CN109216591A - Battery Ni material, cathode and battery shell material - Google Patents

Battery Ni material, cathode and battery shell material Download PDF

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Publication number
CN109216591A
CN109216591A CN201810612544.1A CN201810612544A CN109216591A CN 109216591 A CN109216591 A CN 109216591A CN 201810612544 A CN201810612544 A CN 201810612544A CN 109216591 A CN109216591 A CN 109216591A
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China
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alloy
battery
mass
negative electrode
electrode collector
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CN201810612544.1A
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CN109216591B (en
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织田喜光
井上良二
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Proterial Ltd
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Hitachi Metals Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides battery Ni material, cathode and battery shell material.The battery is made of with Ni material Ni alloy, the Ni alloy include: more than 0.03 mass % and for 0.20 mass % C below, add up to 0.50 mass % additive below and inevitable impurity and as the Ni of remainder.

Description

Battery Ni material, cathode and battery shell material
Technical field
The present invention relates to battery Ni material, use the cathode and battery shell material of battery Ni material.
Background technique
In the prior art, in the lithium ion battery as secondary cell, in order to improve the energy density of battery, it is desirable to Use the negative electrode active material for the amount that can further increase the embeddable of Li (lithium) and abjection.Therefore there are following tendencies: making For negative electrode active material, instead of the carbon material (graphite, graphite) etc. as general negative electrode active material, use and carbon materials Material is compared to the non-carbon system such as the oxide of the Si (silicon) for the amount that can increase the embeddable of Li and abjection and the oxide of Sn (tin) Material.But the embeddable of Li and abjection amount increase in the case where, with charging when Li insertion and electric discharge when The abjection of Li, negative electrode active material are expanded and are shunk, therefore the volume change of negative electrode active material is larger.Therefore, because Big volume change caused by the expansion and contraction of negative electrode active material, and have the metal collection of negative electrode active material to surface configuration Electric body applies big stress repeatedly.Therefore, become to inhibit the big stress due to repeated action in metal current collector The problems such as shape, it is desirable that improve the mechanical strength of tensile strength etc..Also, about metal current collector, in order to inhibit under current collecting efficiency The case where drop, also requires to be low resistance.
In this way, as metal material used in battery, it is desirable that for the metal material of low resistance and high mechanical strength.Separately Outside, such metal material for low resistance and high mechanical strength, can also apply to such as battery other than metal current collector The battery components such as shell material and lead material.
Here, the case where the metal material to low resistance and high mechanical strength coats thermosetting resin and solidified Under, as metal material, it is preferable to use be able to suppress solidification temperature (such as 300 DEG C) in thermosetting resin oxidation and It is able to suppress Ni (nickel) material of the high resistance of metal material.
Then, it is known in the art that the battery used in the battery Ni material.Such battery Ni material, such as There is disclosure in Japanese Patent No. 3741311.
The Ni and inevitable impurity that are 99% or more comprising quality % are disclosed in Japanese Patent No. 3741311 The lead of lithium ion secondary battery nickel material band.The lead nickel material band includes: quality % is 0.03% C below (carbon), 0.01% Si (silicon) below and 0.04% Mn (manganese) below.Wherein, in the lead in nickel material band, C has As CO or CO2Gas reduces the effect of the oxygen content in molten metal, therefore preferably improves the concentration of C to a certain extent and press down The addition for making other deoxidant elements (Si, Mn etc.), from pervious 0.01 mass % it is chosen below be 0.03 mass % or less (preferably 0.008~0.020 mass %).In addition, lead is adjusted to Hv80~190 with the hardness of nickel material band.
But lead is adjusted to the hardness of nickel material band although being described in Japanese Patent No. 3741311 The content of Hv80~190, but do not recorded about lead tensile strength of nickel material band etc..Thus, for example drawing by this In the case that line is applied to lithium ion battery metal current collector with nickel material band (Ni material in the prior art), exists and ask as follows Topic: the mechanical strengths such as tensile strength of Ni material in the prior art are simultaneously not high enough, such as due to the big stress of repeated action Etc. external force, the problems such as being deformed in the Ni material of the prior art.And the problem has been identified by aftermentioned experiment.Cause This, it is desirable that the mechanical strengths such as tensile strength are sufficiently high and low-resistance battery Ni material.
Summary of the invention
The present invention is completed to solve technical problem as described above, and it is an object of the present invention to provide one kind The mechanical strengths such as tensile strength are sufficiently high and low-resistance battery Ni material, use the cathode and battery case of battery Ni material Material.
The composition that present inventor is conceived to above-mentioned Ni material in the prior art has made intensive studies, result The following structures that can be realized above-mentioned purpose are invented.The battery of the first aspect of the present invention is made of with Ni material Ni alloy, should Ni alloy include: more than 0.03 mass % and for 0.20 mass % C below, add up to 0.50 mass % additive below and Inevitable impurity and the Ni as remainder.Wherein, " additive " refers to the member intentionally added in Ni alloy Element, " inevitable impurity " refer to the plan that do not add but inevitably include the element in Ni alloy.
As described above, the battery of the first aspect of the present invention is made of with Ni material Ni alloy, which includes: to be more than 0.03 mass % and for 0.20 mass % C below (carbon), add up to 0.50 mass % additive below and inevitably Impurity and Ni as remainder.By adopting such structure, being closed with by the Ni comprising 0.03 mass % C below The case where gold composition battery Ni material, is compared, even if consuming because playing the effect for reducing the oxygen content in Ni alloy (melting Ni) The C of several (such as 0.02 mass % degree), it is (female to strengthen substrate that the C of enough amounts can be also dissolved in Ni alloy Material phase), therefore can be improved the battery mechanical strengths such as the tensile strength of Ni material being made of Ni alloy.Further, since Ni is closed Gold is below containing the 0.20 mass % smaller relative to the solid solution limit (such as in 1300 DEG C of about 0.6 mass %) of Ni than C C, therefore the most C solid solution condition in Ni alloy can be made by rapid cooling.As a result, being regarded to utilize C Strengthen Ni alloy solid solution, therefore can be improved the mechanical strength for the battery Ni material being made of Ni alloy, and since C is solid Molten state, therefore can be improved the corrosion resistance for the battery Ni material being made of Ni alloy.
