CN104805478A - Electrolytic copper foil for negative current collector and manufacturing method thereof - Google Patents
Electrolytic copper foil for negative current collector and manufacturing method thereof Download PDFInfo
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- CN104805478A CN104805478A CN201410043978.6A CN201410043978A CN104805478A CN 104805478 A CN104805478 A CN 104805478A CN 201410043978 A CN201410043978 A CN 201410043978A CN 104805478 A CN104805478 A CN 104805478A
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Abstract
The invention discloses electrolytic copper foil for a negative current collector and a manufacturing method thereof. The manufacturing method comprises the following steps of forming electrolytic copper foil on the surface of a negative pole by a copper sulphate electrolyte electrolysis method, and separating the electrolytic copper foil from the surface of the negative pole. The copper sulphate electrolyte comprises a polyether compound, sulfonate of active organic sulfide and chlorine. The electrolytic copper foil obtained by the manufacturing method can be used in the field of secondary cells and does not deform or fracture in charging and discharging. The electrolytic copper foil obtained by the manufacturing method has good elastic energy and toughness, does not easily deform or fracture after repeated charging and discharging of a cell and obviously improves charging-discharging cycle characteristics.
Description
Technical field
The present invention relates to a kind of electrolytic copper foil, refer to a kind of the negative electrode collector electrolytic copper foil with elastomeric property and high tenacity and the manufacture method thereof that are applied to lithium secondary battery especially.
Background technology
Press, lithium secondary battery is used in portable type electronic product such as intelligent mobile phone, panel computer, music player, digital camera etc. as its propulsion source more, along with user is for the miniaturization of portable type electronic product and high mechanization demand, the characteristic of lithium secondary battery also relative being required promotes, and is even more important with the cycle index of electrical capacity, charge velocities and discharge and recharge in many characteristics of lithium secondary battery.
For the purpose of high-capacitance, the positive active development of current industry has the negative material of the charge/discharge capacity of the theoretical capacity significantly surmounting carbon material, using the negative electrode active material as lithium secondary battery, wherein more attract attention so that alloyed metal (AM) material can be carried out with lithium (Li) containing silicon (Si) with tin (Sn) etc. again.
But in the electrode of this type of lithium-ion secondary cell, active substance (such as silicon) can cause volumetric expansion about 4 times because absorbing storage lithium ion in process of charging, and releases lithium ion and shrink in time discharging.So repeatedly carry out discharge and recharge, the volume of electroactive substance layer also can expand thereupon and shrink, and causes active substance micronization and peels off from current collector.In addition, because electroactive substance layer is closely then in current collector, therefore the volumetric expansion of electroactive substance layer, contraction can to current collector produce very large stress make current collector generation fold, also may cause the problems such as the Copper Foil of current collector deforms, fracture when more serious.
In addition, traditional lithium secondary battery when reaching the target of rapid charge, often meet with electrical capacity declines, the electrical capacity of charge and discharge cycles reduces time ahead of time, degradation problem under battery performance.Wherein can cause the reason that battery performance declines, be considered to relevant with adaptation between Copper Foil with negative material or surface impurity on the one hand; Be then that lithium secondary battery lithium ion in time charging is acquired to negative material on the other hand, in time discharging, then disengage lithium ion.But negative material can expand when obtaining lithium ion and the meeting reinstatement when disengaging lithium ion, and the load of battery repeated charge is applied on Copper Foil and it may be made to deform, and even can rupture when situation is serious; Thus, if can peel off from negative material when Copper Foil deforms, the cycle efficiency for charge-discharge of battery is declined, and if Copper Foil occurs battery performance can be made cannot to maintain long stability when rupturing.
Therefore, the present inventor is because the copper foil for negative electrode current collector of traditional lithium secondary battery has its necessity improved really, then the design of association area and professional manufacturing experience is engaged in for many years with it, Upgrading is carried out energetically for copper foil for negative electrode current collector characteristic, under the discretion of each side's condition is considered, finally develop the present invention.
Summary of the invention
Main purpose of the present invention is, a kind of negative electrode collector electrolytic copper foil and the manufacture method thereof with elastomeric property and high tenacity are provided, the Copper Foil that method is obtained thus has good elasticity energy and toughness, even if repeatedly carry out the charging of battery and electric discharge is also less likely to occur distortion or fracture, the cycle characteristics promoting charge and discharge therefore to be shown.
