WO2011055680A1 - リチウムイオン電池集電体用銅箔 - Google Patents
リチウムイオン電池集電体用銅箔 Download PDFInfo
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- WO2011055680A1 WO2011055680A1 PCT/JP2010/069185 JP2010069185W WO2011055680A1 WO 2011055680 A1 WO2011055680 A1 WO 2011055680A1 JP 2010069185 W JP2010069185 W JP 2010069185W WO 2011055680 A1 WO2011055680 A1 WO 2011055680A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a copper foil for a lithium ion battery current collector, and more particularly to a copper foil for a negative electrode current collector of a lithium ion secondary battery using an aqueous binder.
- Lithium ion batteries are characterized by high energy density and relatively high voltage, and are widely used for small electronic devices such as notebook computers, video cameras, digital cameras, and mobile phones. In the future, it is expected to be used as a power source for large equipment such as electric vehicles and distributed power sources for general households.
- an electrode body of a lithium ion battery generally has a stack structure in which a positive electrode 11, a separator 12, and a negative electrode 13 are wound or stacked in dozens.
- the positive electrode is composed of a positive electrode current collector made of aluminum foil and a positive electrode active material made of a lithium composite oxide such as LiCoO 2 , LiNiO 2 and LiMn 2 O 4 provided on the surface thereof
- the negative electrode is composed of a negative electrode current collector made of copper foil and a negative electrode active material made of carbon or the like provided on the negative electrode current collector.
- the positive electrodes and the negative electrodes are welded by the tabs (14, 15), respectively.
- a positive electrode and a negative electrode are connected with the tab terminal made from aluminum or nickel, this is also performed by welding. The welding is usually performed by ultrasonic welding.
- Solvent-based binders and water-based binders generally have different coating properties on the copper foil surface, because this depends on the wettability between the copper foil surface and the solvent or water. In order to improve the coatability of the copper foil, it is necessary to improve the water wettability of the copper foil surface. As the wettability, a method of measuring and evaluating a contact angle when a certain amount of droplets is held on the surface of a target material is widely used. The smaller the contact angle, the better the wettability.
- Japanese Patent No. 2970724 describes a method of evaporating the rolling oil on the surface of the copper foil by heating the copper foil at 180 ° C. or higher by inert gas or evacuation.
- Japanese Patent No. 2970727 describes a method in which the surface roughness (Ra) of the final rolling roll is less than 1.0 ⁇ m, the surface roughness of the material is reduced, and the rolling oil entering the recess is reduced.
- At least one surface of a copper foil is a metal selected from at least one of nickel, cobalt, tungsten, and molybdenum, or phosphorus that is a metalloid metal with these metals,
- a barrier layer formed with boron is formed, then a chromate treatment using trivalent chromium as a chromium source is performed on the formed barrier layer, and a silane coupling treatment is performed on the obtained trivalent chromate film
- adhesion and rust prevention properties are improved.
- this invention makes it the 1st subject to provide the copper foil for the collectors of the lithium ion battery which improved the wettability and the antirust property in a good balance.
- This invention makes it the 2nd subject to provide the method of manufacturing such copper foil.
- this invention makes it a 3rd subject to provide the lithium ion battery which used the copper foil which concerns on this invention as a collector.
- the present inventor conducted researches to solve the above problems, and confirmed that the wettability was improved by applying a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. However, it was confirmed that the anticorrosion property was inferior to the surface treatment with an azole compound widely used for copper. As a result of further research, the inventors have found a clue to solving the problem by surface treatment with a mixed solution of a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and an azole surface treatment agent.
- the present invention completed based on the above knowledge is lithium in which a mixed layer of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is formed on at least a part of the copper foil surface. It is copper foil for ion battery collectors.
- the water-soluble organic compound contains a group represented by the following general formula (1).
- X represents a residue excluding active hydrogen in a compound having active hydrogen.
- the X is a hydroxyl group, a phenoxy group, a halogen, an organic acid ester (RCOO), an amino group, an alkoxy group (RO), an alkyl mercapto group (RS), or the like.
- R1 and R2 are each a kind selected from the group consisting of a hydroxyalkyl group, an ether group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.
- R3, R4 and R5 are each selected from the group consisting of hydrogen, hydroxyalkyl group, ether group, aromatic substituted alkyl group, unsaturated hydrocarbon group and alkyl group.
- the group represented by the formula (1) undergoes addition reaction with the compound XH in which the epoxy group has active hydrogen according to the following reaction formula (5). It is obtained by.
- the compound having an epoxy group in the reaction formula (5) is a water-soluble epoxy resin having a glycidoxy group or a silane coupling agent having a glycidoxy group.
