WO2014119582A1 - 電解銅箔、該電解銅箔を用いたリチウムイオン二次電池用電極、該電極を用いたリチウムイオン二次電池 - Google Patents
電解銅箔、該電解銅箔を用いたリチウムイオン二次電池用電極、該電極を用いたリチウムイオン二次電池 Download PDFInfo
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- WO2014119582A1 WO2014119582A1 PCT/JP2014/051859 JP2014051859W WO2014119582A1 WO 2014119582 A1 WO2014119582 A1 WO 2014119582A1 JP 2014051859 W JP2014051859 W JP 2014051859W WO 2014119582 A1 WO2014119582 A1 WO 2014119582A1
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- copper foil
- electrolytic copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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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
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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 an electrolytic copper foil having a low profile electrolytic deposition surface, high mechanical strength, and hardly changing mechanical strength even when heated at a high temperature.
- the present invention relates to a secondary battery in which the electrolytic copper foil is used as a secondary battery current collector, an active material is deposited on the current collector to form a secondary battery electrode, and the electrode is incorporated.
- the electrolytic copper foil of the present invention can be suitably used for rigid printed wiring boards, flexible printed wiring boards, electromagnetic wave shielding materials, and the like using the electrolytic copper foil as a conductive material.
- electrolytic copper foil and electrolytic copper alloy foil are distinguished and expressed.
- electrolytic copper foil When it is not necessary, it is expressed as “electrolytic copper foil”, and mechanical strength indicates tensile strength.
- This wiring-integrated suspension has the following three types. a. A type in which a flexible printed circuit board called FSA (flex suspension assembly) method is processed and bonded using an adhesive b. Type C.TSA (Trace Suspension / Assembly) type called stainless steel foil-polyimide resin-copper foil laminated body processed into a predetermined shape by etching
- the laminate formed by the TSA method is manufactured using a material having a stainless steel foil thickness of about 12 to 30 ⁇ m, a polyimide layer thickness of about 5 to 20 ⁇ m, and a copper alloy foil thickness of about 7 to 14 ⁇ m.
- a polyimide resin solution is applied onto a stainless steel foil as a base. After the application, the solvent is removed by preheating, and then further heat treatment is performed to perform imidization. Subsequently, a copper alloy foil is superposed on the imidized polyimide resin layer and laminated by thermocompression bonding at a temperature of about 300 ° C. to produce a laminate composed of stainless steel layer / polyimide layer / copper alloy layer.
- Plating concentrates on high current areas where electricity can easily flow without adding chlorine or additives to the copper sulfate plating bath (locations close to the anode, the end of the cathode, the tip of sharp objects, etc.) State (plated surface becomes more uneven).
- the electrolytic copper foil is made by adding chlorine and an organic compound as additives to an electrolytic solution containing copper sulfate and sulfuric acid.
- Many organic additives usually have an effect of suppressing crystal growth, and are considered to be taken into crystal grain boundaries. In this case, the mechanical strength tends to improve as the amount of the organic additive taken into the crystal grain boundary increases (Non-patent Document 1: Shiga Shoji; Metal Surface Technology Vol31, No10, p573 (1980)).
- the present inventors have an electrolytic copper alloy foil that has a low profile surface bonded to a polyimide resin base material and excellent mechanical strength, and an electrolytic copper alloy foil that is suitable for applications using a polyimide resin as a binder resin. Attempts were made to add various metals to the copper foil to improve its heat resistance. However, it has been difficult to incorporate a metal capable of improving the heat resistance of the copper foil into the electrolytic copper foil. That is, there has been a problem that the metal that improves the heat resistance of the copper foil is a metal that is difficult to incorporate into the copper foil.
- the electrolytic copper foil of the present invention is characterized by containing a metal present as an oxide in an acidic solution having a pH of 4 or less and containing 0.005 to 0.04 wt% of chlorine.
- the preferable content of the metal component in the electrolytic copper foil is 0.0001 wt% or more.
- a more preferable content of the metal component in the electrolytic copper foil is 0.001 to 1.320 wt%.
- the metal component of the electrolytic copper foil is preferably one or more metal components selected from titanium (Ti), molybdenum (Mo), vanadium (V), bismuth (Bi), and tellurium (Te).
- the tensile strength at room temperature of the electrolytic copper foil is preferably 650 MPa or more, and the tensile strength measured at room temperature after heat treatment at 300 ° C. for 1 hour is preferably 450 MPa or more.
- the electrical conductivity of the electrolytic copper foil at room temperature is 60% IACS or more.
- the electrode for a lithium ion secondary battery of the present invention is characterized by using the electrolytic copper foil of the present invention as a current collector.
- the above-mentioned “contains at least one of Ti, Mo, V, Bi, and Te” means that each metal is contained alone or two or more of them are contained simultaneously.
- the balance is substantially made of copper means that copper contains inevitable impurities derived from raw materials or the like, or allows a trace amount of additives due to an electrolytic foil manufacturing process or the like to be included. Is the meaning.
- the amount of metal present as an oxide in an acidic solution having a pH of 4 or less contained in the electrolytic copper foil is preferably 0.0001 wt% or more.
- the content of a metal present as an oxide in an acidic solution having a pH of 4 or less is 0.0001 wt% or less, the effect of adding the metal hardly appears.
- a more preferable range of the metal content in the foil is 0.001 to 1.320 wt%.
- the reason why the metal contained in the electrolytic copper foil is limited to a metal present in an acidic solution having a pH of 4 or less is that the pH of the electrolytic solution is 4 or less, and the metal present as an oxide in such an acidic electrolytic solution is copper. This is because it is easily taken into the foil. That is, in the copper foil containing less than 0.0001 wt% of the metal, the mechanical strength measured at room temperature after the heat treatment at 300 ° C. for 1 hour shows a tendency for the strength to decrease as in the case where the metal is not contained.
- a metal present as an oxide at pH 4 or lower means a pH of 4 or lower in the potential-pH diagram shown in M. Pourbaix®'s Atlas® of electrochemical® equilibria® in aqueous solution. Pergamon® Press (1966).
- the added metal component is a metal that is detected as solid particles in the particle size distribution measurement by DLS (Dynamic Light Scattering) of the electrolytic solution to which the metal is added.