In addition, first aspect battery in Ni material, as described above, Ni alloy is by the inclusion of total 0.50 mass % Additive below and inevitable impurity, the additive and inevitable impurity phase in Ni alloy other than C are for Ni Content it is small, therefore the high resistance of Ni alloy caused by being able to suppress because of additive and inevitable impurity.Such knot Fruit be the battery being made of Ni alloy can be made sufficiently high with mechanical strengths such as the tensile strength of Ni material, and be low resistance.
Further, in the battery of first aspect in Ni material, as described above, by the content for making the C in Ni alloy 0.20 mass % is hereinafter, be able to suppress because the excessive solid solution of C causes the mechanical strength of Ni alloy excessive so as to cause being rolled Processability decline whens system etc..By adopting such structure, Ni alloy is enabled to be easily worked, can obtain by Ni alloy Constituting, mechanical strengths such as tensile strength are sufficiently high and low-resistance battery Ni material.Wherein, it is had confirmed that by aftermentioned experiment, By making the 0.20 mass % of content of the C in Ni alloy hereinafter, being able to suppress the battery being made of the Ni alloy machine of Ni material Tool intensity becomes excessive.
Further, in the battery of first aspect in Ni material, as described above, by making battery Ni material by based on Ni The Ni alloy of ingredient is constituted, and compared with the generally Cu used in negative electrode collector (copper) or Cu alloy, can be effectively inhibited The corrosion occurred by use environment and the corrosion because of the generation of sour or alkali.
Above-mentioned first aspect battery in Ni material, preferably Ni alloy include 0.10 mass % or more, 0.20 mass % with Under C.If, due to the C containing 0.10 mass % or more, can be further increased by Ni alloy structure using such structure At the battery mechanical strengths such as the tensile strength of Ni material.
Above-mentioned first aspect battery in Ni material, preferably tensile strength is 700MPa or more.If as Structure, then battery has the enough tensile strength of 700MPa or more with Ni material, therefore is for example being used for battery with Ni material In the case that surface configuration has the metal current collector of negative electrode active material, even if the expansion and contraction because of negative electrode active material cause Big volume change caused by big stress repetition act on battery Ni material, can also be reliably suppressed because of stress repeatedly And the problems such as battery is deformed with Ni material.
Above-mentioned first aspect battery in Ni material, preferably Ni alloy includes to add up to 0.30 mass % addition below Object and inevitable impurity.If using such structure, in Ni alloy, additive other than C and inevitably Impurity phase is sufficiently small for the content of Ni, by Ni alloy structure caused by capable of more inhibiting because of additive and inevitable impurity At battery Ni material high resistance.
Thickness is set i.e. with desired purposes and mechanical strength etc. in Ni material, is considered in the battery of above-mentioned first aspect Can, preferred thickness is 30 μm or less.If using such structure, by using the electricity with 30 μm of small thickness below Pond Ni material, is able to suppress the enlargement of the battery using battery Ni material, and is capable of providing the mechanical strengths such as tensile strength Sufficiently high battery Ni material.In addition, above-mentioned first aspect battery in Ni material, preferred thickness is 1 μm or more, in order to make It is easy to manufacture, preferably 3 μm or more, further for making it easy to volume production, preferably 5 μm or more.If as Structure is capable of providing then by using the battery Ni material of the thickness at least with 1 μm or more with desired tensile strength Etc. mechanical strengths battery Ni material.
Above-mentioned first aspect battery in Ni material, be added with Mn, Si and Al as additive preferably in Ni alloy In one kind or two or more element.If using such structure, added with a kind in Mn, Si and Al in Ni alloy Or in the case where element of more than two kinds, the consumption that C occurs by deoxidation is effectively inhibited using the deoxidation of additive, together When can remove O (oxygen) in Ni alloy (melting Ni).In addition, in the case where Mn is added in Ni alloy, in addition to can It removes except O, additionally it is possible to remove the S (sulphur) in Ni alloy (melting Ni).As a result, solid by being realized using C The battery that the Ni alloy of molten reinforcing is constituted is with can effectively inhibit the problems such as embrittlement occurred by O or S in Ni material.
The cathode of the second aspect of the present invention includes: the battery Ni material of above-mentioned first aspect；With configuration in battery Ni The cathode material comprising negative electrode active material and thermosetting resin on the surface of material.By adopting such structure, even if because of cathode Big stress repetition caused by big volume change caused by the expansion and contraction of active material acts on battery Ni material, also leads to It crosses so that the mechanical strengths such as the tensile strength of battery Ni material are sufficiently high, can be reliably suppressed due to stress repeatedly in battery The problems such as deformation generated with Ni material.In addition, it is same as above-mentioned first aspect, pass through the Ni by realizing solution strengthening using C Alloy is constituted, and can be improved the mechanical strength of battery Ni material, and by being made of the Ni alloy that C is solid solution condition, can Improve the corrosion resistance of battery Ni material.Further, by using by comprise more than 0.03 mass % and for 0.20 mass % with Under C and remainder be Ni the battery Ni material that constitutes of Ni alloy, even if in order to keep the thermosetting resin of cathode material solid Change and configure battery Ni material under high temperature environment, is also able to suppress battery Ni material and aoxidizes.By using such Structure is able to suppress the high resistance of battery Ni material.Moreover, inhibit the oxidation of battery Ni material due to not needing And solidify thermosetting resin in the sufficiently low nonoxidizing atmosphere of oxygen content, therefore can easily make cathode.
