CN208608301U - Secondary battery cathode electrode current collector material - Google Patents

Secondary battery cathode electrode current collector material Download PDF

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Publication number
CN208608301U
CN208608301U CN201821236448.3U CN201821236448U CN208608301U CN 208608301 U CN208608301 U CN 208608301U CN 201821236448 U CN201821236448 U CN 201821236448U CN 208608301 U CN208608301 U CN 208608301U
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crystalline phase
area
layer
cuo
superficial layer
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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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 secondary battery cathode electrode current collector material of the utility model, including the Cu material for the plate being made of Cu or Cu alloy, Cu material has at least in plate face contains CuO crystalline phase and Cu2The superficial layer of O crystalline phase, the area by CuO crystalline phase/(area+Cu of CuO crystalline phase in superficial layer2The area of O crystalline phase) area ratio (percentage) that finds out is 22.0% or more.

Description

Secondary battery cathode electrode current collector material
Technical field
The utility model relates to secondary battery cathode electrode current collector material, it is related to including the layer being made of Cu (copper) or Cu alloy The secondary battery cathode electrode current collector material of (material).
Background technique
At present it is known that there is the secondary battery cathode electrode current collector material of the layer (material) including being made of Cu or Cu alloy.In this way Secondary battery cathode electrode current collector material for example have in Japanese Unexamined Patent Publication 2003-132894 bulletin disclosure.
In Japanese Unexamined Patent Publication 2003-132894 bulletin, disclose be made of Cu or Cu alloy, surface is by Cu2O covering Negative electrode collector (secondary battery cathode electrode current collector material).
But present inventor has found, in the negative electrode collector documented by Japanese Unexamined Patent Publication 2003-132894 bulletin There is following problems: antirust is insufficient, in an atmosphere oxidation progress, the contact resistance between negative electrode collector and active material Increase, is also increased using the resistance in the battery unit of negative electrode collector.
Wherein, it is generally accepted that chromic acid salt treatment is carried out for antirust: passing through the secondary electricity that will be made of Cu or Cu alloy Pond negative electrode collector is impregnated in the solution containing 6 valence Cr (chromium) with material, forms passivating film on surface.But due to processing after Solution contained in 6 valence Cr will increase carrying capacity of environment, so from the viewpoint of carrying capacity of environment carry out chromic acid salt treatment can not It takes.
Utility model content
The utility model is proposed to solve above-mentioned such problems, and a purpose of the utility model is benefit With the method other than forming passivating film by chromic acid salt treatment, the secondary battery negative pole collection with sufficient rust-proof effect is provided Electric body material.
Present inventor has made intensive studies to solve the above-mentioned problems, as a result, it has been found that: in Cu material (Cu layers) More than defined ratio to contain CuO (copper oxide (II)) crystalline phase rather than Cu on superficial layer2O (cuprous oxide (I)), thus It is able to suppress the progress of oxidation and generates rust-proof effect.Based on the discovery that so as to complete the utility model.
That is, the secondary battery cathode electrode current collector material of the first aspect of the utility model, including be made of Cu or Cu alloy Plate Cu material, Cu material at least in plate face have contain CuO crystalline phase and Cu2The superficial layer of O crystalline phase, in superficial layer By area/(area+Cu of CuO crystalline phase of CuO crystalline phase2The area of O crystalline phase) area ratio (percentage) that finds out is 22.0% or more.Wherein, so-called " area of CuO crystalline phase " refers to, is using x-ray photoelectron spectroscopy (XPS:X-ray Photoelectron Spectroscopy) obtain Cu2p narrow scan spectrum when Cu2p3/2Peak in, be based on CuO and Cu2O Peak, the area of CuO crystalline phase is relative to CuO crystalline phase and Cu2The ratio (area ratio) of total area of O crystalline phase.Together Sample, so-called " Cu2The area of O crystalline phase " refers to, the above-mentioned CuO and Cu based on XPS2Calculated by the peak of O, Cu2O crystalline phase Area relative to CuO crystalline phase and Cu2The ratio (area ratio) of total area of O crystalline phase.Also, so-called " Cu alloy " is Refer to the alloy of the Cu (copper) containing 50 mass % or more.
In the secondary battery cathode electrode current collector material of the first aspect of the utility model, as described above, by plate Cu material at least plate face have containing area ratio be 22.0% or more CuO crystalline phase superficial layer, be able to suppress oxidation exist The progress in the region of the specific surface layer for the Cu material being made of Cu or Cu alloy in the inner part.Even if not utilizing chromate to handle as a result, Passivating film is formed, sufficient rust-proof effect can be also generated, therefore, utilizes the side other than chromic acid salt treatment forms passivating film Method is capable of providing the secondary battery cathode electrode current collector material with sufficient rust-proof effect.As a result, being able to suppress in atmosphere The progress of middle oxidation is able to suppress the negative electrode collector being made of the secondary battery cathode electrode current collector for the Cu material for including plate with material With the contact resistance between the negative electrode active material layer on the surface (plate face of the Cu material of plate) for being bonded in the negative electrode collector Increase.Moreover, the progress in the specific surface layer zone oxidation in the inner part of Cu material can be inhibited using CuO crystalline phase, this Point is confirmed by aftermentioned experiment.
Also, the secondary battery cathode electrode current collector material of the second aspect of the utility model includes the covering material of plate, should The Cu layer that covering material includes core layer made of metal and engages with core layer and be made of Cu or Cu alloy, covering material is at least At Cu layers, the surface of opposite side has and contains CuO crystalline phase and Cu in a thickness direction with the face of core layer is engaged2O crystallization The superficial layer of phase, the area by CuO crystalline phase/(area+Cu of CuO crystalline phase in superficial layer2The area of O crystalline phase) it finds out Area ratio (percentage) be 22.0% or more.
In the secondary battery cathode electrode current collector material of the second aspect of the utility model, even being suitable for core layer It is also the same with the secondary battery cathode electrode current collector material of above-mentioned first aspect in the case where Cu layers of covering material, at least exist Cu layers with to engage the face of core layer the surface of opposite side has containing area ratio in a thickness direction be 22.0% or more The superficial layer of CuO crystalline phase, thus, it is possible to the Cu layer being made of Cu or Cu alloy specific surface layer in the inner part region inhibition The progress of oxidation.Sufficient rust-proof effect, therefore benefit can be generated not utilizing chromate processing formation passivating film as a result, With the method formed in addition to chromic acid salt treatment other than passivating film is formed, it is capable of providing comprising the covering with sufficient rust-proof effect The secondary battery cathode electrode current collector material of material.
In the secondary battery cathode electrode current collector material of above-mentioned second aspect, preferably core layer is by Ni, Ni alloy, Fe or Fe Alloy is constituted.With this configuration, then Cu layers of big core of mechanical strength ratio are able to use in covering material of the core layer with Cu layers Material layer.As a result, for example in the feelings for using secondary battery cathode electrode current collector to use material as the negative electrode collector of lithium ion secondary battery Under condition, it can reliably fight and be answered caused by the dilation due to the negative electrode active material configured on negative electrode collector Power.As a result, being able to suppress a problem that generating wrinkle or breakage on negative electrode collector.Moreover, so-called " Ni alloy " " Fe alloy " refers to the alloy of the Ni (nickel) containing 50 mass % or more and Fe (iron) respectively.
In the secondary battery cathode electrode current collector material of above-mentioned first aspect or second aspect, preferably in superficial layer by The area of the CuO crystalline phase/(area+Cu of CuO crystalline phase2The area of O crystalline phase) area ratio (percentage) that finds out is 30.0% or more.With this configuration, since the area of the CuO crystalline phase in superficial layer increases, so only with CuO crystalline phase The amount that area correspondingly increases, it will be able to be reliably suppressed the progress of oxidation in the specific surface layer region in the inner part of Cu material.
