BATTERY STRUCTURES, SELF-ORGANIZING STRUCTURES AND RELATED METHODS

• US 20110151324A1
• Filed: 09/20/2010
• Published: 06/23/2011
• Est. Priority Date: 10/20/2000
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: MOOREHEAD, William D., CHIANG, Yet-Ming
• Granted Patent: US 8,206,468 B2
• Time in Patent Office: Days
• US Class Current: 429/210
• CPC Class Codes: B33Y 80/00 Products made by additive manufacturing
• CPC Class Codes: G02F 1/1524 Transition metal compounds
• CPC Class Codes: G02F 2001/1555 Counter electrode
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• 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 11/26 characterised by their structure, e.g. multi-layered, porosity or surface features
• CPC Class Codes: H01G 11/28 arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01M 10/0436 Small-sized flat cells or batteries for portable equipment
• CPC Class Codes: H01M 10/0472 Vertically superposed cells with vertically disposed plates
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/025 with shapes other than plane or cylindrical
• CPC Class Codes: H01M 4/808 Foamed, spongy materials
• CPC Class Codes: H01M 6/18 with solid electrolyte
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49002 : Electrical device making
• CPC Class Codes: Y10T 29/49108 : Electric battery cell making
• CPC Class Codes: Y10T 29/49115 : including coating or impregnating
• CPC Class Codes: Y10T 29/49224 : with coating

Abstract

An energy storage device includes a first electrode comprising a first material and a second electrode comprising a second material, at least a portion of the first and second materials forming an interpenetrating network when dispersed in an electrolyte, the electrolyte, the first material and the second material are selected so that the first and second materials exert a repelling force on each other when combined. An electrochemical device, includes a first electrode in electrical communication with a first current collector; a second electrode in electrical communication with a second current collector; and an ionically conductive medium in ionic contact with said first and second electrodes, wherein at least a portion of the first and second electrodes form an interpenetrating network and wherein at least one of the first and second electrodes comprises an electrode structure providing two or more pathways to its current collector.

Claims

1. A method for producing a bipolar device comprising:

providing a medium, a first electroactive material and a second electroactive material, wherein the medium is electronically-insulating and ionically-conductive;

combining the first and second electroactive materials and the medium, wherein the first electroactive material has lower density than the second electroactive material and the first and the second electroactive materials float or sink at a different rate in the medium;

segregating at least a portion of the first electroactive material into a first spatial region that is essentially free of the second electroactive material to form a first network of electronically-connected first electroactive material; and

segregating at least a portion of the second electroactive material into a second spatial region that is essentially free of the first electroactive material to form a second network of electronically-connected second electroactive material.

2. The method of claim 1, wherein segregating at least a portion of the first electroactive material comprises allowing at least a portion of the first electroactive material to float to the first spatial region, and wherein the first spatial region is above the second spatial region.

3. The method of claim 1, wherein segregating at least a portion of the first electroactive material comprises allowing at least a portion of the first electroactive material to sink to the first spatial region, and wherein the first spatial region is above the second spatial region.

4. The method of claim 1, wherein segregating at least a portion of the second electroactive material comprises allowing at least a portion of the second electroactive material to float to the second spatial region, and wherein the second spatial region is below the first spatial region.

5. The method of claim 1, wherein segregating at least a portion of the second electroactive material comprises allowing at least a portion of the second electroactive material to sink to the second spatial region, and wherein the second spatial region is below the first spatial region.

6. The method of claim 1, wherein the first electroactive material is in the form of particles of a first type.

7. The method of claim 1, wherein the second electroactive material is in the form of particles of a second type.

8. The method of claim 1, further comprising providing a first current collector in electronic communication with the first network and a second current collector in electronic communication with the second network.

