Electrode materials with high surface conductivity

• US 6,855,273 B2
• Filed: 06/21/2002
• Issued: 02/15/2005
• Est. Priority Date: 04/30/1999
• Status: Expired due to Term

• Current Assignee: ACEP Inc., CNRS, Universite De Montreal, L'
• Original Assignee: ACEP Inc., Centre National De La Recherche Scientifique, Universite De Montreal, L'
• Inventors: Simoneau, Martin, Ravet, Nathalie, Armand, Michel, Besner, Simon, Vallée, Alain, Magnan, Jean-François
• Primary Examiner(s): KOPEC, MARK T
• Application Number:
  US10/175,794
• Publication Number:
  US 20020195591A1
• Time in Patent Office: 970 Days
• Field of Search: 252/506, 427/122, 427/216, 427/217, 427/376.6
• US Class Current: 252/506
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01G 11/44 Raw materials therefor, e.g. resins or coal
• CPC Class Codes: H01G 11/48 Conductive polymers
• CPC Class Codes: H01G 11/86 specially adapted for electrodes carbonisation or activation of carbon for the manufacture of electrodes H01G11/34
• CPC Class Codes: H01G 9/042 characterised by the material H01G11/22 takes precedence
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/48 of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/50 of manganese
• CPC Class Codes: H01M 4/52 of nickel, cobalt or iron
• CPC Class Codes: H01M 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors

Abstract

The present invention concerns electrode materials capable of redox reactions by electrons and alkaline ions exchange with an electrolyte. The applications are in the field of primary (batteries) or secondary electrochemical generators, super capacitors and light modulating system of the super capacitor type.

Claims

1. A process for making an alkali-metal ion-reversible electrode material comprising the steps of:

(a) providing an alkali-based complex oxide of the general formula

A_aM_mZ_zO_oN_nF_f

wherein;

A comprises an alkali metal;

M comprises at least one transition metal, and optionally at least one non-transition metal, or mixtures thereof;

Z comprises at least one non-metal;

O is oxygen;

N is nitrogen; and

F is fluorine,

where Z and O are such that the complex oxide is selected from the group consisting of sulfates, phosphates, silicates, oxysulfates, oxyphosphates or oxysilicates and mixtures thereof;

where a ≧

0.1;

m, o, and z>

0; and

n and f≧

0 and selected to ensure electroneutrality in said complex oxide;

where said alkali-based complex oxide stabilizes all or part of the transition metal ion of M in its lower oxidation level (not considering

     0) and conducts alkali metal ions; and

(b) contacting said complex oxide with a carbonaceous precursor under conditions of temperature, time and pressure effective to give a conductive carbon coating on said complex oxide, said carbon coating being in a non powdery form, substantially homogeneous and covering all or most of the surface with a thin film of carbon that is optimized to give electronic conductivity in said complex oxide, without blocking alkali ion exchanges at the surface of said material and without reducing the transition metal of said alkali-based complex oxide to a metallic state, the carbon coated alkali-based complex oxide having mixed electron and alkali-ion conductivity and alkali-ion-exchange capability for use in a battery.

2. The process according to claim 1 wherein said pyrolysing step is carried out under vacuum.

3. The process according to claim 1 wherein said pyrolysing step is carried out under non oxidizing conditions.

4. The process according to claim 1 wherein said pyrolysing step is carried out under reducing conditions.

5. The process according to claim 1 wherein said carbonaceous material precursor is in a form selected from the group consisting of solid, liquid, and gas.

6. The process according to claim 5 wherein said carbonaceous material precursor is in solid form, and is selected from the group consisting of a polymer, a solid hydrocarbon, and derivatives and mixtures thereof.

7. The process according to claim 6 wherein said carbonaceous material precursor is in solid form and comprises a polymer.

8. The process according to claim 7 wherein said polymer is selected from the group consisting of polyolefins, polybutadienes, polyvinylic alcohol, phenol condensation products, polymers derived from furfurylic alcohol, polymers derivatives of styrene, divinylbenzene, acrytonitrile, vinyl acetate, cellulose, starch and its esters, and mixtures thereof.

9. The process according to claim 7 wherein the step of pyrolysin:

said carbonaceous material precursor further comprises the step of dispersing a polymer or polymer mixture with said complex oxide or with precursors of said complex oxide, and pyrolysing the dispersion to obtain said electrode material.

10. The process according to claim 6 wherein said pyrolysing generates CO and is carried out under conditions to obtain a carbon deposit as a result of the disproportionation equilibrium reaction:

2CO→

C+CO₂.

11. The process according to claim 5 wherein said carbonaceous material precursor material is in liquid form and is selected from the group consisting of a liquid solution of a polymer, a liquid monomer, a liquid hydrocarbon, and mixtures and derivatives thereof.

12. The process according to claim 5 wherein said carbonaceous material precursor is in gaseous form and is selected from the group consisting of gaseous hydrocarbons, CO, CO precursors, and mixtures thereof.

13. The process according to claim 12 wherein said carbonaceous material precursor in gaseous form includes hydrogen.

14. The process according to claim 12 wherein said carbonaceous precursor in gaseous form is formed in situ during pyrolysis.

15. The process according to claim 14 wherein said pyrolysing is carried out at a temperature lower than 900°

C.

16. The process according to claim 12 wherein said pyrolysing is carried out with CO under conditions to obtain a carbon deposit as a result of the disproportionation equilibrium reaction:

2CO→

C+CO₂.

17. The process according to claim 1, wherein said alkali-based complex oxide is provided by pyrolysing at least one complex oxide precursor under conditions effective to give said complex oxide.

18. The process according to claim 17, wherein pyrolysing the at least one complex oxide precursor is carried out simultaneously with the formation of the carbon coating on said complex oxide.

19. The process according to claim 1, wherein step (b) is carried out by heating and pyrolyzing said carbonaceous precursor in the presence of said complex oxide.

20. The process according to claim 1, wherein step (b) is carried out by heating and pyrolyzing said carbonaceous precursor in the presence of alkali-based complex oxide precursors.

21. The process according to claim 20, wherein the complex oxide is selected from the group consisting of LiFePO₄ and LiMnPO₄ and mixtures and solutions thereof.

22. The process according to claim 1, wherein A comprises lithium and the complex oxide is lithium based.

23. The process according to claim 1, wherein Z comprises phosphorus.

24. The process according to claim 23 wherein ZO comprises a phosphate.

25. The process according to claim 1, wherein step (b) is carried out under conditions that result in formation of a thin coating of carbon that covers substantially all of the surface of the complex oxide.

26. The process according to claim 1, wherein step (b) is carried out under conditions that result in formation of a thick carbon coating that does not block all of the surface of the complex oxide and permits alkali ion exchange.