- the water-soluble organic compound contains an imidazole group in the molecule.
- an intermediate layer composed of an azole compound or a chromate layer is formed between the copper foil surface and the mixed layer.
- the azole compound is a benzotriazole-based compound.
- the benzotriazole-based compound is 1,2,3-benzotriazole.
- the copper foil according to the present invention is for a negative electrode current collector of a lithium ion secondary battery.
- the present invention is a lithium ion battery using the copper foil according to the present invention as a current collector.
- the mixed solution contains 0.01 to 0.25 g / L of an azole compound, and a hydroxyl group and a line in the molecule.
- a water-soluble organic compound having a chain ether bond is contained at 0.5 to 20 g / L.
- the copper foil according to the present invention improves the rust prevention and water wettability in a well-balanced manner. Therefore, it can be suitably used as a current collector for a lithium ion battery.
- FIG. 1 is a schematic diagram of a stack structure of a lithium ion battery.
- FIG. 2 shows an example of N, Si, and C depth profiles obtained by an XPS apparatus obtained when measuring the thickness of a mixed organic film of silane coupling obtained by hydrolyzing an azole compound and an epoxy group.
- FIG. 3 shows N, O, and C of an azole compound and an XPS apparatus obtained by measuring the thickness of a mixed organic film of a compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond. An example of a depth profile is shown.
- Copper foil base material any of an electrolytic copper foil and a rolled copper foil may be sufficient as copper foil.
- the “copper foil” includes a copper alloy foil. There is no restriction
- copper alloys such as Cu—Cr—Zr copper alloys to which Cr, Zr, etc. are added.
- the thickness of the copper foil is not particularly limited and may be appropriately selected depending on the required characteristics. Generally, the thickness is 1 to 100 ⁇ m, but when used as a current collector of a lithium secondary battery negative electrode, a battery having a higher capacity can be obtained by thinning the copper foil. From such a viewpoint, it is typically 2 to 50 ⁇ m, more typically about 5 to 20 ⁇ m.
- the surface treatment is performed using a mixed solution of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule.
- a mixed solution of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is contacted by dipping, coating, spraying, etc., and then dried to dry the azole compound and water-soluble
- the epoxy resin is reacted with copper on the surface of the copper foil and fixed on the surface of the copper foil.
- the anti-rust property of the azole compound is utilized, and the anti-rust property and water wettability to the negative electrode active material are obtained by a mixed layer of the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule.
- the balance is improved.
- a benzotriazole compound generally known to have particularly good rust prevention properties is preferable.
- it does not limit as a benzotriazole type compound What kind of thing may be sufficient from the objective of the above-mentioned this invention.
- benzotriazole compounds examples include 1,2,3-benzotriazole, 1-methylbenzotriazole, carboxybenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, tolyltriazole, Examples thereof include benzotriazole compounds such as naphthotriazole, 5-nitrobenzotriazole, and phenazinotriazole.
- the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule contains a group represented by the following general formula (1).
- X represents a residue excluding active hydrogen in a compound having active hydrogen.
- Specific examples of such X include a hydroxyl group, a saturated or unsaturated hydrocarbon group containing a hydroxyl group, a phenol group, a carboxyl group, an organic acid containing a carboxyl group, a secondary amino group, and an imidazole group. .
- R1 and R2 are each a kind selected from the group consisting of a hydroxyalkyl group, an ether group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.
- R3, R4 and R5 are each one selected from the group consisting of hydrogen, hydroxyalkyl group, ether group, aromatic substituted alkyl group, unsaturated hydrocarbon group and alkyl group.
- the water-soluble organic compounds are further represented by glycol ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monophenyl ether, and the following general formulas (A) to (G).
- glycol ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monophenyl ether, and the following general formulas (A) to (G).
- the compound having an epoxy group is a compound to which a hydroxyl group is imparted by hydrolysis, or obtained by addition reaction with an amine compound, or obtained by addition reaction with an imidazole compound.
- R6 represents a hydroxyl group or an alkyl group having 1 to 5 carbon atoms
- R7 represents an alkylene group having 1 to 10 carbon atoms which may contain oxygen
- R8 represents an alkyl group having 1 to 5 carbon atoms.
- L represents 2 or 3)
- n an integer of 1 to 4.
- n an integer of 1 to 30.
- n an integer of 1 to 5.
- the other surface treatment is performed after one surface treatment, that is, overcoating or overcoating can be considered, but after surface treatment of the azole compound, hydroxyl and linear in the molecule
- surface treatment is performed with a water-soluble organic compound having an ether bond
- the rust resistance is reduced, and the surface of the azole compound after the surface treatment with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule.