9. The method of claim 1, wherein the first electroactive material comprises at least one of LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂ doped with Al, Li(Fe,Mn)PO₄, LiFePO₄, LiFePO₄ doped with one or more of Mg, Al, Ti, Nb, Ta, Zr, or W, Li₂Fe₂(SO₄)₃, V₂O₅, V₆O₁₁, C, amorphous carbon, graphite, mesocarbon microbeads, Li, LiAl, Li₉Al₄, Li₃Al, Zn, LiZn, Ag, LiAg, Li₁₀Ag₃, B, Li₅B₄, Li₇B₆, Ge, Si, Li₁₂Si₇, Li₂₁Si₈, Li₁₃Si₄, Li₂₁Si₅, Sn, Li₅Sn₂, Li₁₃Sn₅, Li₇Sn₂, Li₂₂Sn₅, Sb, Li₂Sb, Li₃Sb, Bi, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₂O₃, MnO₂, Mn₃O₄, CoO, NiO, FeO, LiFe₂O₄, TiO₂, LiTi₂O₄, glass with a Sn—

B—

P—

O compound and mesocarbon microbeads coated with at least one of poly(o-methoxyaniline), poly(3-octylthiophene), and poly(vinylidene fluoride).

10. The method of claim 1, wherein the second electroactive material comprise at least one of LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂ doped with Al, Li(Fe,Mn)PO₄, LiFePO₄, LiFePO₄ doped with one or more of Mg, Al, Ti, Nb, Ta, Zr, or W, Li₂Fe₂(SO₄)₃, V₂O₅, V₆O₁₁, C, amorphous carbon, graphite, mesocarbon microbeads, Li, LiAl, Li₉Al₄, Li₃Al;

Zn, LiZn, Ag, LiAg, Li₁₀Ag₃, B, Li₅B₄, Li₇B₆, Ge, Si, Li₁₂Si₇, Li₂₁Si₈, Li₁₃Si₄, Li₂₁Si₅, Sn, Li₅Sn₂, Li₁₃Sn₅, Li₇Sn₂, Li₂₂Sn₅, Sb, Li₂Sb, Li₃Sb, Bi, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₂O₃, MnO₂, Mn₃O₄, CoO, NiO, FeO, LiFe₂O₄, TiO₂, LiTi₂O₄, glass with a Sn—

B—

P—

O compound and mesocarbon microbeads coated with at least one of poly(o-methoxyaniline), poly(3-octylthiophene), and poly(vinylidene fluoride).

11. The method of claim 1, wherein the medium comprises at least one of poly(ethylene oxide), poly(styrene), poly(acrylonitrile), poly(vinylidene fluoride), diiodomethane, 1,3-diiodopropane, N,N-dimethylformamide, dimethylpropylene urea, ethylene carbonate, diethylene carbonate, dimethyl carbonate, propylene carbonate, a block copolymer lithium electrolyte doped with a lithium salt, glass with at least one of LiI, LiF, LiCI, Li₂O—

B₂O₃—

Bi₂O₃, Li₂O—

B₂O₃—

P₂O₅ and Li₂O—

B₂O₃—

PbO and a sol or gel of the oxides or hydroxides of Ti, Zr, Pb, or Bi.

12. The method of claim 1, wherein the medium comprises a solid polymeric material or a precursor thereto.

13. The method of claim 1, wherein the bipolar device is a battery.

14. A bipolar device made from the method of claim 1.

15. A method for producing a graded porosity electrode comprising:

providing a current collector;

contacting with the current collector a suspension comprising a medium and electroactive particles having a range of differentiated sedimentation rates and packing densities in the medium; and

allowing the particles to settle for a period of time to form an electroactive layer in electronic contact with the current collector;

wherein

the electroactive layer has a graded porosity across the thickness of the electroactive layer.

16. The method of claim 15, wherein the porosity of the electrode is highest at the locations closest to the current collector.

17. The method of claim 15, wherein the porosity of the electrode is lwoest at the locations closest to the current collector.

