JP2006057186A - Method for manufacturing nickel material strip having excellent solderability - Google Patents
Method for manufacturing nickel material strip having excellent solderability Download PDFInfo
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- JP2006057186A JP2006057186A JP2005262100A JP2005262100A JP2006057186A JP 2006057186 A JP2006057186 A JP 2006057186A JP 2005262100 A JP2005262100 A JP 2005262100A JP 2005262100 A JP2005262100 A JP 2005262100A JP 2006057186 A JP2006057186 A JP 2006057186A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 20
- 238000005097 cold rolling Methods 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 description 24
- 239000007789 gas Substances 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 7
- 238000004080 punching Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Secondary Cells (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
Description
本発明は、ハンダ付け性に優れたニッケル材料帯の製造方法に関するものである。 The present invention relates to a method for producing a nickel material band excellent in solderability.
例えば、モバイルパソコンや携帯電話に代表される携帯可能な電子機器には充電式の二次電池が使用されてきているが、機器の高機能化による消費電力の増大と長時間使用の要求から電池にはエネルギー密度の増大と長寿命化が求められている。
特に近年では携帯電話の爆発的な普及により、その待ち受け時間の長時間要求から充電式二次電池としては特にエネルギー密度が高いＬｉイオン二次電池の採用が増加しており、このＬｉイオン二次電池は反応活物質を鉄またはＡｌ製の缶の中に封入し、この缶の周囲に電気の流れる道となる板状のリードと呼ばれるニッケル材料でなる部品を配置している。
このニッケル材料に関しては特開平１１−６１３０２号（特許文献１参照）に、冷間での型打鍛造による成形が容易なニッケル材料として、重量で、Ｃ：０．０１０％以下、かつＮ：０．０１０％以下であり、残部が実質上Ｎｉからなる冷間成形性のすぐれたニッケル材料が提案されている。
For example, rechargeable secondary batteries have been used for portable electronic devices such as mobile personal computers and mobile phones. Is required to increase the energy density and extend the life.
In particular, due to the explosive spread of mobile phones in recent years, the adoption of Li-ion secondary batteries with particularly high energy density is increasing as rechargeable secondary batteries due to the long request for standby time. In a battery, a reaction active material is enclosed in a can made of iron or Al, and a part made of a nickel material called a plate-like lead serving as a path for electricity to flow is disposed around the can.
Regarding this nickel material, Japanese Patent Application Laid-Open No. 11-61302 (see Patent Document 1) describes a nickel material that can be easily formed by cold stamping and forging. C: 0.010% or less by weight and N: 0 A nickel material having an excellent cold formability of 0.010% or less and the balance being substantially Ni is proposed.
上述した特許文献１に示されたニッケル材料は、冷間での型打鍛造による成形が容易なニッケル材料を実現することを目的とするものである。
例えば上述のＬｉイオン二次電池のリードにニッケル材料が使用される場合、ニッケル材料帯はプレスによる打抜き加工や、曲げ加工が施されると共に優れたハンダ付け性求められるが、優れたハンダ付け性を付与できるニッケル材料帯の製造方法については、何ら検討がなされていないのが現状である。
本発明の目的は、例えばＬｉイオン二次電池のリードのようにハンダ付けされるニッケル材料用として、優れたハンダ付け性を付与できるニッケル材料帯の製造方法を提供することである。
The nickel material disclosed in Patent Document 1 described above is intended to realize a nickel material that can be easily formed by cold stamping forging.
For example, when a nickel material is used for the lead of the above-described Li-ion secondary battery, the nickel material band is required to be stamped or bent by a press and to have excellent solderability, but excellent solderability. At present, no study has been made on a method for producing a nickel material band that can be imparted.
The objective of this invention is providing the manufacturing method of the nickel material belt | band | zone which can provide the outstanding solderability, for example for the nickel material soldered like the lead | read | reed of a Li ion secondary battery.
