CN114361461B - Flexible current collector core layer, current collector, pole piece, battery and preparation method of battery - Google Patents

Flexible current collector core layer, current collector, pole piece, battery and preparation method of battery Download PDF

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Publication number
CN114361461B
CN114361461B CN202210020852.1A CN202210020852A CN114361461B CN 114361461 B CN114361461 B CN 114361461B CN 202210020852 A CN202210020852 A CN 202210020852A CN 114361461 B CN114361461 B CN 114361461B
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layer
current collector
flexible current
collector core
porous conductive
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CN114361461A (en
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庄志
石广钦
熊磊
虞少波
刘连静
杨强
姚志刚
陈宇
费海洁
晏小祥
程跃
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Shanghai Energy New Materials Technology Co Ltd
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Shanghai Energy New Materials Technology Co Ltd
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Priority to PCT/CN2022/087607 priority patent/WO2023130611A1/en
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention provides a flexible current collector core layer, a current collector, a pole piece, a battery and a preparation method thereof, wherein the flexible current collector core layer can be obtained only by the processes of mixing, melting and extruding the materials of an insulating support layer and the porous conductive layer, casting the cast piece and stretching, namely, one-step processing and forming are realized, the process is simplified, the production cost is greatly reduced, in the stretching process, the melting point of the polyolefin material in the first polyolefin material and the flame-retardant polyolefin material of the adopted insulating support layer is not higher than 136 ℃, and at the moment, when the stretching process is carried out, the porous conductive layer can generate gaps on the surface, and the insulating support layer in the interior is in a compact structure.

Description

Flexible current collector core layer, current collector, pole piece, battery and preparation method of battery
Technical Field
The invention belongs to the field of batteries, and particularly relates to a flexible current collector core layer, a current collector, a pole piece, a battery and a preparation method of the battery.
Background
Along with the increasing demand of people on the whole energy density of the lithium battery, the adverse effect brought by the metal structure current collector on the improvement of the energy density of the battery is gradually emphasized, and in order to solve the problem, in recent years, the inside is an insulating supporting layer and a conductive layer to form a core layer structure, and the outer layer is a conductive metal layer flexible current collector, so that the whole mass density of the current collector of the composite structure is reduced, the whole energy density of the battery can be obviously improved, meanwhile, the flexibility of a polymer part adopted in the current collector is better, and the pole piece 'powder dropping' phenomenon caused by mechanical deformation and the internal expansion of an active substance can be effectively lightened.
Patent document (CN 111384404 a) discloses an ultra-light conductive agent fluid, specifically discloses a material with positive temperature effect of resistance, namely PCT (Positive Temperature Coefficient) material, in which a supporting layer adopts a material with positive temperature effect of resistance with increased temperature, a graphene film of a conductive enhancement layer is deposited on the surface of a PCT material of the supporting layer to form a graphene/macromolecule PTC film/graphene sandwich structure, then a laser is adopted to punch a film surface to prepare a flexible superconducting current collector with high porosity.
Patent literature (CN 112510210A) discloses a composite current collector, a preparation method thereof and a secondary battery, and specifically discloses a method for coating a conductive polymer layer on an insulating support layer and then plating a metal layer on the conductive polymer layer to obtain the composite current collector.
In the prior art, the technology of preparing the porous flexible current collector by adopting special processing means such as laser drilling and the like or coating the flexible polymer supporting layer with the conductive layer is high in cost, delamination and falling, complex in process or high in mass production difficulty and the like.
Disclosure of Invention
The first object of the present invention is to provide a flexible current collector core layer, which uses a first polyolefin material or/and a flame retardant polyolefin material as a material of an insulating support layer, wherein the melting point of the first polyolefin material is not higher than 136 ℃, and simultaneously uses a second polyolefin material and a conductive filler as a material of a porous conductive layer, and the production cost is greatly reduced by reducing a nonmetallic part in the flexible current collector core layer.
The second objective of the present invention is to provide a current collector, in which conductive metal layers are disposed on two sides of the porous conductive layer of the flexible current collector core layer, and because the surface roughness of the porous conductive layer is very high, when the conductive metal layer is added by other technical means, no additional processing is needed, the preparation process is simplified, and the time cost can be saved.
A third object of the present invention is to provide a pole piece, which is formed by forming an electrode active material layer on the surface of the aforementioned current collector, so that the pole piece can be applied to a battery.