In the secondary battery cathode electrode current collector material of above-mentioned first aspect or second aspect, preferably superficial layer also contains Cu (OH)2Crystalline phase, the area by CuO crystalline phase/(area+Cu of CuO crystalline phase in superficial layer2Area+the Cu of O crystalline phase (OH)2The area of crystalline phase) area ratio (percentage) that finds out is 15.0% or more.With this configuration, then not only containing CuO crystalline phase and Cu2O crystalline phase but also contain Cu (OH)2In the superficial layer of crystalline phase, by the way that there is area ratio in superficial layer For 15.0% or more CuO crystalline phase, the progress of oxidation can be inhibited in the specific surface layer region in the inner part of Cu material.Also, Cu(OH)2(Kocide SD) is more unstable, such as negative because bonding on secondary battery cathode electrode current collector material via resin material Heat the etc. when active material of pole can make Cu (OH)2Variation is CuO.That is, also containing Cu (OH) by superficial layer2Crystallization Phase can further increase the area ratio of CuO crystalline phase using heating etc..
In the secondary battery cathode electrode current collector material of above-mentioned first aspect or second aspect, preferably 10 points of superficial layer are put down Equal roughness is 0.30 μm or more.With this configuration, then concave-convex surface can be being formed to be roughened to a certain degree On layer, negative electrode active material is reliably configured.
At this point, the resin material for being preferred for being bonded negative electrode active material is arranged on surface.With this configuration, then Because being formed in the increase of the bumps of superficial layer and the surface area of superficial layer, resin material can be made reliably to be sealed at superficial layer On.Thereby, it is possible to so that negative electrode active material is reliably bonded in the table of secondary battery cathode electrode current collector material using resin material On face.
Detailed description of the invention
Fig. 1 be indicate include the use of the utility model first embodiment secondary battery cathode electrode current collector material it is negative The schematic cross section perspective view of the lithium ion secondary battery of pole.
Fig. 2 is the cathode for indicating to have used the secondary battery cathode electrode current collector material of the utility model first embodiment Sectional view.
Fig. 3 is the secondary battery cathode electrode current collector material (negative electrode collector) for indicating the utility model first embodiment The enlarged cross-sectional view on superficial layer periphery.
Fig. 4 is the cathode for indicating to have used the secondary battery cathode electrode current collector material of the utility model second embodiment Sectional view.
Fig. 5 has been expressed as confirmation the utility model effect and the spectrum of the test material 2 in the superficial layer parsing that carries out Curve graph.
Fig. 6 has been expressed as confirmation the utility model effect and the spectrum of the test material 7 in the superficial layer parsing that carries out Curve graph.
Fig. 7 is the schematic perspective view of the disbonded test carried out for illustrating in order to confirm the utility model effect.
Specific embodiment
Hereinafter, the embodiment for being embodied the utility model based on Detailed description of the invention.
[first embodiment]
Firstly, referring to Fig.1~Fig. 3 is for having used the secondary battery negative pole current collection of the first embodiment of the utility model The structure of lithium ion secondary battery 100 (the hereinafter referred to as battery 100) and negative electrode collector 50 of body material (negative electrode collector 50) It is illustrated.
(lithium ion secondary battery)
As shown in Figure 1, battery 100 includes the lid material 2 of the opening of cylindric shell 1, seal casinghousing 1, is configured at shell 1 Interior charge storage element 3.Shell 1 is constituted by plating Ni steel plate, as the negative terminal of battery 100.
In shell 1, charge storage element 3 and electrolyte (not shown) are stored.Lid material 2 is made of aluminium alloy etc., doubles as battery 100 positive terminal.Charge storage element 3 by by anode 4, cathode 5 and be configured at anode 4 and cathode 5 between insulating properties every Film 6 is wound and is formed.Anode 4 includes: the positive electrode collector (not shown) being made of aluminium foil；Be configured at positive electrode collector Surface on positive electrode active material layer (not shown).Positive electrode active material layer includes the positive active materials such as LiMn2O4；With by The adhesive that resin material is constituted.
Battery 100 further include: for connecting the anode conducting wire material 7 of anode 4 and positive terminal (lid material 2)；With for connecting Connect the cathode conducting wire material 8 of cathode 5 and negative terminal (shell 1).Anode is made of with conducting wire material 7 aluminium foil, utilizes resistance welding Etc. on the positive electrode collector and lid material 2 that are engaged in positive 4.Cathode is made of with conducting wire material 8 copper foil, is engaged using resistance welding etc. In on the negative electrode collector 50 (referring to Fig. 2) and shell 1 of cathode 5.
(cathode)
As shown in Fig. 2, cathode 5 includes negative electrode collector 50 and the cathode being configured on the surface 50a of negative electrode collector 50 Active material layer 51.
Negative electrode active material layer 51 includes the cathode being made of C (carbon), Si (silicon), silica, Sn (tin) or tin oxide etc. Active material (not shown)；With the adhesive for being adhered to negative electrode active material on the surface 50a of negative electrode collector 50.
Negative electrode active material inhales storage or release Li with charge and discharge+(lithium ion), volume is increased and decreased as a result,.Therefore, With charge and discharge, apply stress on negative electrode collector 50 repeatedly.
Adhesive is made of resin material.Adhesive is by such as acrylic resin, polyimide resin or fluororesin (example Such as, Kynoar (PVDF)) it constitutes.Wherein, the adhesive being made of acrylic resin is able to use water-based slurry, energy It is enough that easily with coating, mixture layer (negative electrode active material layer 51) is set.Also, the adhesive being made of polyimide resin, Mechanical property is excellent, and mixture layer is difficult to avalanche.
Negative electrode collector 50 is constituted by secondary battery cathode electrode current collector with material, which includes with material The Cu material 52 for the plate (foil-like) being made of Cu or Cu alloy.Moreover, there are so-called C1000 systems for as Cu (fine copper) Oxygen-free copper, dephosphorization oxygen copper, the tough pitch copper of (JIS standard) etc..Also, for Cu alloy, there are C2000 systems (JIS standard) etc.. Moreover, the thickness t1 of negative electrode collector 50, in order to be carried out in battery 100 as a part of charge storage element 3 (referring to Fig.1) Winding is preferably smaller.
Wherein, in the first embodiment, Cu material 52 has superficial layer 53, and the superficial layer 53 is by as antirust treatment Oxidation processes form and contain CuO crystalline phase, Cu2O crystalline phase and Cu (OH)2Crystalline phase.Moreover, the CuO in superficial layer 53 is tied The area ratio (referred to as area ratio A1) of crystal phase, i.e. by the area of CuO crystalline phase/(area+Cu of CuO crystalline phase2O crystalline phase Area) the area ratio A1 (percentage) that finds out is 22.0% or more.Moreover, above-mentioned area ratio A1 is preferably bigger 30.0% Above, further it is 40.0% or more, is more preferably and Cu as the area of CuO crystalline phase2More than the area of O crystalline phase is same 50.0% or more.
Also, the area ratio (referred to as area ratio B1) of the CuO crystalline phase in superficial layer 53, another viewpoint, i.e. by CuO The area of the crystalline phase/(area+Cu of CuO crystalline phase2Area+the Cu (OH) of O crystalline phase2The area of crystalline phase) area that finds out Than B1 (percentage), preferably 15.0% or more.Moreover, above-mentioned area ratio B1 be more preferably bigger 30.0% or more, into One step is 35.0% or more, is still more preferably and Cu as the area of CuO crystalline phase2O crystalline phase and Cu (OH)2Crystalline phase Total area it is same above 50.0% or more.
Moreover, the area ratio of the CuO crystalline phase in superficial layer 53, Cu2The area ratio and Cu (OH) of O crystalline phase2Crystalline phase Area ratio, by carrying out XPS (nickname ESCA:Electron Spectroscopy for Chemical to superficial layer 53 Analysis (chemical analysis electronic spectrum)) and obtain.Specifically, obtaining the narrow scan spectrum of Cu2p using XPS (ESCA). Then, according to Cu2p3/2Combination can peak periphery spectrum, by the peak (933.6eV) of CuO crystalline phase, Cu2The peak of O crystalline phase (932.5eV)、Cu(OH)2The peak (935.1eV) of crystalline phase separates, and obtains CuO, Cu2O and Cu (OH)2The area of each crystalline phase Than.
Later, CuO and Cu are found out2The summation (referred to as total area A0) of the area at the peak of each crystalline phase of O.Then, it asks The peak of CuO crystalline phase area relative to the ratio of total area A0, i.e. by the area of CuO crystalline phase/(CuO crystalline phase Area+Cu2The area of O crystalline phase) value (percentage) that finds out, using the value as above-mentioned area ratio A1.Equally, Cu is found out2O The area at the peak of crystalline phase relative to the ratio of total area A0, i.e. by Cu2The area of O crystalline phase/(area of CuO crystalline phase+ Cu2The area of O crystalline phase) value (percentage) that finds out, using the value as area ratio A2.
