Surface-treated metal plate for batteries

Abstract

To provide a surface-treated metal plate for batteries that has excellent gas generation suppression effects. [Solution] A surface-treated metal plate for batteries is provided, comprising a metal substrate, a nickel layer provided on at least one side of the metal substrate, and a tin layer provided on top of the nickel layer, wherein both of the following formulas (1) and (2) are 2 or more for the tin layer. N(220) / N(200)> (1) N(220) / N(400)> (2) In equations (1) and (2) above, N(220) represents the crystal orientation index of the (220) plane of the tin layer, in equation (1) above, N(200) represents the crystal orientation index of the (200) plane of the tin layer, and in equation (2) above, N(400) represents the crystal orientation index of the (400) plane of the tin layer.

Description

[Technical Field]

[0001] This invention relates to a surface-treated metal plate for batteries that has an excellent effect in suppressing gas generation. [Background technology]

[0002] Among the types of rechargeable batteries that use an alkaline aqueous solution as the electrolyte, so-called alkaline batteries, nickel-cadmium batteries and nickel-metal hydride batteries are widely known and have been put into practical use. In addition, among alkaline rechargeable batteries, air batteries and nickel-zinc batteries, which use nickel hydroxide or similar material for the positive electrode, zinc or similar material for the negative electrode active material, and an alkaline aqueous solution as the electrolyte, are also known.

[0003] One of the challenges to the practical application of zinc-air and nickel-zinc batteries as rechargeable batteries was the problem of hydrogen gas generation during charging and discharging (including natural discharge). If hydrogen gas is generated, and the amount generated becomes too large, it can lead to a decrease in battery performance, an increase in internal pressure, and potentially battery leakage. These problems are particularly pronounced in batteries in which zinc is involved in the battery reaction.

[0004] It is conventionally known that the hydrogen gas generation problem described above can be solved by applying a material with a high hydrogen overpotential to the negative electrode current collector. For example, Patent Document 1 attempts to solve the hydrogen gas generation problem described above by increasing the hydrogen overpotential by using a copper-tin alloy as the material for the negative electrode current collector. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2-75160 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, when used in a practical alkaline secondary battery, the technique described in Patent Document 1 above was insufficient in terms of suppressing gas generation. That is, in order to exhibit sufficient battery performance as an alkaline secondary battery, the concentration of potassium hydroxide in the electrolyte is preferably 20% by weight or more, and in order to achieve higher performance, it is desired to be 25 - 40% by weight. Therefore, in an electrolyte environment with a high concentration as described above, a material with a more excellent gas generation suppression effect is desired.

[0007] In view of the above problems, the inventors of the present invention have intensively studied to develop a current collector material for the negative electrode, a battery tab / lead material, and a surface-treated metal plate for the battery (battery exterior material) that has a more excellent gas generation suppression effect during charge and discharge of an alkaline secondary battery. As a result, it has been found that by configuring the surface-treated metal plate for the battery in a specific manner, the above problems can be solved, and the present invention has been conceived.

Means for Solving the Problems

[0008] As a result of intensive studies to achieve the above object, the inventors of the present invention have found that a surface-treated metal plate for a battery including a metal substrate, a nickel layer provided on at least one surface of the metal substrate, and a tin layer provided on the upper layer of the nickel layer can achieve the above object, and have completed the present invention.

[0009] [1]Aspect 1 of the present invention is a surface-treated metal plate for a battery, comprising a metal substrate, a nickel layer provided on at least one surface of the metal substrate, and a tin layer provided on the upper layer of the nickel layer, and for the tin layer, a surface-treated metal plate for a battery that satisfies that at least one of the following formula (1) or the following formula (2) exceeds 1. N(220) / N(200) (1) N(220) / N(400) (2) In equations (1) and (2) above, N(220) represents the crystal orientation index of the (220) plane of the tin layer, in equation (1) above, N(200) represents the crystal orientation index of the (200) plane of the tin layer, and in equation (2) above, N(400) represents the crystal orientation index of the (400) plane of the tin layer.

[0010] [2] Aspect 2 of the present invention is a surface-treated metal plate for a battery according to aspect 1, further comprising a nickel-tin alloy layer formed between the nickel layer and the tin layer.

[0011] [3] A third aspect of the present invention is a surface-treated metal plate for a battery according to aspect 1 or 2, wherein the metal substrate is an iron-based metal substrate.

[0012] [4] Aspect 4 of the present invention is a surface-treated metal plate for batteries according to any of aspects 1 to 3, wherein the amount of nickel deposited in the nickel layer is 1.0 g / m² 2 Super, 20.0g / m 2 The following is a surface-treated metal plate for batteries.

[0013] [5] Embodiment 5 of the present invention is a surface-treated metal plate for batteries according to any of Embodiments 1 to 4, wherein the amount of tin deposited in the tin layer is 1.0 g / m² 2 More than 15.0g / m 2 The following is a surface-treated metal plate for batteries.

[0014] [6] Embodiment 6 of the present invention is a surface-treated metal sheet for a battery according to any of Embodiments 1 to 5, wherein at least one of formula (1) or formula (2) is 2 or more.

[0015] [7] Aspect 7 of the present invention is a surface-treated metal plate for a battery according to aspect 2, wherein in the nickel-tin alloy layer, the alloy phase is such that diffraction peaks are obtained in the diffraction angle range 2θ = 42 to 43° by X-ray diffraction measurement using CuKα as the radiation source. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a surface-treated metal plate for batteries that has an excellent effect in suppressing gas generation. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 is a cross-sectional view of a surface-treated metal plate for a battery according to an embodiment of the present invention. [Figure 2] Figure 2 is a cross-sectional view of a surface-treated metal plate for a battery according to another embodiment of the present invention. [Figure 3A] Figure 3A is an X-ray diffraction (XRD) chart showing the diffraction peaks of the (200) plane in the tin layer. [Figure 3B] Figure 3B is an X-ray diffraction (XRD) chart showing the diffraction peaks of the (220) plane in the tin layer. [Figure 3C] Figure 3C is an X-ray diffraction (XRD) chart showing the diffraction peaks of the (400) plane in the tin layer. [Figure 4] Figure 4 shows the X-ray diffraction chart of the alloy phase constituting the nickel-tin alloy layer. [Modes for carrying out the invention]

[0018] The surface-treated metal plate for batteries of the present invention is a surface-treated metal plate used in battery applications, for example, as a current collector for the positive or negative electrode, or as a battery container for housing the power generation element of a battery. While not particularly limited, examples of batteries include aqueous batteries using alkaline electrolytes, such as nickel-cadmium batteries, nickel-metal hydride batteries, zinc-air batteries, and nickel-zinc batteries, as well as non-aqueous batteries such as lithium-ion batteries. The surface-treated metal plate for batteries of the present invention is suitably used in aqueous batteries, and is particularly suitable for use as a current collector or battery container in aqueous batteries in which zinc is involved in the battery reaction (e.g., nickel-zinc batteries). Furthermore, the present invention can be applied to either primary or secondary aqueous batteries.