本発明者等は、例えばＬｉイオン二次電池のリード（以下、単にリードと記す）のようなハンダ付けされるニッケル材料に対して、優れたハンダ付け性を付与できる製造条件を鋭意検討した結果、最後の冷間圧延の前に還元性雰囲気中で連続焼鈍を行うことで、リードにも適用可能なニッケル材料帯に優れたハンダ付け性を付与できることを見出し、本発明に到達した。
即ち本発明は、ハンダ付けされるニッケル材料の製造方法であって、質量％９９％以上がニッケルからなるニッケル材料帯材を、露点−３０℃以下の還元性雰囲気中で焼鈍を行った後、圧下率２〜３０％の範囲で最後の冷間圧延を適用し、硬さをＨｖ８０〜１９０のニッケル材料帯材とするハンダ付け性に優れたニッケル材料帯の製造方法である。
好ましくは、上述のニッケル材料は、Ｃ：０．０３％以下、Ｓｉ：０．０１％以下、Ｍｎ：０．０４％以下を含有し、残部はＮｉ及び不可避的不純物でなるハンダ付け性に優れたニッケル材料帯の製造方法である。
As a result of intensive studies on manufacturing conditions capable of imparting excellent solderability to a nickel material to be soldered, such as a lead of a Li-ion secondary battery (hereinafter simply referred to as a lead), for example, the present inventors The present inventors have found that by performing continuous annealing in a reducing atmosphere before the last cold rolling, excellent solderability can be imparted to a nickel material band that can also be applied to leads.
That is, the present invention is a method for manufacturing a nickel material to be soldered, and after annealing a nickel material strip having a mass% of 99% or more made of nickel in a reducing atmosphere having a dew point of −30 ° C. or less, This is a method for producing a nickel material strip excellent in solderability by applying the last cold rolling within a range of 2-30% reduction and making the nickel material strip having a hardness of Hv 80-190.
Preferably, the above nickel material contains C: 0.03% or less, Si: 0.01% or less, Mn: 0.04% or less, and the balance is excellent in solderability including Ni and inevitable impurities. This is a method for manufacturing a nickel material band.
本発明に従えば、優れたなハンダ付け性が得ることができるだけでなく、優れたプレス打抜き性と曲げ加工性を兼備するニッケル材料帯が得られる。 According to the present invention, not only excellent solderability can be obtained, but also a nickel material band having excellent press punching properties and bending workability can be obtained.
本発明の重要な特徴は、優れたハンダ付け性を付与できる製造条件として、最後の冷間圧延の前に還元性雰囲気中で焼鈍を行うことにある。
先ず、本発明で用いるニッケル材料は質量％で９９％以上がニッケルとする。これは、優れたハンダ付け性が求められるニッケル材料帯のうちの一つの用途にリードがあり、このリードにも適用可能とするには、低電気抵抗である必要があるためである。
そして、本発明では製造工程の最終段階の、焼鈍及び最後の冷間圧延の二つの工程を規定した。この理由は、ニッケル材料帯の硬度の調整が冷間圧延と焼鈍との組合せで可能なためである。
つまり、中間段階での工程で硬度を調整するよりも、最終段階での硬度調整が所望の硬度に調整し易いためである。
An important feature of the present invention is that annealing is performed in a reducing atmosphere before the final cold rolling as a manufacturing condition that can provide excellent solderability.
First, the nickel material used in the present invention is 99% or more by mass of nickel. This is because a lead is used in one of the nickel material bands that require excellent solderability, and in order to be applicable to this lead, it is necessary to have a low electrical resistance.
And in this invention, two processes, annealing and the last cold rolling of the last stage of a manufacturing process, were prescribed | regulated. The reason for this is that the hardness of the nickel material band can be adjusted by a combination of cold rolling and annealing.
That is, it is because it is easier to adjust the hardness in the final stage to the desired hardness than in the intermediate stage.
中でも、上述したリードの用途に用いるためには、ハンドリング性やプレス打抜き性、曲げ加工性の３つの特性を満足させる必要がある。そのためには、Ｈｖ８０〜１９０範囲内の硬さに調整しなければならない。そのため、この範囲の硬さに容易に調整することか可能となる最終段階の二つの工程を規定した。
なお、ニッケル材料帯の硬さをＨｖ８０〜１９０の範囲から外れる場合、ハンドリングが困難（Ｈｖ８０未満の場合）になったり、打抜き性や曲げ加工性が阻害される（Ｈｖ１９０を超える場合）ことになり、例えばリードの用途に不向きになる。そのため、本発明ではニッケル材料帯の硬さをＨｖ８０〜１９０の範囲としている。
In particular, in order to use for the above-described lead application, it is necessary to satisfy three characteristics of handling property, press punching property, and bending workability. For that purpose, it is necessary to adjust the hardness within the range of Hv 80 to 190. Therefore, two final steps were defined that could easily be adjusted to this range of hardness.
