TW521453B - Core for alkaline battery and battery using the same - Google Patents

Abstract

Disclosed is to provide core for alkaline battery using thin steel sheet and is excellent in holding characteristics of active substance and battery using the same. The said core is composed of graphite dispersion nickel plating layer or graphite dispersion nickel alloy plating layer, which is formed by graphite dispersed onto a thin steel sheet. The alloy plating layer is preferably nickel-cobalt alloy, nickel-cobalt-iron alloy, nickel manganese alloy, nickel-phosphor alloy or nickel-bismuth alloy and graphite, so it can form a irregular surface, and also provide a core for alkaline battery using thin steel sheet and is excellent in holding characteristics of active substance.

Description

521453 V. Description of the invention (l) '" ----- ^ Invention] The core of the battery for alkaline batteries, such as alkaline batteries, the core of the positive electrode or the negative electrode of the battery, and the electric core. As well as the related electric technology, it has become a battery (secondary battery) battery for various power sources, but it can be used economically for a long period of time, and it is widely used because of small secondary power storage. The battery is light, so this type of alkaline storage battery is usually a negative electrode plate that has been coated with a hydroxide electrode plate and a coated (0 (: (: 1113: [〇11) hydrogen alloy), Closed box-like structure. Nickel plating of the punched metal that has been processed with mechanical door ^ on the negative electrode of the alkaline storage battery and coating the person who has stored chlorine: it is being used. Nickel hydroxide-coated foam is being used. The manufacturing method of foamed nickel is, for example, subjecting the foamed resin to nickel age, and then subjecting it to high-temperature heat treatment in an oxygen-containing gas to volatilize == resin component And made of highly porous support. X jin 'solved. This type of punching metal will appear on the surface of nickel oxide or hydroxide with high resistance due to time-dependent changes in the electrolysis i. Disadvantages of high resistance. For the production of foamed nickel bodies, "In addition to the above problems, there are still a selection of raw materials." The subsequent manufacturing steps are extremely complicated.

Page 5 521453, it is necessary to manage manufacturing under strict manufacturing conditions, and there are often problems that are easy to form expensive. In order to solve the related problems, in order to provide a low-cost and high-performance battery core, the inventors have carefully reviewed the results and found that if the core used as the electrode plate can be alkali-resistant electrolyte, graphite can be dispersed Nickel plating does not form high-resistance oxides or hydroxides, but forms irregularities on the surface. The anchor effect makes the active material retain good properties.

The means for solving the problem, the battery core of the present invention, is formed by attaching an active material to a core that becomes a plate-shaped current collector to form a positive electrode plate and a negative electrode plate, and the two electrode plates are sealed by a separator. The alkaline storage battery in the box is characterized by a graphite dispersion nickel plating or graphite dispersion plating alloy treatment on a thin steel plate to form a convex surface and a core with excellent retention properties with active materials. The ore-recording alloy layer is preferably any one of nickel-ming alloy, nickel-drilling_iron alloy, pitting alloy, nickel-phosphorus alloy, or nickel-bismuth alloy. Graphite layer

It is preferable that the graphite dispersed nickel plating layer or the graphite dispersed plating is a diffusion layer or a nickel layer. i s t a, a graphite dispersed nickel plating layer or a graphite dispersed nickel plating layer is preferably 0 to 1 to 25% by weight. JL Ming's implementation of the shape bear First, after preparing a mild steel plate, graphite dispersion plating is performed on the mild steel plate.

Page 6 521453 V. Description of the invention (3) Nickel or graphite disperse nickel-plated alloy treatment, coating the core body with hydroxide slurry and making the core for alkaline storage battery, and the cloth contains the slurry of the alloy containing hydrogen, ^ The positive electrode plate, or coating on the core, illustrates the invention. A negative plate is formed. The steel plates used in the following are detailed.] The steel plates used in the present invention are steel plates that are continuously converted with low carbon aluminum deoxidized steel plates, and the steel plate is particularly low. It should also be possible to use carbon-titanium Γτη low-alloy steel or non-aging steel with niobium (Nb) and non-aging properties (stability amount% (:: · (chrome), etc.) added to it. This = Times ^ steel plate with 3 ~ 18 heavy processing. Diaosi steel plate can also be perforated in advance [base ore nickel treatment] Surface treatment steel plate is applied before the steel plate. This key nickel treatment is called "base ore "Ni". Substrate ;; II: Adequacy can be ensured even after the core has been formed, and tiles can also be used in the present invention; Temple II: material; ir: ulfamic acid) mineral bath, butterfly gas plating Baths, chlorine, ore baths used in the treatment of nickel and ore, and nickel. In terms of treatment, non-electrolytic ore 'although electroless ore can also be used'. Easy to use. The current density of the 6 shape of the electrolytic method is 3 ~ 80A / dm2. In order to obtain a uniform electroplated layer, it is advisable to perform air stirring with air blowing into the bath, etc. " 521453 V. Description of the invention ( 4)

