JP6778291B1 - Negative current collector of copper foil and lithium ion battery containing it and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel copper foil, a negative electrode current collector of a lithium ion battery containing the same, and a method for manufacturing the same. PROBLEM TO BE SOLVED: To manufacture 15 or more and 100 or less copper foils having a convex portion having a height of 5 nm or more on at least a part of the surface and a density of the convex portions of 3.8 μm. A negative electrode current collector is manufactured using the foil. [Selection diagram] None

Description

The present invention relates to a copper foil, a negative electrode current collector of a lithium ion battery containing the same, and a method for manufacturing the same.

When a large-capacity active material is used in the negative electrode current collector of a lithium ion battery (LIB) for high output and high energy density, the expansion coefficient of the volume of the active material increases during charging and discharging. Therefore, when charging and discharging are repeated, the binder connecting the active material and the current collector breaks, or the binder peels off from the active material interface and the current collector interface, and the cycle characteristics deteriorate. In order to prevent this, an invention is disclosed in which the amount of the binder on the copper foil side is increased to improve the adhesion between the copper foil and the negative electrode mixture layer (see Patent Document 1). Further, an invention is disclosed in which a whisker-shaped copper oxide is formed on the surface of a copper foil plate to increase the surface area to improve the adhesion between the copper foil and the active material (see Patent Document 2).

Japanese Unexamined Patent Publication No. 10-284059 Japanese Unexamined Patent Publication No. 11-307102

An object of the present invention is to provide a novel copper foil, a negative electrode current collector for a lithium ion battery containing the same, and a method for manufacturing the same.

In one embodiment of the present invention, at least a part of the surface has convex portions having a height of 5 nm or more, and in the partial portion, the density of the convex portions is 15 or more and 100 or less on average per 3.8 μm. Is. In the part, the density of the convex portions may be 20 or more and 62 or less on average per 3.8 μm. Further, the three-point standard deviation σ of the partial surface roughness Rz may be 0.5 or less, or 0.3 or less. Further, the average of the surface roughness Rz of the part thereof may be 2 μm or less, or 1.54 μm or less.

Another embodiment of the present invention is a negative electrode current collector of a lithium ion battery containing any of the above copper foils.

A further embodiment of the present invention is a method for manufacturing a negative electrode current collector of a lithium ion battery, which comprises any of the above copper foils, and is a first step of oxidizing the copper surface of the copper foil to form a convex portion. A second step of plating the oxidized copper surface and a third step of manufacturing a negative electrode current collector using the copper foil plated on the copper surface are included. Prior to the second step, a fourth step of melting and / or reducing the copper surface oxidized in the first step may be further included.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a novel copper foil, a negative electrode current collector of a lithium ion battery containing the same, and a method for manufacturing the same.

It is a table summarizing the processing conditions in the 1st step and the 2nd step in Example 1 to Example 7 and Comparative Example 1 to Comparative Example 3 of this invention. 6 is a scanning electron microscope (SEM) image showing a cross section of each copper foil in Examples 1 to 7 and Comparative Examples 1 to 3 of the present invention. It is a figure which shows the coating stability of the solvent-based negative electrode material in the Example of this invention. It is a figure which shows the measuring method of the negative electrode material residual ratio in the Example of this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The object, feature, advantage, and idea thereof of the present invention will be apparent to those skilled in the art from the description of the present specification, and those skilled in the art can easily reproduce the present invention from the description of the present specification. it can. The embodiments and specific examples of the invention described below show preferred embodiments of the present invention and are shown for illustration or explanation purposes, and the present invention is described in them. It is not limited. It will be apparent to those skilled in the art that various modifications can be made based on the description of the present specification within the intent and scope of the present invention disclosed herein.