18. The method of claim 15, wherein the electroactive particles have a range of different particle sizes.

19. The method of claim 15, wherein the electroactive particles have a range of different shapes.

20. The method of claim 15, wherein the electroactive particles having a higher sedimentation rate in the medium have higher packing densities.

21. The method of claim 15, wherein the electroactive particles having a higher sedimentation rate in the medium have lower packing densities.

22. The method of claim 15, wherein the electroactive particles having a lower sedimentation rate in the medium have higher packing densities.

23. The method of claim 15, wherein the electroactive particles having a lower sedimentation rate in the medium have packing lower densities.

24. The method of claim 15, wherein the electroactive particles having a lower sedimentation rate in the medium comprise particles with highly aspected particles.

25. The method of claim 15, wherein the electroactive particles having a lower sedimentation rate in the medium comprise particles with smaller particle sizes.

26. The method of claim 15, wherein the electroactive particles having a higher sedimentation rate in the medium comprise particles with equiaxed particles.

27. The method of claim 15, wherein the electroactive particles having a higher sedimentation rate in the medium comprise particles bigger particle sizes.

28. The method of claim 15, wherein the electroactive particles having a higher sedimentation rate in the medium have higher packing densities.

29. The method of claim 15, wherein the electroactive particles having a lower sedimentation rate in the medium have lower packing densities.

30. The method of claim 28, wherein the electroactive particles having a lower sedimentation rate in the medium have lower packing densities.

31. The method of claim 15, wherein the suspension further comprises fugitive pore former particles, and the method further comprises solidifying the suspension and removing the fugitive particles to form pores.

32. The method of claim 31, wherein the fugitive particles have lower sedimentation rate than the electroactive particles.

33. The method of claim 15, wherein the suspension further comprises a binder.

34. The method of claim 15, wherein the particles are allowed to settle for a few minutes to a few hours.

35. The method of claim 15, wherein the electroactive particles comprises lithium transition metal phosphate particles.

36. The method of claim 31, wherein the fugitive particles comprise particles of an organic or inorganic compound that reacts with oxygen or nitrogen gas to form volatile gaseous species.

37. The method of claim 31, wherein the fugitive particles comprise mesocarbon microbeads (MCMB).

38. The method of claim 31, wherein removing the fugitive particles comprises sublimation of the fugitive particles.

39. The method of claim 31, wherein removing the fugitive particles comprises melting and draining the fugitive particles.

40. The method of claim 31, wherein removing the fugitive particles comprises evaporating the fugitive particles.

41. The method of claim 31, wherein removing the fugitive particles comprises reacting the fugitive particles to form volatile species.

42. The method of claim 41, wherein reacting the fugitive particles to form volatile species comprises contacting the fugitive particles with air or oxygen.

43. A bipolar device made from the method of claim 15.

44. A method for producing a bipolar device comprising:

providing a medium, a first electroactive material and a second electroactive material, wherein the medium is electronically-insulating and ionically-conductive;

combining the first and second electroactive materials and the medium, wherein the first electroactive material has lower density than the medium and floats in the medium; and

the second electroactive material has higher density than the medium and sinks in the medium;

segregating at least a portion of the first electroactive material into a first spatial region that is essentially free of the second electroactive material to form an electronically-connected first electroactive material; and

segregating at least a portion of the second electroactive material into a second spatial region that is essentially free of the first electroactive material to form an electronically-connected second electroactive material.

45. The method of claim 44, wherein segregating at least a portion of the first electroactive material comprises allowing at least a portion of the first electroactive material to float to the first spatial region, and wherein the first spatial region is above the second spatial region.

46. The method of claim 44, wherein segregating at least a portion of the second electroactive material comprises allowing at least a portion of the second electroactive material to sink to the second spatial region, and wherein the second spatial region is below the first spatial region.

