CN219246721U - Composite current collector, battery electrode, battery and electric equipment - Google Patents
Composite current collector, battery electrode, battery and electric equipment Download PDFInfo
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- CN219246721U CN219246721U CN202320166537.XU CN202320166537U CN219246721U CN 219246721 U CN219246721 U CN 219246721U CN 202320166537 U CN202320166537 U CN 202320166537U CN 219246721 U CN219246721 U CN 219246721U
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Abstract
The application provides a composite current collector, a battery electrode, a battery and electric equipment, and belongs to the field of lithium ion batteries. The composite current collector includes a polymer matrix and a conductive layer. In the thickness direction of the polymer matrix, the two sides of the polymer matrix are directly connected with the conductive layers, in the first preset direction, one side end of each of the two conductive layers exceeds the end of the polymer matrix on the side, the inner walls of the two conductive layers and the side wall of the polymer matrix are surrounded to form a U-shaped welding area, the first preset direction is preset to be perpendicular to the thickness direction of the polymer matrix, and the problem that the bonding force between the polymer matrix and the conductive layers is weak can be solved to a certain extent through the composite current collector of the structure.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to a composite current collector, a battery electrode, a battery and electric equipment.
Background
In the prior art, the traditional composite current collector with the U-shaped welding area has the problem that the binding force between a polymer matrix and a conductive layer is weak, so that the conductive layer on the surface of the polymer matrix is easy to fall off.
Disclosure of Invention
The purpose of the application is to provide a composite current collector, a battery electrode, a battery and electric equipment, and the problem that the binding force between a polymer matrix and a conductive layer is weak can be solved to a certain extent.
Embodiments of the present application are implemented as follows:
in a first aspect, embodiments of the present application provide a composite current collector including a polymer matrix and a conductive layer. In the thickness direction of the polymer matrix, the two sides of the polymer matrix are directly connected with the conductive layers, one side end of each of the two conductive layers exceeds the end of the polymer matrix on the side in the first preset direction, the inner walls of the two conductive layers and the side wall of the polymer matrix are surrounded to form a U-shaped welding area, and the first preset direction is preset to be perpendicular to the thickness direction of the polymer matrix.
In the above technical scheme, the two side surfaces of the polymer matrix in the composite current collector are directly connected with the conductive layer, compared with the traditional composite current collector with the U-shaped welding area (the polymer matrix is connected with the conductive layer through an adhesive), the composite current collector with the U-shaped welding area provided by the embodiment of the application has the advantage that the bonding force between the conductive layer and the polymer matrix is firm, and meanwhile, the problems that the surface of the composite current collector foams and folds are caused by bonding the conductive layer and the polymer matrix through the adhesive can be solved.
In some alternative embodiments, the thickness of the polymer matrix is 3 to 6 μm.
In the above technical solution, the thickness of the polymer matrix is limited within a specific range, so that the polymer matrix has a proper thickness, and thus the polymer matrix has proper mechanical properties and electrochemical properties.
In some alternative embodiments, the thickness of the individual conductive layers is 0.5 to 5 μm.
In the technical scheme, the thickness of the single conductive layer is limited in a specific range, so that the single conductive layer has proper thickness, and lower preparation cost can be considered under the condition of ensuring conductivity.
In some alternative embodiments, the sheet resistance of the single conductive layer is 1 to 400mΩ/≡.
In the above technical solution, the thickness of the single conductive layer is limited within a specific range, so that the single conductive layer has a suitable sheet resistance, and thus has a suitable conductivity.
In some alternative embodiments, the orthographic projections of the two conductive layers are completely coincident in the thickness direction of the polymer matrix.
In the technical scheme, the orthographic projections of the two conductive layers in the thickness direction of the polymer matrix are completely overlapped, namely, the two conductive layers are distributed along the thickness direction of the polymer matrix and are symmetrical relative to the polymer matrix, so that the overall structure of the composite current collector is more regular, and meanwhile, the process preparation is also convenient.
In some alternative embodiments, in a first predetermined direction, the other side ends of both conductive layers are aligned with the ends of the polymer matrix on that side.
In the technical scheme, the other side ends of the two conductive layers in the first preset direction are aligned with the end parts of the polymer matrix on the side, so that the composite current collector can be more regular.
In some alternative embodiments, the U-shaped weld area has a dimension of 5 to 10mm in the first predetermined direction.
In the above technical solution, the dimensions of the U-shaped welding area in the first preset direction are limited within a specific range, so that the U-shaped welding area has dimensions of a suitable size, thereby providing a suitable welding width for subsequent welding.
In some alternative embodiments, the conductive layer is made of Al.
In the technical scheme, al is adopted as a conducting layer material, so that the anode current collector most commonly used in the field can be obtained, and the anode current collector can be used in most lithium ion batteries.
In some alternative embodiments, the conductive layer is Cu.
In the technical scheme, cu is adopted as a conductive layer material, so that the cathode current collector most commonly used in the field can be obtained, and the cathode current collector can be used in most lithium ion batteries.
In some alternative embodiments, the polymer matrix is made of polyethylene, biaxially oriented polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, or propylene.
