Electrolytic copper foil and electrode and copper-clad laminate comprising the same

Abstract

Provided are an electrolytic copper foil, and an electrode and a copper-clad laminate comprising the same. The electrolytic copper foil comprises a base copper layer having a drum side and a deposited side; wherein the electrolytic copper foil has a Charpy impact strength from 0.4 J/mm.sup.2 to 5.8 J/mm.sup.2.

Claims

1. An electrolytic copper foil comprising a base copper layer; wherein a Charpy impact strength of the electrolytic copper foil ranges from 0.4 J/mm.sup.2 to 5.8 J/mm.sup.2.

2. The electrolytic copper foil of claim 1, wherein the Charpy impact strength of the electrolytic copper foil ranges from 0.5 J/mm.sup.2 to 5.3 J/mm.sup.2.

3. The electrolytic copper foil of claim 1, wherein the electrolytic copper foil has two opposite surfaces; wherein at least one of the two surfaces of the electrolytic copper foil has an aspect ratio of surface profile from 14 to 693; the aspect ratio of surface profile is a ratio of a mean width of the roughness profile elements (RSm) to a root mean square deviation of the roughness profile (Rq).

4. The electrolytic copper foil of claim 3, wherein the aspect ratio of surface profile ranges from 37 to 506.

5. The electrolytic copper foil of claim 3, wherein the RSm ranges from 9 m to 523 m.

6. The electrolytic copper foil of claim 3, wherein the Rq ranges from 0.14 m to 1.34 m.

7. The electrolytic copper foil of claim 3, wherein the Rq ranges from 0.16 m to 1.25 m.

8. The electrolytic copper foil of claim 1, wherein the base copper layer has a drum side and a deposited side opposite the drum side, and the electrolytic copper foil further comprises at least one surface-treated layer formed on at least one of the drum side and the deposited side of the base copper layer.

9. The electrolytic copper foil of claim 8, wherein the at least one surface-treated layer comprises an anti-corrosion layer.

10. The electrolytic copper foil of claim 8, wherein the at least one surface-treated layer comprises a nodule treated layer.

11. The electrolytic copper foil of claim 10, wherein the at least one surface-treated layer further comprises at least one sub-layer formed on the nodule treated layer; and the at least one sub-layer is selected from the group consisting of: a copper covering layer, a nickel layer, a zinc layer, a chromium layer, and a silane coupling layer.

12. The electrolytic copper foil of claim 8, wherein the at least one surface-treated layer comprises a first surface-treated layer and a second surface-treated layer, which are respectively formed on the drum side and the deposited side of the base copper layer.

13. The electrolytic copper foil of claim 3, wherein the base copper layer has a drum side and a deposited side opposite the drum side, and the electrolytic copper foil further comprises at least one surface-treated layer formed on at least one of the drum side and the deposited side of the base copper layer.

14. The electrolytic copper foil of claim 13, wherein the at least one surface-treated layer comprises an anti-corrosion layer.

15. The electrolytic copper foil of claim 13, wherein the at least one surface-treated layer comprises a nodule treated layer.

16. The electrolytic copper foil of claim 15, wherein the at least one surface-treated layer further comprises at least one sub-layer formed on the nodule treated layer; and the at least one sub-layer is selected from the group consisting of: a copper covering layer, a nickel layer, a zinc layer, a chromium layer, and a silane coupling layer.

17. An electrode for a lithium ion battery comprising the electrolytic copper foil of claim 1, at least one binder, and at least one active substance.

18. A copper-clad laminate comprising the electrolytic copper foil of claim 1 and a resin substrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic perspective view of making an electrolytic copper foil of Example 1.

(2) FIG. 2 is a schematic side view of the electrolytic copper foil of Example 1.

(3) FIG. 3 is a schematic perspective view of making an electrolytic copper foil of Example 10.

(4) FIG. 4A is a schematic side view of the electrolytic copper foil of Example 10.

(5) FIG. 4B is a schematic side view of the electrolytic copper foil of Example 14.

DETAILED DESCRIPTION OF THE DISCLOSURE

(6) Hereinafter, one skilled in the art can easily realize the advantages and effects of the instant disclosure from the following examples. Therefore, it should be understood that the descriptions proposed herein are just preferable examples for the purpose of illustrations only, not intended to limit the scope of the disclosure. Various modifications and variations could be made in order to practice or apply the instant disclosure without departing from the spirit and scope of the disclosure.

(7) (Electrolytic Copper Foil)

Examples 1 to 9

(8) Examples 1 to 9 used the manufacturing apparatus as shown in FIG. 1, and were sequentially subjected to similar processes such as an electrodeposition step and a surface treatment step to obtain the electrolytic copper foils of Examples 1 to 9. The main differences among Examples 1 to 9 were the composition of the electrolyte solutions and the grain size number of the surface of the cathode drums.

