Electrolytic copper foil capable of improving capacity retention rate of secondary battery, electrode including the same, secondary battery including the same, and method of manufacturing the same

Patent metadata

Field	Value
Publication number	US-10547081-B2
Application number	US-201715662785-A
Country	US
Kind code	B2
Filing date	Jul 28, 2017
Priority date	Aug 23, 2016
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

An electrolytic copper foil capable of improving a capacity retention rate of a secondary battery, an electrode including the same, a secondary battery including the same, and a method of manufacturing the same. The electrolytic copper foil, which includes a first surface and a second surface opposite the first surface, includes a copper layer including a matte surface facing the first surface and a shiny surface facing the second surface, and a first protective layer on the matte surface of the copper layer, wherein the first surface has a peak density (PD) of 3 to 110, a texture coefficient [TC(220)] of a (220) plane of 1.32 or less, and a surface roughness (Rz) of 0.5 to 2.7 μm.

First claim

What is claimed is:

1. A method of manufacturing a secondary battery electrolytic copper foil, the method comprising:
forming a copper layer by applying electricity between a positive electrode plate and a rotating negative electrode drum which are disposed in an electrolytic solution containing 70 to 90 g/L of copper ions and 50 to 150 g/L of sulfuric acid to be spaced apart from each other; and
forming a protective layer on the copper layer,
wherein the forming of the copper layer includes:
performing a heat treatment on a copper wire;
pickling the heat-treated copper wire;
preparing the electrolytic solution by introducing the pickled copper wire into sulfuric acid;
performing electroplating by applying electricity between the positive electrode plate and the rotating negative electrode drum at a current density of 40 to 80 A/dm 2 ; and
performing continuous filtration at a flow rate of 31 to 45 m 3 /hr to remove solid impurities from the electrolytic solution while the electroplating is performed,
wherein, while the electroplating is performed, total carbon (TC) in the electrolytic solution is maintained at a range of 0.04 to 0.24 g/L, a concentration of silver (Ag) therein is maintained at a range of 0.03 to 0.19 g/L, and a concentration of iron (Fe) therein is maintained at a range of 0.05 to 0.51 g/L.

2. The method of claim 1 , further comprising:
monitoring the concentration of iron (Fe) in the electrolytic solution while the electroplating is performed; and
replacing all or some of the electrolytic solution when the concentration of iron (Fe) is more than 0.54 g/L.

3. The method of claim 1 , wherein the copper wire is heat-treated at a temperature of 600 to 900° C. for 30 to 60 minutes.

4. The method of claim 1 , wherein the electrolytic solution further includes chloride ion capable of precipitating silver (Ag) in the form of AgCl in order to prevent the concentration of silver (Ag) from exceeding 0.2 g/L by silver (Ag) being introduced into the electrolytic solution while the electroplating is performed.

5. The method of claim 1 , wherein the forming of the copper layer further includes introducing hydrogen peroxide and air into the electrolytic solution while the electroplating is performed.

6. The method of claim 1 , wherein the electrolytic solution further includes an organic additive selected from a group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, and thiourea-based compounds.

7. The method of claim 1 , wherein the electrolytic solution further includes 1 to 10 ppm of ethylene thiourea.

8. The method of claim 1 , wherein the forming of the copper layer includes polishing a surface of the rotating negative electrode drum with an abrasive brush having #800 to #1500 of a particle-size (Grit).

9. The method of claim 1 , wherein:
the forming of the protective layer includes immersing the copper layer in an antirust solution containing 0.5 to 1.5 g/L of Cr; and
a concentration of copper (Cu) in the antirust solution is maintained at 0.1 g/L or less.

10. A secondary battery electrolytic copper foil, which is manufactured by the method of claim 1 , and includes a first surface and a second surface opposite the first surface, the electrolytic copper foil comprising:
a copper layer including a matte surface facing the first surface and a shiny surface facing the second surface; and
a first protective layer on the matte surface of the copper layer,
wherein the first surface has a peak density (PD) of 3 to 110, a texture coefficient [TC(220)] of a (220) plane of 1.32 or less, and a surface roughness (R z )) of 0.5 to 2.7 μm.

