CN113097494A - Current collector and application thereof - Google Patents

Current collector and application thereof Download PDF

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Publication number
CN113097494A
CN113097494A CN202110350293.6A CN202110350293A CN113097494A CN 113097494 A CN113097494 A CN 113097494A CN 202110350293 A CN202110350293 A CN 202110350293A CN 113097494 A CN113097494 A CN 113097494A
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current collector
insulating layer
layer
lithium ion
holes
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CN202110350293.6A
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CN113097494B (en
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赵伟
张赵帅
李素丽
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention provides a current collector and application thereof. The current collector comprises an insulating layer, a first conducting layer and a second conducting layer, wherein the first conducting layer and the second conducting layer are arranged on two functional surfaces of the insulating layer; the insulating layer comprises a first part and a second part, the first part is provided with N first through holes, first electric conductors for connecting the first conducting layer and the second conducting layer are filled in the first through holes, and N is larger than or equal to 1. When the current collector is used for preparing the lithium ion battery, the potential safety hazard caused by large current density of a lug connection area when the lithium ion battery is electrified can be solved, the lug connection can be carried out by adopting a conventional lug connection method, and the preparation process is simple; because the current collector is provided with the insulating layer, when the temperature of the lithium ion battery rises, the insulating layer can be melted and deformed, the current path of the lithium ion battery is cut off, and the safety performance of the lithium ion battery is improved.

Description

Current collector and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a current collector and application thereof.
Background
The lithium ion battery has high energy density and high power density, is a secondary battery with wide application, and has wide application prospect in the fields of consumer electronics, electric vehicles, energy storage and the like. However, under some abuse conditions (such as needling, squeezing, bumping, etc.), lithium ion batteries can cause internal short circuits that can cause thermal runaway leading to safety hazards. Therefore, there is a growing interest in improving the safety performance of lithium ion batteries.
The current collector is an important component of the lithium ion battery, and the performance of the current collector directly influences the performance of the lithium ion battery. The conventional lithium ion battery current collector is made of metal foil, the positive electrode is usually made of metal aluminum foil, the negative electrode is usually made of metal copper foil, and current cannot be cut off under the condition that short circuit occurs inside the battery, so that heat accumulation can be caused, and thermal runaway is finally caused.
In the prior art, the current collector with a three-layer structure of conducting layer-insulating layer-conducting layer is used for a lithium ion battery, so that short-circuit current can be cut off from the inside when the battery is subjected to internal short circuit, and thermal runaway inside the battery is inhibited, thereby greatly improving the safety performance of the battery. However, because the two conductive layers in the current collector with the three-layer structure of "conductive layer-insulating layer-conductive layer" are separated by the insulating layer, electronic conduction cannot be realized between the two conductive layers, when tab connection is performed, the connection process of the tab needs to be greatly changed, so that the manufacturing process is complex, the manufacturing process of the lithium ion battery is complex, the reliability of the manufactured lithium ion battery is reduced, meanwhile, the complex connection process also affects the performance of the battery, especially, a welding spot is too large during tab welding, the internal resistance of the battery is increased, and the internal resistance of the battery obtained by the current collector with the insulating layer in the middle is obviously increased compared with the internal resistance of the battery obtained by the conventional metal foil current collector.
In order to overcome the defect of high internal resistance of a battery prepared by a current collector with a three-layer structure of 'conducting layer-insulating layer-conducting layer', a through hole can be formed in the insulating layer, a conductor is filled in the through hole, the two conducting layers distributed on two sides of the insulating layer are enabled to realize electronic conduction through the conductor, but the safety performance of the current collector obtained through the arrangement is difficult to meet the requirement.
Therefore, it is required to provide a current collector having excellent safety and low internal resistance.
Disclosure of Invention
The invention provides a current collector which has good safety performance and lower internal resistance.
The invention provides a pole piece which has good safety performance and lower internal resistance.
The invention provides an electrochemical device which has low internal resistance and good safety performance.
The invention provides a current collector, which comprises an insulating layer, a first conducting layer and a second conducting layer, wherein the first conducting layer and the second conducting layer are arranged on two functional surfaces of the insulating layer;
the insulating layer comprises a first part and a second part, the first part is provided with N first through holes, first electric conductors connecting the first conducting layer and the second conducting layer are filled in the first through holes, and N is larger than or equal to 1.
The current collector is characterized in that the second part is provided with M second through holes, the second through holes are filled with second electric conductors for connecting the first conductive layer and the second conductive layer, the electric conductivity of the first part is greater than that of the second part, and M is greater than or equal to 1.
The current collector as described above, wherein, on the first functional surface of the insulating layer, a ratio of a total area of the first through holes to an area of the first portion is θ 1, and 7% θ 1 is 80% or less.
The current collector as described above, wherein the area of the second portion in the first functional surface is 80% to 90%.
The current collector as described above, wherein the thickness of the first and/or second conductive layer is 0.1-3 μm.