, The pH of the plating bath is in the pH of the ore bath is preferably in the acidic range of 3.5 to 5.5, 4 0 ~ 60 ° C is better. As for the nickel plating on the substrate, plating without using organic additives, semi-gloss plating or gloss electroplating using organic additives may be used. The nickel adhesion amount of the nickel-nickel layer is preferably from 0.5 to 5 // π1 pass ^ [Formation of the diffusion layer] Any of a and its matte electricity. The substrate is plated and heated to form the 0 layer of the diffusion layer, which can be maintained in the state of electric ore. However, it is advisable to set all or part of the gold-plated layer as a diffusion layer after electroplating. (It is effective in preventing the nickel plating layer from peeling off the steel plate substrate and 25% in preventing oxidizing gas) etc. However, regardless of the above, the continuous quenching for 15 hours requires the non-chemical film and the diffusion layer. It is more appropriate to use the original gas. As for the heat treatment, either. Suitcase. When processing, the box quenching rule is preferably from 30 seconds. Performed under oxidizing or reducing thinning gas, it is more suitable in terms of surface formation. As for the non-oxygen nitrogen, gas, and nitrogen, the so-called inert gases, another suitable use is hydrogen and ammonia cracking gas (75% hydrogen, nitrogen methods include box quenching and continuous quenching. In the case of type quenching, the heat treatment temperature is 45 (It takes a long time to process in a short time in the continuous quenching method. Generally speaking, in about 2 minutes, the box-type quenching is from 6 hours to about L graphite dispersion nickel plating (this graphite dispersion is dispersed (Plating brocade layer), # of the formation] is mainly based on mineral nickel or (other metals with graphite 'such as copper, manganese, iron,

V. Description of the invention (5), nickel, bismuth, and nickel, and a nickel-plated ink bath and further advance Γ: ^, mainly used in this bath to disperse the stone, so that the female clever 1 is formed with graphite dispersion Nickel-plated alloy). In order to disperse the graphite in the plating layer when needed, the same anchoring effect of the generated ore layer can be changed. The precipitation can be modified by the convex precipitates. Retention of active materials in batteries. Or, only two eclipse households. The stone and ink used may be either natural graphite or artificial graphite. In addition, 50% of the finely pulverized graphite with a cumulative diameter of 10 or less is used for ultra-fine graphite with a cumulative diameter of 5㈣ or less, and graphite is particularly liable to fall off. Tucai attached, tired servant ‘: It is advisable to use graphitized carbon black. Graphitized carbon black is a fine carbon black stone; if the average particle size is before or after the value, then the graphite is hydrophobic because of its surface, so keep it in the original state and stir it in the bath. Therefore, it is better to use a surface active agent (graphite dispersant) and make ^ 彳 as the government. Although the graphite dispersant used can be any of cationic gadolinium, anionic, non-ionic, and amphoteric #, it is considered that the adhesion between the steel plate of the broken plate and the forging layer is good and the coating is brittle. ^ When there are few points, it is more suitable to use anionic hair surfactant as a graphite separating agent. Among the anionic surfactants, benzenesulfonic acid or sulfuric acid-based active agents, such as sodium sulfonate, Sodium dodecylbenzenesulfonate, sodium α__ olefin sulfonate, sodium alkylnaphthalenesulfonate, sodium dialkyl sulfosuccinate, and the like are most suitable as the graphite dispersant of the present invention. The method of dispersing fine graphite in electroplating solution is to use graphite powder and

Page 9 521453 V. Description of the invention (6)

