WO2004049476A1 - 非水電解液二次電池用負極集電体およびその製造方法 - Google Patents
非水電解液二次電池用負極集電体およびその製造方法 Download PDFInfo
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- WO2004049476A1 WO2004049476A1 PCT/JP2003/015043 JP0315043W WO2004049476A1 WO 2004049476 A1 WO2004049476 A1 WO 2004049476A1 JP 0315043 W JP0315043 W JP 0315043W WO 2004049476 A1 WO2004049476 A1 WO 2004049476A1
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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
- H01M4/70—Carriers or collectors characterised by shape or form
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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 negative electrode current collector for a non-aqueous electrolyte secondary battery, and more particularly, to a non-aqueous solution capable of preventing a negative electrode active material such as a tin-tin alloy from falling off from the current collector due to charging and discharging.
- the present invention relates to a negative electrode current collector for an electrolyte secondary battery. Background technology.
- Electrolytic copper foil is obtained by performing electrolysis in a sulfuric acid acidic copper sulfate electrolytic bath using a titanium or stainless steel drum as a cathode, dimensional stabilizing electrodes and lead as an anode, and winding the deposited copper as a foil.
- the so-called glossy surface of the copper foil on the drum facing surface has a smooth shape on which the smooth state of the drum surface is transferred.
- the so-called matte surface varies from a smooth state to a rough state depending on the bath composition and electrolysis conditions. In other words, one side of the electrolytic copper foil is always smooth.
- a method is known in which an electrolytic copper foil having such features is further guided into an electrolytic cell, and copper is electrodeposited on both surfaces thereof to roughen both surfaces (Japanese Patent Application Laid-Open No. 6-126016). No. 8). Also known is a method of producing an ultra-thin copper foil having a smooth surface by forming a release layer on a glossy surface of an electrolytic copper foil used as a carrier foil and depositing copper thereon. 1 1 — 3 1 7 5 7 4 publication). Furthermore, an electrolytic copper foil with a carrier foil formed by forming a joining interface layer in which an organic agent and metal particles are mixed on the surface of a copper carrying foil and forming an electrolytic copper foil layer on the joining interface layer.
- the present invention is characterized in that R z of each surface of the current collector is reduced.
- R z of each surface of the current collector is reduced.
- a tin-tin alloy which has recently attracted attention as a high-capacity negative electrode active material.
- the negative electrode undergoes volume expansion due to charge and discharge. It has been found that peeling occurs. Disclosure of the invention
- an object of the present invention is to provide a non-aqueous electrolyte solution that can prevent a negative electrode active material made of a metal or alloy such as a tin-tin alloy from dropping from a current collector due to charge and discharge.
- An object is to provide a negative electrode current collector for a secondary battery. The present inventors have conducted intensive studies to achieve the above object, and as a result,
- the present invention has been made based on the above findings, and is made of a metal foil that can be a current collector of a nonaqueous electrolyte secondary battery, and the roughness of each surface of the foil has a 10-point average surface roughness R z expressed in 3 a 1 0 m, weight per unit area is 4 0 ⁇ 3 2 0 gZm 2 , as an anode active material, a sufficient charging and discharging of possible metallic or alloy supported on one or both sides
- Non-aqueous electrolyte solution characterized by being The object has been achieved by providing a negative electrode current collector for a secondary battery.
- the present invention also provides a method for manufacturing the current collector,
- the metal is deposited on the peripheral surface of the cathode drum by electrolysis, and the deposited metal is peeled off from the peripheral surface to obtain a carrier foil.
- the deposited surface of the carrier foil is subjected to a peeling treatment.
- the present invention provides a method for producing a negative electrode current collector for a non-aqueous electrolyte secondary battery, characterized in that the metal is deposited by the above method, and the deposited metal is separated from the carrier foil to obtain a replica foil.
- a metal or alloy capable of sufficiently charging and discharging is supported as a negative electrode active material on both or one side of a current collector made of a metal foil which can be a current collector of a nonaqueous electrolyte secondary battery.
- the foil has a surface roughness of 3 to 10 tm represented by a 10-point average surface roughness Rz and a weight per unit area of 4
- An object of the present invention is to provide a negative electrode for a non-aqueous electrolyte secondary battery, which has a weight of 0 to 320 g / m 2 .
