BATTERY DESIGNS WITH HIGH CAPACITY ANODE MATERIALS AND CATHODE MATERIALS

• US 20140065464A1
• Filed: 02/26/2013
• Published: 03/06/2014
• Est. Priority Date: 05/04/2012
• Status: Active Grant

• Current Assignee: Ionblox Incorporated (Zenlabs Energy, Inc.)
• Original Assignee: Envia Systems, Inc.
• Inventors: Masarapu, Charan, Anguchamy, Yogesh Kumar, Han, Yongbong, Deng, Haixia, Kumar, Sujeet, Lopez, Herman A.
• Granted Patent: US 9,780,358 B2
• Time in Patent Office: Days
• US Class Current: 429/149
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/446 Initial charging measures
• 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 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/387 Tin or alloys based on tin
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take 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 50/103 prismatic or rectangular H01M50/109, H01M50/11 take precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

Improved high energy capacity designs for lithium ion batteries are described that take advantage of the properties of high specific capacity anode active compositions and high specific capacity cathode active compositions. In particular, specific electrode designs provide for achieving very high energy densities. Furthermore, the complex behavior of the active materials is used advantageously in a radical electrode balancing design that significantly reduced wasted electrode capacity in either electrode when cycling under realistic conditions of moderate to high discharge rates and/or over a reduced depth of discharge.

Claims

1. A lithium ion battery comprising:

an electrode stack comprising a plurality of positive electrode elements, a plurality of negative electrode elements, a separator material separating an adjacent positive electrode element and negative electrode element and a current collector associated with each electrode element, at least one positive electrode element and one negative electrode element comprising an electrode structure coated onto both sides of the respective current collector;

an enclosure; and

electrolyte comprising lithium ions,

wherein each positive electrode has an active material comprising a lithium rich metal oxide, the active material having a specific discharge capacity of at least about 195 mAh/g at C/3 discharged from 4.6 V to 2V against lithium and having a loading from about 13 mg/cm² to about 35 mg/cm² on one side of the current collector and a density from about 2.5 g/cc to about 3 g/cc,

wherein each negative electrode has an active material comprising a silicon based material, the active material having a specific discharge capacity of at least about 700 mAh/g at C/3 discharged from 1.5V to 5 mV against lithium and having a loading from about 2 mg/cm² to about 6 mg/cm² on one side of the current collector and a density from about 0.2 g/cc to about 1.5 g/cc.

2. The lithium ion battery of claim 1 wherein the battery is a pouch cell comprising a foil enclosure with a roughly prismatic shape.

3. The lithium ion battery of claim 1 wherein the lithium rich positive electrode active material comprises a composition approximately represented by the formula Li_1+bNi_α

Mn_β

Co_γ

A_δ

O<sub>2−

z</sub>F_z, where b ranges from about 0.01 to about 0.3, α

ranges from about 0 to about 0.4, β

range from about 0.2 to about 0.65, γ

ranges from 0 to about 0.46, δ

ranges from 0 to about 0.15 and z ranges from 0 to about 0.2 with the proviso that both α and

γ

are not zero, and where A is Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li or combinations thereof.

4. The lithium ion battery of claim 1 wherein the lithium rich metal oxide has a specific discharge capacity of at least about 240 mAh/g.

5. The lithium ion battery of claim 1 wherein the silicon based active material comprises nanostructured elemental silicon.

6. The lithium ion battery of claim 1 wherein the silicon based active material comprises silicon oxide, SiO_x, 0.1≦

x≦

1.9.

7. The lithium ion battery of claim 1 wherein the silicon based active material comprises a carbon composite comprising nanostructured elemental silicon, silicon alloy and/or silicon oxide.

8. The lithium ion battery of claim 1 wherein the silicon based material has a specific discharge capacity of at least about 850 mAh/g.

9. The lithium ion battery of claim 1 wherein during an initial activation charge the battery has a negative electrode charge capacity of about 75% to about 99.5% at a rate of C/20 from an open circuit voltage to 1.5V against lithium relative to the sum of the first activation cycle positive electrode charge capacity at a rate of C/20 from an open circuit voltage to 4.6V against lithium plus the oxidation capacity of any supplemental lithium.