A certain amount or ultrasound with a small amount of this, vermiculite dispersant 1 g / L of the results. Another graphite powder will be about 2 ~

Water dilution, washing machine, alcohol, make the ink fully mixed, and when mixed, the graphite dispersant attached to the mineral liquid at 10m 1 / L is kneaded. Finally, use an emulsifier mixer such as a homogenizer to make it dispersed. In this case, the method of dispersing graphite powder in advance is also effective. After dispersing, stir in the plating solution and add at the same time. The ratio of graphite is preferably about 0.5 to 10% by weight. If the content of graphite is too low in the coating, and there is no anchoring effect, if it exceeds 100 g / L, the fluidity of the electric ore liquid will deteriorate, and various problems will easily occur around the electric ore device: Inhibition of graphite particles can be added in advance

The plating solution in the dispersed plating bath for dispersing graphite is made by using the method of making the pores σ of the lower part of the key liquid circulation tank under the emptyer, and making graphite powder often in the plating bath. If the dispersed state can be maintained well, graphite in a state of 0% ^^ ~ 25% can be dispersed in the plating layer, so that the dispersion is about 丨 ~ \ 〇 and. And, if the formation of graphite dispersion plating can make graphite people. In Trinity, it is advisable to reduce the current density. 3 There are rate improvement examples

The following description is based on the example. Example 1 The steel sheet is quenched and heat-treated at a thickness of 60. Roll steel sheets are used. NaOH aqueous solution (30 g / L) is used.

Page 10

521453 V. Description of the invention (7) Electrode treatment (5A / dm2x 10 seconds) and cathode treatment (5A / dm2x 10 seconds), alkaline degreasing. Next, it was immersed in an aqueous sulfuric acid solution (50 g / L) for about 15 seconds and acid-washed ', and then air-boiled with a Watt plating bath under the following conditions, and at the same time subjected to nickel plating on the substrate. And the anode side is used in a titanium basket made of polypropylene installed with zinc particles inserted: the time of the electric ore is adjusted to the thickness of the electric ore H [the conditions of the substrate] [the composition of the ore bath] Gasification record of nickel sulfate 300g / L 4 5 g / L ·

Uric acid Ug / L [Plating conditions]

Bell bath temperature 55 ± 2 ° C ρΗ 4 · 2 ± 〇 · 2 Current density 20A / dm2 Base ore nickel finished steel sheet system at 5 50 ° C, 8 hours, nitrogen: 94%, hydrogen: 6% gas Under the surroundings, heat diffusion treatment is performed. The thickness of the treated nickel-iron diffused layer was confirmed by glow discharge emission spectrometry-4-4 Tian. ..., [[Heat treatment roll] ~], and, after the steel sheet has been treated, to prevent tensile strain, heat treatment rolls are performed thereafter. ~ X [Graphite disperse nickel plating] Then, use it under the following conditions Graphite dispersion nickel plating bath

Page 11 521453 V. ‘Explanation of Invention (8) " One 'One --- ^ Disperse ore nickel treatment. The graphite dispersion ore nickel bath is also subjected to air conditioning and anode and cathode treatment conditions, which are the same as those of the above-mentioned base nickel: the graphite dispersion nickel plating treatment improves the plating time, and the stone in the bath is added. The amount changes the thickness of the plating and the graphite content dispersed in the plating layer. [Graphite Dispersion Ore Recording Conditions] [Plating Bath Composition]

300g / L 45g / L 45g / L lg / L 5ml / L Nickel Sulfate Nickel Chloride Graphite Dispersant (pi 11 ess) Agent (Sodium Lauryl Sulfate) 2 · 〇m 1 / L [Plating Conditions] Plating bath temperature 6 0 ± 2 ° C pH 4 · 3 ± 0 · 2 Current density 15A / dm2 [Production method of graphite dispersion ore nickel bath] The method of dispersing graphite in a bell bath is as follows. First, a “dilution solution” in which commercially available sodium besylate (graphite dispersant) was diluted 4 mi in 1 L of deionized water was manufactured, and the diluted solution was mixed with 1 Kg of fine powder graphite to form a mixed solution. For the mixed fluidity, add 1 L of deionized water, and use a ultrasonic disperser to make a graphite dispersion plating bath. For fine powder graphite, use graphite powder ASSP50 manufactured by Japan Graphite Industry Co., Ltd. with a cumulative diameter of 6 // m.