For achieving the above object, the present invention is by the following technical solutions: a kind of manufacture method with the negative electrode collector electrolytic copper foil of elastomeric property and high tenacity, comprise the following steps: first, separate out formation one electrolytic copper foil with the electrolytic process of copper sulfate electrolyte in the surface of a negative electrode, wherein said copper sulfate electrolyte comprises polyether compound, the sulfonate of reactive organic sulphur compound and chlorine; Then, described electrolytic copper foil is peeled off from described negative electrode.
In one embodiment of this invention, the sulfuric acid concentration in described copper sulfate electrolyte is 70g/L ~ 100g/L, and copper concentration is 80g/L ~ 100g/L.
In one embodiment of this invention, the polyether compound concentration in described copper sulfate electrolyte is 50ppm ~ 250ppm, and the sulfonate concentration of reactive organic sulphur compound is 0.3ppm ~ 10ppm, and cl concn is 10ppm ~ 50ppm.
In one embodiment of this invention, under the electrolytic process of described copper sulfate electrolyte ties up to the electrolyte temperature of 58 DEG C ~ 62 DEG C, with 50A/dm
2~ 80A/dm
2current density carry out electrolysis.
In one embodiment of this invention, after peeling off the step of described electrolytic copper foil from described negative electrode, also comprise step further and at least one surface of described electrolytic copper foil, form a chromium anti oxidation layer with pickling process or electrolytic process.
According to above-mentioned manufacture method, the present invention separately proposes a kind of negative electrode collector electrolytic copper foil with elastomeric property and high tenacity, it is characterized in that, elasticity can be 60 ~ 100KJ/M
2, and toughness is at least greater than 1500KJ/M
2.
From the viewpoint of mechanical properties, the negative electrode collector electrolytic copper foil tensile strength under normal conditions with elastomeric property and high tenacity of the present invention is at least greater than 300N/mm
2, and unit elongation is at least greater than 10%.
Moreover have in the negative electrode collector electrolytic copper foil of elastomeric property and high tenacity of the present invention, thickness is preferably 8 μm ~ 35 μm and has at least one surface, the roughness Rz on described surface is 1.0 μm ~ 2.5 μm.
Again, have in the negative electrode collector electrolytic copper foil of elastomeric property and high tenacity of the present invention, also comprise a chromium anti oxidation layer, be formed on described surface.
And have in the negative electrode collector electrolytic copper foil of elastomeric property and high tenacity of the present invention, described chromium anti oxidation layer is a chromic salt epithelium.
The present invention at least has following beneficial effect:
Manufacture method of the present invention utilizes the copper sulfate electrolyte containing special additive (comprising polyether compound, the sulfonate of reactive organic sulphur compound and chlorine) to carry out metallide, separate out formed electrolytic copper foil can have elastomeric property and high tenacity, wherein the characteristic of elastomeric property can be improved Copper Foil and easily to deform this defect, the characteristic of high tenacity then can be improved Copper Foil and easily to rupture this another defect, therefore, the negative electrode collector that the present invention is applied in lithium secondary battery can reach the excellent effect of the charge/discharge cycle characteristics maintaining lithium secondary battery.
Above about the explanation of content of the present invention and the explanation of following embodiment in order to illustrate and to explain principle of the present invention, and provide claim of the present invention to explain further.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope photo in the precipitation face of the electrolytic copper foil of comparative example 2.
Fig. 2 is the scanning electron microscope photo with the precipitation face of the negative electrode collector electrolytic copper foil of elastomeric property and high tenacity of embodiment 1.
Fig. 3 is the stress-strain curve diagram with the negative electrode collector electrolytic copper foil drawn test gained of elastomeric property and high tenacity of embodiment 1.
Fig. 4 is the stress-strain curve diagram with the negative electrode collector electrolytic copper foil drawn test gained of elastomeric property and high tenacity of embodiment 2.
Fig. 5 is the stress-strain curve diagram with the negative electrode collector electrolytic copper foil drawn test gained of elastomeric property and high tenacity of embodiment 3.
Fig. 6 is the stress-strain curve diagram with the negative electrode collector electrolytic copper foil drawn test gained of elastomeric property and high tenacity of embodiment 4.
Fig. 7 is the stress-strain curve diagram with the negative electrode collector electrolytic copper foil drawn test gained of elastomeric property and high tenacity of embodiment 5.
Fig. 8 is the stress-strain curve diagram of the electrolytic copper foil drawn test gained of comparative example 1.
Fig. 9 is the stress-strain curve diagram of the electrolytic copper foil drawn test gained of comparative example 2.