In addition, when the hardness of the nickel material band is out of the range of Hv80 to 190, handling becomes difficult (when it is less than Hv80), and punchability and bending workability are hindered (when it exceeds Hv190). For example, it becomes unsuitable for the use of leads. Therefore, in the present invention, the hardness of the nickel material band is in the range of Hv 80 to 190.
そして、この最終段階の工程で行う焼鈍を還元性ガス雰囲気とした理由は、ここで適用する焼鈍は過度に酸化する雰囲気とした場合、材料表面に硬質な酸化被膜が厚く形成され、プレスによる打抜き性や曲げ加工性が阻害されるため、還元性ガス雰囲気とする必要があるためである。
好ましくは、還元性ガス雰囲気中で帯材を連続焼鈍できる還元性ガス雰囲気とするのが良く、Ｈ２ガスやＨ２とＮ２との混合ガス（通称ＡＸガス）雰囲気での焼鈍は過度の酸化層形成を最小限に抑制でき、帯材表面の還元も行えて表面の清浄化の効果もあり、更に上述のように帯材を連続で焼鈍できることから特に望ましい。
And the reason why the annealing performed in the final stage process is a reducing gas atmosphere is that when the annealing applied here is an atmosphere that excessively oxidizes, a hard oxide film is formed thick on the material surface, and punching by press This is because a reducing gas atmosphere is required because the properties and bending workability are hindered.
Preferably, a reducing gas atmosphere that allows continuous annealing of the strip in a reducing gas atmosphere is preferable, and annealing in an atmosphere of H 2 gas or a mixed gas of H 2 and N 2 (commonly referred to as AX gas) is excessive. The formation of an oxide layer can be minimized, the surface of the strip can be reduced, the surface can be cleaned, and the strip can be annealed continuously as described above, which is particularly desirable.
また、前述の還元性雰囲気中での焼鈍時に、露点の最適化を行うことでより確実にニッケル材料表面の酸化層を最小限に抑制することができる。そのための、適正な露点の範囲は−３０℃以下とすると良く、好ましくは露点を−３５℃以下であり、更に好ましくは−４０℃以下とすると良い。
なお、露点の下限は特に限定しないが、−６０℃以下の露点とするためには用いるガスの高純度化を図ったり、配管を変更する場合も生じて、生産コストを上昇させるので、望ましい下限値は−６０℃とすれば十分である。
In addition, the optimization of the dew point during annealing in the reducing atmosphere described above can more reliably suppress the oxide layer on the nickel material surface to a minimum. For this purpose, the proper dew point range is −30 ° C. or lower, preferably the dew point is −35 ° C. or lower, and more preferably −40 ° C. or lower.
The lower limit of the dew point is not particularly limited. However, in order to obtain a dew point of −60 ° C. or lower, the gas used may be highly purified or the piping may be changed, which increases production costs. A value of −60 ° C. is sufficient.
ところで、この焼鈍と最後の冷間圧延を行うタイミングには二通りの方法があり、第一の方法として最後の冷間圧延を行った後、上記の還元性雰囲気中で焼鈍を行うと、例えばリードの用途に好適なＨｖ８０〜１９０の硬さに容易に調整することが可能となり、ハンドリング性やプレス打抜き性、曲げ加工性の３つの特性を満足させる。
還元性雰囲気中の焼鈍条件は、最後の冷間圧延の圧下率によっても左右される場合があるが、温度範囲として５００〜９００℃、時間は０．５〜５分であれば、上記の硬さに容易に調整することが可能である。
By the way, there are two ways to perform this annealing and the last cold rolling, and after performing the last cold rolling as the first method, if annealing is performed in the reducing atmosphere, for example, It becomes possible to easily adjust to a hardness of Hv 80 to 190 suitable for the use of the lead, and satisfies the three characteristics of handling property, press punching property and bending workability.
The annealing conditions in the reducing atmosphere may depend on the final cold rolling reduction, but if the temperature range is 500 to 900 ° C. and the time is 0.5 to 5 minutes, It is possible to adjust easily.