The battery shell material of the third aspect of the present invention includes: the battery Ni material of multiple above-mentioned first aspects；With will be multiple The adhesive portion comprising thermosetting resin that battery is connected to each other with Ni material.By adopting such structure, by using battery The mechanical strengths such as the tensile strength of Ni material are sufficiently high, can be reliably suppressed and deform etc. in battery shell material due tos external force etc. Problem.In addition, it is same as above-mentioned first aspect, by being made of the Ni alloy for realizing solution strengthening using C, it can be improved electricity The mechanical strength of pond Ni material, and by being made of the Ni alloy that C is solid solution condition, it can be improved the corrosion resistant of battery Ni material Corrosion.In addition, even if configuration under high temperature environment, also can be with above-mentioned second party in the thermosetting resin solidification for making adhesive portion The cathode in face similarly inhibits the battery being made of Ni alloy to be aoxidized with Ni material.By adopting such structure, can press down The high resistance of battery processed Ni material, and can easily make battery shell material.
Detailed description of the invention
Fig. 1 is the schematic cross-section for indicating the battery of the cathode using an embodiment of the invention.
Fig. 2 is the sectional view for indicating the cathode of an embodiment of the invention.
Fig. 3 is the schematic diagram for the production method for the blank for illustrating the Ni alloy of an embodiment of the invention.
Fig. 4 is the schematic diagram for the production method for illustrating the Ni sheet alloy of an embodiment of the invention.
Fig. 5 is the production method for the covering material for illustrating to constitute the negative electrode collector of an embodiment of the invention Schematic diagram.
Fig. 6 is the section for indicating to have used the solid state battery of the cathode of first variation of an embodiment of the invention Schematic diagram.
Fig. 7 is the bipolar of the battery Ni material for the second variation for indicating include the use of an embodiment of the invention The schematic cross-section of the solid state battery of electrode.
Fig. 8 is the bipolar electrode of the battery Ni material for the second variation for indicating to have used an embodiment of the invention Sectional view.
Fig. 9 is the section for indicating multiple lithium ion secondary batteries of third variation of an embodiment of the invention Figure.
Specific embodiment
In the following, based on attached drawing, embodiments of the present invention will be described.
Firstly, the battery 100 with reference to Fig. 1 and Fig. 2, to the negative electrode collector 5b for having used an embodiment of the invention Structure be illustrated.Wherein, negative electrode collector 5b is an example of " battery Ni material " in summary of the invention.
(structure of battery)
The battery 100 of an embodiment of the invention, as shown in Figure 1, being the lithium ion secondary electricity of so-called cylinder type Pond.The battery 100 includes: columnar shell 1；By the lid material 2 of the opening sealing of shell 1；With electric power storage of the configuration in shell 1 Element 3.
Charge storage element 3 and electrolyte (not shown) are accommodated in shell 1.Lid material 2 is made of aluminium alloy etc., is also used as battery 100 positive terminal (anode).Charge storage element 3 is by winding anode 4, cathode 5 and configuration between anode 4 and cathode 5 Insulating properties separator 6 and formed.Anode 4 includes positive active materials and the positive electrode collectors including aluminium foil such as LiMn2O4. Positive active material is fixed with using adhesive etc. on the surface of positive electrode collector.It is used in addition, being fixed in anode 4 by lid material The 2 positive wire materials 7 being electrically connected with anode 4.
Cathode 5, as shown in Fig. 2, including cathode material 5a and being fixed with the negative electrode collector of the foil-like of cathode material 5a on two sides 5b.Cathode material 5a for example includes the negative electrode active material that carbon, SnO or SiO etc. are able to carry out insertion and the abjection of Li；Such as Thermosetting resins and the adhesive for negative electrode active material to be fixed on to negative electrode collector 5b such as including polyimide resin.It is negative The negative electrode active material of pole material 5a, insertion and abjection with Li are correspondingly expanded and are shunk respectively.Negative electrode collector 5b is closed by Ni Gold is constituted, and is formed to have the foil-like of 30 μm of thickness t below.Moreover, the expansion and contraction because of negative electrode active material are drawn The big volume change risen, causes big stress repetition to act on negative electrode collector 5b.
In addition, as shown in Figure 1, being fixed with the cathode for the inner bottom surface 1a of shell 1 to be electrically connected with cathode 5 in cathode 5 Lead material 8.Specifically, negative wire material 8 is engaged by ultrasonic fusing with negative electrode collector 5b.In addition, negative wire material 8 It is engaged with the position (not shown) for being not fixed to cathode material 5a.In addition, negative wire material 8 passes through the interior of electric resistance welding and shell 1 Bottom surface 1a engagement.
(composition of Ni alloy)
Here, in the present embodiment, the Ni alloy for constituting negative electrode collector 5b includes: more than 0.03 mass % and is 0.20 mass % C below, 0.50 mass % additive below and inevitable impurity are added up to and as remainder Ni.Wherein, the Ni alloy of negative electrode collector 5b is constituted by using Ni as principal component, and generally used in the negative electrode collector Cu or Cu alloy is compared, excellent corrosion resistance.
(C of Ni alloy)
In the present embodiment, mechanical strength is improved in order to be dissolved the C of enough amounts in Ni alloy, contains Ni alloy Have more than the C of 0.03 mass %.Wherein, in order to be dissolved the C of enough amounts in Ni alloy, preferably Ni alloy includes 0.10 matter The C of % or more is measured, also, more preferably includes the C of 0.15 mass % or more.Here it is considered that by as described above in Ni alloy The C of the middle enough amounts of solid solution, can not only improve the mechanical strength for the negative electrode collector 5b being made of Ni alloy, and can mention Highly corrosion resistant.
In addition, in the present embodiment, making the most C solid solution condition in Ni alloy, on the other hand, in order to inhibit The mechanical strength for the negative electrode collector 5b being made of Ni alloy excessively becomes larger, and contains Ni alloy and limits than C relative to the solid solution of Ni Spend 0.20 sufficiently small mass % C below of (about 0.6 mass %).In addition, in order to inhibit the cathode collection being made of Ni alloy The mechanical strength of electric body 5b excessively becomes larger, and preferably Ni alloy includes 0.18 mass % C below.It can according to content as described above Know, in order to enable the negative electrode collector 5b being made of Ni alloy has the mechanical strength of appropriateness, more preferred Ni alloy includes 0.10 mass % or more, 0.20 mass % C below.
