CN115440990A

CN115440990A - Array base film, battery current collector, battery pole piece, battery and preparation method thereof

Info

Publication number: CN115440990A
Application number: CN202211245525.2A
Authority: CN
Inventors: 庄志; 郭桂略; 蔡裕宏; 刘洋; 虞少波; 程跃
Original assignee: Shanghai Energy New Materials Technology Co Ltd
Current assignee: Shanghai Energy New Materials Technology Co Ltd
Priority date: 2022-10-12
Filing date: 2022-10-12
Publication date: 2022-12-06

Abstract

The application provides an array base film, a battery current collector, a battery pole piece, a battery and a preparation method thereof, and belongs to the field of flexible electronic components. The array base film comprises a plurality of first regions which are distributed in an array mode and second regions which are distributed alternately with the first regions, the first regions comprise organic polymer layers, the second regions comprise organic polymer layers and conductive metal which is located on the surfaces of the organic polymer layers and inside the organic polymer layers, and the problems that a flexible conductive film and a tab are difficult to weld and poor in welding and the like can be solved to a certain extent through the array base film, so that the resistance between the tab and a pole piece is effectively reduced.

Description

Array base film, battery current collector, battery pole piece, battery and preparation method thereof

Technical Field

The application relates to the field of flexible electronic components, in particular to an array base film, a battery current collector, a battery pole piece, a battery and a preparation method of the battery.

Background

In the prior art, metal foils are often used as battery current collectors, but the metal foils do not have energy storage activity but occupy 15 to 30% of the mass of the battery, so that the energy density of the battery is affected, and in addition, the battery current collectors need to have certain mechanical strength, so that the mass proportion of the metal foils in the battery cannot be effectively reduced by reducing the thickness of the metal foils.

Based on this, technical staff has developed a flexible conductive film for replacing traditional metal foil battery mass flow body, and flexible conductive film can effectively reduce the quality ratio of battery mass flow body in the battery, plays the effect that promotes the energy density of battery, but, current flexible conductive film and utmost point ear in the welded process, have the welding difficulty and weld poor scheduling problem, lead to the resistance between utmost point ear and pole piece too high.

Disclosure of Invention

The applicant researches and discovers that the conventional flexible conductive film has the problems of difficult welding, poor welding and the like during welding due to the thin conductive layer and the low melting point of the organic polymer layer because the conductive layer is directly arranged on the two sides of the organic polymer layer and is welded with the electrode lug through the conductive layer.

The application aims to provide an array base film, a battery current collector, a battery pole piece, a battery and a preparation method thereof, which can solve the problems of difficulty in welding a flexible conductive film and a pole lug, poor welding and the like to a certain extent, so that the resistance between the pole lug and the pole piece is effectively reduced.

The embodiment of the application is realized as follows:

in a first aspect, an embodiment of the present application provides an array-based film, which includes a plurality of first regions distributed in an array, and second regions alternately distributed with the first regions, where the first regions include an organic polymer layer, and the second regions include an organic polymer layer and a conductive metal located on a surface and inside of the organic polymer layer.

Among the above-mentioned technical scheme, set up the second region into the form that organic polymer layer combines conductive metal for the second region has the function that runs through electrically conductive, thereby can directly weld with utmost point ear through the conductive metal of second region self, with the intercommunication that realizes the circuit, compare in current flexible conductive thin film, the array base film that this application provided has the advantage that welding process is simple and the welding is comparatively firm when the welding, thereby can effectively reduce the resistance between utmost point ear and pole piece.

In some alternative embodiments, the array distribution is in the form of a linear array; or the array distribution is in the form of a rectangular array.

Among the above-mentioned technical scheme, the array distribution sets up according to above-mentioned form, can make the overall structure of array base film comparatively regular, simultaneously, still is convenient for carry out technology preparation.

In some alternative embodiments, the array-based membrane has a thickness of 500 to 20000nm.

In the above technical solution, the reason why the thickness of the array base film is limited to the above range is: if the thickness is too small (welding has certain requirements on the thickness), it is inconvenient to weld the second region with the tab, and if the thickness is too large, the mass ratio of the array base film in the battery is too large (the mass ratio is equivalent to that of a conventional metal foil), and the effect of effectively improving the energy density of the battery cannot be achieved.

In some alternative embodiments, the conductive metal comprises one or more of Ni, zn, cu, co, mn, ti, ga, ge, sn, sb, zr, mo, al, cr, ag, and alloys of the corresponding elements.

Among the above-mentioned technical scheme, the kind of conductive metal is abundant, can select the conductive metal of suitable kind according to different battery systems to the electric property of assurance battery that can be better.

In a second aspect, embodiments of the present application provide a battery current collector, including a metal conductive layer and an array base film as provided in embodiments of the first aspect. In the thickness direction of the array base film, the metal conducting layer is positioned on one side or two sides of the array base film;

alternatively, a metal bonding layer and an array base film as provided in embodiments of the first aspect are included. The metal bonding layer is positioned on one side or two sides of the first area in the thickness direction of the array base film.