- an electrolytic copper foil as a current collector for a battery, particularly as a current collector for an electrode for a lithium ion secondary battery, a copper foil having higher mechanical strength is required. Therefore, for use as a current collector, the amount of the metal contained in the electrolytic copper foil is preferably 0.001 or more, preferably 1.320 wt% or less.
- the electrolytic copper foil of this embodiment contains 0.005 to 0.04 wt% of chlorine.
- the electrolytic copper foil having a chlorine content of 0.005 wt% or less needs to keep the chlorine concentration in the electrolytic bath for producing the electrolytic copper foil low, so that pinholes are generated in the foil production. This is not preferable because pinholes exist in the copper foil that has been formed.
- an electrolytic copper foil having a chlorine content of 0.04 wt% or more is not preferable because curling tends to occur in the copper foil. Accordingly, the chlorine content is preferably 0.005 to 0.04 wt%.
- the present inventors have sought various manufacturing methods in which the metal is contained in a copper foil as a copper alloy or mixed as a simple substance.
- an electrolytic solution containing chlorine ions even if a large amount of the metal is added to the solution, the metal is not taken into the foil-formed copper foil, and naturally the foil is made with such an electrolytic solution.
- the mechanical strength of the copper foil after heating at normal temperature and after heating was not improved.
- chlorine ions were added to the electrolytic solution, it was found that if the thiourea compound was added to the solution, the metal was taken into the foil depending on the foil production conditions.
- Additives added to the sulfuric acid-copper sulfate-based copper electrolyte are as follows.
- Additive A: Thiourea compound 3 to 20 mg / L
- Additive B: at least one salt of Ti, Mo, V, Bi, Te (when adding a plurality of metals as Ti, Mo, V, Bi, Te, the total amount thereof) 100 to 10,000 mg / L
- Additive C: Chlorine ion 1 to 100 mg / L
- Additive B selected from metal salts of Ti, Mo, V, Bi, and Te dissolved in an acidic electrolyte containing copper sulfate and sulfuric acid and present as an oxide.
- metal salts of Ti, Mo, V, Bi, and Te dissolved in an acidic electrolyte containing copper sulfate and sulfuric acid and present as an oxide.
- sodium salt, ammonium salt, potassium salt and the like for example, sodium salt, ammonium salt, potassium salt and the like.
- Additive C The addition of chloride ions is selected from compounds that dissolve in an electrolytic solution containing copper sulfate and sulfuric acid. For example, hydrochloric acid, sodium chloride, potassium chloride and the like.
- thiourea compounds as organic additives
- an adsorption layer and adsorbing at least one oxide of Ti, Mo, V, Bi, Te on the adsorption layer in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te
- an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te
- Metals present as oxides in acidic solutions of pH 4 or lower, such as Ti, Mo, V, Bi, Te, etc. exist as oxides in acidic solutions.
- metal oxides present as oxides in acidic solutions of pH 4 or lower such as Ti, Mo, V, Bi, Te, etc. are not adsorbed by copper, but into the foil. Ingestion does not occur.
- pH 4 of Ti, Mo, V, Bi, Te, etc. pH 4 of Ti, Mo, V, Bi, Te, etc. It is assumed that the metal present as an oxide in the following acidic solution is taken into the foil together with the thiourea compound.
- the electrolytic copper foil of the present invention contains a metal, a thiourea compound, and chlorine that are present as oxides in an acidic solution of pH 4 or lower such as Ti, Mo, V, Bi, Te, etc. in a sulfuric acid-copper sulfate electrolytic solution. It forms by electrolytic deposition from the electrolyte solution containing.
- Metal oxides present as oxides in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te, etc. present at the grain boundaries are not bonded to or absorbed by the bulk copper crystals. , Mo, V, Bi, and Te oxides are considered to remain at the grain boundaries. Therefore, even when an electrolytic copper foil containing a metal present as an oxide in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te is heated at a high temperature of about 300 ° C., Ti, Mo, V, Metal oxides that exist as oxides in acidic solutions such as Bi and Te that have a pH of 4 or less remain at the grain boundaries, and the copper fine crystals recrystallize due to heat and prevent the crystals from becoming coarse. Conceivable.
- the electrolytic copper foil of the present invention has a low profile and a small decrease in mechanical strength even after being heated at a high temperature of about 300 ° C. Exhibits excellent characteristics not seen in electrolytic copper foils manufactured with liquid.
- an electrolyte containing chlorine ions contains metal and glue existing as oxides in an acidic solution having a pH of 4 or less, such as Ti, Mo, V, Bi, and Te. Even if it added, the metal which exists as an oxide in the acidic solution of pH 4 or less, such as Ti, Mo, V, Bi, and Te, was not taken in in electrolytic copper foil. As a matter of course, the mechanical strength of the electrolytic copper foil made with such an electrolytic solution greatly decreased after being heated at a high temperature of about 300 ° C.
- the metal present as an oxide in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te, etc. It is considered that the thiourea compound added to the sulfuric acid-copper sulfate electrolytic solution forms a complex with the metal element and chlorine in the electrolytic solution.
- the metal present as an oxide in an acidic solution of pH 4 or lower such as Ti, Mo, V, Bi, Te is not added, the metal element added to the electrolytic solution for the electrolytic copper foil foil is copper. It is.
- a copper-thiourea compound is formed in an electrolytic solution containing copper sulfate and sulfuric acid.
- an electrolytic copper foil is formed by copper electrodeposition using this electrolytic solution, the copper-thiourea compound is adsorbed on the grain boundaries, suppressing the growth of crystal nuclei, making the grains finer, and increasing the mechanical strength in the normal state.
- the provided electrolytic copper foil is formed.
- this copper foil is a copper-thiourea compound that exists at the grain boundaries, copper is bound to or absorbed by bulk copper crystals, and the substance present at the grain boundaries is the thiourea compound. Therefore, it is considered that this thiourea compound decomposes when exposed to a high temperature of about 300 ° C., and as a result, the mechanical strength decreases.
