CN115881974B - Composite metal foil, electrode material and battery - Google Patents
Composite metal foil, electrode material and battery Download PDFInfo
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- CN115881974B CN115881974B CN202310154041.5A CN202310154041A CN115881974B CN 115881974 B CN115881974 B CN 115881974B CN 202310154041 A CN202310154041 A CN 202310154041A CN 115881974 B CN115881974 B CN 115881974B
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Abstract
The invention discloses a composite metal foil, which comprises a support body and a conductive layer, wherein the conductive layer is arranged on at least one surface of the support body; the elongation of the composite metal foil is more than or equal to 2%; the peel force of the conductive layer and the support is 0.3N/cm or more. The invention also discloses an electrode material of the battery and the battery using the composite metal foil, and by adopting the technical means of the invention, the problem of lower stripping force and elongation rate of the composite metal foil can be effectively solved by improving the structure of the metal foil, the quality of the metal foil is effectively improved, and the performance effect of the battery using the metal foil is improved.
Description
Technical Field
The invention relates to the technical field of metal foils, in particular to a composite metal foil, an electrode material and a battery.
Background
With the high-speed development of the electronic industry, the metal foil is widely applied to the fields of printed circuit boards, battery electrode materials, chip packaging and the like, and the metal foil plays an important role in conducting circuits and interconnecting components in the printed circuit boards. Currently, pure copper foil is generally used as an electrode material of a new energy battery. The high density of copper results in a thicker battery electrode material, which results in a decrease in the energy density of the lithium battery when copper foil is used as the electrode material.
A novel thin film composite copper foil disclosed in the prior art adopts a thin film as a support, and metal foils are arranged on two sides of the thin film composite copper foil. Namely, copper foil is formed on both sides of the film, and then a film composite metal foil is produced. Compared with the traditional pure metal foil, the weight of the composite metal foil is greatly reduced, and the energy density of the composite metal foil is improved when the composite metal foil is applied to a new energy battery.
However, the thin film composite metal foil in the related art has the following problems: the phase interface difference between the metal foil and the film is large in the use process of the film composite metal foil, so that the adhesion force of the metal foil on the film is poor, the extensibility is low, and the metal foil is easy to deviate, delaminate and even fall off. Therefore, the product can also cause delamination or falling of the metal foil during slitting and transportation, resulting in poor products and product defects. In addition, when the film composite metal foil is used as an electrode material, shrinkage or expansion can be generated in the battery, and the film composite metal foil is layered or falls off due to low elongation and poor stripping force, so that the positive and negative electrode interfaces in the battery are affected, the electrical performance of the battery is deteriorated, and the safety of the battery is also affected.
Disclosure of Invention
The embodiment of the invention aims to provide a composite metal foil, an electrode material and a battery, which can effectively solve the problem of lower stripping force and elongation of the composite metal foil by improving the structure of the metal foil, effectively improve the quality of the metal foil and improve the performance effect of the battery applying the metal foil.
To achieve the above object, an embodiment of the present invention provides a composite metal foil including: a support and a conductive layer disposed on at least one face of the support; the elongation of the composite metal foil is more than or equal to 2%; the peel force of the conductive layer and the support is 0.3N/cm or more.
As an improvement of the above scheme, the support is a single-layer structure or a composite structure composed of at least two layers.
As an improvement of the above, the surface roughness Ra of at least one surface of the support is 0.04 μm or more.
As an improvement of the above, a regulating layer is provided between the support and the conductive layer.
As an improvement of the above, the regulating layer includes at least one of a resin layer, a surface treatment agent, and a coupling agent.
As an improvement of the above-mentioned solution, a plurality of filler particles are provided in the adjustment layer to form a concave-convex structure on a side surface of the adjustment layer away from the support body, so that the conductive layer formed on the side surface of the adjustment layer away from the support body replicates the surface topography of the adjustment layer to have a corresponding concave-convex structure.
As an improvement of the scheme, the adjusting layer comprises a resin layer, and the weight of the filler particles accounts for 1% -30% of the weight of the resin layer.
As an improvement of the scheme, the particle size range of the filler particles is 0.05-15 mu m.
As an improvement of the scheme, in the regulating layer, the quantity of filler particles with the distance of 0.2 mu m less than or equal to D less than 4 mu m accounts for 0% -10%, the quantity of filler particles with the distance of 4 mu m less than or equal to D less than 10 mu m accounts for 50% -90%, and the quantity of filler particles with the distance of D less than or equal to 10 accounts for 0% -30%; wherein the sum of the percentages of the filler particles in the three distance ranges is less than or equal to 100 percent.
As an improvement of the above, the surface roughness Ra of the side of the adjustment layer remote from the support is 0.04 μm or more.
As an improvement of the above, the surface roughness Rz of the side of the adjustment layer away from the support is 0.5 μm or more.
As an improvement of the above-mentioned scheme, the surface roughness of the support and/or the adjustment layer is formed by at least one of etching, polishing, plasma treatment, electroplating, electroless plating, evaporation plating, and sputtering.
The embodiment of the invention also provides an electrode material applied to a battery, wherein the electrode material comprises the composite metal foil.
The embodiment of the invention also provides a battery, and the electrode material of the battery comprises the composite metal foil.
