Composite carbon materials comprising lithium alloying electrochemical modifiers

a technology of lithium alloying and carbon materials, applied in the field of composite carbon materials, can solve the problems of low power performance and limited capacity of graphitic anodes, insufficient current lead acid automobile batteries for next-generation all-electric and hybrid electric vehicles, and material fundamental limitations

Inactive Publication Date: 2014-09-18
GRP 14 TECH INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0034]These and other aspects of the invention will be apparent upon reference to the following detailed description. To this end, various references are set forth herein which describe in more detail certain background information, procedures, compounds and / or compositions, and are each hereby incorporated by reference in their entirety.

Problems solved by technology

For example, current lead acid automobile batteries are not adequate for next generation all-electric and hybrid electric vehicles due to irreversible, stable sulfate formations during discharge.
Traditional lithium ion batteries are comprised of a graphitic carbon anode and a metal oxide cathode; however such graphitic anodes typically suffer from low power performance and limited capacity.
However, these materials are fundamentally limited by the substantial swelling that occurs when they are fully lithiated.
This swelling and shrinkage when the lithium is removed results in an electrode that has limited cycle life and low power.
The solution thus far has been to use very small amounts of alloying electrochemical modifier in a largely carbon electrode, but this approach does not impart the desired increase in lithium capacity.
However none of these processes has proven to combine a scalable process that results in the desired properties.
Hard carbon materials have been proposed for use in lithium ion batteries, but the physical and chemical properties of known hard carbon materials are not optimized for use as anodes in lithium-based batteries.
Thus, anodes comprising known hard carbon materials still suffer from many of the disadvantages of limited capacity and low first cycle efficiency.

Method used

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  • Composite carbon materials comprising lithium alloying electrochemical modifiers
  • Composite carbon materials comprising lithium alloying electrochemical modifiers
  • Composite carbon materials comprising lithium alloying electrochemical modifiers

Examples

Experimental program
Comparison scheme
Effect test

example 1

Monolith Preparation of Wet Polymer Gel

[0417]Polymer gels were prepared using the following general procedure. A polymer gel was prepared by polymerization of resorcinol and formaldehyde (0.5:1) in water and acetic acid (75:25) and ammonium acetate (RC=10, unless otherwise stated). The reaction mixture was placed at elevated temperature (incubation at 45° C. for about 6 h followed by incubation at 85° C. for about 24 h) to allow for gellation to create a polymer gel. Polymer gel particles were created from the polymer gel and passed through a 4750 micron mesh sieve. In certain embodiments the polymer is rinsed in a urea or polysaccharide solution. While not wishing to be bound by theory, it is believed such treatment may either impart surface functionality or alter the bulk structure of the carbon and improve the electrochemical characteristics of the carbon materials.

example 2

Alternative Monolith Preparation of Wet Polymer Gel

[0418]Alternatively to Example 1, polymer gels were also prepared using the following general procedure. A polymer gel was prepared by polymerization of urea and formaldehyde (1:1.6) in water (3.3:1 water:urea) and formic acid. The reaction mixture was stirred at room temperature until gellation to create a white polymer gel. Polymer gel particles were created through manually crushing.

[0419]The extent of crosslinking of the resin can be controlled through both the temperature and the time of curing. In addition, various amine containing compounds such as urea, melamine and ammonia can be used. One of ordinary skill in the art will understand that the ratio of aldehyde (e.g., formaldehyde) to solvent (e.g., water) and amine containing compound can be varied to obtain the desired extent of cross linking and nitrogen content.

example 3

Post-Gel Chemical Modification

[0420]A nitrogen containing hard carbon was synthesized using a resorcinol-formaldehyde gel mixture in a manner analogous to that described in Example 1. About 20 mL of polymer solution was obtained (prior to placing solution at elevated temperature and generating the polymer gel). The solution was then stored at 45° C. for about 5 h, followed by 24 h at 85° C. to fully induce cross-linking. The monolith gel was broken mechanically and milled to particle sizes below 100 microns. The gel particles were then soaked for 16 hours in a 30% saturated solution of urea (0.7:1 gel:urea and 1.09:1 gel:water) while stirring. After the excess liquid was decanted, the resulting wet polymer gel was allowed to dry for 48 hours at 85° C. in air then pyrolyzed by heating from room temperature to 1100° C. under nitrogen gas at a ramp rate of 10° C. per min to obtain a hard carbon containing the nitrogen electrochemical modifier.

[0421]In various embodiments of the above m...

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Abstract

The present application is generally directed to composites comprising a hard carbon material and an electrochemical modifier. The composite materials find utility in any number of electrical devices, for example, in lithium ion batteries. Methods for making the disclosed composite materials are also disclosed.

Description

BACKGROUND[0001]1. Technical Field[0002]The present invention generally relates to composite carbon materials, methods for making the same and devices containing the same.[0003]2. Description of the Related Art[0004]Lithium-based electrical storage devices have potential to replace devices currently used in any number of applications. For example, current lead acid automobile batteries are not adequate for next generation all-electric and hybrid electric vehicles due to irreversible, stable sulfate formations during discharge. Lithium ion batteries are a viable alternative to the lead-based systems currently used due to their capacity, and other considerations. Carbon is one of the primary materials used in both lithium secondary batteries and hybrid lithium-ion capacitors (LIC). The carbon anode typically stores lithium between layered graphite sheets through a mechanism called intercalation. Traditional lithium ion batteries are comprised of a graphitic carbon anode and a metal ox...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): H01M4/36
CPCH01M4/366H01M4/387H01M4/0471H01M4/133H01M4/134H01M4/1393H01M4/1395H01M4/362H01M4/364H01M4/386H01M4/483H01M4/587H01M4/625H01M10/0525H01G9/02H01G11/06H01G11/32H01G11/50Y02T10/70Y02E60/10Y02E60/13
Inventor THOMPKINS, LEAH A.SAKSHAUG, AVERY J.GERAMITA, KATHARINEFEAVER, AARON M.COSTANTINO, HENRY R.KRON, BENJAMIN E.MCADIE, AARON
Owner GRP 14 TECH INC
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