“Flower-like” Li4Ti5O12-multiwalled carbon nanotube composite structures with performance as highrate anode-materials for li-ion battery applications and methods of synthesis thereof

Patent metadata

Field	Value
Publication number	US-11056685-B2
Application number	US-201916250907-A
Country	US
Kind code	B2
Filing date	Jan 17, 2019
Priority date	Jan 17, 2018
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

A method of fabricating nanocomposite anode material embodying a lithium titanate (LTO)-multi-walled carbon nanotube (MWNT) composite intended for use in a lithium-ion battery includes providing multi-walled carbon nanotube (MWNTs), including nanotube surfaces, onto which functional oxygenated carboxylic acid moieties are arranged, generating 3D flower-like, lithium titanate (LTO) microspheres, including thin nanosheets and anchoring the acid-functionalized MWNTs onto surfaces of the 3D LTO microspheres by π-π interaction strategy to realize the nanocomposite anode material.

First claim

What is claimed is:

1. A method of fabricating nanocomposite anode material comprising lithium titanate (LTO)-multi-walled carbon nanotube (MWNT) composite structures intended for use in a lithium-ion battery, the method comprising:
providing multi-walled carbon nanotubes (MWNTs) having surfaces, onto which functional oxygenated carboxylic acid moieties are arranged;
generating 3D flower-like, lithium titanate (LTO) microspheres having constituent nanosheets within the flower-like lithium titanate (LTO) microspheres; and
anchoring the acid-functionalized MWNTs onto surfaces of the 3D LTO flower-like LTO microspheres by π-π interaction strategy to realize the nanocomposite anode material;
wherein the 3D LTO flower-like microspheres are anchored to the acid-functionalized MWNTs by π-π interaction by first dispersing the 3D LTO flower-like microspheres in an ethanolic solution of 4-mercaptobenzoic acid (4-MBA) linker molecules.

2. The method of claim 1 , wherein generating the 3D flower-like, lithium titanate (LTO) microspheres includes synthesizing thin, saw-tooth shaped constituent nanosheets of lithium titanate (LTO) and subjecting the saw-tooth shaped constituent nanosheets to a calcination process in air, at a temperature range of between 400 and 600 degrees Centigrade, for a limited time period, to realize the nanocomposite anode material.

3. The method of claim 2 , wherein the limited time period is in a range of about 1 to about 5 hours.

4. The method of claim 3 , wherein the calcination process in air, occurs at a temperature of about 500 degrees Centigrade, for a limited time period of about 3 hours.

5. The method of claim 1 , wherein the ethanolic solution of 4-mercaptobenzoic acid (4-MBA) linker molecules and 3D LTO flower-like microspheres is stirred to yield 4-MBA functionalized 3D LTO flower-like microspheres in which terminal carboxylic acid groups of the ligand are bound onto Ti sites localized on the 3D LTO flower-like microsphere surfaces by either a monodentate or bidentate coordination mode, to realize molecular-coated LTO product.

6. The method of claim 5 , further including isolating the molecular-coated LTO product by vacuum filtration to remove any unbound 4-MBA linkers and then reacting the molecular-coated LTO product with oxidized MWNTs.

7. The method of claim 6 , wherein the reacting includes sonicating the molecular-coated LTO product in a mixture of ethanol and DMSO solvents to stabilize 7 C- 7 C interactions between phenyl rings within aromatic, conjugated linker molecules and an underlying network comprising the oxidized MWNTs.

8. The method of claim 1 , wherein the providing includes acid-functionalizing the MWNTs, and dispersing the acid-functionalized MWNTs in dimethyl sulfoxide (DMSO) by ultrasonication.

9. The method of claim 1 , wherein the 3D LTO microspheres comprise nanosheets that provide for shortened Li-ion diffusion distances and enhanced contact area with electrolyte, when used in a Li-ion battery.

10. The method of claim 9 , wherein the nanosheets are saw-tooth shaped, which are formed using a hydrothermal process.

11. The method of claim 1 , wherein the MWNTs are fabricated by dispersing pristine MWTNs in a solution of HNO3 by sonication and refluxing to remove any remnant catalysts and carbonaceous impurities and generate the functional, oxygenated carboxylic moieties onto nanotube surfaces of the MWTNs.

12. The method of claim 11 , wherein the HNO3 concentration is 70% by weight.

Assignees

• Univ New York State Res Found

Inventors

• Wong Stanislaus
• Wang Lei
• Mcbean Coray
• Marschilok Amy C
• Takeuchi Kenneth
• Takeuchi Esther S

Classifications

• H01M4/624

  Electric conductive fillers · CPC title

• C01P2002/82

  by IR- or Raman-data · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• C01P2004/80

  Particles consisting of a mixture of two or more inorganic phases · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title