- 1 (a) to 1 (d) are process diagrams showing a method for producing a current collector of the present invention.
- FIGS. 2 (a) to 2 (c) are scanning electron micrograph images showing the surface state of the copper foil during the manufacturing process in the manufacturing method shown in FIGS. 1 (a) to 1 (d).
- 3 (a) to 3 (c) are process diagrams showing another method for manufacturing the current collector of the present invention.
- the current collector is made of a metal that can be a current collector of the nonaqueous electrolyte secondary battery.
- it is preferably made of a metal that can be a current collector of a lithium secondary battery.
- a metal include copper, iron, cobalt, nickel, zinc or silver, and alloys of these metals. It is particularly preferable to use copper or an alloy thereof among these metals. Therefore, the following description will focus on copper foil.
- the copper foil either an electrolytic copper foil or a rolled copper foil is used.
- electrolytic copper foil that can easily make the surface roughness of the copper foil fall within the range described below and that can easily make the copper foil extremely thin.
- electrolytic copper foil is obtained by performing electrolysis in a sulfuric acid acidic copper sulfate electrolytic bath using a rotary drum as a cathode to deposit copper on the peripheral surface of the drum and peeling off the deposited copper.
- the copper foil used in the present invention has a relatively coarse surface roughness of 3 to 10 zm in terms of the roughness of each surface expressed by a 10-point average surface roughness Rz (JISB0601).
- the average point surface roughness Rz is the highest peak from the highest peak to the fifth peak measured in the direction of the longitudinal magnification from the average line of the part extracted by the reference length L from the longitudinal section curve of the copper foil.
- Rz was measured using a surface roughness / profile measuring instrument SEF-30D manufactured by Kosaka Laboratory Co., Ltd.
- each surface of the copper foil has a relatively rough Rz of 3 to 10 im, preferably 4 to 7 m.
- each surface of the copper foil is relatively rough, unlike when carbon or the like is used as the negative electrode active material. It turned out to be good.
- the present inventors speculate that the reason is as follows.
- a negative electrode active material such as tin-tin alloy is generally supported on a current collector made of copper foil by electrolysis. Alternatively, it is supported by applying a paste containing the particles of the negative electrode active material on a current collector. Therefore, the surface of the copper foil is flat. When it is smooth, the electrodeposited layer of the active material is also formed smoothly.
- the active material expands in volume due to charging and discharging of the battery, the active material does not travel to the extent of the volume expansion, causing cracks in the active material layer or pulling the active material into fine particles. Powdering and exfoliation occur.
- the surface of the copper foil is relatively rough, the electrodeposited layer of the active material is formed more coarsely than when the surface of the copper foil is smooth. That is, the surface of the electrodeposited layer is relatively uneven. These irregularities provide an escape area for the active material of the volume expansion when the volume expansion of the active material occurs due to charging and discharging of the battery. As a result, the active material is hardly pulverized or peeled off, and the battery life is prolonged.
- each surface of the copper foil need not be the same value, and it is sufficient that all surfaces are within the above range. Also, the unevenness (surface profile) on each side of the copper foil need not be the same. However, it is preferable that each surface has the same surface profile as possible from the viewpoint of improving the performance of the battery. A method for producing a copper foil having such a surface profile will be described later.
- the Rz value of each surface of the copper foil must be in the range described above, and in addition, the size (height and depth) of the irregularities on each surface is relatively uniform, and is exceptionally high. It is preferable that there are no convex parts and deep concave parts.
- the maximum height R nax is appropriate.
- R raax is defined by the largest value among the five values obtained when the roughness curve is equally divided and the interval between the highest peak and the deepest valley is determined for each interval.
- R on each surface of the copper foil is 3.3 to 11.5 im, particularly 4.5 to 8 ⁇ .
- the thickness of the copper foil constituting the current collector is preferably small from the viewpoint of improving the performance of the battery.
- the thickness of the copper foil is 5 to 20 im, especially 8 to 15 It is preferable to be in a very thin state of about m.
- the relatively large value of Rz of 3 to 10 m mentioned above makes the definition of the thickness of the copper foil unclear. There is a risk. Therefore, in the present invention, the thickness per unit area of the copper foil is used as a measure of the thickness instead of the thickness of the copper foil.