The current collector as described above, wherein the insulating layer has a thickness of 1 to 20 μm.
The current collector as described above, wherein the insulating layer comprises a polymer.
The current collector as described above, wherein the insulating layer further comprises an inorganic insulating material;
the inorganic insulating material comprises at least one of aluminum oxide, silicon carbide, silicon oxide, glass fiber, titanium dioxide, zirconium dioxide, magnesium hydroxide, aluminum hydroxide, boehmite, barium sulfate, barium titanate, aluminum titanate, zinc oxide, boron nitride, aluminum nitride, magnesium nitride, attapulgite, zinc phosphate or zinc borate.
The invention further provides a pole piece, wherein the pole piece comprises the current collector and an active layer, and the active layer is arranged on the functional surface of the first conducting layer and/or the second conducting layer corresponding to the second part.
The invention also provides an electrochemical device, which comprises the pole piece.
The current collector comprises an insulating layer, a first conducting layer and a second conducting layer, wherein the first conducting layer and the second conducting layer are arranged on two functional surfaces of the insulating layer; the insulating layer comprises a first part and a second part, the first part is provided with N first through holes, first electric conductors connecting the first conducting layer and the second conducting layer are filled in the first through holes, and N is larger than or equal to 1. According to the current collector, the first conductive layer and the second conductive layer corresponding to the first part are communicated through the first conductive body filled in the first through hole, so that the first part has lower internal resistance and can show better conductive performance. In the application process of the lithium ion battery, the characteristic of high conductivity of the first part is beneficial to leading out more electrons, so that excessive accumulation of electrons is avoided, and the safety performance of the current collector is improved; meanwhile, the performance of rapidly leading out electrons is also beneficial to improving the overcharge performance and the energy density of the lithium ion battery. The first conductor conducts the first conducting layer and the second conducting layer, so when the current collector is used for preparing the lithium ion battery, the conventional pole lug connection method can be adopted for pole lug connection, and the preparation process is simple; the current collector provided by the invention is provided with the insulating layer, when the temperature of the lithium ion battery rises, the insulating layer can be melted and deformed, the current path of the lithium ion battery is cut off, and the safety performance of the lithium ion battery can also be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings used in the description of the embodiments of the present invention or the related art are briefly introduced below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic structural view of a current collector in some embodiments of the present invention.
Description of reference numerals:
1: a first conductive layer;
2: a second conductive layer;
3: a first portion;
4: a second portion.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a schematic structural view of a current collector in some embodiments of the present invention. As shown in fig. 1, the present invention provides a current collector comprising an insulating layer and a first conductive layer 1 and a second conductive layer 2 disposed on both functional surfaces of the insulating layer;
the insulating layer comprises a first part 3 and a second part 4, the first part 3 is provided with N first through holes, first electric conductors connected with the first conducting layer 1 and the second conducting layer 2 are filled in the first through holes, and N is larger than or equal to 1.
In the present invention, the functional surfaces of the insulating layer refer to two surfaces oppositely disposed with the largest area of the insulating layer. In the invention, the first conductive layer 1 is arranged on the first functional surface of the insulating layer, and the second conductive layer 2 is arranged on the second functional surface of the insulating layer. The insulating layer of the present invention is divided into a first portion 3 and a second portion 4 in the length direction, and the sectional areas of the respective sections of the first portion 3 in the thickness direction are equal to each other, and the sectional areas of the respective sections of the second portion 4 in the thickness direction are equal to each other.
In the preparation process of the lithium ion battery, the surfaces, far away from the insulating layer, of the first conducting layer 1 and/or the second conducting layer 2 corresponding to the first part 3 are used for connecting tabs, and the surfaces, far away from the insulating layer, of the first conducting layer 1 and the second conducting layer 2 used for connecting the tabs are referred to as tab connection areas; the surface of the first conductive layer 1 and/or the second conductive layer 2 away from the insulating layer corresponding to the second portion 4 is used for disposing an active layer, and the surface of the first conductive layer 1 and the second conductive layer 2 away from the insulating layer for disposing an active layer is hereinafter referred to as an active layer disposing region.
The current collector of the invention comprises a first conducting layer 1, an insulating layer and a second conducting layer 2 from top to bottom in sequence. The first portion 3 of the insulating layer is provided with a first through hole, and since the first conductive layer 1 and the second conductive layer 2 corresponding to the first portion 3 are communicated through the first conductive body filled in the first through hole, the first portion 3 has lower internal resistance and can exhibit better conductive performance. In the application process of the lithium ion battery, the current density of the tab connection area is often higher, so that the high conductivity characteristic of the first part 3 is beneficial to leading out more electrons, and the current collector is maintained in a low electron density state, so that the safety performance of the current collector is improved; meanwhile, the performance of rapidly leading out electrons is also beneficial to improving the overcharge performance and the energy density of the lithium ion battery.