- the treatment is performed, the water wettability is lowered, and the water wettability and the rust preventive property cannot be made compatible.
- the surface treatment is performed at once with a mixed solution of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, whereby the hydroxyl group and the linear ether bond are formed in the molecule.
- the water wettability obtained with the water-soluble organic compound possessed and the rust prevention obtained by the surface treatment with the azole compound were made compatible.
- An intermediate layer composed of an azole compound is further formed between the mixed layer formed of the azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule and the copper foil. Also good.
- the outermost surface has a mixed layer formed of an azole compound and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule.
- an intermediate layer composed of an azole compound is formed between the mixed layer and the copper foil, thus further improving rust prevention. Can do.
- a chromate treatment layer may be formed as the intermediate layer.
- the antirust property can be further improved by providing an intermediate layer formed of the chromate treatment layer.
- the surface of the copper foil is May be treated with a water-soluble organic compound having a hydroxyl group and a linear ether bond, and a mixed layer may be provided thereon. Thereby, water wettability improves further.
- FIG. 2 shows the result of analyzing the mixed organic film of an azole compound and a silane coupling agent hydrolyzed with an epoxy group using an XPS apparatus.
- the average thickness D 0 of the mixed layer is preferably 1.0 to 5.0 nm, and more preferably 1.5 to 4.0 nm. Further, even when an intermediate layer is further formed between the mixed layer and the copper foil, D 0 is similarly 1.0 to 5.0 nm with respect to the total average thickness of the mixed layer and the intermediate layer. Is preferable, and 1.5 to 4.0 nm is more preferable.
- FIG. 3 shows the depth of N, O, and C by an XPS apparatus obtained when measuring the thickness of an organic film of an azole compound and a compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond. An example of a profile is shown.
- the azole compound and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule can be used by dissolving in a solvent such as ethanol or water.
- a solvent such as ethanol or water.
- concentration of the azole compound and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is increased, the formed organic film is thickened, and the concentration is decreased when the concentration is decreased.
- numerator is formed.
- the concentration of the azole compound is 0.01 to 0.25 g / L, preferably 0.
- the concentration of the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is 0.5 to 20 g / L, preferably 1 to 10 g / L.
- a lithium ion battery can be produced by conventional means using a negative electrode composed of a current collector made of a copper foil according to the present invention and an active material layer formed thereon.
- the lithium ion battery includes a lithium ion primary battery and a lithium ion secondary battery in which lithium ions in the electrolyte are responsible for electrical conduction.
- the negative electrode active material include, but are not limited to, carbon, silicon, tin, germanium, lead, antimony, aluminum, indium, lithium, tin oxide, lithium titanate, lithium nitride, indium-tin oxide, indium Examples thereof include a tin alloy, a lithium-aluminum alloy, and a lithium-indium alloy.
- Example 1 In order to examine the effect of surface treatment with a mixed solution of an azole compound and a water-soluble epoxy resin on properties, Examples and Comparative Examples were created under the following conditions. Various conditions and test results are shown in Table 1 below.
- [Manufacture of rolled copper foil] A tough pitch copper ingot having a thickness of 200 mm and a width of 600 mm was manufactured and rolled to 10 mm by hot rolling.
- the work roll diameter is 60 mm
- the work roll surface roughness Ra is 0.03 ⁇ m
- the final pass rolling speed is 400 m / min
- the workability is 20%. It finished to 10 ⁇ m.
- the viscosity of the rolling oil was 9.0 cSt (25 ° C.).
- the obtained rolled copper foil had an Ra of 0.11 ⁇ m.
- the azole compound is 1,2,3-benzotriazole (hereinafter referred to as BTA), and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is represented by the following reaction formula (6): “Denacol EX-521” manufactured by Nagase ChemteX Corporation was used by opening the epoxy group and adding a hydroxyl group. (Where n ⁇ 3)
- the thickness of the organic film (mixed layer or a layer formed of a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule or BTA alone) is measured in the depth direction of the copper foil with an XPS apparatus while sputtering with argon.
- the elemental analysis was performed, O and N were detected, and the depth of the C detected amount larger than the background level (in terms of SiO 2 ) was defined as the organic film thickness, and the average value of any five locations was the organic film thickness. The average value was used.
- XPS equipment (ULVAC-PHI, Model 5600MC) ⁇ Degree of vacuum: 5.7 ⁇ 10 ⁇ 7 Pa
- X-ray Monochromatic AlK ⁇
- X-ray output 210W incident angle 45 °
- Ion beam ion species Ar + , acceleration voltage 3 kV, sweep area 3 mm ⁇ 3 mm, sputtering rate 2.3 nm / min (SiO 2 conversion)
- Example 1-11 the surface treatment was performed with a mixed solution of BTA and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule.