The technical scheme provided by the embodiment of the application is suitable for polymer materials of the systems, and can provide more implementable modes, so that the technical scheme provided by the embodiment of the application is convenient to popularize and apply.
In a second aspect, embodiments of the present application provide a battery electrode comprising a composite current collector as provided by the embodiments of the first aspect.
In a third aspect, embodiments of the present application provide a battery comprising a battery electrode as provided in the embodiments of the second aspect.
In a fourth aspect, embodiments of the present application provide a powered device comprising a battery as provided in the embodiments of the third aspect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural view of a composite current collector provided in a comparative example (i.e., a composite current collector of a conventional structure) of the present application;
fig. 2 is a schematic structural diagram of a composite current collector according to an embodiment of the present application.
Icon: 10-composite current collector; 100-a conductive layer; 200-a polymer matrix; 300-an adhesive layer; 400-U-shaped welding area; a-thickness direction of the polymer matrix; b-a first preset direction.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, which are generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, as provided in the accompanying drawings, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
The terms "horizontal," "vertical," and the like do not denote that the component is required to be absolutely horizontal or overhanging, but may be slightly inclined. As "horizontal" merely means that its direction is more horizontal than "vertical", and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the present application, it should also be noted that, unless explicitly specified and limited otherwise, the terms "connected," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art in a specific context.
At present, the lithium ion battery is widely applied to the fields of new energy automobiles, energy storage, 3C numbers and the like because of the excellent performances of high energy density, high working voltage, long cycle life and the like. Along with the development of society and the competition of enterprises, higher requirements are put on the energy density of lithium batteries.
In order to improve the energy density of the battery, a person skilled in the art uses a high molecular polymer as a substrate film, prepares a metal conductive layer with a certain thickness on the substrate film by means of physics, chemistry, electrochemistry and the like, and can prepare a special structure with a conductor layer/a polymer layer/a conductor layer.
However, the conventional composite current collector can only realize connection between the tab and the single-side conductive layer, and the impedance of the welding point is increased due to the insulation property of the polymer, so that the situation of difficult welding and cold welding often occurs in the welding process, and the welding success rate is low.
Based on this, referring to fig. 1, in some prior arts, a person skilled in the art uses a polymer matrix 200 as a base film, and bonds conductive layers 100 on two side surfaces thereof by an adhesive to prepare a composite current collector 10 with a U-shaped welding area 400, and compared with a conventional composite current collector 10, the composite current collector 10 with the structure has a single U-shaped welding area 400, which can improve the welding success rate of the composite current collector 10 and the tab.
However, the composite current collector 10 of this structure has the following problems due to the presence of the adhesive layer 300 between the conductive layer 100 and the base film:
the adhesive A has poor mechanical properties, so that the bonding force between the conductive layer 100 and the substrate film is poor, and the adhesive is easy to fail in electrolyte, so that the conductive layer 100 on the surface of the polymer layer is easy to fall off.
The process difficulty of mutual adhesion of the conductive layer 100 and the substrate film is high, and the defects of wrinkling, bubbles and the like on the surface of the current collector are easily caused, so that the performance of the corresponding battery is influenced.
Based on this, the inventors have creatively studied and found that: the metal is directly deposited on the surface of the polymer matrix 200 to obtain the conductive layer 100, and the conductive layer 100 and the polymer matrix 200 are directly connected together, so that the bonding force between the conductive layer 100 and the polymer matrix 200 can be improved, and meanwhile, the problems of surface foaming, wrinkling and the like of the composite current collector 10 caused by bonding the conductive layer 100 and the polymer matrix 200 together through an adhesive can be solved.
In a first aspect, referring to fig. 2, an embodiment of the present application provides a composite current collector 10 comprising a polymer matrix 200 and a conductive layer 100. In the thickness direction a of the polymer matrix, the two sides of the polymer matrix 200 are directly connected with the conductive layers 100, in the first preset direction b, one side end of the two conductive layers 100 exceeds the end of the polymer matrix 200 on the side, the inner walls of the two conductive layers 100 and the side wall of the polymer matrix 200 form a U-shaped welding area, and the first preset direction b is preset to be perpendicular to the thickness direction a of the polymer matrix.
It should be noted that, the first preset direction b is not limited, and may be a length direction of the polymer matrix 200 or a width direction of the polymer matrix 200, and in this embodiment, the first preset direction b is a width direction of the polymer matrix 200.
In this application, the two side surfaces of the polymer matrix 200 in the composite current collector 10 are directly connected with the conductive layer 100, and compared with the conventional composite current collector 10 with the U-shaped welding area 400 (the polymer matrix 200 is connected with the conductive layer 100 through an adhesive), the composite current collector 10 with the U-shaped welding area 400 provided in this application has the advantage that the bonding force between the conductive layer 100 and the polymer matrix 200 is firm, and meanwhile, the problems of surface foaming and wrinkling of the composite current collector 10 caused by bonding the conductive layer 100 and the polymer matrix 200 together through an adhesive can be improved.
It should be noted that the thickness of the polymer matrix 200 is not limited and may be adjusted according to practical needs.
As an example, the thickness of the polymer matrix 200 is 3-6 μm, such as, but not limited to, any one point value or a range value between any two of 3 μm, 4 μm, 5 μm, and 6 μm.