In addition, as the first conductor conducts the first conducting layer 1 and the second conducting layer 2, when the current collector is used for preparing the lithium ion battery, the conventional pole lug connection method can be adopted for pole lug connection, and the preparation process is simple; the current collector is provided with the insulating layer, and when the temperature of the lithium ion battery rises, the insulating layer can be melted and deformed, so that a current path of the lithium ion battery is cut off, and the safety performance of the lithium ion battery is improved.
It is understood that each first via hole may be partially filled with the first conductive body, or may be entirely filled with the first conductive body, as long as the first conductive layer 1 and the second conductive layer 2 can be electrically connected. The size and shape of the first through hole are not limited in the invention, and all through holes which can be filled with the first electric conductor are within the protection scope of the invention. The present invention is not limited to the specific material of the first conductive layer, and any material that can make the first conductive layer 2 and the second conductive layer 2 electrically conductive is within the scope of the present invention.
In some embodiments of the present invention, the second portion 4 is provided with M second through holes, the second through holes are filled with a second electric conductor connecting the first conductive layer 1 and the second conductive layer 2, the electric conductivity of the first portion 3 is greater than that of the second portion 4, and M ≧ 1.
It is understood that each second via hole may be partially filled with the second conductive body, or may be completely filled with the second conductive body, as long as the first conductive layer 1 and the second conductive layer 2 can be electrically conducted. The size and shape of the second through hole are not limited in the invention, and all through holes which can be filled with the second electric conductor are within the protection scope of the invention. The present invention is not limited to the specific material of the second conductor, and any material that can make the first conductive layer 1 and the second conductive layer 2 conductive is within the scope of the present invention.
The size and the shape of the second through hole can be the same as or different from those of the first through hole; the material of the second electrical conductor may or may not be the same as the material of the first electrical conductor, as long as the electrical conductivity of the first portion 3 is greater than the electrical conductivity of the second portion 4. In the present invention, the material of the first conductor and/or the second conductor may be the same as or different from the material of the first conductive layer 1 and/or the second conductive layer 2.
Specifically, the shape of the first through hole and/or the second through hole in the present invention may be at least one of a circle, an ellipse, a triangle, a rectangle, a square, or a diamond.
The material of the first conductor, the second conductor, the first conductive layer 1, and the second conductive layer 2 of the present invention may be at least one selected from a metal conductive material and a carbon-based conductive material.
The metal conductive material can be at least one selected from aluminum, copper, nickel, titanium, silver, nickel-copper alloy or aluminum-zirconium alloy; the carbon-based conductive material may be at least one selected from graphite, carbon black, graphene, carbon fiber, and carbon nanotube.
According to the invention, the second through hole is formed in the second part 4, and the first conducting layer 1 and the second conducting layer 2 are communicated through the second conductor filled in the second through hole, so that the conductivity of the first part 3 is greater than that of the second part 4, the potential safety hazard of uneven current density distribution of the current collector during the working of a battery can be solved, the safety performance of the lithium ion battery is improved, and the internal resistance of the current collector can be further reduced.
In the invention, if the total area of the first through hole and the second through hole is too large, the area of the insulating material is reduced, and when the temperature of the battery is increased, less insulating material is melted and deformed, so that the current path of the lithium ion battery is difficult to cut off, and the safety performance of the battery is reduced. If the total area of the first through hole is too small, the conductivity between the first conductive layer 1 and the second conductive layer 2 corresponding to the first part 3 is reduced, so that excessive electrons on the current collector cannot be led out, and the potential safety hazard of the lithium ion battery is increased. In some embodiments of the present invention, on the first functional surface of the insulating layer, a ratio of a total area of the first through holes to an area of the first portion 3 is θ 1, 7% θ 1 ≦ 80%; on the first functional surface of the insulating layer, the ratio of the total area of the second through holes to the area of the second portion 4 is θ 2, where θ 2 is greater than 0 and less than or equal to 5%.
In the present invention, since the sectional areas of the respective sections of the first portion 3 in the thickness direction are equal to each other, the area of the first portion 3 on the first functional surface is also equal to the area of the first portion 3 on the second functional surface, and the values of θ 1 and θ 2 on the second functional surface are the same as on the first functional surface.
In particular embodiments, θ 1 may be 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%.
θ 2 may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.
According to the invention, by setting the ratio of the total area of the first through holes to the area of the first part 3 and the ratio of the total area of the second through holes to the second part 4, the potential safety hazard generated by the lithium ion battery with unevenly distributed current density of the current collector during the operation of the battery can be better solved, the safety performance of the lithium ion battery is improved, and the internal resistance of the lithium ion battery is reduced.
In some embodiments of the invention, the area of the second portion 4 in the first functional surface is 80% to 90%.
Since the sectional areas of the respective sections of the insulating layer in the thickness direction are equal to each other, the areas of the first functional surface and the second functional surface are equal, so that the area of the second portion 4 in the second functional surface is 80% to 90%.
Specifically, the area of the second portion 4 in the first functional surface may be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%.