[0019] An embodiment of the present invention will be described below with reference to the drawings.

[0020] Figure 1 is a cross-sectional view of a surface-treated metal plate 10 for a battery according to an embodiment of the present invention. As shown in Figure 1, the surface-treated metal plate 10 for a battery according to this embodiment comprises a nickel layer 30 provided on both sides of a metal substrate 20, and a tin layer 40 provided on top of the nickel layer 30.

[0021] Furthermore, while Figure 1 illustrates an embodiment in which the nickel layer 30 and tin layer 40 are formed on both sides of the metal substrate 20, in this embodiment, it is sufficient for the nickel layer 30 and tin layer 40 to be formed on at least one side of the metal substrate 20, and it is not particularly limited to the embodiment in which the nickel layer 30 and tin layer 40 are formed on both sides of the metal substrate 20. In addition, in this embodiment, the nickel layer 30 and tin layer 40 may be formed on the side where gas generation suppression is required. For example, when the surface-treated metal plate 10 for batteries according to this embodiment is used as a current collector for the positive or negative electrode (for example, as a current collector for the negative electrode of a nickel-zinc battery), or as a lead material or tab material, the nickel layer 30 and tin layer 40 can be formed on both sides of the metal substrate 20. Furthermore, when the surface-treated metal plate 10 for batteries according to this embodiment is used as a battery container such as a container or electrode can, the nickel layer 30 and tin layer 40 can be formed on the surface of the metal substrate 20 that faces the inner surface of the battery. In particular, it is desirable to form the nickel layer 30 and tin layer 40 when the inner surface of the battery is exposed to the negative electrode potential. The surface that faces the outer surface of the battery is not particularly limited, but it can be left untreated.

[0022] <Metal base material 20> As the metal substrate 20, a metal plate based on iron is preferably used. Although not particularly limited, specifically, steel plates such as low carbon steel (carbon content 0.01 to 0.15 wt%), ultra-low carbon steel with a carbon content of 0.003 wt% or less, and non-aging ultra-low carbon steel obtained by adding Ti, Nb, etc. to ultra-low carbon steel can be used, and among these, low carbon steel and ultra-low carbon steel can be preferably used. In addition, as the metal substrate 20, electrolytic foil made of pure iron (electrolytic foil with an iron content of 99.9 wt% or more) can be used. Furthermore, when the surface-treated metal plate 10 for batteries according to this embodiment is used as a current collector for the positive or negative electrode, the metal substrate 20 may be a perforated plate or perforated foil having through holes.

[0023] The thickness of the metal substrate 20 is not particularly limited, but for example, when used as a current collector, it is preferably 0.005 to 2.0 mm, more preferably 0.01 to 0.8 mm, even more preferably 0.025 to 0.8 mm, and especially preferably 0.025 to 0.3 mm. When used as a battery container, it is preferably 0.1 to 2.0 mm, more preferably 0.15 to 0.8 mm, and even more preferably 0.15 to 0.5 mm. The method for measuring the thickness of the metal substrate 20 is, but is not limited to, measuring the thickness with a micrometer.

[0024] <Nickel layer 30> As shown in Figure 1, the surface-treated metal plate 10 for batteries according to this embodiment comprises nickel layers 30 formed on both sides of a metal substrate 20. In this embodiment, nickel layers 30 are formed on both sides of the metal substrate 20, but the embodiment is not limited to this configuration, and it is sufficient if nickel layers 30 are formed on at least one side of the metal substrate 20. The presence or absence of nickel layers 30 can be confirmed by X-ray diffraction (XRD) measurement using CuKα as a radiation source.

[0025] The amount of nickel deposited in the nickel layer 30 is preferably 0.5 g / m². 2 Super, 20.0g / m 2 The following, and more preferably 1.0 g / m² 2More than 15.0 g / m 2 or less, more preferably 2.0 g / m 2 More than 10.0 g / m 2 or less, particularly preferably 3.0 g / m 2 More than 10.0 g / m 2 or less. The nickel deposition amount can be determined by performing fluorescent X-ray measurement or ICP emission spectroscopic analysis on the surface-treated metal plate 10 for batteries. The nickel deposition amount described above represents the deposition amount on one side of the metal substrate 20.

[0026] Further, the thickness of the nickel layer 30 is preferably 0.05 to 2.00 μm, more preferably 0.10 to 1.50 μm, still more preferably 0.20 to 1.20 μm, and particularly preferably 0.30 to 1.00 μm. The thickness of the nickel layer 30 can be obtained by converting the nickel deposition amount obtained by the above method into thickness based on the density of nickel (g / m 3 ), (dividing the nickel deposition amount by the density), but it is not limited thereto. Thickness measurement by cross-sectional observation of a scanning electron microscope (SEM), thickness measurement by a transmission electron microscope (TEM), measurement by a high-frequency glow discharge emission spectroscopic analyzer, etc. are applicable.

[0027] The method for forming the nickel layer 30 is not particularly limited, but a method of electroplating nickel on the metal substrate 20 using a nickel plating bath is suitable. As the nickel plating bath, plating baths commonly used in nickel plating, that is, Watts bath, sulfamic acid bath, fluoborate bath, chloride bath, etc. can be used. For example, the nickel layer can be formed using a Watts bath having a bath composition of nickel sulfate 200 to 350 g / L, nickel chloride 20 to 60 g / L, and boric acid 10 to 50 g / L, at pH 3.0 to 4.8 (preferably pH 3.6 to 4.6), bath temperature 50 to 70 °C, and current density 10 to 2 40 A / dm 2 (preferably 20 to 30 A / dm

[0028] <Tin layer 40> As shown in Figure 1, the surface-treated metal plate 10 for batteries according to this embodiment includes a tin layer 40 formed on top of a nickel layer 30. The tin layer 40 can be formed by tin plating on the nickel layer 30. The presence or absence of the tin layer 40 can be confirmed by X-ray diffraction (XRD) measurement using CuKα as a radiation source, similar to the nickel layer 30 described above.

