CN102899519A - Rolled copper foil and negative electrode of lithium ion secondary battery using same - Google Patents
Rolled copper foil and negative electrode of lithium ion secondary battery using same Download PDFInfo
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- CN102899519A CN102899519A CN2012100397943A CN201210039794A CN102899519A CN 102899519 A CN102899519 A CN 102899519A CN 2012100397943 A CN2012100397943 A CN 2012100397943A CN 201210039794 A CN201210039794 A CN 201210039794A CN 102899519 A CN102899519 A CN 102899519A
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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
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- C22C9/00—Alloys based on copper
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- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C22C9/10—Alloys based on copper with silicon as the next major constituent
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Abstract
The invention relates to rolled copper foil and a negative electrode of lithium ion secondary battery using the same. The rolled copper foil not only is of high intensity, high heat resistance, high conductive rate and good processing ability and the like, and has high tightness of the resin contained in a negative electrode active material layer without applying coarse processing such as plating of electro-deposition particles on a surface of the copper foil. The rolled copper foil is characterized by comprising a main component of Cu, adding elements A containing one or more elements atomic radius is smaller than that of the Cu, and copper alloy containing unavoidable impurities, wherein variation of the atomic distance is below -0.002pm when a total of (atomic radius difference of each adding element of the adding element A and the Cu) plus (atom% of each adding element) is taken as the variation of atom distance caused by the adding element, and a total quantity of the adding element A is below 1.0 weight%.
Description
Technical field
The present invention relates to be suitable for lithium-ion secondary cell current collector, have the rolled copper foil of excellent resin closed and use the lithium ion secondary battery negative pole of this rolled copper foil.
Background technology
Lithium-ion secondary cell is also high owing to can obtaining high-voltage, energy density, therefore the battery that is used as the electronicss such as mobile personal computer (mobile PC), mobile termination, and as the driving battery of automobile, also just in many mechanisms, research and develop actively.
The essential structure of lithium-ion secondary cell is, repeatedly discharge and recharge by the lithium ion in the ionogen is mobile between the positive plate that is insulated by barrier film and negative plate, importantly find the material that to realize ionogen, barrier film, positive plate and the negative plate of this structure with high cycle characteristics.
The employed negative plate of lithium-ion secondary cell is made of the negative electrode collector take Copper Foil as material and the negative electrode active material layer that forms thereon usually.
With regard to the Copper Foil that consists of negative electrode collector, use the rolled copper foil that the rolling processing of thick lath (plain bar) enforcement of making by casting is made, the electrolytic copper foil that from the electrolytic solution that contains cupric ion, the metallic copper galvanic deposit is made.Wherein, rolled copper foil has the such feature that can control the copper crystal tissue of Copper Foil and copper alloy foil by making up rolling processing and heat treated.
The negative electrode active material layer that forms on the surface of Copper Foil mainly has the thickness about 100 μ m, can by the tackiness agents such as the carbon granules such as electrographite, natural graphite or coke and polyvinylidene difluoride (PVDF) (PVdF) and conductive auxiliary agent are mixed together in form pulp-like in METHYLPYRROLIDONE (NMP) equal solvent after, be coated on it on surface of Copper Foil and make its dry solidification and obtain.
For lithium-ion secondary cell, if repeatedly discharge and recharge, then owing to following expansion, the contraction of carbon granules of occlusion, the disengaging of lithium, carbon is easily peeled off from Copper Foil, thereby might cause the deteriorated etc. of the reduction of interelectrode short circuit, cell container and cycle characteristics.Therefore, as the negative electrode collector Copper Foil, require the high adaptation with the carbon that consists of negative electrode active material layer.Can be improved to some extent during with tackiness agent ratio in increasing slurry of the adaptation of carbon, but because the electroconductibility of electrode reduces on the contrary, not be effective way therefore.
Therefore, in order to address this problem, be known as in advance roughening, implement to form concavo-convex surface treatment at copper foil surface.As the method for roughened, the methods such as plating of known sandblasting, rolling, the mechanical mill that utilizes the uneven surface roll, electrolytic polishing, chemical grinding and galvanic deposit grain, in these methods, the plating of galvanic deposit grain especially commonly used.Proposed in the patent documentation 1～3 to process by utilizing these methods to carry out surface roughening, thereby sought with the raising of the adaptation of negative electrode active material layer and concentrate on the copper foil for lithium ion secondary battery that the stress of negative electrode collector relaxes when discharging and recharging.In these patent documentations, with regard to aforementioned patent document 1, weaken on the contrary in order to solve anchor effect inhomogeneous and the roughening particle that roughness is high, thereby can't obtain such problem of the high adaptation of negative electrode collector and negative electrode active material, take to implement repeatedly the method for plating processing or reflow treatment, had complicated structure with the roughening particle that utilizes low roughening degree at copper foil surface.
In addition, disclose in the patent documentation 4 for the strength of joint of the current collector that improves lithium ion battery and shell resin and the copper alloy current collector has been carried out the method for etch processes, as the method that the adaptation that makes copper collector and resin improves, usually carry out surface roughening and process.