次に、第二の方法として還元性雰囲気中で焼鈍を行った後、圧下率２〜３０％の最後の冷間圧延を行っても、例えばリードの用途に好適なＨｖ８０〜１９０の硬さに容易に調整することか可能となると共に、上述の第一の方法では得られない効果を得ることができる。具体的には良好なハンダ付け性の確保であり、これが本発明方法である。
つまり、最終の圧延後に還元性雰囲気中で焼鈍を行う第一の方法では、表面には僅かながら酸化膜が形成される場合がある。形成された酸化膜は、その後、特別な酸化膜除去処理を施すか、或いは、新たなハンダ付けを良好にする層を形成しなければならない場合が生じる。
Next, after annealing in a reducing atmosphere as the second method, even if the final cold rolling with a reduction ratio of 2 to 30% is performed, the hardness of Hv80 to 190 suitable for the use of leads, for example, It becomes possible to adjust easily, and effects that cannot be obtained by the first method described above can be obtained. Specifically, ensuring good solderability is the method of the present invention.
That is, in the first method of annealing in a reducing atmosphere after the final rolling, a slight oxide film may be formed on the surface. The formed oxide film may be subjected to a special oxide film removing process or a new soldering layer may be formed after that.
一方で、還元性雰囲気中での焼鈍を行った後、最後の冷間圧延を行う本発明方法においては、良好なハンダ付け性を付与できる。
この理由は明らかではないが、次のように推測している。
還元性雰囲気中での焼鈍を行った後、最後の冷間圧延を行うと、還元性雰囲気での焼鈍時に形成された硬質な酸化層が圧延により破壊され、一部に新生面が露出する。
この新生面を露出させることがハンダ付け性に良好な結果を及ぼすものと推測している。そのため、本発明方法を用いれば、良好なハンダ付け性を確保でき、例えばリードの製造方法として最適である。
On the other hand, in the method of the present invention in which the final cold rolling is performed after annealing in a reducing atmosphere, good solderability can be imparted.
The reason for this is not clear, but is presumed as follows.
When the final cold rolling is performed after annealing in a reducing atmosphere, the hard oxide layer formed during annealing in the reducing atmosphere is broken by rolling, and a new surface is exposed in part.
It is speculated that exposing this new surface has good results on solderability. Therefore, if the method of the present invention is used, good solderability can be ensured, and for example, it is optimal as a lead manufacturing method.
この本発明方法では還元性雰囲気中での焼鈍時に形成された硬質な酸化層を圧延により破壊させることが重要なため、Ｈｖ８０〜１９０の硬さに調整することが可能で、且つ硬質な酸化層を圧延により破壊させることができる適正な圧下率で最後の冷間圧延を行うと良い。
そのため、本発明方法を適用するには、還元性雰囲気中で焼鈍条件にも左右されるが、最後の冷間圧延の圧下率を２〜３０％とするのが良い。圧下率が２％未満であれば、リードに求められる硬さに満たない場合、或いは更に表面の硬質な酸化層の破壊が十分に行なえない場合がある。一方で、圧下率が３０％を超えると、リードに求められる硬さの上限（Ｈｖ１９０）を超えてしまい、リード用途に不向きとなる。そのため、本発明の第二の製造方法では圧下率を２〜３０％の範囲とした。好ましくは２〜３０％の範囲である。
なお、本発明方法を適用する場合、最後の冷間圧延前に行う還元性雰囲気中で焼鈍の条件は温度範囲として５００℃〜９００℃、時間は０．５〜５分であれば良い。
In the method of the present invention, since it is important to break the hard oxide layer formed during annealing in a reducing atmosphere by rolling, it is possible to adjust the hardness to Hv 80 to 190, and the hard oxide layer It is preferable to perform the final cold rolling at an appropriate reduction ratio that can be broken by rolling.
Therefore, in order to apply the method of the present invention, although it depends on annealing conditions in a reducing atmosphere, it is preferable that the rolling reduction of the last cold rolling is 2 to 30%. If the rolling reduction is less than 2%, the hardness required for the lead may not be achieved, or the hard oxide layer on the surface may not be sufficiently destroyed. On the other hand, if the rolling reduction exceeds 30%, it exceeds the upper limit of hardness (Hv190) required for the lead, which is unsuitable for lead applications. Therefore, in the second production method of the present invention, the rolling reduction is set in the range of 2 to 30%. Preferably it is 2 to 30% of range.
In addition, when applying the method of this invention, the conditions of annealing in the reducing atmosphere performed before the last cold rolling should just be 500 to 900 degreeC as time range, and time should be 0.5 to 5 minutes.