[0029] The tin layer 40 satisfies the condition that at least one of the following equations (1) or (2) regarding the crystal orientation index of the (220), (200), and (400) planes is greater than 1. It is more preferable that both equations (1) and (2) are greater than 1. N(220) / N(200) (1) N(220) / N(400) (2) In equations (1) and (2) above, N(220) represents the crystal orientation index of the (220) plane of the tin layer 40, in equation (1) N(200) represents the crystal orientation index of the (200) plane of the tin layer 40, and in equation (2) N(400) represents the crystal orientation index of the (400) plane of the tin layer 40.

[0030] The crystal orientation indices of the (220), (200), and (400) planes of the tin layer 40 are not particularly limited as long as at least one of formula (1) or formula (2) above is greater than 1. However, in order to further enhance the gas generation suppression effect, at least one of formula (1) or formula (2) above is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. Furthermore, in order to significantly enhance the gas generation suppression effect, both formula (1) and formula (2) above are preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. The upper limit of formula (1) or formula (2) above is not particularly limited, but is usually 300 or less, and preferably 200 or less. Furthermore, equation (1) (N(220) / N(200)) above represents the ratio of the crystal orientation index of the (220) plane of tin layer 40 to the (200) plane of tin layer 40, and equation (2) (N(220) / N(400)) represents the ratio of the crystal orientation index of the (220) plane of tin layer 40 to the (400) plane of tin layer 40.

[0031] The crystal orientation index (N(220)) of the (220) plane of the tin layer 40 can be determined by the following method. That is, after measuring the diffraction intensity of each crystal plane on the surface of the tin layer 40 using an X-ray diffractometer, the diffraction peaks of the obtained tin and the diffraction peaks of standard tin powder can be used to calculate the index using the Willson and Rogers method (described in "K.S. Willson and J. A. R. J. R. J. R. J. R. J. J. R. J. R. J. J. R. J. R. J. J. R. J. R. J. J. R. J. J. R. J. R. J. J. R. J. J. R. J. J. R. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J. R. J. J N(220)=IF(220) / IFR(220) In the above formula, IF(220) is the ratio of X-ray diffraction intensity from the (220) plane, and IFR(220) is the ratio of the theoretical X-ray diffraction intensity of standard tin powder. IF(220) and IFR(220) can be determined as follows. IF(220)=I(220) / [I(200)+I(101)+I(220)+I(301)+I(112)+I(400)+I(321)+I(420)+I(411)+I(312)+I(501)] IFR(220)=IR(220) / [IR(200)+IR(101)+IR(220)+IR(301)+IR(112)+IR(400)+IR(321)+IR(420)+IR(411)+IR(312)+IR(501)] In the above formula, I(hkl) is the X-ray diffraction intensity from the (hkl) plane, and IR(hkl) is the X-ray diffraction intensity from the (hkl) plane as described in 00-004-0673 of the ICDD PDF-2 2014 database for standard tin powder (h, k, and l are integers from 0 to 5). The diffraction angles for each crystal plane of tin are those described in the aforementioned database.

[0032] The crystal orientation index (N(200)) of the (200) plane and the crystal orientation index (N(400)) of the (400) plane of the tin layer 40 can be determined using the same calculation method as the crystal orientation index of the (220) plane. That is, the crystal orientation index of the (200) plane and the crystal orientation index of the (400) plane can be calculated based on the following formula. N(200)=IF(200) / IFR(200) N(400)=IF(400) / IFR(400)

[0033] The reasons why having the above configuration is desirable in this embodiment are as follows. In other words, as mentioned above, one of the challenges to the practical application of alkaline secondary batteries is the problem of hydrogen gas generation. Hydrogen gas is generated when the conditions for hydrogen gas generation are met under conditions where chemical reactions other than the battery reaction (self-discharge) occur, for example, due to the formation of a local galvanic cell between dissimilar metals inside the battery. For example, in nickel-zinc batteries, zinc or zinc oxide is present during charging, and the zinc dissolves during discharge. However, since zinc is one of the metals with a low potential among the metals used in aqueous batteries, the amount of discharge when a local galvanic cell state is formed between it and other metals used in the battery is large, making it easy to meet the conditions for hydrogen gas generation.

[0034] Excessive hydrogen gas generation can lead to decreased battery performance and leakage problems. Specifically, when hydrogen gas is generated due to self-discharge, electrons that should be contributing to the battery reaction are consumed by the hydrogen gas generation, leading to a decrease in battery performance. The more hydrogen gas generated, the greater the decrease in battery performance. Furthermore, leakage may occur due to an increase in internal pressure, leading to a decrease in safety. Note that self-discharge here includes both side reactions during charging and discharging (chemical reactions including the hydrogen gas generation process) and chemical reactions that occur outside of charging and discharging, i.e., in a state of natural standing.

[0035] To avoid such battery performance degradation and leakage problems, it is necessary to suppress hydrogen gas generation as much as possible. In particular, current collector materials are components that are more prone to hydrogen gas generation because zinc and other elements from the electrolyte precipitate on their surface and come into direct contact with it, and they are also components that are prone to self-discharge. One known method to reduce this hydrogen gas generation is to use materials with a high hydrogen overpotential, and in this embodiment, tin (Sn) in the tin layer 40 can be said to be a material with a high hydrogen overpotential. However, even when using tin (Sn) with a high hydrogen overpotential, it was confirmed that there are differences in the effectiveness of suppressing hydrogen gas generation depending on the crystal orientation state of the tin layer.

[0036] Therefore, the inventors diligently investigated materials that would further enhance the hydrogen gas generation suppression effect described above, and through repeated experiments, they found that controlling the crystal orientation indices of the (220), (200), and (400) planes of the tin layer 40 so that at least one of equations (1) or (2) described above exceeds 1 results in a superior hydrogen gas generation suppression effect. Furthermore, by forming the tin layer 40 on top of the nickel layer 30, it is easier to control the crystal orientation indices of the tin layer 40, and if dissolution occurs in a part of the tin layer 40 depending on the type of electrolyte applied to the alkaline secondary battery, the nickel layer 30 is formed, making it possible to suppress the dissolution of the metal substrate 20 into the electrolyte.