Compared with the prior art, the composite metal foil disclosed by the invention comprises a support body and a conductive layer, wherein the conductive layer is arranged on at least one surface of the support body; the elongation of the composite metal foil is more than or equal to 2%; the peel force of the conductive layer and the support is 0.3N/cm or more. Compared with the pure metal foil in the prior art, the composite metal foil provided by the embodiment of the invention has the advantages that the support body is arranged in the middle of the composite metal foil, so that the weight of the composite metal foil is greatly reduced, and the energy density of a new energy battery applying the composite metal foil is further improved. In addition, the elongation of the composite metal foil is optimized, the overall elongation of the composite metal foil is improved, and when the composite metal foil is applied to the field of new energy batteries, the composite metal foil with high elongation can effectively reduce the adverse effect of stress generated by a battery electrode during charging and discharging on an electrode material; meanwhile, the invention optimizes the stripping force between the conductive layer and the supporting body, effectively improves the stripping force between the supporting body and the conductive layer, and ensures that the supporting body and the conductive layer have better cohesiveness. The composite metal foil provided by the invention is a high-performance and high-adaptability metal foil material, and the problems of low stripping force and low elongation of the composite metal foil can be effectively solved by improving the structure of the metal foil, so that the quality of the metal foil is improved, and the performance effect of a new energy battery applying the metal foil is further improved.
Drawings
FIG. 1 is a schematic structural view of a first composite metal foil according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a second composite metal foil according to an embodiment of the present invention;
FIG. 3 is a schematic structural view of a third composite metal foil according to an embodiment of the present invention;
FIG. 4 is a schematic structural view of a fourth composite metal foil according to an embodiment of the present invention;
FIG. 5 is a schematic structural view of a fifth composite metal foil according to an embodiment of the present invention;
FIG. 6 is an electron microscope image of the conditioning layer surface of a composite metal foil in an embodiment of the invention;
FIG. 7 is a schematic structural view of a sixth composite metal foil according to an embodiment of the present invention;
FIG. 8 is a schematic view of the distance D of filler particles from the surface of a conditioning layer in an embodiment of the present invention;
wherein, 1, a supporting body; 2. a conductive layer; 3. a regulating layer; 4. a concave-convex structure; 41. filler particles.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description and claims, it should be understood that the terms "upper," "lower," "left," "right," "front," "rear," "top," "bottom," "inner," "outer," and the like indicate an orientation or positional relationship based on that shown in the drawings, merely to facilitate description of the embodiments of the invention, and do not indicate or imply that the devices or components referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the embodiments of the invention.
Furthermore, the terms first, second and the like in the description and in the claims, are used for descriptive purposes only and are not necessarily for describing relative importance or to indicate the number of features indicated or to imply a sequence or order. The terms are interchangeable where appropriate. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature.
The embodiment of the invention provides a composite metal foil, which comprises a support body 1 and a conductive layer 2, wherein the conductive layer 2 is arranged on at least one surface of the support body 1; the elongation of the composite metal foil is more than or equal to 2%; the peeling force between the conductive layer 2 and the support 1 is 0.3N/cm or more.
As an alternative embodiment, referring to fig. 1, a schematic structural diagram of a first composite metal foil provided in an embodiment of the present invention is provided, where the conductive layer 2 is disposed on either side surface of the support 1. As another alternative embodiment, referring to fig. 2, a schematic structural diagram of a second composite metal foil provided in the embodiment of the present invention is provided, where the conductive layers 2 are respectively disposed on two opposite surfaces of the support 1.
In practical application, the composite metal foil can be applied to the field of new energy batteries, and can also be applied to other various fields, such as the field of circuit boards, the field of semiconductor materials, the field of cables, and the like. In an alternative embodiment, when the composite metal foil is applied in the field of circuit boards, the composite metal foil is pressed together with the circuit board substrate through the conductive layer 2. In another alternative embodiment, when the composite metal foil is applied to the field of new energy batteries, the composite metal foil is used as an electrode material of the battery, active materials for battery reaction are arranged on the surface of the conductive layer 2, and the conductive layer 2 is tightly adhered to the electrode active materials.
The elongation percentage of the composite metal foil is optimized, and the elongation percentage of the composite metal foil is more than or equal to 2%, for example, can be 2%, 2.2%, 2.5%, 2.6%, 2.8%, 3%, 3.2%, 3.5%, 3.7%, 4%, 4.5%, 5%, 5.5%, 6.0%, 6.5%, 7.2%, 8%, 9% and the like, so that the overall elongation percentage of the composite metal foil is improved, and when the composite metal foil is applied to the field of new energy batteries, the composite metal foil with high elongation percentage can effectively reduce the adverse effect of stress generated by battery electrodes during charging and discharging on electrode materials; meanwhile, the peeling force between the conductive layer 2 and the support body 1 is optimized, and the peeling force between the conductive layer 2 and the support body 1 is more than or equal to 0.3N/cm, for example, the peeling force between the support body 1 and the conductive layer 2 can be effectively improved by 0.3N/cm, 0.5N/cm, 0.7N/cm, 0.9N/cm, 1.2N/cm, 1.3N/cm, 1.5N/cm, 1.6N/cm, 1.8N/cm, 1.9N/cm, 2N/cm, 2.2N/cm, 2.5N/cm, 3N/cm and the like, so that the support body 1 and the conductive layer 2 have better adhesion. The composite metal foil provided by the invention is a high-performance and high-adaptability metal foil material, and the problems of low stripping force and low elongation of the composite metal foil can be effectively solved by improving the structure of the metal foil, so that the quality of the metal foil is improved, and the performance effect of a new energy battery applying the metal foil is further improved.
