CN109216591B - Ni material for battery, negative electrode and battery case material - Google Patents
Ni material for battery, negative electrode and battery case material Download PDFInfo
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- CN109216591B CN109216591B CN201810612544.1A CN201810612544A CN109216591B CN 109216591 B CN109216591 B CN 109216591B CN 201810612544 A CN201810612544 A CN 201810612544A CN 109216591 B CN109216591 B CN 109216591B
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- 239000000463 material Substances 0.000 title claims abstract description 176
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 189
- 239000000654 additive Substances 0.000 claims abstract description 52
- 239000012535 impurity Substances 0.000 claims abstract description 48
- 239000007773 negative electrode material Substances 0.000 claims description 41
- 230000000996 additive effect Effects 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 229920001187 thermosetting polymer Polymers 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 133
- 238000012360 testing method Methods 0.000 description 51
- 239000011572 manganese Substances 0.000 description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 16
- 239000006104 solid solution Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000008602 contraction Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000005098 hot rolling Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
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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
- H01M50/116—Primary casings; Jackets or wrappings 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a Ni material for a battery, a negative electrode and a battery case material. The Ni material for a battery is composed of a Ni alloy including: more than 0.03 mass% and 0.20 mass% or less of C, 0.50 mass% or less in total of additives and inevitable impurities, and Ni as the remainder.
Description
Technical Field
The present invention relates to a Ni material for a battery, and a negative electrode and a battery case material using the Ni material for a battery.
Background
In the related art, in a lithium ion battery as a secondary battery, in order to improve the energy density of the battery, it is desirable to use an anode active material capable of further increasing the amount of Li (lithium) that can be inserted and extracted. Therefore, there is a tendency that: as the negative electrode active material, a non-carbon material such as an oxide of Si (silicon) or an oxide of Sn (tin) is used instead of a carbon material (graphite) or the like, which is a general negative electrode active material, in which the amount of Li that can be inserted and extracted is increased as compared with the carbon material. However, when the amount of Li that can be inserted and extracted increases, the negative electrode active material expands and contracts with the insertion of Li during charging and the extraction of Li during discharging, and therefore the volume change of the negative electrode active material is large. Therefore, a large stress is repeatedly applied to the metal current collector having the negative electrode active material disposed on the surface thereof due to a large volume change caused by expansion and contraction of the negative electrode active material. Therefore, in order to suppress the occurrence of deformation and the like in the metal current collector due to a large stress repeatedly acting, it is required to improve the mechanical strength such as tensile strength. In addition, the metal current collector is required to have low resistance in order to suppress a decrease in current collection efficiency.
As described above, a metal material used for a battery is required to have low resistance and high mechanical strength. Such a metal material having low electric resistance and high mechanical strength can be applied to battery components other than the metal current collector, for example, battery case materials, lead materials, and the like.
Here, when a thermosetting resin is applied to a metal material having low electrical resistance and high mechanical strength and cured, it is preferable to use, as the metal material, a Ni (nickel) material that can suppress oxidation even at the curing temperature of the thermosetting resin (for example, 300 ℃) and can suppress an increase in electrical resistance of the metal material.
Therefore, a Ni material for a battery used in a battery is known in the related art. Such a Ni material for a battery is disclosed in, for example, japanese patent No. 3741311.
Japanese patent No. 3741311 discloses a nickel material ribbon for a lead of a lithium ion secondary battery, which contains 99% by mass or more of Ni and inevitable impurities. The nickel material band for the lead comprises: 0.03% or less by mass of C (carbon), 0.01% or less by mass of Si (silicon), and 0.04% or less by mass of Mn (manganese). Wherein, in the nickel material band for the lead, C is used as CO or CO2Since the gas has the effect of reducing the oxygen content in the molten metal, it is preferable to increase the concentration of C to some extent and suppress the addition of other deoxidizing elements (Si, Mn, etc.), and 0.03 mass% or less (preferably 0.008 to 0.020 mass%) is selected from the conventional 0.01 mass% or less. Furthermore, the hardness of the nickel material band for the lead is adjusted to Hv 80-190.
However, although japanese patent No. 3741311 describes adjusting the hardness of the nickel material tape for lead to Hv80 to 190, no description is made about the tensile strength and the like of the nickel material tape for lead. Therefore, for example, when this nickel material tape for a lead (Ni material in the related art) is applied to a metal current collector for a lithium ion battery, there are the following problems: the conventional Ni material is not sufficiently high in mechanical strength such as tensile strength, and has a problem such as deformation due to external force such as large stress repeatedly applied. This problem has been confirmed by experiments described later. Therefore, a Ni material for a battery is required to have sufficiently high mechanical strength such as tensile strength and low resistance.
Disclosure of Invention
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a Ni material for a battery, which has a sufficiently high mechanical strength such as tensile strength and a low resistance, and a negative electrode and a battery case material using the Ni material for a battery.
The inventors of the present application have made intensive studies with a view to the composition of the Ni material in the above-described conventional art, and as a result, have invented the following structure that can achieve the above object. The Ni material for a battery according to the first aspect of the present invention is made of a Ni alloy including: more than 0.03 mass% and 0.20 mass% or less of C, 0.50 mass% or less in total of additives and inevitable impurities, and Ni as the remainder. Here, "additive" refers to an element intentionally added to the Ni alloy, and "inevitable impurity" refers to an element which is not intended to be added but is inevitably contained in the Ni alloy.