[0037] By controlling the crystal orientation indices of the (200), (220), and (400) planes of the tin layer 40 so that at least one of equation (1) or (2) above is greater than 1, the uniformity of the tin plating constituting the tin layer 40 can be improved, thereby suppressing gas generation during charging and discharging. On the other hand, if the crystal orientation index of the (200) plane or (400) plane is large and neither equation (1) nor (2) above is satisfied, the tin plating becomes non-uniform, a part of the nickel layer 30 is exposed from the tin layer 40, and gas tends to be generated more easily during charging and discharging.

[0038] The amount of tin deposited in the tin layer 40 is preferably 1.0 to 15.0 g / m².2 More preferably 2.0 to 15.0 g / m² 2 And more preferably 2.0 to 13.0 g / m² 2 The most preferred amount is 3.0 to 13.0 g / m². 2 By keeping the amount of tin deposited in the tin layer 40 within the above range, gas generation during charging and discharging can be effectively suppressed. The amount of tin deposited can be determined by performing X-ray fluorescence measurement or ICP emission spectroscopy on the surface-treated metal plate 10 for the battery. Note that the above amount of tin deposited represents the amount deposited on one side of the metal substrate 20.

[0039] The lower limit of the thickness of the tin layer 40 is preferably 0.05 μm or more, more preferably 0.10 μm or more, even more preferably 0.20 μm or more, and particularly preferably 0.50 μm or more. If the thickness of the tin layer 40 is too small, the crystal orientation index of the tin layer 40 cannot be properly controlled, and gas generation tends to become significant. The upper limit of the thickness of the tin layer 40 is not particularly limited, but is preferably 2.0 μm or less, more preferably 1.5 μm or less, and even more preferably 1.0 μm or less. The thickness of the tin layer 40 is determined by the amount of tin deposited using the above method and the density of tin (g / m³). 3 This can be determined by converting it to thickness (by dividing the amount of tin deposition by the density) based on the given formula, but it is not limited to this method. Thickness measurement by cross-sectional observation with a scanning electron microscope (SEM), thickness measurement with a transmission electron microscope (TEM), and measurement with a high-frequency glow discharge emission spectrometer are also applicable.

[0040] The method for controlling the crystal orientation indices of the (220), (200), and (400) planes of the tin layer 40 so that at least one of the above-mentioned equations (1) or (2) is greater than 1 is not particularly limited, but examples include adding a small amount of nickel to the tin plating bath used to form the tin layer 40, adding an additive to the tin plating bath, and combining these methods.

[0041] For the formation of the tin layer 40, a ferrostan bath, MSA bath, halogen bath, sulfuric acid bath, etc., can be used, further containing the aforementioned trace amounts of nickel and / or additives. Of these, a sulfuric acid bath is preferred, and a bath composition of 10-60 g / L of tin ions and 25-110 mL / L of sulfuric acid, further containing the aforementioned trace amounts of nickel and / or additives, is preferred. In particular, a bath composition of 10-60 g / L of tin ions and 25-60 mL / L of sulfuric acid, further containing the aforementioned trace amounts of nickel and / or additives, is especially preferred.

[0042] In the method of adding a small amount of nickel to a tin plating bath, the amount of nickel added is preferably 10 to 200 ppm by weight, more preferably 10 to 100 ppm by weight, and particularly preferably 20 to 100 ppm by weight.

[0043] Examples of additives to be added to the tin plating bath include ethoxylated naphthol and ethoxylated naphthol sulfonic acid. Commercially available products include Technistan TP Additive manufactured by Technic Japan and UTB 230R manufactured by Ishihara Chemical Co., Ltd. Of these, Technistan TP Additive manufactured by Technic Japan is preferred, and the amount to be added to the tin plating bath is preferably 10 to 100 mL / L, and more preferably 40 to 100 mL / L.

[0044] In the plating conditions for forming the tin layer 40, the current density is preferably 1.0 to 30.0 A / dm 2 And more preferably 2.0~15.0 A / dm 2 The current is particularly preferably 4.0 to 15.0 A / dm 2 Furthermore, the temperature of the plating bath is preferably 25 to 60°C, and more preferably 35 to 55°C.

[0045] <Nickel-tin alloy layer 50> Figure 2 is a cross-sectional view of a surface-treated metal plate for a battery according to another embodiment of the present invention.

[0046] As shown in Figure 2, the surface-treated metal plate 10a for batteries according to this embodiment may further include a nickel-tin alloy layer 50 between the nickel layer 30 and the tin layer 40 described above. By including the nickel-tin alloy layer 50, even if the tin layer 40 dissolves due to immersion in the electrolyte, the nickel-tin alloy layer 50 is formed, thus providing excellent suppression of gas generation and resistance to the electrolyte.

[0047] The nickel-tin alloy layer 50 is not particularly limited, but as an alloy phase, it is a nickel-tin alloy (hereinafter referred to as "Ni-Sn") which yields diffraction peaks in the diffraction angle range of 2θ = 42~43° by X-ray diffraction measurement using CuKα as a source. 42-43 It is preferable to include the following in the nickel-tin alloy layer 50: Ni-Sn 42-43 By controlling the content, it is easier to maintain the crystal orientation of tin in the tin layer 40 formed on top of the nickel-tin alloy layer 50. Furthermore, it is possible to increase the tin (Sn) content on the surface of the nickel-tin alloy layer 50, resulting in a surface-treated metal plate 10a for batteries that is excellent in both gas generation suppression and electrolyte resistance. It was also confirmed that the diffraction peaks in the diffraction angle range 2θ = 42~43° are different from the diffraction peaks of pure nickel, pure tin, and pure iron.

[0048] The thickness of the nickel-tin alloy layer 50 is not particularly limited, but is preferably 0.05 to 2.00 μm, more preferably 0.05 to 1.50 μm, and even more preferably 0.10 to 1.00 μm. By setting the thickness of the nickel-tin alloy layer 50 within the above range, the gas generation suppression effect and electrolyte resistance can be further enhanced. The thickness of the nickel-tin alloy layer 50 can be determined by thickness measurement by cross-sectional observation with a scanning electron microscope (SEM), measurement with a high-frequency glow discharge emission spectrometer, etc.