In the invention, in the first functional surface, if the area of the second part 4 is too large, the area of the first part 3 is too small, the area provided with the first through hole is smaller, more electrons cannot be led out, the safety performance of the lithium ion battery is influenced, and the tab connection area is smaller, so that the connection of tabs is influenced; if the area of the second portion 4 is too small, the area of the active layer installation region is too small, which is not favorable for the charge and discharge performance of the lithium ion battery. According to the invention, by setting the area of the second part 4, the active layer can be fully arranged without affecting the safety performance of the battery and the connection of the lugs, so that the charge and discharge performance of the lithium ion battery is improved.
In the invention, if the thickness of the first conductive layer 1 and/or the second conductive layer 2 is too thick, the energy density of the lithium ion battery is reduced, and if the thickness of the first conductive layer 1 and/or the second conductive layer 2 is too thin, the mechanical performance of the current collector is reduced, and the safety performance of the lithium ion battery is affected. In some embodiments of the present invention, the thickness of the first conductive layer 1 and/or the second conductive layer 2 is 0.1 to 3 μm. The thickness of the first conductive layer 1 and/or the second conductive layer 2 within this range not only can provide the current collector with higher energy density and conductivity, but also can provide the current collector with higher mechanical strength.
Specifically, the thickness of the first conductive layer 1 and/or the second conductive layer 2 may be: 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.2 μm, 1.5 μm, 2.0 μm, 2.5 μm, 3.0 μm.
It is understood that the thicknesses of the first conductive layer 1 and the second conductive layer 2 of the present invention may be the same or different.
In some embodiments of the present invention, the thickness of the insulating layer is 1 to 20 μm, and the insulating layer has a thickness within this range, so that the insulating layer is not easily broken during processing and use, and the mechanical strength of the current collector can be improved, and the safety performance of the lithium ion battery can be improved by the insulating layer having a sufficient thickness.
In a specific embodiment, the thickness of the insulating layer may be 20 μm, 19 μm, 18 μm, 17 μm, 16 μm, 15 μm, 14 μm, 13 μm, 12 μm, 11 μm, 10 μm, 9 μm, 8 μm, 7 μm, 6 μm, 5 μm, 4 μm, 3 μm, 2 μm, 1 μm.
Further, in order to reduce the overall thickness of the current collector, the thickness of the insulating layer may be 1 to 8 μm.
In some embodiments of the invention, the insulating layer comprises a polymer. The polymer material is easier to melt and deform at high temperature, so that a current path of the lithium ion battery is cut off, and the safety performance of the lithium ion battery is improved.
Specifically, the polymer may be selected from at least one of a poly (terephthalate), a Polyamide (PA), a Polyimide (PI), a Polyethylene (PE), a polypropylene (PP), a Polystyrene (PS), a polyvinyl chloride (PVC), a poly (paraphenylene terephthalamide), a polypropylene, an acrylonitrile-butadiene-styrene copolymer, a polyvinyl formal, a polyvinyl butyral, a polyurethane, a polyacrylonitrile, a polyvinyl acetate, a polyoxymethylene, a phenol resin, an epoxy resin, an acrylic resin, a urea resin, an amino resin, a formaldehyde resin, a furan resin, a chloroprene rubber, a Polytetrafluoroethylene (PTFE), a polyvinylidene fluoride (PVDF), a silicone rubber, a polycarbonate, a polysulfone, a polyethersulfone, or a polyphenylene oxide. The polymer may also be selected from at least one of derivatives, cross-links or copolymers of the above polymers. Further, the above-mentioned polyethylene terephthalate may be polyethylene terephthalate (PET).
In some embodiments of the present invention, the insulating layer further includes an inorganic insulating material, and the inorganic insulating material is added to the insulating layer, so that the mechanical strength of the insulating layer can be improved, and thus the mechanical strength of the current collector can be improved.
The inorganic insulating material includes at least one of alumina, silicon carbide, silicon oxide, glass fiber, titanium dioxide, zirconium dioxide, magnesium hydroxide, aluminum hydroxide, boehmite, barium sulfate, barium titanate, aluminum titanate, zinc oxide, boron nitride, aluminum nitride, magnesium nitride, attapulgite, zinc phosphate, or zinc borate.
In one embodiment, the current collector of the invention is obtained by a preparation method comprising the following steps:
s1: dividing the insulating layer into a first part and a second part in the length direction, and arranging a first through hole in the first part of the insulating layer in a laser drilling or mechanical drilling mode;
and S2, attaching a first conductive layer and a second conductive layer on the two surfaces of the insulating layer with holes obtained in the step S1 by at least one of coating, vapor deposition, chemical plating or electroplating, wherein the material of the first conductive layer and/or the material of the second conductive layer enter the first through holes to form a first electric conductor.
Specifically, the coating in S2 includes at least one of roll transfer coating, spray coating, printing, extrusion coating, blade coating, and gravure coating. The specific process of coating is as follows: and uniformly mixing the conductive powder, the binder, the dispersant and the solvent to form conductive slurry, and then coating the conductive slurry on the first functional surface of the insulating layer to form a first conductive layer, and/or coating the conductive slurry on the second functional surface of the insulating layer to form a second conductive layer.