(additive of Ni alloy)
In addition, a kind or 2 kinds in Mn, Si and Al can also be contained as additive in Ni alloy in present embodiment Above element.Specifically, as after the O and S removed in Ni alloy (melting Ni) as a result, can also contain in Ni alloy There are total 0.30 mass % Mn, Si and Al below.Specifically, 0.19 mass % or more 0.24 can also be contained in Ni alloy Quality % Mn below.In addition, can make to contain 0.03 mass % in Ni alloy to remove the O in Ni alloy (melting Ni) Above 0.05 mass % Si below can also make below containing 0.002 mass % or more, 0.012 mass % in Ni alloy Al.In addition, considering the deoxidation effect of C in order to remove the O in Ni alloy (melting Ni), by the way that Al is used as additive, inhibiting Ni The total amount of the additive contained in alloy.In addition, being added to remove the S in Ni alloy (melting Ni) by the way that Mn to be used as Add object, inhibits the total amount of the additive contained in Ni alloy.In the case, total 0.25 can also be contained in Ni alloy Quality % Al below and Mn.
In addition, in the present embodiment, as additive, can also will have and improve Ni alloy (negative electrode collector 5b) The Nb (niobium) of the property of mechanical strength etc., the yttriums such as V (vanadium) and Ta (tantalum) add in NI alloy.But it is above-mentioned Yttrium may hinder the cost of Ni alloy (negative electrode collector 5b) to reduce, and not be added in NI alloy preferably, Therefore preferably containing total 0.05 mass % or less (preferably 0.03 mass % or less).
(the inevitable impurity of Ni alloy)
In addition, in the present embodiment, in Ni alloy, as inevitable impurity, in addition to comprising Co, Cu, Fe and Mg, Sometimes the O and S also removed as far as possible comprising hope.For example, sometimes in Ni alloy, as inevitable impurity, He Jihan There is 0.09 mass % Co, Cu, Fe and Mg below.Specifically, sometimes in Ni alloy, as inevitable impurity, contain There is 0.01 mass % Co below.In addition, sometimes in Ni alloy, as inevitable impurity, containing 0.04 mass % with Under Cu.In addition, as inevitable impurity, containing 0.04 mass % Fe below sometimes in Ni alloy.In addition, having When in Ni alloy, as inevitable impurity, contain 0.001 mass % Mg below.In addition, in order to inhibit Ni alloy Embrittlement removes O and S as inevitable impurity as much as possible, and O and S is not contained preferably in Ni alloy, but is existed O and 0.005 mass % or less (preferably 0.002 mass % containing 0.002 mass % or less (preferably 0.001 mass % or less) The case where following) S.In addition, in order to inhibit the high resistance of Ni alloy (negative electrode collector 5b) and the deterioration of processing performance, to the greatest extent Possibly limitation is containing Co, Cu, Fe and Mg as inevitable impurity, such as preferably makes 0.06 matter of Co, Cu, Fe and Mg Amount % is hereinafter, be further 0.03 mass % hereinafter, being 0.01 mass % or less more preferable.
(content of the additive of Ni alloy and inevitable impurity)
Herein, in order to inhibit the high resistance of Ni alloy (negative electrode collector 5b), it is preferably such that Ni alloy without containing above-mentioned Additive and above-mentioned inevitable impurity.Then, in the present embodiment, above-mentioned in order to inhibit the high resistance of Ni alloy Additive and above-mentioned inevitable impurity are suppressed to total 0.50 mass % or less in Ni alloy.In addition, in order to inhibit The high resistance of Ni alloy, above-mentioned additive and above-mentioned inevitable impurity suppression are formed in Ni alloy and add up to 0.30 matter Measure % or less preferably, suppression, which is formed in Ni alloy, adds up to 0.05 mass % or less more preferably.
(tensile strength of negative electrode collector)
In addition, the tensile strength for the negative electrode collector 5b being made of above-mentioned Ni alloy is 700MPa or more.By using this The structure of sample, negative electrode collector 5b are able to bear the stress of the repeated action due to volume change of negative electrode active material.Wherein, it bears The tensile strength of electrode current collector 5b can pull test method based on the metal material as defined in JIS Z2241 and obtain.In addition, in order to Alternate stress is preferably born, the preferably tensile strength of negative electrode collector 5b is 900MPa or more.In addition, passing through aftermentioned embodiment It is confirmed with comparative example, C, additive and the inevitable impurity contained in above-mentioned Ni alloy adds up to 0.30 mass % In situation below, the negative electrode collector 5b being made of above-mentioned Ni alloy has the tensile strength of 700MPa or more.
(volume resistivity of negative electrode collector)
In addition, the volume resistivity for the negative electrode collector 5b being made of above-mentioned Ni alloy is 15 × 10-8Ω m or less.It is logical It crosses using such structure, the power loss for being able to suppress negative electrode collector 5b becomes larger.In addition, in order to inhibit negative electrode collector 5b Power loss become larger, preferably the volume resistivity of negative electrode collector 5b be 12 × 10-8Ω m is hereinafter, more preferably 11 × 10-8Ω m is hereinafter, further preferably 10 × 10-8Ω m or less.In addition, the C contained in above-mentioned Ni alloy, additive and Adding up in 0.30 mass % situation below for inevitable impurity, confirms also by aftermentioned embodiment and comparative example, The negative electrode collector 5b being made of above-mentioned Ni alloy has 15 × 10-8Ω m volume resistivity below.
Then, the manufacture with reference to Fig. 2~Fig. 5, to the cathode 5 for having used the negative electrode collector 5b being made of above-mentioned Ni alloy Method is illustrated.