- the copper foil preferably has a weight per unit area of 40 to 320 gZm 2 , particularly preferably 44 to 180 gZm 2 . When converting between weight and thickness per unit area, a copper density of 8.96 cm 3 was used.
- Copper foil constituting the collector is its tensile strength 2 5 kgf Zmm 2 or more, it is preferable from the viewpoint of workability at the time of battery assembly is improved in particular 3 5 kgf Zmm 2 or more.
- the copper foil preferably has an elongation of more than 2% and not more than 20%, particularly preferably not less than 4% and not more than 15%.
- Tensile strength and elongation are measured using an Autograph AG-I manufactured by Shimadzu Corporation under the conditions of a gauge length of 5 Om m and a tensile speed of 50 mmZin.
- a copper foil having such mechanical properties can be obtained, for example, by appropriately adjusting the type, Z or concentration of various additives such as chlorine and glue added to the electrolytic bath.
- a carrier copper foil is manufactured by electrolysis.
- the method of electrolysis is as described above. That is, using a rotating drum as a cathode, electrolysis is performed in a sulfuric acid acidic copper sulfate electrolytic bath to deposit copper on the drum peripheral surface.
- the carrier copper foil is obtained by peeling the deposited copper from the peripheral surface of the drum. This carrier copper foil is used as a ⁇ for the intended copper foil. Therefore, it is preferable to make the thickness relatively large to provide sufficient strength. As shown in FIG.
- the cross section of the carrier copper foil 1 has a smooth glossy surface on one surface and a matted surface 1a on the other surface.
- the glossy surface is the surface facing the drum peripheral surface
- the matt surface 1a is the deposition surface.
- the matte surface la is suitable for electrolysis conditions. Rz is adjusted to about 3 to 10 m by making appropriate adjustments.
- Fig. 2 (a) shows an electron micrograph of an example of the surface condition of the mat surface 1a.
- the matte surface 1 of the carrier copper foil 1 is peeled off.
- the release treatment agent include, for example, the nitrogen-containing compounds and the sulfur-containing compounds described in paragraphs [0 0 3 7] to [0 3 8] of JP-A-11131754 described above.
- the surface of the replica copper foil 2 facing the carrier copper foil that is, the surface facing the mat surface (hereinafter, this surface is referred to as a lower surface) 2b has a complementary shape to the mat surface.
- the surface shape of the upper surface 2a of the replica copper foil 2 is adjusted so that Rz is about 3 to 1 ⁇ by appropriately adjusting the electrolysis conditions.
- Electrolytic conditions for obtaining such a surface shape include, for example, when a copper sulfate solution is used in the electrolytic bath, for example, the concentration of copper is 30 to 100 g / 1, and the concentration of sulfuric acid is 50 to 50 g.
- the concentration of chlorine should be 3 O ppm or less
- the liquid temperature should be 30 ⁇ 80 ° C
- the current density should be 1 ⁇ : LOO AZdm 2 .
- the copper concentration should be 10 to 5 Og
- the potassium pyrophosphate concentration should be 100 to 700 g / 1
- the solution temperature should be 30 to 6 g.
- the pH should be 8 to 12
- the current density should be 1 to 10 AZdm 2 .
- the carrier copper foil 1 Peel off the replica copper foil 2 from In the replica copper foil 2 thus obtained, the Rz of each surface is 3 to 10 m.
- This replica copper foil 2 is used as a current collector. Since the lower surface 2b of the replica copper foil 2 has a shape complementary to the mat surface 1a of the carrier copper foil 1, the surface shape of the lower surface 2b is not uniform, so that the active material such as a tin-tin alloy can be used. May be somewhat unsuitable for electrodeposition.
- An electron micrograph of an example of the surface condition of the lower surface 2b is shown in FIG. 2 (b). Therefore, as a post-process, a small amount of copper 3 is precipitated by electrolysis as shown in Fig. 1 (d) on the lower surface 2b of the replica copper foil 2, that is, on the surface facing the carrier copper foil in the replica copper foil 2.
- the thin layer 3 it is preferable to form the thin layer 3 to adjust the surface unevenness of the lower surface 2b, and the formation of the thin layer 3 also has the advantage that the surface unevenness of the lower surface 2b becomes closer to that of the upper surface 2a.