In the above technical solution, the battery current collector includes the array base film provided in the first aspect, and can directly realize welding with the tab through the second region of the array base film, compared with a conventional metal foil current collector, the mass ratio of the battery current collector in the battery can be effectively reduced, and the effect of improving the energy density of the battery is achieved; meanwhile, the structure of the conductive metal in the current collector of the battery is more in variety, and more implementable modes can be provided, so that the popularization and the application are facilitated.

In some alternative embodiments, the metal conductive layer has a thickness of 200 to 5000nm.

In the technical scheme, the thickness of the metal conducting layer is limited in the range, so that the metal conducting layer has proper thickness, and the metal conducting layer is ensured to have better conductivity.

In some optional embodiments, the metal conductive layer is disposed corresponding to both the first region and the second region.

In the technical scheme, the metal conducting layer is arranged according to the form, and compared with the situation that the metal conducting layer is only arranged corresponding to the first area, the thickness of the conducting metal in the second area can be properly increased, so that the metal conducting layer and the electrode lug can be conveniently welded.

In a third aspect, embodiments of the present application provide a battery current collector, which includes a non-metal conductive layer and an array base film as provided in embodiments of the first aspect. The non-metal conducting layer is positioned on one side or two sides of the first area in the thickness direction of the array base film.

In a fourth aspect, embodiments of the present application provide a battery pole piece, including a battery current collector as provided in the second or third aspect, and an active coating on a surface of the battery current collector.

In a fifth aspect, embodiments of the present application provide a battery, including a battery pole piece as provided in the fourth aspect.

In a sixth aspect, embodiments of the present application provide a method for preparing an array-based film, including the steps of:

and forming a plurality of first areas distributed in an array manner and second areas alternately distributed with the first areas, wherein the first areas comprise the organic polymer layer, and the second areas comprise the organic polymer layer and the conductive metal positioned on the surface and the inner part of the organic polymer layer.

According to the technical scheme, the array base film is prepared according to the process, and when the array base film is welded with the tab, the array base film has excellent performances of simple welding process, firm welding and the like.

In some alternative embodiments, the preparation of the array-based film comprises the steps of:

mixing a polymer raw material for preparing the array base film with a solvent to obtain a first precursor solution;

adding inorganic particles into part of the first precursor solution and mixing to obtain a second precursor solution;

preparing a polymer layer by alternately using the first precursor liquid and the second precursor liquid; wherein the first precursor liquid corresponds to the first area, and the second precursor liquid corresponds to the second area;

immersing the polymer layer into the pore-forming solution to dissolve the inorganic particles in the second region and form pores;

and applying raw materials for preparing the conductive metal into the holes, and forming the conductive metal by an electroless deposition technology.

In some alternative embodiments, the second region has a sheet resistance of 50 to 10000 mO/\9633;.

In the technical scheme, the sheet resistance of the corresponding second area under the preparation process is limited in the range, so that the resistance value between the pole piece and the pole lug after welding is appropriate.

In some alternative embodiments, the inorganic particles have a particle size of 100 to 2000nm.

In the above technical solution, the reason why the particle size of the inorganic particles is limited to the above range is that: if the particle diameter is too little on the one hand, the hole of formation is also less, is not convenient for conductive metal to get into and fills in the hole, and on the other hand if the hole is too big, the hole of formation is also too big, appears the gap easily during conductive metal fills, leads to electric conductive property to descend, and simultaneously, the hole is too big still leads to the membrane material to break at tensile in-process emergence easily.

In some alternative embodiments, the inorganic particles comprise one or more of inorganic salt particles, transition metal oxide particles, transition metal sulfide particles, elemental metals, and alloys thereof.

In the technical scheme, the inorganic particles are rich in types, so that more implementable embodiments are provided in the pore-forming stage, and conductive metal can be conveniently formed in the second region.

preparing a polymer layer by using the first precursor liquid;

applying a conductive metal to the surface and interior of the polymer layer at intervals using an intermittent ion implantation technique to form a conductive metal; in the polymer layer, the area without the conductive metal is the first area, and the area with the conductive metal is the second area.

In some alternative embodiments, the second region has a sheet resistance of 10-5000m Ω/\9633;.

In the technical scheme, the sheet resistance of the corresponding second area under the preparation process is limited in the range, so that the pole piece and the pole lug can have a resistance value with a proper size after being welded.

In some alternative embodiments, the energy of the ion implantation is 30 to 80keV and/or the dose of the ion implantation is 0.5 to 5 x 10 in applying the conductive metal spacers to the surface and inside of the polymer layer using a batch type ion implantation technique ¹⁷ ions/cm ² 。

In the technical scheme, the energy of ion implantation is limited in the range, so that the implantation energy is in a proper range, and the ions can better penetrate through the organic polymer layer to fulfill the aim of applying conductive metal; and limiting the ion implantation dosage in the range to ensure that the ion implantation dosage is in a proper range, so as to ensure that the content of the conductive metal in the second region has a proper mass ratio to ensure the conductivity of the second region.

In a seventh aspect, an embodiment of the present application provides a method for preparing a battery current collector, including the following steps:

providing an array base film as provided in embodiments of the first aspect; and

forming a metal conducting layer on one side or two sides of the array base film or forming a nonmetal conducting layer on one side or two sides of the first area in the thickness direction of the array base film;

or, forming a metal bonding layer on one side or two sides of the first region in the thickness direction of the array base film;

alternatively, the non-metal conductive layer is formed on one side or both sides of the first region in the thickness direction of the array base film.