(production of negative electrode collector)
Firstly, the negative electrode collector 5b that production is made of Ni alloy.Specifically, as shown in figure 3, in melting furnace 101 Melting Ni in addition be more than 0.03 mass % and for 0.20 mass % C below and make become add up to 0.50 mass % with Under additive and the addition material (more than one kind or two kinds of Mn, Si and Al) of content of inevitable impurity make later It is cast and is cooled down with casting die.Wherein, addition addition material (additive) into melting Ni as needed.By using in this way Mode, the blank 151 (with reference to Fig. 4) of Ni alloy can be made, which comprises more than 0.03 mass % and for 0.20 matter Measure % C below, total 0.50 mass % additive below and inevitable impurity and the Ni as remainder.
Then, as shown in figure 4, carrying out hot rolling by the blank 151 to Ni alloy, the hot rolled plate 251 of Ni alloy is made. Specifically, the blank 151 of Ni alloy is heated to closing than Ni in the state of being configured with blank 151 of Ni alloy in furnace 102 The high temperature (hot-rolled temperature) of the recrystallization temperature of gold.Then, the blank 151 of the Ni alloy after heating is taken out out of furnace 102, It is rolled using Rolling roller 103, thus carries out hot rolling.By using such mode, the hot rolled plate of Ni alloy can be made Material 251.Later, it for hot rolled plate 251 after cooling, anneals at 900 DEG C or so, using Rolling roller 104 with defined Reduction ratio carries out cold rolling.In addition, above-mentioned cold rolling and above-mentioned annealing can be repeated according to necessity.Finally, appropriate by carrying out Ground cutting etc. makes the negative electrode collector 5b (referring to Fig. 5) of the foil-like with 30 μm of thickness below.
(production of cathode)
Later, in cathode of the two sides of the negative electrode collector 5b of the foil-like configuration comprising negative electrode active material and thermosetting resin Material 5a (refers to Fig. 2).Specifically, as shown in figure 5, the two sides coating in the negative electrode collector 5b of foil-like includes negative electrode active material The coating material 105a of matter and thermosetting resin.Then, it is being set as higher than the solidification temperature of thermosetting resin (such as 300 DEG C) In the drying oven 105 of temperature, configuration is coated with the negative electrode collector 5b stipulated time of coating material 105a and is heat-treated, thus Solidify thermosetting resin.Wherein, in drying oven 105, in order to inhibit the oxidation of Ni, preferably low pressure (evacuation) to one Determine the low pressure atmosphere of degree.By using such mode, the two sides that can be produced on the negative electrode collector 5b of foil-like is configured with The cathode 5 (referring to Fig. 2) of cathode material 5a comprising negative electrode active material and thermosetting resin.
At this point, by constituting the negative electrode collector 5b of foil-like by Ni, compared with the case where being made of Cu, it is difficult to by oxygen Change.Accordingly it is also possible to which not making is the sufficiently low nonoxidizing atmosphere of oxygen content in drying oven 105.
The effect > of < present embodiment
Present embodiment can obtain effect below.
In the present embodiment, as described above, the Ni alloy of negative electrode collector 5b is constituted by comprising more than 0.03 matter It measures % and is 0.20 mass % C below, adds up to 0.50 mass % additive below and inevitable impurity and conduct The Ni alloy of the Ni of remainder is constituted.By adopting such structure, with by the Ni alloy comprising 0.03 mass % C below The case where constituting negative electrode collector is compared, even if consuming because of the effect that performance reduces the oxygen content in Ni alloy (melting Ni) The C of several (such as 0.02 mass % degree), also can make the C of enough amounts be solid-solution in Ni alloy and make substrate (base material Phase) strengthen, therefore the mechanical strengths such as the tensile strength of negative electrode collector 5b can be made to improve using C.In addition, because Ni alloy contains There are the 0.20 mass % below C smaller relative to the solid solution limit (such as at 1300 DEG C, substantially 0.6 mass %) of Ni than C, institute The most C solid solution condition in Ni alloy can be made by chilling.It is believed that as a result, due to closing Ni using C The solution strengthening of gold, therefore can be improved the mechanical strength for the negative electrode collector 5b being made of Ni alloy, and since C is solid solution State, therefore can be improved the corrosion resistance for the negative electrode collector 5b being made of Ni alloy.
In addition, in the present embodiment, by making Ni alloy comprising total 0.50 mass % additive below and not Evitable impurity, the additive and inevitable impurity phase in Ni alloy other than C are small for the content of Ni, therefore can The high resistance of Ni alloy caused by inhibiting because of additive and inevitable impurity.As a result, can make by Ni The mechanical strengths such as the tensile strength of negative electrode collector 5b that alloy is constituted are sufficiently high, and make the low electricity of negative electrode collector 5b Resistance.Therefore, even if stress repetition big caused by volume change big because of caused by the expansion and contraction of negative electrode active material is made It is sufficiently high by mechanical strengths such as the tensile strength that makes negative electrode collector 5b for negative electrode collector 5b, also can reliably it press down Make the problem being deformed etc. due to stress repeatedly in negative electrode collector 5b.
In addition, in the present embodiment, by making the 0.20 mass % of content of the C in Ni alloy hereinafter, being able to suppress The mechanical strength of Ni alloy is made to become excessive so that carrying out under processing performance when rolling etc. because of the excessive solid solution of C Drop.By using such mode, Ni alloy is enabled to be easily worked, the tensile strength etc. being made of Ni alloy can be obtained Mechanical strength is sufficiently high and is low-resistance negative electrode collector 5b.
It is and general by by being constituted negative electrode collector 5b by the Ni alloy of principal component of Ni in addition, in the present embodiment Cu or Cu alloy for negative electrode collector is compared, can effectively inhibit the corrosion occurred by use environment and because acid or Alkali and the corrosion occurred.
In addition, in the present embodiment, preferably Ni alloy includes 0.10 mass % or more, 0.20 mass % C below.Such as Fruit in this manner, then by the C containing 0.10 mass % or more, can further increase the cathode being made of Ni alloy The mechanical strengths such as the tensile strength of collector 5b.