== Copper foil ==
The copper foil disclosed in the present specification may be a rolled copper foil, an electrolytic copper foil, or a copper alloy foil. The thickness of the copper foil is not particularly limited, but is preferably the thickness used for the negative electrode current collector of a lithium ion battery, for example, 5 μm to 100 μm, and the thickness of the copper foil according to the application is included in the range. Can be selected. Further, the surface roughness of the copper foil is not particularly limited, and any roughness of the copper foil can be used. However, if the surface roughness is too large, the tensile strength is lowered or the negative electrode material is filled to the bottom of the unevenness. The adhesion is reduced without it. Further, if the surface roughness is large and the number of convex portions is small, electricity is concentrated on the convex portions and the battery characteristics are deteriorated due to the peeling of the active material. Therefore, the surface roughness is preferably 2 μm or less.

This copper foil has convex portions having a height of 5 nm or more on at least a part of the surface, and the density of the convex portions is preferably 15 or more and 100 or less on average per 3.8 μm, and 20 or more and 62 on average. The following is more preferable. The number of convex parts is counted as a convex part when the length extending perpendicular to the line segment connecting the minimum points of the concave parts at both ends of the convex part is 5 nm or more in the photographed image of the cross section of the scanning electron microscope. .. The height of the convex portion can be calculated by Rz defined in JIS B 0601: 2001 using a confocal scanning electron microscope.

The three-point standard deviation σ of the surface roughness Rz of a part of the surface having a convex portion having a height of 5 nm or more is preferably 0.5 or less, and more preferably 0.3 or less. The smaller the 3-point standard deviation σ of Rz, the more uniform the unevenness. The average Rz is preferably 2 μm or less, and more preferably 1.54 μm or less. The smaller the average of Rz, the smaller the unevenness.

These properties are preferable configurations when the copper foil is used in the negative electrode current collector. Although the principle is not particularly limited, if the number of convex portions is small, the surface area of the copper foil becomes small, so that the adhesion of the copper foil to the negative electrode becomes poor, and as a result, the holding capacity becomes low. When the number of convex parts is small, it is necessary to increase Rz in order to increase the surface area. When Rz is large, the current concentrates on the convex parts, so that the copper foil and the active material are easily separated and the capacity is maintained. The rate becomes smaller. Further, even when the three-point standard deviation of the surface roughness Rz, that is, the variation is large, the current tends to be concentrated when used in the negative electrode current collector, and as a result, the capacity retention rate becomes low.

== Manufacturing method of negative electrode current collector for copper foil and lithium-ion battery ==
The method for producing a copper foil disclosed in the present specification further adjusts a first step of oxidizing the copper surface of the copper foil to form fine convex portions and a convex portion formed on the surface of the oxidized copper foil. The second step is to manufacture a negative electrode current collector for a lithium ion battery by using a copper foil having a convex portion on the copper surface adjusted. The second step includes at least one step of plating, reducing or dissolving the oxidized copper surface. Hereinafter, each step will be described in detail.

(1) First step (oxidation step)
In the first step, first, the copper surface of the copper foil is oxidized with an oxidizing agent to form a layer containing copper oxide, and a convex portion is formed on the surface.

The oxidizing agent is not particularly limited, and for example, an aqueous solution or buffer solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate or the like can be used, but sodium chlorite or hypochlorite can be used. It is preferable to use an aqueous solution containing sodium chlorite. By using these, a suitable surface shape can be formed. Various additives (for example, phosphates such as trisodium phosphate dodecahydrate and surface active molecules) may be added to the oxidizing agent. Surface active molecules include porphyrin, porphyrin-membered ring, expanded porphyrin, ring-reduced porphyrin, linear porphyrin polymer, porphyrin sandwich coordination complex, porphyrin sequence, silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane. , (3-Aminopropyl) trimethoxysilane, (1- [3- (trimethoxysilyl) propyl] urea) ((l- [3- (Trimethoxysilyl) propyl] urea)), (3-aminopropyl) triethoxy Silane, ((3-glycidyloxypropyl) trimethoxysilane), (3-chloropropyl) trimethoxysilane, (3-glycidyloxypropyl) trimethoxysilane, dimethyldichlorosilane, 3- (trimethoxysilyl) propylmethacrylate, Ethyltriacetoxysilane, triethoxy (isobutyl) silane, triethoxy (octyl) silane, tris (2-methoxyethoxy) (vinyl) silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, Examples thereof include chlorotriethoxysilane, ethylene-trimethoxysilane, amines, and sugars. In addition to the oxidizing agent, an alkaline compound such as sodium hydroxide or potassium hydroxide may be contained.