According to the technical scheme, the battery current collector is prepared according to the process, and when the battery current collector is welded with the lug, the battery current collector has excellent performances of simple welding process, firm welding and the like.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.

Fig. 1 is a schematic structural diagram of an array base film provided in an embodiment of the present application at a front view angle;

fig. 2 is a schematic structural diagram of an array base film provided in an embodiment of the present application in a top view;

fig. 3 is a schematic structural diagram of another array base film provided in the embodiments of the present application in a front view;

fig. 4 is a schematic structural diagram of another array-based film provided in the embodiments of the present application at a front view angle;

fig. 5 is a schematic structural diagram of a current collector of a battery provided in an embodiment of the present application in a front view;

fig. 6 is a schematic structural diagram of a current collector of a battery provided in an embodiment of the present application in a front view;

fig. 7 is a schematic structural diagram of a battery pole piece provided in an embodiment of the present application in a front view;

fig. 8 is a schematic structural diagram of another battery pole piece provided in an embodiment of the present application in a front view.

Icon: 10-array base film; 100-a first area; 200-a second region; 20-a metal conductive layer; 30-a non-metallic conductive layer; 1-a battery current collector; 2-a battery pole piece; 40-active coating.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that "and/or" in the present application, such as "feature 1 and/or feature 2" refers to "feature 1" alone, "feature 2" alone, and "feature 1" plus "feature 2" alone.

In addition, in the description of the present application, the meaning of "a plurality" of "one or more" means two or more unless otherwise specified; the range of "numerical value a to numerical value b" includes both values "a" and "b", and "unit of measure" in "numerical value a to numerical value b + unit of measure" represents both "unit of measure" of "numerical value a" and "numerical value b".

The following describes an array base film, a battery current collector, a battery pole piece, a battery and a preparation method thereof in embodiments of the present application.

Referring to fig. 1, in a first aspect, an embodiment of the present application provides an array-based film 10, including a plurality of first regions 100 distributed in an array, and second regions 200 alternately distributed with the first regions 100, where the first regions 100 include an organic polymer layer, and the second regions 200 include an organic polymer layer and a conductive metal located on a surface and inside of the organic polymer layer.

In this application, set up the second region 200 into the form that organic polymer layer combines conductive metal, make the second region 200 have the function that runs through electrically conductively, thereby can directly weld with utmost point ear through the conductive metal of second region 200 self, in order to realize the intercommunication of circuit, compare in current flexible conductive thin film, the array base film 10 that this application provided has the advantage that welding process is simple and the welding is comparatively firm when the welding, thereby can effectively reduce the resistance between utmost point ear and pole piece.

It should be noted that, compared with a flexible conductive film (i.e., a hollow structure without a supporting portion for supporting conductive metal) in which a welding region is only provided with conductive metal and no organic polymer layer, the second region 200 of the array base film 10 provided by the present application has an organic polymer layer, so that when the array base film is welded to a tab, a welding portion can be effectively supported, thereby ensuring that the array base film 10 has high tensile strength; in addition, compared to a flexible conductive film in which a solder pad is formed as a through hole and filled with a conductive metal layer (the through hole reduces the mechanical strength of the film, and the difficulty and requirement of the corresponding process are high), the array base film 10 provided in the present application also has an advantage of ensuring that the mechanical properties and the workability of the film are improved.

The distribution of the arrays in the array base film 10 is not limited, and may be adjusted according to actual needs.

Referring to fig. 2-4, as an example, the array distribution is in the form of a linear array; or the array distribution is in the form of a rectangular array.

In this embodiment, the array distribution is set according to the above form, so that the overall structure of the array base film 10 is relatively regular, and meanwhile, the process preparation is facilitated.

Fig. 2 shows an array base film 10 obtained by stretching a film in a longitudinal direction (i.e., a longitudinal direction), fig. 3 shows an array base film 10 obtained by stretching a film in a width direction (i.e., a transverse direction), and fig. 4 shows an array base film 10 obtained by stretching a film in both the longitudinal direction (i.e., the longitudinal direction) and the width direction (i.e., the transverse direction).

It should be noted that, in consideration of the carrying capacity of the array base film 10 to the energy storage active material and the convenience in welding, the size of the first region 100 may be set to be larger than that of the second region 200, and it is understood that the specific sizes of the first region 100 and the second region 200 are not limited, and may be correspondingly adjusted according to the specification of the tab.

As an example, when the array distribution is in the form of a linear array and the film is stretched in the machine direction, the first region 100 has a dimension in the machine direction of 5 to 500cm, such as, but not limited to, a dimension of any one or a range of values between 5cm, 10cm, 20cm, 50cm, 100cm, 200cm, 300cm, 400cm, and 500 cm; the second region 200 has a dimension in the longitudinal direction of 1-20 cm, such as, but not limited to, a dimension of any one of 1cm, 3cm, 4cm, 5cm, 10cm, 15cm, and 20cm, or a range of values between any two.

In other possible embodiments, when the array distribution is in the form of a linear array and the film is stretched in the transverse direction, the size of the second region 200 in the transverse direction is 1/100 to 1/5 of the array base film 10.

It should be noted that the thickness of the array base film 10 is not limited, and can be specifically adjusted according to actual needs.