Embodiment
The present invention is directed to lithium-ion secondary cell and propose a kind of electrolytic copper foil and manufacture method thereof that can be used as the conductor of concentrated electronics when battery discharge chemical reaction occurs, if the present invention finds that carrying out with the copper sulfate electrolyte containing special additive the electrolytic copper foil that metallide formed can have good elasticity energy and toughness, the negative electrode collector that described electrolytic copper foil is applied to lithium secondary battery can prevent from deforming because of repeated charge or rupturing, thus the charge/discharge cycle characteristics of lithium secondary battery can obtain obvious improvement.
Below will describe feature of the present invention and the technology used in the present invention means in detail, those of ordinary skill in the art can understand advantage of the present invention and effect easily by the content of this specification sheets, and under not departing from spirit of the present invention, carry out various modification and change, to implement or to apply method of the present invention.
The present invention proposes a kind of manufacture method with the negative electrode collector electrolytic copper foil of elastomeric property and high tenacity, comprise and first perform first step: separate out formation one electrolytic copper foil with the electrolytic process of copper sulfate electrolyte in the surface of a negative electrode, wherein said copper sulfate electrolyte comprises polyether compound, the sulfonate of reactive organic sulphur compound and chlorine; Perform second step more afterwards: peel off described electrolytic copper foil from described negative electrode.
In first step, the manufacture of electrolytic copper foil adopts continuous seepage mode, specifically, prior to pumping into copper sulfate electrolyte between rotating cathode and the anode (as lead anode or ru oxide anode) be oppositely arranged, then utilize electrolytic reaction to separate out copper in cathode surface, and will the electrolytic copper foil spinning negative electrode of precipitation divest continuously and batch.
In the present embodiment, the manufacture of electrolytic copper foil comprise that copper cash dissolves, the manufacture of electrolytic solution and electrolytic copper foil three road program.First, copper cash to be inserted in the dissolving tank that sulfuric acid is housed and to be blown into air, make it dissolve and form copper-bath; Then, described copper-bath squeezes into adjustment tank by shifting pump after filter, adds special additive simultaneously and makes concentration analysis and adjust to form electrolytic solution; Finally, described electrolytic solution carries out electrolysis program via squeezing in raw paper tinsel machine after heat exchanger adjustment temperature again, and electrolytic solution completes Posterior circle blowback dissolving tank in electrolysis.
What deserves to be explained is, the special additive selected by the present invention comprises polyether compound, the sulfonate of reactive organic sulphur compound and chlorine; For bestowing elasticity energy and the toughness of electrolytic copper foil excellence, sulfuric acid concentration in copper sulfate electrolyte after adjustment is preferably between 70g/L to 100g/L, copper concentration is preferably between 80g/L to 100g/L, polyether compound concentration is preferably between 50ppm to 250ppm, the sulfonate concentration of reactive organic sulphur compound is preferably between 0.3ppm to 10ppm, and cl concn is preferably then between 10ppm to 50ppm.In actual applications, polyether compound can be but is not limited to polyoxyethylene glycol (PEG), polypropylene glycol (PPG) etc., and the sulfonate of reactive organic sulphur compound can be but is not limited to 3-sulfydryl-1-propanesulfonic acid sodium salt, two (3-sulfapropyl) two sulphur etc.
Further it, when using above-mentioned copper sulfate electrolyte to carry out metallide, preferred liquid temperature is set between 58 DEG C to 62 DEG C, and preferred current density is then set in 50A/dm
2to 80A/dm
2, and the present embodiment utilize surfaceness adjust in for the negative electrode in scope and insoluble anode to carry out electrolysis.By this, its elasticity of the electrolytic copper foil formed can be 60 ~ 100KJ/M
2, and toughness is at least greater than 1500KJ/M
2.
If it should be noted that, elasticity energy is lower than 60KJ/M
2, then rapid charge and electric discharge time, current collector cannot maintain recoverable deformation, cause tension set, fold and make negative material peel off or battery performance decline; If elasticity energy is higher than 100KJ/M
2, then material is too firm, is unfavorable for processing.What deserves to be explained is further, the characteristic of elastomeric property can improve the defect that Copper Foil easily deforms, and the characteristic of high tenacity then can improve the defect that Copper Foil easily occurs to rupture.