As a preferred embodiment, the support 1 has a single-layer structure or a composite structure composed of at least two layers.
When the support body 1 is formed by laminating two or more layers of structures, each layer of structure can be made of the same material or different materials and can be adjusted according to actual use requirements.
Specifically, the material of the support 1 is at least one selected from polybutylene terephthalate, polyamide, polyterephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, aramid, acrylonitrile-butadiene-styrene, poly-p-phenylene terephthalamide, polyethylene, polyoxymethylene, epoxy resin, phenolic resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, polycarbonate, polyvinyl alcohol, polyethylene glycol.
It should be noted that the specific type of the material of the support body 1 may be selected according to the actually required function, and is not limited to the specific type, as long as the performance requirement can be met, and the detailed description thereof will not be repeated.
In a preferred embodiment, the surface roughness Ra of at least one surface of the support 1 is 0.04 μm or more.
The arithmetic average roughness Ra is specifically an arithmetic average of absolute values of ordinate values Z (x) of the profile over a sampling length, and the ordinate values Z (x) refer to distances from points on the profile to a center line of the profile. The arithmetic mean roughness Ra is an arithmetic mean deviation for assessing the surface profile, which is able to adequately reflect the characteristics of the surface microscopic geometry in terms of height.
More preferably, the surface roughness Ra of at least one surface of the support 1 is preferably 0.05 to 3 μm, and may be, for example, 0.08 μm, 0.09 μm, 0.10 μm, 0.8 μm, 1.2 μm, 1.5 μm, 2.0 μm, 2.3 μm, 2.8 μm, etc., although other values that meet the conditions may be set according to the actual situation, and the present invention is not limited thereto.
In addition, the surface of the supporting body 1 can be provided with a hole structure, the hole structure can be a through hole or/and a blind hole, and the surface of the supporting body 1 is provided with the through hole and/or the blind hole, so that the conductive layer 2 or the adjusting layer 3 attached to the surface of the supporting body 1 can be better attached to the surface of the supporting body 1, and the technical effect of improving the stripping force and the extensibility can be achieved. The existence of the through holes or the blind holes on the surface of the support body 1 is beneficial to the part of the conductive layer 2 or the adjusting layer 3 to extend into the through holes and/or the blind holes, so that a certain anchoring effect is achieved, and the stripping force and the elongation of the product are further improved.
Other reagents may be added to the support 1, for example, flame retardant or other reagents, and may be set as required by those skilled in the art.
For better technical effects, the support 1 is subjected to surface treatment to further improve the peeling force and the elongation, and the surface treatment is not limited to etching, polishing, plasma treatment, electroplating, electroless plating, evaporation plating, sputtering, corona and other treatment methods. In addition, the surface of the composite metal foil can be treated to realize corresponding product functionalization. For example, etching, polishing, plasma treatment, electroplating, electroless plating, evaporative plating, sputtering, corona and oxidation prevention treatments, etc., the specific manner of surface treatment and the location of treatment are the choices made by those skilled in the art according to actual needs.
As a preferred embodiment, a conditioning layer 3 is provided between the support 1 and the conductive layer 2. Referring to fig. 3, a schematic structural diagram of a third composite metal foil according to an embodiment of the present invention is provided, where the composite metal foil has a three-layer structure, the adjusting layer 3 is disposed on at least one side surface of the supporting body 1, and the conductive layer 2 is disposed on a side surface of the adjusting layer 3 away from the supporting body; referring to fig. 4, a schematic structural diagram of a fourth composite metal foil according to an embodiment of the present invention is provided, where the composite metal foil has a five-layer structure, and the adjusting layer 3 and the conductive layer 2 are sequentially disposed on two opposite surfaces of the support body 1, respectively.
It should be noted that, the adjusting layer 3 may be one or more layers, and is set according to actual requirements, which does not affect the beneficial effects obtained by the present invention.
By adopting the technical means of the embodiment of the invention, the adjusting layer 3 is arranged between the supporting body 1 and the conductive layer 2, and the adjusting layer 3 has better cohesiveness with the supporting body 1 and the conductive layer 2, thereby effectively improving the stripping force between the supporting body 1 and the conductive layer 2; the adjustment layer 3 can increase the elongation of the conductive layer 2, thereby increasing the elongation of the entire metal foil.
As a preferred embodiment, the conditioning layer 3 includes at least one of a resin layer, a surface treatment agent, and a coupling agent.
Wherein the material of the resin layer is at least one selected from phenolic, alkyd, amino, polyester, epoxy, polyurethane, acrylic, vinyl, fluororesin or cyanate, polystyrene, vinyl acetate, polyamide, polyimide, carbamate and melamine.
It should be noted that the specific type of the adjustment layer 3 may also be selected according to the function required by the actual metal foil, and is not limited to the specific type described above, as long as the improvement of the peeling force between the support and the conductive layer 2 and the improvement of the ductility of the composite metal foil can be satisfied, and the description thereof will not be repeated.
By adopting the technical means of the embodiment of the invention, the material of the regulating layer 3 is further optimized, and the regulating layer 3 made of any one material or any two or more materials can ensure that the regulating layer 3 has better cohesiveness with the support body 1 and the conductive layer 2, so that the stripping force between the support body 1 and the conductive layer 2 is improved, the electrolyte resistance of the electrode material of the new energy battery applying the composite metal foil can be improved, the use efficiency of the battery is improved, and meanwhile, the regulating layer 3 made of the material also has higher ductility and stronger impact resistance, and the composite metal foil has stronger ductility and tensile strength.