[0049] In the surface-treated metal plate 10a for batteries, the total amount of nickel deposited in the nickel-tin alloy layer 50 and the nickel deposited in the nickel layer 30 is preferably 1.0 g / m². 2 Super, 20.0g / m2 The following, and more preferably 1.5 g / m² 2 Super, 15.0g / m 2 The following, and more preferably 2.0 g / m² 2 Super, 10.0g / m 2 The following, and particularly preferably 3.0 g / m² 2 Super, 10.0g / m 2 The following applies. Furthermore, the total amount of tin deposited in the nickel-tin alloy layer 50 and the tin deposited in the tin layer 40 is preferably 1.0 to 15.0 g / m². 2 More preferably 2.0 to 15.0 g / m² 2 And more preferably 2.0 to 13.0 g / m² 2 The most preferred amount is 3.0 to 13.0 g / m². 2 That is the case.

[0050] Furthermore, the thickness of the nickel layer 30 and the tin layer 40 in the surface-treated metal plate 10a for batteries are within the same range as those of the surface-treated metal plate 10 for batteries described above.

[0051] The method for forming the nickel-tin alloy layer 50 is not particularly limited, but by forming a nickel layer 30 on a metal substrate 20 using the method described above, and then forming a tin layer 40 in this order with controlled crystal orientation indices for the (220), (200), and (400) planes, diffusion occurs at the interface between the nickel layer 30 and the tin layer 40, thereby forming the nickel-tin alloy layer 50. In particular, it is possible to form the nickel-tin alloy layer 50 by controlling the process so that at least one of equation (1) or (2) described above is greater than 1.

[0052] Furthermore, to further promote the formation of the nickel-tin alloy layer 50, it is preferable to use a room temperature diffusion treatment. The treatment temperature during the room temperature diffusion treatment is not particularly limited, but is preferably 0°C or higher and less than 50°C, and the treatment time (period) is not particularly limited, but is preferably 5 days or more, more preferably 7 days or more, even more preferably 10 days or more, and particularly preferably 30 days or more. By performing the room temperature diffusion treatment, the nickel-tin alloy layer 50 is formed with Ni-Sn as the alloy phase. 42-43 It may be made to primarily contain [this].

[0053] Furthermore, the surface-treated metal plates 10 and 10a for batteries according to the embodiments of the present invention may further include an iron-nickel diffusion layer as a layer below the nickel layer 30. In the embodiment of the surface-treated metal plate 10 for batteries shown in Figure 1, a nickel layer 30 is formed on a metal substrate 20, and an iron-nickel diffusion layer is formed by heat treatment. Then, a tin layer 40 is formed on top of the nickel layer 30, thereby obtaining a structure that includes an iron-nickel diffusion layer in addition to the nickel layer 30 and the tin layer 40. In the embodiment of the surface-treated metal plate 10a for batteries shown in Figure 2, a nickel layer 30 is formed on a metal substrate 20, and an iron-nickel diffusion layer is formed by heat treatment. Then, a tin layer 40 is formed on top of the nickel layer 30, and further room-temperature diffusion treatment is performed, thereby obtaining a structure that includes an iron-nickel diffusion layer in addition to the nickel layer 30, nickel-tin alloy layer 50, and tin layer 40. Furthermore, as a method for forming the iron-nickel diffusion layer, it is also conceivable to form a tin layer 40 on top of the nickel layer 30 and then perform heat treatment to form the iron-nickel diffusion layer. However, with this method, it is difficult to control the crystal orientation state of the tin layer 40, and Ni-Sn 42-43 This is undesirable because a nickel-tin alloy layer 50 containing the above-mentioned material cannot be obtained. Therefore, it is preferable to have a configuration in which a nickel layer 30 is formed as described above, an iron-nickel diffusion layer is formed by heat treatment, and then a tin layer 40 is formed on top of the nickel layer 30, or a configuration in which an iron-nickel diffusion layer is formed, a tin layer 40 is formed on top of the nickel layer 30, and then a nickel-tin alloy layer 50 is formed between the nickel layer 30 and the tin layer 40.

[0054] The heat treatment conditions for forming the iron-nickel diffusion layer are not particularly limited, but when heat treatment is performed by box annealing, the heat treatment temperature should preferably be between 400°C and 600°C, more preferably between 450°C and 600°C, and the soaking time should preferably be between 0.5 and 8 hours. When heat treatment is performed by continuous annealing, the heat treatment temperature should preferably be between 600°C and 900°C, more preferably between 600°C and 800°C, and the heat treatment time should preferably be between 3 and 120 seconds.

[0055] The surface-treated metal plate 10 for batteries according to this embodiment comprises a metal substrate 20, a nickel layer 30 formed on at least one side of the metal substrate 20, and a tin layer 40 formed as an upper layer of the nickel layer 30. The crystal orientation index of the tin layer 40 satisfies the condition that at least one of the above formulas (1) or (2) is greater than 1, and is capable of exhibiting an excellent gas generation suppression effect. Furthermore, in the case of the surface-treated metal plate 10a for batteries which further comprises a nickel-tin alloy layer 50 between the nickel layer 30 and the tin layer 40, it exhibits a gas generation suppression effect and electrolyte resistance. Therefore, the surface-treated metal plates 10 and 10a for batteries according to the embodiment of the present invention can be preferably used as current collectors or battery containers for positive or negative electrodes, taking advantage of these characteristics, and are more preferably used as current collectors or battery containers in alkaline secondary batteries using alkaline electrolytes, and are particularly preferably used as current collectors or battery containers in nickel-zinc batteries. [Examples]

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The evaluation methods for each characteristic are as follows.

[0057] <Measurement of nickel and tin deposits> For the surface-treated metal plates 10 and 10a obtained in each of the examples and comparative examples, the nickel adhesion amount and the tin adhesion amount were quantified by the calibration curve method using fluorescence X-ray (XRF) measurement. The fluorescence X-ray device used was the ZSX100e manufactured by Rigaku Corporation. In the fluorescence X-ray measurement, it was confirmed that the metal elements contained in each layer of the nickel layer 30, nickel-tin alloy layer 50, and tin layer 40 of the surface-treated metal plate could be quantified by the calibration curve method.