In addition, in the present embodiment, the tensile strength of negative electrode collector 5b is 700MPa or more.By using such Mode, since negative electrode collector 5b has the enough tensile strength of 700MPa or more, even if because of the expansion of negative electrode active material Negative electrode collector 5b is acted on the stress repetition for shrinking big caused by caused big volume change, can be also reliably suppressed The problem being deformed etc. due to stress repeatedly in negative electrode collector 5b.
In addition, in the present embodiment, preferably Ni alloy includes total 0.30 mass % additive below and can not keep away The impurity exempted from.If in this manner, in Ni alloy, additive and inevitable impurity phase other than C for The content of Ni is sufficiently small, therefore is made of caused by capable of further suppressing because of additive and inevitable impurity Ni alloy Negative electrode collector 5b high resistance.
In addition, in the present embodiment, by making the thickness t of negative electrode collector 5b be 30 μm hereinafter, being able to suppress makes With the enlargement of the battery of negative electrode collector 5b, and it is capable of providing the sufficiently high negative electrode collector of the mechanical strengths such as tensile strength 5b。
In addition, in the present embodiment, adding by element more than one kind or two kinds of Mn, Si and Al in Ni alloy In in the case where, the consumption that C occurs by deoxidation is effectively inhibited using the deoxidation of additive, and can remove Ni conjunction O (oxygen) in gold (melting Ni).In addition, by Mn addition in Ni alloy, other than it can remove O, moreover it is possible to Enough remove the S (sulphur) in Ni alloy (melting Ni).As a result, being added by one kind or two kinds of Mn, Si and Al element In the case where in Ni alloy, it can effectively inhibit in the cathode collection being made of the Ni alloy for realizing solution strengthening using C The problems such as embrittlement occurred in electric body 5b by O or S.
In addition, in the present embodiment, it is negative comprising the adhesive with negative electrode active material and including thermosetting resin In the cathode 5 of pole material 5a, using the negative electrode collector 5b being made of Ni alloy, which comprises more than 0.03 mass % and is 0.20 mass % C below, remainder include Ni.By adopting such structure, even if thermosetting in order to make cathode material 5a Property resin solidification and by negative electrode collector 5b configuration under high temperature (such as 300 DEG C) environment, be also able to suppress negative electrode collector 5b Oxidation.As a result, it is possible to inhibit the high resistance of negative electrode collector 5b.Moreover, in order to inhibit negative electrode collector 5b's Oxidation and the curing process of thermosetting resin carried out in the sufficiently low nonoxidizing atmosphere of oxygen content, becoming can not also be upper It states in nonoxidizing atmosphere and carries out, therefore can easily make cathode 5.
[embodiment]
Then, with reference to Fig. 3~Fig. 5, for being illustrated for the test for confirming the effect of above embodiment and carrying out.
In testing, the different a variety of Ni sheet alloys of composition have been made.For prepared Ni sheet alloy, measurement The tensile strength of index as mechanical strength and the volume resistivity of index as resistance.
(production of the Ni sheet alloy of test material)
Firstly, having made 1~7 (reference table of test material based on Fig. 3~above embodiment shown in fig. 5 manufacturing method 1) Ni sheet alloy.Specifically, add C and additive about test material 2~7, in the melting Ni in melting furnace so that Each element is obtained melting Ni to be cast and being cooled down using casting die, has thus made test material after defined containing ratio Ni alloy blank.On the other hand, it about test material 1, is added to additive with not adding C, has made the blank of Ni alloy. That is, the containing ratio of the C in the Ni sheet alloy of test material 1 is inevitable impurity levels.Moreover, as test material 1~7 The composition of Ni sheet alloy, achieving shown in following table 1 composition, (element other than Ni and C is additive and inevitably Impurity).Wherein, it tests in the inevitable impurity contained by material 1~7, O is 0.002 mass % in any test material Below.In addition, in inevitable impurity contained by test material 1~7, S be 0.002 mass % in any test material with Under.
In addition, in test material 3 and 4, C, additive and inevitable impurity add up to 0.30 mass % or less.This Outside, in test material 1, it is the 0.040 mass % (conjunction of Mn, Al and Si that Mn, which is 0.007 mass %, Si for 0.215 mass %, Al, Be calculated as 0.262 mass %, Mn and Al adds up to 0.222 mass %), Fe is 0.02 mass %, and Co, Cu and Mg, which are respectively, to be less than 0.01 mass % (Co, Cu, Fe and Mg's is total less than 0.20 mass %).In addition, Mn is 0.001 matter in test material 3 % is measured, Al is that 0.004 mass %, Si is the 0.009 mass % (conjunction for adding up to 0.014 mass %, Mn and Al of Mn, Al and Si It is calculated as 0.005 mass %), respectively less than 0.01 mass %, (Co, Cu, Fe and Mg's is total less than 0.20 matter by Co, Cu, Fe and Mg Measure %).In addition, it is 0.014 mass % (Mn, Al that Mn, which is 0.020 mass %, Si for 0.001 mass %, Al, in test material 4 With Si add up to 0.035 mass %, Mn and Al add up to 0.021 mass %), Co, Cu, Fe and Mg are respectively less than 0.01 matter Measure % (Co, Cu, Fe and Mg's is total less than 0.20 mass %).
Wherein, the containing ratio for testting the C in the Ni sheet alloy of material 1,2 and 5~7, does not meet the Ni in summary of the invention The containing ratio (more than 0.03 mass % and being 0.20 mass % or less) of C in alloy.In addition, in the Ni alloy of test material 1~7 In any alloy of plate, the total of element (additive and inevitable impurity) other than Ni and C is all satisfied summary of the invention In Ni alloy in additive and inevitable impurity total containing ratio (0.50 mass % or less).Such result It is that the Ni sheet alloy of test material 3 and 4 belongs to embodiment (example of the present invention), the Ni sheet alloy of test material 1,2 and 5~7 belongs to Comparative example.