On the other hand, with regard to the Copper Foil of the negative electrode collector that consists of lithium-ion secondary cell, not only improve the adaptation with above-mentioned negative electrode active material layer, and require to have as high strength raw-material fundamental characteristics, all the time, high heat resistance, high conductivity (Guide Electricity leads) and good processibility etc.As its method, the various elements such as Cr, Zr, Ag, Sn, Zn, Fe, Ni, Mg, P have been proposed in Cu, to add in the patent documentation 5～9.In addition, disclose in the patent documentation 10 containing in the situation that makes electric conductivity reduce such impurity element, reduced as far as possible its total use level.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-87561 communique
Patent documentation 2: TOHKEMY 2009-272086 communique
Patent documentation 3: TOHKEMY 2006-216518 communique
Patent documentation 4: TOHKEMY 2010-205507 communique
Patent documentation 5: TOHKEMY 2000-303128 communique
Patent documentation 6: TOHKEMY 2002-363669 communique
Patent documentation 7: Japanese kokai publication hei 11-339811 communique
Patent documentation 8: TOHKEMY 2009-242871 communique
Patent documentation 9: TOHKEMY 2006-40674 communique
Patent documentation 10: Japanese kokai publication hei 11-86871 communique
Summary of the invention
The problem that invention will solve
But, with regard to the method for record in the aforementioned patent document 1～4, because roughened is necessary operation, so the cost rising, cause that the high price of lithium-ion secondary cell is formatted.In addition, when carrying out the volume production of Copper Foil, need to carry out the precision control for the treatment of condition for applicable above-mentioned surface roughening treatment process, in the situation that speed up processing and processing in a large number is difficult to the stable uniform quality that obtains.Therefore, not only from the viewpoint of cost, also from the viewpoint of quality, adopt above-mentioned surface roughening treatment process can greatly hinder electromobile etc. to use extensively the popularizing of equipment of lithium-ion secondary cell.
In addition, in the aforementioned patent document 5～10, improve the method that the lithium ion secondary battery negative pole current collector is used intensity, thermotolerance, electric conductivity and the processibility etc. of Copper Foil although disclose, but for the raising of the adaptation of negative electrode active material layer, this technical task and solution are not provided record or enlightenment.Thus, in the conventional art, as the method for raising with the adaptation of negative electrode active material layer, only has the way that adopts the surface roughening treatment process.
The object of the present invention is to provide a kind of be intended to solve problem points in the conventional art as described above, not only have high strength, high heat resistance, high conductivity or a good processibility, and on copper foil surface, do not implement to utilize the galvanic deposit grain plating etc. roughened and with negative electrode active material layer in the high rolled copper foil of the adaptation of contained resin and used the lithium ion secondary battery negative pole of this rolled copper foil.
Solve the method for problem
The present invention has carried out various researchs in order to reach above-mentioned purpose, consequently, certain the specific correlationship that exists between atomic radius by utilizing the interpolation element in the rolled copper foil and the resin closed of addition and Copper Foil, make the composition optimizing of adding element, thereby realize, have following formation.
(1) the invention provides a kind of lithium-ion secondary cell current collector rolled copper foil, it is characterized in that, have take Cu as principal constituent, contain the interpolation elements A that comprises the one kind or two or more atomic radius element less than Cu and inevitably the copper alloy of impurity form, to (consist of the atomic radius that respectively adds element and Cu poor of described interpolation elements A) * summation of (respectively adding the atom % of element) is when adding the variable quantity of the caused interatomic distance of elements A, the variable quantity of this interatomic distance is below-0.002 micromicron (pm), and the total amount that described copper alloy is formed is during as 100 weight part, and the total amount of described interpolation elements A is below 1.0 % by weight.
(2) the invention provides aforementioned (1) described lithium-ion secondary cell current collector rolled copper foil, it is characterized in that, described interpolation elements A is one kind or two or more (wherein, except Fe and the two kinds of interpolation elements that consist of of P) that are selected from the element in the element set that is comprised of B, Be, Co, Cr, Fe, Ga, Ge, Mn, Ni, P, S and Si.
(3) the invention provides aforementioned (1) or (2) described lithium-ion secondary cell current collector rolled copper foil, it is characterized in that, the total amount that described copper alloy is formed is during as 100 weight part, and the total amount of described interpolation elements A is below 0.5 % by weight.
(4) the invention provides each described lithium-ion secondary cell current collector rolled copper foil in aforementioned (1)～(3), except described interpolation elements A, further contain the interpolation element B that comprises the one kind or two or more atomic radius element larger than Cu.
(5) the invention provides each described lithium-ion secondary cell current collector rolled copper foil in aforementioned (1)～(4), it is characterized in that, described interpolation element B is be selected from element in the element set that is comprised of Ag, Al, In, Mg, Sn, Ti, Zn and Zr one kind or two or more.
(6) the invention provides each described lithium-ion secondary cell current collector rolled copper foil in aforementioned (1)～(5), the variable quantity of described interatomic distance is below-0.007 micromicron (pm).
(7) the invention provides each described lithium-ion secondary cell current collector rolled copper foil in aforementioned (4)～(6), it is characterized in that, when forming copper alloy as 100 weight part, the total amount of described interpolation elements A and interpolation element B is below 0.5 % by weight.
(8) the invention provides each described lithium-ion secondary cell current collector rolled copper foil in aforementioned (1)～(7), have the following thickness of 20 μ m.