- the thickness of the mixed organic film with a water-soluble organic compound having an ether bond is in the range of 1.0 to 5.0 nm. For this reason, it has shown favorable characteristics in all of water wettability, rust prevention property, and weldability.
- Comparative Example 1-12 the surface treatment was not performed, the organic film was not present on the surface, the weldability was good and the water wettability was not bad, but the rust preventive property was poor, the water wettability and the rust preventive property.
- the rust prevention property is poor at any concentration, and only a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule can simultaneously satisfy water wettability, rust prevention property and weldability. Indicates that it is not possible.
- the surface treatment was performed only with BTA, and then the surface treatment was performed with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. is doing.
- Comparative Example 1-20 the surface treatment was carried out only with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and then the surface treatment was carried out with BTA. The water wettability improving effect of the water-soluble organic compound having an ether bond is reduced.
- Example 2 The sample surface-treated by the following method was evaluated according to Example 1. Various conditions and test results are shown in Table 2 below. [surface treatment] About the rolled copper foil and the electrolytic copper foil having a thickness of 10 ⁇ m manufactured as in Example 1, the azole-based compound having the concentration shown in Table 1 and the aqueous solution of each silane coupling agent obtained by hydrolyzing the epoxy group, and both A mixed aqueous solution was prepared, dipped in this for 3 seconds, and then dried with a dryer.
- BTA 1,2,3-benzotriazole
- H a compound of the following general formula (H) was used as a silane coupling agent obtained by hydrolyzing an epoxy group.
- R 9 represents a hydroxyl group or an alkyl group having 1 to 5 carbon atoms
- R 10 represents an alkyl group having 1 to 10 carbon atoms which may contain oxygen. Is shown.
- Example 3 The sample surface-treated by the following method was evaluated according to Example 1. Various conditions and test results are shown in Table 3 below.
- An aqueous solution of each of the compounds to which was added and an aqueous solution in which both were mixed were prepared, immersed in this for 3 seconds, and then dried with a drier.
- the azole compound is 1,2,3-benzotriazole (hereinafter referred to as BTA), and the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is Nagase Chem as shown in the following reaction formula (7).
- BTA 1,2,3-benzotriazole
- the water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is Nagase Chem as shown in the following reaction formula (7).
- a product obtained by adding imidazole to an epoxy group of “Denacol EX-521” manufactured by Tex Co., Ltd. was used.
- R11 is an imidazole group, and n ⁇ 3.
- Examples 3-1 to 3-11 are surface-treated with a mixed solution of BTA and a compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule.
- the mixed organic film thickness of the compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is in the range of 1.0 to 5.0 nm. For this reason, it has shown favorable characteristics in all of water wettability, rust prevention property, and weldability.
- Comparative Example 3-12 the surface treatment was not performed, no organic film was present on the surface, the weldability was good and the water wettability was not bad, but the rust preventive property was poor, the water wettability and the rust preventive property. And weldability cannot be satisfied at the same time.
- Comparative Examples 3-13 to 3-15 the surface treatment was performed only with BTA. The lower the treatment liquid concentration, the better the weldability, and the higher the treatment liquid concentration, the better the rust prevention property. However, even at any concentration, water wettability is poor, and BTA alone indicates that water wettability, rust prevention and weldability cannot be satisfied at the same time.
- Comparative Example 3-19 was surface-treated with a compound in which an imidazole group was added to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule after the surface treatment with BTA alone.
- the antirust effect of BTA is reduced.
- the surface treatment was performed only with a compound in which an imidazole group was added to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule, and then the surface treatment was performed with BTA.
- the effect of improving the wettability of a compound obtained by adding an imidazole group to a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule is low.
- Example 4 The sample surface-treated by the following method was evaluated by the method described in Example 1 or the following method. Various conditions and test results are shown in Table 4 below.
- the plate thickness is 6 ⁇ m, it is 18 to 34, if the plate thickness is 10 ⁇ m, 11 to 20 sheets, if the plate thickness is 20 ⁇ m, 6 to 10 copper foils are torn at the welded portion, “ ⁇ ”, When the plate thickness is 6 ⁇ m, 1 to 17 sheets, when the plate thickness is 10 ⁇ m, 1 to 10 sheets, and when the plate thickness is 20 ⁇ m, 1 to 5 copper foils were torn at the welded portion, “ ⁇ ”, and no copper foil was torn. The case was set as “x”. Before peeling the copper foil, the welded portion of the outermost copper foil that was in contact with the horn was magnified 20 times with an actual microscope to confirm that there were no cracks before peeling test Carried out.