As a preferred embodiment, the surface roughness Ra of the conditioning layer 3 on the side remote from the support 1 is 0.04 μm or more.
More preferably, the surface roughness Ra of the adjustment layer 3 on the side away from the support 1 is 0.1 to 3 μm.
In the embodiment of the present invention, the roughness Ra of the surface of the adjusting layer 3 on the side far from the supporting body 1, that is, the surface near the conductive layer 2 is optimized, wherein the roughness Ra is 0.1 to 3 μm, for example, may be 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.9 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.3 μm, 2.7 μm, 3 μm, etc., and of course, other values meeting the conditions may also be set according to the actual situation, and are not specifically limited herein.
As a preferred embodiment, the surface roughness Rz of the side of the regulating layer 3 facing away from the support 1 is not less than 0.5 μm.
The roughness Rz is the sum of the average value of the n largest contour peak heights and the average value of the n largest contour valley depths in the sampling length, and n is more than or equal to 1; preferably, n=5. The roughness Rz can sufficiently reflect the peak height of the profile.
In the embodiment of the present invention, the roughness Rz of the surface of the adjusting layer 3 on the side far from the support 1 is optimized, preferably, the roughness satisfies 0.5. Ltoreq.rz. Ltoreq.3. Mu.m, for example, 0.5. Mu.m, 0.7. Mu.m, 0.9. Mu.m, 1.0. Mu.m, 1.2. Mu.m, 1.5. Mu.m, 1.8. Mu.m, 2. Mu.m, 2.3. Mu.m, 2.7. Mu.m, 3. Mu.m, etc., and of course, other values satisfying the conditions may be set according to the actual situation, and the specific limitation is not made here.
By adopting the technical means of the embodiment of the invention, the peeling force between the regulating layer 3 and the conductive layer 2 can be effectively improved by controlling the roughness Ra and the surface roughness Rz of the surface of the regulating layer 3, which is close to the conductive layer 2, so that the cohesiveness between the regulating layer 3 and the conductive layer 2 is improved, and the adverse phenomena of wrinkling, foaming, separation and the like between the conductive layer 2 and the regulating layer 3 are avoided; and moreover, the surface of the adjusting layer 3 has a certain roughness, so that the surface morphology of the conductive layer 2, which replicates the adjusting layer 3, also has a corresponding roughness, the ductility of the conductive layer 2 can be effectively improved, and the ductility of the composite metal foil is improved.
As a preferred embodiment, the surface roughness of the adjustment layer 3 is formed by at least one of adding filler particles, etching, polishing, plasma treatment, electroplating, electroless plating, evaporation plating, and sputtering.
Further, referring to fig. 5, which is a schematic structural diagram of a fifth composite metal foil provided in an embodiment of the present invention, a surface of the adjusting layer 3 on a side away from the supporting body 1 has a concave-convex structure 4, so that the conductive layer 2 formed on the surface of the adjusting layer 3 on the side away from the supporting body 1 replicates the surface topography of the adjusting layer 3 to have a corresponding concave-convex structure 4.
In the embodiment of the present invention, referring to fig. 6, an electron microscope image of a surface of a conditioning layer 3 of a composite metal foil far away from a support body 1 in the embodiment of the present invention is shown, in the production process of the composite conditioning layer 3, by including a concave-convex structure 4 in a micro-morphology of a surface of a side of the conditioning layer 3 far away from the support body 1, and further disposing a conductive layer 2 on a surface of a side of the conditioning layer 3 far away from the support body 1, that is, a surface of a side having the concave-convex structure 4, thereby, the conductive layer 2 replicates a morphology structure of the conditioning layer 3, and thus has a corresponding concave-convex structure property, so that the micro-morphology of the conductive layer 2 has a structure form similar to a spring, and the conductive layer 2 has a certain elongation, and thus the overall elongation of the composite metal foil is improved.
The embodiment of the invention provides a composite metal foil, which comprises a support body 1, a regulating layer 3 and a conductive layer 2, wherein the surface of one side of the regulating layer 3 far away from the support body 1 is provided with a concave-convex structure 4, so that the conductive layer formed on the surface of one side of the regulating layer 3 far away from the support body 1 replicates the surface morphology of the regulating layer 3 and is provided with a corresponding concave-convex structure 4. Compared with the pure metal foil in the prior art, the composite metal foil provided by the embodiment of the invention has the advantages that the support body 1 is arranged in the middle of the composite metal foil, the overall weight of the composite metal foil is obviously reduced, and the energy density of the composite metal foil applied to a new energy battery is further improved. In addition, the adjusting layer 3 arranged between the supporting body 1 and the conductive layer 2 can enable the supporting body 1 and the conductive layer to have good cohesiveness, effectively improve the peeling force between the supporting body 1 and the conductive layer 2, and reduce the bad conditions of bubbling, wrinkling, cracking and the like of the composite metal foil; in addition, the surface of the adjusting layer 3 is provided with the concave-convex structure 4, so that the conductive layer 2 replicates the shape of the concave-convex structure 4, the extensibility of the conductive layer 2 is improved, and the extensibility of the whole metal foil is further improved. Through the improvement to the metal foil structure, the problem that the stripping force and the extensibility of the composite metal foil are lower can be effectively solved, the quality of the metal foil is improved, and further the performance effect of the new energy battery applying the metal foil is improved.