Page 12 521453 V. Description of the Invention (ίο) Confirmation. 8 // m。 The thickness of the iron-nickel diffusion layer is 2. 8 // m. After quenching and heat-treating the rolls, the nickel-cobalt-iron alloy plating with graphite dispersed was performed under the following conditions. The plating bath was also subjected to air agitation, and the anode and cathode treatment conditions were the same as those of the aforementioned nickel plating on the substrate. The method of dispersing graphite is also the same as in Example 1. [Composition of plating bath] 300g / L nickel sulfate 45g / L nickel chloride 45g / L boric acid 5g / L iron sulfate 5g / L graphite 30g / L dispersant 5ml / L [plating conditions] plating bath temperature 60 ± 2 pH 4. 3 ± 0 · 2 current density 15A / dm2 By this graphite dispersing alloy can be obtained cobalt content of 2.3% by weight, iron content of 1% by weight, graphite content of 0.7% by weight of graphite plating dispersion Nickel alloy layer. In addition, using this treated steel sheet, a core was produced in the same manner as in Example 1. The active material was applied, and the results of the measured characteristics are summarized in Table 1. Example 8 The same method as in Example 1 was performed using a plated original plate with a thickness of 60 / m.

Page 14 521453 V. Description of the invention (12) The same method as in Example 1 was used to degreasing, pickling, and nickel-plating the base plate with a thickness of β 〇 # m. After the underlying nickel plating treatment, diffusion heating treatment was performed under the same conditions as in Example 1, and after the heat treatment roll treatment was performed, the nickel-phosphorus alloy having graphite dispersed therein was electroplated under the following conditions. This ore bath was also air-stirred, and the anode conditions were the same as those in the foregoing case of nickel plating. The method of dispersing graphite is the same as in Example 1. [Composition of plating bath]

Nickel sulfate 280g / L Nickel chloride 45g / L

Boric acid 45g / L

Phosphorous acid 5g / L

Graphite 1 5 g / L

Dispersant 4ml / L [Plating Conditions]

Chain bath temperature 6 5 ± 2 ° C PH 1.2 ± 0 · 2 Current density 15A / dm2 By combining this graphite dispersing alloy with a composite key, a graphite-plated disperse nickel with a disk content of 0% and a graphite content of 0.3% by weight can be obtained. Alloy layer. · 2 weights > In addition, using this treated steel sheet, the same method as in Example 1 was used to fabricate the active material-the active material was applied, and the results of the measured characteristics were summarized in Table 1 '

521453 V. Description of the invention (13) Grease, pickling, nickel plating on the substrate. Diffusion heating treatment was performed under the same conditions as the base nickel plating treatment, and the hot spot was electroplated under the following conditions as in Example i. After graphite-dispersed nickel ~ gold and L_roller treatment were performed, the bath was also air-stirred. And anode and cathode treated strip alloy. The situation is the same for the oblique nickel plating. The graphite dispersion method is the same as that described above. "Only Phase 1 of Example [Plating Bath Composition]

Nickel sulfate 24Qg / L sulfate sulfate 1 g / L

EDTA-2Na 20g / L Dispersant 5ml / L

Graphite 20g / L

No money agent 2. 0 m 1 / L [Plating conditions]