(9) With reference to FIG. 1, the manufacturing apparatus for electrolytic copper foil 40 comprised an electrodeposition equipment 10, a series of guide rollers 20 and a surface treatment equipment 30. The electrodeposition equipment 10 comprised a cathode drum 11, an anode plate 12, a copper electrolyte solution 13 and a feed pipe 14. The cathode drum 11 was rotatable and the anode plate 12 was set below the cathode drum 11 and surrounded the lower half of the cathode drum 11. A space existed between the cathode drum 11 and the anode plate 12 to allow the copper electrolyte solution 13 to be introduced through the feed pipe 14. The surface treatment equipment 30 comprised an anti-corrosion treatment tank 31 and two sets of the first electrode plates 311a and 311b disposed therein. The series of guide rollers 20 comprised a first guide roller 211, a second guide roller 212, a third guide roller 213, and a set of an air knife 22 and a take-up roller 23. The series of guide rollers 22 were used for transporting a bare copper foil, a surface-treated copper foil and the product, and finally the obtained electrolytic copper foil 40 was wound on the take-up roller 23.

(10) The methods for producing the electrolytic copper foils 40 of Examples 1 to 9 with the manufacturing apparatus as shown in FIG. 1 were described as follows.

(11) First, the copper electrolyte solution 13 was prepared for the electrodeposition step, and the composition therein was as follows.

(12) 1. Essential solution:

(13) (1) copper sulfate (CuSO.sub.45H.sub.2O): 315 g/L; and

(14) (2) sulfuric acid: 95 g/L.

(15) 2. Additives:

(16) (1) chloride ion (derived from HCl, which was purchased from RCI Labscan Ltd.): 35 mg/L;

(17) (2) lead ion (Pb.sup.2+): 5 ppm;

(18) (3) PVP: 2.5 mg/L to 5.0 mg/L; and

(19) (4) UPS: 2.5 mg/L.

(20) Among them, the content ratios of the leveler (i.e. PVP) and the accelerator (i.e. UPS) in the copper electrolyte solution 13 for producing the electrolytic copper foils 40 of Examples 1 to 9 were listed in Table 1. Moreover, the grain size numbers of the cathode drums 11 for producing the electrolytic copper foils 40 of Examples 1 to 9 were also listed in Table 1.

(21) In the electrodeposition step, the copper electrolyte solution 13 was controlled at the temperature of 52 C. A current with a current density of 40 A/dm.sup.2 flowed between the cathode drum 11 and the anode plate 12 to make copper ions in the copper electrolyte solution 13 electrodeposited on the surface of the cathode drum 11 to form the bare copper foil. Subsequently, the bare copper foil was peeled off from the cathode drum 11 and guided to the first guide roller 211.

(22) First Surface Treatment

(23) Subsequently, the bare copper foil was transported to the surface treatment equipment 30 through the first guide roller 211 to undergo a first surface treatment. The bare copper foil was immersed in the anti-corrosion treatment tank 31, which was full of a chromate solution, and two surface-treated layers 42 were respectively attached on both of the surfaces of the bare copper foil through an electrodeposition step by using the two sets of the first electrode plates 311a and 311b.

(24) The composition of the chromate solution and the manufacturing parameters of the first surface treatment were listed below.

(25) 1. The composition of the chromate solution: chromic acid (CrO.sub.3): 1.5 g/L.

(26) 2. The manufacturing parameters:

(27) (1) temperature of the chromate solution: 25 C.;

(28) (2) current density: 0.5 A/dm.sup.2; and

(29) (3) duration of treatment: 2 seconds.

(30) After completion of the first surface treatment, the bare copper foil which has been processed with the anti-corrosion treatment was guided to the second guide roller 212 and then was dried by the air knife 22. After that, the foresaid copper foil was guided to the take-up roller 23 through the third guide roller 213, so the foresaid copper foil was wound to obtain the electrolytic copper foil 40.

(31) According to the foresaid process, the electrolytic copper foils of Examples 1 to 9 were respectively obtained. With reference to FIG. 2, the electrolytic copper foil 40 of each Example comprised a base copper layer 41 (i.e. the bare copper foil was not treated with the anti-corrosion treatment) and two surface-treated layers 42. The base copper layer 41 comprised a deposited side 411 and a drum side 412 opposite the deposited side 411. The surface-treated layers 42 comprised a first surface-treated layer 42a (i.e. first chromium layer) and a second surface-treated layer 42b (i.e. second chromium layer). The first surface-treated layer 42a directly covered the deposited side 411 of the base copper layer 41, and the second surface-treated layer 42b directly covered the drum side 412 of the base copper layer 41.