As the additive used in this oxidation step, an additive that appropriately suppresses the formation of convex portions on the surface due to oxidation, such as a silane coupling agent containing a silicon compound, is preferable, whereby the unevenness of the surface becomes finer. , The height of the convex portion becomes more uniform. By manufacturing the current collector of the lithium ion battery using a copper foil having a uniform height of the convex portion on the surface, it is possible to reduce a partial variation in the coating amount of the negative electrode material with respect to the unevenness. As a result, the flow of current is not uneven and the battery characteristics are improved. And productivity is also improved.

The oxidation reaction conditions are not particularly limited, but the liquid temperature of the oxidizing agent is preferably 40 to 95 ° C, more preferably 45 to 80 ° C. The reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.

Prior to this oxidation step, degreasing by alkaline treatment or cleaning by acid treatment may be performed as a pretreatment. The specific method of alkali treatment or acid treatment is not particularly limited, but the alkali treatment is, for example, preferably 30 to 50 g / L, more preferably 40 g / L alkaline aqueous solution, for example, sodium hydroxide aqueous solution, 30 to 50. It can be carried out by washing with water after treating at ° C. for about 0.5 to 2 minutes. The acid treatment can be carried out, for example, by immersing the copper surface in sulfuric acid at a liquid temperature of 20 to 50 ° C. and 5 to 20% by weight for 1 to 5 minutes, and then washing with water. After the acid treatment, a weaker alkaline treatment may be performed in order to reduce uneven treatment and prevent the acid used in the cleaning treatment from being mixed into the oxidizing agent. This alkaline treatment is not particularly limited, but is preferably 0.1 to 10 g / L, more preferably 1 to 2 g / L alkaline aqueous solution, for example, sodium hydroxide aqueous solution at 30 to 50 ° C. for about 0.5 to 2 minutes. It can be done by processing. Further, as a pretreatment, a treatment such as etching may be performed to physically roughen the copper surface, but the shape of the convex portion formed on the copper surface at that time is generally a copper crystal to be treated. Since it depends on the properties, the physical roughening treatment alone does not result in fine irregularities, and in order to obtain a copper foil having fine irregularities, it is necessary to go through this oxidation step.

(2) Second Step The second step includes at least one step of (2-1) plating treatment step, (2-2) reduction treatment step, and (2-3) dissolution treatment step. The plating treatment step may be performed after the reduction treatment step or after the dissolution treatment. The copper surface is roughened so as to have fine protrusions by the oxidation treatment in the first step, but the protrusions formed on the copper surface are further adjusted by the second step of the present invention. Each process of the second step will be described below.

(2-1) Plating Treatment Step In this step, the oxidized copper surface is plated with a metal other than copper to adjust the convex portion of the oxidized copper surface. As the plating method, known techniques can be used. For example, as a metal other than copper, tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold, platinum, or Various alloys can be used. The plating method is not particularly limited, and plating can be performed by electrolytic plating, electroless plating, vacuum vapor deposition, chemical conversion treatment, or the like. Electrolytic plating is preferable, and as compared with electroless plating, metallic copper is easily reduced and excellent in power collection.

In the case of electroless nickel plating, it is preferable to perform treatment using a catalyst. As the catalyst, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and salts thereof are preferably used. As the reducing agent used in the case of electroless nickel plating, it is preferable to use a reducing agent in which copper and copper oxide do not have catalytic activity. Examples of the reducing agent in which copper and copper oxide do not have catalytic activity include hypophosphates such as sodium hypophosphite.