- the reason why the tensile strength is remarkably lowered is that the compound existing at the grain boundary is an organic compound as described above, and the organic compound is heated by heating at about 300 ° C. It is considered that the mechanical strength decreases because it is easily decomposed.
- an electrolytic solution containing copper sulfate and sulfuric acid contains at least one kind of metal, thiourea compound, and chlorine, which are present as oxides in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te. Since the copper electrodeposition is performed with the electrolytic solution containing to form a copper foil, the metal present as an oxide in an acidic solution of pH 4 or less such as Ti, Mo, V, Bi, Te, etc. added to the electrolytic solution is an oxide. And adsorb on copper together with thiourea compounds.
- the growth of crystal nuclei is suppressed and the crystal grains are refined by the metal oxides and thiourea compounds present as oxides in an acidic solution of pH 4 or lower such as adsorbed Ti, Mo, V, Bi, Te.
- An electrolytic copper foil having a large mechanical strength in a normal state is formed.
- the electrolytic copper foil of the present invention has metal oxides and thiourea compounds present as oxides in an acidic solution of pH 4 or lower such as Ti, Mo, V, Bi, Te, etc., at the grain boundaries. Therefore, unlike the case of the copper-thiourea compound, the oxide of the metal present as an oxide in an acidic solution of pH 4 or lower such as Ti, Mo, V, Bi, Te is bonded to the bulk copper crystal, or It is considered that the metal oxides and thiourea compounds existing as oxides in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, and Te remain at the grain boundaries without being absorbed.
- metal oxides existing as oxides in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te, etc. remain at the crystal grain boundaries. It works to prevent fine crystals from being recrystallized by heat and coarsening of the crystals.
- the size of the precipitate such as an oxide is preferably 0.5 to 20 nm because the pinning effect is most exhibited and the growth of crystal grains can be suppressed even at a high temperature.
- the size of the precipitate is 20 to 50 nm, although the pinning effect is exhibited, it cannot be said that the crystal growth is completely suppressed.
- the pinning effect is exhibited even when the size of the precipitate is 50 to 100 nm, a large number of crystal grains are observed.
- the amount of metal present as an oxide in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te added to the electrolyte is preferably 100 to 10,000 mg / L.
- the addition amount of the metal present as an oxide in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te, etc. is set to 100 mg / L or more below which Ti, Mo, V, Bi, Te, etc.
- the addition of a thiourea compound succeeded in incorporating Ti, Mo, V, Bi, and Te into the copper foil.
- the amount of thiourea compound to be added is 3 to 20 mg / L. If it is less than 3 mg / L, it exists as an oxide in an acidic solution of Ti, Mo, V, Bi, Te or the like in copper foil in a copper foil.
- the tensile strength at room temperature after heat treatment at 300 ° C.
- the amount of chlorine ion added is 1 to 100 mg / L. Addition of less than 1 mg / L of chlorine ions is not preferable because many pinholes are generated in the foil, and addition of more than 100 mg / L of chloride ions causes a significant increase in surface roughness or curling. Therefore, the chlorine ion is preferably in the range of 1 to 100 mg / L, particularly preferably 15 to 50 mg / L. By making a foil with an electrolytic solution containing such an amount of chlorine ions, 0.005 to 0.04 wt% of chlorine can be contained in the electrolytic copper foil.
- the electrolytic copper foil is copper sulfate to which at least one kind of metal existing as an oxide in an acidic solution of pH 4 or lower such as Ti, Mo, V, Bi, Te, a thiourea compound, and a chlorine ion is added in the specified amount.
- a current density 30 to 100 A / dm 2 and a liquid temperature of 30 to 70 ° C.
- the mechanical strength at room temperature after 300 ° C. ⁇ 1 hour heat treatment of the electrolytic copper foil to be formed by adding ammonium ion or nitrate ion to the electrolytic solution of the present invention can be further improved.
- the amount of ammonium ions added to the electrolyte is 1 to 15 g / L, and the amount of nitrate ions is 50 to 200 mg / L.
- electrolytic copper having a tensile strength at room temperature after heat treatment at 300 ° C. for 1 hour of 450 MPa or more and a conductivity of 60% IACS or more.
- a foil can be produced.
- the current collector (copper foil) constituting the negative electrode current collector of the lithium ion secondary battery needs to withstand heat treatment of usually 300 ° C. ⁇ 1 hour when a polyimide binder is used. That is, an active material composition prepared by adding a solvent to a mixture of an active material, a conductive material and a binder to a surface of a current collector for a lithium ion secondary battery and applying a lithium ion secondary battery through a drying process. The negative electrode of the secondary battery is used. In the drying process, a heat treatment of 300 ° C. ⁇ 1 hour is required.
- the tensile strength measured at room temperature after heat treatment at 300 ° C. for 1 hour is 450 MPa or more. Satisfactory performance is required.
- active materials such as Si and Sn have poor electronic conductivity compared to active materials such as carbon. If the conductivity of the active material is poor, the internal resistance of the electrode increases, and the cycle characteristics deteriorate. Therefore, the copper foil as a current collector is required to have a conductivity of 60% or more.
- the copper foil containing a metal present as an oxide in an acidic solution having a pH of 4 or less such as Ti, Mo, V, Bi, Te, etc. of the present invention satisfies various characteristics required by the current collector for a secondary battery. Therefore, such an electrolytic copper foil is used as a current collector, and silicon, germanium, tin, or an alloy compound thereof or an active material containing them as a main component is deposited on the current collector as an electrode. An excellent lithium ion secondary battery can be manufactured and provided.
- An electrolytic solution containing the following copper sulfate and sulfuric acid is used as a basic bath composition, and an electrolytic solution to which chlorine ions, Ti, Mo, V, Bi, Te, and thiourea organic additives in amounts shown in Table 1 are added is used.
- An electrolytic copper foil was made under the following electrolysis conditions using a noble metal oxide-coated titanium as an anode and a titanium rotating drum as a cathode.
- the electrolytic copper foil thus formed was subjected to a rust prevention treatment under the following conditions.
- the formed electrolytic copper foil (untreated copper foil) was immersed in a CrO 3 ; 1 g / L aqueous solution for 5 seconds, subjected to chromate treatment, washed with water and dried.