As described above, the Ni material for a battery according to the first aspect of the present invention is made of a Ni alloy including: more than 0.03 mass% and 0.20 mass% or less of C (carbon), 0.50 mass% or less in total of additives and unavoidable impurities, and Ni as the remainder. With such a configuration, even if a small amount (for example, about 0.02 mass%) of C is consumed by the effect of reducing the oxygen content in the Ni alloy (molten Ni), a sufficient amount of C can be dissolved in the Ni alloy to strengthen the base material (base material phase), as compared with the case where the Ni material for the battery is made of a Ni alloy containing 0.03 mass% or less of C, so that the mechanical strength such as tensile strength of the Ni material for the battery made of the Ni alloy can be improved. Further, since the Ni alloy contains 0.20 mass% or less of C less than the solid solution limit of C to Ni (for example, about 0.6 mass% at 1300 ℃), most of C in the Ni alloy can be brought into a solid solution state by rapid cooling. As a result, it is considered that the mechanical strength of the battery Ni material made of the Ni alloy can be improved because the Ni alloy can be solid-solution strengthened by C, and the corrosion resistance of the battery Ni material made of the Ni alloy can be improved because C is in a solid-solution state.
In the Ni material for a battery according to the first aspect, since the Ni alloy contains 0.50 mass% or less of the additive and the unavoidable impurity in total and the content of the additive and the unavoidable impurity other than C in the Ni alloy is small relative to Ni as described above, the increase in the resistance of the Ni alloy due to the additive and the unavoidable impurity can be suppressed. As a result, the mechanical strength such as tensile strength of the Ni material for a battery made of the Ni alloy can be sufficiently increased, and the resistance can be reduced.
Further, in the Ni material for a battery according to the first aspect, as described above, by setting the content of C in the Ni alloy to 0.20 mass% or less, it is possible to suppress a reduction in workability at the time of rolling or the like due to an excessive increase in mechanical strength of the Ni alloy caused by excessive solid solution of C. With such a configuration, the Ni alloy can be easily processed, and a low-resistance Ni material for a battery, which is made of the Ni alloy and has a sufficiently high mechanical strength such as tensile strength, can be obtained. However, it has been confirmed through experiments described below that the mechanical strength of a Ni material for a battery made of a Ni alloy can be suppressed from becoming too high by setting the C content in the Ni alloy to 0.20 mass% or less.
Further, in the Ni material for a battery according to the first aspect, as described above, by making the Ni material for a battery be made of a Ni alloy containing Ni as a main component, corrosion due to the use environment and corrosion due to acid or alkali can be effectively suppressed as compared with Cu (copper) or a Cu alloy generally used for a negative electrode current collector.
In the Ni material for a battery according to the first aspect, the Ni alloy preferably contains 0.10 mass% to 0.20 mass% of C. With such a configuration, since C is contained in an amount of 0.10 mass% or more, the mechanical strength such as tensile strength of the Ni material for a battery made of the Ni alloy can be further improved.
In the Ni material for a battery according to the first aspect, the tensile strength is preferably 700MPa or more. With such a configuration, the Ni material for a battery has a sufficient tensile strength of 700MPa or more, and therefore, for example, when the Ni material for a battery is used for a metal current collector having a negative electrode active material disposed on the surface thereof, even if a large stress due to a large volume change caused by expansion and contraction of the negative electrode active material is repeatedly applied to the Ni material for a battery, it is possible to reliably prevent the Ni material for a battery from being deformed due to the repeated stress.
In the Ni material for a battery according to the first aspect, the Ni alloy preferably contains an additive and inevitable impurities in an amount of 0.30 mass% or less in total. With such a configuration, the content of the additive other than C and the unavoidable impurity in the Ni alloy is sufficiently small relative to the content of Ni, and the increase in the resistance of the Ni material for a battery made of the Ni alloy due to the additive and the unavoidable impurity can be further suppressed.
In the Ni material for a battery according to the first aspect, the thickness may be set in consideration of the desired use, mechanical strength, and the like, and is preferably 30 μm or less. With such a configuration, by using the Ni material for a battery having a small thickness of 30 μm or less, it is possible to provide the Ni material for a battery having a sufficiently high mechanical strength such as tensile strength while suppressing an increase in size of the battery using the Ni material for a battery. In the Ni material for a battery according to the first aspect, the thickness is preferably 1 μm or more, more preferably 3 μm or more for ease of production, and further more preferably 5 μm or more for ease of mass production. With such a configuration, by using a Ni material for a battery having a thickness of at least 1 μm, it is possible to provide a Ni material for a battery having a desired mechanical strength such as tensile strength.
In the Ni material for a battery according to the first aspect, 1 or 2 or more elements of Mn, Si, and Al are preferably added as additives to the Ni alloy. With such a configuration, when 1 or 2 or more elements of Mn, Si, and Al are added to the Ni alloy, the consumption of C due to deoxidation is effectively suppressed by the deoxidation effect of the additive, and O (oxygen) in the Ni alloy (molten Ni) can be removed. Further, in the case where Mn is added to the Ni alloy, S (sulfur) in the Ni alloy (molten Ni) can be removed in addition to O. As a result, in the Ni material for a battery made of the Ni alloy solution-strengthened by C, problems such as embrittlement due to O or S can be effectively suppressed.
The anode of the second aspect of the invention includes: the Ni material for a battery according to the first aspect; and a negative electrode material disposed on the surface of the Ni material for a battery and containing a negative electrode active material and a thermosetting resin. With such a configuration, even when a large stress due to a large volume change caused by expansion and contraction of the negative electrode active material is repeatedly applied to the Ni material for a battery, the mechanical strength such as tensile strength of the Ni material for a battery is sufficiently high, and thus, problems such as deformation of the Ni material for a battery due to the repeated stress can be reliably suppressed. Further, similarly to the first aspect, the mechanical strength of the Ni material for a battery can be improved by forming the Ni alloy with C solid-solution strengthened, and the corrosion resistance of the Ni material for a battery can be improved by forming the Ni alloy with C in a solid-solution state. Further, by using a Ni material for a battery made of a Ni alloy containing more than 0.03 mass% and 0.20 mass% or less of C and the balance of Ni, oxidation of the Ni material for a battery can be suppressed even when the Ni material for a battery is placed in a high-temperature environment in order to cure the thermosetting resin of the negative electrode material. With such a configuration, the Ni material for the battery can be prevented from increasing in resistance. Furthermore, since it is not necessary to cure the thermosetting resin in a non-oxidizing atmosphere having a sufficiently low oxygen content in order to suppress oxidation of the Ni material for a battery, the negative electrode can be easily produced.