As a preferred embodiment, referring to fig. 7, which is a schematic structural diagram of a sixth composite metal foil provided in the embodiment of the present invention, the embodiment of the present invention is further implemented on the basis of the above embodiment, and the adjusting layer 3 is provided with a plurality of filler particles 41 to form the concave-convex structure 4 on the surface of the adjusting layer 3 on the side far from the support body 1.
In the embodiment of the invention, a plurality of filler particles 41 are mixed in the adjusting layer 3, the roughness of the surface of the adjusting layer 3 far away from the supporting body 1 is mainly realized by adding the filler particles 41, and due to the distribution of the plurality of filler particles 41 in the adjusting layer 3, the surface of the adjusting layer 3 far away from the supporting body 1 forms a certain concave-convex structure 4, which is beneficial to the conductive layer 2 arranged on the surface to be carved with the shape of the concave-convex structure 4 on the surface to form a corresponding concave-convex structure, so that the extensibility of the conductive layer 2 is improved, the extensibility of the composite metal foil is further improved, the adhesiveness between the conductive layer 2 and the supporting body 1 is improved, the peeling force between the supporting body 1 and the conductive layer 2 is improved, and the phenomena of foaming, wrinkling, cracking and the like of the composite metal foil are reduced.
The filler particles 41 also provide the surface of the adjustment layer 3 on the side close to the support 1 with a certain roughness, and further improve the adhesion between the adjustment layer 3 and the support 1.
Preferably, the material of the filler particles is at least one selected from silica, aluminum hydroxide, calcium carbonate, titanium dioxide, aluminum oxide, magnesium hydroxide, magnesium carbonate, silicon carbide, barium sulfate, mica powder, silicon micropowder, talcum powder and kaolin.
The specific type of filler particles may be selected according to the function required for the actual metal foil, and is not limited to the specific type described above, as long as the improvement of the peeling force between the support and the conductive layer 2 and the improvement of the ductility of the composite metal foil are satisfied. The shape of the filler particles 41 in fig. 7 is merely exemplary, and the filler particles 41 may be in other shapes such as clusters, ice-forming, stalactites, dendrites, etc. due to differences in process means and parameters. The filler particles 41 in the embodiment of the present invention are not limited to the shape shown in the drawings and described above, and any filler particles 41 having a function of providing the surface roughness 4 and the roughness of the adjustment layer 3 are within the scope of the present invention. Also, in practice, the conditioning layer 3 of the composite metal foil may be formed first, and then the filler particles 41 may be formed on the conditioning layer 3 by other processes; of course, the conditioning layer 3 of the composite metal foil and the filler particles 41 may also be a unitary structure formed by a one-shot molding process. The material of the filler particles 41 may be the same as or different from that of the adjustment layer 3, and is not limited thereto.
As a preferred embodiment, based on the above example, the adjustment layer 3 includes a resin layer, and the ratio of the weight of the filler particles 41 to the weight of the resin layer is 1% -30%, more preferably 5% -20%, and most preferably 10% -15%;
and/or the filler particles have a particle diameter of 0.05 to 15 μm, more preferably 0.1 to 10 μm.
The particle diameter of the filler particles 41 refers to the maximum value of the width and/or height of the filler particles.
In the embodiment of the present invention, the adjusting layer 3 includes a resin layer, and the weight ratio of the filler particles 41 in the resin layer is optimized, and the weight ratio of the filler particles 41 in the resin layer is improved to 5% -20%, for example, may be 5%, 10%, 11%, 12%, 13%, 14%, 15%, 18%, 20%, etc., or may be other percentage values satisfying 5% -20%, which is set according to actual use conditions, and is not specifically limited herein. The particle size of each filler particle 41 itself is optimized, and the particle size of each filler particle 41 may be controlled to be in the range of 0.1 to 10 μm, for example, 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 6.8 μm, 7 μm, 7.2 μm, 7.5 μm, 7.8 μm, 8 μm, 9.5 μm, 10 μm, etc., and may be set depending on the actual use, although the particle size is not particularly limited thereto. Preferably, 50% or more of the filler particles have a particle diameter of 2 to 5 μm.
By adopting the technical means of the embodiment of the invention, the weight proportion and the grain diameter of the filler particles are controlled, so that the concave-convex structure 4 and the roughness of the surface of the regulating layer 3 are more reasonable, the regulating layer 3 has excellent adhesiveness to the conductive layer 2, the stripping force between the regulating layer 3 and the conductive layer 2 is improved, and the surface of the conductive layer 2 which replicates the surface morphology of the regulating layer also has certain concave-convex structure property, thereby effectively improving the ductility of the conductive layer 2 and improving the ductility of the composite metal foil.
In the embodiment of the present invention, the concave-convex structure 4 of the adjustment layer 3 is formed by adding the filler particles 41 to the adjustment layer 3, and the conductive layer 2 adjacent to the adjustment layer 3 replicates the concave-convex structure 4 on the surface of the adjustment layer 3, so that the ductility of the conductive layer 2 is effectively improved, and the overall ductility of the composite metal foil is further improved.
As a preferred embodiment, referring to FIG. 8, a schematic diagram of a distance D between filler particles on the surface of a regulating layer 3 in an embodiment of the present invention, wherein the distance between the regulating layer 3 and the nearest filler particles satisfies that the distance D is less than or equal to 0.2 μm and less than 4 μm, the quantity of filler particles is 0% -10%, the quantity of filler particles is 50% -90%, the quantity of filler particles is less than or equal to 4 μm and less than 10 μm, and the quantity of filler particles is 0% -30%, the distance between the regulating layer 3 and the nearest filler particles satisfies that the distance D is more than or equal to 10 μm; wherein the sum of the percentages of the filler particles in the three distance ranges is less than or equal to 100 percent.