In this embodiment, limiting the thickness of the polymer matrix 200 to a specific range enables the polymer matrix 200 to have a suitable thickness, thereby enabling the polymer matrix 200 to have suitable mechanical and electrochemical properties.
It should be noted that the thickness of the single conductive layer 100 is not limited and may be adjusted according to practical needs.
As an example, the thickness of the single conductive layer 100 is 0.5-5 μm, such as, but not limited to, a thickness of any one or a range of values between any two of 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, and 5 μm.
In this embodiment, the thickness of the single conductive layer 100 is limited to a specific range, so that the single conductive layer 100 can have an appropriate thickness, thereby enabling a low manufacturing cost while ensuring conductivity.
It should be noted that the sheet resistance of the single conductive layer 100 is not limited and may be adjusted according to practical needs.
As an example, the sheet resistance of the single conductive layer 100 is 1 to 400mΩ/∈s, such as, but not limited to, a range value between any one point value or any two of 1mΩ/∈s, 50mΩ/∈s, 100mΩ/∈s, 200mΩ/∈s, 300mΩ/∈s, and 400mΩ/∈s.
In this embodiment, the thickness of the single conductive layer 100 is limited to a specific range, so that the single conductive layer 100 can have a suitable sheet resistance and thus a suitable conductivity.
It is understood that the relative positions of the two conductive layers 100 may be adjusted in consideration of the regularity of the composite current collector 10 and the ease of preparation.
As an example, in the thickness direction a of the polymer matrix, the orthographic projections of the two conductive layers 100 completely coincide.
In this embodiment, the orthographic projections of the two conductive layers 100 in the thickness direction a of the polymer matrix are completely coincident, that is, the two conductive layers 100 are distributed along the thickness direction a of the polymer matrix and symmetrical with respect to the polymer matrix 200, so that the overall structure of the composite current collector 10 is relatively regular, and meanwhile, the process preparation is also convenient.
In other possible embodiments, the orthographic projections of the two conductive layers 100 in the thickness direction a of the polymer matrix may also be partially coincident, i.e. one conductive layer 100 is longer and the other conductive layer 100 is shorter.
It is understood that the relative positional relationship of the conductive layer 100 and the other side of the polymer matrix 200 in the first preset direction b may also be adjusted in consideration of the regularity of the composite current collector 10.
As an example, in the first preset direction b, the other side ends of both conductive layers 100 are aligned with the ends of the polymer matrix 200 at the side.
In this embodiment, both the other side ends of the two conductive layers 100 in the first preset direction b are aligned with the ends of the polymer matrix 200 at the side, enabling the composite current collector 10 to be more regular.
In other possible embodiments, in the first preset direction b, it is also possible that the other side end of one of the conductive layers 100 is aligned with the end of the polymer base at that side.
It should be noted that the size of the U-shaped welding area 400 in the first preset direction b is not limited, and may be adjusted according to actual needs.
As an example, in the first preset direction b, the size of the U-shaped welding area is 5 to 10mm, such as, but not limited to, any one point value or a range value between any two of 5mm, 6mm, 7mm, 8mm, 9mm and 10mm.
In this embodiment, the dimension of the U-shaped land 400 in the first preset direction b is limited to a specific range, and the U-shaped land 400 can be made to have a suitable size, thereby providing a suitable welding width for subsequent welding.
It should be noted that the material of the conductive layer 100 is not limited and may be adjusted according to practical needs.
As an example, the material of the conductive layer 100 is Al.
In this embodiment, al is used as a material of the conductive layer 100, and a positive electrode current collector most commonly used in the art can be obtained so as to be used in most lithium ion batteries.
As an example, the material of the conductive layer 100 is Cu.
In this embodiment, cu is used as the material of the conductive layer 100, so that the negative electrode current collector most commonly used in the art can be obtained, so that it can be used in most lithium ion batteries.
It should be noted that the material of the polymer matrix 200 is not limited, and may be selected according to the conventional method in the art.
As an example, the material of the polymer matrix 200 is polyethylene, biaxially oriented polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, or propylene.
In this embodiment, the technical scheme provided in the embodiment of the present application is applicable to the polymer materials of the above multiple systems, and can provide more possible embodiments, so that the technical scheme provided in the embodiment of the present application is convenient to popularize and apply.
It should be noted that the structures not specifically described or defined may be arranged according to the conventional options in the art.
In order to better understand the technical scheme, the following detailed description is given by specific preparation process.
As an example, the method of preparing the composite current collector includes the steps of:
providing a polymer matrix; depositing metal on the two side surfaces of the polymer matrix to obtain a polymer matrix with a conductive layer; and removing the part of the polymer matrix corresponding to the edge area of the conductive layer to obtain the composite current collector with the U-shaped welding area.
It should be noted that "providing a polymer matrix" herein means that the polymer matrix may be obtained by direct purchase or may be prepared according to a conventional process in the art.
It should be noted that the specific manner of metal deposition is not limited and may be performed in a conventional manner in the art.
As an example, in the step of depositing the metal, at least one of physical vapor deposition and electroless plating is employed; wherein, the physical vapor deposition comprises at least one of a vacuum evaporation mode, a magnetron sputtering mode and an ion beam evaporation coating mode.