- the chromate treatment is performed here, it goes without saying that the silane coupling agent treatment may be performed after the benzotriazole-based treatment, the silane coupling agent treatment, or the chromate treatment.
- the electrical conductivity was calculated by first measuring the resistance value of a 20 mm ⁇ 200 mm copper foil and then dividing the measured resistance value by the cross-sectional area of the copper foil.
- Measurement of chlorine content Chlorine content was calculated by dissolving a certain weight of electrolytic copper foil with an acid and then quantifying the chlorine in the solution by silver nitrate titration.
- the chemical bonding state and electronic state of oxides contained in the electrolytic copper alloy were analyzed by the XAFS (X-ray Absorption Fine Structure) method.
- XAFS X-ray Absorption Fine Structure
- a sample is irradiated with X-rays while changing X-ray energy, and a chemical bond state and an electronic state in the sample can be analyzed from the obtained X-ray absorption spectrum.
- Other methods for obtaining an X-ray absorption spectrum include a transmission method for obtaining an X-ray absorption spectrum from the intensity of incident X-rays and the intensity of transmitted X-rays, and the intensity of fluorescent X-rays emitted from a sample along with X-ray absorption. There is a fluorescence method for measuring.
- the fluorescent method described above is effective in such a case.
- XAFS measurement can be performed even with a trace amount of elements by taking a wider X-ray irradiation area than the optical axis system.
- the purpose of this measurement is to know the chemical bonding state and electronic state of Ti, Mo, V, Bi, and Te in the high-strength copper foil.
- the amount of Ti, Mo, V, Bi, and Te is very small, and the transmission
- the fluorescence method was selected because it was difficult to obtain an XAFS spectrum by this method.
- SPring-8 industrial use beam line BL14B2 was used.
- the measured X-ray energy range was 10,000 to 10434 eV.
- the particle size of the metal component in the foil is determined by SAXS (small angle X-ray scattering) and USAXS (ultra small angle X-ray scattering). X-ray scattering) was determined by analysis. The SAXS / USAXS measurement was performed at the Spring-8 industrial use beamline BL19B2.
- Fig. 1 (a) shows a simple optical axis diagram of SAXS (USAXS) measurement.
- Incident X-rays 14 generated from the X-ray source 13 including the shutter 15 are irradiated to the sample 27 through the monochromator 17, the first pinhole 19, the second pinhole 21, and the third pinhole 25.
- the detector 35 is provided at the end of the optical axis and detects transmitted X-rays 29 or scattered X-rays 31.
- the scattered X-ray 31 is measured by the detector 35, as shown in FIG. 1B, the incident X-ray 14 is irradiated to the sample 27 without passing through the attenuator 23, and the transmitted X-ray 29 is irradiated by the beam stopper 33. The light is shielded and the scattered X-ray 31 is measured by the detector 35.
- the intensity of the incident X-ray 14 is weakened with the attenuator 23, and then the sample 27 is irradiated with the incident X-ray 14.
- the transmitted X-ray 35 is measured by the detector 35 without shielding the transmitted X-ray 29 by the beam stopper 33.
- ⁇ is the wavelength of the incident X-ray.
- ⁇ 0.068 nm
- L 4.2 m (SAXS)
- L 42 m (USAXS).
- the fine particles are considered to be MoO 3 from the results of TEM observation and XAFS measurement. Therefore, X-ray scattering from MoO 3 can be extracted by subtracting the SAXS intensity of the pure copper foil from the SAXS data of the Mo-containing electrolytic copper foil. Using this extracted data, in order to calculate the number density of MoO 3, a scattering cross section was obtained from scattered X-rays, and fitting was performed. The measured X-ray scattering intensity I (q) and the scattering cross section d ⁇ / d ⁇ (q) are in the relationship of equation (2).
- ⁇ 0 is the intensity of the direct beam
- ⁇ is the correction term by the detector
- S is the irradiation area
- T is the transmittance
- d ⁇ / d ⁇ (q) is a scattering cross section
- ⁇ 2 is an atomic scattering factor
- dN is a particle number density
- V is a particle volume
- F is a particle shape factor
- N (r) is a particle size distribution function.
- a lithium ion secondary battery was prepared using the electrolytic copper foil produced in the example as a current collector, and a cycle life test was performed.
- Powdered Si alloy-based active material (average particle size 0.1 ⁇ m to 10 ⁇ m) is mixed in a ratio (weight ratio) of 85 and binder (polyimide) at a ratio (weight ratio) of 15 and dispersed in N-methylpyrrolidone (solvent).
- a slurry was obtained.
- this slurry was applied to both surfaces of the prepared electrolytic copper foil having a thickness of 12 ⁇ m, dried and compression-formed with a roller press, and then sintered at 300 ° C. for 1 hour in a nitrogen atmosphere to obtain a negative electrode.
- the negative electrode mixture after molding had the same film thickness of 20 ⁇ m on both sides.
- Lithium Ion Secondary Battery A three-electrode cell for evaluation was constructed with the following configuration in a glove box under an argon atmosphere. Negative electrode: Si alloy negative electrode prepared above Counter electrode, reference electrode: Lithium foil Electrolytic solution: 1 mol / L LiPF 6 / EC + DEC (3: 7 vol%)
- the constructed cell was taken out from the box into the atmosphere, and charge / discharge measurement was performed in an atmosphere at 25 ° C. Charging was performed at a constant current up to 0.02 V with respect to the standard unipolar potential of Li, and thereafter, charging was terminated when the current decreased by 0.05 C at CV (while being at a constant potential). C indicates a charge / discharge rate. Discharging was performed at a constant current up to 1.5 V (Li standard) at 0.1 C. Charging / discharging was repeated with the same current equivalent to 0.1 C.
- Tables 1 and 2 show the cycle life of the electrodes manufactured under each condition. An electrode having a cycle life of less than 100 times was rejected, 100 times to less than 120 times was a good range, and 120 times or more was an optimum range. Further, as an evaluation of the charge / discharge performance, the battery was disassembled after 100 cycles of charge / discharge, and the deformation and fracture of the foil were observed. The results are shown in Tables 1 and 2 as the deformation of the foil.