The filler particles 41 filled in the adjustment layer 3 are spaced apart from other filler particles by a predetermined distance, and, referring to fig. 8, if any filler particle a has a filler particle b closest to the filler particle a, the distance between the center of the filler particle a and the center of the filler particle b is defined as a distance D. If several particles are clustered together, one agglomerate is calculated, and the distance between the centers of the agglomerates is defined as the distance between the agglomerates.
In the embodiment of the invention, the distance D between the filler particles a mixed in the regulating layer 3 and the filler particles b nearest to the filler particles and the quantity ratio of the filler particles a are optimized, and in the regulating layer 3, the distance D corresponding to 0% -10% of the filler particles a is set to be 0.2 μm < D < 4 μm, for example, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 1.3 μm, 1.8 μm, 2 μm, 2.5 μm, 3 μm, 3.3 μm, 3.6 μm and 3.9 μm;50% -90% of the filler particles have a corresponding distance D of 4 μm < D < 10 μm, for example 4 μm, 4.5 μm, 4.8 μm, 5 μm, 5.3 μm, 5.8 μm, 6 μm, 6.5 μm, 7 μm, 7.3 μm, 7.6 μm, 7.8 μm, 8 μm, 8.5 μm, 9 μm, 9.4 μm, 9.7 μm, 9.9 μm; the distance D corresponding to 0% -30% of the filler particles satisfies D.gtoreq.10 μm, for example, 10 μm, 10.5 μm, 10.8 μm, 11 μm, 11.5 μm, 11.8 μm, 12 μm, 12.5 μm, 13 μm, 13.5 μm, 14 μm, 14.5 μm, 15 μm; wherein the sum of the percentages of the filler particles a in the three distance ranges is less than or equal to 100 percent.
That is, in the embodiment of the present invention, the proportion of the number of filler particles with the distance D of 4 to 10 μm is set to be the largest, and the proportion of the number of filler particles with the distance D of 0.2 to 4 μm and the number of filler particles with the distance D of more than 10 μm is smaller or even 0, and the filler particles with different distance ranges and different number distribution proportions are mutually matched.
Preferably, the number of filler particles whose distance from the nearest filler particle satisfies 0.2 μm.ltoreq.D < 4 μm is 3% -7%, the number of filler particles whose distance from the nearest filler particle satisfies 4 μm.ltoreq.D < 10 μm is 65% -85%, and the number of filler particles whose distance from the nearest filler particle satisfies 10 μm.ltoreq.D < 18 μm is 5% -22%.
By adopting the technical means of the embodiment of the invention, the distance D between the filler particles and the nearest filler particles and the quantity distribution of the filler particles with different distances D are controlled, so that the surface structure of the regulating layer 3 is effectively improved, the surface structure effectively improves the adhesiveness of the surface of the regulating layer 3, and the stripping force between the supporting body 1 and the conductive layer 2 is further improved. The conductive layer 2 is arranged on the surface of the adjusting layer 3, so that the surface of the conductive layer 2, which is close to the side of the adjusting layer 3, replicates the surface morphology of the conductive layer 2, and further the extensibility of the conductive layer 2 for replicating the surface morphology of the conductive layer is effectively improved, the problem that the stripping force and extensibility of the composite metal foil are lower is effectively solved, the quality of the composite metal foil is improved, and further the performance effect of a new energy battery applying the composite metal foil is improved. The relief structure 4 in the adjustment layer 3 in this embodiment is realized by adding filler particles, and the surface morphology can also be realized by other means, such as etching, polishing, plasma treatment, electroplating, electroless plating, evaporation plating, sputtering, in a specific way that is set by a person skilled in the art as required.
In this embodiment, the composite metal foil may have a symmetrical structure or an asymmetrical structure. The symmetrical structure is characterized in that the supporting body 1 is taken as the center, and the two sides of the supporting body 1 are respectively provided with a conductive layer 2 with the same thickness or a regulating layer 3 and a conductive layer 2 with the same thickness. That is, the composite metal foil exhibits a centrally symmetrical structure with the support 1, wherein the materials used for the adjustment layer 3 and/or the conductive layer 2 may be the same or different. The asymmetric structure is characterized in that the supporting body 1 is taken as the center, the conductive layers 2 with different thicknesses or the adjusting layers 3 with different thicknesses and the conductive layers 2 are arranged on two sides of the supporting body 1, or the conductive layers 2 or the adjusting layers 3 and the conductive layers 2 are arranged on one side of the supporting body 1.
In this embodiment, the surfaces of the support 1 and the adjustment layer 3 are subjected to a surface treatment as required by those skilled in the art, and the surface treatment is performed by at least one selected from etching, polishing, plasma treatment, electroplating, electroless plating, vapor plating, and sputtering. Wherein, the surfaces of the support body 1 and the adjusting layer 3 can be combined by adopting the same or different surface treatment modes to realize the surface treatment.