The fourth object of the present invention is to provide a battery, which is formed by assembling the positive electrode plate and the negative electrode plate with the separator and the electrolyte, wherein the current collector in the adopted electrode plate has a flexible current collector core layer, and the porous conductive layer in the flexible current collector core layer has the characteristic of a hole part structure, so that the stress generated by the internal expansion of the active material in the battery can be eliminated, the service life of the battery is effectively prolonged, and the problems mentioned above are further optimized.
The fifth object of the present invention is to provide a method for preparing a flexible current collector core layer, wherein after the material of an insulating support layer and the material of a porous conductive layer are added into an extruder, the flexible current collector core layer can be obtained through mixing, melting extrusion, casting and stretching processes, wherein the stretching temperature is 90-140 ℃, and the stretching ratio is 1-5 times, so that the porous conductive layer structures on two sides are stretched to obtain the characteristics of having a hole structure under the temperature, the surface roughness of the porous conductive layer is improved, and meanwhile, the problem of poor bonding strength of the insulating support layer and the porous conductive layer is solved by adopting a mode of synchronous extrusion of a die head.
A sixth object of the present invention is to provide a method for preparing a flexible current collector, which uses the flexible current collector core layer obtained by the above steps, and forms a conductive metal layer on the surface of the porous conductive layer therein, so as to generate the current collector.
To achieve the first object, the present invention provides a flexible current collector core layer, comprising:
an insulating support layer; and
The porous conducting layers are arranged on two sides of the insulating supporting layer;
the insulating support layer comprises a first polyolefin material and/or a flame-retardant polyolefin material, wherein the melting points of the first polyolefin material and the polyolefin material in the flame-retardant polyolefin material are not higher than 136 ℃;
the porous conductive layer comprises a second polyolefin material and a conductive filler.
Preferably, the first polyolefin material and the second polyolefin material are at least one of polyethylene, polypropylene, ethylene-vinyl acetate, ethylene-propylene copolymer, ethylene-octene copolymer, polyethylene terephthalate, polybutylene terephthalate, and the first polyolefin material is different from the second polyolefin material.
Preferably, the polyethylene is at least one of high density polyethylene, low density polyethylene and linear low density polyethylene.
Preferably, the high density polyethylene has a melt index of 0.7g/10min to 2.0g/10min.
Preferably, the high density polyethylene is melt-blended at a temperature of 125℃to 136 ℃.
Preferably, the low density polyethylene is melt-phase at a temperature of 125℃to 130 ℃.
Preferably, the second polyolefin material is the polypropylene.
Preferably, the polypropylene has a melt index of 4.0g/10min to 10.0g/10min.
Preferably, the flame retardant filled in the flame retardant polyolefin material is at least one of halogen flame retardant, phosphorus-nitrogen flame retardant and inorganic flame retardant.
Preferably, the material of the insulating support layer further comprises ethylene-vinyl acetate copolymer.
Preferably, the ethylene-vinyl acetate copolymer has a melt temperature of 85℃to 90 ℃. Preferably, the melting point of the first polyolefin material is not higher than 130 ℃.
Preferably, the insulating support layer is a dense structure without holes.
Preferably, the porous conductive layer has a porosity of 10% to 80%.
Preferably, the pore size of the porous conductive layer is 0.02 μm to 1 μm.
Preferably, the surface roughness of the porous conductive layer is 0.025 μm to 2 μm.
Preferably, the conductive filler is at least one of a carbon-based conductive material or a metal oxide material.
Preferably, the carbon-based conductive material is at least one of conductive carbon black, graphite, graphene or carbon nanotubes.
Preferably, the carbon-based conductive material is subjected to surface modification by at least one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Preferably, when the carbon-based conductive material is a carbon nanotube, the diameter is 5nm-15nm, and the length is 0.1 μm-2 μm.
Preferably, the metal oxide material comprises at least one of a metal oxide of Ti, V, sn, zn or a metal oxide of Ti, V, sn, zn doped with a metal oxide.
Preferably, the metal oxide material is at least one of TiO2, ti4O7, V2O3, VO2, snO2, znO doped whisker or powder.
Preferably, when the conductive filler is particulate, the particle size of the conductive filler is 10nm-500nm.
Preferably, when the conductive filler is whisker or fiber, the diameter is 0.005 μm-2 μm and the length is 0.05 μm-3 μm.
Preferably, the mass ratio of the conductive filler in the porous conductive layer is 10% -45%.