(9) the invention provides a kind of lithium ion secondary battery negative pole, it is characterized in that, use each described lithium-ion secondary cell current collector rolled copper foil in aforementioned (1)～(8), do not carry out this lithium-ion secondary cell current collector processed and comprised in the formation of the surface of described rolled copper foil adhesive resin with the surface roughening of rolled copper foil negative electrode active material layer.
The invention effect
Rolled copper foil of the present invention is take Cu as principal constituent, when adding the element of the one kind or two or more function with further raising intensity, thermotolerance or processibility etc., by making its addition optimizing, can not implement that surface roughening is processed and improve with negative electrode active material layer in the adaptation of contained resin, can help the long lifetime of lithium-ion secondary cell and the raising of security.Further be set in below the prescribed value by the total amount of will add element, can keep high conductivity, therefore can seek the raising of the capacity of lithium-ion secondary cell.
In addition, with regard to rolled copper foil of the present invention, element as the function with at least one raising in the characteristics such as the intensity of making, thermotolerance or processibility, by not only adding the atomic radius element less than Cu, also add simultaneously the atomic radius element larger than Cu according to the mode of variable quantity below prescribed value based on the interatomic distance of addition (atom %), can further improve in the characteristics such as intensity, thermotolerance, electroconductibility and processibility at least any, the wide ranges of the alloy composition that can be suitable for as rolled copper foil.In addition, with regard to rolled copper foil of the present invention, be below the 20 μ m by making thickness, rolled copper foil shared volume fraction in lithium ion secondary battery cathode reduces, therefore negative electrode active material can be fully filled, thereby the volume energy density of battery can be improved.
In addition, formed the lithium ion secondary battery negative pole of the negative electrode active material layer that contains adhesive resin on the surface of rolled copper foil of the present invention owing to can omit the surface roughening treatment process that became the high major cause of cost in the past, therefore can obtain with low cost the lithium ion battery of high-performance, high reliability and high life, industrially be extremely effective.
Description of drawings
Fig. 1 is the figure of the example of the expression atomic radius element set A less than Cu.
Fig. 2 is expression when adding atomic radius than the little element of Cu, the figure of the variation of the atomic arrangement that causes at rolling surface.
Fig. 3 is the figure of the example of the expression atomic radius element set B larger than Cu.
Fig. 4 is expression when adding atomic radius than the large element of Cu, the figure of the variation of the atomic arrangement that causes at rolling surface.
Fig. 5 is the schema of an example of the manufacturing process of expression rolled copper foil of the present invention.
Fig. 6 be the Cu alloy material of expression in the embodiments of the invention alloy composition, add total amount, the variable quantity of interatomic distance, the cross cut test (Acer Disk Mu Try test of element) result of determination and the figure of the measurement result of intensity and electric conductivity.
Fig. 7 is the figure of the measurement result of the result of determination of variable quantity, cross cut test of the alloy composition of the Cu alloy material in expression other embodiment of the present invention and the comparative example, the total amount of adding element, interatomic distance and intensity and electric conductivity.
Embodiment
Below, for embodiments of the present invention, Yi Bian be elaborated on one side with reference to accompanying drawing.
＜the mechanism that improves with the adaptation of resin 〉
With regard to having the Copper Foil that adds element, because the atomic radius that adds element is with the difference of the atomic radius (128pm) of Cu produce deformation (askew body) in lattice after, because the homogenizing of this deformation of generation makes the interatomic distance variation.In addition, according to the addition that adds element, the deformation quantity that produces in the lattice changes, thereby can adjust the variable quantity of interatomic distance.
If the atomic radius that adds element i is made as Ri, is made as Xi with utilizing atom % regulation to add element atom % during shared ratio in rolled copper foil, then the variation delta R of the interatomic distance of Copper Foil can calculate by following formula (1).
ΔR＝∑(Ri-128)×Xi (1)
Herein, the atom % of each element can mechanically be calculated by % by weight and the nucleidic mass of each element in whole Constitution Elements, is determined uniquely by the alloying constituent of aforementioned rolled copper foil.
The present invention is conceived to the variation delta R of above-mentioned interatomic distance, find Δ R can improve when negative with negative electrode active material layer in the adaptation of the resin that contains as tackiness agent, thereby finish.Namely, think and finish based on following new opinion: change owing to adding element if be considered as, carry out homogenizing by rolling processing etc. afterwards and the interatomic distance of rolled copper foil during equalization is compared with the interatomic distance of Cu and reduced, then the adaptation with resin improves.In addition we know, aforementioned Δ R less (as the absolute value of Δ R, becoming large), raising is larger with the effect of the adaptation of resin.
Among the present invention, if Δ R be not-below the 0.002pm, then can not get improving the effect with the adaptation of resin.Among the present invention, in order significantly to improve the adaptation with resin, the value of preferred Δ R further is-below the 0.007pm.Δ R can at random adjust according to atomic radius and the ratio in rolled copper foil (atom %) of adding element.Δ R can reduce by the ratio (atom %) of increase adding element, but it is worth when too small, and the sometimes decline of the electric conductivity of rolled copper foil becomes significantly, and perhaps the deformation of lattice becomes large, the internal stress increase.The lower value of Δ R can at random determine according to these characteristics, but among the present invention, for the increase of the decline that prevents electric conductivity, intracrystalline internal stress becomes significantly and is set as-1.000pm.But owing to saturated tendency being arranged at Δ R during less than-0.400pm with the raising effect of the adaptation of resin, so among the present invention, Δ R is-0.002～-scope of 1.000pm, be preferably-0.007～-scope of 0.400pm.