Also, find out CuO, Cu2O and Cu (OH)2The summation (referred to as total area B 0) of the area at the peak of each crystalline phase. Then, the ratio of the area relative to total area B 0 at the peak of CuO crystalline phase is found out, i.e. by the area of CuO crystalline phase/(CuO knot Area+the Cu of crystal phase2Area+the Cu (OH) of O crystalline phase2The area of crystalline phase) value (percentage) that finds out, using the value as upper The area ratio B1 stated.Equally, Cu is found out2The area at the peak of O crystalline phase relative to the ratio of total area B 0, i.e. by Cu2O crystallization The area of the phase/(area+Cu of CuO crystalline phase2Area+the Cu (OH) of O crystalline phase2The area of crystalline phase) value (percentage that finds out Rate), using the value as area ratio B2.Equally, Cu (OH) is found out2Peak area relative to total area B 0 ratio, i.e. by Cu(OH)2The area of the crystalline phase/(area+Cu of CuO crystalline phase2Area+the Cu (OH) of O crystalline phase2The area of crystalline phase) it finds out Value (percentage), using the value as area ratio B3.
Moreover, Cu (OH)2It is more unstable, when because on negative electrode collector 50 via adhesive configuration negative electrode active material Heat etc. can change as CuO.Thereby, it is possible to further increase the area ratio of CuO crystalline phase.
Also, CuO crystalline phase, Cu can also be contained in superficial layer 532O crystalline phase and Cu (OH)2Knot other than crystalline phase Crystal phase.
Also, superficial layer 53 is formed in a manner of covering Cu material 52 by the substantially entire surface throughout Cu material 52.Moreover, surface Layer 53 is formed in the surface (plate face) of the bonding negative electrode active material layer 51 of at least Cu material 52, can also be along Cu material The surface of the end face (in Fig. 2, the left side and the right side of Cu material 52) of thickness direction (Z-direction) is not formed.Also, superficial layer 53 Thickness t2 is 50nm hereinafter, sufficiently small compared with Cu material 52.As a result, can press down when being engaged with cathode conducting wire material 8 System contact resistance due to superficial layer 53 increases.Also, the thickness t2 of superficial layer 53 is preferably 20nm or less.As a result, surface The thickness t2 of layer 53 is very small, therefore the appearance as negative electrode collector 50, is barely perceivable the crystallization for constituting superficial layer 53 The color of phase is (for example, the black or Cu of CuO2The rufous of O), and observe the color for constituting Cu the or Cu alloy of Cu material 52 (for example, being orange red for Cu).Moreover, in Fig. 2, in order to show it can be readily appreciated that being illustrated turgidly table The thickness t2 of surface layer 53.
Also, the surface 50a of 53 side of superficial layer of negative electrode collector 50 (has cathode in Fig. 2 for the cementation of superficial layer 53 The part of active material layer 51 and the part for being exposed to outside), using the roughening treatment for being directed to Cu material 52, it is formed with fine Bumps.Also, the thickness t2 for being formed in concave-convex at least part specific surface layer 53 on Cu material 52 is big, as a result, such as Fig. 3 institute As amplifying and turgidly indicating, superficial layer 53 is actually formed in a manner of covering each of Cu material 52 bumps, rather than Neat stratiform as shown in Figure 2.Then, negative electrode active material layer 51 enters and is formed in the bumps of Cu material 52, mentions as a result, The adaptation of high negative electrode collector 50 and negative electrode active material layer 51.
Moreover, in the negative electrode collector 50 being roughened by roughening treatment, the surface based on JIS B0601:1994 The arithmetic average roughness Ra of 53 side of layer, preferably 0.06 μm or more, more preferably 0.075 μm or more.Also, it is based on JIS B 10 mean roughness Rz of 53 side of superficial layer of 0601:1994, preferably 0.30 μm or more, more preferably 0.35 μm or more. Moreover, 10 mean roughness Rz of 53 side of superficial layer, particularly preferably 0.40 μm or more.Negative electrode active material layer 51 as a result, Cementation state relative to negative electrode collector 50 is good state.
(manufacturing method of negative electrode collector)
Secondly, the negative electrode collector 50 of the first embodiment for the utility model (use by secondary battery cathode electrode current collector Material) manufacturing method be simply illustrated.
Firstly, preparing the Cu material 52 for the foil-like being made of Cu or Cu alloy.Then, it is carried out at roughening for Cu material 52 Reason.In roughening treatment, so-called soft etching is carried out using the slightly acidic water solution containing potassium sulfate.As a result, in Cu material 52 Surface form fine bumps.Moreover, etching (dissolution) can be made slowly to carry out, therefore can by carrying out soft etching The Cu material 52 for the foil-like for inhibiting thickness small is hastily etched and excessive dissolution.
Then, it for having been carried out after the Cu material 52 of roughening treatment is neutralized, carries out as antirust treatment Oxidation processes.In antirust treatment, the surface oxidation of the Cu material 52 of roughening treatment will be had been carried out using aquae hydrogenii dioxidi. At this point, being easily formed CuO crystalline phase if increasing the ratio (concentration) of the hydrogen peroxide in aquae hydrogenii dioxidi.Specifically, logical It crosses and uses the aquae hydrogenii dioxidi for being calculated as 0.5% or more with mass percent concentration, the area ratio of CuO crystalline phase can be made 15.0% or more.Moreover, in order to increase the area ratio of CuO crystalline phase, it is preferable to use with mass percent concentration be calculated as 1.0% with On aquae hydrogenii dioxidi.It is formed as a result, on the surface of Cu material 52 and contains CuO crystalline phase and Cu2O crystalline phase and CuO crystalline phase The superficial layer 53 that area ratio is 15.0% or more.As a result, production negative electrode collector 50.
Later, negative electrode active material layer 51 is formed on the superficial layer 53 of made negative electrode collector 50.Specifically, Slurry containing negative electrode active material and adhesive is coated on to two surfaces of the thickness direction (Z-direction) of negative electrode collector 50 On layer 53, it is allowed to dry, solidification.The cementation negative electrode active material layer 51 on the superficial layer 53 of negative electrode collector 50 as a result, production Cathode 5.
The effect > of < first embodiment
In the first embodiment, following such effect can be obtained.
In the first embodiment, as described above, area ratio (area ratio by making the CuO crystalline phase in superficial layer 53 A1) it is 22.0% or more, oxygen can be inhibited in the region in the inner part of specific surface layer 53 for the Cu material 52 being made of Cu or Cu alloy The progress of change.Even if chromate processing is not utilized to form passivating film as a result, sufficient rust-proof effect can be also generated, therefore, benefit The method other than passivating film is formed with by chromic acid salt treatment, being capable of providing with sufficient rust-proof effect includes plate Cu material Secondary battery cathode electrode current collector is with material (negative electrode collector 50).As a result, being able to suppress the progress aoxidized in an atmosphere, and press down Make the negative electrode collector 50 being made of secondary battery cathode electrode current collector with material and the negative electrode active being bonded on negative electrode collector 50 The increase of contact resistance between material layer 51.
Also, in the first embodiment, the area ratio (area ratio A1) of the CuO crystalline phase preferably in superficial layer 53 is 50.0% or more, that is to say, that the area of the CuO crystalline phase in superficial layer 53 is Cu2The area of O crystalline phase it is same more than. With this configuration, due to that can have the area of CuO crystalline phase to be greater than Cu2The superficial layer 53 of the area of O crystalline phase, so only The amount correspondingly increased with the area of CuO crystalline phase, it will be able to the region in the inner part of specific surface layer 53 of Cu material 52 reliably Inhibit the progress of oxidation.