It should be noted that the specific process of the electroless plating treatment and the components and proportions of the corresponding reagents used are not limited, and may be selected and set according to conventional methods in the art.
As an example, during the electroless plating process, the plating solution includes CuSO 4 Complexing agent-triethanolamine, na 2 CO 3 Potassium sodium tartrate, thiourea, naOH and formaldehyde; wherein, cuSO 4 The concentration of the complexing agent-triethanolamine is 5-7 g/L, the concentration of the complexing agent-triethanolamine is 8-10 mg/L, and the concentration of Na is 2 CO 3 The concentration of the sodium potassium tartrate is 8-10 mg/L, the concentration of the sodium potassium tartrate is 70-75 g/L, the concentration of the thiourea is 0.005-0.01 g/L, the concentration of formaldehyde is 8-10 mg/L, naOH is used as a pH regulator until the pH of the solution is 12, the treatment temperature is 40-50 ℃ and the treatment time is 10-30 min.
It should be noted that, based on different metal deposition processes, the preparation process may be adjusted accordingly in consideration of the effect of metal deposition.
As an example, prior to the step of electrolessly depositing the metal, the method further comprises sequentially roughening, sensitizing, and activating the polymer matrix.
It should be noted that the specific processes of roughening, sensitization and activation treatment, and the components and proportions of the corresponding reagents used are not limited, and may be selected and set according to conventional methods in the art.
As an example, during the roughening treatment, the roughening liquid includes sulfuric acid, water, and chromic acid; wherein, the volume ratio of sulfuric acid to water in the coarsening liquid is 4:6, chromic acid is taken as an additive component until the mixed solution is saturated, the treatment temperature is 60-70 ℃, and the treatment time is 20-30 min.
As an example, during the sensitization process, the sensitization solution includes SnCl and HCl; wherein, the concentration of SnCl is 0.05-0.1 g/L, the concentration of HCl is 0.2-0.4 g/L, and the treatment time is 2-4 min.
As an example, during the activation treatment, the activation liquid includes AgNO 3 And ammonia; wherein AgNO 3 The concentration of (2) is 3-5 g/L, ammonia water is used as an additive component until the solution becomes transparent, and the treatment time is 5-10 min.
It will be appreciated that, since different kinds of metals have different physicochemical properties, the preferred process of deposition may be selected or adjusted according to actual needs, taking into account the effect of metal deposition.
As an example, the metal is Al, and in the step of metal deposition, the metal Al is deposited on the surface of the polymer matrix by using a vacuum evaporation method in a physical vapor deposition manner to form a conductive layer; wherein the vacuum degree is 1.3X10 -4 ～1.3×10 -2 In the Pa range, the treatment temperature is 500-2500 ℃.
It can be understood that, since the vapor deposition temperature affects the compactness of the conductive layer, the better the compactness is, the stronger the bonding force between the conductive layer and the polymer matrix is, and the vapor deposition temperature can be further limited in consideration of the bonding strength between the formed conductive layer and the polymer matrix.
As an example, the metal is Cu, and the step of thickening the conductive layer after the step of depositing the metal is completed and before the step of removing the portion of the polymer matrix corresponding to the edge region of the conductive layer is further included.
It should be noted that the manner of the thickening process is not limited, and may be set according to a conventional selection in the art.
As an example, in the step of thickening the conductive layer, at least one of an acidic bright copper plating method and an alkaline pyrophosphate copper plating method is used.
It should be noted that the process parameters in the thickening process are not limited and can be adjusted according to actual needs.
As an example, in the step of conducting the conductive layer thickening treatment by the acid bright copper plating method, the treatment time is 2 to 5min, such as, but not limited to, a treatment time of any one or a range value between any two of 2min, 3min, 4min and 5 min; the current density is 0.5-1.5A/dm 2 For example, but not limited to, a current density of 0.5A/dm 2 、1.0A/dm 2 And 1.5A/dm 2 Any one or any range value therebetween.
As an example, in the step of conducting the conductive layer thickening treatment by the alkaline pyrophosphate copper plating method, the treatment time is 4 to 10 minutes, such as, but not limited to, a treatment time of any one or a range value between any two of 4 minutes, 6 minutes, 8 minutes and 10 minutes; the current density is 0.2-0.8A/dm 2 For example, but not limited to, a current density of 0.2A/dm 2 、0.4A/dm 2 、0.6A/dm 2 And 0.8A/dm 2 Any one or any range value therebetween.
It should be noted that the components and proportions of the relevant reagents used in each thickening process are not limited, and may be selected and set according to conventional methods in the art.
As an example, in the step of conducting layer thickening treatment by acid bright copper plating, the main salt includes CuSO 4 ·5H 2 O：150～220g/L，H 2 SO 4 : 50-70 g/L, and the inorganic salt additive comprises Cl - : 20-80 mg/L, and the organic additive comprises thiazolidinethione: 00005-0.001 g/L, sodium polydihexa-di-propane sulfonate: 0.01-0.02 g/L, PEG-6000: 0.03-0.05 g.