Moreover, described electrolytic copper foil is a kind of extra thin copper foil, its thickness about between 8 μm to 35 μm, and has a glossy surface contacted with the surface of rotating cathode and another surface relative to glossy surface, and wherein said surface is because its roughness (Surface Roughness; Refer to 10 average roughness value Rz) between 1.0 μm ~ 2.5 μm, therefore be rendered as even surface (precipitation face); With the electrolytic copper foil manufactured by general traditional method unlike, relative to glossy surface another surface because electrolysis to separate out crystallization of copper different from growth rate, usually have many rough chevron structures, this surface is also known as making uneven surface.
In addition, carry out optimization by electrolytic condition, described electrolytic copper foil can have so-called tensile strength under normality and at least be greater than 300N/mm
2and unit elongation is at least greater than the excellent mechanical properties of 10%, this mechanical characteristics is not only enough to be used in the bending of flexible printed wiring board, is also fully applicable to the negative electrode collector of the lithium secondary battery formed by expanding compress behavior.
In second step, by the sur-face peeling of described electrolytic copper foil spinning negative electrode and be rolled into raw paper tinsel volume, then carry out checking and cut into end product packaging and accumulating.In the present embodiment, the ripple glaze of trimming is every centimetre less than 2, and amplitude is no more than 0.5cm, and cutting ear material is recycled to dissolving tank recycling further.
Preferably, in order to improve thermotolerance and the weathering (oxidation-resistance) of electrolytic copper foil, the present invention can utilize impregnation or plating mode in the precipitation face of electrolytic copper foil or two-sided upper formation Alloy Plating coating, chromate coating and/or silane coupled layer further.
［ embodiment ］
Please refer to table one and table two, display embodiments of the invention, but and not intended to be limits the invention to following examples.Hereinafter high-ranking officer is with experimental data such as elasticity energy, toughness and other are as tensile strength, unit elongation, 0.2% skew yield strength, modulus of elasticity etc., is proved Characteristic of the present invention.As shown in Table 1, embodiment 1 ~ 5 uses the experiment sample of the copper sulfate electrolyte of the additive containing different ratio, and comparative example 1 ~ 2 uses the check sample of the copper sulfate electrolyte of the additive containing different ingredients composition.
(embodiment 1)
In electrolyzer, import copper concentration: 88g/L, sulfuric acid concentration: 95g/L, Polyethylene glycol: 60mg/L, two (3-sulfapropyl) two sulphur concentrations: 2mg/L, chlorine ion concentration: 40mg/L and make copper sulfate electrolyte.Further, electrolyte temperature is adjusted to: 60 DEG C, current density: 60A/dm
2, making copper separate out surface in rotating cathode, then stripping to manufacture the electrolytic copper foil that thickness is 18 μm continuously in the copper on the surface of rotating cathode by separating out.
To the electrolytic copper foil of embodiment 1, separate out the SEM photo in face and be illustrated in Fig. 2, the known negative electrode collector electrolytic copper foil with elastomeric property and high tenacity of the present invention has smoothly and surface uniformly.Moreover, implement tensile strength test based on IPC-TM-650, evaluate elasticity energy, toughness, tensile strength, unit elongation, the results are shown in table two, and make stress-strain(ed) curve, as shown in Figure 3.
(embodiment 2)
In electrolyzer, import copper concentration: 88g/L, sulfuric acid concentration: 95g/L, Polyethylene glycol: 80mg/L, two (3-sulfapropyl) two sulphur concentrations: 3mg/L, chlorine ion concentration: 35mg/L and make copper sulfate electrolyte.Further, electrolyte temperature is adjusted to: 60 DEG C, current density: 60A/dm
2, making copper separate out surface in rotating cathode, then stripping to manufacture the electrolytic copper foil that thickness is 12 μm continuously in the copper on the surface of rotating cathode by separating out.
To the electrolytic copper foil of embodiment 2, implement tensile strength test based on IPC-TM-650, evaluate elasticity energy, toughness, tensile strength, unit elongation, the results are shown in table two, and make stress-strain(ed) curve, as shown in Figure 4.
(embodiment 3)
In electrolyzer, import copper concentration: 88g/L, sulfuric acid concentration: 95g/L, Polyethylene glycol: 200mg/L, two (3-sulfapropyl) two sulphur concentrations: 6mg/L, chlorine ion concentration: 40mg/L and make copper sulfate electrolyte.Further, electrolyte temperature is adjusted to: 60 DEG C, current density: 58A/dm
2, making copper separate out surface in rotating cathode, then stripping to manufacture the electrolytic copper foil that thickness is 18 μm continuously in the copper on the surface of rotating cathode by separating out.