47. The method of claim 44, wherein the first electroactive material is in the form of particles of a first type.

48. The method of claim 44, wherein the second electroactive material is in the form of particles of a second type.

49. The method of claim 44 further comprising providing a first current collector in electronic communication with the electronically-connected first electroactive material and a second current collector in electronic communication with the electronically-connected second electroactive material.

50. The method of claim 44, wherein the first electroactive material comprises at least one of LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂ doped with Al, LiFePO₄, Li(Fe,Mn)PO₄, LiFePO₄ doped with one or more of Mg, Al, Ti, Nb, Ta, Zr, or W, Li₂Fe₂(SO₄)₃, V₂O₅, V₆O₁₁, C, amorphous carbon, graphite, mesocarbon microbeads, Li, LiAl, Li₉Al₄, Li₃Al, Zn, LiZn, Ag, LiAg, Li₁₀Ag₃, B, Li₅B₄, Li₇B₆, Ge, Si, Li₁₂Si₇, Li₂₁Si₈, Li₁₃Si₄, Li₂₁Si₅, Sn, Li₅Sn₂, Li₁₃Sn₅, Li₇Sn₂, Li₂₂Sn₅, Sb, Li₂Sb, Li₃Sb, Bi, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₂O₃, MnO₂, Mn₃O₄, CoO, NiO, FeO, LiFe₂O₄, TiO₂, LiTi₂O₄, glass with a Sn—

B—

P—

O compound and mesocarbon microbeads coated with at least one of poly(o-methoxyaniline), poly(3-octylthiophene), and poly(vinylidene fluoride).

51. The method of claim 44, wherein the second electroactive material comprise at least one of LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂ doped with Al, Li(Fe,Mn)PO₄, LiFePO₄, LiFePO₄ doped with one or more of Mg, Al, Ti, Nb, Ta, Zr, or W, Li₂Fe₂(SO₄)₃, V₂O₅, V₆O₁₁, C, amorphous carbon, graphite, mesocarbon microbeads, Li, LiAl, Li₉Al₄, Li₃Al;

Zn, LiZn, Ag, LiAg, Li₁₀Ag₃, B, Li₅B₄, Li₇B₆, Ge, Si, Li₁₂Si₇, Li₂₁Si₈, Li₁₃Si₄, Li₂₁Si₅, Sn, Li₅Sn₂, Li₁₃Sn₅, Li₇Sn₂, Li₂₂Sn₅, Sb, Li₂Sb, Li₃Sb, Bi, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₂O₃, MnO₂, Mn₃O₄, CoO, NiO, FeO, LiFe₂O₄, TiO₂, LiTi₂O₄, glass with a Sn—

B—

P—

O compound and mesocarbon microbeads coated with at least one of poly(o-methoxyaniline), poly(3-octylthiophene), and poly(vinylidene fluoride).

52. The method of claim 44, wherein the medium comprises at least one of poly(ethylene oxide), poly(styrene), poly(acrylonitrile), poly(vinylidene fluoride), diiodomethane, 1,3-diiodopropane, N,N-dimethylformamide, dimethylpropylene urea, ethylene carbonate, diethylene carbonate, dimethyl carbonate, propylene carbonate, a block copolymer lithium electrolyte doped with a lithium salt, glass with at least one of LiI, LiF, LiCI, Li₂O—

B₂O₃—

Bi₂O₃, Li₂O—

B₂O₃—

P₂O₅ and Li₂O—

B₂O₃—

PbO and a sol or gel of the oxides or hydroxides of Ti, Zr, Pb, or Bi.

53. The method of claim 44, wherein the bipolar device is a battery.

54. A bipolar device made from the method of claim 44.

55. A bipolar device, comprising:

a medium, a first current collector, a second current collector, a first electroactive material, and a second electroactive material, wherein

the medium is electronically-insulating and ionically-conductive;

the first electroactive material has lower density than the medium and floats in the medium;

the second electroactive material has higher density than the medium and sinks in the medium;

at least a portion of the first electroactive material is electronically-connected and occupies a first spatial region which is essentially free of the second electroactive material;

at least a portion of the second electroactive material is electronically-connected and occupies a second spatial region which is essentially free of the first electroactive material and is below the first spatial region; and

the first current collector is in electronic communication with the electronically-connected first electroactive material and the second current collector is in electronic communication with the electronically-connected second electroactive material.