- the Ti, Mo, V, Bi, Te content of the electrolytic copper alloy foil containing at least one kind of Ti, Mo, V, Bi, Te is preferably 0.0001 wt% or more, particularly 0.001-1.320 wt. % Is preferred. Outside this range, wrinkles were observed after the charge / discharge test.
- the conductivity tends to be as low as less than 70% IACS, but practically 60% IACS or more.
- the amount of Ti, Mo, V, Bi, Te incorporated in the foil is 0.0001 wt% or more, preferably 0.001 to 1.320 wt. %, More preferably 0.001-1.000 wt%.
- the tensile strength at room temperature is 650 MPa or more
- the tensile strength measured at room temperature after heat treatment at 300 ° C. ⁇ 1 hour is 450 MPa or more
- the conductivity is 60% IACS or more.
- An electrolytic copper foil could be created.
- this invention is an electrolytic copper foil excellent in mechanical strength, and can be used suitably also in the use in the printed wiring board field bonded with a polyimide film.
- the present invention is a lithium ion secondary battery using a Si or Sn alloy-based active material, and adheres between the current collector (copper foil) and the active material against the large expansion and contraction of the Si or Sn alloy-based active material. It is an excellent electrolytic copper foil that can retain its properties with a polyimide binder, has battery characteristics of 100 cycles or more of charge / discharge, and does not deform as a current collector (copper foil).
- Table 2 shows the evaluation results of Comparative Examples 1 to 5.
- the foil was made with an electrolytic solution to which ethylenethiourea and Mo were added. However, since the amount of Mo added was small, Mo could not be taken into the foil. Accordingly, the mechanical strength in the normal state is large, but the mechanical strength is significantly lowered after the heat treatment at 300 ° C. for 1 hour.
- Comparative Examples 2 and 3 are foils made with a composition to which glue is added as an organic additive.
- This copper foil has a low mechanical strength in a normal state, and the mechanical strength is remarkably lowered to 250 MPa or less after heat treatment at 300 ° C. for 1 hour.
- the measurement result of the amount of Mo in the copper foil was less than 0.0001 wt%, which is the lower limit of detection.
- Comparative Examples 4 and 5 as an example that does not exist as an oxide in an electrolyte solution having a pH of 4 or lower and dissolves as ions, Fe and Ni are added to form a foil. However, Fe and Ni are not taken into the foil, and thus the mechanical strength in the normal state is large, but the mechanical strength is significantly lowered after the heat treatment at 300 ° C. ⁇ 1 hour. Further, in the lithium ion secondary battery using the electrolytic copper foil of Comparative Examples 1 to 5 as a current collector, the current collector (copper foil) was deformed after 100 cycles of charge / discharge, and the battery was not used practically. There is a problem with the characteristics.
- the negative electrode collector for secondary batteries using the electrolytic copper foil in any one of the above is provided.
- the electrolytic copper foil according to any one of the above is used as a negative electrode current collector for a secondary battery, and on its surface, silicon, germanium, tin, an alloy compound thereof or a main component thereof.