Plating bath temperature 4 5 ± 2 ° C pH 1 · 5 Current density 10A / dm2 Based on this graphite dispersion alloy, a graphite-plated nickel alloy layer containing 4 wt. Herein, the graphite content is the same. Using this treated steel sheet, the same method as in Example 丨 is to apply the active material, and the results of the measured characteristics are encapsulated in the core body I ~ 1 〇 Comparative Example 1 and Example 1 In the same method, an electroplated original plate with a thickness of 60 Am is used to remove 521453. V. Description of the invention (14) Grease, pickling, and nickel plating on the substrate. After the nickel-plating treatment on the substrate, a diffusion heating treatment was performed under the same conditions, and after performing the heating step as in Example 1, the nickel-plating replating was performed. ... treatment roll treatment The characteristics and battery measurement of the steel plates of the examples and comparative examples. The properties are as follows: (1) Graphite content in the plating film The carbon content in the electric steel plate lg was measured by infrared absorption described in J S-G-1 2 11 and then determined. The carbon content of two is based on the difference between the two as the content of the electric ore coating; The ratio was observed with a digital microscope (digita 丨 micrOscope, made by Qiyuanshi, type: VH__), and the graphite plating was dispersed and plated: the surface of the plate was photographed with a magnification of 500 times, and the photograph was taken at a percentage U Η 7, (3) The test method for the retention of the active substance is positive. The h-shaped system uses a coater to dissolve 4% carboxylic acid methyl cellulose in water. Acrylic acid and styrene-ethyl ethene co-water 5 secrets and 5 weights of active material, coated on the surface of the core board to make the thickness after drying at 80C '30 minutes to a single side of about 300 # m (Approximately 6 0 β m on both sides). The moon shape of the negative electrode is made of a slow acid methyl cellulose aqueous solution using an applicator.

P.18 521453 V. Description of the invention (15) 50% by weight, hydrogen storage alloy LmNi4 QCoQ 4 Mn0.4AlQ 5 with a particle size below 200mesh, 100% by weight, Ni powder (2 5 5 manufactured by Inco) 1 0 The weight of the active substance Wu made of acrylic acid and styrene copolymer resin is 5 weight percent, and the surface is coated to 80%. The thickness after drying for 30 minutes was about 300 am on one side (about 600 / zm on both sides). After drying, the positive electrode and the negative electrode were made into a thickness of 400 A m by a roller film pressing method. In this way, the electrode plate coated with the active substance was immersed in an aqueous solution of t 6 · 3 Molar concentration K0Η for 丨 0 days, and the retention of the active substance was evaluated visually-when the shedding of the bioshell was less than 10% It is expressed as 〇, when the deactivation of the active substance exceeds 10%, it indicates △, and when the deactivation of the active substance exceeds 20%, it is indicated. The results are shown in Table 1.

521453 on page 19 5. Description of the invention (16) | Comparative Example 1 Example 10 Example 9 Example 8 Example 7 Example 6 Example 5 Example 4 Example 3 Example 2 Example 1 CT * > 敕K) 〇ι— ^ K) o to K) Lh K) Lh H— ^ o 1— ^ H— ^ to to b Substrate nickel plating thickness (μηι) Ni plating (replating) Ni-Bi alloy plating Ni- P alloy Ni-Mn alloy plating Ni-Co-Fe alloy plating Ni plating Ni j plating Ni j plating Ni plating Ni plating Ni plating bath type graphite dispersion electric forging! Ο Lh o U) bpoo U) to U) o Lh os Graphite content (% by weight) Η—a k > OJ 1— 1— ^ Lh On Lh 〇1 ^ 0 1— ^ On 1— ^ 1— ^ o U \ plating thickness ο b〇00 00 K) Ό 1— * 1— * Os U) oo U) ip characteristics X 〇〇〇〇〇〇〇〇〇〇t > Retention of the positive electrode active material X 〇〇〇〇〇〇〇〇〇〇 > 菡 > t 泰泰 丰 涔 面^^ Congratulations page 20 521453

Page 21

Claims (1)