In this way, by obtaining the metal layer that maintains the fine irregularities formed in the first step, the surface is protected and the stability of the composite copper foil with time is improved. The thickness of the plating is not particularly limited, but if it is too thick, the number of convex portions is reduced due to leveling, resulting in a smaller RSm, a reduced surface area, and a decrease in power collection, which deteriorates battery characteristics. Therefore, 1 μm or less is desirable. ..

In the plating process, it is difficult to make the plating uniform unless the purity of copper is increased, preferably pure copper. Therefore, it is common to remove the oxide film on the surface and perform plating treatment. In the method of the present disclosure, by forming a suitable shape with an oxide film and then performing a plating treatment, it is possible to obtain the adhesion and battery characteristics required for manufacturing a current collector of a lithium ion battery.

(2-2) Reduction Treatment Step In this step, copper oxide formed on the copper foil is reduced using a chemical solution containing a reducing agent (reducing chemical solution), and the number and length of irregularities are adjusted.

As the reducing agent, DMAB (dimethylamine borane), diborane, sodium borohydride, hydrazine and the like can be used. The chemical solution for reduction is a liquid containing a reducing agent, an alkaline compound (sodium hydroxide, potassium hydroxide, etc.), and a solvent (pure water, etc.).

(2-3) Melting treatment step In this step, the oxidized copper surface is dissolved with a dissolving agent to adjust the convex portion of the oxidized copper surface. The dissolving agent used in this step is not particularly limited, and examples thereof include a chelating agent and a biodegradable chelating agent. Specifically, EDTA (ethylenediaminetetraacetic acid), DHEG (diethanolglycine), GLDA (L-glutamate diacetic acid / tetrasodium), EDDS (ethylenediamine-N, N'-disuccinic acid), HIDS (3-hydroxy) -2,2'-Sodium iminodisuccinate), MGDA (3 sodium methylglycine diacetate), ASDA (4Na aspartate diacetate), HIDA (N-2-hydroxythyliminodiacetic acid disodium salt), sodium gluconate, ethidronate (hydroxyl) Ethanediphosphonic acid) and the like.

The pH of the solubilizer is not particularly limited, but it is preferably alkaline, and the pH is 9.0 to 14.0 because the amount of dissolution is large when it is acidic, it is difficult to control the treatment, and uneven treatment is likely to occur. Is more preferable, the pH is more preferably 9.0 to 10.5, and the pH is even more preferably 9.8 to 10.2.

In this step, the copper surface is treated until the solubility of copper oxide is 35-99%, preferably 50-99% and the thickness of CuO is 4-300 nm, preferably 8-200 nm. Here, the thickness of CuO can be measured by SERA (manufactured by ECI). Under these conditions, the number and length of surface irregularities become suitable, and processing unevenness is reduced. Therefore, a pilot experiment is conducted in advance, and conditions such as temperature and time are set so that such a copper oxide layer can be obtained. It is preferable to set it. The dissolution rate means the ratio of copper oxide dissolved and removed from the copper surface to the copper oxide on the copper surface.

As described above, by performing the second step on the copper foil, it is possible to manufacture a composite copper foil suitable for the negative electrode current collector of the lithium ion battery in which the convex portion on the surface is adjusted.

The copper foil produced in these second steps may be subjected to a coupling treatment using a silane coupling agent or the like, a chromate treatment, or a rust prevention treatment using benzotriazoles or the like.

(3) Third step (manufacturing step of negative electrode current collector)
Using the copper foil treated as described above, a negative electrode current collector for a lithium ion battery can be manufactured according to a known method to manufacture a negative electrode. For example, a negative electrode material containing a carbon-based active material is prepared and dispersed in a solvent or water to prepare an active material slurry. After applying this active material slurry to the copper foil, it is dried to evaporate the solvent and water. Then, it is pressed, dried again, and then the negative electrode current collector is formed into a desired shape. The negative electrode material may contain silicon, a silicon compound, germanium, tin, lead, etc., which have a theoretical capacity larger than that of the carbon-based active material. Further, as the electrolyte, not only an organic electrolytic solution in which a lithium salt is dissolved in an organic solvent but also a polymer composed of polyethylene oxide, polyvinylidene fluoride or the like may be used. It can be applied not only to lithium-ion batteries but also to lithium-ion polymer batteries.