The method for measuring the morphology or size parameters of the filler particles on the surface of the adjusting layer 3, including parameters such as particle size, quantity, distance and the like, is based on photographing of the morphology of the surface by a scanning electron microscope and statistics by combining measurement, statistics and analysis software. The specific method comprises the following steps:
(1) And (5) preparing a sample. And (3) randomly cutting a sample with a certain size on the whole copper foil product, preparing the sample according to the detection requirement of a scanning electron microscope, selecting a proper multiple (generally 2000-10000 times) under the scanning electron microscope, observing the section and the surface morphology of the copper foil sample, and shooting a morphology graph.
(2) Repeating the above steps for multiple times to obtain multiple topography maps of the same product, and carrying out statistics and analysis by means of statistics and analysis software.
In a preferred embodiment, the thickness of the support 1 is 2 to 8. Mu.m, for example, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 4.8 μm, 5 μm, 5.2 μm, 5.5 μm, 6 μm, 6.3 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm. Of course, other values satisfying this thickness range may be set as appropriate. Preferably, the thickness of the support 1 is 4.5-7 μm.
As a preferred embodiment, the conductive layer 2 is at least one metal of copper, aluminum, nickel, chromium, zinc, silver, gold, and titanium or an alloy containing at least one of the foregoing metals.
In the embodiment of the invention, the material of the conductive layer 2 is optimized, and the conductive layer 2 comprises a single metal conductive layer and/or an alloy conductive layer; the single metal conductive layer is made of any one material of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium, and the alloy conductive layer is made of any two or more materials of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium, or can be made of any two or more materials of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium and other materials by mixing.
When the composite metal foil is applied to the field of new energy batteries, the composite metal foil is used as a component of an electrode material of a battery, the surface of one side of the conductive layer 2 far away from the regulating layer 3 is tightly adhered with an electrode active substance, so that the falling phenomenon of the electrode active substance from the surface of the composite metal foil is reduced, the adhesion uniformity of electrolyte on the surface of a metal foil product and the electrode material active substance is obviously improved, the dimensional stability of the battery material and the uniformity and reliability of an electrochemical reaction process are improved, the electrochemical reaction efficiency is improved, the energy density of the battery is improved, the quality and the application life of the battery are improved, the problems of sticking and tilting in the process of coating the active substance and winding are also reduced, and the conveying efficiency and the product yield of the production process of the electrode material of the battery are improved. At the same time, the roughness of the side surface must not be too high, which would otherwise reduce the efficiency of the battery electrode.
As a preferred embodiment, the regulating layer 3 is formed on the surface of the support 1 by at least one method selected from the group consisting of knife coating, spray coating, electrophoretic coating, dip coating, and roll coating;
preferably, in this embodiment, a first conductive layer is disposed between the support 1 and the conductive layer 2, where the thickness of the first conductive layer is 1-100 nm. Then thickening treatment is carried out on the surface of the first conductive layer, so that the conductive layer 2 is formed; the first conductive layer is formed by at least one mode selected from vacuum sputtering, evaporation plating, magnetron sputtering, chemical plating, electroplating and chemical deposition.
It should be noted that the specific type of the material of the support body 1 may be selected according to the actually required function, and is not limited to the specific type, as long as the performance requirement can be met, and the detailed description thereof will not be repeated.
Electrolyte resistance, peel strength and elongation of a general metal foil and a composite metal foil of the structure of the embodiment of the present invention were respectively tested by way of specific examples, in which,
a represents the composite metal foil of the embodiment structure of the invention, and comprises composite metal foils A1, A2 and A3.
The composite metal foil A1 is: and coating a layer of silane coupling agent on two sides of the PET film, and electroplating a layer of copper foil on the surface of the silane coupling agent.
The composite metal foil A2 is: and coating a layer of polyurethane on both sides of the PET film, and electroplating a layer of copper foil on the surface of the polyurethane.
The composite metal foil A3 is: a polyurethane layer containing fumed silica (10 wt%) was coated on both sides of the PET film, and a copper foil layer was plated on the surface of the resin.
The common metal foil is as follows: and directly evaporating a layer of copper foil on both sides of the PET film.
Electrolyte resistance test of composite metal foil a and plain metal foil is shown in table 1:
TABLE 1
| Common metal foil | Composite metal foil A1 | Composite metal foil A2 | Composite metal foil A3 |
| Copper foil is directly peeled off | No abnormal appearance, no change in peeling | No abnormal appearance, no change in peeling | No abnormal appearance, no change in peeling |
In the process of testing the electrolyte resistance of the composite metal foil, the composite metal foil needs to be soaked in the electrolyte for 24 hours or 48 hours at room temperature.
Peel strength test of composite metal foil a and plain metal foil is shown in table 2:
TABLE 2
| Common metal foil (N/cm) | Composite metal foil A1 | Composite metal foil A2 | Composite metal foil A3 |
| 0.15 | 1.17 | 1.72 | 2.97 |
Elongation test of composite metal foil a and ordinary metal foil the following table is shown in table 3:
TABLE 3 Table 3
| Common metal foil (N/CM) | Composite metal foil A1 | Composite metal foil A2 | Composite metal foil A3 |
| MD:1.3~1.6% TD:1.6~1.7% | MD:2.7~3.7% TD:2.1~2.7% | MD:6.5~7.7% TD:7.4~7.6% | MD:5.5~6.9% TD:5.0~5% |
The MD direction of the composite metal foil refers to the longitudinal direction of the composite metal foil, and the TD direction of the composite metal foil refers to the width direction of the metal foil. Compared with the conventional method of laminating the common metal foil on the PET film, the composite metal foil provided by the embodiment of the invention has the advantages that the peeling strength is high, the electrolyte resistance is better, the extensibility is greatly improved, the problems of lower peeling force and extensibility of the composite metal foil can be effectively solved by improving the metal foil structure in the mode of the embodiment of the invention, the quality of the metal foil is improved, and the performance effect of a new energy battery applying the metal foil is further improved.