次に、本発明では以下の範囲で好ましい化学組成を規定した。その理由を以下に述べる。
Ｃ：０．０３％以下
Ｃは溶解工程において不可避的に混入される元素であるが、この元素には脱酸元素としての特徴がある。すなわち、Ｃはある程度の量が入っているとＣＯやＣｏ２ガスとして溶湯中の酸素量を低減させる働きがある。
更に、溶湯中の酸素量を低減させる働きを持つ元素としてＡｌ、Ｓｉ、Ｍｎ、Ｃｒ、Ｔｉ、Ｍｇ、Ｃａ等が知られているが、Ｃをある程度入れておくことでこれら脱酸元素の使用量を抑える効果もあり、結果としてニッケル材料を高純度に保てる。
Next, in the present invention, a preferable chemical composition is defined in the following range. The reason is described below.
C: 0.03% or less C is an element inevitably mixed in the melting step, and this element is characterized as a deoxidizing element. That is, when a certain amount of C is contained, it serves to reduce the amount of oxygen in the molten metal as CO or Co2 gas.
Furthermore, Al, Si, Mn, Cr, Ti, Mg, Ca, etc. are known as elements that have the function of reducing the amount of oxygen in the molten metal. There is also an effect of reducing the amount, and as a result, the nickel material can be kept in high purity.
また、従来から知られているＣ量では０．０１ｍａｓｓ％以下としているものが殆どであるが、Ｃをむしろ若干高目にしてでもＳｉ、Ｍｎ等の添加を抑える方が、ニッケル材料製のリードとした時の材料表面の酸化膜厚さを一定量以下に抑えることが可能となり、最表面近傍のＯ量の調整が行い易い。
そこで本発明ではＣは若干高めとすることが最適であることを確認し、敢えてＣ量は０．０３ｍａｓｓ％以下の管理とした。望ましくは０．００８〜０．０２０ｍａｓｓ％の範囲である。
In addition, most of the conventionally known C amounts are 0.01 mass% or less, but the lead made of nickel material is better to suppress the addition of Si, Mn, etc. even if C is made slightly higher. It is possible to suppress the oxide film thickness on the material surface to a certain amount or less, and the amount of O in the vicinity of the outermost surface can be easily adjusted.
Therefore, in the present invention, it was confirmed that it is optimal to slightly increase C, and the amount of C was dared to be controlled to 0.03 mass% or less. Desirably, it is the range of 0.008-0.020 mass%.
Ｓｉ：０．０１％以下
Ｓｉはニッケルの溶解の際にも脱酸元素として重要な働きをしている。しかしながら、Ｓｉの含有量が増えるとニッケル材料の表面に硬いＳｉＯ２の酸化膜が形成され易く、ハンダ付け性を阻害し易くなるだけでなく、プレス加工性や、曲げ加工性が劣化し易くなる。そこでＳｉは０．０１ｍａｓｓ％以下で管理することとした。
Ｍｎ：０．０４％以下
Ｍｎは同じく溶湯中の酸素を低減する脱酸剤として使用されるが、Ｍｎの添加量が多くなるとＳｉと同様にニッケル材料の表面にＭｎの酸化膜を厚く形成され易く、ハンダ付け性を阻害し易くなるだけでなく、プレス打ち抜き性に悪影響を及ぼしたり、プレス金型を傷つけたりして、結果的に金型の寿命を低下させるという問題を生じ易くなる。
このためＭｎ量は０．０４ｍａｓｓ％以下とした。
Si: 0.01% or less Si also plays an important role as a deoxidizing element when nickel is dissolved. However, when the Si content increases, a hard SiO 2 oxide film is likely to be formed on the surface of the nickel material, which not only hinders solderability but also tends to deteriorate press workability and bending workability. . Therefore, Si was managed at 0.01 mass% or less.
Mn: 0.04% or less Mn is also used as a deoxidizer to reduce oxygen in the molten metal. However, as the amount of Mn added increases, a Mn oxide film is formed thickly on the surface of the nickel material as with Si. Not only does it easily hinder solderability, but it also tends to cause problems such as adversely affecting the press punchability or damaging the press mold, resulting in a decrease in the life of the mold.
For this reason, the amount of Mn was made into 0.04 mass% or less.