[0058] <X-ray diffraction (XRD) measurement (presence or absence of nickel layer 30 and tin layer 40)> For the surface-treated metal plates 10 and 10a for batteries obtained in each of the examples and comparative examples, the presence or absence of the nickel layer 30 and the tin layer 40 was confirmed by performing X-ray diffraction (XRD) measurement. As the X-ray diffraction measurement device, SmartLab manufactured by Rigaku Corporation was used, and the obtained surface-treated metal plate for batteries cut into 30 mm × 30 mm was used as the measurement sample. The specific measurement conditions for the X-ray diffraction (XRD) measurement were as follows. (Device configuration) · X-ray source: CuKα · Goniometer radius: 300 nm · Optical system: Concentration method (Incident side slit system) · Solar slit: 5° · Longitudinal restriction slit: 5 mm · Divergence slit: 1 / 2° (Receiving side slit system) · Scattering slit: 1 / 2° · Solar slit: 5° · Receiving slit: 0.3 mm · Monochromation method: Counter monochromator method · Detector: Scintillation counter (Measurement parameters) · Tube voltage - tube current: 45 kV 200 mA · Scanning axis: 2θ / θ · Scanning mode: Continuous · Measurement range: 2θ 30 to 100° · Scanning speed: 10° / n · Step: 0.05°

[0059] For the obtained peak intensity values, background removal was performed using the integrated powder X-ray analysis software PDXL manufactured by Rigaku Corporation, and data analysis was carried out. Regarding the method for confirming the presence or absence of the nickel layer 30 and the tin layer 40, it was determined based on the presence or absence of the diffraction peaks of nickel and tin. The diffraction peaks of nickel were determined based on the peaks of the (200) plane that appear at a diffraction angle 2θ = 51 - 53°, the peaks of the (220) plane that appear at a diffraction angle 2θ = 76 - 77°, and the peaks of the (311) plane that appear at a diffraction angle 2θ = 92 - 94° (ICDD PDF card 03 - 065 - 2865). Also, the diffraction peaks of tin were determined based on the peaks of the (200) plane that appear at a diffraction angle 2θ = 30 - 31°, the peaks of the (220) plane that appear at a diffraction angle 2θ = 43.5 - 44.1°, and the peaks of the (400) plane that appear at a diffraction angle 2θ = 63.5 - 64.2° (ICDD PDF card 00 - 004 - 0673).

[0060] <X-ray Diffraction (XRD) Measurement (Crystal Orientation Index of Tin Layer 40)> For the battery surface-treated metal plates 10 and 10a obtained in each example and comparative example, after measuring the diffraction intensity of each crystal plane of tin on the surface of the tin layer 40 by the above-described X-ray diffraction (XRD) measurement method, using the obtained diffraction intensity of tin and the diffraction intensity of standard tin powder, the crystal orientation indices of the (220) plane, (200) plane, and (400) plane on the surface of the tin layer 40 were respectively obtained, and the ratios of the crystalline orientation indices, N(220) / N(200), and N(220) / N(400) were calculated. The diffraction angles of each crystal plane of tin and the diffraction angles of each crystal plane of the standard tin powder were those described in database 00 - 004 - 0673 of the diffraction ICDD PDF - 2 2014.

[0061] <X-ray Diffraction (XRD) Measurement (Presence or Absence of Nickel-Tin Alloy Layer 50)> For each example and comparative example, the presence or absence of the nickel-tin alloy layer 50 was confirmed for the surface-treated metal plates 10 and 10a for batteries obtained using the X-ray diffraction (XRD) measurement method described above. The presence or absence of the nickel-tin alloy layer 50 was determined by checking for diffraction peaks that do not correspond to the diffraction peaks of nickel, tin, and iron, and that appear at a diffraction angle of 2θ = 42-43°. Specifically, diffraction peaks that appear at a diffraction angle of 2θ = 42-43° do not correspond to the diffraction angles described in ICDD PDF card 03-065-2865 (nickel), ICDD PDF card 00-004-0673 (tin), and ICDD PDF card 03-065-4899 (iron), and can be determined to be diffraction peaks originating from the nickel-tin alloy. Therefore, if a diffraction peak was confirmed at this angle, it was determined that the nickel-tin alloy layer 50 was present.

[0062] <Evaluation of gas generation suppression by measuring corrosion current density before the anode reaction> The gas generation suppression effect was evaluated for the surface-treated metal plates 10 and 10a for batteries obtained in each example and comparative example by measuring the corrosion current density when immersed in an alkaline solution. The corrosion current density was measured under the following conditions, and the corrosion current density generated between the test electrode and the counter electrode in a 30 wt% potassium hydroxide solution (unit: mA / cm²) was measured. 2 ) was measured. • Measuring device: Hokuto Denko Co., Ltd. HZ7000 • Test electrode: Zn plate (evaluation area 20mm x 20mm, thickness 0.5mm) • Counter electrode: Measurement sample (measuring diameter φ6mm) ·Measurement method: Non-resistance ammeter

[0063] Specifically, as a test simulating a local cell with deposited Zn, a Zn plate was used as the counter electrode, and the resulting surface-treated metal plates 10 and 10a for the cell were immersed in an alkaline solution. The corrosion current density was then measured using an electrochemical measurement system to evaluate the suppression of gas generation. A lower corrosion current density after 30 seconds of immersion in the alkaline solution indicates a higher gas generation suppression effect. A corrosion current density of 0.15 mA / cm² is considered effective. 2The following is designated as "A+", with a corrosion current density of 0.20 mA / cm². 2 The following is "A", with a corrosion current density of 0.25 mA / cm². 2 The following is designated "B", with a corrosion current density of 0.25 mA / cm². 2 Anything exceeding this level was rated as "C".

[0064] <Evaluation of gas generation suppression by measuring corrosion current density after anode reaction> Furthermore, regarding the obtained surface-treated metal plates 10 and 10a for batteries, if we assume their use in zinc secondary batteries, depending on the battery design, the zinc layer of the negative electrode active material may thicken after repeated charging and discharging. To remove the excessively thick zinc layer, it is assumed that a discharge reaction (anodic reaction) will be performed to a state close to an over-discharge state. As a test to simulate such a state, an anodic reaction test was performed using an alkaline solution (30 wt% potassium hydroxide solution), and the corrosion current density of the surface-treated metal plates 10 and 10a for batteries after the anodic reaction test was measured in the same manner as above. The corrosion current density was 20 mA / cm². 2 The following is designated as "A+", with a corrosion current density of 30 mA / cm². 2 The following is designated "A", with a corrosion current density of 40 mA / cm². 2 The following is designated "B", with a corrosion current density of 40 mA / cm². 2 Anything exceeding this level was rated as "C".