- the degree of copper deposition should be about 2 ⁇ m or less, which is a range in which an extremely thin and uniform thin layer 3 is formed on the surface of the lower surface 2b and does not affect the value of Rz.
- Fig. 2 (c) shows an electron micrograph of an example of the state of the lower surface 2b whose surface shape has been adjusted in this way. The processed replica copper foil 2 is then used as a current collector Another preferred method of manufacturing the current collector of the present invention is shown in FIGS.
- the same operations as those shown in FIGS. 1 (a) to 1 (c) described with respect to the above-described manufacturing method are performed.
- the lower surface of the replica copper foil 2 is subjected to a peeling treatment as shown in Fig. 3 (a). This can be performed in the same manner as the peeling process performed on the matte surface la.
- copper is deposited on the surface by electrolysis.
- the second replica copper foil 4 is formed on the surface 2b.
- the second replica copper foil 4 is formed so as to have a weight per unit area of 40 to 320 gZm 2 .
- the surface shape of the surface facing the replica copper foil of the second replica copper foil 4, that is, the surface facing the lower surface 2b is complementary to the lower surface 2b.
- the surface shape of the upper surface 4a of the second replica copper foil 4 is the same as the shape of the matte surface 1a of the carrier copper foil 1 manufactured first.
- the Rz of the upper surface 4a of the second replica copper foil 4 also has an Rz of 3 to 1 0 tm.
- the surface shape of the lower surface 4a of the second replica copper foil 4 is adjusted so that Rz is about 3 to 10 m by appropriately adjusting the conditions of electrolysis.
- the electrolysis conditions for obtaining such a surface shape can be the same as the electrolysis conditions for the previously produced replica copper foil 2.
- the second replica copper foil 4 is peeled from the replica copper foil 2 on the peeling-treated surface.
- the Rz of each surface is 3 to 10 m.
- each surface has an approximate surface irregular shape. Therefore, each surface is in a state suitable for depositing tin-tin alloy.
- This second replica copper foil 4 can be used as a current collector.
- a method of performing a roughening treatment and / or an anti-rust treatment is exemplified.
- the adhesiveness between the foil and the negative electrode active material is increased, and the battery characteristics are improved.
- the granular metal is coated with a dense plating layer so as not to impair the unevenness due to the granular metal. Processing.
- the plating process in the first stage is called so-called plating, and the plating process in the second stage is called so-called covering.
- Such a roughening treatment is known as a method for roughening the surface of a copper foil for a printed circuit.
- Burning is plating in which a granular metal is precipitated by a current near the critical current density. Covering is performed by coating a non-granular dense plating layer with a current at or below the critical current density. This is plating that precipitates to cover the granular metal.
- Examples of the prevention treatment include (i) metal plating treatment, (ii) chromate treatment, and (ill) silane coupling treatment.
- metal plating treatment zinc, nickel, cobalt, or an alloy thereof is plated on the surface of the foil to prevent corrosion of the foil (corrosion of copper in this embodiment). From the viewpoint of preventing copper corrosion, it is preferable to perform zinc or zinc alloy plating.
- alloy plating such as zinc-copper, zinc-nickel, zinc-cobalt, zinc-nickel-copper, zinc-nickel-cobalt, and zinc-copper-tin can be mentioned.
- the foil is treated with a solution containing chromic acid or a dichromate as a main component to form a surface protective coating.
- the protection film formed by this treatment is, for example, a chromium-containing metal layer, a chromium alloy layer made of a copper-chromium alloy, or a chromium oxide layer.
- the chromate treatment is specified in, for example, JISZ103.
- the surface of the foil is treated with a silicon-containing compound generally known as a silane coupling agent.
- a silicon-containing compound generally known as a silane coupling agent.
- X is a hydrolyzable substituent such as an alkoxy group or a halogen
- R is a substituent having a functional group such as a vinyl group, an epoxy group, or an amino group that easily reacts with organic substances.
- the order of the roughening treatment and the protection treatment There is no particular limitation on the order of the roughening treatment and the protection treatment. For example, only the roughening process may be performed, or only one of the above-mentioned (1) to (iii) protection processes may be performed.