Comparative Examples 1 to 4

(32) Electrolytic copper foils of Comparative Examples 1 to 4 were used as the controls of the electrolytic copper foils of Examples 1 to 9, which were produced by similar process used to manufacture the electrolytic copper foils of Examples 1 to 9. The main differences between the processes of Examples and Comparative Examples were that the content ratios between the leveler and the accelerator in the copper electrolyte solution (PVP: 2.0 mg/L to 8.25 mg/L and UPS: 2.5 mg/L) and the grain size number of the surface of the cathode drums used. The above parameters were all listed in Table 1. In addition, the structures of the electrolytic copper foils of Comparative Examples 1 to 4 were as shown in FIG. 2.

Examples 10 to 14

(33) Examples 10 to 14 used the manufacturing apparatus as shown in FIG. 3, and were sequentially subjected to the substantially same processes such as an electrodeposition step and multiple surface treatment steps to obtain the electrolytic copper foils of Examples 10 to 14. The main difference among Examples 10 to 14 were the parameters of the multiple surface treatment steps and the desired surfaces to be treated.

(34) With reference to FIG. 3, the manufacturing apparatus for electrolytic copper foil 40 comprised an electrodeposition equipment 10, a series of guide rollers 20 and a surface treatment equipment 30. The electrodeposition equipment 10 comprised a cathode drum 11, an anode plate 12, a copper electrolyte solution 13 and a feed pipe 14. The anode plate 12 was set below the cathode drum 11 and surrounded the lower half of the cathode drum 11. A space existed between the cathode drum 11 and the anode plate 12 to allow the copper electrolyte solution 13 to be introduced through the feed pipe 14. The surface treatment equipment 30 comprised a pickling treatment tank 32, a nodule treatment tank 33 and a set of the second electrode plates 331 disposed therein, a copper covering treatment tank 34 and a set of the third electrode plates 341 disposed therein, a nickel plating tank 35 and a set of the fourth electrode plates 351 disposed therein, a zinc plating tank 36 and two sets of the fifth electrode plates 361a and 361b disposed therein, a chromium plating tank 37 and two sets of the sixth electrode plates 371a and 371b disposed therein, a silane coupling agent spraying equipment 38 and a drier 39. The series of guide rollers 20 comprised a first guide roller 211, a second guide roller 212, a third guide roller 213, a fourth guide roller 214, a fifth guide roller 215, a sixth guide roller 216, a seventh guide roller 217 and a take-up roller 23. The series of guide rollers 22 were used for transporting a bare copper foil, a copper foil which was subjected to each surface treatment, and the product, and finally the electrolytic copper foil 40 was obtained by being wound on the take-up roller 23.

(35) The methods for producing the electrolytic copper foils 40 of Examples 10 to 14 with the manufacturing apparatus as shown in FIG. 3 were described as follows.

(36) Electrodeposition Step

(37) Examples 10 to 14 were all subjected to the same electrodeposition step. In the electrodeposition step, the copper electrolyte solution 13 was controlled at the temperature of 52 C., and a current with a current density of 40 A/dm.sup.2 flowed between the cathode drum 11 and the anode plate 12 to make copper ions in the copper electrolyte solution 13 electrodeposited on the surface of the cathode drum 11 to form the bare copper foil. Subsequently, the bare copper foil was peeled off from the cathode drum 11 and guided to the first guide roller 211. The composition of foresaid copper electrolyte solution 13 was identical to the copper electrolyte solution used for Example 7, and the surface of foresaid cathode drum 11 also had the same grain size number with the cathode drum used for Example 7.

(38) Surface Treatment Steps

(39) Since the surface treatment steps for Examples 10 to 14 had some difference, the surface treatment steps employed in the Examples were each described below.

(40) Electrolytic Copper Foil of Example 10: Obtained Through a Second Surface Treatment

(41) The second surface treatment included the following seven surface treatment procedures, and those parameters in each surface treatment procedure were as follows.

(42) I. Pickling Treatment:

(43) The bare copper foil of Example 10 was transported to the pickling tank 32 through the first guide roller 211, and foresaid bare copper foil was immersed into a pickling solution to clean both sides of the bare copper foil. The composition of the pickling solution and the concerned manufacturing parameters were listed below.

(44) 1. The composition of the pickling solution:

(45) (1) copper sulfate (CuSO.sub.45H.sub.2O): 200 g/L; and

(46) (2) sulfuric acid: 100 g/L.

(47) 2. The manufacturing parameters:

(48) (1) temperature of the pickling solution: 25 C.; and

(49) (2) duration of treatment: 5 seconds.

(50) After a completion of the above procedure, the bare copper foil which has been subjected to the pickling treatment was guided to the second guide roller 212 and then was transported to the nodule treatment tank 33. With reference to FIG. 4A, in this Example, the bare copper foil after the pickling treatment corresponded to the base copper foil 41 of the instant disclosure, which comprised a deposited side 411 and a drum side 412 opposite to the deposited side 411.

(51) II. Nodule Treatment:

(52) The bare copper foil after the pickling treatment was immersed into a roughening solution of the nodule treatment tank 33, and the deposited side 411 was subjected to an electrodeposition process by the second electrode plates 331 to form a nodule treated layer 421 attached thereon. The composition of the roughening solution and the concerned manufacturing parameters were listed below.

