Positive electrode for lithium ion secondary battery and lithium ion secondary battery including the same

• US 9,608,288 B2
• Filed: 07/16/2015
• Issued: 03/28/2017
• Est. Priority Date: 07/17/2014
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Matsuda, Yasuaki, Yamada, Takanobu, Matsui, Masaki, Aihara, Yuichi, Imanishi, Nobuyuki
• Primary Examiner(s): Le, Emily
• Assistant Examiner(s): Wills, Monique
• Application Number:
  US14/800,907
• Publication Number:
  US 20160020487A1
• Time in Patent Office: 621 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 10/0562 Solid materials
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• 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 4/139 Processes of manufacture
• 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 4/1397 of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/366 as layered products
• 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 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/622 being polymers
• 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

Abstract

A positive electrode for a lithium ion secondary battery, the positive electrode including: a coated particle including a positive active material particle and a reactive layer on the surface of the positive active material particle; and a sulfide-containing solid electrolyte particle which is in contact with the coated particle, wherein the reactive layer includes a reactive element other than lithium and oxygen, wherein the reactive element has a reactivity with the sulfide-containing solid electrolyte particle which is greater than with a reactivity of the reactive element with a transition metal element included in the positive active material particle, and wherein a ratio of a thickness of the reactive layer to a particle diameter of the positive active material particle is in a range of about 0.0010 to about 0.25.

Claims

1. A positive electrode for a lithium ion secondary battery, the positive electrode comprising:

a coated particle comprising a positive active material particle and a reactive layer on a surface of the positive active material particle; and

a sulfide-containing solid electrolyte particle which is in contact with the coated particle,

wherein the reactive layer comprises a reactive element other than lithium and oxygen, wherein the reactive element has a reactivity with the sulfide-containing solid electrolyte particle which is greater than a reactivity of the reactive element with a transition metal element included in the positive active material particle,

wherein the reactive element comprises at least one selected from aluminum, magnesium, zirconium, titanium, tantalum, sodium, potassium, calcium, strontium, barium, indium, molybdenum, lanthanum, cobalt, and manganese, and

wherein a content of the reactive layer, other than lithium and oxygen, consists of the reactive element, and

wherein a ratio of a thickness of the reactive layer to a particle diameter of the positive active material particle is in a range of about 0.0010 to about 0.25.

2. The positive electrode of claim 1, wherein the reactive element has a standard enthalpy of formation for sulfide that is less than a standard enthalpy of formation for sulfide of the transition metal element included in the positive active material particle.

3. The positive electrode of claim 2, wherein a standard enthalpy of formation for sulfide of the reactive element is less than about −

80 kiloJoules per mole.

4. The positive electrode of claim 1, wherein a first initiation temperature of an exothermic reaction of a first mixture, which comprises a 1:

1 mass ratio of the coated particle and the sulfide-containing solid electrolyte particle, is greater than a second initiation temperature of an exothermic reaction of a second mixture, which comprises a 1;

1 mass ratio combination of the positive active material particle, which is not covered with the reactive layer, and the sulfide containing solid electrolyte particle, when analyzed by differential scanning calorimetry.

5. The positive electrode of claim 4, wherein the initiation temperature for the exothermic reaction of the first mixture is greater than 250°

C.

6. The positive electrode of claim 5, wherein a temperature at which a calorific value of the first mixture reaches a greatest value is greater than 330°

C.

7. The positive electrode of claim 1, wherein at least a portion of the reactive element is included in the positive active material particle in the form of a solid solution.

8. The positive electrode of claim 1, wherein the reactive element includes at least one selected from aluminum, cobalt, manganese, and magnesium.

9. The positive electrode of claim 1, wherein the sulfide-containing solid electrolyte particle comprises phosphorus.

10. A lithium ion secondary battery comprising:

the positive electrode of claim 1;

a negative electrode comprising a negative active material; and

a solid electrolyte layer disposed between the positive electrode and the negative electrode, the solid electrolyte layer comprising a sulfide-containing solid electrolyte particle.

11. A process of making a positive electrode for a lithium ion secondary battery, the process comprising:

providing a sulfide-containing solid electrolyte particle;

providing a positive active material particle containing a transition metal;

coating the positive active material particle with a reactive layer comprising a reactive element other than lithium and oxygen, wherein the reactive element has a reactivity with the sulfide-containing solid electrolyte particle which is greater than a reactivity of the reactive element with a transition metal element included in the positive active material particle,

wherein the reactive element comprises at least one selected from aluminum, magnesium, zirconium, titanium, tantalum, sodium, potassium, calcium, strontium, barium, indium, molybdenum, lanthanum, cobalt, and manganese, and

wherein a content of the reactive layer other, than lithium and oxygen, consists of the reactive element; and

contacting the sulfide-containing solid electrolyte particle with the coated particle, wherein a ratio of a thickness of the reactive layer to a particle diameter of the positive active material particle is in a range of about 0.0010 to about 0.25 to make the positive electrode.

12. The process of claim 11, wherein at least a portion of the reactive element is included in the positive active material particle in the form of a solid solution.

13. A process of making a lithium ion secondary battery having a positive electrode and a negative electrode, the process comprising:

disposing a solid electrolyte layer comprising a sulfide-containing solid electrolyte particle coated with a reactive layer between the positive electrode and the negative electrode, wherein the positive electrode comprises

a coated particle comprising a positive active material particle and a reactive layer on a surface of the positive active material particle, and

a sulfide-containing solid electrolyte particle which is in contact with the coated particle,

wherein the reactive layer comprises a reactive element other than lithium and oxygen, wherein the reactive element has a reactivity with the sulfide-containing solid electrolyte particle which is greater than a reactivity of the reactive element with a transition metal element included in the positive active material particle,

wherein the reactive element comprises at least one selected from aluminum, magnesium, zirconium, titanium, tantalum, sodium, potassium, calcium, strontium, barium, indium, molybdenum, lanthanum, cobalt, and manganese, and

wherein a content of the reactive layer, other than lithium and oxygen, consists of the reactive element, and

wherein a ratio of a thickness of the reactive layer to a particle diameter of the positive active material particle is in a range of about 0.0010 to about 0.25.

14. The process of claim 13, wherein the sulfide-containing solid electrolyte particle comprises phosphorus.