The embodiment of the invention also provides a comparison test condition of the composite metal foil with different filler particle distance distribution and a common metal foil, wherein the composite metal foil A with the structure of the embodiment of the invention also comprises composite metal foils A4, A5 and A6, and the specific conditions are shown in the following table 4.
TABLE 4 Table 4
| Composite metal foil A | Composite metal foil A4 | Composite metal foil A5 | Composite metal foil A6 |
| 0.2μm≤D＜4μm | 5% | 10% | 8% |
| 4μm≤D＜10μm | 65% | 70% | 90% |
| D≥10μm | 30% | 20% | 2% |
The test of peel strength, elongation and electrolyte resistance of the composite metal foil with the structure of the embodiment of the invention and the common metal foil is shown in table 5:
TABLE 5
| Composite metal foil of the invention | Peel strength (N/cm) | Elongation (%) | Electrolyte resistant |
| Composite metal foil A4 | 2.00 | MD:5.00~6.42% TD:6.1~6.20% | No change |
| Composite metal foil A5 | 1.98 | MD:4.3~4.60% TD:4.4~4.70% | No change |
| Composite metal foil A6 | 1.96 | MD:7.24~7.82% TD:6.60~6.90% | No change |
| Common metal foil | 0.15 | MD:1.3~1.68% TD:1.6~1.76% | Copper foil is directly peeled off |
Therefore, the control of the distribution of the distance between the filler particles can ensure not only good peeling strength, but also good elongation of the composite metal foil, and the obtained data are relatively uniform, so that the composite metal foil with stable performance can be prepared.
The embodiment of the invention also provides an electrode material applied to a battery, wherein the electrode material comprises the composite metal foil provided by any one of the embodiments.
The embodiment of the invention also provides a battery, and an electrode material of the battery comprises the composite metal foil provided by any one of the embodiments.
It should be noted that, the structure of the composite metal foil may refer to the structure of the metal foil described in any of the foregoing embodiments, and will not be described herein.
Compared with the prior art, the application of the metal foil as the electrode carrier of the battery has the following advantages: the metal foil structure is improved, the multilayer composite structure that the regulating layers and the conducting layers are respectively arranged on two sides of the support body is adopted, and the surface morphology of the regulating layers is optimized, so that the thickness and the weight of the whole metal foil can be obviously reduced, the overlarge density, thickness and weight of the metal foil are avoided, and the energy density of a new energy battery applying the composite metal foil is further improved. In addition, the peeling force between the support body and the conductive layer is effectively improved, the defects of bubbling, wrinkling, cracking and the like of the composite metal foil are reduced, the overall extensibility of the composite metal foil is effectively improved, the quality of the metal foil is improved, and the performance effect of a new energy battery applying the metal foil is improved.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (10)
1. A composite metal foil comprising: a support and a conductive layer disposed on at least one face of the support; the elongation of the composite metal foil is more than or equal to 2%; the peel force of the conductive layer and the support is greater than or equal to 0.3N/cm; the conductive layer is made of a metal material;
providing a regulating layer between the support and the conductive layer; the regulating layer comprises at least one of resin and coupling agent; the adjusting layer is internally provided with a plurality of filler particles to form a concave-convex structure on the surface of one side of the adjusting layer, which is far away from the supporting body, so that the conductive layer formed on the surface of one side of the adjusting layer, which is far away from the supporting body, replicates the surface morphology of the adjusting layer to have a corresponding concave-convex structure;
in the regulating layer, the quantity of filler particles with the distance of D being less than or equal to 0.2 mu m and less than 4 mu m accounts for 0% -10%, the quantity of filler particles with the distance of D being less than or equal to 4 mu m and less than 10 mu m accounts for 50% -90%, and the quantity of filler particles with the distance of D being less than or equal to 10 mu m accounts for 0% -30%; wherein the sum of the percentages of the filler particles in the three distance ranges is less than or equal to 100 percent.
2. The composite metal foil according to claim 1, wherein the support is a single layer structure or a composite structure of at least two layers.
3. The composite metal foil according to claim 1, wherein the surface roughness Ra of at least one surface of the support is 0.04 μm or more.
4. The composite metal foil of claim 1, wherein the conditioning layer comprises a resin layer, and wherein the filler particles are present in an amount of 1% to 30% by weight of the resin layer.
5. The composite metal foil according to claim 1 or 4, wherein the filler particles have a particle size in the range of 0.05 to 15 μm.
6. The composite metal foil according to claim 1, wherein a surface roughness Ra of a side of the adjustment layer remote from the support is 0.04 μm or more.
7. The composite metal foil according to claim 1, wherein a surface roughness Rz of a side of the adjustment layer remote from the support is 0.5 μm or more.
8. The composite metal foil according to claim 6 or 7, wherein the surface roughness of the support and/or the adjustment layer is formed by at least one of etching, polishing, plasma treatment, electroplating, electroless plating, evaporation plating, sputtering.
9. An electrode material for use in a battery, characterized in that the electrode material comprises a composite metal foil according to any one of claims 1 to 8.
10. A battery, characterized in that the electrode material of the battery comprises a composite metal foil according to any one of claims 1 to 8.
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