(53) 1. The composition of the roughening solution:

(54) (1) copper sulfate (CuSO.sub.45H.sub.2O): 200 g/L; and

(55) (2) sulfuric acid: 100 g/L.

(56) 2. The manufacturing parameters:

(57) (1) temperature of the roughening solution: 25 C.;

(58) (2) current density: 40 A/dm.sup.2; and

(59) (3) duration of treatment: 5 seconds.

(60) After a completion of the above procedure, the copper foil which has been subjected to the nodule treatment was guided to the third guide roller 213 and then was transported to the copper covering treatment tank 34.

(61) III. Copper Covering Treatment:

(62) The copper foil after the nodule treatment was immersed into a copper covering solution of the copper covering treatment tank 34, and the nodule treated layer 421 was subjected to an electrodeposition process by the third electrode plates 341 to form a copper covering layer 422 attached thereon. The composition of the copper covering solution and the concerned manufacturing parameters were listed below.

(63) 1. The composition of the copper covering solution:

(64) (1) copper sulfate (CuSO.sub.45H.sub.2O): 320 g/L; and

(65) (2) sulfuric acid: 100 g/L.

(66) 2. The manufacturing parameters:

(67) (1) temperature of the copper covering solution: 40 C.;

(68) (2) current density: 20 A/dm.sup.2; and

(69) (3) duration of treatment: 5 seconds.

(70) After a completion of the above procedure, the copper foil which has been subjected to the copper covering treatment was guided to the fourth guide roller 214 and then was transported to the nickel plating tank 35.

(71) IV. Nickel Plating:

(72) The copper foil after the copper covering treatment was immersed into a nickel electrolyte solution of the nickel plating tank 35, and the copper covering layer 422 was subjected to an electrodeposition process by the fourth electrode plates 351 to form a nickel layer 423 attached thereon. The composition of the nickel electrolyte solution and the concerned manufacturing parameters were listed below.

(73) 1. The composition of the nickel electrolyte solution:

(74) (1) nickel(II) sulfate (NiSO.sub.46H.sub.2O): 170 g/L to 200 g/L; and

(75) (2) boric acid: 20 g/L to 40 g/L.

(76) 2. The manufacturing parameters:

(77) (1) temperature of the nickel electrolyte solution: 20 C.;

(78) (2) current density: 0.5 A/dm.sup.2; and

(79) (3) duration of treatment: 10 seconds.

(80) After a completion of the above procedure, the copper foil which has been subjected to the nickel plating was guided to the fifth guide roller 215 and then was transported to the zinc plating tank 36.

(81) V. Zinc Plating:

(82) The copper foil after the nickel plating was immersed into a zinc electrolyte solution of the zinc plating tank 36, and the nickel layer 423 and the drum side 412 were respectively subjected to an electrodeposition process by the two sets of the fifth electrode plates 361a and 361b to form a first zinc layer 424a attached on the nickel layer 423 and a second zinc layer 424b attached on the drum side 412. The composition of the zinc electrolyte solution and the concerned manufacturing parameters were listed below.

(83) 1. The composition of the zinc electrolyte solution:

(84) (1) zinc sulfate (ZnSO.sub.47H.sub.2O): 5 g/L to 15 g/L; and

(85) (2) ammonium trioxovanadate(V): 0.1 g/L to 0.4 g/L.

(86) 2. The manufacturing parameters:

(87) (1) temperature of the zinc electrolyte solution: 20 C.;

(88) (2) current density: 0.5 A/dm.sup.2; and

(89) (3) duration of treatment: 10 seconds.

(90) After a completion of the above procedure, the copper foil which has been subjected to the zinc plating was guided to the sixth guide roller 216 and then was transported to the chromium plating tank 37.

(91) VI. Chromium Plating:

(92) The copper foil after the zinc plating was immersed into a chromium electrolyte solution of the chromium plating tank 37, and the first zinc layer 424a and the second zinc layer 424b were respectively subjected to an electrodeposition process by the two sets of the sixth electrode plates 371a and 371b to form a first chromium layer 425a attached on the first zinc layer 424a and a second chromium layer 425b attached on the second zinc layer 424b. The composition of the chromium electrolyte solution and the concerned manufacturing parameters were listed below.

(93) 1. The composition of the chromium electrolyte solution:

(94) (1) chromic acid (CrO.sub.3): 1.6 g/L to 1.8 g/L.

(95) 2. The manufacturing parameters:

(96) (1) temperature of the chromium electrolyte solution: 45 C.;

(97) (2) current density: 2.7 A/dm.sup.2; and

(98) (3) duration of treatment: 10 seconds.

(99) After a completion of the above procedure, the copper foil which has been subjected to the chromium plating was guided to the seventh guide roller 217.