- a chromate treatment or a silane coupling treatment can be performed after the metal plating treatment. After the metal plating treatment, the chromate treatment and the silane coupling treatment can be performed in this order. Further, a chromate treatment may be performed first, followed by a silane coupling treatment. Roughening treatment and prevention treatment can also be combined. For example, first, a roughening process can be performed, and then a protection process can be performed. The order of the prevention process can be as described above.
- a negative electrode active material is supported on each surface or one surface of the copper foil produced by each of the above methods to form a negative electrode for a non-aqueous electrolyte secondary battery.
- a metal or alloy capable of sufficiently charging and discharging is used.
- metals or alloys include Group 13 and 14 elements of the periodic table.
- tin, aluminum, germanium, or an alloy of these metals can be used.
- tin or a tin alloy it is particularly preferable to use tin or a tin alloy.
- Tin alloys include tin-copper, tin-bismuth, tin-iron, tin-cobalt, and the like. These metals or alloys are supported by being deposited on copper foil by electrolysis. Alternatively, it is supported by applying a paste containing particles of these metals or alloys on the current collector.
- a non-aqueous electrolyte secondary battery provided with such a negative electrode has a positive electrode in addition to the negative electrode.
- the form of the battery may be any of a cylindrical type, a square type, a coin type, a button type and the like.
- the active material is prevented from falling off at the negative electrode even after repeated charging and discharging, and the life of the battery is greatly extended.
- the present invention is not limited to the above embodiment.
- a description has been given centering on copper, which is a preferable example, as a metal that can be a current collector of a nonaqueous electrolyte secondary battery.
- the present invention is not limited to copper, and examples thereof include iron, cobalt, The same applies to other metals and alloys such as nickel, zinc or silver or alloys of these metals.
- the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to such an embodiment.
- Copper foil was manufactured according to the method shown in FIGS. 1 (a) to 1 (c).
- the Rz of the matte surface of the carrier copper foil during the manufacturing process was 3.2 m and the thickness was 18 jti m.
- the weight per unit area of the obtained copper foil (replica copper foil) and Rz and Rz of each surface are as shown in Table 1. The table also shows the tensile strength and elongation of the copper foil.
- a copper foil was obtained in the same manner as in Example 1 except that Rz on the mat surface of the carrier copper foil in the manufacturing process was 4.7 m and the thickness was 35 im.
- R z ⁇ beauty R "ax weight and each surface per unit area of the resulting copper foil (replica foil) are as shown in Table 1. The tensile strength and elongation of the copper foil in the same table also It is also described.
- Example 3 The steps shown in FIGS. 1A to 1C were the same as in Example 2. Thereafter, as a subsequent step, copper was deposited by electrolysis on the lower surface of the replica copper foil to form a thin layer.
- the weight per unit area of the obtained steel foil (replica copper foil with a thin copper layer formed on the lower surface) and the Rz and Rnax of each surface are as shown in Table 1. The tensile strength and elongation of the foil are also described.
- the steps shown in FIGS. 1A to 1C were the same as in Example 2. However, the weight per unit area of the replica copper foil was set to 98 e gZm 2 . After that, a second replica copper foil was obtained from the replica copper foil according to the method shown in FIGS. 3 (a) to 3 (c). The weight per unit area of the obtained copper foil (second replica copper foil) and Rz and Rnax of each surface are as shown in Table 1. The table also shows the tensile strength and elongation of the copper foil.
- Example 6 is the same as Example 5 except that the silane coupling treatment was not performed.
- Example 7 is the same as Example 5 except that neither chromate treatment nor silane coupling treatment was performed.
- Example 8 is the same as Example 5 except that all the protection processes are not performed.
- Table 1 shows the weight per unit area of the obtained copper foil (replica copper foil), and Rz and Rfflax of each surface. The table also shows the tensile strength and elongation of the copper foil. (Comparative Example 1)
- Example 2 The carrier copper foil in Example 1 was used as it was. (Comparative Example 2)
- Tin was deposited on the surfaces of the copper foils obtained in Examples 1 to 4 and Comparative Examples 1 and 2 by electrolysis to produce electrodes.
- the amount of tin deposited was 14.6 g / m 2 .
- tin paste was applied to the surfaces of the copper foils obtained in Examples 5 to 8 to form electrodes.
- the carried amount of tin was 44.5 gZm 2 .
