Positive electrode active material, positive electrode, battery, battery pack, electronic device, electric vehicle, power storage device, and power system

• US 10,559,810 B2
• Filed: 07/09/2015
• Issued: 02/11/2020
• Est. Priority Date: 07/31/2014
• Status: Active Grant

• Current Assignee: Murata Manufacturing Co Limited
• Original Assignee: Murata Manufacturing Co Limited
• Inventors: Yanagihara, Asuki, Nakasato, Shingo, Niwata, Yuki, Hosoya, Yosuke
• Primary Examiner(s): Zeng, Lingwen R
• Application Number:
  US15/324,924
• Publication Number:
  US 20170207444A1
• Time in Patent Office: 1,678 Days
• CPC Class Codes: B60K 6/46 Series type
• CPC Class Codes: B60K 6/48 Parallel type
• CPC Class Codes: B60L 50/64 Constructional details of batteries specially adapted for electric vehicles
• CPC Class Codes: B60L 53/16 Connectors, e.g. plugs or sockets, specially adapted for charging electric vehicles
• CPC Class Codes: B60L 58/10 for monitoring or controlling batteries
• CPC Class Codes: C01B 25/12 Oxides of phosphorus
• CPC Class Codes: C01B 25/30 Alkali metal phosphates
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: C01B 35/1027 Oxides
• CPC Class Codes: C01D 15/04 Halides
• CPC Class Codes: C01F 5/02 Magnesia
• CPC Class Codes: C01F 5/28 Fluorides
• CPC Class Codes: C01F 7/02 Aluminium oxide; Aluminium hydroxide; Aluminates
• CPC Class Codes: C01G 23/005 Alkali titanates
• CPC Class Codes: C01G 23/047 Titanium dioxide
• CPC Class Codes: C01G 25/02 Oxides
• CPC Class Codes: C01G 41/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/1242 of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
• CPC Class Codes: C01G 51/42 containing alkali metals, e.g. LiCoO2
• CPC Class Codes: C01G 51/50 : of the type [MnO2]n- , e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
• CPC Class Codes: C01G 51/66 : containing alkaline earth metals, e.g. SrCoO3
• CPC Class Codes: C01G 53/04 : Oxides; Hydroxides
• CPC Class Codes: C01G 53/42 : containing alkali metals, e.g. LiNiO2
• CPC Class Codes: C01G 53/50 : of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/54 : one element only
• CPC Class Codes: C01P 2002/82 : by IR- or Raman-data
• CPC Class Codes: C01P 2004/82 : two phases having the same anion, e.g. both oxidic phases
• CPC Class Codes: C01P 2004/84 : one phase coated with the other
• CPC Class Codes: C01P 2006/40 : Electric properties
• 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 10/425 : Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing printed circuits H05K1/00
• 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 2220/30 : Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 2300/0037 : Mixture of solvents
• 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 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/366 : as layered products
• CPC Class Codes: H01M 4/483 : for non-aqueous cells H01M4/485 takes precedence
• CPC Class Codes: H01M 4/502 : for non-aqueous cells H01M4/505 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 4/523 : for non-aqueous cells H01M4/525 takes precedence
• 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 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/623 : fluorinated polymers
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: H01M 4/661 : Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 50/211 : adapted for pouch cells
• CPC Class Codes: H01M 50/213 : adapted for cells having curved cross-section, e.g. round or elliptic H01M50/209, H01M50/216 take precedence
• CPC Class Codes: H01M 50/249 : specially adapted for aircraft or vehicles, e.g. cars or trains constructional details of batteries specially adapted for electric vehicles B60L50/64
• CPC Class Codes: H01M 50/251 : specially adapted for stationary devices, e.g. power plant buffering or backup power supplies
• CPC Class Codes: H01M 50/417 : Polyolefins
• CPC Class Codes: H01M 50/426 : Fluorocarbon polymers
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02T 10/62 : Hybrid vehicles
• CPC Class Codes: Y02T 10/70 : Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y02T 10/7072 : Electromobility specific charging systems or methods for batteries, ultracapacitors, supercapacitors or double-layer capacitors
• CPC Class Codes: Y02T 90/14 : Plug-in electric vehicles

Abstract

A positive electrode active material includes: a particle including a lithium composite oxide; a first layer that is provided on a surface of the particle and includes a lithium composite oxide; and a second layer that is provided on a surface of the first layer. The lithium composite oxide included in the particle and the lithium composite oxide included in the first layer have the same composition or almost the same composition, the second layer includes an oxide or a fluoride, and the lithium composite oxide included in the first layer has lower crystallinity than the lithium composite oxide included in the particle.

Claims

1. A positive electrode active material comprising:

a particle including a lithium composite oxide;

a first layer that is provided on a surface of the particle and includes a lithium composite oxide; and

a second layer that is provided on a surface of the first layer,

wherein the lithium composite oxide included in the particle and the lithium composite oxide included in the first layer have the same constituent elements and the same atomic ratio or a difference between atomic ratios of the constituent elements of the core particles and the first covering layer is within 10 atom %,

the second layer includes an oxide or a fluoride, and

the lithium composite oxide included in the first layer has lower crystallinity than the lithium composite oxide included in the particle.