Also, in the first embodiment, the area ratio (area ratio B1) of the CuO crystalline phase preferably in superficial layer 53 is 15.0% or more.With this configuration, then not only containing CuO crystalline phase and Cu2O crystalline phase and contain Cu (OH)2Crystallization It is 15.0% or more CuO crystalline phase by the way that there is area ratio B1 in superficial layer 53 in the superficial layer 53 of phase, it can be in Cu material 52 The region in the inner part of specific surface layer 53 inhibit the progress of oxidation.Also, by superficial layer 53 also containing living using bonding cathode Heat etc. when property material layer 51 can change the Cu (OH) for CuO2Crystalline phase can more increase the area ratio of CuO crystalline phase (area ratio B1) therefore can be reliably suppressed the progress of oxidation in the region in the inner part of specific surface layer 53 of Cu material 52.
Also, in the first embodiment, preferably 10 mean roughness of superficial layer 53 are 0.30 μm or more.If this Sample is constituted, can be to be roughened to be formed on concave-convex superficial layer 53 reliably cementation negative electrode active material to a certain degree Layer 51.
Also, surface 50a in the first embodiment, is configured at for being bonded the adhesive of negative electrode active material.By This can reliably be glued using the increase of the surface area for the bumps and superficial layer 53 for being formed in superficial layer 53 on superficial layer 53 Tie adhesive.As a result, can reliably bond negative electrode active on the surface 50a of negative electrode collector 50 using adhesive Substance.Therefore, even if along with charge and discharge and in the case where applying stress repeatedly on negative electrode collector 50, the generation of wrinkle It is suppressed, negative electrode active material (negative electrode active material layer 51) can be reliably suppressed from the surface 50a of negative electrode collector 50 Fall off.
[second embodiment]
Secondly, being illustrated referring to Fig. 4 to the cathode 105 of the second embodiment of the utility model.In the second embodiment party It is different from the cathode 5 of first embodiment in the cathode 105 of formula, the example being made of for negative electrode collector 150 covering material 157 Son is illustrated.Moreover, marking identical symbol for similarly being constituted with first embodiment, omitting the description.
(cathode)
As shown in figure 4, cathode 105 includes negative electrode collector 150 and is configured on the surface 150a of negative electrode collector 150 Negative electrode active material layer 51.
Negative electrode collector 150 is constituted by secondary battery cathode electrode current collector with material, the secondary battery cathode electrode current collector material packet The covering material 157 of the plate of 3 layers of construction is included, which includes: core layer 154 made of metal；Respectively with core material A pair of of the Cu layer 155 and 156 layer 154 engagement and be made of Cu or Cu alloy.Cu layer 155 and the face of the side Z1 of core layer 154 connect It closes, and the face bonding of the side Z2 of Cu layer 156 and core layer 154.Then, in covering material 157, in core layer 154 and Cu layers 155 interface and the interface of core layer 154 and Cu layer 156, mutual layer form interatomic bond because of diffusion annealing, securely It is bonded together.Moreover, the thickness t11 of negative electrode collector 150, in order to which a part in battery as charge storage element is rolled up Around preferably smaller.
Core layer 154 is made of the big metal of mechanical strength ratio Cu layer 155 and 156.Such as preferred core layer 154 by Ni, Ni alloy, Fe or Fe alloy are constituted.Moreover, there are so-called NW2200 systems (JIS standard) etc. for as Ni (pure nickel).And And as Ni alloy for, there are Ni-Nb alloys and Ni-Ta alloy etc..Moreover, there are so-called for as Fe (pure iron) SPCC (JIS standard) etc..Also, for Fe alloy, there are stainless steel (ferrite, austenite, be precipitated solidification system and Martensitic) etc..For example, existing as the stainless steel for solidifying system is precipitated by the Cr of 17 mass %, the Ni of 7 mass %, 1 matter Measure Al, other additives and the inevitable impurity of %, the SUS631 (JIS standard) that surplus Fe is constituted.
Wherein, in this second embodiment, Cu layer 155 and Cu layer 156 are respectively provided with superficial layer 158 and 159.Superficial layer 158 and 159 is all same as the superficial layer 53 of above-mentioned first embodiment, contains what is formed by the oxidation processes as antirust treatment CuO crystalline phase, Cu2O crystalline phase and Cu (OH)2Crystalline phase.Moreover, the area ratio of the CuO crystalline phase in superficial layer 158 and 159 (area ratio A1), i.e. by the area of CuO crystalline phase/(area+Cu of CuO crystalline phase2The area of O crystalline phase) area ratio that finds out A1 (percentage) is 22.0% or more.Moreover, above-mentioned area ratio A1, preferably bigger 30.0% or more, be further 40.0% or more, be more preferably and Cu as the area of CuO crystalline phase250.0% or more more than the area of O crystalline phase is same.
Also, in superficial layer 158 and 159, the area ratio (area ratio B1) of the CuO crystalline phase in another viewpoint, i.e. By area/(area+Cu (OH) of CuO crystalline phase of CuO crystalline phase2The area of crystalline phase) the area ratio B1 (percentage) that finds out Preferably 15.0% or more.Moreover, above-mentioned area ratio B1, more preferably bigger 30.0% or more, be further 35.0% More than, more preferably it is and Cu as the area of CuO crystalline phase2O and Cu (OH)2More than total area of crystalline phase is same 50.0% or more.
Also, CuO crystalline phase, Cu can be contained in superficial layer 158 and 1592O crystalline phase and Cu (OH)2Other than crystalline phase Crystalline phase.
Also, superficial layer 158 and 159 is respectively formed in other than the face of Cu layer 155 and 156 engaged with core layer 154 Surface.Specifically, superficial layer 158 be formed in it is other than the face for the side Z2 of Cu layer 155 engaged with core layer 154, the side Z1 Face and side.Equally, superficial layer 159 is formed in other than the face for the side Z1 of Cu layer 156 engaged with core layer 154, the side Z2 Face and side.That is, superficial layer 158 and 159 is respectively formed in the position for not covering core layer 154 of Cu layer 155 and 156 It sets.Moreover, surface of the superficial layer 158 and 159 at least formed on the bonding negative electrode active material layer 51 of Cu layer 155 and 156, It (is not Cu layer 155 and 156 in Fig. 4 in the end face along thickness direction (Z-direction) of covering material 157 (negative electrode collector 150) The left side and the right side) formed can also be on surface.Also, the thickness t12b of the thickness t12a of superficial layer 158 and superficial layer 159 is It is 50nm or less.As a result, the thickness t12a of superficial layer 158 and the thickness t12b of superficial layer 159 are very small, therefore, as The appearance of negative electrode collector 150 is barely perceivable the color for the crystalline phase for constituting superficial layer 158 and 159 (for example, CuO's is black Color or Cu2The rufous of O), and observe the color for constituting Cu the or Cu alloy of Cu layer 155 and 156 (for example, in the feelings for Cu It is orange red under condition).Moreover, in Fig. 4, in order to show it can be readily appreciated that illustrating the thickness of superficial layer 158 in an exaggerated manner Spend the thickness t12b of t12a and superficial layer 159.
Also, the surface 150a of the side Z1 positioned at 158 side of superficial layer of negative electrode collector 150 (is superficial layer in Fig. 4 The part of 158 cementation negative electrode active material layer 51 and be exposed to external part) and negative electrode collector 150 positioned at superficial layer The side Z2 of 159 sides surface 150a (in Fig. 4 for superficial layer 159 cementation negative electrode active material layer 51 part and be exposed to External part), it is utilized respectively and is directed to the roughening treatment of Cu layer 155 and 156 and forms fine bumps.Specifically, base Arithmetic average roughness Ra in the surface side 150a of JIS B 0601:1994, preferably 0.06 μm or more, more preferably 0.075 μm or more.Also, 10 mean roughness Rz of the surface side 150a based on JIS B 0601:1994, preferably 0.30 μm or more, more preferably 0.35 μm or more.Moreover, 10 mean roughness Rz of the surface side 150a, particularly preferably 0.40 μm More than.