The vapor deposition method in S2 includes at least one of a vacuum evaporation method, a thermal evaporation method, an electron beam evaporation method, or a magnetron sputtering method.
The second aspect of the present invention provides a pole piece, including the current collector and the active layer, where the active layer is disposed on the functional surface of the first conductive layer 1 and/or the second conductive layer 2 corresponding to the second portion 4.
The pole piece of the invention comprises the current collector, and the active layer can be arranged on the surface of the first conducting layer 1 far away from the insulating layer, can also be arranged on the surface of the second conducting layer 2 far away from the insulating layer, and can also be simultaneously arranged on the surfaces of the first conducting layer 1 and the second conducting layer 2 far away from the insulating layer. The tab connecting area is used for connecting tabs. Because the first conductor filled in the first through hole communicates the first conducting layer 1 with the second conducting layer 2, the conductivity of the first part 3 can be improved, the first part 3 with high conductivity can lead out excessive electrons, and the potential safety hazard caused by large current density in a tab connecting area when the lithium ion battery is electrified can be solved. The first conductor is used for conducting the first conducting layer 1 and the second conducting layer 2, so that a conventional lug connection mode can be adopted, the welding spot of the lug is small, the manufacturing process is simple, and the manufacturing cost is low.
The active layer in the present invention may be a positive electrode active layer or a negative electrode active layer.
The positive electrode active material in the positive electrode active layer according to the present invention may be any known positive electrode active material in the art, and any positive electrode active material capable of reversibly intercalating or deintercalating ions is within the scope of the present invention. For example, the positive active material may be a lithium transition metal composite oxide, wherein the transition metal may be at least one of Mn, Fe, Ni, Co, Cr, Ti, Zn, V, Al, Zr, Ce, or Mg.
The lithium transition metal composite oxide can be doped with an element with large electronegativity, such as S, F, Cl or I, so that the positive active material has high structural stability and electrochemical performance. Illustratively, the lithium transition metal composite oxide may be LiMn2O4、LiNiO2、LiCoO2、LiNi1-yCoyO2(0<y<1)、LiNiaCobAl1-a-bO2(0<a<1，0<b<1，0<a+b<1)、LiMn1-m-nNimConO2(0<m<1，0<n<1，0<m+n<1)、LiMPO4(M may be at least one of Fe, Mn or Co) or Li3V2(PO4)3At least one of (1).
The negative active material in the negative active layer in the present invention may be any known negative active material in the art, and any negative active material capable of performing reversible intercalation or deintercalation of ions is within the scope of the present invention. For example, the negative active material may be metallic lithium, natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composite, SiO, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2At least one of a lithium titanate having a spinel structure and a Li-Al alloy.
The active layer may further include a conductive agent. In some embodiments, the conductive agent is selected from at least one of graphite, superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, or carbon nanofibers.
The active layer may further include a binder. In some embodiments, the binder is selected from at least one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR), Nitrile Butadiene Rubber (NBR), water based acrylic, polyvinyl alcohol, polyvinyl butyral, polyurethane, fluorinated rubber, carboxymethyl cellulose (CMC), or polyacrylic acid (PAA).
The positive electrode sheet of the present invention may be prepared according to a conventional method in the art. Dispersing the positive active material, the conductive agent and the binder in a solvent (N-methyl pyrrolidone) to form uniform positive active slurry, coating the positive active slurry on a current collector, and drying to obtain the positive plate.
The negative electrode sheet of the present invention may be prepared according to a conventional method in the art. Dispersing a negative electrode active material, a conductive agent, a binder, a thickening agent and a dispersing agent in a solvent, wherein the solvent can be NMP or deionized water, forming uniform negative electrode active slurry, coating the negative electrode active slurry on a current collector, and drying to obtain a negative electrode sheet.
In a third aspect, the invention provides an electrochemical device comprising the above-mentioned pole piece.
The electrochemical device of the present invention may include, but is not limited to, a lithium ion secondary battery, a lithium primary battery, a sodium ion battery, or a magnesium ion battery.
In a specific embodiment, the electrochemical device of the present invention includes a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte. Wherein the positive plate and/or the negative plate comprises the current collector.
The separator of the present invention is not particularly limited, and any known porous separator having electrochemical stability and chemical stability may be used, and may be at least one of glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator may be a single layer or a multilayer.
In the present invention, the electrolytic solution includes an organic solvent and an electrolyte salt. As the organic solvent as a medium for transporting ions in the electrochemical reaction, an organic solvent known in the art for an electrolyte of an electrochemical device may be used. As the source of the ions, electrolyte salts known in the art for electrolytes of electrochemical devices can be used.
