Method for modifying cathode material and lithium battery employing the cathode material

• US 9,112,239 B2
• Filed: 12/11/2009
• Issued: 08/18/2015
• Est. Priority Date: 12/31/2008
• Status: Active Grant

• Current Assignee: Industrial Technology Research Institute
• Original Assignee: Industrial Technology Research Institute
• Inventors: Wu, Hung-Chun, Wang, Fu-Ming, Yang, Chang-Rung, Pan, Jing-Pin, Su, Ching-Yi, Wang, Tsung-Hsiung, Cheng, Chin-Shu, Hsu, Jung-Mu
• Primary Examiner(s): APICELLA, KARIE O
• Application Number:
  US12/635,904
• Publication Number:
  US 20100167129A1
• Time in Patent Office: 2,076 Days
• Field of Search: 429/213.95, 429/122, 429/232, 296/231
• US Class Current: 1/1
• 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 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• 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 4/621 Binders
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 4/623 fluorinated polymers
• CPC Class Codes: H01M 4/624 Electric conductive fillers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 4/626 Metals
• CPC Class Codes: H01M 50/574 Devices or arrangements for the interruption of current
• CPC Class Codes: H01M 50/581 in response to temperature
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y10T 29/49108 Electric battery cell making

Abstract

The invention provides a lithium battery, including: a cathode plate and an anode plate; a separator disposed between the cathode plate and the anode plate to define a reservoir region; and an electrolyte filled in the reservoir region. A thermal protective film is provided to cover a material of the cathode plate or the anode plate. When a battery temperature rises over an onset temperature of the thermal protective film, it undergoes a crosslinking reaction to inhibit thermal runaway. A method for fabricating the lithium ion battery is also provided.

Claims

1. A lithium battery, comprising

a cathode plate and an anode plate;

a separator disposed between the cathode plate and the anode plate to define a reservoir region;

an electrolyte filled in the reservoir region; and

a non-crosslinked thermal protective film encapsulating an electrode material powder of the cathode plate or the anode plate, wherein the non-crosslinked thermal protective film is capable of undergoing a crosslinking reaction when a battery temperature rises over an onset temperature, and the onset temperature is between about 80°

C. and 280°

C.

2. The lithium battery as claimed in claim 1, wherein the thermal protective film covers the material of the cathode plate, which comprises a lithium mixed metal oxide, a conductive additive and a binder.

3. The lithium battery as claimed in claim 2, wherein the lithium mixed metal oxide comprises LiMnO₂, LiMn₂O₄, LiCoO₂, Li₂Cr₂O₇, Li₂CrO₄, LiNiO₂, LiFeO₂, LiNi_xCo_1-xO₂(0<

x<

1), LiMPO₄ (M is a transition metal), LiMn_0.5Ni_0.5O₂, LiNi_xCo_yMn_zO₂ (x+y+z=1), LiNi_xCo_yAl_zO₂(x+y+z=1), LiMc_0.5Mn_1.5O₄ (Mc is a bivalent metal), or combinations thereof.

4. The lithium battery as claimed in claim 2, wherein the conductive additive comprises carbon black, graphite, acetylene black, nickel powder, aluminum powder, titanium powder, stainless steel powder or combinations thereof.

5. The lithium battery as claimed in claim 2, wherein the binder comprises polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), polyamide, melamine resin, or combinations thereof.

6. The lithium battery as claimed in claim 1, wherein the thermal protective film comprises a nitrogen-containing polymer.

7. The lithium battery as claimed in claim 6, wherein the nitrogen-containing polymer is a reaction product of (A) amines, amides, imides, maleimides or imines with (B) diones.

8. The lithium battery as claimed in claim 7, wherein the diones (B) comprise barbituric acid, barbituric acid derivatives, acetylacetone, or acetylacetone derivatives.

9. The lithium battery as claimed in claim 8, wherein the nitrogen-containing polymer is a reaction product of barbituric acid and a bismaleimide monomer.

10. The lithium battery as claimed in claim 1, wherein the onset temperature is between about 100°

C. and 220°

C.

11. The lithium battery as claimed in claim 1, wherein the onset temperature is between about 130°

C. and 200°

C.

12. The lithium battery as claimed in claim 1, further comprising a sealant structure wrapped around the cathode plate, the anode plate, the separator, and the electrolyte.

13. The lithium battery as claimed in claim 1, wherein the thermal protective film shows N−

1s or S−

1s signals when analyzed by an X-ray photoelectron spectroscopy (XPS).

14. The lithium battery as claimed in claim 1, wherein the thermal protective film has a thickness of not less than 25 nm.

15. The lithium battery as claimed in claim 1, wherein a ratio of peak areas of transition metal 2p signal of the thermal protective film at 5 minutes to 0 minutes is greater than 6 according to an X-ray photoelectron spectroscopy (XPS) analysis.