The battery case material of the third aspect of the invention includes: a plurality of Ni materials for a battery according to the first aspect; and an adhesive portion containing a thermosetting resin for connecting the plurality of cells to each other with a Ni material. With such a configuration, the mechanical strength such as tensile strength of the Ni material for a battery is sufficiently high, and thus, the problem of deformation or the like of the battery case material due to external force or the like can be reliably suppressed. Further, similarly to the first aspect, the mechanical strength of the Ni material for a battery can be improved by forming the Ni alloy with C solid-solution strengthened, and the corrosion resistance of the Ni material for a battery can be improved by forming the Ni alloy with C in a solid-solution state. In addition, even if the battery is placed in a high-temperature environment when the thermosetting resin in the adhesive portion is cured, oxidation of the Ni material for the battery made of the Ni alloy can be suppressed in the same manner as in the negative electrode of the second aspect. With such a configuration, the battery case material can be easily produced while suppressing the increase in resistance of the Ni material for the battery.
Drawings
Fig. 1 is a schematic sectional view showing a battery using a negative electrode according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view showing a negative electrode according to an embodiment of the present invention.
Fig. 3 is a schematic diagram for explaining a method of manufacturing a Ni alloy billet according to an embodiment of the present invention.
Fig. 4 is a schematic view for explaining a method of manufacturing a Ni alloy sheet material according to an embodiment of the present invention.
Fig. 5 is a schematic diagram for explaining a method of producing a clad material constituting a negative electrode current collector according to an embodiment of the present invention.
Fig. 6 is a schematic cross-sectional view showing a solid-state battery using a negative electrode according to a first modification of an embodiment of the present invention.
Fig. 7 is a schematic cross-sectional view showing a solid-state battery including a bipolar electrode using a Ni material for a battery according to a second modification of the embodiment of the present invention.
Fig. 8 is a sectional view showing a bipolar electrode using a Ni material for a battery according to a second modification of the embodiment of the present invention.
Fig. 9 is a sectional view showing a plurality of lithium ion secondary batteries according to a third modification of the embodiment of the present invention.
Detailed Description
Embodiments of the present invention will be described below with reference to the drawings.
First, the structure of a battery 100 using a negative electrode current collector 5b according to an embodiment of the present invention will be described with reference to fig. 1 and 2. The negative electrode current collector 5b is an example of the "Ni material for a battery" in the invention.
(Structure of Battery)
As shown in fig. 1, battery 100 according to one embodiment of the present invention is a so-called cylindrical lithium ion secondary battery. The battery 100 includes: a cylindrical housing 1; a lid member 2 for sealing the opening of the case 1; and an electric storage element 3 disposed in the case 1.
The case 1 houses therein the power storage element 3 and an electrolyte (not shown). The cover 2 is made of an aluminum alloy or the like and also serves as a positive electrode terminal (battery positive electrode) of the battery 100. The storage element 3 is formed by winding a positive electrode 4, a negative electrode 5, and an insulating separator 6 disposed between the positive electrode 4 and the negative electrode 5. The positive electrode 4 contains a positive electrode active material such as lithium manganate and a positive electrode current collector including aluminum foil. A positive electrode active material is fixed to the surface of the positive electrode current collector with a binder or the like. A positive electrode lead 7 for electrically connecting the lid 2 and the positive electrode 4 is fixed to the positive electrode 4.
As shown in fig. 2, the negative electrode 5 includes a negative electrode material 5a and a foil-shaped negative electrode current collector 5b having the negative electrode material 5a fixed to both surfaces thereof. The negative electrode material 5a includes, for example: a negative electrode active material capable of Li insertion and extraction, such as carbon, SnO, or SiO; and a binder including a thermosetting resin such as a polyimide resin, for example, and used to fix the negative electrode active material to the negative electrode collector 5 b. The negative electrode active material of the negative electrode material 5a expands and contracts according to insertion and extraction of Li. The negative electrode current collector 5b is made of a Ni alloy, and is formed in a foil shape having a thickness t of 30 μm or less. In addition, a large stress is repeatedly applied to the negative electrode current collector 5b due to a large volume change caused by expansion and contraction of the negative electrode active material.
As shown in fig. 1, a negative lead 8 for electrically connecting the inner bottom surface 1a of the case 1 and the negative electrode 5 is fixed to the negative electrode 5. Specifically, the negative electrode lead 8 is joined to the negative electrode current collector 5b by ultrasonic welding. The negative electrode lead 8 is joined to a portion (not shown) to which the negative electrode material 5a is not fixed. The negative lead 8 is joined to the inner bottom surface 1a of the case 1 by resistance welding.
(composition of Ni alloy)
Here, in the present embodiment, the Ni alloy constituting the negative electrode current collector 5b includes: more than 0.03 mass% and 0.20 mass% or less of C, 0.50 mass% or less in total of additives and unavoidable impurities, and Ni as the remainder. Among these, the Ni alloy constituting the negative electrode current collector 5b is superior in corrosion resistance to Cu or a Cu alloy generally used for negative electrode current collectors, because Ni is the main component.
(C of Ni alloy)
In the present embodiment, the Ni alloy contains more than 0.03 mass% of C in order to dissolve a sufficient amount of C in the Ni alloy and improve the mechanical strength. Among them, in order to make a sufficient amount of C solid-solutionized in the Ni alloy, the Ni alloy preferably contains 0.10 mass% or more of C, and more preferably contains 0.15 mass% or more of C. Here, it is considered that, by dissolving a sufficient amount of C in the Ni alloy as described above, not only the mechanical strength of the negative electrode current collector 5b made of the Ni alloy can be improved, but also the corrosion resistance can be improved.