521453 _H 6)} l uuuuo_ · Ί- η_a_d_ t, Shen: Qing patent, the positive electrode plate is formed on the body and! 1〜2 5 重量 ％ 的 Graphic dispersion, the foregoing core of the battery in which the two electrode plates are enclosed in a box 丨! The core for an alkaline storage battery made of a nickel-plated layer or a graphite-dispersed nickel-plated alloy layer is formed by forming a diffusion layer or a nickel layer below the plating layer. -Mn () 〇 ();-!. r) 7TV! P ^) ii) !; .ρκ 23 if 2002. 〇ί). 30. 02: ^ / 士 X2L Application date: No. 01. ^ 3 m Other: _a_ Amendment number: 89100003 H〇IU 44.; (The fields above 0 ^ are filled by the Bureau) [Invention patent specification 521453, Invention name: Chinese alkaline battery core and CORE FOR ALKALINE BATTERY AND BATTERY USING THE SAME battery using this core English name of the inventor (Chinese) 1. Omura et al. 2. Name of Yumori Ryufu (English) 1.0HMURA HITOSHI 2. T0M0M0RI TATSUO Nationality 1. Japanese version 2. Japanese version 2. Domicile and residence 1. In the Toyo Steel Sheet Technology Co., Ltd., one of the Tokai Steel 1296, Shimatsu City, Yamaguchi Prefecture, Japan Name (Name) (Chinese) 1. Toyo Kohan Co., Ltd. Name (Name) (English) 1. T0Y0 KOHAN Co., Ltd. Nationality 1. Japanese Residence and Residence (Office) 1. Chiyoda-ku, Tokyo, Japan Shibanmachi 2 Fandi 12 ^ Representative name (Chinese) 1. Tanabe Hiroichi Representative name (English) l.TANABE HIR0KAZU 89100003-1497TYJP-91013.ptc Page 1 2002. 09. 30.001 521453 Date of amendment application: Case No .: 89100003 Category: —--------, \ 1, Special. Year ~ Month ~ ^ Supplement (The above columns are filled out by the Bureau.) Description of invention patent Chinese Λ Name of invention English (Chinese) 3. Name of heroic inventor of Omura (English) 3. Omura Hideo Nationality 3. Japanese residence and residence 3. East of Shimomatsu, Yamaguchi Prefecture, Japan Name of the company (Tokyo Steel Sheet Technology Co., Ltd.) in Tokai Steel Sheet Co., Ltd. (1296), Name (Name) (Chinese) Name (Name) (English) Applicant's Nationality, Residence (Office) Name of Representative (Chinese) Name of Representative (English) 89100003-1497TYJP-91013.ptc Page 2 2002.09. 30.002 ^ 145¾ ^ 145¾ Amend Description of the invention (9) When the cross section of the plated steel plate was observed under magnification with an electron microscope, it was recognized that graphite was being dispersed in a dot-like manner, and measured by f, line absorption method (JI s G 1 2 11) Graphite content in the mineral film. Based on the results of investigations on the relationship between the amount of graphite outside the money hole and the graphite content in the graphite dispersion coating, the amount of the dispersant added to the plating solution was set to a fixed value. It is recognized that there is a roughly proportional relationship between these. That is, the amount of graphite added to ^ ow = 5 ~ 100g / L, the stone content of the surface-treated steel sheet II = medium 2.5%. The soil warfare is 0. Moreover, the amount of dispersant added is 10 ml / L, and the amount of the dispersant is proportional to the amount of stone. Above this value, saturation is reached. -Containing Example ϋ = Application: Under the same conditions, several kinds of improved molybdenum: the thickness of the layer, the amount of dispersant added, and the surface-treated soil containing the graphite ratio were also 'using this treated steel plate, and examples 1 Apply the active material f at the same time, and use the results of the measurement characteristics to remove the entire garment: Example J. An extremely low-carbon aluminum deoxidizing plate with a thickness of 100 em was used for degreasing, pickling, and substrate cleaning. Steel plate 89100003-1497TYJP-91013 Page 13 Month Amendment No. 891000 V. Description of the Invention (11) Grease, pickling, base nickel. Diffusion heating treatment is performed under the same conditions after the substrate recording process. 'Processing heat treatment = After Example i, f plating is performed under the following conditions. Graphite-dispersed nickel ~ L roller treatment. The plating is also stirred with air. , And anode and cathode treatment bar Meng alloy. The same applies to the aforementioned nickel plating. Graphite = pieces, the same as 1. Zhengwan Department and Examples [Plating bath composition] Nickel sulfate 280g / L Nickel chloride 5g / L Boric acid 33g / L Manganese sulfate 1 5g / L Graphite 40g / L Dispersant 1 0m1 / L Non-pitting agent 2.0ml / L [Plating Conditions] Bath temperature 6 0 ± 2 〇C pH 4. 0 ± 0.2 Current density 10A / dm2 By this graphite-dispersed alloy plating, a graphite-plated nickel-dispersed alloy layer having a rapid rate of 0.7% by weight and a graphite-containing rate of 10% by weight can be obtained. A core was produced in the same manner as in Example 1 using this treated steel sheet, and the results of the measured characteristics were summarized in Table 1 by applying an active material. Example 9