As an example, the array base film 10 has a thickness of 500 to 20000nm, such as, but not limited to, any one or a range between any two of 500nm, 1000nm, 5000nm, 10000nm, 15000nm and 20000nm.

In this embodiment, the thickness of the array base film 10 is limited to the above range because: if the thickness is too small (welding has certain requirement on thickness), it is inconvenient to weld the second region 200 to the tab, and if the thickness is too large, the mass ratio of the array base film 10 in the battery is too large (mass ratio is equivalent to that of a conventional metal foil), which cannot effectively increase the energy density of the battery.

It should be noted that the kind of the conductive metal is not limited, and can be adjusted according to actual needs.

As an example, the conductive metal includes one or more of Ni, zn, cu, co, mn, ti, ga, ge, sn, sb, zr, mo, al, cr, ag, and alloys of the corresponding elements.

In the embodiment, the conductive metal is rich in types, and the conductive metal with a proper type can be selected according to different battery systems, so that the electrical performance of the battery can be better ensured.

Referring to fig. 5, in a second aspect, the present application provides a battery current collector 1, including a metal conductive layer 20 and an array base film 10 as provided in the first aspect. The metal conductive layer 20 is positioned at one side or both sides of the array base film 10 in the thickness direction of the array base film 10;

alternatively, a metal adhesive layer (not shown in the figure) and the array base film 10 provided as an embodiment of the first aspect are included. The metal adhesive layer is positioned at one side or both sides of the first region 100 in the thickness direction of the array base film 10.

In the application, the battery current collector 1 includes the array base film 10 provided in the embodiment of the first aspect, and welding with a tab can be directly achieved through the second region 200 of the array base film 10, so that compared with a conventional metal foil current collector, the mass ratio of the battery current collector 1 in a battery can be effectively reduced, and an effect of improving the energy density of the battery is achieved; meanwhile, the structure of the conductive metal in the battery current collector 1 is more in variety, and more implementable modes can be provided, so that the popularization and the application are facilitated.

It should be noted that the thickness of the metal conductive layer 20 is not limited, and can be adjusted according to actual needs.

As an example, the metal conductive layer 20 has a thickness of 200 to 5000nm, such as, but not limited to, a thickness of any one of 200nm, 500nm, 1000nm, 2000nm, 3000nm, 4000nm, and 5000nm, or a range between any two.

In this embodiment, the thickness of the metal conductive layer 20 is limited to the above range, so that the metal conductive layer 20 can have a suitable thickness to ensure good conductivity.

It should be noted that the material of the conductive metal layer is not limited, and can be adjusted according to actual needs.

As an example, the material of the metal conductive layer 20 includes, but is not limited to, common metal Al, transition metal and its corresponding alloy (e.g., cobalt, nickel, copper, titanium, zinc, manganese, chromium, silver, etc.). Since the metal conductive layer 20 may be welded to the tab, the metal conductive layer 20 may be provided only in correspondence with the first region 100, or may be provided in correspondence with both the first region 100 and the second region 200.

As an example, the metal conductive layer 20 is disposed corresponding to both the first region 100 and the second region 200.

In this embodiment, by providing the metal conductive layer 20 in the above-described manner, the thickness of the conductive metal in the second region 200 can be increased as appropriate, compared to providing only the metal conductive layer 20 corresponding to the first region 100, thereby facilitating welding with the tab.

The metal adhesive layer and the metal conductive layer are made of the same metal material.

The thickness of the metal adhesive layer is not limited, and may be adjusted according to actual needs.

As an example, the thickness of the metal adhesive layer is 500 to 5000nm.

Referring to fig. 6, in a third aspect, the present embodiment provides a battery current collector 1, which includes a non-metal conductive layer 30 and an array base film 10 as provided in the first embodiment. The non-metal conductive layer 30 is positioned at one side or both sides of the first region 100 in the thickness direction of the array base film 10.

It should be noted that, since both surfaces of the solder are required to be made of metal materials, when the conductive layer is made of nonmetal, the conductive layer can be disposed only corresponding to the first region 100.

It should be noted that the material of the non-metal conductive layer 30 is not particularly limited, and may be adjusted according to actual needs.

As one example, the non-metallic conductive layer 30 includes one or more of conductive carbon black, carbon nanotubes, and graphene.

Referring to fig. 7 and 8, in a fourth aspect, an embodiment of the present application provides a battery pole piece 2, including a battery current collector 1 as provided in the second or third aspect, and an active coating 40 on a surface of the battery current collector 1.

It is to be noted that the kind of the active coating layer 40 is not particularly limited and may be set according to the conventional selection in the art.

In a fifth aspect, embodiments of the present application provide a battery, including a battery pole piece as provided in the third aspect.

and forming a plurality of first areas distributed in an array and second areas alternately distributed with the first areas, wherein the first areas comprise the organic polymer layer, and the second areas comprise the organic polymer layer and the conductive metal positioned on the surface and the inner part of the organic polymer layer.

In the application, the array base film is prepared according to the process, and when the array base film is welded with the lug, the array base film has excellent performances of simple welding process, firm welding and the like.

In the preparation process of the array base film, the stretching direction of the film material is not limited, and the film material may be stretched in the longitudinal direction, the transverse direction, or both the longitudinal direction and the transverse direction.

