METHOD FOR PRODUCING LITHIUM ION SECONDARY BATTERY

• US 20160308258A1
• Filed: 12/08/2014
• Published: 10/20/2016
• Est. Priority Date: 01/09/2014
• Status: Active Grant

• Current Assignee: Nissan Motor Co., Ltd.
• Original Assignee: Nissan Motor Co., Ltd.
• Inventors: OGIHARA, Wataru, TANAKA, Hideaki
• Granted Patent: US 10,461,378 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• 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 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 10/446 Initial charging measures
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0445 Forming after manufacture of the electrode, e.g. first charge, cycling
• 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 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/1393 of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/483 for non-aqueous cells H01M4/485 takes precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/623 : fluorinated polymers
• CPC Class Codes: H01M 4/661 : Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 50/414 : Synthetic resins, e.g. thermoplastics or thermosetting resins
• CPC Class Codes: H01M 50/429 : Natural polymers
• CPC Class Codes: H01M 50/489 : Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• CPC Class Codes: H01M 50/497 : Ionic conductivity
• 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

Abstract

A method for producing a lithium ion secondary battery comprising the positive electrode active material of formula (1), Li_(2-0.5x)Mn_1-xM_1.5xO₃ (x satisfies 0<x<1) . . . (1) (M in the formula is a lithium-containing transition metal oxide expressed by Ni_aCo_bMn_cM1_d (in which 0<a≦0.5, 0≦b≦0.33, 0<c≦0.5, and 0≦d≦0.1 are satisfied, the sum of a, b, c, and d becomes 1, and M1 in the formula is an element selected from Li, V, Al, Zr, Ti, Nb, Fe, Cu, Cr, Mg, and Zn)). The method comprises a step to repeat charge-discharge multiple times (charge-discharge interval), and comprises a step to discharge a at a lower current density than the current density during charge a, during the discharge of the multiple charges-discharges, or, a step to discharge b at a lower current density than the current density during charge a after the electromotive force is naturally recovered by idle b after each charge-discharge.

Claims

1. A method for producing a lithium ion secondary battery comprising a solid solution positive electrode active material represented by the following composition formula:

Li(2-0.5x)Mn1-xM1.5xO3 wherein x satisfies 0<

x<

1 and M is a lithium-containing transition metal oxide expressed by NiaCobMncM1d wherein 0<

a≦

0.5, 0≦

b≦

0.33, 0<

c≦

0.5, and 0≦

d≦

0.1 are satisfied, the sum of a, b, c, and d becomes 1, and M1 is an element selected from Li, Al, Zr, Ti, and Nb,

the method comprising;

repeatedly charging and discharging the lithium ion secondary battery; and

the discharging of the lithium ion secondary battery being carried out at a lower current density than a current density during the charging of the lithium ion secondary battery, during each of the charging and discharging.

2. The method for producing the lithium ion secondary battery according to claim 1, wherein

the discharging of the lithium ion secondary battery at the lower current density is carried out at a constant current density until reaching a lower limit value of a battery voltage by the discharging of the lithium ion secondary battery at the lower current density.

10. The method of producing the lithium ion secondary battery to claim 1, wherein

the lower current density is less than 0.1 C.

11. The method of producing the lithium ion secondary battery to claim 1, wherein

a lower limit value of a battery voltage after the discharging of the lithium ion secondary battery at the lower current density is set to 3.0-2.0V.

12. The method of producing the lithium ion secondary battery to claim 1, wherein

an upper limit potential of each of the repeatedly charging and discharging of the lithium ion secondary battery is increased in a stepwise manner.

13. The method of producing the lithium ion secondary battery to claim 1, wherein

the lithium ion secondary battery comprises a negative electrode active material layer represented by α

(silicon-based material)+β

(carbon material)+γ

(binder)+η

(conductive assistant), where α

, β

, γ

, and η

represent a weight % in the negative electrode active material layer, satisfy α

+β

+γ

+η

=100, 80≦

α

+β

≦

98, 3≦

α

≦

40, 40≦

β

≦

95, 1≦

γ

≦

10, 1≦

η

≦

10, and the silicon-based material is a material having silicon as a main element.