なお、本発明のニッケル材料において、以下の元素はハンダ付け性を阻害しない範囲で含有しても良い。質量％として示す。
Ｐ：０．００３％以下、Ｓ：０．００３％以下、Ｃｒ：０．００５％以下、Ｍｏ：０．０５％以下、Ｃｕ：０．０５％以下、Ａｌ：０．０５％以下、Ｔｉ：０．０５％以下、Ｆｅ：０．０５％以下、Ｍｇ：０．００２％以下、Ｃａ：０．００２％以下、Ｈ：５ｐｐｍ以下、Ｎ：２０ｐｐｍ以下、Ｏ：３０ｐｐｍ以下
なお、本発明ではニッケルが質量％で９９％以上としているが、更に低電気抵抗とするには質量％で９９．９％以上がニッケルであるのが好ましく、前述の各元素と上述したＣ，Ｓｉ，Ｍｎとの総和を０．１％未満とするのが良い。
In the nickel material of the present invention, the following elements may be contained within a range that does not impair solderability. It is shown as mass%.
P: 0.003% or less, S: 0.003% or less, Cr: 0.005% or less, Mo: 0.05% or less, Cu: 0.05% or less, Al: 0.05% or less, Ti: 0.05% or less, Fe: 0.05% or less, Mg: 0.002% or less, Ca: 0.002% or less, H: 5 ppm or less, N: 20 ppm or less, O: 30 ppm or less In the present invention, nickel Is 99% or more by mass%, but in order to further reduce the electric resistance, it is preferable that 99.9% or more by mass is nickel, and the sum of the above-mentioned elements and the above-mentioned C, Si, Mn. Is preferably less than 0.1%.
電解ニッケルを真空誘導炉で溶解し、インゴットに鋳造した。
このインゴットを熱間圧延により加工して厚さ５０ｍｍの直方体形状のスラブにし、更に熱間圧延後、冷間圧延と焼鈍とを繰返した。
そして本発明例用として最後の冷間圧延（仕上げ圧延）前に、還元性雰囲気中（ＡＸガス（Ｈ２：Ｎ２＝３：１））で８００℃、１分の連続炉での焼鈍を行い、最後に１０％の圧下率で仕上げの冷間圧延を行って板厚０．１５ｍｍリチウムイオン二次電池用リード用の帯材に圧延成形した。（以下、本発明工程と記す）
Electrolytic nickel was melted in a vacuum induction furnace and cast into an ingot.
The ingot was processed by hot rolling to form a rectangular parallelepiped slab having a thickness of 50 mm, and after hot rolling, cold rolling and annealing were repeated.
And before the final cold rolling (finish rolling) for the present invention example, annealing is performed in a reducing furnace (AX gas (H2: N2 = 3: 1)) at 800 ° C. for 1 minute in a continuous furnace, Finally, cold rolling was performed at a rolling reduction of 10% to form a strip for a lead for a lithium ion secondary battery having a thickness of 0.15 mm. (Hereinafter referred to as the present invention process)
また、比較例用として、３０％の圧下率で仕上げ冷間圧延を行い、還元性雰囲気中（ＡＸガス（Ｈ２：Ｎ２＝３：１））で６００℃、０．５分の連続炉での焼鈍を行い板厚０．１５ｍｍリチウムイオン二次電池用リード用の材料に圧延成形した。（以下、比較工程と記す）
なお、化学組成を表１に示すが、本発明例ニッケル材料と比較例用ニッケル材料の化学組成は同一であり、上述した二つの実施例ともに還元性ガス雰囲気での焼鈍時の露点は−４０℃である。
In addition, as a comparative example, finish cold rolling is performed at a reduction rate of 30%, and in a reducing furnace (AX gas (H2: N2 = 3: 1)) at 600 ° C. for 0.5 minutes in a continuous furnace. It annealed and rolled and formed into the material for lead | read | reed for plate | board thickness 0.15mm lithium ion secondary battery. (Hereafter referred to as the comparison process)
The chemical composition is shown in Table 1. The nickel composition of the present invention and the nickel material for the comparative example have the same chemical composition, and the dew point during annealing in a reducing gas atmosphere is -40 in both of the above-described examples. ° C.
次に、上述の本発明の二工程で得られたニッケル材料帯の硬さをビッカース硬度計にて硬さを測定した。測定結果を表２に示す。
更に、ハンダ付け性テストを行った。テストは長さ２０ｍｍ×幅５ｍｍの試験片を５枚作製し、フラックスにはＦＮ１０１Ｃを用いて、温度２３５℃のハンダ曹に浸漬し、引き上げる試験とした。ハンダ曹に浸漬した面積のうち、面積率で９０％を超える面積にハンダが付いたものに○印を、８０〜９０％のものは△印、８０％未満のものは×印を付して示す。試験結果を表２に示す。
Next, the hardness of the nickel material band obtained in the above-described two steps of the present invention was measured with a Vickers hardness meter. The measurement results are shown in Table 2.