As an example, the preparation of the array-based film includes the steps of:

and applying raw materials for preparing the conductive metal into the hole, and forming the conductive metal by an electroless deposition technology.

It should be noted that the specific processes and steps involved in the electroless deposition process are not particularly limited, and may be performed according to conventional operations in the art.

It is to be noted that the kind of the polymer raw material is not limited.

As an example, the polymer feedstock includes one or more of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate, and polycarbonate.

It should be noted that the sheet resistance of the second area is not limited.

As an example, the second region has a sheet resistance of 50-10000 mOhm/\9633, such as, but not limited to, 50 mOhm/\9633, 100 mOhm/\9633, 500 mOhm/\9633, 1000 mOhm/\ 9633, 5000 mOhm/\9633, and 10000 mOhm/\9633, or a range between any two.

In this embodiment, the sheet resistance of the corresponding second region in the manufacturing process is limited to the above range, so that after the pole piece and the tab are welded, a resistance value with an appropriate magnitude is formed between the pole piece and the tab.

It should be noted that the particle size of the inorganic particles is not limited, and can be defined according to actual needs.

As an example, the inorganic particles have a particle size of 100 to 2000nm, such as, but not limited to, a particle size of any one or a range between any two of 100nm, 500nm, 1000nm, 1500nm, and 2000nm.

In this embodiment, the reason why the particle diameter of the inorganic particles is limited to the above range is that: if the particle diameter is too little on the one hand, the hole of formation is also less, is not convenient for conductive metal to get into and fills in the hole, and on the other hand if the hole is too big, the hole of formation is also too big, appears the gap easily during conductive metal fills, leads to electric conductive property to descend, and simultaneously, the hole is too big still leads to the membrane material to break at tensile in-process emergence easily.

It is to be noted that the kind of the inorganic particles is not limited.

As one example, the inorganic particles include one or more of inorganic salt particles, transition metal oxide particles, transition metal sulfide particles, elemental metals, and alloys thereof.

In this embodiment, the inorganic particles are abundant, allowing more possible embodiments of the pore-forming stage, thereby facilitating the formation of conductive metal in the second region.

It is to be noted that the kind of the inorganic salt particles is not limited.

As an example, the inorganic salt particles include NaCl, KCl, feCl ₂ 、FeCl ₃ 、NH ₄ Cl、Na ₂ CO ₃ 、K ₂ CO ₃ 、Na ₂ SO ₄ And K ₂ SO ₄ One or more of (a).

It is to be noted that the kind of the transition metal oxide particles is not limited.

As an example, the transition metal oxide particles include ZnO, fe ₂ O ₃ 、Fe ₃ O ₄ 、Cu ₂ O, cuO, niO and Co ₃ O ₄ One or more of (a).

It is to be noted that the kind of the transition metal sulfide particles is not limited.

As an example, the transition metal sulfide particles include one or more of ZnS, feS, cuS, and CoS.

It is to be noted that the kind of the metal element is not limited.

As an example, the elemental metal includes one or more of Cu, fe, al, ni, co, mn, and Zn.

As an example, the preparation of the array-based film includes the steps of:

preparing a polymer layer by using the first precursor liquid;

applying a conductive metal spacer to the interior of the polymer layer using a batch ion implantation technique to form a conductive metal; in the polymer layer, the area without the conductive metal is the first area, and the area with the conductive metal is the second area.

It should be noted that the sheet resistance of the second area is not limited.

As an example, the second region has a sheet resistance of 10-5000m Ω/\9633, such as, but not limited to, 10m Ω/\9633, 100m Ω/\9633, 500m Ω/\9633, 1000m Ω/\9633, and 5000m Ω/\9633ora range between any two thereof.

It should be noted that, in the ion implantation process, the energy of the ion implantation and the dose of the ion implantation are not limited, and may be adjusted according to actual needs.

As an example, in applying the conductive metal spacers to the surface and inside of the polymer layer using an intermittent ion implantation technique, the energy of the ion implantation is 30-80 keV, such as but not limited to a point value or a range value between any two of 30keV, 40keV, 50keV, 60keV, 70keV, and 80 keV; and/or the dosage of ion implantation is 0.5-5 x 10 ¹⁷ ions/cm ² For example, but not limited to, a dosage of 0.5X 10 ¹⁷ ions/cm ² 、1×10 ¹⁷ ions/cm ² 、2×10 ¹⁷ ions/cm ² 、3×10 ¹⁷ ions/cm ² 、4×10 ¹⁷ ions/cm ² And 5X 10 ¹⁷ ions/cm ² Or any range value therebetween.

In this embodiment, the energy for ion implantation is limited to the above range so that the implantation energy is in an appropriate range, thereby being able to penetrate the organic polymer layer well for the purpose of applying the conductive metal; and limiting the ion implantation dosage in the range to ensure that the ion implantation dosage is in a proper range, so as to ensure that the content of the conductive metal in the second region has a proper mass ratio to ensure the conductivity of the second region.

In the ion implantation process, the steps and processes that are not particularly limited or described are not limited, and may be performed according to the conventional operations in the art.

forming a metal conducting layer on one side or two sides of the array base film in the thickness direction of the array base film;

In the application, the battery current collector is prepared according to the process, and when the battery current collector is welded with the lug, the battery current collector has the advantages of simple welding process, firm welding and the like.