(100) VII. Silane Coupling Treatment:

(101) On the way that the copper foil after the chromium plating was introduced to the take-up roller 23 through the seventh guide roller 217, a solution comprising a silane coupling agent was sprayed onto the surface of the first chromium layer 425a by the silane coupling agent spraying equipment 38 to form a silane coupling layer 426 attached on the first chromium layer 425a. The composition of the solution comprising the silane coupling agent and the concerned manufacturing parameters were listed below.

(102) 1. The composition of the solution comprising the silane coupling agent:

(103) (1) 3-glycidoxypropyl trimethoxysilane (product name: KBM 403): an aqueous solution of 0.25 wt %.

(104) 2. The manufacturing parameters:

(105) (1) duration of treatment: 10 seconds.

(106) After a completion of the second surface treatment, the copper foil which has been subjected to the silane coupling treatment was guided to the drier 39. After that, the foresaid copper foil was guided to the take-up roller 23, so the foresaid copper foil was wound to obtain the electrolytic copper foil 40.

(107) Electrolytic Copper Foil of Example 11: Obtained Through a Third Surface Treatment

(108) The process used to manufacture the electrolytic copper foil of Example 11 was similar to the process used to manufacture the electrolytic copper foil of Example 10 except that the second surface treatment used in Example 10 was replaced with the third surface treatment used in Example 11. The difference between the second and third surface treatments was the respective current density in the nodule treatment procedures; wherein the current density in the nodule treatment of the third surface treatment was 35 A/dm.sup.2.

(109) Electrolytic Copper Foil of Example 12: Obtained Through a Fourth Surface Treatment

(110) The process used to manufacture the electrolytic copper foil of Example 12 was similar to the process used to manufacture the electrolytic copper foil of Example 10 except that the second surface treatment used in Example 10 was replaced with the fourth surface treatment used in Example 12. The difference between the second and fourth surface treatments was the respective current density in the nodule treatment procedures; wherein the current density in the nodule treatment of the fourth surface treatment was 20 A/dm.sup.2.

(111) Electrolytic Copper Foil of Example 13: Obtained Through a Fifth Surface Treatment

(112) The process used to manufacture the electrolytic copper foil of Example 13 was similar to the process used to manufacture the electrolytic copper foil of Example 10 except that the second surface treatment used in Example 10 was replaced with the fifth surface treatment used in Example 13. The difference between the second and fifth surface treatments was the respective current density in the nodule treatment procedures; wherein the current density in the nodule treatment of the fifth surface treatment was 55 A/dm.sup.2.

(113) Electrolytic Copper Foil of Example 14: Obtained Through a Sixth Surface Treatment

(114) The process used to manufacture the electrolytic copper foil of Example 14 was similar to the process used to manufacture the electrolytic copper foil of Example 10 except that the second surface treatment used in Example 10 was replaced with the sixth surface treatment used in Example 14. The differences between the second and sixth surface treatments were the respective current density in the nodule treatment procedures and the surface to be subjected to the nodule treatment procedures; wherein the current density in the nodule treatment of the sixth surface treatment was 30 A/dm.sup.2, and the surface subjected to the nodule treatment procedure of the sixth surface treatment was the drum side 412. Therefore, the nickel layer 423 and the deposited side 411 were respectively subjected to the zinc plating of the sixth surface treatment.

(115) According to the foresaid process, the electrolytic copper foils of Examples 10 to 14 were respectively obtained.

(116) With reference to FIG. 4A, the electrolytic copper foil 40 of Examples 10 to 13 respectively comprised a base copper layer 41 and a first surface-treated layer 42a and a second surface-treated layer 42b. The base copper layer 41 comprised a deposited side 411 and a drum side 412 opposite to the deposited side 411. The surface-treated layer 42a was deposited on the deposited side 411 of the base copper layer 41, and comprised the nodule treated layer 421 on the deposited side 411, the copper covering layer 422, the nickel layer 423, the first zinc layer 424a, the first chromium layer 425a and the silane coupling layer 426 in order. The second surface-treated layer 42b was deposited on the drum side 412 of the base copper layer 41, and comprised the second zinc layer 424b on the drum side 412 and the second chromium layer 425b in order.

(117) In addition, with reference to FIG. 4B, the electrolytic copper foil 40 of Example 14 comprised a base copper layer 41 and a first surface-treated layer 42a and a second surface-treated layer 42b. The base copper layer 41 comprised a deposited side 411 and a drum side 412 opposite to the deposited side 411. The surface-treated layer 42a was deposited on the drum side 412 of the base copper layer 41, and comprised the nodule treated layer 421 on the drum side 412, the copper covering layer 422, the nickel layer 423, the first zinc layer 424a, the first chromium layer 425a and the silane coupling layer 426 in order. The second surface-treated layer 42b was deposited on the deposited side 411 of the base copper layer 41, and comprised the second zinc layer 424b and the second chromium layer 425b in order.