Preferably, the thickness of the flexible current collector core layer is 5-20 μm.
Preferably, the density of the flexible current collector core layer is 5g/m 2 -15g/m 2 。
Preferably, the thickness ratio of the insulating support layer to the porous conductive layer is 1:0.2-10.
Preferably, the insulating support layer and the porous conductive layer are formed by one-step extrusion in a multilayer coextrusion mode.
To achieve the second object, the present invention provides a current collector, comprising:
the flexible current collector core layer of any of claims 1-22; and
And the conductive metal layers are arranged on two sides of the porous conductive layer.
Preferably, the material of the conductive metal layer is at least one of aluminum, copper, nickel, titanium, silver, nickel-copper alloy and aluminum-zirconium alloy.
Preferably, the thickness of the conductive metal layer is 0.5 μm to 3 μm.
Preferably, the volume resistivity of the conductive metal layer is 15 Ω·cm to 250 Ω·cm.
In order to achieve the third object, the present invention provides a pole piece, comprising:
the current collector of any one of claims 23-25; and
And an electrode active material layer formed on the surface of the current collector.
Preferably, the current collector has a thickness of 8 μm to 18 μm.
Preferably, the density of the current collector is 15g/m 2 -35g/m 2 . To achieve the fourth object, the present invention provides a battery, comprising:
a positive electrode sheet as claimed in claim 26, and having a positive polarity;
a negative electrode sheet as in claim 26, and said sheet having a negative polarity;
The diaphragm is arranged between the positive pole piece and the negative pole piece to isolate the positive pole piece from the negative pole piece; and
And the electrolyte is filled between the positive pole piece and the negative pole piece, so that the positive pole piece is electrically connected with the negative pole piece.
In order to achieve the fifth object, the present invention provides a method for preparing a core layer of a flexible current collector, comprising the steps of:
respectively adding an insulating support layer material and a porous conductive layer material into an extruder for melting and plasticizing to generate and extrude an insulating support layer melting raw material and a porous conductive layer melting raw material to a die head;
the insulating supporting layer melting raw material and the porous conducting layer melting raw material are synchronously extruded through the die head and are drawn into a casting film, the structure of the casting film comprises an insulating supporting layer and a porous conducting layer, and the porous conducting layers are respectively arranged on two sides of the insulating supporting layer; and
The casting film is subjected to a stretching procedure to generate a flexible current collector core layer, wherein the stretching procedure is longitudinal and transverse stretching, the stretching temperature is 90-140 ℃, and the stretching ratio is 1-5 times.
Preferably, the casting film is cooled by a cooling roller to obtain a casting sheet, and the temperature of the cooling roller is 50-130 ℃.
In order to achieve the sixth object, the present invention provides a method for preparing a current collector, comprising the steps of:
respectively adding an insulating support layer material and a porous conductive layer material into an extruder for melting and plasticizing to generate and extrude an insulating support layer melting raw material and a porous conductive layer melting raw material to a die head;
the insulating supporting layer melting raw material and the porous conducting layer melting raw material are synchronously extruded through the die head and are drawn into a casting film, the structure of the casting film comprises an insulating supporting layer and a porous conducting layer, and the porous conducting layers are respectively arranged on two sides of the insulating supporting layer;
the casting film is subjected to a stretching procedure to generate a flexible current collector core layer, wherein the stretching procedure is longitudinal and transverse stretching, the stretching temperature is 90-140 ℃, and the stretching ratio is 1-5 times; and
And forming a conductive metal layer on the surfaces of the porous conductive layers on the two sides of the flexible current collector core layer respectively through a mechanical rolling process, a bonding process, a vapor deposition process or an electroless plating process to generate a current collector.
Preferably, the electroless plating includes at least one of alkaline plating and acid plating.
Preferably, the casting film is cooled by a cooling roller to obtain a casting sheet, and the temperature of the cooling roller is 50-130 ℃. The invention has the advantages that the insulating support layer material and the porous conductive layer are synchronously extruded by a multilayer extrusion technology, so that the flexible current collector core layer is output in an integral structure, the strength of the flexible current collector core layer is improved, the service life of the current collector is prolonged, furthermore, the preparation method of the flexible current collector core layer provided by the invention can obtain the flexible current collector core layer only through the processes of mixing, melting extrusion, casting sheet and stretching, namely, one-step processing and forming, the process is simplified, the production cost is greatly reduced, and in the stretching process, the melting point of the first polyolefin material adopted by the process is not higher than 136 ℃ because the stretching temperature is 90-140 ℃, at the moment, when the stretching process is carried out, the porous conductive layer generates a gap on the surface, and meanwhile, the insulating support layer in the interior is in a compact structure, so that the insulating support layer can have good supporting force in the production process, and the phenomenon of film breakage is reduced.