It should be noted that the preparation method of the metal conductive layer is not limited, and can be adjusted according to actual situations.

As an example, when the conductive layer is a metal conductive layer, it may be prepared using a metal deposition technique.

It is noted that the type of metal deposition technique is not limited and may be one or more of chemical vapor deposition, atomic layer deposition, physical vapor deposition, electroless plating, and electroplating.

It should be noted that the bonding process of the metal bonding layer is not limited, and can be performed according to the conventional operation in the art.

It should be noted that the preparation method of the non-metal conductive layer is not limited, and can be adjusted according to actual situations.

When the conductive layer is a non-metal conductive layer, one or more of coating and screen printing may be employed.

It should be noted that, in order to better use the prepared battery current collector for battery assembly to obtain a battery product with better electrical properties, the parameters of the battery current collector prepared by the method may be defined.

As an example, taking the conductive layer as a metal conductive layer, the sheet resistance of the battery current collector is 10-10000m omega/\9633, the tensile strength is 200-600MPa, and the peel strength is 300-800N/m.

As an example, the conductive layer is taken as a metal bonding layer, the sheet resistance of the battery current collector is 2-5000m omega/\ 9633, and the tensile strength is 200-500MPa.

It should be noted that, because the prepared battery current collector is distributed in an array, that is, the plurality of first areas and the plurality of second areas exist at the same time, considering the welding and matching with the tabs, it can be determined whether the battery current collector needs to be cut according to actual needs (for example, when a pole piece is welded with a single tab, the battery current collector needs to be cut, and when the pole piece is welded with multiple tabs, the battery current collector does not need to be cut).

It should be noted that, since the battery current collector belongs to the upstream product of the battery pole piece, and the array base film belongs to the upstream product of the battery current collector (that is, the preparation method of the battery pole piece includes the preparation methods of the battery current collector and the array base film at the same time), the present application can be described by the preparation method of the battery pole piece.

The features and properties of the present application are described in further detail below with reference to examples.

Example 1

The embodiment of the application provides a preparation method of a battery pole piece, which comprises the following steps:

preparation of S1 array base membrane

Dissolving polypropylene, polyethylene, polystyrene, polyvinyl chloride, polypropylene ethylene, polytetrafluoroethylene, polyvinylidene fluoride, silicon rubber, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate or polycarbonate in a mixed solvent of white oil and dichloromethane, fully dispersing and dissolving, dividing into two parts, and adding 500nm Cu into one part ₂ And mixing the O and Cu particles uniformly to obtain a second precursor solution, and using the untreated part as the first precursor solution.

And alternately using the first precursor solution and the second precursor solution to prepare the organic polymer layer according to a wet film-making process, wherein the organic polymer layer is prepared by longitudinal stretching, the sizes of the first region and the second region in the longitudinal direction are respectively 20cm and 1cm, and the thickness of the organic polymer layer (namely the array base film) is 5000nm.

The organic polymer layer was immersed in 0.05M dilute hydrochloric acid for 10min, then rinsed with deionized water, and then SnCl was used ₂ -PdCl ₂ As sensitizers and activators, niSO ₄ And CuSO ₄ As main salt, naH ₂ PO ₂ Depositing a chemical plating system which is a reducing agent in a second area to obtain Ni-Cu conductive metal so as to prepare and obtain an array base film; wherein the sheet resistance of the second region is 1000m omega/\9633;.

S2 preparation of battery current collector

Taking the array base film prepared in the step S1 as a substrate, and then forming Al conducting layers on two sides of the array base film through a physical vapor deposition technology to prepare a battery current collector; wherein the thickness of the Al conductive layer is 1000nm.

S3 preparation of battery pole piece

And taking the battery current collector substrate prepared in the step S2 as a substrate, and then forming an active coating on the two sides of the battery current collector corresponding to the first area by an intermittent coating technology to prepare the battery pole piece.

Example 2

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: cu ₂ The grain diameter of O and Cu particles is 100nm, the thickness of the array basement membrane is 500nm, al conducting layers are formed on two sides of the array basement membrane through a chemical vapor deposition technology, the thickness of the Al conducting layers is 200nm, and the sheet resistance of the second area is 10000m omega/\96330.

Example 3

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: cu ₂ The grain diameter of O and Cu particles is 2000nm, the thickness of the array base film is 20000nm, al conductive layers are formed on two sides of the array base film through an electroless deposition technology, the thickness of the Al conductive layers is 5000nm, and the sheet resistance of the second area is 50m omega/\9633.

Example 4

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: the second region has a dimension in the longitudinal direction of 2cm.

Example 5

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: the second region has a dimension in the longitudinal direction of 3cm.

Example 6

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: the second region has a dimension in the longitudinal direction of 5cm.

Example 7

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: and forming Cu conductive layers on two sides of the array base film by a physical vapor deposition technology.

Example 8

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 4 in that: and forming Cu conductive layers on two sides of the array base film by a physical vapor deposition technology.

Example 9

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 5 in that: and forming Cu conductive layers on two sides of the array base film through a physical vapor deposition technology.