In the present embodiment, most of C in the Ni alloy is in a solid solution state, while the Ni alloy contains 0.20 mass% or less of C sufficiently smaller than the solid solution limit (approximately 0.6 mass%) of C with respect to Ni in order to suppress excessive increase in mechanical strength of the negative electrode current collector 5b made of the Ni alloy. In order to suppress an excessive increase in mechanical strength of the negative electrode current collector 5b made of a Ni alloy, the Ni alloy preferably contains 0.18 mass% or less of C. As described above, in order to provide the negative electrode current collector 5b made of the Ni alloy with appropriate mechanical strength, it is more preferable that the Ni alloy contains 0.10 mass% to 0.20 mass% of C.
(additive of Ni alloy)
In the present embodiment, 1 or 2 or more elements of Mn, Si, and Al may be contained as additives in the Ni alloy. Specifically, as a result of removing O and S in the Ni alloy (molten Ni), Mn, Si, and Al may be contained in the Ni alloy in a total amount of 0.30 mass% or less. Specifically, the Ni alloy may contain 0.19 mass% to 0.24 mass% of Mn. In order to remove O in the Ni alloy (molten Ni), Si may be contained in the Ni alloy in an amount of 0.03 mass% to 0.05 mass%, or Al may be contained in the Ni alloy in an amount of 0.002 mass% to 0.012 mass%. In addition, in order to remove O in the Ni alloy (molten Ni), the total amount of the additive contained in the Ni alloy may be suppressed by using Al as an additive in consideration of the deoxidation effect of C. In addition, in order to remove S in the Ni alloy (molten Ni), Mn may be used as an additive to suppress the total amount of the additive contained in the Ni alloy. In this case, the Ni alloy may contain 0.25 mass% or less of Al and Mn in total.
In the present embodiment, as an additive, a rare metal element such as Nb (niobium), V (vanadium), or Ta (tantalum), which has a property of improving the mechanical strength of the Ni alloy (negative electrode current collector 5b), may be added to the Ni alloy. However, the rare metal element may inhibit the cost reduction of the Ni alloy (negative electrode current collector 5b), and is preferably not added to the Ni alloy, and therefore the total content is preferably 0.05 mass% or less (preferably 0.03 mass% or less).
(unavoidable impurities of Ni alloy)
In addition, in the present embodiment, the Ni alloy may contain, as inevitable impurities, O and S that are desired to be removed as much as possible, in addition to Co, Cu, Fe, and Mg. For example, the Ni alloy may contain 0.09 mass% or less of Co, Cu, Fe, and Mg in total as inevitable impurities. Specifically, the Ni alloy may contain 0.01 mass% or less of Co as an inevitable impurity. In addition, the Ni alloy may contain 0.04 mass% or less of Cu as an inevitable impurity. In addition, the Ni alloy may contain 0.04 mass% or less of Fe as an inevitable impurity. In addition, the Ni alloy may contain 0.001 mass% or less of Mg as an inevitable impurity. In order to suppress embrittlement of the Ni alloy, it is preferable to remove as much as possible O and S, which are inevitable impurities, and it is preferable that the Ni alloy does not contain O and S, but O is contained in an amount of 0.002 mass% or less (preferably 0.001 mass% or less) and S is contained in an amount of 0.005 mass% or less (preferably 0.002 mass% or less). In order to suppress the increase in resistance and the deterioration in workability of the Ni alloy (negative electrode current collector 5b), the inclusion of Co, Cu, Fe, and Mg as inevitable impurities is limited as much as possible, and, for example, Co, Cu, Fe, and Mg are preferably 0.06 mass% or less, more preferably 0.03 mass% or less, and still more preferably 0.01 mass% or less.
(contents of additives and unavoidable impurities of Ni alloy)
Here, in order to suppress the increase in the resistance of the Ni alloy (negative electrode current collector 5b), it is preferable that the Ni alloy does not contain the additive and the inevitable impurities. In the present embodiment, the additive and the inevitable impurity are suppressed to 0.50 mass% or less in total in the Ni alloy in order to suppress the increase in resistance of the Ni alloy. In order to suppress the increase in the resistance of the Ni alloy, the additive and the inevitable impurities are preferably suppressed to 0.30 mass% or less in total in the Ni alloy, and more preferably to 0.05 mass% or less in total in the Ni alloy.
(tensile Strength of negative Current collector)
The tensile strength of the negative electrode current collector 5b made of the Ni alloy is 700MPa or more. With such a structure, the negative electrode current collector 5b can withstand stress repeatedly applied due to a volume change of the negative electrode active material. The tensile strength of the negative electrode current collector 5b can be obtained by a metal material tensile test method defined in JIS Z2241. In order to withstand the repetitive stress well, the tensile strength of the negative electrode current collector 5b is preferably 900MPa or more. It is confirmed from examples and comparative examples described later that the negative electrode current collector 5b made of the Ni alloy has a tensile strength of 700MPa or more when the total of C, additives, and unavoidable impurities contained in the Ni alloy is 0.30 mass% or less.
(volume resistivity of negative electrode Current collector)
The negative electrode current collector 5b made of the Ni alloy has a volume resistivity of 15 × 10-8Omega m or less. With such a configuration, it is possible to suppress an increase in power loss of the negative electrode current collector 5 b. In order to suppress an increase in power loss of the negative electrode current collector 5b, the volume resistivity of the negative electrode current collector 5b is preferably 12 × 10-8Omega. m or less, more preferably 11X 10-8Omega. m or less, more preferably 10X 10-8Omega m or less. In addition, when the total of C, additives, and inevitable impurities contained in the Ni alloy is 0.30 mass% or less, it is confirmed by examples and comparative examples described later that the negative electrode current collector 5b made of the Ni alloy has a size of 15 × 10-8Volume resistivity of not more than Ω · m.
Next, a method for producing the negative electrode 5 using the negative electrode current collector 5b made of the Ni alloy will be described with reference to fig. 2 to 5.