Among the present invention, although not clear about improving with the details of the mechanism of the adaptation of resin, can followingly think.
With regard to the variation delta R of interatomic distance, the atomic radius of element i is made as Ri, when atom % is made as Xi, thinks that in the negative electrode active material layer of copper foil surface coating contained resin is to be solidified at copper foil surface by the atom of copper foil surface and the valence f. and the mutual steady state that intermolecular forces was determined of resin that consist of between the atom of resin.Therefore think, the geometric match of certain the specific periodic molecular structure that has by the resin of optimizing as organic compound and the interatomic distance of copper foil surface, can further improve the steady state of the resin that solidifies at copper foil surface, help to make the resin closed raising of Copper Foil.Usually the periodic molecular structure that occurs in the resin is less than the interatomic distance of copper, therefore can infer, and be negative value by the variation delta R that makes interatomic distance, be specially-below the 0.002pm, can make the resin closed raising of Copper Foil.
＜have an interpolation elements A of the atomic radius less than Cu 〉
Among the present invention, for the variable quantity that makes the Copper Foil Atom spacing take Cu as principal constituent is negative value, in the copper alloy of Copper Foil, add one kind or two or more atomic radius than the little element of Cu as adding elements A.As the atomic radius element less than Cu, various elements are arranged, but the decline of electric conductivity is little and can improve the element of intensity, thermotolerance or the processibility of Copper Foil, preferred B, Be, Co, Cr, Fe, Ga, Ge, Mn, Ni, P, S and Si shown in Figure 1 when making an addition in the copper alloy.Among Fig. 1, with the atomic radius contrast expression of these elements.The atomic radius of each element shown in Figure 1 is the literature value of quoting from ball kind " Japanese Metallkunde meeting Knitting metal デ one タ Block Star Network ".The present invention is except element shown in Figure 1, and the amount that can also decline to a great extent with the physical property such as intensity, electric conductivity and processibility that do not make Copper Foil is added the (atomic radius: 120pm), O (atomic radius: 73pm) or N (atomic radius: the element such as 75pm) such as Se.
Fig. 2 is the figure that schematically illustrates of the variation of the atomic arrangement that causes at rolling surface when adding atomic radius than the little element of Cu.As shown in Figure 2, replaced by interpolation element shown in Figure 1 owing to the copper atom in the lattice deformation that imports by rolling processing etc. and homogenized at rolling surface, in the lattice of copper foil surface, the mode that reduces fifty-fifty with the interatomic distance between element works.Thus, the interatomic distance of Copper Foil is compared with the situation of fine copper and is reduced, and the variable quantity that makes interatomic distance is negative value.Herein, during the mean change quantity not sufficient 0pm of interatomic distance and surpass-0.002pm, the importing of adding the caused deformation of element be local, deformation quantity is little, so the variation of the caused interatomic distance of homogenizing is very little, can't fully obtain to improve the effect with the adaptation of resin.Among the present invention, the mean change amount of interatomic distance is-0.002pm is following, preferred-when 0.007pm is following, can improve play effect of the present invention such with adaptation resin.
The use of lithium-ion secondary cell is to the engine contour output power input of power supply of power truck or electromobile, the direction transition of high capacity.When height is exported discharging and recharging of power input, because the electric current that flows in lithium-ion secondary cell is large, if therefore the direct current resistance of battery current collector is large, then increase falls in the initial voltage with the product representation of the direct current resistance of the electric current that flows in lithium-ion secondary cell and lithium-ion secondary cell, is difficult to obtain the capacity of sufficient lithium-ion secondary cell.Therefore, by reducing the direct current resistance of lithium-ion secondary cell, can suppress initial voltage and fall, guarantee the capacity of sufficient lithium-ion secondary cell.
Therefore, among the present invention, the total amount that the copper alloy that consists of Copper Foil is formed is during as 100 weight part, and the addition of the element that atomic radius is less than Cu need to be set in below 1 % by weight, is preferably below 0.5 % by weight.If its addition surpasses 1 % by weight, then because the electric conductivity of Copper Foil significantly reduces, when therefore using Copper Foil as the lithium-ion secondary cell current collector, can't fully guarantee the capacity of lithium ion battery.If the addition at atomic radius little element than Cu surpasses the reduction of also wanting to suppress electric conductivity in the situation of 1 % by weight, need then to carry out that copper alloy forms studies in great detail, the appending etc. of the change of the manufacture method of Copper Foil and condition etc. or new manufacturing process, be difficult to obtain the cheaply rolled copper foil as effect of the present invention.If the addition of the element that atomic radius is less than Cu is below 1 % by weight, then can simplify copper alloy and form, manufacture method can not followed large change yet, can access desirable rolled copper foil.In addition, if the addition of the atomic radius element less than Cu is below 0.5 % by weight, then can significantly suppress the reduction of the electric conductivity of Copper Foil.Among the present invention, the electric conductivity of Copper Foil is more than the 70%IACS, be preferably more than the 80%IACS, and be below 0.5 % by weight by the addition that makes the atomic radius element less than Cu, can easily satisfy more than the 80%IACS.Herein, 1ACS represents with the comparative figure that " the standard annealed copper wire " that will be called International Anneald Copper Standard (international annealed copper cash standard) wire as 100% time has the electroconductibility of several %.