- Example 4-9 the surface treatment was performed with a mixed solution of BTA and a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule.
- the thickness of the mixed organic film with a water-soluble organic compound having an ether bond is in the range of 1.0 to 5.0 nm. For this reason, various copper alloys also show good characteristics in all of wettability, rust prevention and weldability.
- Comparative Example 4-10 the surface treatment was performed only with BTA, and then the surface treatment was performed with a water-soluble organic compound having a hydroxyl group and a linear ether bond in the molecule. Yes.
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Abstract
Description
本発明において、銅箔は電解銅箔及び圧延銅箔のいずれでもよい。また、「銅箔」には銅合金箔も含まれるものとする。銅箔の材料としては、特に制限はなく、用途や要求特性に応じて適宜選択すればよい。例えば、限定的ではないが、圧延銅箔の場合、高純度の銅(無酸素銅やタフピッチ銅等)の他、Sn入り銅、Ag入り銅、Ni、Si等を添加したCu-Ni-Si系銅合金、Cr、Zr等を添加したCu-Cr-Zr系銅合金のような銅合金が挙げられる。
表面処理は、アゾール系化合物と分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液を用いて行う。表面処理は、銅箔の上下面のうち負極活物質との密着性が要求される少なくとも一面に混合液を浸漬、塗布及び噴霧などによって接触させ、その後、乾燥することでアゾール系化合物及び水溶性エポキシ樹脂を銅箔表面の銅と反応させ、銅箔表面に固定することで行う。
以上の検出結果により分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物及びアゾール系化合物の存在を確認した上で、さらにX線光電子分光分析装置(XPS装置)とアルゴンスパッタとを組み合わせて、深さ方向の元素分析を行い、各元素の分布の様子によって、混合層が形成されているのか、又は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物及びアゾール系化合物による単独の層が形成されているのかを判定する。また、当該深さ方向の元素分析により、混合層の厚みを決定する。XPS装置にて、アゾール系化合物と水溶性エポキシ樹脂の加水分解物、二級アミン付加物、又は、イミダゾール化合物付加物の混合層の場合はN及びOを検出し、且つ、C検出量がバックグラウンドレベルよりも大きい深さ範囲を混合層の厚みとしてこれを複数箇所測定し、その平均値D0を混合層の平均厚みとする。また、アゾール系化合物とエポキシ基を付与したシランカップリング剤の加水分解物の混合層ではSi及びNを検出し、且つ、C検出量がバックグラウンドレベルよりも大きい深さ範囲を混合層の厚みとしてこれを複数箇所測定し、その平均値D0を混合層の平均厚みとすることもできる。例として、アゾール系化合物とエポキシ基を加水分解されたシランカップリング剤の混合有機皮膜につき、XPS装置にて分析した結果を図2に示す。なお、密着性、防錆性及び超音波溶接性の共存を図る観点から、混合層の平均厚みD0は1.0~5.0nmが好ましく、1.5~4.0nmがより好ましい。また、混合層と銅箔との間にさらに中間層が形成されている場合であっても、混合層及び中間層の合計の平均厚みについて、D0は同様に、1.0~5.0nmが好ましく、1.5~4.0nmがより好ましい。また、混合層と中間層とが形成されている場合、それらの厚みの割合として、混合層の方が大きいことが好ましい。図3に、アゾール系化合物及び水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物の有機被膜の厚みを測定する際に得られるXPS装置によるN、O及びCのデプスプロファイルの例を示す。
(実施例1)
アゾール系化合物及び水溶性エポキシ樹脂の混合液による表面処理が特性に与える影響を検討するため、以下の条件で実施例及び比較例を作成した。各種条件及び試験結果を後述の表1に示す。
[圧延銅箔の製造]
厚さ200mm、幅600mmのタフピッチ銅のインゴットを製造し、熱間圧延により10mmまで圧延した。
次に、焼鈍と冷間圧延を繰り返し、最後に冷間圧延で、ワークロール径60mm、ワークロール表面粗さRaを0.03μmとし、最終パスの圧延速度400m/分、加工度20%として厚さ10μmに仕上げた。圧延油の粘度は9.0cSt(25℃)であった。得られた圧延銅箔はRaが0.11μmであった。
特許第4115240号の実施例に記載された電解液を用いて電解して、10μmの電解銅箔を製造した。得られた電解銅箔はRaが0.12μmであった。