11. The electrolytic copper foil of claim 10 , further comprising a second protective layer on the shiny surface of the copper layer,
wherein the second surface has a PD of 3 to 110, a texture coefficient [TC(220)] of a (220) plane of 1.32 or less, and a surface roughness (R z )) of 0.5 to 2.7 μm.

12. The electrolytic copper foil of claim 11 , wherein:
a difference between the PDs of the first and second surfaces is 95 or less;
a difference between the texture coefficients [TC(220)] of the (220) planes of the first and second surfaces is 0.53 or less; and,
a difference between the surface roughnesses (R z ) of the first and second surfaces is 0.8 μm or less.

13. The electrolytic copper foil of claim 12 , wherein each of the first and second protective layers includes chromium (Cr).

14. The electrolytic copper foil of claim 10 , wherein the electrolytic copper foil has a yield strength of 21 to 63 kgf/mm 2 and an elongation of 3% or more at room temperature.

15. A secondary battery electrode comprising:
an electrolytic copper foil being manufactured by the method of claim 1 , and including a first surface and a second surface opposite the first surface; and
a first active material layer on the first surface of the electrolytic copper foil,
wherein the electrolytic copper foil includes:
a copper layer including a matte surface facing the first surface and a shiny surface facing the second surface; and
a first protective layer on the matte surface of the copper layer, and

wherein the first surface has a PD of 3 to 110, a texture coefficient [TC(220)] of a (220) plane of 1.32 or less, and a surface roughness (R z ) of 0.5 to 2.7 μm.

16. The secondary battery electrode of claim 15 , wherein:
the electrolytic copper foil further includes a second protective layer on the shiny surface of the copper layer;
the secondary battery electrode further includes a second active material layer on the second protective layer; and
the second surface has a PD of 3 to 110, a texture coefficient [TC(220)] of a (220) plane of 1.32 or less, and a surface roughness (R z ) of 0.5 to 2.7 μm.

17. The secondary battery electrode of claim 16 , wherein:
a difference between the PDs of the first and second surfaces is 95 or less;
a difference between the texture coefficients [TC(220)] of the (220) planes of the first and second surfaces is 0.53 or less; and
a difference between the surface roughnesses (R z ) of the first and second surfaces is 0.8 μm or less.

18. The secondary battery electrode of claim 16 , wherein each of the first and second active material layers comprises at least one active material selected from a group consisting of carbon, a metal such as Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe, an alloy containing the metal, an oxide of the metal, and a composite of the metal and carbon.

19. The secondary battery electrode of claim 18 , wherein each of the first and second active material layers comprises Si.

20. A secondary battery comprising:
a cathode;
an anode opposite to the cathode and including a secondary battery electrode;
an electrolyte configured to provide an environment in which lithium ions may move between the cathode and the anode; and
a separator configured to electrically insulate the cathode from the anode,
wherein the secondary battery electrode is manufactured by the method of claim 1 , and comprises:
an electrolytic copper foil including a first surface and a second surface opposite the first surface; and
a first active material layer on the first surface of the electrolytic copper foil,
wherein the electrolytic copper foil includes:
a copper layer including a matte surface facing the first surface and a shiny surface facing the second surface; and
a first protective layer on the matte surface of the copper layer, and
wherein the first surface has a PD of 3 to 110, a texture coefficient

Assignees

• Ls Mtron Ltd
• Kcf Tech Co Ltd

Inventors

• Kim Seung Min
• Jin Shan Hua

Classifications

• C25D1/20

  Separation of the formed objects from the electrodes {with no destruction of said electrodes} · CPC title

• H01M4/0407

  by coating on an electrolyte layer · CPC title

• C25D1/00 Primary

  Electroforming · CPC title

• H01M4/0438

  by electrochemical processing (electroless electrochemical plating C23C18/54) · CPC title

• H01M4/386

  Silicon or alloys based on silicon · CPC title