Method of preparation of carbon materials for use as electrodes in rechargeable batteries

• US 5,882,621 A
• Filed: 05/09/1997
• Issued: 03/16/1999
• Est. Priority Date: 12/07/1995
• Status: Expired due to Fees

• Current Assignee: Sandia Corporation (Martin Marietta Corporation)
• Original Assignee: Sandia Corporation (Martin Marietta Corporation)
• Inventors: Ingersoll, David, Doddapaneni, Narayan, Crocker, Robert W., Firsich, David W., Wang, James C. F.
• Primary Examiner(s): Straub, Gary P.
• Assistant Examiner(s): Hendrickson, Stuart L.
• Application Number:
  US08/853,971
• Time in Patent Office: 676 Days
• Field of Search: 264/29.7, 423/445 R, 423/447.6, 429/218
• US Class Current: 423/445.00R
• CPC Class Codes: C01B 32/05 Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
• CPC Class Codes: C04B 35/524 obtained from polymer precursors, e.g. glass-like carbon material
• CPC Class Codes: D01F 11/129 Intercalated carbon- or graphite fibres
• CPC Class Codes: H01G 11/24 characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
• CPC Class Codes: H01G 11/34 characterised by carbonisation or activation of carbon
• CPC Class Codes: H01G 11/50 specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

A method of producing carbon materials for use as electrodes in rechargeable batteries. Electrodes prepared from these carbon materials exhibit intercalation efficiencies of ≈80% for lithium, low irreversible loss of lithium, long cycle life, are capable of sustaining a high rates of discharge and are cheap and easy to manufacture. The method comprises a novel two-step stabilization process in which polymeric precursor materials are stabilized by first heating in an inert atmosphere and subsequently heating in air. During the stabilization process, the polymeric precursor material can be agitated to reduce particle fusion and promote mass transfer of oxygen and water vapor. The stabilized, polymeric precursor materials can then be converted to a synthetic carbon, suitable for fabricating electrodes for use in rechargeable batteries, by heating to a high temperature in a flowing inert atmosphere.

Claims

1. A method of producing carbon materials for use as electrodes in rechargeable batteries, comprising the steps of:

a) heating a carbonizable polymer material selected from the group consisting of polyacrylonitrile, co-polymers of polyacrylonitrile and mixtures thereof in a step-wise manner at a fixed rate of heating to a temperature in an inert atmosphere while simultaneously agitating the polymer material to form a pretreated product;

b) cooling the pretreated product;

c) heating the pretreated product in an oxygen containing atmosphere in a step-wise manner at a fixed rate of heating to a temperature while simultaneously agitating the pretreated product to form a stabilized polymer product;

d) carbonizing the stabilized polymer product by heating in a step-wise manner to a temperature in an inert atmosphere, thereby forming a carbon material having a surface area of less than 10 m² /g wherein the step-wise heating comprises;

i. heating the stabilized polymer product in an inert atmosphere to about 300°

C. at a rate of less than 5°

C./min;

ii. maintaining the temperature at about 300°

C. for about 2 hours;

iii. raising the temperature to about 370°

C. at a rate of less than 5°

C./min;

iv. maintaining the temperature at about 370°

C. for about 5 hours;

v. raising the temperature from about 370°

C. to at least 800°

C. at a rate less than 5°

C./min;

and vi. maintaining the temperature at least 800°

C. for about 6 hours.

2. The method of claim 1, wherein co-polymers of (PAN) are selected from the group consisting of itaconic acid, acrylic acid, methacrylic acid, vinyl acetate, styrene, divinyl benzene, vinyl chloride and vinylidene chloride and combinations thereof.

3. The method of claim 1, further including the step of adding a pore former material consisting of area.

4. The method of claim 1 wherein said step of carbonizing produces a powder having a symmetric branched morphology with randomly oriented domains shown by transmission electron microscopy to contain approximately 4 to 10 lattice planes extending approximately 20 to 50 Å

in the lateral dimension, d₀₀₂ lattice spacing on the order of 3.5 to 3.7 Å

, a Raman spectrum showing peaks of near equal height at 1360 cm^-1 and 1580 cm^-1, and a BET surface area of less than about 10 m² /g and an average particle size of less than 35 μ

m.