10. The lithium ion battery of claim 1 further comprising supplemental lithium in an amount with an oxidation capacity corresponding to about 5% to about 150% of the irreversible capacity loss of the negative electrode.

11. The lithium ion battery of claim 1 wherein during an initial activation charge the battery has a negative electrode charge capacity of about 115% to about 165% at a rate of C/20 from an open circuit voltage to 1.5V against lithium relative to the sum of the first activation cycle positive electrode charge capacity at a rate of C/20 from an open circuit voltage to 4.6V against lithium plus the oxidation capacity of any supplemental lithium.

12. A lithium ion battery comprising:

an electrode stack comprising;

3-50 positive electrode elements each comprising a current collector and a positive electrode structure on a surface of the current collector with at least one electrode element having an electrode structure on both sides of the current collector;

3-50 negative electrode elements each comprising a current collector and a positive electrode structure on a surface of the current collector with at least one electrode element having an electrode structure on both sides of the current collector; and

a separator material separating an adjacent positive electrode element and negative electrode element;

an enclosure that encloses the electrode stack; and

electrolyte comprising lithium ions,

wherein each positive electrode has an active material comprising a lithium rich metal oxide, an area along one side from about 100 cm² to about 400 cm², a loading from about 13 mg/cm² to about 35 mg/cm² one side of the respective current collector and a density from about 2.5 g/cc to about 3 g/cc, and

wherein each negative electrode comprises a silicon based active material, a loading from about 3 mg/cm² to about 6 mg/cm² on one side of the respective current collector and a density from about 0.8 g/cc to about 1.2 g/cc,

the battery having an energy density from about 250 Wh/kg to about 550 Wh/kg.

13. The lithium ion battery of claim 12 wherein during an initial activation charge the battery has a negative electrode charge capacity of about 115% to about 165% at a rate of C/20 from an open circuit voltage to 1.5V against lithium relative to the sum of the first activation cycle positive electrode charge capacity at a rate of C/20 from an open circuit voltage to 4.6V against lithium plus the oxidation capacity of any supplemental lithium.

14. The lithium ion battery of claim 12 wherein the electrode stack has 5-35 positive electrode elements and 5-35 negative electrode elements and wherein the battery has an energy density from about 300 Wh/kg to about 500 Wh/kg.

15. The lithium ion battery of claim 12 wherein the battery has a volumetric energy density from about 500 Wh/l to about 900 Wh/l.

16. The lithium ion battery of claim 12 wherein the battery is a pouch cell comprising a foil enclosure with a roughly prismatic shape and a ceramic separator.

17. The lithium ion battery of claim 12 wherein the lithium rich positive electrode active material is approximately represented by the formula Li_1+bNi_α

Mn_β

Co_γ

A_δ

O<sub>2−

z</sub>F_z, where b ranges from about 0.01 to about 0.3, α

ranges from about 0 to about 0.4, β

range from about 0.2 to about 0.65, γ

ranges from 0 to about 0.46, δ

ranges from 0 to about 0.15 and z ranges from 0 to about 0.2 with the proviso that both α and

γ

are not zero, and where A is Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li or combinations thereof.

18. The lithium ion battery of claim 12 wherein the silicon based active material comprises nanostructured elemental silicon, silicon alloy and/or silicon oxide.

19. The lithium ion battery of claim 12 further comprising supplemental lithium in an amount with an oxidation capacity corresponding to about 5% to about 150% of the irreversible capacity loss of the negative electrode.

20. The lithium ion battery of claim 12 wherein the positive electrode active material has a specific discharge capacity of at least about 200 mAh/g at C/3 discharged from 4.6V to 2V against lithium and the negative electrode active material has a specific discharge capacity of at least about 750 mAh/g at C/3 discharged against lithium.

21. The lithium ion battery of claim 12 wherein the positive electrode has a surface area along one side from about 100 cm² to about 300 cm².