14. The method of producing the lithium ion secondary battery to claim 13, wherein

the silicon-based material is SiOx wherein x is a number of oxygen atoms that satisfies a valence of Si, and is in a range of 0.5≦

x≦

1.5), or at least one type selected from a group consisting of SixTiyGezAa, SixTiyZnzAa, SixTiySnzA, SixSnyAlzAa, SixSnyVzAa, SixSnyCzA, SixZnyVzAa, SixZnySnzAa, SixZnyAlzAa, SixZnyCzAa, SixAlyCzAa, SixAlyNbzAa where A represents inevitable impurities and x, y, z, and a represent values of weight % satisfying 0<

x<

100, 0<

y<

100, 0<

z<

100, 0≦

a<

0.5, and x+y+z+a=100).

15. The method of producing the lithium ion secondary battery to claim 1, wherein

the lithium ion secondary battery comprises a positive electrode active material layer represented by e (solid solution positive electrode active material)+f (binder)+g (conductive assistant), where e, f, and g represent the weight % in the positive electrode active material layer and satisfy e+f+g=100, 80≦

e≦

98, 1≦

f≦

10, and 1≦

g≦

10.

3. A method for producing a lithium ion secondary battery comprising a solid solution positive electrode active material represented by the following composition formula:

Li(2-0.5x)Mn1-xM1.5xO3 wherein x satisfies 0<

x<

1 and M is a lithium-containing transition metal oxide expressed by NiaCobMncM1d wherein 0<

a≦

0.5, 0≦

b≦

0.33, 0<

c≦

0.5, and 0≦

d≦

0.1 are satisfied, the sum of a, b, c, and d becomes 1, and M1 is an element selected from Li, Al, Zr, Ti, and Nb,

the method comprising;

repeatedly charging and discharging the lithium ion secondary battery; and

the discharging of the lithium ion secondary battery being carried out at a lower current density than a current density during the charging of the lithium ion secondary battery that is carried out after an electromotive force is naturally recovered by standing idle after each of the discharging of the lithium ion secondary battery.

4. The method for producing the lithium ion secondary battery according to claim 3, wherein

the lower current density is less than 0.1 C.

5. The method for producing the lithium ion secondary battery according to claim 3, wherein

a lower limit value of a battery voltage after the discharging of the lithium ion secondary battery at the lower current density is set to 3.0-2.0V.

6. The method for producing the lithium ion secondary battery according to claim 3, wherein

an upper limit potential of each of the repeatedly charging and discharging of the lithium ion secondary battery is increased in a stepwise manner.

7. The method of producing the lithium ion secondary battery according to claim 3, wherein

the lithium ion secondary battery comprises a negative electrode active material layer represented by α

(silicon-based material)+β

(carbon material)+γ

(binder)+η

(conductive assistant), where α

, β

, γ

, and η

represent a weight % in the negative electrode active material layer, satisfy α

+β

+γ

+η

=100, 80≦

α

+β

≦

98, 3≦

α

≦

40, 40≦

β

≦

95, 1≦

γ

≦

10, 1≦

η

≦

10, and the silicon-based material is a material having silicon as a main element.

8. The method of producing the lithium ion secondary battery according to claim 7, wherein

the silicon-based material is SiOx wherein x is a number of oxygen atoms that satisfies a valence of Si, and is in a range of 0.5≦

x≦

1.5), or at least one type selected from a group consisting of SixTiyGezAa, SixTiyZnzAa, SixTiySnzA, SixSnyAlzAa, SixSnyVzAa, SixSnyCzA, SixZnyVzAa, SixZnySnzAa, SixZnyAlzAa, SixZnyCzAa, SixAlyCzAa, SixAlyNbzAa where A represents inevitable impurities and x, y, z, and a represent values of weight % satisfying 0<

x<

100, 0<

y<

100, 0<

z<

100, 0≦

a<

0.5, and x+y+z+a=100).

9. The method of producing the lithium ion secondary battery according to claim 3, wherein

the lithium ion secondary battery comprises a positive electrode active material layer represented by e (solid solution positive electrode active material)+f (binder)+g (conductive assistant), where e, f, and g represent the weight % in the positive electrode active material layer and satisfy e+f+g=100, 80≦

e≦

98, 1≦

f≦

10, and 1≦

g≦

10.