Moreover, passing through the blank heating in the Ni alloy that will test material to the temperature higher than the recrystallization temperature of Ni alloy The state of (hot-rolled temperature) carries out hot rolling, has made the hot rolled plate of Ni alloy.At this point, so that hot rolled plate with a thickness of The mode of 2mm has carried out hot rolling.Later, the survey of the harmful crackle of upper problematic degree is used for not generating in hot rolling Material (hot rolled plate) is tested, has carried out cold rolling in room temperature (25 DEG C).Later, it in order to remove the deformation generated by cold rolling, carries out Annealing.By the way that cold rolling and annealing is repeated, the test material (Ni sheet alloy) of the thickness with 0.4mm has been made.
Then, the tensile strength of prepared test material (Ni sheet alloy) is measured.Specifically, with Ni alloy sheets The rolling direction of material is to pull the mode in direction, cuts No. JIS13B dipstick that multiple JIS Z2241 are recorded from test material. Then, pulling test is carried out according to JIS Z2241, measures the tensile strength of multiple dipsticks.Later, by multiple dipsticks Tensile strength of the average value of tensile strength as prepared test material.In addition, measuring test material according to JISC2525 Volume resistivity.Following tables 1 describes the result (tensile strength) and body of the pulling test of test material (Ni sheet alloy) Product resistivity.
[table 1]
(test result of Ni alloy)
As shown in table 1, test material 1~4 has made Ni sheet alloy with not generating harmful crackle, and in test material 5 Harmful crackle is produced in~7, therefore fails to be fabricated to Ni sheet alloy.Specifically, in test material 5~7, in hot rolling When, produce the harmful crackle using upper problematic degree.It is thought that because testting containing for the C added in material 5~7 Have that rate is larger, therefore the mechanical strength of Ni alloy improves, but ductility has dropped, therefore produces crackle.As a result, It is able to confirm that the processing performance decline carried out when rolling etc. in the case where Ni alloy contains the C for having more than 0.20 mass %, and In the case where Ni alloy contains 0.20 mass % C below, it is able to suppress the decline of processing performance.
In addition, as the containing ratio of C becomes larger, the tensile strength of Ni sheet alloy becomes larger in test material 1~4.That is, It tests in the Ni sheet alloy of material 1~4, the containing ratio of C is more than the test of 0.03 mass % (and being 0.20 mass % or less) The Ni sheet alloy of material 3 and 4 resists compared with the containing ratio of C is the Ni sheet alloy of 0.03 mass % test material 1 and 2 below Tensile strength becomes larger.Specifically, tensile strength is less than 700MPa in the Ni sheet alloy of test material 1 and 2, and in test material 3 In 4 Ni sheet alloy, tensile strength is 700MPa or more (900MPa or more).It is able to confirm that by using such structure Arrive, C containing ratio be more than 0.03 mass % (and for 0.20 mass % or less) Ni alloy in, can sufficiently improve machine Tool intensity (tensile strength).
On the other hand, in test material 1~4, as the containing ratio of C becomes larger, the volume resistivity of Ni sheet alloy also becomes Greatly.Specifically, the volume resistivity of the Ni sheet alloy of test material 1 and 2 is 7.6 × 10-8Ω m is hereinafter, and test 3 He of material The volume resistivity of 4 Ni sheet alloy is respectively 9.4 × 10-8Ω m and 10.3 × 10-8Ω·m.But it is believed that test material The volume resistivity of 3 and 4 Ni sheet alloy is 15 × 10-8Ω m or less (10.5 × 10-8Ω m or less) value, with survey The volume resistivity for testing the Ni sheet alloy of material 1 and 2 is compared, and is not the big value of problematic degree in use.
In addition, being able to confirm that in test material 1~4, by the conjunction for making the containing ratio of additive and inevitable impurity It is calculated as 0.50 mass % or less (0.30 mass % or less), it is suppressed that volume resistivity becomes larger.And then think, in test material 3 and 4 In, by make the containing ratio of additive and inevitable impurity add up to 0.50 mass % or less (0.05 mass % with Under), it has been reliably suppressed volume resistivity and has become larger.
[variation]
It is not to this in addition, being to illustrate in all respects it is believed that the embodiments and examples recorded above The limitation of invention.The scope of the present invention is not illustrated to indicate by above-mentioned embodiments and examples, by summary of the invention It indicates, further comprises all changes (variation) in the meaning and range being equal with summary of the invention.
For example, in the above-described embodiment, list " the battery Ni material " in summary of the invention being applied to lithium ion two The example of the negative electrode collector 5b of primary cell (battery 100), but the present invention is not limited to this.It in the present invention, can also be with " battery Ni material " in summary of the invention is applied to other than the negative electrode collector of lithium ion secondary battery.For example, it is also possible to such as The first variation of present embodiment shown in fig. 6 is such, by " the battery Ni material " in summary of the invention be used as so-called lithium from The negative electrode collector 205b of monopole type cathode 205 in sub- solid state battery 200.Wherein, lithium ion solid battery 200 includes: list Polar form anode 204, monopole type cathode 205 and configure in z-direction monopole type anode 204 and monopole type cathode 205 between Solid electrolyte 206.Monopole type anode 204 includes: positive material 4a；With the side (side Z2) in stack direction (Z-direction) Surface configuration has the positive electrode collector 204b of positive material 4a.Monopole type cathode 205 includes: cathode material 5a；With on stack direction The surface configuration of the other side (side Z1) have the negative electrode collector 205b of cathode material 5a.
In this way, " the battery Ni material " in summary of the invention is used as the negative electrode collector 205b of lithium ion solid battery 200, i.e., Big stress repetition caused by big volume change because of caused by the expansion and contraction of negative electrode active material is set to act on cathode collection Electric body 205b can also be reliably suppressed the problem being deformed etc. due to stress repeatedly in negative electrode collector 205b.In turn, By using the negative electrode collector 205b being made of Ni alloy, wherein the Ni alloy comprises more than 0.03 mass % and is 0.20 Quality % C below and 0.50 mass % additive below and inevitable impurity being added up to, remainder includes Ni, It is same as above embodiment, even if negative electrode collector 205b configuration is existed in order to solidify the thermosetting resin of cathode material 5a Under hot environment (for example, 300 DEG C or more 350 DEG C hereinafter, including at higher temperature 300 DEG C or more 400 DEG C hereinafter, waiting), also can Enough inhibit the high resistance of negative electrode collector 205b.