Also, the thickness t15 of thickness t14 and the Cu layer 156 of thickness t13, Cu layer 155 of core layer 154 ratio (t14: T13:t15), it is able to carry out appropriate adjustment.For example, arrive in order to balance should ensure Cu layer 155 and 156 sufficient conductivity and Ensure the high mechanical strength of core layer 154 again, the ratio (t14:t13:t15) of preferred thickness be in (1:8:1) to (3:4: 3) range of left and right.That is, the thickness t13 of core layer 154 is preferably in the thickness of covering material 157 (negative electrode collector 150) 40% or more 80% or less the Zuo You range of t11 is spent, the thickness t15 difference of thickness t14 and the Cu layer 156 of Cu layer 155 is preferred 10% or more 30% or less the Zuo You range of thickness t11 in covering material 157 (negative electrode collector 150).Therefore, core layer 154 thickness t13 is preferably greater than the thickness t15 of thickness t14 and the Cu layer 156 of Cu layer 155.At this point, further increasing cathode In the case where the mechanical strength of collector 150, preferably increase the ratio of the thickness of the core layer 154 of high mechanical strength.Also, In the case where the conductivity for further increasing negative electrode collector 150, preferably increase the small Cu layer 155 and 156 of volume resistivity The ratio of thickness.
Also, in order to can easily be done rolling, property and the Cu layer 156 of preferably Cu layer 155 in sandwich rolling Property is close.That is, it is preferred that making Cu layers while making Cu the or Cu alloy of 156 same composition of Cu layer 155 and Cu layer The thickness t15 of 155 thickness t14 and Cu layer 156 is roughly equal.Moreover, other compositions of second embodiment and above-mentioned first The composition of embodiment is identical.
(manufacturing method of negative electrode collector)
Secondly, the negative electrode collector 150 of the second embodiment for the utility model (use by secondary battery cathode electrode current collector Material) manufacturing method be simply illustrated.
Firstly, preparing the covering material 157 of 3 layers of construction, which includes moving back via cold rolling (sandwich rolling) and diffusion A pair of of Cu layer 155 and 156 that fire is formed by core layer 154 and engages respectively with core layer 154.Then, real with above-mentioned first It is same to apply mode, covering material 157 (a pair of of Cu layer 155 and 156) is roughened.In roughening treatment, use Slightly acidic water solution containing potassium sulfate carries out so-called soft etching.Moreover, being selected compared with core layer 154 in the soft etching Etch to selecting property Cu layer 155 and 156.Surface other than the face of a pair of of Cu layer 155 and 156 engaged with core layer 154 as a result, Form fine bumps.
Then, it for having been carried out after the covering material 157 of roughening treatment is neutralized, carries out at as antirust The oxidation processes of reason.In antirust treatment, similarly to the first embodiment, using aquae hydrogenii dioxidi, it will have been carried out thick Surface other than the face of a pair of of Cu layer 155 and 156 of roughening processing engaged with core layer 154 is aoxidized.As a result, in a pair Surface other than the face of Cu layer 155 and 156 engaged with core layer 154, is respectively formed containing CuO crystalline phase and Cu2O crystalline phase And the superficial layer 158 and 159 that the area ratio (area ratio A1) of CuO crystalline phase is 22.0% or more.In another viewpoint, respectively Form the superficial layer 158 and 159 that the area ratio (area ratio B1) of CuO crystalline phase is 15.0% or more.As a result, production cathode Collector 150.
Later, negative electrode active material layer 51 is formed on the superficial layer 158 and 159 of made negative electrode collector 150.By This, makes cathode 105.
The effect > of < second embodiment
In this second embodiment, following such effect can be obtained.
In this second embodiment, as described above, area ratio by making the CuO crystalline phase in superficial layer 158 and 159 (area ratio A1) is 22.0% or more, similarly to the first embodiment, in the ratio for the Cu layer 155 being made of Cu or Cu alloy The region of the specific surface layer 159 of the region in the inner part of superficial layer 158 and Cu layer 156 in the inner part is able to suppress the progress of oxidation.By This can also generate sufficient rust-proof effect, therefore, at chromate even if chromate processing is not utilized to form passivating film Reason forms the method other than passivating film, is capable of providing the secondary electricity including plate covering material 157 with sufficient rust-proof effect Pond negative electrode collector is with material (negative electrode collector 150).As a result, be able to suppress the progress aoxidized in an atmosphere, and inhibit by The negative electrode active material that the negative electrode collector 150 and negative electrode collector 150 that secondary battery cathode electrode current collector material is constituted are bonded The increase of contact resistance between layer 51.
Also, core layer 154 preferably in this second embodiment, is constituted by Ni, Ni alloy, Fe or Fe alloy.If this Sample is constituted, and in core layer 154 and the covering material 157 of Cu layer 155 and 156, is able to use mechanical strength greater than 155 He of Cu layer 156 core layer 154.Thereby, it is possible to reliably fight due to the negative electrode active material being configured on negative electrode collector 150 Stress caused by dilation.Moreover, other effects of second embodiment are same as the composition of above-mentioned first embodiment.
[embodiment]
Secondly, for being illustrated for the experiment (embodiment) for confirming the effect of the utility model and carrying out.In this reality With in novel example, change the condition of antirust treatment (oxidation processes) to make multiple secondary battery cathode electrode current collector materials.Then, Superficial layer parsing, corrosion test, surface roughness measurement are carried out with material for made multiple secondary battery cathode electrode current collectors And disbonded test.
(the 1st embodiment)
In the 1st embodiment, as raw material, the plate covering of 3 layers of construction of second embodiment shown in Fig. 4 is used Material 157.At this point, using the Ni-Nb alloy containing 5 mass %Nb as core layer 154.Also, as Cu layer 155 and 156, It uses oxygen-free copper (C1020, JIS standard).Moreover, making 10 μm of thickness t11 of covering material 157.Also, make the thickness of Cu layer 155 Spend t14, core layer 154 thickness t13, Cu layer 156 thickness t15 ratio (t14:t13:t15) be 1:3:1.
Then, for covering material 157, production without the test material 1 of roughening treatment and antirust treatment (oxidation processes), Only be roughened and without the test material 2 of antirust treatment and being roughened the test material 3 with antirust treatment ~7.Moreover, in roughening treatment, 30 DEG C are maintained at using containing the potassium sulfate for being calculated as 5% with mass percent concentration The slightly acidic water solution of temperature condition carries out so-called soft etching.
It,, will using aquae hydrogenii dioxidi for having carried out the covering material 157 of roughening treatment also, in antirust treatment The surface other than the face of the Cu layer 155 and 156 of the covering material 157 of roughening treatment engaged with core layer 154 has been carried out to carry out Oxidation.Specifically, containing the H for being calculated as 0.1% with mass percent concentration in test material 32O2The mistake of (hydrogen peroxide) In hydrogen oxide water, impregnate covering material 157 15 seconds.At this point, aquae hydrogenii dioxidi to be maintained to 20 DEG C of temperature condition.In test material In 4, in addition to using containing the H for being calculated as 0.5% with mass percent concentration2O2Aquae hydrogenii dioxidi this point other than, remaining condition with It is identical to test material 3.In test material 5, in addition to using containing the H for being calculated as 1.0% with mass percent concentration2O2Hydrogen peroxide Other than this point of water, remaining condition is identical as test material 3.
In test material 6, the point and use being roughened in addition to 2 times of times to test material 2~5 are remained Other than the point of the aquae hydrogenii dioxidi of 40 DEG C of temperature condition, remaining condition is identical as test material 5.In test material 7, in addition to using Contain the H that 5.0% is calculated as with mass percent concentration2O2Aquae hydrogenii dioxidi this point other than, remaining condition with test material 6 it is identical. Roughening treatment condition and antirust condition is shown in table 1.Moreover, concentration shown in table 1 is mass percent concentration.
[table 1]
(superficial layer parsing)
Then, test material 1~7 it is respective in, utilize XPS (ESCA) connecing with core layer 154 to Cu layer 155 and 156 The crystalline phase of superficial layer of the removing in the surface of the end face of test material thickness direction (Z-direction) other than the face of conjunction is solved Analysis.Then, area ratio (area ratio A1, area ratio B1), the Cu of the respective CuO crystalline phase of test material 1~7 are obtained2O crystallization The area ratio (area ratio A2, area ratio B2) and Cu (OH) of phase2The area ratio (area ratio A3, area ratio B3) of crystalline phase.Specifically Ground is said, as recorded in the first embodiment, the narrow scan spectrum of Cu2p is obtained using XPS (ESCA).Later, from Cu2p3/2Combination can peak periphery spectrum in by the peak (933.6eV) of CuO crystalline phase, Cu2The peak of O crystalline phase (932.5eV) and Cu (OH)2The peak (935.1eV) of crystalline phase is separated.Then, CuO, Cu are obtained2O and Cu (OH)2It is each From crystalline phase area ratio (area ratio A1~A3, area ratio B1~B3).As an example, material 2 will be tested and tests the light of material 7 Spectrum is shown in Fig. 5 and Fig. 6.Moreover, in fig. 5 and fig., horizontal axis is to combine energy (eV), and the longitudinal axis is every counting in 1 second (c/s), Show the spectrum and CuO, Cu of actual measurement2O and Cu (OH)2The corresponding spectrum of respective crystalline phase and their synthesis light Spectrum.