As an example, in the step of conducting layer thickening treatment by alkaline pyrophosphate copper plating, the main salt includes copper pyrophosphate: 20-50 g/L complexing agent potassium pyrophosphate: p ratio is 7-9 (P ratio is ratio of pyrophosphate and Cu ion), and the auxiliary complexing agent comprises ammonium citrate and/or NH 4 Cl (concentration is 3-5 g/L), and the brightening agent comprises at least one of 2-mercaptothiazine, glycine and 2-mercaptobenzimidazole (concentration is 0.01-0.02 g/L).
It will be appreciated that since Cu is easily oxidized, the conductive layer may be passivated after the thickening process is completed to effectively avoid oxidation of Cu.
It should be noted that the specific process of the passivation treatment is not limited and may be performed according to a conventional operation in the art.
As an example, during the passivation process, the passivation solution includes a BTA corrosion inhibitor: 15-25 mg/L of ammonium molybdate: 15-25 mg/L, and the passivation time is 1-5 min.
It should be noted that the manner of removing the polymer matrix is not limited and may be set according to the conventional selection in the art.
As an example, in the step of removing the portion of the polymer matrix corresponding to the edge region of the conductive layer, at least one of a chemical etching method, a physical heat-melting method, and a heat shrinkage method is used.
As an example, in the step of removing the polymer matrix by chemical etching, the chemical etching liquid includes an organic solvent and/or an inorganic solvent; wherein the inorganic solvent comprises at least one of concentrated sulfuric acid and trichloroacetic acid; the organic solvent includes at least one of phenol, tetrachloroethane, chlorophenol, nitrobenzene, m-cresol, tetrachloroethylene, decalin, tetrahydronaphthalene, xylene, and alpha-chloronaphthalene.
It should be noted that, in the step of removing the polymer matrix by chemical etching, specific process parameters are not limited and may be adjusted according to actual needs.
As an example, in the step of chemically etching to remove the polymer matrix, the treatment temperature is 20 to 150 ℃, such as, but not limited to, a treatment temperature of any one or any range between any two of 20 ℃, 50 ℃, 100 ℃ and 150 ℃.
As an example, in the step of removing the polymer matrix by physical heat-melting and/or heat-shrinking, the heating means includes at least one of infrared heat radiation means, laser heat ablation means, and resistive contact heating means.
It should be noted that the process parameters in each heating mode are not particularly limited, and may be adjusted according to actual needs.
As an example, in the heating by the infrared heat radiation method, at least one of the following conditions a to C is satisfied:
the A treatment wavelength is 3 to 5 μm, such as, but not limited to, a treatment wavelength of any one or any range between two of 3 μm, 4 μm and 5 μm.
The B processing power is 5 to 50W, such as, but not limited to, a processing power of any one or any range between two of 5W, 10W, 20W, 30W, 40W, and 50W.
The treatment time C is 10 to 60 seconds, such as, but not limited to, a treatment time of any one or any range between 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds and 60 seconds.
As an example, in the heating by the laser thermal ablation method, at least one of the following conditions D to F is satisfied:
the D treatment wavelength is 808-1064 nm, such as, but not limited to, a range of values between any one or any two of 808nm, 900nm, 1000nm, and 1064 nm.
E the processing power is 5-50W, such as, but not limited to, a range of values between any one or any two of 5W, 10W, 20W, 30W, 40W and 50W.
The treatment time F is 5 to 20 seconds, such as, but not limited to, a treatment time of any one or any range between two of 5 seconds, 10 seconds, 15 seconds and 20 seconds.
As an example, in a process of heating by a resistive contact heating method, the processing temperature is 100 to 500 ℃, such as, but not limited to, a processing temperature of any one or any range between two of 100 ℃, 200 ℃, 300 ℃, 400 ℃ and 500 ℃; the treatment time is 10 to 30 seconds, such as, but not limited to, a treatment time of any one or any range between 10 seconds, 20 seconds, and 30 seconds.
In the process of preparing the composite current collector, steps or processes not specifically described or defined are not limited, and may be performed according to conventional operations in the art.
In a second aspect, embodiments of the present application provide a battery electrode comprising a composite current collector 10 as provided by embodiments of the first aspect.
The specific type of the battery electrode is not limited, and may be adjusted according to the type of the composite current collector 10.
Illustratively, the composite current collector 10 is a positive current collector, and the battery electrode is a battery positive electrode; the composite current collector 10 is a negative current collector, and the battery electrode is the battery negative electrode.
In a third aspect, embodiments of the present application provide a battery comprising a battery electrode as provided in the embodiments of the second aspect.
The battery electrode may be a positive electrode or a negative electrode of the battery.
The structure or unit (such as electrolyte composition and ratio, separator material, and case material) not specifically described in the battery may be selected according to the conventional manner in the art.
In a fourth aspect, embodiments of the present application provide a powered device comprising a battery as provided in the embodiments of the third aspect.
It should be noted that the type of the electric equipment is not limited, and is, for example, a mobile phone, a portable device, a notebook computer, a battery car, an electric automobile, a ship, a spacecraft, an electric toy, an energy storage device, an electric tool, and the like.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment of the application provides a preparation method of a composite current collector, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using absolute ethyl alcohol and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is made of polyethylene terephthalate (PET), and has a thickness of 4.5 μm and a width of 63mm.