[0065] The anode reaction test was conducted under the following conditions. • Electrochemical measuring instrument: Hokuto Denko Co., Ltd. HZ7000 • Test electrode: Measurement sample (evaluation area 20mm x 20mm) • Opposite electrode: Cu plate ·Reference electrode: Ag / AgCl (KCl saturated) • Electrolyte: 30% by weight potassium hydroxide solution ·Current density: 50mA / cm 2 • Measurement method: Chronopotentiometry • Electrical capacity: 21C / cm² 2

[0066] <Example 1> First, as the metal substrate 20, a cold-rolled sheet (60 μm thick) of low-carbon aluminum-killed steel having the chemical composition shown below was prepared. C: 0.04 wt%, Mn: 0.32 wt%, Si: 0.01 wt%, P: 0.012 wt%, S: 0.014 wt%, remainder: Fe and unavoidable impurities

[0067] Next, the prepared metal substrate 20 was subjected to electrolytic degreasing and acid pickling by sulfuric acid immersion, and then nickel plating was performed under the following conditions to form nickel layers 30 on both sides of the metal substrate 20. The nickel plating conditions were as follows. The nickel plating processing time was set to ensure that the amount of nickel deposited was as shown in Table 1. (Bath composition: Watt bath) Nickel sulfate hexahydrate: 250g / L Nickel chloride hexahydrate: 45 g / L Boric acid: 30g / L (Plating conditions) Bath temperature: 60℃ pH: 4.0~5.0 Agitation: Air agitation or jet agitation Current density: 10A / dm 2

[0068] Next, a tin layer 40 was formed on the metal substrate 20 on which the nickel layer 30 had been formed, by tin plating. The conditions for tin plating were as follows. The tin plating time was set such that the amount of tin deposited was as shown in Table 1, and a surface-treated metal plate 10 for batteries was obtained. The above-described measurements were then performed on the obtained surface-treated metal plate 10 for batteries. The results are shown in Table 1. (Bath composition) Tin ions: 20g / L Sulfuric acid: 45mL / L Additive (product name "Technistan TP Additive", manufactured by Technistan Japan): 50 mL / L Nickel: 50 ppm by weight (Plating conditions) pH: 1 or less Bath temperature: 45℃ Current density: 5A / dm 2

[0069] <Example 2> A steel sheet having a nickel layer and a tin layer was obtained in the same manner as in Example 1. The obtained steel sheet having the nickel layer and tin layer was subjected to room temperature diffusion treatment at a temperature of 25°C for a period of 180 days to obtain a surface-treated metal sheet 10a for batteries having a nickel-tin alloy layer 50. The treatment times for nickel plating and tin plating were set to achieve the nickel and tin deposition amounts shown in Table 1. The obtained surface-treated metal sheet 10a for batteries was then subjected to the measurements described above. The results are shown in Table 1.

[0070] <Examples 3-5> A surface-treated metal plate 10a for batteries was obtained in the same manner as in Example 2, except that the time period during the room-temperature diffusion treatment was changed to the conditions shown in Table 1. The treatment times for nickel plating and tin plating were set to the amounts of nickel and tin deposited, respectively, as shown in Table 1. The above-described measurements were then performed on the obtained surface-treated metal plate 10a for batteries. The results are shown in Table 1.

[0071] <Example 6> A surface-treated metal plate 10a for batteries was obtained in the same manner as in Example 2, except that the thickness of the metal substrate 20 was changed to 25 μm and the time period in the room-temperature diffusion treatment was changed to the conditions shown in Table 1. The treatment times for nickel plating and tin plating were set to the amounts of nickel and tin deposited, respectively, as shown in Table 1. The above-described measurements were then performed on the obtained surface-treated metal plate 10a for batteries. The results are shown in Table 1.

[0072] <Examples 7-8> A surface-treated metal plate 10a for batteries was obtained in the same manner as in Example 2, except that the current density conditions in tin plating and the time elapsed in the room-temperature diffusion treatment were changed to the conditions shown in Table 1. The treatment times for nickel plating and tin plating were set to the amounts of nickel and tin deposited, respectively, as shown in Table 1. The above-described measurements were then performed on the obtained surface-treated metal plate 10a for batteries. The results are shown in Table 1.

[0073] <Examples 9-10> A surface-treated metal plate 10a for batteries was obtained in the same manner as in Example 2, except that the current density conditions for nickel plating and tin plating, and the time elapsed in the room-temperature diffusion treatment were changed to the conditions shown in Table 1. The treatment times for nickel plating and tin plating were set to ensure that the amount of nickel and tin deposited were the amounts shown in Table 1. The above-described measurements were then performed on the obtained surface-treated metal plate 10a for batteries. The results are shown in Table 1.

[0074] <Examples 11-12> A surface-treated metal plate 10a for batteries was obtained in the same manner as in Example 2, except that the current density conditions in nickel plating and tin plating, the amount of additive added in the tin plating bath, and the time elapsed in the room temperature diffusion treatment were changed to the conditions shown in Table 1. The treatment times for nickel plating and tin plating were set to ensure that the amount of nickel and tin deposited were the amounts shown in Table 1. The above-described measurements were then performed on the obtained surface-treated metal plate 10a for batteries. The results are shown in Table 1.

[0075] <Example 13> A surface-treated metal plate 10a for batteries was obtained in the same manner as in Example 7, except that the thickness of the metal substrate 20 was changed to 110 μm. The nickel plating and tin plating treatment times were set to ensure that the nickel and tin deposition amounts were as shown in Table 1. The above-described measurements were then performed on the obtained surface-treated metal plate 10a for batteries. The results are shown in Table 1.

[0076] <Comparative Examples 1-2> A surface-treated metal plate was obtained in the same manner as in Example 2, except that neither additives nor nickel were added to the tin plating bath, and the current density conditions for tin plating and the time elapsed in the room-temperature diffusion treatment were changed to the conditions shown in Table 1. The treatment times for nickel plating and tin plating were set to achieve the nickel and tin deposition amounts shown in Table 1. The results are shown in Table 1.

[0077] <Comparative Example 3> A surface-treated metal plate was obtained in the same manner as in Comparative Example 1, except that room-temperature diffusion treatment was not performed. The treatment times for nickel plating and tin plating were set to achieve the nickel and tin deposition amounts shown in Table 1. The results are shown in Table 1.

[0078] <Comparative Example 4> A surface-treated metal plate was obtained in the same manner as in Comparative Example 3, except that 50 ppm by weight of nickel was added to the tin plating bath. The treatment times for nickel plating and tin plating were set to achieve the nickel and tin deposition amounts shown in Table 1. The results are shown in Table 1.