[Evaluation copper foil and surface roughening treatment of copper foil]
As Examples and Comparative Examples, the following copper foils were used and the described treatments were carried out.

In Examples 1 to 3, the surface treatment layer on the matte surface of a commercially available copper foil (B-Foil manufactured by Targray) was removed, and various surface treatments were applied. In Examples 4 to 7, the surface treatment layer of a commercially available copper foil (NC-WS manufactured by Furukawa Electric Co., Ltd.) was removed, and the surface treatment described later was performed. Comparative Example 1 is a matte surface of a commercially available copper foil (B-Foil manufactured by Tarray), Comparative Example 2 is a commercially available copper foil (NC-WS manufactured by Furukawa Electric Co., Ltd.), and Comparative Example 3 is a commercially available copper foil. (B-Foil manufactured by Targray) A shiny surface (cathode contact surface) was used.

The processing conditions in the first step and the second step are summarized in the table of FIG. The same pretreatment conditions and negative electrode material coating conditions were used in Examples and Comparative Examples.

(1) Pretreatment [Alkaline degreasing treatment]
The copper foil was immersed in a sodium hydroxide aqueous solution at a liquid temperature of 50 ° C. and 40 g / L for 1 minute, and then washed with water.

[Acid cleaning treatment]
The copper foil subjected to the alkaline degreasing treatment was immersed in a sulfuric acid aqueous solution having a liquid temperature of 25 ° C. and 10% by weight for 2 minutes, and then washed with water.

[Pre-dip processing]
The acid-washed copper foil was immersed in a chemical solution for predip at a solution temperature of 40 ° C. and 1.2 g / L of sodium hydroxide (NaOH) for 1 minute.

(2) First step (oxidation treatment)
First, as the first step, an alkaline aqueous solution (20 g / L sodium hydroxide, 60 g / L sub) is applied to the copper foils of Example 1, Example 2, Example 3, Example 4, Example 5, and Example 7. It was oxidized with sodium chlorite (2 g / L 3-glycidyloxypropyltrimethoxysilane). The treatment temperature and treatment time were 1 minute at 45 ° C. for Example 1, 2 minutes at 73 ° C. for Examples 2, 3, 4, and 7, and 3 minutes at 73 ° C. for Example 5.

The copper foil of Example 6 was oxidized with an alkaline aqueous solution (20 g / L sodium hydroxide, 60 g / L sodium chlorite) at 73 ° C. for 8 minutes. The copper foils of Comparative Examples 1 to 3 are not subjected to surface treatment such as oxidation treatment of the present invention.

(3) Second Step Next, as the second step, the copper foil subjected to the oxidation treatment of the first step is subjected to (3-1) dissolution treatment, (3-2) plating treatment, and (3). -3) One or more types of reduction treatment were performed.

(3-1) Dissolution Treatment For the copper foils of Examples 2, 3 and 7, after the oxidation treatment of (2), the solvent L-tetrasodium diglutamate (38 g / L) was used. , 55 ° C. was used for dissolution treatment. The treatment time was 1 minute for Example 2, 2 minutes for Example 3, and 3 minutes for Example 7.

(3-2) Plating treatment After the oxidation treatment of (2) for the copper foils of Examples 1 and 4, the dissolution of (3-1) for the copper foils of Examples 2 and 3 After the treatment, electrolytic plating was performed using an electrolytic solution for nickel plating (450 g / L nickel sulfamate, 40 g / L boric acid). The current density was 1 (Å / dm2) and the time was 15 (seconds). The other copper foils were not plated.

(3-3) Reduction Treatment For the copper foils of Examples 5 and 6, after the oxidation treatment of (2), a solvent (5 g / L dimethylamine borane, 5 g / L sodium hydroxide) was used at room temperature. The reduction treatment was carried out by allowing the mixture to stand for 3 minutes.