2. The positive electrode active material according to claim 1,

wherein, in Raman spectra, a peak intensity ratio E/A between an intensity A of a peak in a range of 550 cm⁻

1 or more and 650 cm<sup>−

1</sup> or less and an intensity E of a peak in a range of 450 cm<sup>−

1</sup> or more and 500 cm<sup>−

1</sup> or less satisfies a relation represented by the following expression (1)

0.1<

E/A<

0.35 

 

(1).

3. The positive electrode active material according to claim 1,

wherein the oxide and the fluoride included in the second layer include at least one of Li, Ti, V, Cr, Mn, Fe, Co, Ni, Mn, Cu, Na, Mg, Al, Si, K, Ca, Zn, Ga, Sr, Y, Zr, Nb, Mo, Ba, La, W, Bi, P and B.

4. The positive electrode active material according to claim 3,

wherein the oxide included in the second layer is a lithium composite oxide.

5. The positive electrode active material according to claim 4,

wherein the lithium composite oxide included in the second layer has an average composition that is represented by the following expression (A)

Li_wM_xN_yO_2-zX_z 

 

(A)

(where w is 0.8<

w<

1.2, x+y is 0.9<

x+y<

1.1, y is 0≤

y≤

0.1, and z is 0≤

z<

0.05;

M is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Mn and Cu;

N is at least one of Na, Mg, Al, Si, K, Ca, Zn, Ga, Sr, Y, Zr, Nb, Mo, Ba, La, W and Bi;

X is at least one of F, Cl and S).

6. The positive electrode active material according to claim 1,

wherein the second layer has an amount whose ratio is 0.1 mol % or more and 10 mol % or less with respect to a total amount of the particle, the first layer, and the second layer.

7. The positive electrode active material according to claim 1,

wherein the lithium composite oxide included in the particle has an average composition that is represented by the following expression (B)

Li_wM_xN_yO_2-zX_z 

 

(B)

(where w is 0.8<

w<

1.2, x+y is 0.9<

x+y<

1.1, y is 0≤

y<

0.1, and z is 0≤

z<

0.05;

M is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Mn and Cu;

N is at least one of Na, Mg, Al, Si, K, Ca, Zn, Ga, Sr, Y, Zr, Nb, Mo, Ba, La, W and Bi;

X is at least one of F, Cl and S).

8. The positive electrode active material according to claim 1,

wherein the lithium composite oxide included in the particle has an average composition that is represented by the following expression (C)

Li_xCo_1-yM_yO_2-zX_z 

 

(C)

(where x is 0.8<

x<

1.2, y is 0≤

y<

0.15, and z is 0≤

z<

0.05;

M is at least one of Ti, V, Cr, Mn, Fe, Ni, Mn, Cu, Na, Mg, Al, Si, K, Ca, Zn, Ga, Sr, Y, Zr, Nb, Mo, Ba, La and W;

X is at least one of F, Cl and S).

9. A positive electrode comprising:

a positive electrode active material that includes

a particle including a lithium composite oxide,

a first layer that is provided on a surface of the particle and includes a lithium composite oxide, and

a second layer that is provided on a surface of the first layer,

wherein the lithium composite oxide included in the particle and the lithium composite oxide included in the first layer have the same composition or a difference between atomic ratios of the constituent elements of the core particles and the first covering layer is within 10 atom %,

the second layer includes an oxide or a fluoride, and

the lithium composite oxide included in the first layer has lower crystallinity than the lithium composite oxide included in the particle.

10. A battery comprising:

a positive electrode including a positive electrode active material;

a negative electrode; and

an electrolyte,

wherein the positive electrode active material includes

a particle including a lithium composite oxide,

a first layer that is provided on a surface of the particle and includes a lithium composite oxide, and

a second layer that is provided on a surface of the first layer, and

wherein the lithium composite oxide included in the particle and the lithium composite oxide included in the first layer have the same composition or a difference between atomic ratios of the constituent elements of the core particles and the first covering layer is within 10 atom %,

the second layer includes an oxide or a fluoride, and

the lithium composite oxide included in the first layer has lower crystallinity than the lithium composite oxide included in the particle.

11. A battery pack comprising:

the battery according to claim 10.

12. An electronic device comprising:

the battery according to claim 10,

wherein the electronic device receives power supply from the battery.

13. An electric vehicle comprising:

the battery according to claim 10;

a conversion device configured to perform conversion into driving power of the vehicle upon reception of power supply from the battery; and

a control device configured to perform information processing regarding vehicle control based on information regarding the battery.

14. A power storage device comprising:

the battery according to claim 10,

wherein the power storage device supplies power to an electronic device connected to the battery.

15. The power storage device according to claim 14, comprising:

a power information control device configured to transmit and receive a signal to and from another device via a network,

wherein the power storage device performs charge/discharge control of the battery based on information received by the power information control device.

16. A power system comprising:

the battery according to claim 10,

wherein the power system receives power supply from the battery, or allows power to be supplied to the battery from a power generation apparatus or a power network.