , wherein the nanostructures of the one or more polymer nanocomposite nanofibers are dispersed in a substantially uniform manner along the length of the nanofiber.

18. The battery of claim 12 , wherein the one or more polymer nanocomposite nanofibers each further comprise a lithium metal oxide having a formula of:
Li a M b X c ,
wherein M comprises one or more metal element selected from Fe, Ni, Co, Mn, V, Ti, Zr, Ru, Re, Pt, Bi, Pb, Cu, Al, Li, or a combination thereof;
wherein X comprises one or more non-metals selected from C, N, O, P, S, SO 4 , PO 4 , Se, halide, F, CF, SO 2 , SO 2 Cl 2 , I, Br, SiO 4 , BO 3 , or a combination thereof; and
wherein a is in a range of 1-5, b is in a range of 0-2, and c is in a range of 0-10.

19. The battery of claim 12 , wherein the one or more polymer nanocomposite nanofibers each comprise a hollow core surrounded by a continuous tube of matrix material.

20. The battery of claim 12 , wherein the one or more polymer nanocomposite nanofibers are porous and each comprise one or more of:
(e) a plurality of pores with an average diameter of at least 1 nm;
(f) a specific surface area of at least 100 m 2 /g;
(g) a porosity of at least 20%;
(h) a plurality of pores having a substantially uniform shape, substantially uniform size and/or substantially uniform distribution across the nanofiber; and
wherein the porous nanofiber is produced by heating to carbonize or selectively remove a polymer and/or polymer phase or by chemically treating to remove carbon.

Assignees

• Univ Cornell

Inventors

• Joo Yong Lak
• Hansen Nathaniel S
• Cho Daehwan
• Kim Kyoung Woo

Classifications

• H01M50/446 Primary

  Composite material consisting of a mixture of organic and inorganic materials · CPC title

• D01D5/003 Primary

  the material being a polymer solution or dispersion (D01D5/0053 takes precedence) · CPC title

• D01F1/09

  for making electroconductive or anti-static filaments · CPC title

• D01F1/10

  Other agents for modifying properties · CPC title

• D01F9/20

  from polyaddition, polycondensation or polymerisation products (D01F9/145, D01F9/16, D01F9/18 take precedence) · CPC title