(corrosion test)
Also, to the respective carry out corrosion test of test material 1~7.Specifically, test material 1~7 is respectively arranged at guarantor Hold for temperature 60 C, relative humidity 85% Constant Temperature and Humidity Chambers in, keep 40 hours.Then, pass through observation test material 1~7 The table of the end face of removing edge test material thickness direction (Z-direction) other than the face of Cu layer 155 and 156 engaged with core layer 154 The extent of corrosion in face carries out antirust evaluation.
Moreover, antirust evaluation is carried out by the variation with the tone on the surface of visual observation test material.Specifically, Not to be roughened and the color (orange red) on the surface of the Cu material (oxygen-free copper) of antirust treatment and be roughened The color (pink) for handling and utilizing the surface of the Cu material (oxygen-free copper) of the antirust treatment of aquae hydrogenii dioxidi is evaluation criteria color, It is conceived to the color (black) and Cu of CuO crystalline phase2The color (rufous) of O crystalline phase.Visually observation test material, with evaluation base Quasi- color is that same tone does not confirm the situations of substantial variations, is judged as and does not carry out substantive corrosion (oxidation), as taking The case where obtaining the high rust-proof effect more than desired is labeled as circle mark (zero).In addition, confirming from evaluation criteria color slightly Variation is the situation of the tone of rufous, be judged as corrosion (oxidation) carry out slightly any but do not influence it is practical, as achieving The case where desired rust-proof effect, is labeled as triangular sign (△).In addition, it is dark brown for confirming from evaluation criteria color significant change The situation of the tone of color is judged as and corroded (oxidation), the case where as desired rust-proof effect is unsatisfactory for, is labeled as Fork mark (×).In addition, confirm the situation for changing the tone for dark brown significantly from evaluation criteria color, be judged as significantly into It has gone corrosion (oxidation), the case where as rust-proof effect cannot be played, has been labeled as double fork marks (××).
The result of superficial layer parsing and corrosion test is shown in table 2.
[table 2]
As superficial layer parsing and corrosion test as a result, area ratio A1 about superficial layer, is carrying out at roughening Test material 4 (55.1%)~examination that the area ratio A1 of CuO crystalline phase in the superficial layer of reason and antirust treatment is 22.0% or more It tests in material 7 (90.5%), confirms and obtain desired rust-proof effect.In particular, the area ratio A1 in CuO crystalline phase is In 62.0% or more test material 6 (74.8%) and test material 7 (90.5%), confirms and obtain high rust-proof effect.It is another Aspect, the area ratio A1 of the CuO crystalline phase in the superficial layer for having carried out roughening treatment and antirust treatment are less than 22.0% Test material 3 (21.9%) in, confirm and be unsatisfactory for desired rust-proof effect.In particular, in the area ratio A1 of CuO crystalline phase In small test material 2 (9.9%), confirms and there is no rust-proof effect.
Also, about the area ratio B1 in superficial layer, in the superficial layer for having carried out roughening treatment and antirust treatment In test material 4 (32.9%)~test material 7 (49.4%) that the area ratio B1 of CuO crystalline phase is 15.0% or more, confirms and obtain Obtained desired rust-proof effect.In particular, the test material 6 for being 39.0% or more in the area ratio B1 of CuO crystalline phase (46.4%) it and in test material 7 (49.4%), confirms and obtains high rust-proof effect.On the other hand, it is being roughened The area ratio B1 of CuO crystalline phase in the superficial layer of processing and antirust treatment is in test material 3 (14.9%) less than 15.0%, It confirms and is unsatisfactory for desired rust-proof effect.In particular, the test material 2 (8.3%) small in the area ratio B1 of CuO crystalline phase In, it confirms and there is no rust-proof effect.
Also, for 22.0% or more the area ratio A1 for making the CuO crystalline phase in superficial layer, preferably make in superficial layer The area ratio B1 of CuO crystalline phase is 15.0% or more, obtains rust-proof effect as test material 4~7, distinguishes: in antirust treatment In, it needs using containing the H for being calculated as 0.5% or more with mass percent concentration2O2Aquae hydrogenii dioxidi more than room temperature (20 DEG C) Temperature under the conditions of carry out as defined in it is more than test period (15 seconds).
In addition, not being roughened the test material 1 with antirust treatment, rust-proof effect is obtained.It is thought that because Are as follows: in test material 1, due to the degreasing for the strength for not carrying out usually carrying out with roughening treatment and antirust treatment, institute Lubricating oil when rolling remains in surface, and the progress of corrosion (oxidation) is inhibited because remaining in the lubricating oil on surface.
In addition, the concentration of hydrogen peroxide when may validate that according to the result of test material 3~5 through raising antirust treatment, The area ratio A1 and area ratio B1 of the CuO crystalline phase in superficial layer can be further increased.Moreover, according to the knot of test material 5 and 6 Fruit may validate that by rising temperature when antirust treatment, can further increase the area of the CuO crystalline phase in superficial layer Than A1 and area ratio B1.Moreover, although it is believed that by extending test period further, even down to concentration to a certain degree (for example, concentration that 0.5% is calculated as with mass percent concentration of test material 3), can also make the CuO crystalline phase in superficial layer Area ratio A1 is 22.0% or more, makes 15.0% or more the area ratio B1 of the CuO crystalline phase in superficial layer, still, secondary electricity The growth of time (productive temp time) required for the manufacture of pond negative electrode collector material is undesirable.
Also, about area ratio A1, A2, the area ratio B1 and B2 in superficial layer, confirm the area ratio in CuO crystalline phase A1 (B1) compares Cu2Area in the area ratio A2 (B2) of O crystalline phase big test material 4~7, with the CuO crystalline phase in superficial layer Cu is not up to than A1 (B1)2The test material 2 of the area ratio A2 (B2) of O crystalline phase is compared with 3, achieves higher rust-proof effect. Also, about the area ratio B1 and B3 in superficial layer, confirms and be greater than Cu (OH) in the area ratio B1 of CuO crystalline phase2Crystallization In the test material 5~7 of the area ratio B3 of phase, Cu is not up to the area ratio B1 of the CuO crystalline phase in superficial layer2O crystalline phase The test material 2 of area ratio B3 is compared with 3, achieves higher rust-proof effect.
And it is possible to think: because configuring negative electrode active material via adhesive on secondary battery cathode electrode current collector material When hot grade reason, Cu (OH)2It can change as CuO.It is therefore contemplated that: after negative electrode collector is made, CuO crystallization The area ratio of phase is bigger, and rust-proof effect improves.
(surface roughness measurement)
Then, in each test material of test material 1~7,155 He of Cu layer is determined using surface roughness measurement machine The surface roughness on the surface of the end face of the removing edge test material thickness direction other than 156 face engaged with core layer 154.And And as surface roughness, arithmetic average roughness Ra and 10 mean roughness based on JIS B 0601:1994 are determined Rz.Moreover, the surface roughness measurement device (Surfcom480A, the contact pilotage radius that are manufactured using company, Tokyo Seimitsu Co., Ltd It is 2 μm, scanning speed is 0.3mm/ seconds), cutoff value is set as 0.25mm, scanning distance (measured length) is set as 1.25mm。
(disbonded test)
Also, in each test material of test material 1~7, with the face of Cu layer 155 and 156 engaged with core layer 154 The surface of bonding negative electrode active material layer 51 in addition is object, determines the adaptation with adhesive.Specifically, such as Fig. 7 Shown, other than the face of the test respective Cu layer 155 of material 1~7 engaged with core layer 154 surface, is configured with as bonding The acrylic resin of agent (resin material).Specifically, test material 1~7 each test material Cu layer 155 and core layer 154 engagement the sides Z2 face and thickness direction (Z-direction) be opposite side the side Z1 surface, using spreader with 200 μm Thickness is coated with polyacrylic acid aqueous solution.Then, by the test material 1~7 after coating in the drying for being set as 150 DEG C of temperature conditions It is kept for 5 minutes in machine, is allowed to dry, solidification as a result,.Z1 other than the face of Cu layer 155 engaged with core layer 154 as a result, The surface of side forms the acrylate resin layer of 5 μ m thicks.