The addition of the element that atomic radius is less than Cu changes according to the atomic radius that adds element, get final product for the following amount of-0.002pm so long as satisfy the variable quantity of the interatomic distance of above-mentioned Copper Foil, but particularly, be more than 0.05 % by weight, more than preferred 0.10 % by weight by making it, not only can improve the adaptation with resin, the effect of also can be improved intensity, thermostability or the processibility of adding the rolled copper foil that element brings.
In addition, have in the interpolation elements A of the atomic radius less than Cu, add with regard to the element with regard to being consisted of by two kinds of Fe and P, in the embodiment 1 of aforementioned patent document 7, although invention thought is fully different from the present invention, but owing to having put down in writing the rolling paper tinsel of copper alloy that has same composition, do not carry out the surface roughening processing, therefore get rid of outside the present invention.
＜have an interpolation element B of the atomic radius larger than Cu 〉
Among the present invention, except above-mentioned atomic radius than the little element of Cu, by in the copper alloy of Copper Foil, add one kind or two or more atomic radius than the large element of Cu as adding element B, can further improve in the characteristics such as intensity, thermotolerance, electroconductibility and processibility of rolled copper foil at least any.As the atomic radius element larger than Cu, various elements are arranged, but can improve the element of intensity, thermotolerance, electroconductibility or the processibility of Copper Foil when making an addition in the copper alloy, preferred Ag, Al, In, Mg, Sn, Ti, Zn and Zr shown in Figure 3.Among Fig. 3, with the atomic radius contrast expression of these elements.The present invention is except element shown in Figure 3, and the amount that can also decline to a great extent with the physical property such as intensity, electric conductivity and processibility that do not make Copper Foil is added the (atomic radius: 155pm), Sb (atomic radius: 215pm) or Bi (atomic radius: the element such as 160pm) such as Cd.
Herein, when adding atomic radius and being compared to the large element of the Cu of principal constituent, the interatomic distance of copper foil surface increases.Fig. 4 only uses that the atomic radius element larger than Cu is added in the copper alloy, the figure that schematically illustrates of the variation of the atomic arrangement that causes at rolling surface when only importing this element in the lattice of copper.As shown in Figure 4, and homogenized at rolling surface, in the lattice of copper foil surface, the mode that increases fifty-fifty with the interatomic distance between element works by rolling processing etc. in the deformation that is imported by interpolation element substitution shown in Figure 3 owing to the copper atom in the lattice.Thus, the interatomic distance of Copper Foil is compared increase with the situation of fine copper, the variable quantity that makes interatomic distance on the occasion of.The variable quantity of the interatomic distance of copper foil surface be on the occasion of the time, descend with the adaptation of resin.Therefore, among the present invention, need to determine kind and the addition of the element that atomic radius is larger than Cu so that because the mean change amount of the interatomic distance of the Copper Foil that above-mentioned interpolation elements A and the element B of adding produce is following for-0.002pm, preferably-below the 0.007pm.Like this, though add one kind or two or more atomic radius than the large element of Cu as adding element B, also can guarantee and the adaptation of resin, can access the lithium-ion secondary cell current collector Copper Foil that plays effect of the present invention.
In addition, same with the situation of above-mentioned interpolation elements A, add element B when adding in a large number, the decline of the electric conductivity of Copper Foil is remarkable, and the result can't fully guarantee the capacity of lithium ion battery.Therefore, among the present invention, when forming copper alloy as 100 weight part, the total amount of above-mentioned interpolation elements A and interpolation element B is below 1.0 % by weight, is preferably below 0.5 % by weight.The electric conductivity of Copper Foil also is more than the 70%IACS, more preferably more than the 80%IACS in the combination of above-mentioned interpolation elements A and interpolation element B.
The thickness of＜rolled copper foil 〉
Among the present invention, the thickness of rolled copper foil can be determined according to the characteristic of lithium ion battery, but be preferably below the 20 μ m.For the thick rolled copper foil of Thickness Ratio 20 μ m, in the lithium-ion secondary cell with its manufacturing, the shared volume fraction of rolled copper foil increases, and can't fully fill negative electrode active material, might cause the decline of volume energy density.
The manufacture method of＜rolled copper foil 〉
Fig. 5 is the schema of an example of the manufacture method of expression rolled copper foil of the present invention.
At first, preparation is as the ingot casting (ingot bar) (operation 1) of raw-material copper alloy.Herein, as copper alloy, use with Cu as principal constituent, contain interpolation elements A with atomic radius less than Cu, preferably contain the one kind or two or more interpolation element that comprises the element that is selected from B, Be, Co, Cr, Fe, Ga, Ge, Mn, Ni, P, S and Si, and the content that adds element is the following copper alloy of 1 % by weight.When wanting further to improve any in the characteristic of intensity, thermotolerance, electroconductibility and processibility of Copper Foil, use is except aforementioned interpolation elements A, also contain interpolation element B with atomic radius larger than Cu, preferably contain the one kind or two or more interpolation element that comprises the element that is selected from Ag, Al, In, Mg, Sn, Ti, Zn and Zr, and to comprise the total content that adds elements A and add the interpolation element of element B be the following copper alloy of 1 % by weight.