Example 10

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 6 in that: and forming Cu conductive layers on two sides of the array base film by a physical vapor deposition technology.

Example 11

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: cu ₂ The particle size of the O and Cu particles was 50nm.

Example 12

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: cu ₂ The particle size of the O and Cu particles was 2500nm.

Example 13

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: the thickness of the array base film was 400nm.

Example 14

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 1 in that: the thickness of the array basal membrane is 20500nm.

Example 15

preparation of S1 array base film

Dissolving polypropylene, polyethylene, polystyrene, polyvinyl chloride, polypropylene ethylene, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate or polycarbonate into a mixed solvent of white oil and dichloromethane, and fully dispersing and dissolving to obtain a first precursor solution.

And preparing the organic polymer layer by using the first precursor solution according to a wet film preparation process, wherein the organic polymer layer is prepared by adopting longitudinal stretching, and the thickness of the organic polymer layer (namely the array base film) is 5000nm.

By using intermittent ion implantationApplying Zn metal ions to the surface and inside of the organic polymer layer to form Zn conductive metal to prepare an array base film; wherein, in the array basement membrane, the area without Zn conductive metal is the first area, the area with Zn conductive metal is the second area, the sheet resistance of the second area is 1000m omega/\9633, the energy of ion implantation is 50keV, the dosage of ion implantation is 2 x 10 ¹⁷ ions/cm ² 。

S2 preparation of battery current collector

S3 preparation of battery pole piece

And taking the battery current collector base material prepared in the step S2 as a substrate, and then forming an active coating in the area corresponding to the first area on the two sides of the battery current collector by using an intermittent coating technology to prepare a battery pole piece.

Example 16

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 15 in that: applying Ni metal ions to the surface and the interior of the organic polymer layer by intermittent ion implantation to form Ni conductive metal, the second region having a sheet resistance of 5000 mO/\96330, the ion implantation energy of 30keV and the ion implantation dose of 0.5 × 10 ¹⁷ ions/cm ² 。

Example 17

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 15 in that: applying Cu metal ions to the surface and the interior of the organic polymer layer by using a batch ion implantation technique to form a Cu conductive metal, the sheet resistance of the second region being 10m omega/\9633, the energy of the ion implantation being 80keV, and the dose of the ion implantation being 5 x 10 ¹⁷ ions/cm ² 。

Example 18

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 15 in that: the second region has a dimension in the longitudinal direction of 2cm.

Example 19

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 15 in that: the second region has a dimension in the longitudinal direction of 3cm.

Example 20

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 15 in that: the second region has a dimension in the longitudinal direction of 5cm.

Example 21

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 15 in that: and forming Cu conductive layers on two sides of the array base film through a physical vapor deposition technology.

Example 22

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 18 in that: and forming Cu conductive layers on two sides of the array base film through a physical vapor deposition technology.

Example 23

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 19 in that: and forming Cu conductive layers on two sides of the array base film by a physical vapor deposition technology.

Example 24

The embodiment of the application provides a preparation method of a battery pole piece, which is different from the embodiment 20 in that: and forming Cu conductive layers on two sides of the array base film through a physical vapor deposition technology.

Comparative example 1

The application provides a preparation method of a battery pole piece, which comprises the following steps:

preparation of S1 array base film

The method comprises the steps of preparing an organic polymer layer by using a first precursor solution according to a wet film preparation process, wherein the organic polymer layer is prepared by adopting longitudinal stretching, and the thickness of the organic polymer layer (namely the array base film) is 5000nm so as to prepare the array base film.

S2 preparation of battery current collector

S3 preparation of battery pole piece

Comparative example 2

The application and the comparative example provide a preparation method of a battery pole piece, and the difference between the preparation method and the comparative example 1 is as follows: and forming Cu conductive layers on two sides of the array base film by a physical vapor deposition technology.

Test example 1

Test of welding strength of battery pole piece and pole lug

The test method comprises the following steps: the battery pole pieces prepared in the embodiments 1 to 24 and the comparative examples 1 and 2 are respectively labeled, then, a tension tester of an Shimadzu electronic universal tester AGS-X-10kN type is adopted, the pole lug is clamped by a clamp, then, the tension value N of the pole lug pulled off from the current collector and the pole lug width are tested by the tension tester to be D, and then, the pole lug welding strength F = N/D can be calculated.

TABLE 1 test results of the weld strength of the battery pole piece and tab

Referring to table 1, as can be seen from comparison between examples 1 to 10 and examples 15 to 24 and comparative examples 1 to 2, the battery pole piece prepared by the preparation method provided in the embodiment of the present application has significantly higher welding strength between the battery pole piece and the tab compared to the battery pole piece prepared by the conventional preparation method.

As is clear from comparison of example 1 with examples 11 to 12, when the particle diameter of the inorganic particles is not within the predetermined range, the welding strength between the electrode sheet and the tab obtained by the preparation is lowered.

As is clear from example 1 and examples 13 to 14, when the thickness of the array base film is not within the predetermined range, the welding strength between the electrode sheet and the tab prepared is reduced.

Test example 2

Weld pass Rate Performance test

The test method comprises the following steps:

the battery pole pieces prepared in examples 1 to 24 and comparative examples 1 and 2 were combined and paired to assemble different battery samples, then the assembled batteries were numbered, and then the welding pass rate, the welding average resistance, the first cycle discharge average power, and the 50 th cycle discharge average power were tested for the corresponding batteries.