Placing the polymer matrix subjected to degreasing and cleaning in a vacuum evaporator to deposit metal Al, so as to obtain a polymer matrix with a conductive layer; wherein the vacuum degree is 1.3X10 -3 Pa, the treatment temperature was 1300 ℃, and the thickness of the single conductive layer was 1. Mu.m.
Placing one side edge of the polymer matrix with the conductive layer into an infrared heat radiator for heating so as to remove part of the polymer matrix in the region and obtain a composite current collector with a U-shaped welding area; wherein the width of the edge area is 5mm, the treatment wavelength is 4 μm, the treatment power is 27W, and the treatment time is 20s.
Example 2
The embodiment of the application provides a preparation method of a composite current collector with a U-shaped welding area, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using isopropanol and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is biaxially oriented polypropylene (BOPP), has a thickness of 4.5 μm and a width of 63mm.
Placing the polymer matrix subjected to degreasing and cleaning in a vacuum evaporator to deposit metal Al, so as to obtain a polymer matrix with a conductive layer; wherein the vacuum degree is 1.3X10 -2 Pa, the treatment temperature was 1350 ℃, and the thickness of the single conductive layer was 1.5. Mu.m.
Soaking one side edge of the polymer matrix with the conductive layer in chemical etching solution to remove part of the polymer matrix in the region, so as to obtain a composite current collector with a U-shaped welding area; wherein the width of the edge area is 8mm, the chemical etching solution is dimethylbenzene, the treatment temperature is 130 ℃, and the treatment time is 10min.
Example 3
The embodiment of the application provides a preparation method of a composite current collector with a U-shaped welding area, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using acetone and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is made of PET, has a thickness of 4.5 μm and a width of 63mm.
Placing the polymer matrix subjected to degreasing and cleaning in a vacuum evaporator to deposit metal Al, so as to obtain a polymer matrix with a conductive layer; wherein the vacuum degree is 1.3X10 -3 Pa, the treatment temperature was 1400 ℃, and the thickness of the single conductive layer was 1.0. Mu.m.
Placing one side edge of the polymer matrix with the conductive layer in a laser ablation area to remove part of the polymer matrix in the area, so as to obtain a composite current collector with a U-shaped welding area; wherein the width of the edge area is 10mm, the processing wavelength is 808nm, the processing power is 25W, and the processing time is 10s.
Example 4
The embodiment of the application provides a preparation method of a composite current collector with a U-shaped welding area, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using absolute ethyl alcohol and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is made of Polyethylene (PE), has a thickness of 4.5 μm and a width of 63mm.
Placing the polymer matrix subjected to degreasing and cleaning in a vacuum evaporator to deposit metal Al, so as to obtain a polymer matrix with a conductive layer; wherein the vacuum degree is 1.3X10 -3 Pa, the treatment temperature was 1300 ℃, and the thickness of the single conductive layer was 1.0. Mu.m.
Contacting one side edge of the polymer matrix with the conductive layer with a heating resistor to remove part of the polymer matrix in the region, thereby obtaining a composite current collector with a U-shaped welding area; wherein the width of the edge area is 20mm, the treatment temperature is 160 ℃, and the treatment time is 10s.
Example 5
The embodiment of the application provides a preparation method of a composite current collector with a U-shaped welding area, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using absolute ethyl alcohol and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is made of PET, has a thickness of 4.5 μm and a width of 63mm.
Coarsening, sensitizing and activating the polymer matrix after degreasing and cleaning in sequence; in the roughening treatment process, the roughening liquid comprises sulfuric acid, water and chromic acid; wherein, the volume ratio of sulfuric acid to water in the coarsening liquid is 4:6, chromic acid is taken as an additive component until the mixed solution is saturated, the treatment temperature is 65 ℃, and the treatment time is 20min; during the sensitization treatment, the sensitization liquid comprises SnCl and HCl; wherein, the concentration of SnCl is 0.1g/L, the concentration of HCl is 0.3g/L, and the treatment time is 3min; during the activation treatment, the activating solution comprises AgNO 3 And ammonia; wherein AgNO 3 The concentration of (2) was 4g/L, ammonia was used as an additive until the solution became transparent, and the treatment time was 10 minutes.
Placing the polymer matrix subjected to roughening, sensitization and activation treatment in an electroless plating solution to deposit metal Cu, so as to obtain a polymer matrix with a conductive layer; during the electroless plating process, the plating solution includes CuSO 4 Complexing agent-triethanolamine, na 2 CO 3 Potassium sodium tartrate, thiourea, naOH and formaldehyde; wherein, cuSO 4 The concentration of the complexing agent-triethanolamine is 6g/L, the concentration of the Na is 9mg/L 2 CO 3 The concentration of (2) is 9mg/L, the concentration of potassium sodium tartrate is 75g/L, the concentration of thiourea is 0.01g/L, the concentration of formaldehyde is 9mg/L, naOH is used as a pH regulator until the pH of the solution is 12, the treatment temperature is 50 ℃, the treatment time is 20min, and the thickness of a single conductive layer is 100nm.
