Lithium Secondary Battery

Patent metadata

Field	Value
Publication number	US-2025118743-A1
Application number	US-202218294616-A
Country	US
Kind code	A1
Filing date	Oct 5, 2022
Priority date	Oct 5, 2021
Publication date	Apr 10, 2025
Grant date	—

Abstract

The present invention relates to a lithium secondary battery which includes a positive electrode including an overlithiated manganese-based oxide, in which an amount of manganese among total metals excluding lithium is greater than 50 mol % and a ratio (Li/Me) of the number of moles of the lithium to the number of moles of the total metals excluding the lithium is greater than 1, as a positive electrode active material; a negative electrode including a silicon-based negative electrode active material; a separator disposed between the positive electrode and the negative electrode; and an electrolyte, and satisfies Equation (1).

0.25
A

≤
B
≤

0
.
6

⁢
A

Equation
⁢

(
1
)

In Equation (1), A is a discharge curve area in a voltage range of 2.0 V to 4.6 V of a dQ/dV graph obtained by differentiating a graph of battery discharge capacity Q and voltage V after one cycle which are measured while charging the lithium secondary battery at 0.1 C to 4.6 V and then discharging the lithium secondary battery at 0.1 C to 2.0 V, and B is a discharge curve area in a voltage range of 2.0 V to 3.5 V of the dQ/dV graph.

First claim

1 . A lithium secondary battery comprising:
a positive electrode including a positive electrode active material comprising an overlithiated manganese-based oxide, in which an amount of manganese among total metals excluding lithium is 50 mol % or more and a ratio (Li/Me) of a number of moles of the lithium to a number of moles of the total metals excluding the lithium is greater than 1; a negative electrode including a negative electrode active material including a silicon-based negative electrode active material; a separator disposed between the positive electrode and the negative electrode; and an electrolyte, wherein the lithium secondary battery satisfies Equation (1):

0.25
A

≤
B
≤

0
.
6

⁢
A

Equation
⁢

(
1
)

wherein, in Equation (1), A is a discharge curve area in a voltage range of 2.0 V to 4.6 V of a dQ/dV graph obtained by differentiating a graph of battery discharge capacity Q and voltage V after one cycle which are measured while charging the lithium secondary battery at 0.1 C to 4.6 V and discharging the lithium secondary battery at 0.1 C to 2.0 V, and B is a discharge curve area in a voltage range of 2.0 V to 3.5 V of the dQ/dV graph.

2 . The lithium secondary battery of claim 1 , wherein the lithium secondary battery satisfies Equation (1-1):

0.3
A

≤
B
≤

0
.
5

⁢
A

Equation
⁢

(

1
-
1

)

wherein, in Equation (1-1), A is a discharge curve area in a voltage range of 2.0 V to 4.6 V of a dQ/dV graph obtained by differentiating a graph of battery discharge capacity Q and voltage V after one cycle which are measured while charging the lithium secondary battery at 0.1 C to 4.6 V and discharging the lithium secondary battery at 0.1 C to 2.0 V, and B is a discharge curve area in a voltage range of 2.0 V to 3.5 V of the dQ/dV graph.

3 . The lithium secondary battery of claim 1 , wherein the overlithiated manganese-based oxide is represented by [Formula 1]:
Li a Ni b Co c Mn d M e O 2   [Formula 1]
wherein, in Formula 1, 1<a, 0≤b≤0.5, 0≤c≤0.1, 0.5≤d<1.0, and 0≤e≤0.2, and M is at least one selected from the group consisting of aluminum (Al), boron (B), cobalt (Co), tungsten (W), magnesium (Mg), vanadium (V), titanium (Ti), zinc (Zn), gallium (Ga), indium (In), ruthenium (Ru), niobium (Nb), tin (Sn), strontium (Sr), and zirconium (Zr).

4 . The lithium secondary battery of claim 3 , wherein, in Formula 1, 1.1≤a≤1.5, 0.1≤b≤0.4, 0≤c≤0.05, 0.5≤d≤0.80, and 0≤e≤0.1.

5 . The lithium secondary battery of claim 1 , wherein the positive electrode active material has a D 50 of 2 μm to 10 μm.

6 . The lithium secondary battery of claim 1 , wherein the positive electrode active material has a Brunauer-Emmett-Teller (BET) specific surface area of 1 m 2 /g to 10 m 2 /g.

7 . The lithium secondary battery of claim 1 , wherein the positive electrode has an initial irreversible capacity of 5% to 70%.

8 . The lithium secondary battery of claim 1 , wherein the positive electrode has an electrode density of 2.5 g/cc to 3.8 g/cc.

9 . The lithium secondary battery of claim 1 , wherein the silicon-based negative electrode active material has an initial efficiency of 60% to 95%.

10 . The lithium secondary battery of claim 1 , wherein the negative electrode further comprises a conductive agent and a binder,
wherein the conductive agent comprises single-walled carbon nanotubes.

11 . The lithium secondary battery of claim 1 , wherein the silicon-based negative electrode active material has a D 50 of 3 μm to 8 μm.

12 . The lithium secondary battery of claim 1 , wherein the negative electrode has a negative electrode active material layer which has a porosity of 20% to 70%.

13 . The lithium secondary battery of claim 1 , wherein the negative electrode active material further includes a carbon-based negative electrode active material, wherein the silicon-based negative electrode active material is a silicon oxide, and
an N/P ratio of the lithium secondary battery is in a range of 100% to 150%.

14 . The lithium secondary battery of claim 13 , wherein the negative electrode has a multilayer structure including two or more negative electrode material mixture layers.

15 . The lithium secondary battery of claim 1 , wherein the negative electrode active material consists of silicon (Si), and
an N/P ratio of the lithium secondary battery is in a range of 150% to 300%.

16 . The lithium secondary battery of claim 1 , wherein the lithium secondary battery has a number of times reaching 80% lifetime of 560 times or more, and has an energy density of 450 Wh/L or more.

17 . The lithium secondary battery of claim 1 , wherein the overlithiated manganese-based oxide has a two-phase crystalline structure in which a layered phase and a rock salt phase are mixed,
wherein the two-phase crystalline structure is represented by Formula 2:
X Li 2 MnO 3 ·(1−X)Li[Ni 1-y-z-w Mn y Co z M w ]O 2   [Formula 2]

wherein, in the Formula 2, M is at least one selected from the group consisting of Al, B, Co, W, Mg, V, Ti, Zn, Ga, In, Ru, Nb, Sn, Sr, and Zr, 0.2≤X≤0.5, 0.4≤y<1, 0≤z≤0.1, and 0≤w≤0.2.

18 . The lithium secondary battery of claim 1 , wherein the negative electrode further includes a carbon-based negative electrode active material.

19 . A method of manufacturing the lithium secondary battery of claim 1 , comprising:
preparing the positive electrode including the positive electrode active material comprising the overlithiated manganese-based oxide; preparing the negative electrode the negative electrode including the negative electrode active material; positioning the separator between the positive and negative electrodes.

20 . The method of claim 19 , wherein the preparing of the negative electrode includes providing a multilayer negative electrode coating.

Assignees

• Lg Energy Solution Ltd

Inventors

• Park Byung Chun
• Jung Wang Mo
• Park Sin Young
• Hur Hyuck
• Kim Dong Hwi

Classifications

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/587

  for inserting or intercalating light metals · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/364

  as mixtures · CPC title