- An electrode for a secondary battery is provided in which an active material is deposited.
- a secondary battery using the secondary battery electrode is provided.
- a sulfuric acid-copper sulfate electrolyte solution is added with at least one kind of metal salt existing as an oxide in an acidic solution having a pH of 4 or less, chloride ions as an additive,
- a method for producing an electrolytic copper foil is provided, which comprises an electrolytic copper foil containing at least one kind of metal present as an oxide in an acidic solution having a pH of 4 or less, and the balance being copper.
- the metal present as an oxide in an acidic solution having a pH of 4 or less is contained at 0.0001 wt% or more, the tensile strength at room temperature is 650 MPa or more, and measured at room temperature after heat treatment at 300 ° C. ⁇ 1 hour
- a method of manufacturing a foil is provided.
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Abstract
Description
本発明は、前記電解銅箔を二次電池用集電体とし、該集電体に活物質を堆積して二次電池用電極とし、該電極を組み込んだ二次電池に関するものである。
本発明の電解銅箔は、該電解銅箔を導電材としたリジッドプリント配線板、フレキシブルプリント配線板、電磁波シールド材料等に好適に採用することができる。
a.FSA(フレックス サスペンション アッセンブリ)法と呼ばれるフレキシブルプリント基板を加工し接着剤を用いて張り合わせたタイプ
b.CIS(サーキット・インテグレーティッド・サスペンション)法と呼ばれるポリイミド樹脂の前駆体であるアミック酸を形状加工した後、イミド化し更にポリイミド上にメッキ加工を施すことにより配線を形成するタイプ
c.TSA(トレース・サスペンション・アッセンブリ)法と呼ばれるステンレス箔-ポリイミド樹脂-銅箔からなる積層体をエッチング加工により所定の形状に加工するタイプ
ラミネート後に積層体に反りを生じさせないためには、加熱時の寸法変化ができるだけ小さい銅合金箔の提供が求められている。
TAB製品においては、製品のほぼ中央部に位置するデバイスホールに配されるインナーリード(フライングリード)に対し、ICチップの複数の端子を直接ボンディングする。このボンディングはボンディング装置を用いて、瞬間的に通電加熱し、一定のボンディング圧を付加して行う。このとき、電解銅箔をエッチング形成して得られたインナーリードが、ボンディング圧で引っ張られて伸びるという問題がある。
さらには、電解銅箔の強度が低いと塑性変形してインナーリードにたるみが発生し、著しい場合には破断する可能性がある。
従って、インナーリードの線幅を細線化するには、使用する電解銅箔は低粗度化された粗面を持ち、かつ高強度であることが要求される。
負極の形成法としては、負極活物質とバインダー樹脂(活物質と銅箔基板とを結着することを目的に添加される)を溶剤に溶かしたスラリーを銅箔基板上に塗布し、バインダー樹脂の硬化温度以上の温度で乾燥させた後、プレスすることで形成する方法が一般的である。
近年、電池の高容量化に伴い着目されている、理論容量の高いケイ素、スズ、ゲルマニウム合金系材料などからなる活物質は、充放電時のリチウムの挿入脱離に伴う体積膨張率が大きく、上述したバインダー樹脂では強度が足りない。そこで、銅基板との接着強度の高いポリイミド系樹脂が好ましく使用されてきている。しかし、ポリイミド系樹脂は上述したバインダー樹脂と違い、硬化温度が300℃程度と高く、この加熱条件に耐え得る負極集電体(銅箔)が要求されている。
有機添加剤は通常は結晶の成長を抑制する効果のあるものが多く、結晶粒界に取り込まれると考えられている。
この場合、結晶粒界に取り込まれる有機添加剤の量が多いほど機械的強度が向上する傾向にある(非特許文献1:志賀章二;金属表面技術 Vol31, No10,p573 (1980))。
しかし圧延銅箔は電解銅箔に比べると高価であり、幅、厚さ等の要求を満足させることが難しい。
しかし、銅箔の耐熱性を改善できる金属を電解銅箔中に取り込むことは困難であった。即ち、銅箔の耐熱性を改善する金属は銅箔中に取り込み難い金属であることが問題となっていた。
また、本発明はポリイミドフィルムと張り合わせるプリント配線板分野における用途において機械的強度に優れた電解銅箔を提供することを目的とする。
更に本発明は、Si又はSn合金系活物質を用いるリチウムイオン二次電池で、Si又はSn合金系活物質の大きな膨張、収縮に対して、集電体(銅箔)と活物質との密着性をポリイミドバインダーにより保持し、集電体(銅箔)が変形しない電解銅箔を提供することを目的とする。
また、本発明者等は、たとえば、HDDサスペンション材料、TAB材料として、或いはSi又はSn合金系活物質の大きな膨張、収縮を繰り返す活物質に対して、ポリイミドバインダーの使用を可能とし、集電体(銅箔)として変形しない電解銅箔の開発に成功した。
前記電解銅箔の前記金属成分のより好ましい含有量は、0.001~1.320wt%である。
pH4以下の酸性溶液中で酸化物として存在する金属は、本実施形態ではチタン(Ti)、モリブデン(Mo)、バナジウム(V)、ビスマス(Bi)、テルル(Te)が好ましく使用できる。
即ち、本実施形態の電解銅箔はTi、Mo、V、Bi、Teの少なくとも1種類を含有し、残部が実質的に銅からなる電解銅箔である。
なお、上記「Ti、Mo、V、Bi、Teの少なくとも1種類を含有し」とは、それぞれの金属が単独で、或いは2種類以上が同時に含有される、との意味である。また、「残部が実質的に銅からなる」とは、銅に、原料等に由来する不可避的不純物が含まれ、或いは電解製箔プロセス等による微量の添加物が含まれることを許容する、との意味である。
pH4以下の酸性溶液中で酸化物として存在する金属の含有量が0.0001wt%以下では前記金属を添加した効果が殆ど現れない。なお、箔中の前記金属の含有量のより好ましい範囲は0.001~1.320wt%である。
電解銅箔に含まれる金属をpH4以下の酸性溶液中に存在する金属と限定するのは、電解液のpHが4以下であり、このような酸性電解液中で酸化物として存在する金属が銅箔中に取り込まれ易いためである。
即ち、前記金属を0.0001wt%未満含有した銅箔では300℃×1時間の熱処理後に常温で測定した機械的強度は、前記金属を含有しない場合と同様、強度が低下する傾向を示す。
本実施形態において、塩素の含有量が0.005wt%以下の電解銅箔は、該電解銅箔を製箔する電解浴中の塩素濃度を低く抑える必要性から、製箔中にピンホールが発生しやすくなり、製箔した銅箔にピンホールが存在するため好ましくない。また、塩素の含有量が0.04wt%以上の電解銅箔は、銅箔にカールが発生しやすくなり好ましくない。