上記の通り製造した板厚10μmの圧延銅箔及び電解銅箔につき、表1に記載の濃度のアゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物各単独の水溶液、及び、両者を混合した水溶液を準備し、これに3秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3-ベンゾトリアゾール(以下、BTA)を、また、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、下記反応式(6)に示すとおり、ナガセケムテックス社製の「デナコールEX-521」のエポキシ基を開環させて水酸基を付加したものを用いた。
(1)銅箔を30mm×60mmの大きさに切り出した。
(2)試料(1)を硫化水素暴露試験機(H2S:3ppm、40℃、50RH%)に入れ、20分間保持した。
(3)試料を(2)の試験機から取り出し、銅箔表面の色調を確認した。
(4)試験後の銅箔表面の色調が試験前と同じものを「○」、試験前と比較して、薄い赤褐色に変色したものを「△」、表面全体が紫あるいは青色に変色したものを「×」とした。
協和界面科学株式会社製接触角計CA-D型を用い、室温(25℃)にて1.52mmφの純水の液滴を滴下することで接触角を測定し、接触角60°未満を「◎」、60~70°を「○」、70~80°を「△」、80°を超えると「×」とした。
(1)銅箔を100mm×150mmの大きさに切り出し、30枚重ねた。
(2)ブランソン社製のアクチュエータ(型番:Ultraweld L20E)にホーン(ピッチ0.8mm、高さ0.4mm)を取り付けた。アンビルは0.2mmピッチを使用した。
(3)溶接条件は、圧力40psi、振幅60μm、振動数20kHz、溶接時間は0.1秒とした。
(4)上記条件で溶接した後、銅箔を1枚ずつ剥離したときに、21枚以上の銅箔が溶接部分で破れた場合を「◎」、11~20枚の銅箔が溶接部分で破れた場合を「○」、1~10枚の銅箔が溶接部分で破れた場合を「△」、一枚も銅箔が破れなかった場合を「×」とした。なお、銅箔を剥離する前に、ホーンに接触していた最表層の銅箔の溶接部分を実態顕微鏡にて20倍で拡大観察し、クラックが発生していないことを確認してから剥離試験を実施した。
有機皮膜(混合層、又は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物又はBTA単独で形成された層)の厚みは、アルゴンスパッタしながらXPS装置で銅箔の深さ方向について元素分析し、O及びNを検出し、且つ、C検出量がバックグラウンドレベルよりも大きな深さ範囲(SiO2換算)を有機皮膜厚みとし、任意の5カ所の平均値を有機皮膜厚みの平均値とした。
・装置:XPS装置(アルバックファイ社、型式5600MC)
・真空度:5.7×10-7Pa
・X線:単色AlKα、X線出力210W、入射角45°、取り出し角45°
・イオン線:イオン種Ar+、加速電圧3kV、掃引面積3mm×3mm、スパッタリングレート2.3nm/min(SiO2換算)
実施例1-1~1-11は、BTAと分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で表面処理をしており、更に、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合有機皮膜厚が1.0~5.0nmの範囲にある。このため、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。
比較例1-12は、表面処理未実施であり、表面に有機皮膜が存在せず、溶接性は良好で水濡れ性も悪くはないが、防錆性が悪く、水濡れ性、防錆性及び溶接性を同時に満足させることはできない。
比較例1-13~1-15は、BTAのみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど防錆性が良好である。しかしながら、いずれの濃度であっても水濡れ性が悪く、BTAのみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
比較例1-16~1-18は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど水濡れ性が良好である。しかしながら、いずれの濃度であっても防錆性が悪く、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
また、比較例1-19は、BTAのみで表面処理を行った後、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物で表面処理を行っており、BTAの防錆効果が低下している。
また、比較例1-20は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみで表面処理を行った後、BTAで表面処理を行っており、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の水濡れ性改善効果が低下している。
以下の方法で表面処理した試料につき、実施例1に従い評価した。各種条件及び試験結果を後述の表2に示す。
[表面処理]
実施例1の通り製造した板厚10μmの圧延銅箔及び電解銅箔につき、表1に記載の濃度のアゾール系化合物及びエポキシ基を加水分解させたシランカップリング剤各単独の水溶液、及び、両者を混合した水溶液を準備し、これに3秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3-ベンゾトリアゾール(以下、BTA)また、エポキシ基を加水分解させたシランカップリング剤として、下記一般式(H)の化合物を用いた。
実施例2-1~2-11は、BTAとエポキシ基を加水分解させたシランカップリング剤との混合液で表面処理をしており、更に、エポキシ基を加水分解させたシランカップリング剤との混合有機皮膜厚が1.0~5.0nmの範囲にある。このため、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。
比較例2-12は、表面処理未実施であり、表面に有機皮膜が存在せず、溶接性は良好で水濡れ性も悪くはないが、防錆性が悪く、水濡れ性、防錆性及び溶接性を同時に満足させることはできない。