[0079] <Comparative Example 5> A surface-treated metal plate was obtained in the same manner as in Example 2, except that nickel was not added to the tin plating bath, and the amount of additives added to the tin plating bath and the duration of the room-temperature diffusion treatment were changed to the conditions shown in Table 1. The nickel plating and tin plating treatment times were set to ensure that the nickel and tin deposition amounts were as shown in Table 1. The results are shown in Table 1.

[0080] <Comparative Example 6> A surface-treated metal plate was obtained in the same manner as in Example 4, except that the amount of tin deposited was changed to the conditions shown in Table 1. The processing times for nickel plating and tin plating were set to the amounts of nickel deposited and tin deposited as shown in Table 1. The results are shown in Table 1.

[0081] [Table 1]

[0082] As shown in Table 1, with surface-treated metal plates 10 and 10a satisfying the condition that at least one of equations (1) or (2) above is greater than 1 in the crystal orientation indices of the (200), (220), and (400) planes of the tin layer 40, the corrosion current density was reduced and gas generation was effectively suppressed before and after the anodic reaction (Examples 1 to 13).

[0083] More specifically, in Examples 1 to 13, if at least one of equations (1) or (2) relating to the crystallinity orientation index of the tin layer 40 is greater than 1, the corrosion current density before the anodic reaction is 0.25 mA / cm². 2 The results were as follows, confirming that the gas generation suppression effect was excellent. Furthermore, in Examples 1 to 10, both equations (1) and (2) were 2 or higher, confirming that the gas generation suppression effect was even better. In addition, in Examples 1 to 6, both equations (1) and (2) were 10 or higher, confirming that the gas generation suppression effect was even more remarkably superior.

[0084] Furthermore, in Examples 2 to 13, a nickel-tin alloy layer 50 was further provided between the nickel layer 30 and the tin layer 40. As shown in Table 1, the corrosion current density results after the anodic reaction confirmed that the presence of the nickel-tin alloy layer 50 even after the anodic reaction suppresses gas generation and also provides excellent resistance to electrolytes.

[0085] More specifically, in Examples 2 to 13, the alloy phase constituting the nickel-tin alloy layer 50 is Ni-Sn 42-43 These surface-treated metal plates 10a for batteries mainly contain [a specific substance], and the corrosion current density after the anode reaction is 40 mA / cm². 2 The following results were obtained, confirming that it has a gas generation suppression effect while also exhibiting excellent resistance to electrolytes. Furthermore, when forming the nickel-tin alloy layer 50, it was confirmed that the gas generation suppression effect in the nickel-tin alloy layer 50 was superior when the crystal orientation index of the tin layer 40 formed on top of the nickel layer 30 was controlled so that both equations (1) and (2) were 2 or greater. In particular, when both equations (1) and (2) were 10 or greater in the crystal orientation index of the tin layer 40, the corrosion current density after the anode reaction was 20 mA / cm². 2 The following results were obtained, confirming that the gas generation suppression effect is remarkably superior.

[0086] On the other hand, in Comparative Examples 1 to 6, since the surface-treated metal plates did not exceed 1 in either equation (1) or (2) relating to the crystal orientation index of the tin layer 40, it was confirmed that the corrosion current density before and after the anodic reaction was greater than that in Examples 1 to 13.

[0087] Figures 3A to 3C show the X-ray diffraction (XRD) charts of the tin layer 40 obtained by X-ray diffraction (XRD) measurement for the surface-treated metal plate 10a for battery in Example 9. Figure 3A is an X-ray diffraction chart showing the diffraction peak of the (200) plane of the tin layer 40, Figure 3B is an X-ray diffraction chart showing the diffraction peak of the (220) plane of the tin layer 40, and Figure 3C is an X-ray diffraction chart showing the diffraction peak of the (400) plane of the tin layer 40. Using the diffraction peaks of the (200), (220), and (400) planes of the tin layer 40 detected in this way, the ratio of the crystal orientation index of the tin layer 40 was calculated. Similarly, for the surface-treated metal plates 10 and 10a for battery obtained in Examples 1 to 8 and 10 to 13, the ratio of the crystal orientation index of the tin layer 40 was calculated using the diffraction peaks of the (200), (220), and (400) planes of the tin layer 40.

[0088] Figure 4 shows the X-ray diffraction chart of the alloy phase constituting the nickel-tin alloy layer detected in Example 9. As shown in Figure 4, in the surface-treated metal plate 10a for batteries obtained in Example 9, diffraction peaks were obtained in the diffraction angle range 2θ = 42-43° by X-ray diffraction measurement, confirming the formation of the nickel-tin alloy layer 50. Similarly, diffraction peaks were also obtained in the diffraction angle range 2θ = 42-43° in the surface-treated metal plates 10a for batteries obtained in Examples 2-8 and 10-13. [Explanation of Symbols]

[0089] 10,10a... Surface-treated metal sheets for batteries 20...Metal base material 30…Nickel layer 40...Tin layer 50…Nickel-tin alloy layer

Claims

1. A surface-treated metal plate for batteries, Metal substrate and A nickel layer provided on at least one side of the aforementioned metal substrate, The nickel layer comprises a tin layer provided on top of the nickel layer, A surface-treated metal plate for batteries that satisfies the condition that both equation (1) and equation (2) below are 2 or more for the tin layer. N(220) / N(200) (1) N(220) / N(400) (2) In equations (1) and (2) above, N(220) represents the crystal orientation index of the (220) plane of the tin layer, in equation (1) N(200) represents the crystal orientation index of the (200) plane of the tin layer, and in equation (2) N(400) represents the crystal orientation index of the (400) plane of the tin layer.

2. The surface-treated metal plate for a battery according to claim 1, further comprising a nickel-tin alloy layer formed between the nickel layer and the tin layer.

3. The surface-treated metal plate for a battery according to claim 1 or 2, wherein the metal substrate is an iron-based metal substrate.

4. The amount of nickel deposited in the nickel layer is 1.0 g / m². ２ It is extremely high, at 20.0 g / m ２ The surface-treated metal plate for batteries according to claim 1 or 2, which is as follows:

5. The amount of tin deposited in the aforementioned tin layer is 1.0 g / m². ２ Above, 15.0g / m ２ The surface-treated metal plate for batteries according to claim 1 or 2, which is as follows:

6. The surface-treated metal plate for batteries according to claim 2, wherein in the nickel-tin alloy layer, diffraction peaks are obtained in the diffraction angle range 2θ = 42 to 43° by X-ray diffraction measurement using CuKα as the source as the alloy phase.

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