Ion-conducting structures, devices including ion-conducting structures, and methods for use and fabrication thereof

Patent metadata

Field	Value
Publication number	US-11901505-B2
Application number	US-202217750062-A
Country	US
Kind code	B2
Filing date	May 20, 2022
Priority date	Aug 22, 2019
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

An ion-conducting structure comprises a metal-fibril complex formed by one or more elementary nanofibrils. Each elementary nanofibril can be composed of a plurality of cellulose molecular chains with functional groups. Each elementary nanofibril can also have a plurality of metal ions. Each metal ion can act as a coordination center between the functional groups of adjacent cellulose molecular chains so as to form a respective ion transport channel between the cellulose molecular chains. The metal-fibril complex can comprise a plurality of second ions. Each second ion can be disposed within one of the ion transport channels so as to be intercalated between the corresponding cellulose molecular chains. In some embodiments, the metal-fibril complex is formed as a solid-state structure.

First claim

The invention claimed is:

1. An ion-conducting structure, comprising:
a metal-fibril complex formed by one or more elementary nanofibrils, each elementary nanofibril being composed of a plurality of cellulose molecular chains with functional groups, each elementary nanofibril having a plurality of metal ions, each metal ion acting as a coordination center between the functional groups of adjacent cellulose molecular chains so as to form a respective ion transport channel between the cellulose molecular chains,
wherein the metal-fibril complex comprises a plurality of second ions, each second ion being disposed within one of the ion transport channels so as to be intercalated between the corresponding cellulose molecular chains, and
wherein the metal-fibril complex is a solid-state structure having a conductivity of at least 10 4 S/cm.

2. The ion-conducting structure of claim 1 , wherein the metal-fibril complex further comprises polysaccharide, poly(vinyl chloride) (PVC), poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), poly(ethyl methacrylate) (PEMA), poly(methyl methacrylate) (PMMA), poly(ethylene terephthalate) (PET), polyethylene (PE), poly(ethylene naphthalate) (PEN), polyamide (PA), poly(vinylidene chloride) (PVDC), poly lactic acid (PL A), or combinations thereof.

3. The ion-conducting structure of claim 1 , wherein the plurality of metal ions comprises copper (Cu), zinc (Zn), aluminum (Al), calcium (Ca), iron (Fe), or combinations thereof.

4. The ion-conducting structure of claim 1 , wherein the plurality of second ions comprises lithium (Li+), sodium (Na+), potassium (K+), magnesium (Mg+), protons (H+), or combinations thereof.

5. The ion-conducting structure of claim 1 , wherein a width of each ion transport channel is about 1 nm, and a spacing between adjacent ion transport channels within each elementary nanofibril is less than 2 nm.

6. The ion-conducting structure of claim 1 , wherein each elementary nanofibril comprises 12-36 cellulose molecular chains, inclusive.

7. The ion-conducting structure of claim 1 , wherein the metal-fibril complex has a plurality of the elementary nanofibrils and is formed as a sheet, film, or membrane.

8. The ion-conducting structure of claim 1 , wherein a total content of water within the metal-fibril complex is less than or equal to 10 wt %.

9. An ion-conducting structure, comprising:
a metal-fibril complex formed by one or more elementary nanofibrils, each elementary nanofibril being composed of a plurality of polymer molecular chains with functional groups, each elementary nanofibril having a plurality of metal ions, each metal ion acting as a coordination center between the functional groups of adjacent molecular chains so as to form a respective ion transport channel between the molecular chains,
wherein the metal-fibril complex comprises a plurality of second ions, each second ion being disposed within a respective one of the ion transport channels so as to be intercalated between the corresponding molecular chains, and
wherein the metal-fibril complex is a solid-state structure having a conductivity of at least 10 −4 S/cm.

10. The ion-conducting structure of claim 9 , wherein the metal-fibril complex comprises polysaccharide, poly(vinyl chloride) (PVC), poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), poly(ethyl methacrylate) (PEMA), poly(methyl methacrylate) (PMMA), poly(ethylene terephthalate) (PET), polyethylene (PE), poly(ethylene naphthalate) (PEN), polyamide (PA), poly(vinylidene chloride) (PVDC), polylactic acid (PLA), or combinations thereof.

11. The ion-conducting structure of claim 9 , wherein each polymer molecular chain comprises a naturally-occurring polysaccharide, and the naturally-occurring polysaccharide comprises cellulose, chitosan, chitin, or combinations thereof.

12. The ion-conducting structure of claim 9 , wherein the plurality of metal ions comprises copper (Cu), zinc (Zn), aluminum (Al), calcium (Ca), iron (Fe), or combinations thereof.

13. The ion-conducting structure of claim 9 , wherein the plurality of second ions comprises lithium (Li+), sodium (Na+), potassium (K+), magnesium (Mg+), protons (H+), or combinations thereof.

14. The ion-conducting structure of claim 9 , wherein a width of each ion transport channel is less than 2 nm.

15. The ion-conducting structure of claim 9 , wherein a content of total liquid within the metal-fibril complex is less than or equal to 10 wt %.

16. A method, comprising:
(a) forming a metal-fibril complex by immersing a plurality of elementary nanofibrils within an alkaline solution and a plurality of metal ions dissolved therein, each elementary nanofibril being composed of a plurality of polymer molecular chains with functional groups, the immersing being such that hydrogen bonds between adjacent functional groups of the polymer molecular chains are broken so as to expose the functional groups and such that the dissolved metal ions from the alkaline solution form coordination bonds with the exposed functional groups; and
(b) intercalating second ions between adjacent molecular chains of the metal-fibril complex by immersing the metal-fibril complex in a first solution having a plurality of the second ions dissolved therein.

17. The method of claim 16 , further comprising:
(c) replacing free liquid in the metal-fibril complex by immersing the metal-fibril complex in an organic solvent.

18. The method of claim 17 , further comprising:
(d) drying the metal-fibril complex such that a total content of liquid within the metal-fibril complex is less than 10 wt %, thereby forming the metal-fibril complex with intercalated second ions as a solid-state ion conducting structure.

19. The method of claim 18 , wherein the first solution is the organic solvent, and the intercalating of (b) and the replacing free liquid of (c) are performed simultaneously.

20. The method of claim 18 , wherein the first solution is separate from the organic solvent, and the intercalating of (b) is performed before or after the replacing free liquid of (c).

Assignees

• Univ Maryland

Inventors

• Hu Liangbing
• Li Tian
• Yang Chunpeng
• Zhang Xin
• Briber Robert M
• Wu Meiling

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• Y02E60/50

  Fuel cells · CPC title

• H01M8/0243

  in the form of mixtures · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M50/44

  Fibrous material · CPC title