56. The bipolar device of claim 55, wherein the first electroactive material is in the form of particles of a first type.

57. The bipolar device of claim 55, wherein the second electroactive material is in the form of particles of a second type.

58. The bipolar device of claim 55, wherein the first electroactive material comprises at least one of LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂ doped with Al, LiFePO₄, Li(Fe,Mn)PO₄, LiFePO₄ doped with one or more of Mg, Al, Ti, Nb, Ta, Zr, or W, Li₂Fe₂(SO₄)₃, V₂O₅, V₆O₁₁, C, amorphous carbon, graphite, mesocarbon microbeads, Li, LiAl, Li₉Al₄, Li₃Al, Zn, LiZn, Ag, LiAg, Li₁₀Ag₃, B, Li₅B₄, Li₇B₆, Ge, Si, Li₁₂Si₇, Li₂₁Si₈, Li₁₃Si₄, Li₂₁Si₅, Sn, Li₅Sn₂, Li₁₃Sn₅, Li₇Sn₂, Li₂₂Sn₅, Sb, Li₂Sb, Li₃Sb, Bi, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₂O₃, MnO₂, Mn₃O₄, CoO, NiO, FeO, LiFe₂O₄, TiO₂, LiTi₂O₄, glass with a Sn—

B—

P—

O compound and mesocarbon microbeads coated with at least one of poly(o-methoxyaniline), poly(3-octylthiophene), and poly(vinylidene fluoride).

59. The bipolar device of claim 55, wherein the second electroactive material comprise at least one of LiCoO₂, LiCoO₂ doped with Mg, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnO₂ doped with Al, Li(Fe,Mn)PO₄, LiFePO₄, LiFePO₄ doped with one or more of Mg, Al, Ti, Nb, Ta, Zr, or W, Li₂Fe₂(SO₄)₃, V₂O₅, V₆O₁₁, C, amorphous carbon, graphite, mesocarbon microbeads, Li, LiAl, Li₉Al₄, Li₃Al;

Zn, LiZn, Ag, LiAg, Li₁₀Ag₃, B, Li₅B₄, Li₇B₆, Ge, Si, Li₁₂Si₇, Li₂₁Si₈. Li₁₃Si₄, Li₂₁Si₅, Sn, Li₅Sn₂, Li₁₃Sn₅, Li₇Sn₂, Li₂₂Sn₅, Sb, Li₂Sb, Li₃Sb, Bi, LiBi, Li₃Bi, SnO₂, SnO, MnO, Mn₂O₃, MnO₂, Mn₃O₄, CoO, NiO, FeO, LiFe₂O₄, TiO₂, LiTi₂O₄, glass with a Sn—

B—

P—

O compound and mesocarbon microbeads coated with at least one of poly(o-methoxyaniline), poly(3-octylthiophene), and poly(vinylidene fluoride).

60. The bipolar device of claim 55, wherein the medium comprises at least one of poly(ethylene oxide), poly(styrene), poly(acrylonitrile), poly(vinylidene fluoride), diiodomethane, 1,3-diiodopropane, N,N-dimethylformamide, dimethylpropylene urea, ethylene carbonate, diethylene carbonate, dimethyl carbonate, propylene carbonate, a block copolymer lithium electrolyte doped with a lithium salt, glass with at least one of LiI, LiF, LiCI, Li₂O—

B₂O₃—

Bi₂O₃, Li₂O—

B₂O₃—

P₂O₅ and Li₂O—

B₂O₃—

PbO and a sol or gel of the oxides or hydroxides of Ti, Zr, Pb, or Bi.