- a non-aqueous electrolyte secondary battery was produced as follows. The irreversible capacity (%), the initial capacity (mA hZ g), the capacity retention rate for 20 cycles (%), and the charge / discharge efficiency at 10 cycles (%) were evaluated by the following methods. The results are shown in Tables 1 and 2. Of non-aqueous electrolyte secondary batteries
- Example 2 89.6 40.2 4.8 10 900 98 99.7 Copper foil Lower surface 2b 5 5.4 ref. Jamaica upper surface 2a 4.8 5.2
- Example 3 98.6 40.0 5.0 10 900 98 99.7 Copper foil * Lower surface 2b 4.8 5.3 Second reflex. Jamaica Top 4a 4.7 5.2
- Example 4 89.6 40.3 4.7 10 900 98 99.7 Copper foil Lower surface 4b 4.6 5.1 Carrier Glossy surface 1.6 1.9
- Comparative Example 1 161.3 41.2 10.4 20 900 75 97 Copper foil Matte surface 3.2 3.8 Carrier glossy surface 1.7 2.0
- the negative electrode was made by depositing tin by electrolysis on the surface of a copper foil,
- the negative electrode was fabricated by applying tin paste to the surface of a copper foil,
- the secondary battery using the copper foil obtained in each example as a negative electrode current collector uses the copper foil of the comparative example as the negative electrode current collector. It shows that the irreversible capacity and the initial capacity are almost the same as those of the secondary battery, and that the 20-cycle capacity retention ratio and the charge / discharge efficiency are further improved as compared with the secondary battery of the comparative example.
- the 20 cycle capacity retention ratio was improved in Examples 1 to 4 in which a negative electrode was prepared by applying tin plating to a copper foil.
- Examples 5 to 8 in which a negative electrode was prepared by applying a tin paste to a copper foil the 20 cycle capacity retention ratio was improved. It should be noted that they are almost equivalent, that is, the cycle characteristics are almost equivalent.
- the negative electrode active material made of a metal or an alloy such as a tin-tin alloy falls off from the current collector due to charge and discharge. Can be prevented. Therefore, a secondary battery using this current collector has a low deterioration rate even after repeated charging and discharging, and has a significantly longer life.
Abstract
Description
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AU2003302288A AU2003302288A1 (en) | 2002-11-27 | 2003-11-25 | Negative electrode collector for nonaqueous electrolyte secondary battery and method for manufacturing same |
JP2004555039A JPWO2004049476A1 (ja) | 2002-11-27 | 2003-11-25 | 非水電解液二次電池用負極集電体およびその製造方法 |
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Cited By (13)
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WO2007015419A1 (ja) * | 2005-08-02 | 2007-02-08 | Matsushita Electric Industrial Co., Ltd. | リチウム二次電池用負極およびその製造方法 |
JP2007053084A (ja) * | 2005-07-21 | 2007-03-01 | Sumitomo Titanium Corp | リチウム二次電池用負極の製造方法 |
JP2008226800A (ja) * | 2007-03-16 | 2008-09-25 | Fukuda Metal Foil & Powder Co Ltd | リチウム二次電池負極集電体用銅箔およびその製造方法 |
US20090104518A1 (en) * | 2004-10-06 | 2009-04-23 | Luc Nedelec | Battery module comprising an energy storing element whereof the contact is activated by mutual layer tightening |
JP2009231072A (ja) * | 2008-03-24 | 2009-10-08 | Sanyo Electric Co Ltd | リチウム二次電池及びその製造方法 |