Then, implement the hot-rolled process (operation 2) carry out hot rolling.Behind the hot-rolled process, make the copper bar that is known as " blank " by the process annealing operation (operation 4) of repeatedly implementing aptly to carry out cold rolling cold rolling process (operation 3) and the cold rolling workhardness that causes of mitigation.Next, carry out blank anneal operation (operation 4 ').In the blank anneal operation, preferred its processing deformation in the past of fully mitigation.
Afterwards, the blank after the annealing is implemented final cold rolling process (operation 5 is also referred to as " finish rolling operation " sometimes) and the rolled copper foil (operation 6 is also referred to as " precision work Copper Foil " sometimes) of manufacturing specific thickness.In the final cold rolling process (operation 5), be more than 85% and less than 95% by making total degree of finish, except with respect in the past high degree of finish rolled copper foil, can reduce beyond total passage (パ ス) number of rolling process, the difficulty of the excessive caused rolling machining control of work hardening can also be avoided, load reduction and cost degradation to producing apparatus can be helped.Herein, total degree of finish is defined by following formula (2).
Total degree of finish (%)={ 1-(thickness of slab of the thickness of slab/blank behind the final cold rolling process) } * 100 (2)
Rolled copper foil behind the final cold rolling process is supplied to negative plate manufacturing process (operation 7).In the carrying out of operation 7, in (for example, the drying process after the negative electrode active material coating) or the drying process behind the combination lithium-ion secondary cell, usually carry out the thermal treatment under 100～200 ℃.
The rolled copper foil of the present invention of making by the manufacture method with such feature has high strength, high heat resistance, high conductivity and good processibility etc., can take into account high resin adaptation and cost degradation simultaneously.
The manufacture method of＜lithium ion secondary battery negative pole 〉
Negative plate manufacturing process shown in Figure 5 (operation 7) is described.The rolled copper foil of making through operation shown in Figure 5 1～6 is owing to having the high resin adaptation, therefore do not carry out surface roughening and processes and directly form negative electrode active material layer thereon.Negative electrode active material layer can use the system such as the carbon that will comprise hard carbon, soft carbon, the graphite such as electrographite, natural graphite system, and the particles oxide based or alloy systems such as Sn, Si composite wood such as lithium titanate evenly are mixed in the mixture that forms in the resin glue.At this moment, for the resin glue before the coating, consider the coating on even mixing or the rolled copper foil, in order to reduce viscosity, usually using the solvent that comprises n-methyl-2-pyrrolidone (NMP) equal solvent is tackiness agent.In addition, consider and use the caused operability of solvent to descend and carrying capacity of environment, also can use aqueous adhesive.Even mixing and when coating of resin glue can be carried out, the resin glue that does not contain solvent or water can also be used.When containing solvent or water, behind the coating resin tackiness agent, under 100～200 ℃, carry out as described above drying, thereby make current collector.As resin glue, so long as the resin that fluorine resin, polyacrylic ester or the styrene butadiene rubbers (SBR) etc. such as polyvinylidene difluoride (PVDF) (PVdF) have thermotolerance, physical strength and chemical stability just can use various resin glues.
Suitable lithium ion secondary battery negative pole constitutes among the present invention, directly formation comprises the mixture of particle and resin system tackiness agent as the formation of negative electrode active material layer on the rolled copper foil that does not carry out the surface roughening processing, and described particle comprises carbon system or the graphite system with electroconductibility.The rolled copper foil of the lithium ion secondary battery negative pole the application of the invention that obtains like this and have high strength, thermotolerance, high conductivity and good processibility, and do not have the high resin adaptation owing to carrying out the surface roughening processing yet, therefore can obtain with low cost the lithium ion secondary battery negative pole of high-performance, high reliability and high life.
Embodiment
Below more specify the present invention based on embodiment and comparative example, but the present invention is not limited to following embodiment.
[embodiment 1～26, comparative example 1～12]
Take oxygen free copper as mother metal, the copper alloy of melting Fig. 6 and alloy composition shown in Figure 7, casting ingot casting.Ingot casting is implemented hot rolling and formed sheet material, and after with order cold rolling, blank anneal sheet material being implemented, the degree of finish with 85～95% is implemented finally cold rolling, and making thickness is 10 μ m, thereby obtains the rolled copper foil of embodiment 1～26 and comparative example 1～12.
＜evaluation method 〉
Evaluation content separately is as described below.
(1) cross cut test
As with the evaluation method of the adaptation of resin, carry out following cross cut test.After the rolled copper foil of gained coating is adhesive resin as the solvent that polyvinylidene difluoride (PVDF) (PVdF) is solved homogeneously in n-methyl-2-pyrrolidone (NMP) gained of adhesive resin in embodiment 1～24 and comparative example 1～12, under 100～200 ℃, carry out drying, thereby make material that tackiness agent is formed at dry solidification on the copper foil surface (below be called the adhesive coated Copper Foil).