(preparation of negative electrode Current collector)
First, the negative electrode current collector 5b made of a Ni alloy is produced. Specifically, as shown in fig. 3, C is added in an amount exceeding 0.03 mass% and not more than 0.20 mass% to the molten Ni in the melting furnace 101, and an additive (one or 2 or more of Mn, Si, and Al) is added so that the total content of the additive and the inevitable impurities is not more than 0.50 mass%, and then casting and cooling are performed using a casting die. In this case, an additive (additive) is added to the molten Ni as necessary. By adopting such a method, a billet 151 (see fig. 4) of a Ni alloy containing more than 0.03 mass% and 0.20 mass% or less of C, 0.50 mass% or less in total of additives and inevitable impurities, and the balance of Ni can be produced.
Then, as shown in fig. 4, the billet 151 of the Ni alloy is hot-rolled to produce a hot-rolled plate 251 of the Ni alloy. Specifically, in a state where the Ni alloy billet 151 is arranged in the furnace 102, the Ni alloy billet 151 is heated to a temperature (hot rolling temperature) higher than the recrystallization temperature of the Ni alloy. Then, the heated Ni alloy billet 151 is taken out of the furnace 102 and rolled by using the rolling rolls 103, thereby performing hot rolling. In this manner, the hot-rolled plate 251 of Ni alloy can be produced. Thereafter, the cooled hot-rolled plate 251 is annealed at about 900 ℃, and cold-rolled at a predetermined reduction ratio using the rolling rolls 104. The cold rolling and the annealing can be repeated as necessary. Finally, by appropriate cutting or the like, a foil-like negative electrode current collector 5b having a thickness of 30 μm or less is produced (see fig. 5).
(preparation of cathode)
Then, negative electrode materials 5a containing a negative electrode active material and a thermosetting resin are disposed on both surfaces of the foil-shaped negative electrode current collector 5b (see fig. 2). Specifically, as shown in fig. 5, a coating material 105a containing a negative electrode active material and a thermosetting resin is coated on both surfaces of a foil-shaped negative electrode current collector 5 b. Then, the negative electrode current collector 5b coated with the coating material 105a is disposed in a drying furnace 105 set at a temperature higher than the curing temperature (for example, 300 ℃) of the thermosetting resin and heat-treated for a predetermined time, thereby curing the thermosetting resin. Among them, in the drying furnace 105, a low-pressure atmosphere which is reduced in pressure (vacuum) to a certain extent is preferable in order to suppress oxidation of Ni. By adopting such a method, a negative electrode 5 (see fig. 2) in which negative electrode materials 5a containing a negative electrode active material and a thermosetting resin are arranged on both surfaces of a foil-shaped negative electrode current collector 5b can be produced.
At this time, the foil-like negative electrode current collector 5b is made of Ni, and thus is less likely to be oxidized than the case of Cu. Therefore, the inside of the drying furnace 105 may not be a non-oxidizing atmosphere having a sufficiently low oxygen content.
< Effect of the present embodiment >
The present embodiment can obtain the following effects.
In the present embodiment, as described above, the Ni alloy constituting the negative electrode current collector 5b is composed of a Ni alloy containing more than 0.03 mass% and 0.20 mass% or less of C, 0.50 mass% or less of additives and inevitable impurities in total, and the balance of Ni. By adopting such a configuration, even if a small amount (for example, about 0.02 mass%) of C is consumed by the action of reducing the oxygen content in the Ni alloy (molten Ni), a sufficient amount of C can be dissolved in the Ni alloy to strengthen the base material (base material phase) as compared with the case where the negative electrode current collector is made of a Ni alloy containing 0.03 mass% or less of C, and thus the mechanical strength such as tensile strength of the negative electrode current collector 5b can be improved by C. Further, since the Ni alloy contains 0.20 mass% or less of C less than the solid solution limit of C to Ni (for example, at 1300 ℃, approximately 0.6 mass%), most of C in the Ni alloy can be brought into a solid solution state by rapid cooling. As a result, it is considered that the mechanical strength of the negative electrode current collector 5b made of the Ni alloy can be improved by strengthening the solid solution of the Ni alloy with C, and the corrosion resistance of the negative electrode current collector 5b made of the Ni alloy can be improved because C is in a solid solution state.
In the present embodiment, the Ni alloy contains 0.50 mass% or less of additives and unavoidable impurities in total, and the content of additives and unavoidable impurities other than C in the Ni alloy is small relative to the content of Ni, so that the increase in resistance of the Ni alloy due to the additives and the unavoidable impurities can be suppressed. As a result, the mechanical strength such as tensile strength of the negative electrode current collector 5b made of Ni alloy can be sufficiently increased, and the negative electrode current collector 5b can have low resistance. Therefore, even if a large stress due to a large volume change caused by expansion and contraction of the negative electrode active material is repeatedly applied to the negative electrode current collector 5b, the mechanical strength such as the tensile strength of the negative electrode current collector 5b is sufficiently high, and thus, it is possible to reliably suppress the occurrence of a problem such as deformation in the negative electrode current collector 5b due to the repeated stress.
In the present embodiment, the content of C in the Ni alloy is 0.20 mass% or less, whereby it is possible to suppress the mechanical strength of the Ni alloy from becoming too high due to excessive solid solution of C and the workability of the Ni alloy from being lowered when rolling or the like is performed. In this manner, the Ni alloy can be easily processed, and the negative electrode current collector 5b made of the Ni alloy can be obtained which has a sufficiently high mechanical strength such as tensile strength and has a low resistance.
In addition, in the present embodiment, by constituting the negative electrode current collector 5b with a Ni alloy containing Ni as a main component, corrosion due to the use environment and corrosion due to acid or alkali can be effectively suppressed as compared with Cu or a Cu alloy generally used for a negative electrode current collector.
In the present embodiment, the Ni alloy preferably contains 0.10 mass% to 0.20 mass% of C. In this manner, by containing 0.10 mass% or more of C, the mechanical strength such as tensile strength of the negative electrode current collector 5b made of a Ni alloy can be further improved.