(4) Measurement of height and number of convex portions and surface roughness When the cross section of the copper foil treated in (1) to (3) was observed with a scanning microscope (SEM), FIG. 2 I got a picture of. Using this photographed image, the number of convex parts in the cross section was measured. The number of convexes is counted as a convex part when the length extending perpendicular to the line segment connecting the minimum points of the concave parts at both ends of the convex part is 5 nm or more in the photographed image of the cross section of the scanning electron microscope. ..

Further, the surface roughness Rz was measured using a confocal scanning electron microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.), and calculated by the Rz defined in JIS B 0601: 2001. As the measurement conditions, the scan width was 100 μm, the scan type was an area, the Light source was Blue, and the cutoff value was 1/5. The object lens was set to x100, the contact lens was set to x14, the digital zoom was set to x1, and the Z pitch was set to 10 nm. Data at three locations were acquired and the standard deviation was calculated. Moreover, Rz was set as the average value of three places.

As described above, in each of the samples of the examples, the average number of convex portions having a height of 5 nm or more is 10 or more per 3.8 μm, the average Rz is 2.00 μm or less, and the standard deviation is 0.3 or less. there were.

(5) Coating of negative electrode material (5-1) Coating of water-based negative electrode material The copper foils of Example 1, Example 2, Example 3, and Comparative Example 1 were used for evaluation.

Graphite (MTI EQ-Lib-MCMB), acetylene black (Denka Li-400), CMC (carboxymethyl cellulose Daicel Finechem CMC Daicel 2200), SBR (styrene butadiene rubber Nippon Zeon BM-400B), Si (Tekna Advanced) (Made by Materials) to the prescribed formulation (graphite: 86.5% by weight, acetylene black: 1.5% by weight, CMC: 5.0% by weight, SBR: 2.5% by weight, Si: 4.5% by weight) Weighed so that the viscosity was adjusted using pure water.

Then, the mixture was stirred with a planetary stirrer until graphite, acetylene black, CMC, and Si became uniform, and finally SBR was added, and further stirring was performed. The coating thickness was set to 150 μm with a bar coater and applied to the copper foil. After the coating, the mixture was dried at 70 ° C. for 2 hours to remove water, and pressed using a roll press so that the thickness of the negative electrode material was 30 μm, and the copper foil and the negative electrode material were brought into close contact with each other. Then, it was dried at 70 ° C. for 12 hours in a vacuum and reduced pressure dryer.

(5-2) For the application evaluation of the solvent-based negative electrode material, the copper foils of Example 4, Example 5, Example 6, Comparative Example 1, Comparative Example 2 and Comparative Example 3 were used.

Using graphite (manufactured by Nippon Graphite), acetylene black (manufactured by Denka Li-400), PVDF (manufactured by polyvinylidene fluoride Kureha L # 1120), a predetermined formulation (graphite: 85% by weight, acetylene black: 5% by weight, PDVF: 10% by weight) was weighed. The viscosity was adjusted using NMP as the solvent.

Then, graphite, acetylene black, and PVDF were stirred with a planetary stirrer until they became uniform, and the coating thickness was set to 150 μm with a bar coater and coated on the copper foil. After the coating, the mixture was dried at 80 ° C. for 2 hours to remove the solvent, and pressed using a roll press so that the thickness of the negative electrode material was 30 μm, and the copper foil and the negative electrode material were brought into close contact with each other. Then, it was dried at 120 ° C. for 12 hours in a vacuum and reduced pressure dryer.

FIG. 3 is a diagram showing the coating stability of the solvent-based negative electrode agent. The left side of FIG. 3 is Example 4, in which the adhesion is good because there are many convex portions, and the negative electrode agent is uniformly applied due to the capillary phenomenon. On the other hand, the right side of FIG. 3 is Comparative Example 1, and since the number of convex portions is small, neither the adhesion force nor the capillary phenomenon can be obtained, and a large amount of peeling occurs partially.