For example, the organic solvent used for the lithium ion secondary battery may be at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Butylene Carbonate (BC), fluoroethylene carbonate (FEC), Methyl Formate (MF), Methyl Acetate (MA), Ethyl Acetate (EA), Propyl Acetate (PA), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Methyl Butyrate (MB), Ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), Sulfolane (SF), dimethylsulfone (MSM), methylethylsulfone (EMS), and diethylsulfone (ESE). In a specific embodiment, two or more of the organic solvents described above may be selected.
For example, the electrolyte salt for a lithium ion secondary battery may be lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (b)LiBF4) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium hexafluoroantimonate (LiSbF)6) Lithium difluorophosphate (LiPF)2O2) Lithium 4, 5-dicyano-2-trifluoromethylimidazole (LiDTI), lithium bis (oxalato) borate (LiBOB), lithium triflate (LiTFS), lithium bis (malonato) borate (LiBMB), lithium difluoro (oxalato) borate (LiDFOB), lithium bis (difluoromalonato) borate (LiBDFMB), (oxalato) lithium borate (LiMOB), (difluoromalonato oxalato) lithium borate (LiDFMOB), lithium tris (oxalato) phosphate (LiTOP), lithium tris (difluoromalonato) phosphate (LiTDFMP), lithium tetrafluorooxalato phosphate (LiTFOP), lithium difluoro (LiDFOP), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl imide (LiFSI), (fluorosulfonyl) (trifluoromethanesulfonyl) imide (LiN (SO)2F)(SO2CF3) Lithium nitrate (LiNO), lithium nitrate (LiNO)3) Lithium fluoride (LiF), LiN (SO)2RF)2Or LiN (SO)2F)(SO2RF) Wherein R isF＝CnF2n+1And n is an integer of 2 to 10.
The electrochemical device provided by the invention has the advantages of high safety performance, low internal resistance and simple manufacturing process due to the pole piece.
The invention is further illustrated by the following specific examples in which all parts, percentages, and ratios recited in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and used as such without further treatment, and the equipment used in the examples is commercially available.
Examples 1 to 32
The current collector of this example was prepared by the following steps:
s1: the insulating layer is divided into a first part and a second part in the length direction, wherein in the first functional surface, the area of the second part is phi, and phi is more than or equal to 80% and less than or equal to 99%. Punching round holes (or not punching holes) on the second part of the insulating layer at equal intervals by a laser punching or mechanical punching mode to obtain second through holes, and controlling the total area ratio theta 2 of the second through holes to be more than or equal to 0 and less than or equal to 5 percent; then, punching round holes on the first part of the insulating layer at equal intervals in the same way to obtain first through holes, and controlling the total area percentage theta 1 of the first through holes to be more than or equal to 7% and less than or equal to 80%; (ii) a The thickness of the insulating layer was D1, μm.
S2, attaching a first conductive layer on the first functional surface of the insulating layer provided with the through hole obtained in the step S1 by at least one of coating, vapor deposition, chemical plating or electroplating, and then attaching a second conductive layer on the second functional surface of the insulating layer provided with the through hole obtained in the step S1 by the same method, wherein the material of the first conductive layer and/or the second conductive layer forms a first conductor in the first through hole to communicate the first conductive layer with the second conductive layer, and the material of the first conductive layer and/or the second conductive layer forms a second conductor in the second through hole to communicate the first conductive layer with the second conductive layer;
wherein the first conductive layer has a thickness of D21, μm, the second conductive layer has a thickness of D22, μm, and the electrical conductivity of the first portion is greater than the electrical conductivity of the second portion.
The relevant materials and parameters were varied to obtain a series of current collectors, designated C1-C32, with the information on the current collector preparation shown in table 1.
TABLE 1
Figure BDA0003001933920000121
Figure BDA0003001933920000131
Figure BDA0003001933920000141
Comparative examples 33 to 36
The procedure for preparing the current collector of comparative example 33 was substantially the same as example 8, with the only difference that:
in S1, the through holes were uniformly provided over the entire insulating layer, and the ratio of the total area of the through holes to the area of the first functional surface of the insulating layer was 15%, which was denoted as C33.
The procedure for preparing the current collector of comparative example 34 was substantially the same as example 24, except that:
in S1, the through holes were uniformly provided over the entire insulating layer, and the ratio of the total area of the through holes to the area of the first functional surface of the insulating layer was 15%, which was denoted as C34.
The procedure for preparing the current collector of comparative example 35 is substantially the same as example 8, with the only difference that:
in S1, the through holes were uniformly provided over the entire insulating layer, and the ratio of the total area of the through holes to the area of the first functional surface of the insulating layer was 1%, which was denoted as C35.
The procedure for preparing the current collector of comparative example 36 was substantially the same as that of example 24, except that:
in S1, the through holes were uniformly provided over the entire insulating layer, and the ratio of the total area of the through holes to the area of the first functional surface of the insulating layer was 1%, which was denoted as C36.
Comparative examples 37 to 38
The procedure for preparing the current collector of comparative example 37 was substantially the same as example 8, with the only difference that:
in S1, no via hole is provided in the insulating layer, and this is denoted as C37.