従って、塩素の含有量は0.005~0.04wt%が好適である。
しかし、電解液に塩素イオンを添加しても、液中にチオ尿素系化合物を添加すると製箔条件によっては前記金属が箔中に取り込まれる、との知見を得た。
即ち、300℃×1時間の熱処理後に常温で測定した引張り強さが450MPa以上の銅箔を下記基本電解浴組成、電解条件で製箔することにより、前記金属が箔内に取り込まれた電解銅箔を製箔することができる。
Cu=50~150g/L
H2SO4=20~200g/L
電解条件:
電流密度=30~100A/dm2
液温=30~70℃
添加剤A:チオ尿素系化合物=3~20mg/L
添加剤B:Ti、Mo、V、Bi、Teの塩の少なくとも1種(Ti、Mo、V、Bi、Teとして、複数の金属を添加するときはその合計量)=100~10,000mg/L
添加剤C:塩素イオン=1~100mg/L
>N-C(=S)-N<
チオ尿素系化合物の例としては、チオ尿素、N,N‐ジエチルチオ尿素、テトラメチルチオ尿素、エチレンチオ尿素である。しかし、これらは後述する実施例で使用したものを例示しているに過ぎず、以上で述べたような構造的特徴を有し、同様の効果を発揮する化合物であれば、いずれの化合物も使用可能である。
Ti、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属は酸性溶液中では酸化物として存在するが、塩素を含む電解液を用いた銅電析では銅の析出面上を塩素イオンが被覆しているため、Ti、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属の酸化物は銅に吸着されず、箔中への取り込みが起こらない。該電解液にチオ尿素系化合物を添加すると、[=S]構造が塩素イオンよりも優先的に銅上に吸着して銅に有機分子の吸着層を形成する。該吸着層上にTi、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属の酸化物が吸着することにより、Ti、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属はチオ尿素系化合物と一緒に箔中に取り込まれるものと推考される。
従って、Ti、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属を含有する電解銅箔は300℃程度の高温で加熱しても、Ti、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属の酸化物は結晶粒界にとどまり、銅の微細結晶が熱により再結晶し、結晶が粗大化するのを防ぐ働きをすると考えられる。
当然のことながら、このような電解液で製箔した電解銅箔は、300℃程度の高温で加熱した後に機械的強度が大きく低下した。
Ti、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属が添加されていない場合は、電解銅箔製箔用の電解液に添加されている金属元素は銅である。従って、硫酸銅と硫酸を含有する電解液中で銅-チオ尿素系化合物が形成される。この電解液による銅電析で電解銅箔を形成すると、銅-チオ尿素系化合物が結晶粒界に吸着され、結晶核の成長を抑制し、結晶粒を微細化し、常態で大きな機械的強度を備えた電解銅箔を形成する。
一般に銅箔を300℃程度の高温で加熱した場合に引張強度が著しく低下する理由は、上記のように結晶粒界に存在する化合物が有機化合物であり、該有機化合物は300℃程度の加熱により分解しやすいため、機械的強度が低下すると考えられる。
添加するチオ尿素系化合物の量を3~20mg/Lとするのは、3mg/L未満では銅箔中にTi、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属を規定量取り込むことができず、300℃×1時間の熱処理後の常温での引張強度が450MPa以下となり、20mg/Lを超えて添加すると銅箔中にTi、Mo、V、Bi、TeなどのpH4以下の酸性溶液中で酸化物として存在する金属が入りすぎ、引張強度が高くなり過ぎ、或いは伸びが小さくなり、好ましくない性質が現れるためで、添加量は3~20mg/Lが好ましい範囲である。
電解液に添加するアンモニウムイオンの量は1~15g/L、硝酸イオンの量は50~200mg/Lが適している。加熱処理後の常温での機械的強度をさらに向上させる際には、電解液にアンモニアイオンまたは硝酸イオンを添加することが好ましい。
下記の硫酸銅と硫酸を含有する電解液を基本浴組成とし、表1に示す量の塩素イオン、Ti、Mo、V、Bi、Te、チオ尿素系有機添加剤を添加した電解液を用いて貴金属酸化物被覆チタンを陽極に、チタン製回転ドラムを陰極として、下記電解条件で電解銅箔を製箔した。
基本電解浴組成
Cu=50~150g/L
H2SO4=20~200g/L
電解条件
電流密度 30~100A/dm2
温度 30~70℃
このようにして製箔した電解銅箔に下記条件で防錆処理を施した。
製箔した電解銅箔(未処理銅箔)をCrO3;1g/L水溶液に5秒間浸漬して、クロメート処理を施し、水洗後乾燥させた。
なお、ここでは、クロメート処理を行ったが、ベンゾトリアゾール系処理、或いはシランカップリング剤処理、又はクロメート処理後にシランカップリング剤処理を行ってもよいことは勿論である。
表2に示す量の塩素、Mo、Fe、Ni、エチレンチオ尿素または膠を添加した硫酸銅と硫酸を含有する電解液を用いて貴金属酸化物被覆チタンを陽極に、チタン製回転ドラムを陰極として、下記電解条件で電解銅箔を製箔した。
電解条件
電流密度 30~100A/dm2
温度 30~70℃
このようにして製箔した銅箔に実施例と同様の表面処理を行った。
銅箔中のTi、Mo、V、Bi、Te、Fe、Ni、の含有量の測定
Ti、Mo、V、Bi、Teの含有量は、一定重量の電解銅箔を酸で溶解した後、溶液中のTi、Mo、V、Bi、TeをICP発光分光分析法により求めた。
使用機器 :ICPS-7000(島津製作所)
銅箔の引張強度の測定
銅箔の引張強度は、IPC-TM-650に基づいて箔の加熱前と加熱後に付き測定した。
使用機器 : AG-I (島津製作所)
導電率は、まず20mm×200mmの銅箔の抵抗値を測定した後、測定した抵抗値を銅箔の断面積で割って算出した。
塩素含有量の測定
塩素含有量は、一定重量の電解銅箔を酸で溶解した後、溶液中の塩素を硝酸銀滴定により定量を行い、算出を行った。
電解銅合金中に含有される酸化物の化学結合状態や電子状態の解析をXAFS(X線微細吸収構造:X-ray Absorption Fine Structure)法で行った。XAFS法では、試料にX線エネルギーを変化させながらX線を照射し、得られたX線吸収スペクトルから試料中の化学結合状態や電子状態の解析を行うことができる。
その他、X線吸収スペクトルを得る手法として、入射したX線の強度と透過したX線の強度からX線吸収スペクトルを求める透過法、X線の吸収に伴って試料から発せられる蛍光X線の強度を測定する蛍光法がある。
金属材料などの添加元素を分析対象とするとき、その添加量は微量であり透過法でのXAFSスペクトルを得ることは困難である。この様な場合に有効なのが上記に記した蛍光法である。蛍光法の特徴としては、その光軸系よりX線の照射面積が広く取れることにより微量成分の元素でもXAFS測定が可能となる。
本測定では高強度銅箔中のTi、Mo、V、Bi、Teの化学結合状態や電子状態を知ることが目的であり、Ti、Mo、V、Bi、Teの量は微量であり、透過法でXAFSスペクトルを得るには困難であることから蛍光法を選択した。