According to JIS H 8602, the grid of making 25 (1mm is square) on the binder film of aforementioned adhesion agent coated copper foil of cutter (below be called the cross cut test sheet).
The cellulose film band is sticked on the aforementioned cross cut test sheet, and the situation that grid of binder film is not also peeled off from Copper Foil when peeling off the cellulose film band is judged to be non-defective unit, even the situation that has a grid to peel off also is judged to be substandard products.
100 cross cut test sheets that the rolled copper foil that uses embodiment 1～24 and comparative example 1～12 is made carry out aforementioned judgement, with the example of 0 of substandard products be denoted as zero, the example of 1～5 of substandard products is denoted as △, the example of substandard products more than 6 is denoted as *, evaluation result is shown in Fig. 6 and Fig. 7.
(2) intensity of rolled copper foil
After the rolled copper foil of gained in embodiment 1～24 and the comparative example 1～12 cut out the test film of wide 15mm, long 200mm, this test film is carried out tension test, measure the intensity of rolling parallel direction according to ASTM E-345, show the result in Fig. 6 and Fig. 7.
(3) electric conductivity of rolled copper foil
After the rolled copper foil of gained in embodiment 1～24 and the comparative example 1～12 cut out the test film of wide 15mm, long 200mm, measure the resistance of this test film by four terminals measurement methods, calculate electric conductivity, show the result in Fig. 6 and Fig. 7.
From Fig. 6 and embodiment 1～24 shown in Figure 7 as can be known, the present invention is by containing the variable quantity that makes interatomic distance for-such interpolation elements A below the 0.002pm or adding elements A and add element B in copper alloy, even thereby do not carry out the roughened of copper foil surface, also good with the adaptation of resin.In addition, the variable quantity of interatomic distance is-when 0.007pm is following, significantly improves (embodiment 1～3,5～16,18～23) with the adaptation of resin.Relative therewith, shown in the comparative example 1～2 of Fig. 7, the variable quantity of interatomic distance even be negative value, also improves with the adaptation of resin more than 0.00 and in the scope of less than 0.002 time.In addition, interatomic distance is in the situation of such interpolation element set, can't obtain the adaptation (comparative example 4～12 of Fig. 7) with resin.
The present invention not only can improve the adaptation with resin, and interpolation elements A or interpolation elements A and interpolation element B by containing trace, thereby has higher intensity and electric conductivity as rolled copper foil.Relative therewith, when the content of the interpolation element in the copper alloy surpasses 1.0 % by weight, the decline of electric conductivity become significantly (comparative example 3 of Fig. 7).Therefore, the rolled copper foil of comparative example 3 can't obtain as the satisfiable capacity of lithium-ion secondary cell, can not use as current collector.In addition, when the content of the interpolation element in the copper alloy surpasses 0.5 % by weight, the decline of electric conductivity becomes large ( embodiment 13,16 of Fig. 6), to applicable restricted with purposes such as power supplys of the engine of the power truck that requires high-output power, high capacity or electromobile.
The present invention improves the purpose such with the adaptation of resin in order to reach, need to contain add the elements A group any one as adding element.Except adding the elements A group, further contain in the situation of the atomic radius interpolation element B group larger than Cu take the variable quantity of interatomic distance as-mode below the 0.002pm, not only improve with the adaptation of resin as can be known, and can improve at least any characteristic in intensity and the electric conductivity (with reference to the contrast of embodiment 1 with embodiment 18, embodiment 6 and embodiment 17,19,22 contrast, the contrast of embodiment 7 and embodiment 21).And with in the situation of adding element B, compare when only having the elements A of interpolation, although also find sometimes the decline of other characteristics, should descend little, can not cause large impact to the characteristic as current collector.Therefore, when improving each characteristic, can freely be chosen in according to characteristic that should be preferential the combination of the interpolation element that contains in the rolled copper foil, the scope of copper alloy composition broadens.In addition, if also take in and when selecting to add element the cost degradation of the lithium-ion secondary cell that then can go far towards finally to obtain for the cost that adds element, the easness of acquisition etc.
Fig. 6 and embodiment 1～24th shown in Figure 7, the evaluation result when using particularly polyvinylidene difluoride (PVDF) (PVdF) as resin glue, but among the present invention, use in the situation of aqueous adhesive of its outer resin glue, for example styrene butadiene rubbers (SBR), also confirmed to obtain the evaluation result identical with embodiment 1～21., after the aqueous adhesive of styrene butadiene rubbers (SBR) is coated on the rolled copper foil, under 100～200 ℃, carry out drying herein, make making the tackiness agent material that dry solidification forms on copper foil surface as the sample of estimating usefulness.
According to the present invention, by in the copper alloy take Cu as principal constituent, take the variable quantity of interatomic distance as-0.002pm, preferably-the following mode of 0.007pm contains the interpolation element, it is below 1.0 % by weight that the total amount that simultaneously copper alloy is formed makes the content that adds element during as 100 weight part, below preferred 0.5 % by weight, thereby can access and not only have high strength, high thermostability, high conductivity and good processibility, and do not implement that surface roughening is processed and with negative electrode active material layer in the high rolled copper foil of the adaptation of contained resin and use the lithium ion secondary battery negative pole of this rolled copper foil.In addition, Copper Foil of the present invention not only goes for lithium-ion secondary cell, can also be as other the secondary cell collector Copper Foil that requires same characteristic, and availability is high.