Later, resin band is pasted on the surface of acrylate resin layer.Then, it will be set using cupping machine (not shown) Rouge band vertically stretches, i.e., stretches on the thickness direction (Z-direction) of covering material 157.Then, it obtains and is produced in test material 1~7 The load applied when raw removing by cupping machine, by the load (N) divided by the width L (mm) of resin band, acquire test material 1~ 7 dhering strength (N/mm).
Surface roughness measurement and the result of disbonded test are shown in Table 3.Moreover, " foil/resin " shown in table 3 refers to The meaning between covering material and acrylate resin layer, " resin/band " refer to the meaning between acrylate resin layer and resin band.
[table 3]
As surface roughness measurement and disbonded test as a result, in the test material 1 without roughening treatment, wrapping Removing is produced between layer material and acrylate resin layer.Also, dhering strength also as low as 0.03N/mm.It is considered that this be because Are as follows: it is not roughened in test material 1, in the photons of the configuration acrylate resin layer of covering material, arithmetic is flat Equal roughness Ra and 10 mean roughness Rz are small.On the other hand, in the test material 2~7 for having carried out roughening treatment, Removing is produced between acrylate resin layer and resin band.That is, closely sealed strong between covering material and acrylate resin layer Degree is greater than the dhering strength (0.24N/mm or so) between acrylate resin layer and resin band.It is considered that this is because: trying It tests and has carried out roughening treatment in material 2~7, thus the arithmetic average roughness on the surface of the configuration acrylate resin layer of covering material Ra and 10 mean roughness Rz are fully big.Especially it is considered that: in 10 average roughness of the photons of covering material It spends in the test material 2~7 that Rz is 0.30 μm or more, the dhering strength between covering material and acrylate resin layer is fully high.And And, it is believed that: in the test material 4~7 that 10 mean roughness Rz of the photons of covering material are 0.35 μm or more, packet Dhering strength between layer material and acrylate resin layer is more fully high.
(the 2nd embodiment)
In the 2nd embodiment, in addition to use SUS631 as core layer 154 this point other than, using with above-mentioned 1st embodiment Same covering material 157.Moreover, having made for covering material 157 without roughening treatment and antirust treatment (oxidation processes) Test material 11 and be roughened the test material 12~14 with antirust treatment.Moreover, in roughening treatment, with it is upper The same condition of test material 1~5 for stating the 1st embodiment carries out soft etching.
In addition, in antirust treatment, it is same with above-mentioned 1st embodiment for having carried out the covering material 157 of roughening treatment Sample, using aquae hydrogenii dioxidi, by being connect with core layer 154 for the Cu layer 155 and 156 for the covering material 157 for having carried out roughening treatment Surface other than the face of conjunction is aoxidized.Specifically, being calculated as in test material 12 containing with mass percent concentration 1.0% H2O2In the aquae hydrogenii dioxidi of (hydrogen peroxide), covering material 157 is impregnated 15 seconds.At this point, aquae hydrogenii dioxidi is kept For 15 DEG C of temperature condition.In test material 12, in addition to using containing the H for being calculated as 3.0% with mass percent concentration2O2Mistake Other than this point of hydrogen oxide water, remaining is condition same as test material 11.In test material 14, in addition to using containing with quality hundred Specific concentration is divided to be calculated as 5.0% H2O2Aquae hydrogenii dioxidi this point other than, remaining is and the same condition of test material 11.It will be coarse Change treatment conditions and antirust condition is shown in Table 4.Moreover, concentration shown in table 4 is mass percent concentration.
[table 4]
Then, same as the 1st embodiment, carry out superficial layer parsing and corrosion test.Superficial layer parsing and corrosion test As a result it is shown in Table 5.
[table 5]
It is being roughened with corrosion test as a result, about the area ratio A1 in superficial layer as superficial layer parsing The test material 12 (22.3%) that the area ratio A1 of CuO crystalline phase in the superficial layer of processing and antirust treatment is 22.0% or more~ It tests in material 14 (64.8%), confirms and obtain desired rust-proof effect.In particular, confirming the face with CuO crystalline phase Test material 13 (23.8%) of the product than A1 less than 25.0% or more is compared, and is 30.0% or more in the area ratio A1 of CuO crystalline phase Test material 14 (the 64.8% of 60.0% or more) in, achieve high rust-proof effect.
Also, about the area ratio B1 in superficial layer, in the superficial layer for having carried out roughening treatment and antirust treatment In test material 12 (19.6%)~test material 14 (43.4%) that the area ratio B1 of CuO crystalline phase is 15.0% or more, confirm Obtain desired rust-proof effect.In particular, the test material 14 for being 21.0% or more in the area ratio B1 of CuO crystalline phase In (the 43.4% of 40.0% or more), confirms and achieve high rust-proof effect.
Rust-proof effect is achieved with the test material 11 of antirust treatment moreover, not being roughened.It can consider this Be because are as follows: it is same as above-mentioned 1st embodiment, test material 11 in, due to without along with roughening treatment and antirust treatment And the degreasing of the strength usually carried out presses down so lubricating oil when rolling remains in surface because remaining in the lubricating oil on surface The progress of corrosion (oxidation) is made.
Also, according to test material 12~14 result may validate that it is same as above-mentioned 1st embodiment, pass through improve antirust The concentration of hydrogen peroxide when processing can further increase the area ratio A1 and area ratio B1 of the CuO crystalline phase in superficial layer.
Also, about the area ratio A1 in superficial layer, 2, area ratio B1 and B2, it may validate that the area in CuO crystalline phase It is greater than Cu than A1 (B1)2Area in the test material 14 of the area ratio A2 (B2) of O crystalline phase, with the CuO crystalline phase in superficial layer It is less than Cu than A1 (B1)2The test material 12 of the area ratio A2 (B2) of O crystalline phase is compared with 13, obtains higher rust-proof effect. And it is possible to confirm: about the area ratio B1 and B3 in superficial layer, being greater than Cu (OH) in the area ratio B1 of CuO crystalline phase2Knot In the test material 14 of the area ratio B3 of crystal phase, it is less than Cu with the area ratio B1 of the CuO crystalline phase in superficial layer2The face of O crystalline phase Test material 12 of the product than B3 is compared with 13, achieves higher rust-proof effect.
In addition, it is same as the 1st embodiment, carry out surface roughness measurement and disbonded test.Surface roughness measurement and The result of disbonded test is shown in Table 6.Moreover, " foil/resin " shown in table 6 refers between covering material and acrylate resin layer The meaning, " resin/band " refers between acrylate resin layer and resin band.
[table 6]
As surface roughness measurement and disbonded test as a result, same as above-mentioned 1st embodiment, do not carrying out it is thick In the test material 11 of roughening processing, removing is produced between covering material and acrylate resin layer.Also, dhering strength is also small, For 0.02N/mm.On the other hand, in the test material 12~14 for having carried out roughening treatment, in acrylate resin layer and resin band Between produce removing.That is, dhering strength between covering material and acrylate resin layer be greater than acrylate resin layer and Dhering strength (0.24N/mm or so) between resin band.Especially it is possible to think: 10 points of the photons of covering material are average In the test material 12~14 that roughness Rz is 0.35 μm or more, the dhering strength between covering material and acrylate resin layer is fully It is high.
According to the 1st embodiment and the 2nd embodiment as a result, may validate that the material regardless of core layer, in superficial layer In the covering material that the area ratio A1 of CuO crystalline phase is 22.0% or more, sufficient rust-proof effect is all achieved.And it is possible to really Recognize: regardless of the material of core layer, in the covering material that the area ratio B1 of the CuO crystalline phase in superficial layer is 15.0% or more, all Achieve sufficient rust-proof effect.As a result, it is possible to speculate: even by the above-mentioned first embodiment for not having core layer Cu material 52 constitute secondary battery cathode electrode current collector material, if the area ratio A1 of the CuO crystalline phase in superficial layer is 22.0% or more, it can also obtain sufficient rust-proof effect.And it is possible to speculate: even by not having the above-mentioned of core layer The secondary battery cathode electrode current collector material that the Cu material 52 of first embodiment is constituted, if the face of the CuO crystalline phase in superficial layer Product is 15.0% or more than B1, can also obtain sufficient rust-proof effect.