測定に関してはSPring-8の産業利用ビームラインBL14B2を使用した。測定したX線のエネルギー範囲は10000~10434eVとした。
箔中における金属(無機添加物)の粒径は、SAXS(small angle X-ray scattering、小角X線散乱)とUSAXS(ultra small angle X-ray scattering、極小角X線散乱)測定の解析によって求めた。SAXS・USAXS測定においてはSpring-8の産業利用ビームラインBL19B2で行った。
q=4πsinθ/λ・・・(1)
次に実施例で製箔した電解銅箔を集電体として、リチウムイオン二次電池を作成し、サイクル寿命試験を行った。
粉末状のSi合金系活物質(平均粒径0.1μm~10μm)を85、バインダー(ポリイミド)を15の比率(重量比)で混合し、N-メチルピロリドン(溶剤)に分散させて活物質スラリーとした。
次いで、このスラリーを、作成した12μm厚の電解銅箔両面に塗布し、乾燥後ローラープレス機で圧縮形成し、その後、窒素雰囲気下、300℃で1時間焼結し、負極とした。この負極は、成形後の負極合剤の膜厚が両面共に20μmと同一であった。
アルゴン雰囲気下のグローブボックス内で、以下の構成で評価用三極式セルを構築した。
負極:上記で作製のSi合金系負極
対極、参照極:リチウム箔
電解液:1mol/L LiPF6/EC+DEC(3:7vol%)
充電はLiの標準単極電位基準に対して0.02Vまで定電流で行い、その後はCVで(定電位のまま)電流が0.05C低下した時点で充電終了とした。なお、Cは充放電レートを示す。放電は定電流にて0.1Cで1.5V(Li基準)まで行った。同じ0.1C相当電流で充放電を繰り返した。
充放電性能の評価として、放電容量が1サイクル目の放電容量の70%に達するまでのサイクル数を測定し、これをサイクル寿命とし、サイクル寿命100回以上の電極を実用上使用可能と判断し、合格レベルとした。各条件で製造した電極のサイクル寿命を表1及び表2に示す。サイクル寿命100回未満の電極を不合格、100回以上120回未満を良好な範囲、120回以上を最適な範囲とした。
また、充放電性能の評価として、充放電100サイクルを行った後電池を分解し、箔の変形、破断を観察した。その結果を箔の変形として表1、2に示す。シワ等の変形がないものに対しては○を、シワ等の変形が生じたものは不合格とし×を付した。
Ti、Mo、V、Bi、Teの少なくとも1種含有電解銅合金箔のTi、Mo、V、Bi、Te含有量は0.0001wt%以上であることが好ましく、特に0.001~1.320wt%であることが好ましい。この範囲を外れると充放電試験後にしわの発生が見られた。
Ti、Mo、V、Bi、Teの取り込み量が0.001wt%以上となる条件においては、300℃×1時間の熱処理後の常温での引張強度が460MPa以上と特に耐熱性に優れている。
しかし、Ti、Mo、V、Bi、Te取り込み量が1.320wt%より多い箔においては、導電率が70%IACS未満と低くなる傾向にあるが、実用的には60%IACS以上であれば支障がなく、また、Ti、Mo、V、Bi、Te取り込み量が0.001wt%より少ない箔においては300℃×1時間の熱処理後の常温での引張強度の強さが460MPaより僅かに落ちるが450MPaよりは強く、実用的には支障のない範囲であることから、箔中のTi、Mo、V、Bi、Teの取り込み量は0.0001wt%以上、好ましくは0.001~1.320wt%、より好ましく0.001~1.000wt%である。
また、本発明は機械的強度に優れた電解銅箔であり、ポリイミドフィルムと張り合わせるプリント配線板分野における用途においても好適に用いることができる。
更に本発明は、Si又はSn合金系活物質を用いるリチウムイオン二次電池で、Si又はSn合金系活物質の大きな膨張、収縮に対して、集電体(銅箔)と活物質との密着性をポリイミドバインダーで保持でき、充放電100サイクル以上の電池特性が得られ、集電体(銅箔)として変形しない優れた電解銅箔である。
比較例1は、エチレンチオ尿素とMoを添加した電解液で製箔しているが、Moの添加量が少なかったために、箔中にMoを取り込むことができなかった。従って常態での機械的強度は大きいが、300℃×1時間の熱処理後では機械的強度が著しく低下している。
この銅箔は常態での機械的強度も小さく、300℃×1時間の熱処理後では機械的強度が250MPa以下と著しく低下する。この銅箔中のMo量の測定結果は検出下限の、0.0001wt%未満であった。
電解液中に膠を添加したが、膠は[=S]を持たないため、膠では、塩素イオンよりも優先的に銅上に吸着して銅上に有機分子の吸着層を形成することができず、Mo酸化物は銅上に吸着されず、箔中へのMoの取り込みが起こらず、電解Cu-Mo箔は形成されなかったものと推考される。
更に比較例1~5の電解銅箔を集電体としたリチウムイオン二次電池では、充放電100サイクル以下で集電体(銅箔)に変形が発生し、実用的に使用するには電池特性に問題がある。
また、本発明によれば、上記いずれかに記載の電解銅箔を、二次電池用負極集電体として用い、その表面に、シリコン、ゲルマニウム、錫又はそれらの合金化合物またはそれらを主成分とする活物質が堆積されている、二次電池用電極が提供される。
本発明によれば、硫酸-硫酸銅系電解液に、添加剤として、チオ尿素系化合物、pH4以下の酸性溶液中で酸化物として存在する金属塩の少なくとも1種類、塩素イオンを添加し、電解析出により、pH4以下の酸性溶液中で酸化物として存在する金属の少なくとも1種類を含有し、残部が銅からなる電解銅箔を製造する、電解銅箔の製造方法が提供される。
14・・・入射X線
15・・・シャッター
17・・・モノクロメーター
19・・・第1ピンホール
21・・・第2ピンホール
23・・・減衰器
25・・・第3ピンホール
27・・・試料
29・・・透過X線
31・・・散乱X線
33・・・ビームストッパー
35・・・検出器
Claims (8)
- pH4以下の酸性溶液中で酸化物として存在する金属またはその酸化物を含有し、塩素を0.005~0.04wt%含有することを特徴とする電解銅箔。
- 前記金属成分の含有量が、0.0001wt%以上である請求項1に記載の電解銅箔。
- 前記金属成分の含有量が、0.001~1.320wt%である請求項1に記載の電解銅箔。
- 前記金属成分がチタン(Ti)、モリブデン(Mo)、バナジウム(V)、ビスマス(Bi)、テルル(Te)から選ばれる1種以上である請求項1~3のいずれかに記載の電解銅箔。
- 常温での引張強度が650MPa以上であり、300℃で1時間の熱処理後に常温で測定した引張強度が450MPa以上である請求項1~4のいずれかに記載の電解銅箔。
- 常温での導電率が60%IACS以上である請求項1~5のいずれかに記載の電解銅箔。
- 請求項1~6のいずれかに記載の電解銅箔を集電体として使用するリチウムイオン二次電池用電極。
- 請求項7に記載の電池用電極を負極とするリチウムイオン二次電池。
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WO2018211916A1 (ja) * | 2017-05-18 | 2018-11-22 | 富士フイルム株式会社 | 孔あき金属箔、孔あき金属箔の製造方法、二次電池用負極および二次電池用正極 |
JP2019536212A (ja) * | 2016-11-11 | 2019-12-12 | イルジン マテリアルズ カンパニー リミテッドIljin Materials Co., Ltd. | 二次電池用電解銅箔及びその製造方法 |
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