Thickening a single conductive layer in a polymer matrix with a conductive layer by an acidic bright copper plating mode for 1 mu m, and then passivating the thickened conductive layer;wherein in the step of conducting layer thickening treatment by adopting an acid bright copper plating mode, the main salt comprises CuSO 4 ·5H 2 O：220g/L，H 2 SO 4 :70g/L, inorganic salt additive including Cl - :80mg/L, organic additives including thiazolidinethione: 0.001g/L, sodium polydihexa-di-propane sulfonate: 0.02g/L, PEG-6000:0.05g, current density of 1.5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the In the passivation process, the passivation solution comprises a BTA corrosion inhibitor: 20mg/L, ammonium molybdate: 20mg/L, and the passivation time is 2min.
Placing one side edge of the polymer matrix with the conductive layer into an infrared heat radiator for heating so as to remove part of the polymer matrix in the region and obtain a composite current collector with a U-shaped welding area; wherein the width of the edge area is 5mm, the treatment wavelength is 5 μm, the treatment power is 36W, and the treatment time is 15s.
Example 6
The embodiment of the application provides a preparation method of a composite current collector with a U-shaped welding area, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using isopropanol and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is made of polypropylene (PPE), has a thickness of 4.5 μm and a width of 63mm.
Placing the polymer matrix subjected to degreasing and cleaning in a magnetron sputtering coating machine to deposit metal Cu, so as to obtain a polymer matrix with a conductive layer; wherein the vacuum degree is 3×10 -3 Pa, the thickness of the single conductive layer was 100nm.
Thickening a single conductive layer in a polymer matrix with a conductive layer by an acidic bright copper plating mode for 1 mu m, and then passivating the thickened conductive layer; wherein in the step of conducting layer thickening treatment by adopting an acid bright copper plating mode, the main salt comprises CuSO 4 ·5H 2 O：220g/L，H 2 SO 4 :70g/L, inorganic salt additive including Cl - :80mg/L, organic additives including thiazolidinethione: 0.001g/L, sodium polydihexa-di-propane sulfonate: 0.02g/L, PEG-6000:0.05g, during electroplatingThe time is 6min, and the current density is 1.5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the In the passivation process, the passivation solution comprises a BTA corrosion inhibitor: 20mg/L, ammonium molybdate: 20mg/L, and the passivation time is 2min.
Soaking one side edge of the polymer matrix with the conductive layer in chemical etching solution to remove part of the polymer matrix in the region, so as to obtain a composite current collector with a U-shaped welding area; wherein the width of the edge area is 8mm, the chemical etching solution is dimethylbenzene, the treatment temperature is 130 ℃, and the treatment time is 10min.
Example 7
The embodiment of the application provides a preparation method of a composite current collector with a U-shaped welding area, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using acetone and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is made of PET, has a thickness of 4.5 μm and a width of 63mm.
Placing the polymer matrix subjected to degreasing and cleaning in a magnetron sputtering coating machine to deposit metal Cu, so as to obtain a polymer matrix with a conductive layer; wherein the vacuum degree is 3×10 -3 Pa, the thickness of the single conductive layer is 200nm.
Thickening a single conductive layer in a polymer matrix with a conductive layer by an alkaline pyrophosphate copper plating mode for 1 mu m, and then passivating the thickened conductive layer; wherein, in the step of conducting layer thickening treatment by adopting an alkaline pyrophosphate copper plating mode, the main salt comprises copper pyrophosphate: 50g/L, complexing agent potassium pyrophosphate: p ratio is 8 (P ratio is ratio of pyrophosphate and Cu ion), and the auxiliary complexing agent is NH 4 Cl:3g/L, the brightening agent is 2-mercaptobenzimidazole: 0.01g/L, plating time of 6min, current density of 0.4A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the In the passivation process, the passivation solution comprises a BTA corrosion inhibitor: 20mg/L, ammonium molybdate: 20mg/L, and the passivation time is 2min.
Placing one side edge of the polymer matrix with the conductive layer in a laser ablation area to remove part of the polymer matrix in the area, so as to obtain a composite current collector with a U-shaped welding area; wherein the width of the edge area is 10mm, the treatment wavelength is 808nm, the treatment power is 30W, and the treatment time is 10s.
Example 8
The embodiment of the application provides a preparation method of a composite current collector with a U-shaped welding area, which comprises the following steps:
providing a polymer matrix, and then cleaning the polymer matrix by using absolute ethyl alcohol and deionized water in sequence to obtain a polymer matrix after degreasing and cleaning; wherein the polymer matrix is PE, has a thickness of 4.5 μm and a width of 63mm.
Placing the polymer matrix subjected to degreasing and cleaning in a magnetron sputtering coating machine to deposit metal Cu, so as to obtain a polymer matrix with a conductive layer; wherein the vacuum degree is 3×10 -3 Pa, the thickness of the single conductive layer was 100nm.
Thickening a single conductive layer in a polymer matrix with a conductive layer by an alkaline pyrophosphate copper plating mode for 1 mu m, and then passivating the thickened conductive layer; wherein, in the step of conducting layer thickening treatment by adopting an alkaline pyrophosphate copper plating mode, the main salt comprises copper pyrophosphate: 40g/L, complexing agent potassium pyrophosphate: p ratio is 8 (P ratio is ratio of pyrophosphate and Cu ion), and the auxiliary complexing agent is NH 4 Cl:5g/L, the brightening agent is 2-mercaptobenzimidazole: 0.02g/L, plating time of 3min, current density of 0.4A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the In the passivation process, the passivation solution comprises a BTA corrosion inhibitor: 20mg/L, ammonium molybdate: 20mg/L, and the passivation time is 2min.