In the test of the welding pass rate, the resistance between the battery pole piece and the pole lug is lower than 20m omega; in the test of the average power of the first-cycle discharge, the average power is equivalent to that of a conventional metal foil current collector; the 50 th cycle discharge average power was measured to be equivalent to the first cycle discharge voltage and to be 2C-rate.

Table 2 electrical property test results of the battery

As can be seen from table 2, the electrical properties of the battery assembled with the battery pole piece prepared by the preparation method provided in the embodiment of the present application in the aspects of the welding pass rate, the welding average resistance, the first cycle discharge average power, the 50 th cycle discharge average power, and the like are all significantly improved compared with the battery assembled with the conventional battery pole piece.

In the test results of the average resistance between the battery electrode sheet and the tab, (-) represents the average resistance between the negative electrode sheet and the tab, and (+) represents the average resistance between the positive electrode sheet and the tab.

The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.

Claims

1. An array-based film comprises a plurality of first regions distributed in an array manner and second regions alternately distributed with the first regions, wherein the first regions comprise organic polymer layers, and the second regions comprise organic polymer layers and conductive metals positioned on the surfaces and the inner parts of the organic polymer layers.

2. The array-based film of claim 1, wherein the array is distributed in the form of a linear array; or the array is distributed in the form of a rectangular array.

3. The array base film according to claim 1 or 2, wherein the thickness of the array base film is 500 to 20000nm.

4. The array based film of claim 1 or 2, wherein the conductive metal comprises one or more of Ni, zn, cu, co, mn, ti, ga, ge, sn, sb, zr, mo, al, cr, ag, and alloys of the corresponding elements.

5. A battery current collector, comprising:

a metal conductive layer; and

the array base film according to any one of claims 1 to 4, wherein the metal conductive layer is positioned on one side or both sides of the array base film in a thickness direction of the array base film;

alternatively, the first and second electrodes may be,

a metal bonding layer; and

the array base film of any one of claims 1 to 4, wherein the metal adhesive layer is positioned at one side or both sides of the first region in a thickness direction of the array base film.

6. The battery current collector of claim 5, wherein the thickness of the metallic conductive layer is between 200 and 5000nm.

7. The battery current collector of claim 5 or 6, wherein the metallic conductive layer is disposed in correspondence with both the first region and the second region.

8. A battery current collector, comprising:

a non-metallic conductive layer; and

the array substrate film according to any one of claims 1 to 4, wherein the non-metal conductive layer is positioned on one side or both sides of the first region in a thickness direction of the array substrate film.

9. A battery pole piece, comprising:

a battery current collector as claimed in any one of claims 5 to 8 and an active coating on the surface of the battery current collector.

10. A battery comprising the battery pole piece of claim 9.

11. The preparation method of the array base film is characterized by comprising the following steps of:

forming a plurality of first areas distributed in an array mode and second areas distributed with the first areas in an alternating mode, wherein the first areas comprise organic polymer layers, and the second areas comprise organic polymer layers and conductive metals located on the surfaces and the inner portions of the organic polymer layers.

12. The method for preparing the array base film according to claim 11, comprising the steps of:

preparing the polymer layer by alternately using the first precursor liquid and the second precursor liquid; wherein the first precursor liquid corresponds to the first region and the second precursor liquid corresponds to the second region;

immersing the polymer layer into a pore-forming solution to dissolve the inorganic particles in the second region and form pores;

13. The method of claim 12, wherein the square resistance of the second region is 50 to 10000 mOhm/96330.

14. The method of manufacturing an array-based film according to claim 12, wherein the inorganic particles have a particle size of 100 to 2000nm.

15. The method of any one of claims 12-14, wherein the inorganic particles comprise one or more of inorganic salt particles, transition metal oxide particles, transition metal sulfide particles, elemental metals, and alloys thereof.

16. The method for preparing the array base film according to claim 11, comprising the steps of:

preparing the polymer layer by using the first precursor liquid;

applying the conductive metal to the surface and interior of the polymer layer at intervals using an intermittent ion implantation technique to form the conductive metal; wherein, in the polymer layer, a region to which the conductive metal is not applied is a first region, and a region to which the conductive metal is applied is a second region.

17. The method of claim 16, wherein the second region has a sheet resistance of 10 to 5000m Ω/\9633;.

18. The method of claim 16 or 17, wherein the conductive metal is applied to the surface and the inner portion of the polymer layer at intervals by a batch ion implantation method, the energy of the ion implantation is 30-80 keV, and/or the dose of the ion implantation is 0.5-5 x 10 ¹⁷ ions/cm ² 。

19. A preparation method of a battery current collector is characterized by comprising the following steps:

providing a base film of the array as defined in any one of claims 1 to 4; and

forming a metal conductive layer on one side or both sides of the array base film in a thickness direction of the array base film;

alternatively, the first and second electrodes may be,

forming a metal bonding layer on one side or both sides of the first region in a thickness direction of the array base film;

alternatively, the first and second electrodes may be,

and forming a non-metal conductive layer on one side or two sides of the first region in the thickness direction of the array base film.