5. A method for producing carbon materials capable of intercalating lithium for lithium ion rechargeable batteries, comprising the steps of:

a) heating and agitating a carbonizable polymer in an inert atmosphere with a pore forming material consisting of urea to form a pretreated product, wherein the carbonizable polymer is selected from the group consisting of homopolymers and co-polymers of polyacrylonitrile, and mixtures and blends thereof;

b) heating and agitating the pretreated product in an oxygen-containing atmosphere to form a stabilized polymer product; and

c) carbonizing the stabilized polymer product in an inert atmosphere to form a carbon material having BET surface area of less than 10m² /g and capable of intercalating lithium for lithium ion rechargeable batteries.

6. The method according to claim 5, wherein the carbonizable polymer is a copolymer of polyacrylonitrile formed by copolymerizing acrylonitrile and at least one monomer selected from the group consisting of itaconic acid, acrylic acid, methacrylic acid, vinyl acetate, styrene, divinyl benzene, vinyl chloride, and vinylidene chloride.

7. The method according to claim 5, wherein step (a) and step (b) further comprise heating in a step-wise manner.

8. The method according to claim 7, wherein step (a) further comprises:

a) heating the carbonizable polymer to a first temperature of about 175°

C. at a first rate of less than 100°

C./hr; and

b) heating the carbonizable polymer to a second temperature of about 250°

C. at a second rate of less than 5°

C./hr and maintaining the product at 250°

C. for about 6 hours.

9. The method of claim 7, wherein step (b) further comprises:

a) heating the pretreated product to about 100°

C. at a rate of less than 100°

C./hr; and

b) further heating the pretreated product to a temperature of about 250°

C. at a rate of less than 10°

C./min and maintaining the pretreated product at about 250°

C. for about 6 hours.

10. The method of claim 5, wherein step (c) further comprises:

d) heating the stabilized polymer product to a temperature of about 300°

C. at a rate of less than about 5°

C./min and maintaining it at 300°

C. for about 2 hours;

e) further heating the stabilized polymer product to a temperature of about 370°

C. at a rate of less than about 5°

C./min and maintaining it at 370°

C. for 5 hours; and

f) further heating the stabilized polymer product to a temperature of at least 800°

C., and maintaining it at that temperature for about 6 hours to produce a carbon material capable of intercalating lithium for lithium ion rechargeable batteries.

11. A method for producing carbon materials capable of intercalating lithium for lithium-ion rechargeable batteries, consisting essentially of the steps of:

a) heating and agitating a carbonizable polymer with a pore forming material consisting of urea in an inert atmosphere to form a pretreated product;

b) heating and agitating the pretreated product in an oxygen-containing atmosphere to form a stabilized polymer product; and

c) carbonizing the stabilized polymer product in an inert atmosphere to form a carbon material capable of intercalating lithium for use in lithium ion rechargeable batteries.

12. The method according to claim 11, wherein the carbon material is capable of a lithium intercalation capacity of at least 50% LiC₆ after intercalation with lithium.

13. A carbon powder material capable of intercalating lithium for use in lithium ion rechargeable batteries and having a symmetric branched morphology having randomly oriented domains shown by transmission electron microscopy to contain approximately 4 to 10 lattice planes extending approximately 20 to 50 Å

in the lateral dimension, d₀₀₂ lattice spacing of about 3.5 to 3.7 Å

, a Raman spectrum showing peaks of near equal height at 1360 cm-1 and 1580 cm-1, a BET surface area of less than 10 m² /g an average particle size of less than 35 μ

m and a lithium intercalation capacity of at least 50% LiC₆ after intercalation with lithium.

14. The carbon material according to claim 13, wherein the material has a lithium intercalation capacity of at least 80% LiC₆ after intercalation with lithium.

15. The carbon material according to claim 13, wherein the material is formed by a method comprising heating and agitating a carbonizable polymer in an inert atmosphere with a pore forming material to form a pretreated product, heating and agitating the pretreated product in an oxygen-containing atmosphere to form a stabilized polymer product, and carbonizing the stabilized polymer product in an inert atmosphere.

16. A method for producing carbon materials capable of intercalating lithium for use in lithium ion rechargeable batteries, comprising the steps of:

a) heating and agitating a carbonizable polymer in a step-wise manner in an inert atmosphere to form a pretreated product, wherein the carbonizable polymer is in powder form and selected from the group consisting of homopolymers and co-polymers of polyacrylonitrile, and mixtures and blends thereof;

b) heating and agitating the pretreated product in a step-wise manner in an oxygen containing atmosphere to form a stabilized polymer product; and

c) carbonizing the stabilized polymer product in an inert atmosphere with a pore forming material to form a carbon material capable of intercalating lithium for use in lithium ion rechargeable batteries and having a BET surface area of less than 10 m² /g.