The procedure for preparing the current collector of comparative example 38 was substantially the same as example 24, except that:
in S1, no via hole is provided in the insulating layer, and this is denoted as C38.
Comparative examples 39 to 40
The current collector of comparative example 39 was a 10 μm aluminum foil designated C39 and the current collector of comparative example 40 was a 5 μm copper foil designated C40.
Test examples
1. Preparation of pole piece
According to the conventional preparation process of the lithium ion battery positive plate, 97 parts of lithium cobaltate positive electrode, 1.5 parts of acetylene black conductive agent, 1.5 parts of PVDF binder and 60 parts of N-methyl pyrrolidone (NMP) are stirred for 4 hours under vacuum by a double planetary mixer under the conditions of revolution of 30r/min and rotation of 1500r/min, and are dispersed into uniform positive active slurry, then the positive active slurry is coated on a current collector and is baked for 30 minutes at 120 ℃ to be dried, and is rolled under 40 tons of rolling pressure, and is cut into the required positive plate.
According to the conventional preparation process of the lithium ion battery negative plate, 97.5 parts of graphite negative electrode, 1 part of acetylene black conductive agent, 0.5 part of sodium carboxymethylcellulose (CMC), 1 part of Styrene Butadiene Rubber (SBR) binder and 100 parts of deionized water are stirred for 4 hours under vacuum by a double-planet stirrer under the conditions of revolution of 30r/min and rotation of 1500r/min to be dispersed into uniform negative active slurry, then the negative active slurry is coated on a current collector and baked for 30min at 100 ℃ to be dried, rolled under the rolling pressure of 45 tons, and cut into the required negative plate.
In the preparation process of the pole piece, when the current collectors are C1-C32 and C35-C36, the positive active slurry or the negative active slurry is arranged on the functional surface of the first conducting layer corresponding to the second part and the functional surface of the second conducting layer corresponding to the second part; the functional surface of the first conducting layer corresponding to the first part and the functional surface of the second conducting layer corresponding to the first part are provided with tabs.
When the current collectors are C33-C34 and C37-C40, the positive electrode active slurry or the negative electrode active slurry is arranged on the functional surfaces of the first conductive layer and the second conductive layer, and a region for welding a tab is reserved.
A series of pole pieces were obtained and recorded as J1-J40, and the information of the relevant pole pieces is shown in Table 2.
And (3) testing the welding strength of the obtained pole piece, wherein the testing method comprises the following steps:
1) firstly, welding a lug at a corresponding position of a current collector by adopting ultrasonic welding, and welding by adopting an UM-20 model ultrasonic metal welding machine of Shenzhen Spanish high-energy electronic technology Limited; the positive current collector is welded with an aluminum lug with the width of 6mm and the thickness of 0.1mm, and the negative current collector is welded with a nickel lug with the width of 6mm and the thickness of 0.1 mm;
welding parameters are as follows: welding power 3000W, welding frequency 20kHz, welding amplitude 40 μm, welding time 0.42s and welding pressure 0.3 MPa.
2) Adopt LK-108A model tension tester of force control instrument science and technology Limited company to test the welding strength of pole piece, the utmost point ear after will welding is pressed from both sides with anchor clamps, then through the tension tester test utmost point ear from the current collector pulling off the tension value N, utmost point ear width is D, can calculate and obtain utmost point ear welding strength F be N/D. The test results are shown in table 2.
TABLE 2
Figure BDA0003001933920000161
Figure BDA0003001933920000171
As can be seen from table 2, based on a single-factor comparison, the welding strength of the current collector C8 prepared in the example of the present invention is higher than that of the current collectors C35 and C37 prepared in the comparative example; the welding strength of the current collector C24 prepared in the embodiment of the invention is higher than that of the current collectors C36 and C38 prepared in the comparative example.
2. Preparation of lithium ion battery
The positive plate, the negative plate, the Polyethylene (PE) porous diaphragm, the commercially conventional lithium ion battery electrolyte and other necessary lithium ion battery auxiliary materials in table 2 were prepared into batteries by a conventional lithium ion battery preparation process.
Wherein, the positive current collector and the negative current collector of the batteries D1-D16 both adopt the current collectors in the embodiment of the invention;
the positive current collectors of the batteries D17-D18 adopt the current collectors in the embodiment of the invention, and the negative current collectors adopt the current collectors in the comparative example of the invention;
the negative current collectors of the batteries D19-D20 adopt the current collectors in the embodiment of the invention, and the positive current collectors adopt the current collectors in the comparative example of the invention;
the positive electrode current collector and the negative electrode current collector of each of the batteries D21 to D24 were the current collectors of the comparative examples of the present invention.
The information of the lithium ion batteries D1 to D24 is shown in Table 3.
TABLE 3
Figure BDA0003001933920000172
Figure BDA0003001933920000181
Performance testing
1) Battery safety test
The cells in table 3 were subjected to safety tests including needling, heating and overcharging of the cells. The specific test method is as follows:
10 batteries obtained by the same process are tested in parallel, the puncture passing rate after heating and the puncture passing rate after overcharging are respectively calculated, and the test method refers to the GB/T31485-. The test results are shown in table 4.