In addition it is also possible to which the second variation of present embodiment as shown in Figure 7 and Figure 8 is such, by " the electricity of summary of the invention Pond Ni material " is used as the collector 307a of the bipolar electrode 307 in so-called lithium ion solid battery 300.As shown in fig. 7, lithium Ion solid battery 300 includes: the anode 304 and cathode 305 for being located at the surface layer on surface layer and the side Z2 of the side Z1；It is multiple bipolar Electrode 307；With multiple solid electrolytes 306.Multiple bipolar electrodes 307 and multiple solid electrolytes 306 are in z-direction alternately Lamination.
As shown in figure 8, bipolar electrode 307 includes: collector 307a；The surface configured in the side Z1 of collector 307a is just Pole material 4a；Cathode material 5a with configuration on the surface of the side Z2 of collector 307a.In this way, even if summary of the invention " battery use In the case that Ni material " is used as the collector 307a of lithium ion solid battery 300, even if because of the expansion and receipts of negative electrode active material Big stress repetition caused by big volume change caused by contracting acts on collector 307a, can also be reliably suppressed because repeatedly Stress and collector 307a produce deform the problems such as.In turn, by using by comprising more than 0.03 mass % and being 0.20 matter It measures % C below and remainder includes the Ni alloy collector 307a that constitutes of Ni, it is same as above embodiment, i.e., Make in order to make the thermosetting resin of positive material 4a and cathode material 5a solidify and by collector 307a configuration hot environment (such as 300 DEG C) under, also it is able to suppress the high resistance of collector 307a.
In addition it is also possible to which the third variation of present embodiment as shown in Figure 9 is such, by " the battery use of summary of the invention Ni material " is used as a pair (multiple) the case member 401a and 401b of the battery shell material 401 in so-called lithium ion secondary battery 400. As shown in figure 9, lithium ion secondary battery 400 includes: the case member 401a of flat planar；Shell portion with wavy cross sectional shape Part 401b；Adhesive portion 402；And the charge storage element 403 in the space being arranged respectively between case member 401a and case member 401b With electrolyte (not shown).
Adhesive portion 402 includes the thermosetting resin that case member 401a and case member 401b are connected to each other.Charge storage element 403 In, separator 406 is to configure the lamination in z-direction of the mode between anode 404 and cathode 405.Case member 401a by with The anode 404 of charge storage element 403 connects and is also used as positive terminal.In addition, case member 401b pass through it is negative with charge storage element 403 Pole 405 connects and is also used as negative terminal.Also, lithium ion secondary battery 400 is configured in stack direction (Z-direction) Lamination.
In this way, even if " battery Ni material " in summary of the invention is used as the case member 401a of lithium ion secondary battery 400 In the case where 401b, can also it be reliably suppressed due tos external force etc. the problems such as battery shell material 401 is deformed.In turn, lead to It crosses using by comprising more than 0.03 mass % and for 0.20 mass % C below and remainder includes that the Ni alloy of Ni is constituted Case member 401a and 401b, it is same as above embodiment, though in order to solidify the thermosetting resin of adhesive portion 402 and incite somebody to action Case member 401a and 401b are configured under hot environment (such as 300 DEG C), are also able to suppress the height electricity of case member 401a and 401b Resistanceization.
In addition, in the above-described embodiment, show negative electrode collector 5b (battery Ni material) being formed to have 30 μm The example of the foil-like of thickness below, but the present invention is not limited to this.In the present invention, battery also can have with Ni material Thickness more than 30 μm.In addition, battery is not limited to foil-like (plate) with the shape of Ni material.
In addition, in the above-described embodiment, show negative electrode collector 5b (battery Ni material) being applied to lithium-ion electric The example in pond, but the present invention is not limited to this.In the present invention, battery Ni material can also be applied to lithium ion battery Battery in addition.For example, it is also possible to which battery Ni material is applied in sodium-ion battery or magnesium cell etc..

Claims (8)

1. a kind of battery Ni material, it is characterised in that:
Be made of Ni alloy, the Ni alloy include: more than 0.03 mass % and for 0.20 mass % C below, add up to 0.50 Quality % additive below and inevitable impurity and the Ni as remainder.
2. battery as described in claim 1 Ni material, it is characterised in that:
The Ni alloy includes 0.10 mass % or more, 0.20 mass % C below.
3. battery as claimed in claim 1 or 2 Ni material, it is characterised in that:
Tensile strength is 700MPa or more.
4. battery as claimed in claim 1 or 2 Ni material, it is characterised in that:
The Ni alloy includes to add up to 0.30 mass % additive below and inevitable impurity.
5. battery as claimed in claim 1 or 2 Ni material, it is characterised in that:
With a thickness of 30 μm or less.
6. battery as claimed in claim 1 or 2 Ni material, it is characterised in that:
In the Ni alloy, as the additive added with element more than one kind or two kinds of Mn, Si and Al.
7. a kind of cathode characterized by comprising
The battery Ni material being made of Ni alloy, the Ni alloy include: more than 0.03 mass % and below for 0.20 mass % C, 0.50 mass % additive below and inevitable impurity and the Ni as remainder are added up to；With
Configure the cathode material comprising negative electrode active material and thermosetting resin on the surface of battery Ni material.
8. a kind of battery shell material characterized by comprising
The battery Ni material being made of Ni alloy, the Ni alloy include: more than 0.03 mass % and below for 0.20 mass % C, 0.50 mass % additive below and inevitable impurity and the Ni as remainder are added up to；With
The adhesive portion comprising thermosetting resin that multiple batteries are connected to each other with Ni material.
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