US7794878B2 (en) | 2006-01-19 | 2010-09-14 | Panasonic Corporation | Negative electrode for lithium secondary battery and lithium secondary battery using the negative electrode |
JP2011258407A (ja) * | 2010-06-09 | 2011-12-22 | Furukawa Battery Co Ltd:The | リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
WO2013002273A1 (ja) * | 2011-06-28 | 2013-01-03 | 古河電気工業株式会社 | リチウムイオン二次電池、該二次電池の負極電極を構成する集電体、並びに該負極電極集電体を構成する電解銅箔 |
KR101490889B1 (ko) | 2006-06-29 | 2015-02-06 | 소니 가부시끼가이샤 | 전극 집전체 및 그 검사 방법, 전지용 전극 및 그 제조방법과, 2차 전지 및 그 제조 방법 |
JP2017505385A (ja) * | 2013-12-30 | 2017-02-16 | イルジン マテリアルズ カンパニー リミテッドIljin Materials Co., Ltd. | 銅箔、これを含む電気部品及び電池 |
JP2017508890A (ja) * | 2013-12-30 | 2017-03-30 | イルジン マテリアルズ カンパニー リミテッドIljin Materials Co., Ltd. | 銅箔、これを含む電気部品及び電池 |
JP2018031072A (ja) * | 2016-08-23 | 2018-03-01 | エル エス エムトロン リミテッドLS Mtron Ltd. | 電解銅箔、それを含む電極、それを含む二次電池およびその製造方法 |
WO2021170909A1 (en) * | 2020-02-25 | 2021-09-02 | Elcoflex Oy | A coated, printed battery and a method of manufacturing the same |
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US20090104518A1 (en) * | 2004-10-06 | 2009-04-23 | Luc Nedelec | Battery module comprising an energy storing element whereof the contact is activated by mutual layer tightening |
JP2007053084A (ja) * | 2005-07-21 | 2007-03-01 | Sumitomo Titanium Corp | リチウム二次電池用負極の製造方法 |
JP4648879B2 (ja) * | 2005-07-21 | 2011-03-09 | 株式会社大阪チタニウムテクノロジーズ | リチウム二次電池用負極の製造方法 |
US8888870B2 (en) | 2005-08-02 | 2014-11-18 | Panasonic Corporation | Lithium secondary battery |
WO2007015419A1 (ja) * | 2005-08-02 | 2007-02-08 | Matsushita Electric Industrial Co., Ltd. | リチウム二次電池用負極およびその製造方法 |
CN101233629B (zh) * | 2005-08-02 | 2010-06-02 | 松下电器产业株式会社 | 锂二次电池用负极及其制造方法 |
US8080334B2 (en) | 2005-08-02 | 2011-12-20 | Panasonic Corporation | Lithium secondary battery |
US7794878B2 (en) | 2006-01-19 | 2010-09-14 | Panasonic Corporation | Negative electrode for lithium secondary battery and lithium secondary battery using the negative electrode |
KR101490889B1 (ko) | 2006-06-29 | 2015-02-06 | 소니 가부시끼가이샤 | 전극 집전체 및 그 검사 방법, 전지용 전극 및 그 제조방법과, 2차 전지 및 그 제조 방법 |
JP2008226800A (ja) * | 2007-03-16 | 2008-09-25 | Fukuda Metal Foil & Powder Co Ltd | リチウム二次電池負極集電体用銅箔およびその製造方法 |
JP2009231072A (ja) * | 2008-03-24 | 2009-10-08 | Sanyo Electric Co Ltd | リチウム二次電池及びその製造方法 |
JP2011258407A (ja) * | 2010-06-09 | 2011-12-22 | Furukawa Battery Co Ltd:The | リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
WO2013002273A1 (ja) * | 2011-06-28 | 2013-01-03 | 古河電気工業株式会社 | リチウムイオン二次電池、該二次電池の負極電極を構成する集電体、並びに該負極電極集電体を構成する電解銅箔 |
JP5158918B2 (ja) * | 2011-06-28 | 2013-03-06 | 古河電気工業株式会社 | リチウムイオン二次電池、該二次電池の負極電極を構成する集電体、並びに該負極電極集電体を構成する電解銅箔 |
JP2017505385A (ja) * | 2013-12-30 | 2017-02-16 | イルジン マテリアルズ カンパニー リミテッドIljin Materials Co., Ltd. | 銅箔、これを含む電気部品及び電池 |
JP2017508890A (ja) * | 2013-12-30 | 2017-03-30 | イルジン マテリアルズ カンパニー リミテッドIljin Materials Co., Ltd. | 銅箔、これを含む電気部品及び電池 |
JP2018031072A (ja) * | 2016-08-23 | 2018-03-01 | エル エス エムトロン リミテッドLS Mtron Ltd. | 電解銅箔、それを含む電極、それを含む二次電池およびその製造方法 |
US10644320B2 (en) | 2016-08-23 | 2020-05-05 | Kcf Technologies Co., Ltd. | Electrolytic copper foil, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same |
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JPWO2004049476A1 (ja) | 2006-03-30 |
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