2) Battery cycle life test
Referring to the test method in GB/T18287-2013 standard, a battery charge-discharge tester is used for carrying out charge-discharge cycle test on the battery at 25 ℃;
a charge-discharge system: charging to an upper limit voltage by using a 0.5C constant current, then charging to a current reduced to 0.02C by using a constant voltage, standing for 5min, discharging the battery to a lower limit voltage by using the 0.5C constant current, wherein the cycle number is 1 cycle, the cycle number of a battery charge-discharge tester is set to be 5000 times, the battery capacity is continuously attenuated along with the battery cycle, and the cycle number when the capacity is attenuated to 80% of the first discharge capacity is recorded as the cycle life of the battery. The test results are shown in table 4.
3) Internal resistance test of battery
After the battery is fully charged, testing the internal resistance of the battery by using an RBM-200 intelligent battery internal resistance tester of Shenzhen super Cisco technologies Limited;
the charging system is as follows: charging to the upper limit voltage with a constant current of 0.5C, and then charging with a constant voltage until the current is reduced to 0.02C; the frequency of the alternating signal of the tester is set to 1 KHz. The test results are shown in table 4.
TABLE 4
Battery with a battery cell Needle penetration Rate (%) Heating passage (%) Overcharge pass rate (%) Internal resistance (m omega) Cycle life (times)
D1 100％ 100％ 100％ 59 1121
D2 100％ 100％ 100％ 60 1104
D3 100％ 100％ 100％ 62 1086
D4 100％ 100％ 100％ 61 1089
D5 100％ 100％ 100％ 60 1093
D6 100％ 100％ 100％ 59 1098
D7 100％ 100％ 100％ 63 1067
D8 100％ 100％ 100％ 62 1075
D9 100％ 100％ 100％ 61 1082
D10 100％ 100％ 100％ 60 1096
D11 100％ 100％ 100％ 65 1049
D12 100％ 100％ 100％ 66 1043
D13 100％ 100％ 100％ 55 1186
D14 100％ 100％ 100％ 54 1188
D15 100％ 100％ 100％ 53 1190
D16 100％ 100％ 100％ 52 1191
D17 100％ 100％ 100％ 51 1193
D18 100％ 100％ 100％ 50 1200
D19 100％ 100％ 100％ 52 1191
D20 100％ 100％ 100％ 51 1194
D21 70％ 70％ 80％ 63 729
D22 70％ 80％ 90％ 79 487
D23 100％ 100％ 100％ 93 386
D24 0％ 0％ 0％ 48 985
As can be seen from table 4, the safety performance and cycle performance of the lithium ion battery prepared using the current collector of the example of the present invention are much higher than those of the lithium ion battery prepared using the current collector of the comparative example. The internal resistance of the lithium ion battery prepared by adopting the current collector of the embodiment of the invention is lower than that of the lithium ion battery prepared by adopting the current collector of the comparative example.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. A current collector comprising an insulating layer and first and second conductive layers disposed on both functional surfaces of the insulating layer;
the insulating layer comprises a first part and a second part, the first part is provided with N first through holes, first electric conductors connecting the first conducting layer and the second conducting layer are filled in the first through holes, and N is larger than or equal to 1.
2. The current collector of claim 1, wherein the second portion is provided with M second through holes, the second through holes are filled with a second conductor connecting the first conductive layer and the second conductive layer, the conductivity of the first portion is greater than that of the second portion, and M is greater than or equal to 1.
3. The current collector of claim 1 or 2, wherein on the first functional surface of the insulating layer, the ratio of the total area of the first through holes to the area of the first portion is θ 1, 7% θ 1 ≦ 80%.
4. The current collector of claim 3, wherein the area of the second portion in the first functional surface is 80-90%.
5. The current collector of any one of claims 1 to 4, wherein the thickness of the first and/or second electrically conductive layer is 0.1 to 3 μm.
6. The current collector of any one of claims 1 to 5, wherein the insulating layer has a thickness of 1 to 20 μm.
7. The current collector of any one of claims 1 to 6, wherein the insulating layer comprises a polymer.
8. The current collector of claim 7, wherein the insulating layer further comprises an inorganic insulating material;
the inorganic insulating material comprises at least one of aluminum oxide, silicon carbide, silicon oxide, glass fiber, titanium dioxide, zirconium dioxide, magnesium hydroxide, aluminum hydroxide, boehmite, barium sulfate, barium titanate, aluminum titanate, zinc oxide, boron nitride, aluminum nitride, magnesium nitride, attapulgite, zinc phosphate or zinc borate.
9. A pole piece comprising the current collector of any one of claims 1 to 8 and an active layer disposed on the functional surface of the first and/or second conductive layer corresponding to the second portion.
10. An electrochemical device comprising the pole piece of claim 9.
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