Contacting one side edge of the polymer matrix with the conductive layer with a heating resistor to remove part of the polymer matrix in the region, thereby obtaining a composite current collector with a U-shaped welding area; wherein the width of the edge area is 20mm, the treatment temperature is 170 ℃, and the treatment time is 10s.
Comparative example 1
The comparative example of the present application provides a method for preparing a composite current collector, which is different from example 2 only in that: the Al foil is attached to the polymer matrix by an adhesive (leaving a U-shaped weld zone itself).
Comparative example 2
The comparative example of the present application provides a method for preparing a composite current collector, which is different from example 7 only in that: the Cu foil is attached to the polymer matrix by an adhesive (leaving a U-shaped land on its own).
In examples 1 to 8 and comparative examples 1 to 2, the width direction of the polymer matrix was aligned with the width direction of the edge region of the conductive layer.
It should be noted that, the schematic structural diagrams of the composite current collectors prepared in examples 1 to 8 are shown in fig. 2, and the schematic structural diagrams of the composite current collectors prepared in comparative examples 1 to 2 are shown in fig. 1.
Test example 1
Composite current collector performance test
The testing method comprises the following steps:
the preparation of the composite current collectors was performed according to the preparation methods of examples 1 to 8 and comparative examples 1 to 2, and then, each of the prepared composite current collectors was numbered, and then, each sample was tested for tab welding success rate, peel strength between the conductive layer and the polymer matrix, and tensile strength of the composite current collector.
It should be noted that, considering the reliability of the experimental data, 100 samples were prepared for each preparation method.
Table 1 composite current collector performance test
| Sample name | Peel strength (N/m) | Tensile Strength (MPa) | Success rate of welding (%) |
| Example 1 | 420-450 | 200-220 | 100 |
| Example 2 | 430-460 | 280-320 | 100 |
| Example 3 | 420-450 | 210-230 | 65 |
| Example 4 | 350-380 | 200-230 | 100 |
| Example 5 | 380-400 | 240-260 | 100 |
| Example 6 | 440-470 | 230-250 | 100 |
| Example 7 | 450-480 | 300-340 | 70 |
| Example 8 | 400-430 | 200-230 | 100 |
| Comparative example 1 | 200-250 | 260-280 | 100 |
| Comparative example 2 | 200-240 | 200-240 | 260-280 |
The peel strength and tensile strength in table 1 are each a test result distribution range of 100 test samples, and thus are expressed as range values.
Referring to table 1, it is apparent from the test results of examples 1 to 8 and comparative examples 1 to 2 that the composite current collectors (polymer matrix and conductive layer are directly connected) of the corresponding structures of examples 1 to 8 have greater peel strength than the composite current collectors (polymer matrix and conductive layer are indirectly connected through an adhesive) of the corresponding structures of comparative examples 1 to 2, thereby indicating that the polymer matrix and conductive layer are directly connected, and the bonding force between the polymer matrix and conductive layer can be improved, thereby improving the bonding stability of the polymer matrix and conductive layer, as compared with the bonding stability of the polymer matrix and conductive layer.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (13)
1. A composite current collector, comprising:
a polymer matrix; and
a conductive layer;
in the thickness direction of the polymer matrix, the two sides of the polymer matrix are directly connected with the conductive layers, one side end of each of the two conductive layers exceeds the end of the polymer matrix on the side in a first preset direction, the inner walls of the two conductive layers and the side wall of the polymer matrix surround to form a U-shaped welding area, and the first preset direction is preset to be perpendicular to the thickness direction of the polymer matrix.
2. The composite current collector of claim 1, wherein said polymer matrix has a thickness of 3 to 6 μm.
3. The composite current collector of claim 1 wherein the thickness of the individual conductive layers is from 0.5 to 5 μm.
4. The composite current collector of claim 1 wherein the sheet resistance of each of said conductive layers is 1 to 400mΩ/≡.
5. A composite current collector according to any one of claims 1 to 4 wherein the orthographic projections of the two conductive layers are fully coincident in the thickness direction of the polymer matrix.
6. The composite current collector of claim 5 wherein, in said first predetermined direction, the other side ends of both said conductive layers are aligned with the ends of said polymer matrix on that side.
7. The composite current collector of claim 5 wherein said U-shaped weld zone has a dimension of 5-10 mm in said first predetermined direction.
8. The composite current collector according to any one of claims 1 to 4, wherein the conductive layer is made of Al.
9. The composite current collector according to any one of claims 1 to 4, wherein the conductive layer is Cu.
10. The composite current collector according to any one of claims 1 to 4, wherein the polymer matrix is made of polyethylene, biaxially oriented polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate or propylene.
11. A battery electrode comprising a composite current collector according to any one of claims 1 to 10.
12. A battery comprising the battery electrode of claim 11.
13. A powered device comprising the battery of claim 12.
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