In the present embodiment, the tensile strength of the negative electrode current collector 5b is 700MPa or more. In this manner, since the negative electrode current collector 5b has a sufficient tensile strength of 700MPa or more, even if a large stress due to a large volume change caused by expansion and contraction of the negative electrode active material is repeatedly applied to the negative electrode current collector 5b, it is possible to reliably suppress the occurrence of a problem such as deformation in the negative electrode current collector 5b due to the repeated stress.
In the present embodiment, the Ni alloy preferably contains 0.30 mass% or less of additives and unavoidable impurities in total. In this manner, since the content of the additive other than C and the unavoidable impurity in the Ni alloy is sufficiently small relative to the content of Ni, the increase in resistance of the negative electrode current collector 5b made of the Ni alloy due to the additive and the unavoidable impurity can be further suppressed.
In the present embodiment, by setting the thickness t of the negative electrode current collector 5b to 30 μm or less, it is possible to provide the negative electrode current collector 5b having a sufficiently high mechanical strength such as tensile strength while suppressing an increase in size of a battery using the negative electrode current collector 5 b.
In the present embodiment, when one or 2 or more elements of Mn, Si, and Al are added to the Ni alloy, the consumption of C by deoxidation is effectively suppressed by the deoxidation effect of the additive, and O (oxygen) in the Ni alloy (molten Ni) can be removed. In addition, when Mn is added to the Ni alloy, S (sulfur) in the Ni alloy (molten Ni) can be removed in addition to O. As a result, when one or 2 elements of Mn, Si, and Al are added to the Ni alloy, the problems such as embrittlement due to O or S in the negative electrode current collector 5b made of the Ni alloy solution-strengthened by C can be effectively suppressed.
In the present embodiment, the negative electrode 5 including the negative electrode material 5a having the negative electrode active material and the binder including the thermosetting resin uses the negative electrode current collector 5b made of a Ni alloy containing more than 0.03 mass% and 0.20 mass% or less of C and the remainder containing Ni. With such a configuration, even when the negative electrode current collector 5b is disposed in a high-temperature (e.g., 300 ℃) environment in order to cure the thermosetting resin of the negative electrode material 5a, oxidation of the negative electrode current collector 5b can be suppressed. As a result, the resistance of the negative electrode current collector 5b can be suppressed from increasing. In addition, the curing treatment of the thermosetting resin performed in the non-oxidizing atmosphere having a sufficiently low oxygen content to suppress oxidation of the negative electrode current collector 5b may not be performed in the non-oxidizing atmosphere, and therefore the negative electrode 5 can be easily manufactured.
[ examples ]
Next, a test performed to confirm the effects of the above embodiment will be described with reference to fig. 3 to 5.
In the tests, various Ni alloy sheets of different compositions were produced. The Ni alloy sheet thus produced was measured for tensile strength as an index of mechanical strength and volume resistivity as an index of electrical resistance.
(preparation of Ni alloy sheet for test Material)
First, Ni alloy sheet materials of test materials 1 to 7 (see table 1) were produced based on the manufacturing method of the above embodiment shown in fig. 3 to 5. Specifically, for test materials 2 to 7, a Ni alloy material of the test material was prepared by adding C and additives to molten Ni in a melting furnace so that each element had a predetermined content ratio, and then casting and cooling the molten Ni using a casting die. On the other hand, as for the test material 1, an additive was added without adding C, and a Ni alloy billet was prepared. That is, the Ni alloy sheet material of test sample 1 had a C content of an inevitable impurity level. Further, as compositions of the Ni alloy sheet materials of test materials 1 to 7, compositions shown in the following table 1 were obtained (elements other than Ni and C were additives and unavoidable impurities). Among the inevitable impurities contained in the test materials 1 to 7, O is 0.002 mass% or less in any of the test materials. In addition, S is 0.002 mass% or less in any of the test materials, among the inevitable impurities contained in the test materials 1 to 7.
In test materials 3 and 4, the total of C, additives, and unavoidable impurities was 0.30 mass% or less. In test material 1, Mn was 0.215 mass%, Al was 0.007 mass%, Si was 0.040 mass% (the total of Mn, Al, and Si was 0.262 mass%, the total of Mn and Al was 0.222 mass%), Fe was 0.02 mass%, and each of Co, Cu, and Mg was less than 0.01 mass% (the total of Co, Cu, Fe, and Mg was less than 0.20 mass%). In test material 3, Mn was 0.001 mass%, Al was 0.004 mass%, and Si was 0.009 mass% (0.014 mass% for the total of Mn, Al, and Si, and 0.005 mass% for the total of Mn and Al), and each of Co, Cu, Fe, and Mg was less than 0.01 mass% (less than 0.20 mass% for the total of Co, Cu, Fe, and Mg). In test material 4, Mn was 0.001 mass%, Al was 0.020 mass%, and Si was 0.014 mass% (total of Mn, Al, and Si was 0.035 mass%, and total of Mn and Al was 0.021 mass%), and each of Co, Cu, Fe, and Mg was less than 0.01 mass% (total of Co, Cu, Fe, and Mg was less than 0.20 mass%).
The content of C in the Ni alloy sheet materials of test materials 1, 2, and 5 to 7 did not satisfy the content of C in the Ni alloy in the invention (more than 0.03 mass% and 0.20 mass% or less). In any of the Ni alloy sheet materials of test materials 1 to 7, the total content of elements (additives and unavoidable impurities) other than Ni and C satisfies the total content (0.50 mass% or less) of the additives and the unavoidable impurities in the Ni alloy in the summary of the invention. As a result, the Ni alloy sheets of test materials 3 and 4 were examples (inventive examples), and the Ni alloy sheets of test materials 1, 2, and 5 to 7 were comparative examples.
Then, the Ni alloy ingot of the test material was hot-rolled in a state of being heated to a temperature (hot-rolling temperature) higher than the recrystallization temperature of the Ni alloy, thereby producing a Ni alloy hot-rolled plate. At this time, hot rolling was performed so that the thickness of the hot-rolled plate was 2 mm. Thereafter, the test material (hot rolled plate) was cold rolled at room temperature (25 ℃) without causing harmful cracking to such an extent that the test material had a problem in use during hot rolling. Thereafter, annealing is performed to remove the strain caused by the cold rolling. By repeating cold rolling and annealing, a test material (Ni alloy sheet) having a thickness of 0.4mm was produced.