(118) Analysis 1: Weight and Average Thickness Per Unit Area of the Electrolytic Copper Foil

(119) Each of the electrolytic copper foils of Examples 1 to 14 (expressed as E1 to E14) and Comparative Examples 1 to 4 (expressed as C1 to C4) was cut into a sample of 100 mm in length and width, and each sample was weighed by the microbalance AG-204 (purchased from Mettler Toledo International Inc.); further, the measured weight value of each sample was divided by its area and then the unit was converted to g/m.sup.2 to obtain the weight per unit area of each of the electrolytic copper foils.

(120) Moreover, according to the standard test method of IPC-TM-650 2.4.18, the density of each of the electrolytic copper foils was about 8.909*10.sup.6 g/m.sup.3. Then, an average thickness of each of the electrolytic copper foils of E1 to E14 and C1 to C4 was respectively calculated by the following formula (I). Therefore, the weight per unit area and average thickness of each of the electrolytic copper foils of E1 to E14 and C1 to C4 were listed in Table 1.
Average thickness of the electrolytic copper foil (m)=weight per unit area/density of the electrolytic copper foil(I)

(121) Analysis 2: Charpy Impact Strength of the Electrolytic Copper Foil

(122) Each of the electrolytic copper foils of E1 to E14 and C1 to C4 was cut into a sample without a notch.

(123) The sample was vertically adhered to the side wall of the stage of the impact tester with three layers of a tape; then, a pendulum of the impact tester was dropped from a specific height to make an impact on the center of the sample. The Charpy impact strength of the sample referred to an amount of energy absorbed per unit area right before fracture. The results were also listed in Table 1. The relevant test conditions were also recorded as follows.

(124) 1. Impact tester: No. 611 manufactured by Toyo Seiki Seisaku-sho, Ltd;

(125) 2. tape: BOPP Packing Tape, 18 mm in width, purchased from Yem Chio Co., Ltd;

(126) 3. size of each sample: 83 mm in length15 mm in width;

(127) 4. temperature: 255 C.;

(128) 5. mass of the pendulum (W): 0.938 kg;

(129) 6. length from the gravity center of the pendulum to the center of rotation (R): 0.20157 m; and

(130) 7. angle of fall (a): 125.58.

(131) Analysis 3: Wrinkle Test of the Electrolytic Copper Foil

(132) The surfaces of the electrolytic copper foils of E1 to E14 and C1 to C4 were each inspected whether wrinkles occurred after using a slitter machine to apply a tension.

(133) Each sample with a width of 1380 mm was fed between two horizontal fixed rolls of the slitter machine (distance: 700 mm), and then the two horizontal fixed rolls were rotated to apply different tensions to the sample. When applying a tension of 10 kg, the surface of the sample was visually observed for wrinkles. As the inspecting results listed in Table 1, no wrinkle on the surface meant pass, and any wrinkle on the surface meant fail.

(134) TABLE-US-00001 TABLE 1 Grain size number Content of the ratio of the surface of Weight Charpy leveler to the per unit Average impact Example the cathode area thickness strength Wrinkle No. accelerator drum (g/m.sup.2) (m) (J/mm.sup.2) test E1 2.0 7.5 53.5 6.0 3.8 Pass E2 1.4 7.5 53.5 6.0 5.3 Pass E3 1.0 7.5 53.5 6.0 0.5 Pass E4 1.0 7 53.5 6.0 0.4 Pass E5 1.4 10 53.5 6.0 5.8 Pass E6 1.3 8 53.5 6.0 2.4 Pass E7 1.1 7.5 53.5 6.0 1.2 Pass E8 1.1 7.5 24.1 2.7 1.3 Pass E9 1.1 7.5 343.0 38.5 1.3 Pass E10 1.1 7.5 106.9 12.0 1.3 Pass E11 1.1 7.5 106.9 12.0 1.3 Pass E12 1.1 7.5 106.9 12.0 1.3 Pass E13 1.1 7.5 106.9 12.0 1.2 Pass E14 1.1 7.5 106.9 12.0 1.3 Pass C1 3.3 7.5 53.5 6.0 0.2 Fail C2 0.8 7.5 53.5 6.0 0.3 Fail C3 1.0 6 53.5 6.0 0.2 Fail C4 1.7 10 53.5 6.0 7.2 Fail

(135) Discussion on Characteristics of the Electrolytic Copper Foils

(136) From the analytical results of Table 1, it demonstrated that the electrolytic copper foils of E1 to E14 with a specific appropriate range of the Charpy impact strength had an improved wrinkle resistance to avoid the occurrence of wrinkles on the surface of the electrolytic copper foils, and then the production yield thereof will be improved. Regardless of the thickness of the electrolytic copper foils, for example, the thicker electrolytic copper foils such as the electrolytic copper foils of E9 to E14 or the thinner electrolytic copper foil such as the electrolytic copper foil of E8, the occurrence of wrinkles on the surface of the electrolytic copper foils could be all mitigated and even avoided. In contrast, referring to the electrolytic copper foils of C1 to C4, which did not control the Charpy impact strength thereof within the specific appropriate range, the electrolytic copper foils of C1 to C4 still had wrinkles, and then were disadvantageous for subsequent applications.