To the electrolytic copper foil of embodiment 3, implement tensile strength test based on IPC-TM-650, evaluate elasticity energy, toughness, tensile strength, unit elongation, the results are shown in table two, and make stress-strain(ed) curve, as shown in Figure 5.
(embodiment 4)
In electrolyzer, import copper concentration: 88g/L, sulfuric acid concentration: 95g/L, Polyethylene glycol: 250mg/L, two (3-sulfapropyl) two sulphur concentrations: 5mg/L, chlorine ion concentration: 35mg/L and make copper sulfate electrolyte.Further, electrolyte temperature is adjusted to: 60 DEG C, current density: 58A/dm
2, making copper separate out surface in rotating cathode, then stripping to manufacture the electrolytic copper foil that thickness is 18 μm continuously in the copper on the surface of rotating cathode by separating out.
To the electrolytic copper foil of embodiment 4, implement tensile strength test based on IPC-TM-650, evaluate elasticity energy, toughness, tensile strength, unit elongation, the results are shown in table two, and make stress-strain(ed) curve, as shown in Figure 6.
(embodiment 5)
In electrolyzer, import copper concentration: 88g/L, sulfuric acid concentration: 95g/L, Polyethylene glycol: 150mg/L, two (3-sulfapropyl) two sulphur concentrations: 3.5mg/L, chlorine ion concentration: 40mg/L and make copper sulfate electrolyte.Further, electrolyte temperature is adjusted to: 60 DEG C, current density: 60A/dm
2, making copper separate out surface in rotating cathode, then stripping to manufacture the electrolytic copper foil that thickness is 12 μm continuously in the copper on the surface of rotating cathode by separating out.
To the electrolytic copper foil of embodiment 4, implement tensile strength test based on IPC-TM-650, evaluate elasticity energy, toughness, tensile strength, unit elongation, the results are shown in table two, and make stress-strain(ed) curve, as shown in Figure 7.
(comparative example 1)
In electrolyzer, import copper concentration: 88g/L, sulfuric acid concentration: 95g/L, Polyethylene glycol: 150mg/L, 3-sulfydryl-1-propanesulfonate salt concn: 7mg/L, polymine concentration: 0.5mg/L, chlorine ion concentration: 40mg/L and make copper sulfate electrolyte.Further, electrolyte temperature is adjusted to: 60 DEG C, current density: 58A/dm
2, making copper separate out surface in rotating cathode, then stripping to manufacture the electrolytic copper foil that thickness is 12 μm continuously in the copper on the surface of rotating cathode by separating out.
To the electrolytic copper foil of comparative example 1, implement tensile strength test based on IPC-TM-650, evaluate elasticity energy, toughness, tensile strength, unit elongation, the results are shown in table two, and make stress-strain(ed) curve, as shown in Figure 8.
(comparative example 2)
In electrolyzer, import copper concentration: 88g/L, sulfuric acid concentration: 95g/L, Natvosol concentration: 5mg/L, gelatin concentration: 0.5mg/L, chlorine ion concentration: 35mg/L and make copper sulfate electrolyte.Further, electrolyte temperature is adjusted to: 70 DEG C, current density: 60A/dm
2, making copper separate out surface in rotating cathode, then stripping to manufacture the electrolytic copper foil that thickness is 12 μm continuously in the copper on the surface of rotating cathode by separating out.
To the electrolytic copper foil of comparative example 2, the SEM photo in precipitation face is illustrated in Fig. 1, the Copper Foil precipitation face of known comparative example 1 is formed with rough texture, dropping fire in the light of this jog can make glossiness [Gs (60 °)] diminish, thus makes surfaceness (Rzjis) become large.Implement tensile strength test based on IPC-TM-650, evaluate elasticity energy, toughness, tensile strength, unit elongation, the results are shown in table two, and make stress-strain(ed) curve, as shown in Figure 9.
Table one
Table two
In table two, so-called tensile strength system represents the value of the situation of the tensile strength test carried out based on IPC-TM-650, and so-called unit elongation system is shown in above-mentioned test, deflection during test piece fracture.In addition, so-called stress-strain(ed) curve represents strain and its chart of stress corresponding, its can use to material apply a fixed load and while and measure continuously made by the data that obtain in the testing of materials of stress and strain when stretching with certain speed.
Can be found by table two, the present invention uses the copper sulfate electrolyte containing special additive to carry out metallide (embodiment 1 ~ 5), compared to the electrolytic copper foil using different electrolytic solution (comparative example 1 ~ 2) gained formed, more suitable elasticity energy and higher toughness can be had; Coordinate the suitable proportioning of each composition selected in additive, described electrolytic copper foil also has other excellent specific properties, such as high-elongation (High Temperature Elongation), pole low roughness (Very Low Profile), very excellent tensile strength and good processing characteristics etc., be applicable to the negative material being applied to secondary cell.