Further, a solderability test was performed. In the test, five test pieces each having a length of 20 mm and a width of 5 mm were prepared, and FN101C was used as a flux. The test was immersed in soldering soda at 235 ° C. and pulled up. Of the areas immersed in soldering soda, those with solder on areas exceeding 90% in area ratio are marked with ○, those with 80-90% are marked with △, and those with less than 80% are marked with ×. Show. The test results are shown in Table 2.
表２の結果から、二つの工程で得られたニッケル材料帯は、硬度がＨｖ１５０程度となっているため、優れたプレス打抜き性及び曲げ加工性を有し、ハンドリング性も良好であることが分かる。
これに加えて、本発明工程Ａで製造したニッケル材料帯では優れたハンダ付け性を有しており、優れたハンダ付け性が求められる用途に供されるニッケル材料帯として最適である。
From the results in Table 2, it can be seen that the nickel material band obtained in the two steps has an excellent press punchability and bending workability because the hardness is about Hv150, and the handling property is also good. .
In addition to this, the nickel material band produced in the step A of the present invention has excellent solderability, and is optimal as a nickel material band used for applications requiring excellent solderability.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008047869A1 (en) * | 2006-10-20 | 2008-04-24 | Sumitomo Metal Industries, Ltd. | Nickel material for chemical plant |
| JP2010090438A (en) * | 2008-10-08 | 2010-04-22 | Sumitomo Metal Ind Ltd | Pure nickel sheet and method for producing pure nickel sheet |
| WO2010064642A1 (en) * | 2008-12-02 | 2010-06-10 | 住友金属工業株式会社 | Nickel material and method for producing nickel material |
| JP2011012330A (en) * | 2009-07-06 | 2011-01-20 | Sumitomo Metal Ind Ltd | Nickel material and method for producing nickel material |
| JP2011074437A (en) * | 2009-09-30 | 2011-04-14 | Dowa Metaltech Kk | Nickel rolled material, method for producing the same, and electrode of cold cathode fluorescent lamp |
| JP2013522456A (en) * | 2010-03-05 | 2013-06-13 | シュトゥート テオドア | Nickel strip manufacturing method |
| KR20190067837A (en) * | 2016-10-07 | 2019-06-17 | 닛폰세이테츠 가부시키가이샤 | Manufacturing method of nickel material and nickel material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008047869A1 (en) * | 2006-10-20 | 2008-04-24 | Sumitomo Metal Industries, Ltd. | Nickel material for chemical plant |
| JP5035250B2 (en) * | 2006-10-20 | 2012-09-26 | 住友金属工業株式会社 | Nickel materials for chemical plants |
| US8986470B2 (en) | 2006-10-20 | 2015-03-24 | Nippon Steel & Sumitomo Metal Corporation | Nickel material for chemical plant |
| JP2010090438A (en) * | 2008-10-08 | 2010-04-22 | Sumitomo Metal Ind Ltd | Pure nickel sheet and method for producing pure nickel sheet |
| WO2010064642A1 (en) * | 2008-12-02 | 2010-06-10 | 住友金属工業株式会社 | Nickel material and method for producing nickel material |
| JP2011012330A (en) * | 2009-07-06 | 2011-01-20 | Sumitomo Metal Ind Ltd | Nickel material and method for producing nickel material |
| JP2011074437A (en) * | 2009-09-30 | 2011-04-14 | Dowa Metaltech Kk | Nickel rolled material, method for producing the same, and electrode of cold cathode fluorescent lamp |
| JP2013522456A (en) * | 2010-03-05 | 2013-06-13 | シュトゥート テオドア | Nickel strip manufacturing method |
| KR20190067837A (en) * | 2016-10-07 | 2019-06-17 | 닛폰세이테츠 가부시키가이샤 | Manufacturing method of nickel material and nickel material |
| KR102149992B1 (en) | 2016-10-07 | 2020-08-31 | 닛폰세이테츠 가부시키가이샤 | Nickel material and manufacturing method of nickel material |
| CN110140236A (en) * | 2016-12-27 | 2019-08-16 | 日立金属株式会社 | The manufacturing method of cathode lead material and cathode lead material |
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