(6) Preparation of coin cell For the production of the coin cell, a sample prepared by coating the negative electrode material (5) was used as the negative electrode. A coin cell was prepared by using 1M LiPF6 / EC-DEC (1: 1) as an electrolytic solution in the coin cell and using a negative electrode, a separator, and a lithium foil.

(7) Measurement of charge / discharge characteristics After producing SEI (Solid Electrolyte Interphase), which is a thin film formed on the surface of the negative electrode by reduction decomposition of the electrolytic solution in one cycle of 0.2C, the discharge is CC-CV (voltage 10 mV, current). (Up to 0.1C) mode, charge is CC (voltage up to 1500 mV) mode, 1C⇒3C⇒5C⇒1C is repeated 3 cycles each at 30 ° C, and then 1C⇒3C⇒5C⇒1C is repeated at 50 ° C. The characteristics of the third cycle of 5C at 50 ° C. were evaluated by repeating 3 cycles each.

(8) Measurement of negative electrode material residual rate As an evaluation of adhesion, the negative electrode material residual rate was calculated using the copper foil after coating of the negative electrode material in (5). First, the weight of the copper foil coated with the negative electrode material is measured. After that, double-sided tape is attached to the plate for fixing, cellophane tape is attached on it so that the adhesive surface of the cellophane tape is in contact with the negative electrode material, and then the negative electrode material surface of the copper foil coated with the negative electrode material is attached to the cellophane tape. Adhesive so that they are in contact with each other, and after applying a pressure of 5 kN / inch2, they are peeled off under 90 ° peel strength test conditions (JIS 0237: 2009) with a peel strength tester (manufactured by Imada), and the amount of negative electrode material remaining on the copper foil side. Was measured. The test method is shown in FIG.

The negative electrode material residual ratio was calculated using the following formula.

Negative electrode material residual ratio [%] = (total weight after test-weight of copper foil) / (total weight before test-weight of copper foil) x 100
Table 2 shows the evaluation results with the water-based negative electrode material. Table 3 shows the evaluation results with the solvent-based negative electrode material.

As described above, a collection of negative electrodes of a lithium ion battery using copper foil having convex portions having a height of 5 nm or more on at least a part of the surface and an average of 15 or more and 100 or less convex portions per 3.8 μm. By manufacturing the electric body, the adhesion between the copper foil and the negative electrode and the capacity retention rate are improved.

Claims (8)

In the photographed image of the cross section of the scanning electron microscope, at least a part of the surface has a convex portion having a length of 5 nm or more extending perpendicular to the line segment connecting the minimum points of the concave portions at both ends.
In the above part, the density of the convex portions is 15 or more and 100 or less on average per 3.8 μm measured in the direction parallel to the surface.
The average of the surface roughness Rz of a part thereof is 2 μm or less.
A copper foil whose surface has a layer containing copper oxide, and the surface of the layer is plated with a metal other than copper. The copper foil according to claim 1, wherein in a part thereof, the density of the convex portions is 20 or more and 62 or less on average per 3.8 μm. The copper foil according to claim 1 or 2, wherein the three-point standard deviation σ of a part of the surface roughness Rz is 0.5 or less. The copper foil according to claim 1 or 2, wherein the three-point standard deviation σ of a part of the surface roughness Rz is 0.3 or less. The copper foil according to any one of claims 1 to 4, wherein the average of the surface roughness Rz of a part thereof is 1.54 μm or less. A negative electrode current collector for a lithium ion battery, comprising the copper foil according to any one of claims 1 to 5. The method for manufacturing a negative electrode current collector for a lithium ion battery according to claim 6.
The first step of oxidizing the copper surface of the copper foil with one or more oxidizing agents selected from sodium chlorite, sodium hypochlorite, potassium chlorate, and potassium perchlorate to form a convex portion, and
A second step of plating the oxidized copper surface with a metal other than copper , and
A third step of manufacturing a negative electrode current collector using the copper foil whose copper surface is plated with a metal other than copper.
Manufacturing method, including. The production method according to claim 7, further comprising a step of dissolving the copper surface oxidized in the first step and / or a fourth step of reducing the copper surface before the second step.