比較例2-13~2-15は、BTAのみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど防錆性が良好である。しかしながら、いずれの濃度であっても水濡れ性が悪く、BTAのみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
比較例2-16~2-18は、エポキシ基を加水分解させたシランカップリング剤のみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど水濡れ性が良好である。しかしながら、いずれの濃度であっても防錆性が悪く、エポキシ基を加水分解させたシランカップリング剤のみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
また、比較例2-19は、BTAのみで表面処理を行った後、エポキシ基を加水分解させたシランカップリング剤で表面処理を行っており、BTAの防錆効果が低下している。
また、比較例2-20は、エポキシ基を加水分解させたシランカップリング剤のみで表面処理を行った後、BTAで表面処理を行っており、エポキシ基を加水分解させたシランカップリング剤の水濡れ性改善効果が低下している。
以下の方法で表面処理した試料につき、実施例1に従い評価した。各種条件及び試験結果を後述の表3に示す。
[表面処理]
実施例1の通り製造した板厚10μmの圧延銅箔及び電解銅箔につき、表3に記載の濃度のアゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物各単独の水溶液、及び、両者を混合した水溶液を準備し、これに3秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3-ベンゾトリアゾール(以下、BTA)また、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、下記反応式(7)に示すとおり、ナガセケムテックス社製の「デナコールEX-521」のエポキシ基にイミダゾールを付加反応させたものを用いた。
実施例3-1~3-11は、BTAと分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物との混合液で表面処理をしており、更に、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物との混合有機皮膜厚が1.0~5.0nmの範囲にある。このため、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。
比較例3-12は、表面処理未実施であり、表面に有機皮膜が存在せず、溶接性は良好で水濡れ性も悪くはないが、防錆性が悪く、水濡れ性、防錆性及び溶接性を同時に満足させることはできない。
比較例3-13~3-15は、BTAのみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど防錆性が良好である。しかしながら、いずれの濃度であっても水濡れ性が悪く、BTAのみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
比較例3-16~3-18は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物のみで表面処理を行っており、処理液濃度が低いほど溶接性が良好で、処理液濃度が高いほど水濡れ性が良好である。しかしながら、いずれの濃度であっても防錆性が悪く、分子中に水酸基と線状エーテル結合を有する水溶性有機化合物にイミダゾール基を付加した化合物のみでは、水濡れ性、防錆性及び溶接性を同時に満足させることができないことを示している。
また、比較例3-19は、BTAのみで表面処理を行った後、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物で表面処理を行っており、BTAの防錆効果が低下している。
また、比較例3-20は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物にイミダゾール基を付加した化合物のみで表面処理を行った後、BTAで表面処理を行っており、分子中に水酸基と線状エーテル結合を有する水溶性有機化合物にイミダゾール基を付加した化合物の水濡れ性改善効果が低下している。
以下の方法で表面処理した試料につき、実施例1で記載の方法又は以下の方法で評価した。各種条件及び試験結果を後述の表4に示す。
無酸素銅に各種元素を添加し、厚さ200mm、幅600mmの銅合金インゴットを製造し、熱間圧延により10mmまで圧延した。
次に、焼鈍と冷間圧延を繰り返し、最後に冷間圧延で、ワークロール径60mm、ワークロール表面粗さRaを0.03μmとし、最終パスの圧延速度400m/分、加工度20%として厚さ6~20μmに仕上げた。圧延油の粘度は9.0cSt(25℃)であった。得られた圧延銅箔はRaが0.11μmであった。
上記の通り製造した板厚6~20μmの圧延銅箔につき、表4に記載の濃度のアゾール系化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物各単独の水溶液、及び、両者を混合した水溶液を準備し、これに5秒間浸漬した後、ドライヤーにて乾燥した。アゾール系化合物は、1,2,3-ベンゾトリアゾール(以下、BTA)を、また、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物は、ナガセケムテックス社製の「デナコールEX-521」のエポキシ基を開環させて水酸基を付加したものを用いた。
(1)銅箔を100mm×150mmの大きさに切り出し、板厚6μmでは50枚、板厚10μmでは30枚、板厚20μmでは15枚重ねた。