(137) Analysis 4: Surface Profile of the Electrolytic Copper Foil

(138) The electrolytic copper foils of E1 to E14 and C1 to C4 were further analyzed for the surface profile of the electrolytic copper foils by a surface roughness meter. According to the standard method of JIS B 0601-2013, a Rq and a RSm of the first surface-treated layer of the electrolytic copper foils of E1 to E9 and C1 to C4 were measured and listed in Table 2, and a Rq and a RSm of the first surface-treated layer of the electrolytic copper foils of E10 to E14 were measured and listed in Table 3. The relevant test conditions were also recorded as follows.

(139) 1. surface roughness meter: SE600 model produced by Kosaka Laboratory Ltd.;

(140) 2. radius of stylus tip: 2 m;

(141) 3. angle of stylus tip: 90;

(142) 4. scan speed: 0.5 mm/sec;

(143) 5. cut-off of the filter: 0.8 mm (c) and 2.5 m (s); and

(144) 6. evaluation length: 4 mm.

(145) In addition, an aspect ratio of surface profile of the electrolytic copper foils of E1 and E14 and C1 to C4 could be calculated according to the obtained RSm and Rq, and the following formula (II). The results were also listed in Tables 2 and 3.
Aspect ratio of surface profile=RSm (m)/Rq (m)(II)

(146) (Electrodes for a Lithium Ion Battery)

(147) A negative electrode slurry was coated on the first surface-treated layer of each of the electrolytic copper foils of E1 to E9 and C1 to C4 respectively. After a completion of coating, the coated electrolytic copper foils were dried and then rolled by a pressing machine to obtain negative electrodes for a lithium ion battery, which were electrodes of Examples 1-A to 9-A (expressed as E1-A to E9-A) and Comparative Examples 1-A to 4-A (expressed as C1-A to C4-A). The negative electrode slurry was composed of 100 parts by weight of a negative electrode active material and 60 parts by weight of 1-Methyl-2-pyrrolidone (NMP). The composition of the negative electrode active material and the concerned manufacturing parameters were listed below.

(148) 1. The composition of the negative electrode active material: (based on the total weight of the negative electrode active material)

(149) (1) mesophase graphite powder (MGP): 93.9 wt %;

(150) (2) conductive additive: 1 wt % of conductive carbon black (Super P);

(151) (3) solvent-based binder: 5 wt % of poly-1,1-difluoroethene (PVDF 6020); and

(152) (4) oxalic acid: 0.1 wt %.

(153) 2. The manufacturing parameters:

(154) (1) coating speed: 5 m/min;

(155) (2) coating thickness: 200 m;

(156) (3) drying temperature: 160 C.;

(157) (4) material, size and hardness of a roller of the pressing machine: made from high-carbon chromium bearing steel (SUJ2); a diameter of 250 mm; and a Rockwell hardness (HRC) of 62 to 65 degrees; and

(158) (5) speed and pressure of rolling: a rate of 1 m/min; a pressure of 3000 pound per square inch (psi).

(159) Analysis 5: Analyzing the Peel Strength of the Electrodes (Peel Strength Test I)

(160) Each of the electrodes of E1-A to E9-A and C1-A to C4-A was cut into a sample. Both surfaces of the sample respectively adhered to a tape and was analyzed for a peel strength between the first surface-treated layer of the electrolytic copper foil and the negative electrode active material of each sample by a universal testing machine, and the analytical results were shown in Table 2. In the case that the first surface-treated layer of the electrolytic copper foil and the negative electrode active material were not separated, the result was recorded as pass, but in the case that the first surface-treated layer of the electrolytic copper foil and the negative electrode active material were separated, the result was recorded as fail. The relevant test conditions were recorded as follows.

(161) 1. universal testing machine: TKS-20N manufactured by IMADA CO., LTD.;

(162) 2. sample size: 100 mm50 mm;

(163) 3. tape: 810 D manufactured 3M Company;

(164) 4. performing temperature: 15 C. to 35 C.;

(165) 5. peeling angle: 90; and

(166) 6. peeling speed: 50 mm/min.