16. A method for fabricating the lithium battery as set forth in claim 1, comprising

providing an electrode material powder;

modifying the electrode material powder with a nitrogen-containing polymer to form a modified electrode material powder;

forming a modified electrode plate comprising the modified electrode material powder, a conductive additive and a binder, wherein the nitrogen-containing polymer encapsulates the modified electrode material powder;

forming a lithium battery comprising the modified electrode plate; and

activating the lithium battery by a charging operation to form a thermal protective film in the modified electrode plate.

17. The method as claimed in claim 16, wherein the electrode material powder is a lithium mixed metal oxide comprising LiMnO₂, LiMn₂O₄, LiCoO₂, Li₂Cr₂O₇, Li₂CrO₄, LiNiO₂, LiFeO₂, LiNi_xCo_1-xO₂ (0<

x<

1), LiMPO₄ (M is a transition metal), LiMn_0.5Ni_0.5O₂, LiNi_xCo_yMn_zO₂ (x+y+z=1), LiNi_xCo_yAl_zO₂ (x+y+z=1), LiMc_0.5Mn_1.5O₄ (Mc is a bivalent metal), or combinations thereof.

18. The method as claimed in claim 17, wherein the modifying comprises modifying the lithium mixed metal oxide powder with a solution of the nitrogen-containing polymer having a solid content of about 1-20%.

19. The method as claimed in claim 16, wherein the nitrogen-containing polymer is a reaction product of (A) amines, amides, imides, maleimides or imines with (B) diones.

20. The method as claimed in claim 16, wherein the diones (B) comprise barbituric acid, barbituric acid derivatives, acetylacetone, or acetylacetone derivatives.

21. The method as claimed in claim 20, wherein the nitrogen-containing polymer is a reaction product of barbituric acid and a bismaleimide monomer.

22. The method as claimed in claim 16, wherein a weight ratio of the modified electrode material powder, the conductive additive, the binder in the modified electrode plate is about 80-93:

0.1-5;

0.1-5.

23. The method as claimed in claim 16, wherein the conductive additive comprises carbon black, graphite, acetylene black, nickel powder, aluminum powder, titanium powder, stainless steel powder or combinations thereof.

24. The method as claimed in claim 16, wherein the binder comprises polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), polyamide, melamine resin, or combinations thereof.

25. The method as claimed in claim 16, wherein the thermal protective film has an onset temperature of about 80°

C. and 280°

C.

26. The method as claimed in claim 16, wherein the thermal protective film shows an N-1s or S-1s signal according to an X-ray photoelectron spectroscopy (XPS) analysis.

27. The method as claimed in claim 16, wherein the thermal protective film has a thickness of not less than 25 nm.

28. The method as claimed in claim 16, wherein a ratio of peak areas of transition metal 2p signal of the thermal protective film at 5 minutes to 0 minutes is greater than 6 according to an X-ray photoelectron spectroscopy (XPS) analysis.

29. A lithium battery, comprising

a cathode plate and an anode plate;

a separator disposed between the cathode plate and the anode plate to define a reservoir region;

an electrolyte filled in the reservoir region; and

a non-crosslinked thermal protective film comprising a nitrogen-containing polymer encapsulating an electrode material powder of the cathode plate or the anode plate, wherein the non-crosslinked thermal protective film is capable of undergoing a crosslinking reaction when a battery temperature rises over an onset temperature, and the onset temperature is between about 80°

C. and 280°

C.

30. The lithium battery as claimed in claim 29, wherein the non-crosslinked thermal protective film is capable of undergoing a crosslinking reaction when a battery temperature rises over an onset temperature between about 80°

C. and 280°

C.

31. The lithium battery as claimed in claim 29, wherein the thermal protective film covers the material of the cathode plate, which comprises a lithium mixed metal oxide, a conductive additive and a binder.

32. The lithium battery as claimed in claim 31, wherein the lithium mixed metal oxide comprises LiMnO₂, LiMn₂O₄, LiCoO₂, Li₂Cr₂O₇, Li₂CrO₄, LiNiO₂, LiFeO₂, LiNi_xCo_1-xO₂ (0<

x<

1), LiMPO₄ (M is a transition metal), LiMn_0.5Ni_0.5O₂, LiNi_xCo_yMn_zO₂ (x+y+z=1), LiMc_0.5O₄ (Mc is a bivalent metal), or combinations thereof.

33. The lithium battery as claimed in claim 31, wherein the conductive additive comprises carbon black, graphite, acetylene black, nickel powder, aluminum powder, titanium powder, stainless steel powder or combinations thereof.

34. The lithium battery as claimed in claim 31, wherein the binder comprises polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), polyamide, melamine resin, or combinations thereof.

35. The lithium battery as claimed in claim 29, wherein the nitrogen-containing polymer is a reaction product of (A) amines, amides, imides, maleimides or imines with (B) diones.

36. The lithium battery as claimed in claim 35, wherein the diones comprise barbituric acid, barbituric acid derivatives, acetylacetone, or acetylacetone derivatives.

37. The lithium battery as claimed in claim 36, wherein the nitrogen-containing polymer is a reaction product of barbituric acid and a bismaleimide monomer.

38. The lithium battery as claimed in claim 29, wherein the onset temperature is between about 100°

C. and 220°

C.