(2)ブランソン社製のアクチュエータ(型番:Ultraweld L20E)にホーン(ピッチ0.8mm、高さ0.4mm)を取り付けた。アンビルは0.2mmピッチを使用した。
(3)溶接条件は、圧力40psi、振幅60μm、振動数20kHz、溶接時間は0.1秒とした。
(4)上記条件で溶接した後、銅箔を1枚ずつ剥離したときに、板厚6μmでは35枚以上、板厚10μmでは21枚以上、板厚20μmでは11枚以上の銅箔が溶接部分で破れた場合を「◎」、板厚6μmでは18~34枚、板厚10μmでは11~20枚、板厚20μmでは6~10枚の銅箔が溶接部分で破れた場合を「○」、板厚6μmでは1~17枚、板厚10μmでは1~10枚、板厚20μmでは1~5枚の銅箔が溶接部分で破れた場合を「△」、一枚も銅箔が破れなかった場合を「×」とした。なお、銅箔を剥離する前に、ホーンに接触していた最表層の銅箔の溶接部分を実態顕微鏡にて20倍で拡大観察し、クラックが発生していないことを確認してから剥離試験を実施した。
水濡れ性、防錆性及び有機皮膜の厚みは、実施例1に記載の方法で評価した。
実施例4-1~4-9は、BTAと分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で表面処理をしており、更に、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合有機皮膜厚が1.0~5.0nmの範囲にある。このため、各種銅合金においても、水濡れ性、防錆性及び溶接性の全てにおいて良好な特性を示している。比較例4-10は、BTAのみで表面処理を行った後、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物で表面処理を行っており、BTAの防錆効果が低下している。比較例4-11は、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物のみで表面処理を行った後、BTAで表面処理を行っており、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の水濡れ性改善効果が低下している。
Claims (14)
- 銅箔表面の少なくとも一部にアゾール化合物及び分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物の混合層が形成されたリチウムイオン電池集電体用銅箔。
- XPSによる深さ方向分析でO及びNを検出し、かつC検出量がバックグラウンドレベルよりも大きい深さ範囲の平均値D0が1.0~5.0nmである請求項1に記載のリチウムイオン電池集電体用銅箔。
- 前記反応式(5)におけるエポキシ基を有する化合物が、グリシドキシ基を有する水溶性エポキシ樹脂、又は、グリシドキシ基を有するシランカップリング剤である請求項5に記載のリチウムイオン電池集電体用銅箔。
- 前記水溶性有機化合物が分子内にイミダゾール基を含む請求項1~6のいずれかに記載のリチウムイオン電池集電体用銅箔。
- 前記銅箔表面と前記混合層との間に、アゾール化合物又はクロメート層で構成された中間層が形成された請求項1~7のいずれかに記載のリチウムイオン電池集電体用銅箔。
- 前記アゾール化合物がベンゾトリアゾール系化合物である請求項1~8のいずれかに記載のリチウムイオン電池集電体用銅箔。
- 前記ベンゾトリアゾール系化合物が1,2,3-ベンゾトリアゾールである請求項9に記載のリチウムイオン電池集電体用銅箔。
- リチウムイオン二次電池負極集電体用である請求項1~10のいずれかに記載のリチウムイオン電池集電体用銅箔。
- 請求項1~11のいずれかに記載の銅箔を集電体として用いたリチウムイオン電池。
- 銅箔表面の少なくとも一部に対し、アゾール化合物と、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物との混合液で表面処理を実施して、前記アゾール化合物及び前記水溶性有機化合物の混合層を形成する工程を含むリチウムイオン電池集電体用銅箔の製造方法。
- 前記混合液は、アゾール化合物を0.01~0.25g/L、及び、分子中に水酸基と線状エーテル結合とを有する水溶性有機化合物を0.5~20g/Lで含む請求項13に記載のリチウムイオン電池集電体用銅箔の製造方法。
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CN201080050535XA CN102640333A (zh) | 2009-11-05 | 2010-10-28 | 锂离子电池集电体用铜箔 |
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JP6012913B1 (ja) * | 2015-01-19 | 2016-10-25 | 古河電気工業株式会社 | リチウムイオン二次電池用表面処理電解銅箔、これを用いたリチウムイオン二次電池用電極およびリチウムイオン二次電池 |
JP2019175802A (ja) * | 2018-03-29 | 2019-10-10 | Jx金属株式会社 | リチウムイオン電池集電体用圧延銅箔及びリチウムイオン電池 |
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JP2020071927A (ja) * | 2018-10-29 | 2020-05-07 | Jx金属株式会社 | リチウムイオン電池集電体用圧延銅箔及びリチウムイオン電池 |
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JP2021103697A (ja) * | 2018-10-29 | 2021-07-15 | Jx金属株式会社 | リチウムイオン電池集電体用圧延銅箔及びリチウムイオン電池 |
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