Claims (9)
1. lithium-ion secondary cell current collector rolled copper foil, it is characterized in that, have take Cu as principal constituent, contain the interpolation elements A that comprises the one kind or two or more atomic radius element less than Cu and inevitably the copper alloy of impurity form, to (consist of the atomic radius that respectively adds element and Cu poor of described interpolation elements A) * summation of (respectively adding the atom % of element) is when adding the variable quantity of the caused interatomic distance of elements A, the variable quantity of this interatomic distance is below-0.002 micromicron, namely-below the 0.002pm, and the total amount that described copper alloy is formed is during as 100 weight part, and the total amount of described interpolation elements A is below 1.0 % by weight.
2. lithium-ion secondary cell current collector rolled copper foil as claimed in claim 1, it is characterized in that, described interpolation elements A is be selected from element in the element set that is comprised of B, Be, Co, Cr, Fe, Ga, Ge, Mn, Ni, P, S and Si one kind or two or more, wherein, except Fe and two kinds of interpolation elements that form of P.
3. lithium-ion secondary cell current collector rolled copper foil as claimed in claim 1 or 2 is characterized in that, the total amount that described copper alloy is formed is during as 100 weight part, and the total amount of described interpolation elements A is below 0.5 % by weight.
4. such as each described lithium-ion secondary cell current collector rolled copper foil in the claim 1～3, except described interpolation elements A, further contain the interpolation element B that comprises the one kind or two or more atomic radius element larger than Cu.
5. such as each described lithium-ion secondary cell current collector rolled copper foil in the claim 1～4, it is characterized in that, described interpolation element B is be selected from element in the element set that is comprised of Ag, Al, In, Mg, Sn, Ti, Zn and Zr one kind or two or more.
6. such as each described lithium-ion secondary cell current collector rolled copper foil in the claim 1～5, the variable quantity of described interatomic distance be-0.007 micromicron following, namely-below the 0.007pm.
7. such as each described lithium-ion secondary cell current collector rolled copper foil in the claim 4～6, it is characterized in that, when forming copper alloy as 100 weight part, the total amount of described interpolation elements A and interpolation element B is below 0.5 % by weight.
8. such as each described lithium-ion secondary cell current collector rolled copper foil in the claim 1～7, has the following thickness of 20 μ m.
9. lithium ion secondary battery negative pole, it is characterized in that, right to use requires each described lithium-ion secondary cell current collector rolled copper foil in 1～8, does not carry out this lithium-ion secondary cell current collector processed and comprised in the formation of the surface of described rolled copper foil adhesive resin with the surface roughening of rolled copper foil negative electrode active material layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011167281A JP2013028857A (en) | 2011-07-29 | 2011-07-29 | Rolled copper foil and lithium ion secondary battery negative electrode using the same |
| JP2011-167281 | 2011-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102899519A true CN102899519A (en) | 2013-01-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100397943A Pending CN102899519A (en) | 2011-07-29 | 2012-02-20 | Rolled copper foil and negative electrode of lithium ion secondary battery using same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2013028857A (en) |
| KR (1) | KR20130014308A (en) |
| CN (1) | CN102899519A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313386A (en) * | 2014-09-24 | 2015-01-28 | 襄阳锦翔光电科技股份有限公司 | Copper alloy for negative current collector of lithium ion battery |
| CN104711448A (en) * | 2013-12-13 | 2015-06-17 | 北京有色金属研究总院 | Copper alloy foil for power battery carrying fluid and processing method thereof |
| CN105779808A (en) * | 2014-12-16 | 2016-07-20 | 北京有色金属研究总院 | High-adhesion copper alloy foil for power battery and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017006970A1 (en) * | 2017-07-22 | 2019-01-24 | Wieland-Werke Ag | Copper casting alloy and casting process |
-
2011
- 2011-07-29 JP JP2011167281A patent/JP2013028857A/en not_active Withdrawn
- 2011-12-21 KR KR1020110138757A patent/KR20130014308A/en not_active Application Discontinuation
-
2012
- 2012-02-20 CN CN2012100397943A patent/CN102899519A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711448A (en) * | 2013-12-13 | 2015-06-17 | 北京有色金属研究总院 | Copper alloy foil for power battery carrying fluid and processing method thereof |
| CN104313386A (en) * | 2014-09-24 | 2015-01-28 | 襄阳锦翔光电科技股份有限公司 | Copper alloy for negative current collector of lithium ion battery |
| CN104313386B (en) * | 2014-09-24 | 2016-07-06 | 襄阳锦翔光电科技股份有限公司 | A kind of lithium ion battery negative collector copper alloy |
| CN105779808A (en) * | 2014-12-16 | 2016-07-20 | 北京有色金属研究总院 | High-adhesion copper alloy foil for power battery and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130014308A (en) | 2013-02-07 |
| JP2013028857A (en) | 2013-02-07 |
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Owner name: SH COPPER INDUSTRY CO., LTD. Free format text: FORMER OWNER: HITACHI CABLE CO., LTD. Effective date: 20130809 |
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Application publication date: 20130130 |