Then, the tensile strength of the test material (Ni alloy plate) thus obtained was measured. Specifically, a plurality of test pieces of JIS13B described in JIS Z2241 were cut from the test material so that the rolling direction of the Ni alloy plate material was the drawing direction. Then, a tensile test was performed in accordance with JIS Z2241, and the tensile strength of a plurality of test pieces was measured. Then, the average value of the tensile strengths of the plurality of test pieces was defined as the tensile strength of the test material prepared. Further, the volume resistivity of the test material was measured in accordance with JISC 2525. The results (tensile strength) and volume resistivity of the tensile test of the test material (Ni alloy plate material) are shown in table 1 below.
[ TABLE 1 ]
(test results of Ni alloy)
As shown in table 1, the Ni alloy sheets were produced without harmful cracks in the test materials 1 to 4, while harmful cracks were produced in the test materials 5 to 7, and therefore, the Ni alloy sheets could not be produced. Specifically, in the test materials 5 to 7, harmful cracks were generated to such an extent that the use thereof was problematic during hot rolling. This is considered to be because the Ni alloy has improved mechanical strength but has reduced ductility and therefore cracks are generated because the content of C added to the test materials 5 to 7 is large. As a result, it was confirmed that the workability at the time of rolling or the like was deteriorated when the Ni alloy contained more than 0.20 mass% of C, and the deterioration of the workability was suppressed when the Ni alloy contained 0.20 mass% or less of C.
In addition, in the test materials 1 to 4, the tensile strength of the Ni alloy sheet material was increased as the content of C was increased. That is, among the Ni alloy sheet materials of test materials 1 to 4, the Ni alloy sheet materials of test materials 3 and 4 having a C content of more than 0.03 mass% (and 0.20 mass% or less) had higher tensile strength than the Ni alloy sheet materials of test materials 1 and 2 having a C content of 0.03 mass% or less. Specifically, in the Ni alloy sheet materials of test materials 1 and 2, the tensile strength was less than 700MPa, and in the Ni alloy sheet materials of test materials 3 and 4, the tensile strength was 700MPa or more (900MPa or more). By adopting such a structure, it has been confirmed that the mechanical strength (tensile strength) can be sufficiently improved in the Ni alloy in which the content of C exceeds 0.03 mass% (and is 0.20 mass% or less).
On the other hand, in the test materials 1 to 4, as the content of C increases, the volume resistivity of the Ni alloy sheet material also changesIs large. Specifically, the Ni alloy sheets of test materials 1 and 2 had a volume resistivity of 7.6X 10-8Omega. m or less, and the volume resistivities of the Ni alloy sheets of test materials 3 and 4 were 9.4X 10, respectively-8Omega. m and 10.3X 10-8Omega.m. However, it is considered that the Ni alloy sheets of test materials 3 and 4 had a volume resistivity of 15X 10-8Omega.m or less (10.5X 10)-8Ω · m or less), is not a large value to the extent of being problematic in use, compared with the volume resistivity of the Ni alloy sheet materials of test materials 1 and 2.
In addition, it was confirmed in test materials 1 to 4 that the increase in volume resistivity was suppressed by making the total content of the additives and the unavoidable impurities 0.50 mass% or less (0.30 mass% or less). Further, it is considered that in the test materials 3 and 4, the increase in volume resistivity was reliably suppressed by making the total content of the additives and the inevitable impurities 0.50 mass% or less (0.05 mass% or less).
[ modified examples ]
The above-described embodiments and examples are to be considered as illustrative in all respects and not restrictive. The scope of the present invention is shown not by the description of the above embodiments and examples but by the summary of the invention, and further includes all changes (modifications) within the meaning and scope equivalent to the summary of the invention.
For example, in the above-described embodiment, the "Ni material for a battery" in the summary of the invention is applied to the negative electrode current collector 5b of the lithium ion secondary battery (battery 100), but the present invention is not limited thereto. In the present invention, the "Ni material for a battery" in the summary of the invention may be applied to other than the negative electrode current collector of the lithium ion secondary battery. For example, as in the first modification of the present embodiment shown in fig. 6, "Ni material for battery" in the summary of the invention may be used as the negative electrode current collector 205b of the unipolar negative electrode 205 in the so-called lithium ion solid-state battery 200. The lithium ion solid-state battery 200 includes: a unipolar positive electrode 204, a unipolar negative electrode 205, and a solid electrolyte 206 disposed between the unipolar positive electrode 204 and the unipolar negative electrode 205 in the Z direction. The unipolar positive electrode 204 includes: a positive electrode material 4 a; and a positive electrode current collector 204b in which the positive electrode material 4a is disposed on one surface (Z2 side) in the stacking direction (Z direction). The unipolar type negative electrode 205 includes: a negative electrode material 5 a; and a negative electrode current collector 205b in which the negative electrode material 5a is disposed on the surface on the other side (Z1 side) in the stacking direction.
As described above, the "Ni material for a battery" in the summary of the invention is used as the negative electrode current collector 205b of the lithium ion solid-state battery 200, and even if a large stress due to a large volume change caused by expansion and contraction of the negative electrode active material is repeatedly applied to the negative electrode current collector 205b, it is possible to reliably suppress the occurrence of a problem such as deformation in the negative electrode current collector 205b due to the repeated stress. Further, by using the negative electrode current collector 205b made of a Ni alloy containing more than 0.03 mass% and 0.20 mass% or less of C, and 0.50 mass% or less in total of additives and inevitable impurities, and the balance containing Ni, similarly to the above embodiment, even when the negative electrode current collector 205b is placed in a high-temperature environment (for example, 300 ℃ to 350 ℃ inclusive, including 300 ℃ to 400 ℃ inclusive, and the like) in order to cure the thermosetting resin of the negative electrode material 5a, it is possible to suppress the increase in resistance of the negative electrode current collector 205 b.