Although using Ni-Nb alloy as core layer also, in above-mentioned 1st embodiment, in above-mentioned 2nd embodiment, Use SUS631 as core layer, but as core layer, even with other than Ni, Ni-Nb alloy Ni alloy, Fe or Fe alloy other than SUS631, if the area ratio A1 of the CuO crystalline phase in the superficial layer of secondary battery cathode electrode current collector material It is 22.0% or more, it will be able to obtain sufficient rust-proof effect.Also, as core layer, Ni, Ni-Nb alloy also can be used Fe alloy other than Ni alloy in addition, Fe or SUS631, if in the superficial layer of secondary battery cathode electrode current collector material The area ratio B1 of CuO crystalline phase is 15.0% or more, then can obtain sufficient rust-proof effect.
And it is possible to speculate: although using oxygen-free copper as Cu layers in above-mentioned 1st and the 2nd embodiment, even Using Cu the or Cu alloy other than oxygen-free copper, if CuO crystalline phase in the superficial layer of secondary battery cathode electrode current collector material Area ratio A1 is 22.0% or more, can also obtain sufficient rust-proof effect.And it is possible to speculate: even with oxygen-free copper Cu or Cu alloy in addition, if the area ratio B1 of the CuO crystalline phase in the superficial layer of secondary battery cathode electrode current collector material is 15.0% or more, it can also obtain sufficient rust-proof effect.
And it is possible to think: although having used acrylic resin as adhesive in above-mentioned 1st and the 2nd embodiment, Even but other resin material (for example, polyimide resin or fluororesin etc.), it is also same as acrylic resin, with this The dhering strength of the covering material of utility model increases.Especially polyimide resin has and covering material compared with acrylic resin Dhering strength increase tendency, it can be considered that: fully increase with the dhering strength of the covering material of the utility model.
[variation]
Moreover, it should think: embodiments and examples of disclosure are not all to illustrate on whole points Restrictive content.The scope of the utility model is not limited to the explanation of above-mentioned embodiments and examples, but by right It is required that range defined, but also including whole changes (changes in the meaning statement and range same with claim Shape example).
For example, in the above-described first embodiment, showing secondary battery cathode electrode current collector material by being formed with superficial layer The example that 53 Cu material 52 is constituted, but the utility model is not limited to this.In the present invention, secondary battery negative pole current collection Body also may include the layer (coating etc.) other than Cu material with material.
In addition, in the above-described 2nd embodiment, showing secondary battery cathode electrode current collector material by being formed with superficial layer The example that the covering material 157 of 158 and 159 3 layers of construction is constituted, but the utility model is not limited to this.For example, secondary cell Negative electrode collector material can also only constitute 2 layers constructions of Cu layers of 1 layer by 1 layer of core layer and with superficial layer covering material structures At.Alternatively, it is also possible to be made of the covering material of the layer other than the Cu layer comprising core layer and with superficial layer.
In addition, showing in above-mentioned first and second embodiment and carrying out having used potassium sulfate as roughening treatment Soft etching example, but the utility model is not limited to this.In the present invention, if it is possible to carry out surface coarse Change, can also the method other than the soft etching by having used potassium sulfate be roughened.Moreover, because secondary battery negative pole The thickness of collector is fully small, so when using hastily Cu material and Cu layers of etching solution is corroded, Cu material and Cu layers of thickness Degree is easy to excessively become smaller.Therefore, in roughening treatment, preferably without using hastily corrosion Cu material and Cu layers of etching solution.
In addition, in the above-described first embodiment, showing to cover Cu material 52 throughout the substantially entire surface of Cu material 52 Mode form the example of superficial layer 53, but the utility model is not limited to this.It in the present invention, can also be with not time And the mode of the substantially entire surface of Cu material forms superficial layer.For example, it is also possible to only be prone to be drawn by the generation (oxidation) become rusty The two sides of the thickness direction of the Cu material for a problem that weldability risen reduces forms superficial layer.
In addition, in the above-described 2nd embodiment, showing in covering material 157, superficial layer 158 is formed in Cu layer 155 The side Z1 face (with the surface of the face opposite side engaged) and side, also, superficial layer 159 is formed in the Z2 of Cu layer 156 The example of face (with the surface of the face opposite side engaged) and side of side, but the utility model is not limited to this.At this In utility model, in covering material, superficial layer can also be not formed at Cu layers of side.
In addition, showing in above-mentioned first and second embodiment and being used to justify with material by secondary battery cathode electrode current collector The example of the lithium ion secondary battery (battery 100) of cartridge type, but the utility model is not limited to this.In the present invention, Secondary cell other than secondary battery cathode electrode current collector can also being used for lithium ion secondary battery with material.Alternatively, it is also possible to incite somebody to action Secondary battery cathode electrode current collector is not used in the pot of the shell 1 of cylindrical shape shown in FIG. 1 with material, and is used for the two of such as laminated-type Primary cell.

Claims (11)

1. a kind of secondary battery cathode electrode current collector material, it is characterised in that:
Cu material including the plate being made of Cu or Cu alloy,
The Cu material has at least in plate face contains CuO crystalline phase and Cu2The superficial layer of O crystalline phase, in the superficial layer by The area of the CuO crystalline phase/(area+Cu of CuO crystalline phase2The area of O crystalline phase) area ratio that finds out, be with percentage 22.0% or more.
2. secondary battery cathode electrode current collector material according to claim 1, it is characterised in that:
The area by CuO crystalline phase/(area+Cu of CuO crystalline phase in the superficial layer2The area of O crystalline phase) face that finds out Product ratio, with percentage for 30.0% or more.
3. secondary battery cathode electrode current collector material according to claim 1 or 2, it is characterised in that:
The superficial layer also contains Cu (OH)2Crystalline phase,
The area by CuO crystalline phase/(area+Cu of CuO crystalline phase in the superficial layer2Area+the Cu (OH) of O crystalline phase2 The area of crystalline phase) area ratio that finds out, with percentage for 15.0% or more.
4. secondary battery cathode electrode current collector material according to claim 1 or 2, it is characterised in that:
10 mean roughness of the photons are 0.30 μm or more.
5. secondary battery cathode electrode current collector material according to claim 4, it is characterised in that:
Resin material for being bonded negative electrode active material is set to surface.
6. a kind of secondary battery cathode electrode current collector material, it is characterised in that:
Covering material including plate, the covering material include core layer made of metal and engaged with the core layer and by Cu or The Cu layer that Cu alloy is constituted,
The covering material at least in described Cu layers and the surface that engages the face of core layer opposite side in a thickness direction, With contain CuO crystalline phase and Cu2The superficial layer of O crystalline phase, the area by CuO crystalline phase/(CuO knot in the superficial layer Area+the Cu of crystal phase2The area of O crystalline phase) area ratio that finds out, with percentage for 22.0% or more.
7. secondary battery cathode electrode current collector material according to claim 6, it is characterised in that:
The core layer is made of Ni, Ni alloy, Fe or Fe alloy.
8. secondary battery cathode electrode current collector material according to claim 6 or 7, it is characterised in that:
The area by CuO crystalline phase/(area+Cu of CuO crystalline phase in the superficial layer2The area of O crystalline phase) face that finds out Product ratio, with percentage for 30.0% or more.
9. secondary battery cathode electrode current collector material according to claim 6 or 7, it is characterised in that:
The superficial layer also contains Cu (OH)2Crystalline phase,
The area by CuO crystalline phase/(area+Cu of CuO crystalline phase in the superficial layer2Area+the Cu (OH) of O crystalline phase2 The area of crystalline phase) area ratio that finds out, with percentage for 15.0% or more.
10. secondary battery cathode electrode current collector material according to claim 6 or 7, it is characterised in that:
10 mean roughness of the photons are 0.30 μm or more.
11. secondary battery cathode electrode current collector material according to claim 10, it is characterised in that:
Resin material for being bonded negative electrode active material is set to surface.
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