In sum, compared to the copper foil for negative electrode current collector of traditional electrolysis tech and lithium secondary battery, manufacture method of the present invention utilizes and (comprises polyether compound containing special proportioning additive, the sulfonate of reactive organic sulphur compound and chlorine) copper sulfate electrolyte carry out metallide, the electrolytic copper foil obtained can have elastomeric property and high tenacity, therefore the negative electrode collector being applied to lithium secondary battery can prevent because volume repeatedly expands along with repeatedly carrying out discharge and recharge and shrinks the distortion or fracture that cause, thus the excellent effect of the charge/discharge cycle characteristics maintaining lithium secondary battery can be reached.
Moreover described electrolytic copper foil also has under normal conditions and is at least greater than 300N/m
2tensile strength and be at least greater than 10% the excellent mechanical characteristics such as unit elongation, this mechanical characteristics is not only enough to be used in the bending of flexible printed wiring board, is also fully applicable to the negative electrode collector of the lithium secondary battery formed by expanding compress behavior.
Although embodiments of the invention disclose as above, but it is not intended to limiting the invention.Those of ordinary skill in field belonging to the present invention, without departing from the spirit and scope of the present invention, when doing various variations and retouching.Therefore, protection scope of the present invention is when being as the criterion depending on the accompanying claim person of defining.
Claims (10)
1. a negative electrode collector electrolytic copper foil, is characterized in that, the elasticity of described electrolytic copper foil at least can be greater than 60KJ/m
2, and the toughness of described electrolytic copper foil is at least greater than 1500KJ/m
2.
2. negative electrode collector electrolytic copper foil according to claim 1, is characterized in that, the tensile strength under described electrolytic copper foil normality is at least greater than 300N/mm
2, and unit elongation is at least greater than 10%.
3. negative electrode collector electrolytic copper foil according to claim 2, is characterized in that, the thickness of described electrolytic copper foil is 8 μm ~ 35 μm and has at least one surface, and the roughness Rz on described surface is 1.0 μm ~ 2.5 μm.
4. negative electrode collector electrolytic copper foil according to claim 3, is characterized in that, described electrolytic copper foil also comprises a chromium anti oxidation layer, and described chromium anti oxidation layer is formed on described surface.
5. negative electrode collector electrolytic copper foil according to claim 4, is characterized in that, described chromium anti oxidation layer is a chromic salt epithelium.
6. a manufacture method for negative electrode collector electrolytic copper foil, is characterized in that, described manufacture method comprises the following steps:
Separate out formation one electrolytic copper foil with the electrolytic process of copper sulfate electrolyte on the surface of a negative electrode, wherein said copper sulfate electrolyte comprises polyether compound, the sulfonate of reactive organic sulphur compound and chlorine; And
Described electrolytic copper foil is peeled off from described negative electrode.
7. the manufacture method of negative electrode collector electrolytic copper foil according to claim 6, is characterized in that, the sulfuric acid concentration in described copper sulfate electrolyte is 70g/L ~ 100g/L, and copper concentration is 80g/L ~ 100g/L.
8. the manufacture method of negative electrode collector electrolytic copper foil according to claim 7, it is characterized in that, the concentration of the polyether compound in described copper sulfate electrolyte is 50ppm ~ 250ppm, the concentration of the sulfonate of reactive organic sulphur compound is 0.3ppm ~ 10ppm, and the concentration of chlorine is 10ppm ~ 50ppm.
9. the manufacture method of negative electrode collector electrolytic copper foil according to claim 6, is characterized in that, the electrolytic process of described copper sulfate electrolyte, under the electrolyte temperature of 58 DEG C ~ 62 DEG C, uses 50A/dm
2~ 80A/dm
2current density carry out electrolysis.
10. the manufacture method of negative electrode collector electrolytic copper foil according to claim 6, it is characterized in that, after peeling off the step of described electrolytic copper foil from described negative electrode, also comprise the step forming a chromium anti oxidation layer with pickling process or electrolytic process at least one surface of described electrolytic copper foil further.
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| CN108306022A (en) * | 2017-01-13 | 2018-07-20 | Ls美创有限公司 | Electrolytic copper foil, electrode, secondary cell and its manufacturing method comprising it |
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