As in the second modification of the present embodiment shown in fig. 7 and 8, the "Ni material for battery" according to the present invention may be used as the current collector 307a of the bipolar electrode 307 in the so-called lithium ion solid-state battery 300. As shown in fig. 7, the lithium-ion solid-state battery 300 includes: a positive electrode 304 and a negative electrode 305 respectively located on the surface layer on the Z1 side and the surface layer on the Z2 side; a plurality of bipolar electrodes 307; and a plurality of solid electrolytes 306. A plurality of bipolar electrodes 307 and a plurality of solid electrolytes 306 are alternately laminated in the Z direction.
As shown in fig. 8, the bipolar electrode 307 includes: the current collector 307 a; a positive electrode material 4a disposed on the surface of the collector 307a on the Z1 side; and a negative electrode material 5a disposed on the surface of the collector 307a on the Z2 side. As described above, even when the "Ni material for a battery" according to the invention is used as the current collector 307a of the lithium ion solid-state battery 300, even if a large stress due to a large volume change caused by expansion and contraction of the negative electrode active material is repeatedly applied to the current collector 307a, it is possible to reliably suppress the occurrence of a problem such as deformation of the current collector 307a due to the repeated stress. Further, by using the current collector 307a made of a Ni alloy containing more than 0.03 mass% and 0.20 mass% or less of C and the balance containing Ni, it is possible to suppress the increase in resistance of the current collector 307a even when the current collector 307a is placed in a high-temperature environment (for example, 300 ℃) in order to cure the thermosetting resin of the positive electrode material 4a and the negative electrode material 5a, as in the above-described embodiment.
Further, as in a third modification of the present embodiment shown in fig. 9, the "Ni material for battery" of the summary of the invention may be used as a pair (a plurality of) case members 401a and 401b of a battery case member 401 in a so-called lithium-ion secondary battery 400. As shown in fig. 9, the lithium ion secondary battery 400 includes: a flat-surface case member 401 a; a case member 401b having a wavy sectional shape; an adhesive portion 402; and an electric storage element 403 and an electrolytic solution (not shown) respectively arranged in a space between the case member 401a and the case member 401 b.
The bonding portion 402 includes a thermosetting resin that connects the case members 401a and 401b to each other. In the storage element 403, the separators 406 are stacked in the Z direction so as to be disposed between the positive electrode 404 and the negative electrode 405. The case member 401a is connected to the positive electrode 404 of the electric storage element 403 and serves as a positive electrode terminal. The case member 401b is connected to the negative electrode 405 of the electric storage element 403, and thereby serves as a negative electrode terminal. The lithium ion secondary battery 400 is configured to be capable of being stacked in the stacking direction (Z direction).
In this way, even in the case where the "Ni material for a battery" of the invention is used as the case members 401a and 401b of the lithium-ion secondary battery 400, it is possible to reliably suppress the occurrence of a problem such as deformation of the battery case member 401 due to an external force or the like. Further, by using the case members 401a and 401b made of a Ni alloy containing more than 0.03 mass% and 0.20 mass% or less of C and the remainder containing Ni, it is possible to suppress the increase in resistance of the case members 401a and 401b even when the case members 401a and 401b are placed in a high-temperature environment (for example, 300 ℃) in order to cure the thermosetting resin of the bonding portion 402, as in the above-described embodiment.
In the above embodiment, the negative electrode current collector 5b (Ni material for battery) is formed in a foil shape having a thickness of 30 μm or less, but the present invention is not limited to this. In the present invention, the Ni material for a battery may have a thickness exceeding 30 μm. The shape of the Ni material for a battery is not limited to foil (plate) shape.
In the above embodiment, the example in which the negative electrode current collector 5b (Ni material for battery) is applied to a lithium ion battery has been described, but the present invention is not limited to this. In the present invention, the Ni material for a battery may be applied to a battery other than a lithium ion battery. For example, the Ni material for a battery may be applied to a sodium ion battery, a magnesium battery, or the like.
Claims (7)
1. A Ni material for a battery, characterized in that:
consists of a single Ni-alloy layer comprising: 0.10 to 0.20 mass% of C, 0.50 mass% or less in total of additives and inevitable impurities, and Ni as the remainder,
the additive is one or more than 2 of Mn, Si and Al.
2. The Ni material for a battery according to claim 1, wherein:
the tensile strength is 700MPa or more.
3. The Ni material for a battery according to claim 1, wherein:
the single Ni alloy layer contains 0.30 mass% or less in total of additives and unavoidable impurities.
4. The Ni material for a battery according to claim 1, wherein:
the thickness is 30 μm or less.
5. The Ni material for a battery according to claim 1, wherein:
the additive is one or more than 2 of Mn of 0.19-0.24 mass%, Si of 0.03-0.05 mass%, and Al of 0.002-0.012 mass%.
6. An anode, comprising:
the Ni material for a battery according to any one of claims 1 to 5; and
and a negative electrode material comprising a negative electrode active material and a thermosetting resin, which is disposed on the surface of the Ni material for a battery.
7. A battery case material, comprising:
a plurality of Ni materials for a battery according to any one of claims 1 to 5; and
and a bonding portion made of a thermosetting resin for connecting the plurality of cells to each other with a Ni material.
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| CN101593828A (en) * | 2008-05-27 | 2009-12-02 | 株式会社神户制钢所 | Anode material for lithium-ion secondary battery and manufacture method thereof and lithium rechargeable battery |
| CN103855368A (en) * | 2012-11-29 | 2014-06-11 | 华为技术有限公司 | Lithium ion secondary cell negative electrode active-material, preparation method of lithium ion secondary cell negative electrode active-material, lithium ion secondary cell negative electrode pole and lithium ion secondary cell |
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| JP2019016587A (en) | 2019-01-31 |
| JP6825603B2 (en) | 2021-02-03 |
| CN109216591A (en) | 2019-01-15 |
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