(167) TABLE-US-00002 TABLE 2 Electrolytic Charpy copper impact Aspect ratio Peel foil No./ strength of surface RSm Rq strength Electrode No. (J/mm.sup.2) profile (m) (m) test I E1/ 3.8 467 126 0.27 Pass E1-A E2/ 5.3 506 167 0.33 Pass E2-A E3/ 0.5 411 308 0.75 Pass E3-A E4/ 0.4 345 283 0.82 Pass E4-A E5/ 5.8 75 18 0.24 Pass E5-A E6/ 2.4 67 26 0.39 Pass E6-A E7/ 1.2 295 174 0.59 Pass E7-A E8/ 1.3 273 169 0.62 Pass E8-A E9/ 1.3 273 172 0.63 Pass E9-A C1/ 0.2 105 21 0.20 Fail C1-A C2/ 0.3 413 417 1.01 Fail C2-A C3/ 0.2 662 523 0.79 Fail C3-A C4/ 7.2 41 9 0.22 Fail C4-A

(168) As the analytical results shown in Tables 1 and 2, since the electrolytic copper foils of E1 to E9 were free from wrinkles, the concerned electrodes of E1-A to E9-A could pass the peel strength test I; that is, it demonstrated that the electrodes comprising the electrolytic copper foils of E1 to E9 indeed had a better adhesion, which was advantageous for the electrodes for a lithium ion battery to have a longer battery life.

(169) <Copper-Clad Laminate>

(170) Each of the electrolytic copper foils of E10 to E14 faced a resin substrate, which was the first surface-treated layer thereof and then was subjected to a lamination step. After that, 10 mm-wide circuits were respectively formed on the electrolytic copper foils of E10 to E14 to obtain copper-clad laminates of Examples 10-A to 14-A (expressed as E10-A to E14-A). The concerned manufacturing parameters were recorded as follows.

(171) 1. resin substrate: a prepreg comprising a dielectric thermoset resin layer (CCP-609G manufactured from Chang Chun Plastics Co., Ltd.); and

(172) 2. temperature, pressure and duration of the lamination step: 200 C., 400 psi, and 120 min.

(173) Analysis 6: Analyzing the Peel Strength of the Copper-Clad Laminate (Peel Strength Test II)

(174) According to a standard method of IPC-TM-650 2.4.8.5, the peel strength of each of the copper-clad laminates of E10-A to E14-A was analyzed. The peel strength referred to the adhesion between the electrolytic copper foil and the substrate. The analytical results were shown in Table 3. In the case that the peel strength of the copper-clad laminate was more than 1.0 kg/cm, the result was represented by ; in the case that the peel strength of the copper-clad laminate was equal to or more than 0.6 kg/cm and equal to or smaller than 1.0 kg/cm, the result was represented by ; and in the case that the peel strength of the copper-clad laminate was equal to or more than 0.1 kg/cm and smaller than 0.6 kg/cm, the result was represented by .

(175) TABLE-US-00003 TABLE 3 Charpy Aspect Electrolytic impact ratio of Peel copper foil No./ strength surface RSm Rq strength test CCL No. (J/mm.sup.2) profile (m) (m) II E10/ 1.3 37 22 0.59 E10-A E11/ 1.3 58 72 1.25 E11-A E12/ 1.3 14 19 1.34 E12-A E13/ 1.2 693 97 0.14 E13-A E14/ 1.3 363 58 0.16 E14-A

(176) As the analytical results shown in Tables 1 and 3, since the electrolytic copper foils of E10 to E14 were free from wrinkles, all of the concerned copper-clad laminates could pass the peel strength test II; that is, it demonstrated that the copper-clad laminates comprising the electrolytic copper foils of E10 to E14 indeed had a good adhesion to the dielectric materials of the resin substrate.

(177) Furthermore, from the comparison results of the peel strengths of Examples 10-A to 14-A, since the aspect ratios of surface profile of the electrolytic copper foils 10, 11 and 14 were within the range of 30 to 400, and even the aspect ratios of surface profile of the electrolytic copper foils 10 and 11 were within the range of 35 to 100, the resulting copper-clad laminates of Examples 10-A, 11-A and 14-A had a higher peel strength. It could be explained that when the surface of an electrolytic copper foil has an aspect ratio of surface profile within the above range, the surface can provide a better anchoring effect, thereby providing a higher adhesion of the surface of the electrolytic copper foil to the dielectric materials. On the one hand, if the aspect ratio of surface profile was too low (e.g. 14), said surface may have a deeper valley (i.e., Rq was too high), thereby causing the attached material such as the resin substrate to fail to fill the valley. As a result, an improvement in adhesion would be less obvious. On the other hand, if the aspect ratio of surface profile was too high ((e.g. 693), the degree of unevenness of the surface was shallower (i.e., Rq was too small), and an improvement in adhesion was thereby also less obvious.

(178) Based on the above results in Tables 1 to 3, the technical means of the instant disclosure can effectively reduce or even avoid the occurrence of wrinkles on the surface of the electrolytic copper foils by controlling the range of the Charpy impact strength of the electrolytic copper foils, thereby realizing an improvement in the yield of making the electrolytic copper foil. Moreover, the technical means of the instant disclosure can provide the electrolytic copper foil a better adhesion in subsequent applications, thereby prolonging the life of the resulting product.

(179) Even though numerous characteristics and advantages of the instant disclosure have been set forth in the foregoing description, together with details of the structure and features of the disclosure, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the disclosure to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.