Drawings
FIG. 1 is a schematic view of a flexible current collector core layer according to an embodiment of the invention;
FIG. 2 is a schematic view of a current collector according to an embodiment of the present invention;
FIG. 3 is a schematic view of a pole piece according to an embodiment of the present invention;
fig. 4 is a schematic view of a battery according to an embodiment of the present invention;
FIG. 5 is a flowchart of a method for manufacturing a flexible current collector core layer according to an embodiment of the invention; and
Fig. 6 is a flowchart of a method for manufacturing a current collector according to an embodiment of the present invention.
Detailed Description
In order to make the above and/or other objects, effects and features of the present invention more comprehensible, preferred embodiments accompanied with figures are described in detail below:
please refer to fig. 1, which is a schematic diagram illustrating a structure of a flexible current collector core layer according to an embodiment of the invention. As shown in the drawing, the flexible current collector core layer 1 of the present invention includes an insulating support layer 11 and a porous conductive layer 12, wherein the porous conductive layer 12 is disposed on two sides of the insulating support layer 11, and is described in detail as follows:
the material of the insulating and supporting layer 11 includes a first polyolefin material or/and a flame retardant polyolefin material, and the melting point of the first polyolefin material and the polyolefin material in the flame retardant polyolefin material is not higher than 136 ℃, in a preferred embodiment, the melting point of the first polyolefin material and the polyolefin material in the flame retardant polyolefin material is not higher than 130 ℃, so that the insulating and supporting layer 11 is a solid structure without holes, in an embodiment, the material of the insulating and supporting layer 11 may be only the first polyolefin material, or a blend of the first polyolefin material and the flame retardant polyolefin material is adopted at the same time, and in an embodiment, the material of the insulating and supporting layer 11 may further include an ethylene-vinyl acetate copolymer material, but is not limited thereto.
Wherein the first polyolefin material may be at least one of polyethylene, polypropylene, ethylene-vinyl acetate, ethylene-propylene copolymer, ethylene-octene copolymer, polyethylene terephthalate, polybutylene terephthalate, and preferably, the polyethylene thereof is at least one of high density polyethylene, low density polyethylene, linear low density polyethylene, but not limited thereto.
The flame retardant filled in the flame retardant polyolefin material is at least one of halogen flame retardant, phosphorus-nitrogen flame retardant and inorganic flame retardant, but not limited to, the halogen flame retardant can be decomposed to generate hydrogen Halide (HX), so that the hydrogen halide eliminates the combustion reaction of the high polymer material to generate active free radicals, for example, the hydrogen Halide (HX) acts with chain reaction active substances in flame to reduce the concentration of the free radicals, thereby slowing down or stopping the chain reaction of combustion and achieving the aim of flame retardance; the action principle of the phosphorus flame retardant is that when the phosphorus flame retardant is heated, a cross-linked solid substance or a carbonized layer with a more stable structure can be generated, the formation of the carbonized layer can further prevent the polymer from pyrolysis, and the thermolysis generated substances in the phosphorus flame retardant can be prevented from entering a gas phase to participate in the combustion process; the phosphorus element in the phosphorus-nitrogen flame retardant can promote the dehydration of cotton fibers to carbon, and the nitrogen element has synergistic efficiency for improving the flame retardant property of the phosphorus element; and inorganic flame retardants are mainly prepared by adding inorganic elements with intrinsic flame retardance into a flame-retardant substrate in the form of simple substances or compounds, fully mixing the flame-retardant substrate with a polymer in a physical dispersion state, and performing flame retardance through chemical or physical changes in a gas phase or a condensed phase.
In one embodiment, the porous conductive layer 12 has a porosity of 10% -80% and a pore size of 0.02 μm-1 μm, and a surface roughness of 0.025 μm-2 μm, but not limited thereto, wherein the material of the porous conductive layer 12 includes a second polyolefin material and a conductive filler.
Wherein the second polyolefin material may be at least one of polyethylene, polypropylene, ethylene-vinyl acetate, ethylene-propylene copolymer, ethylene-octene copolymer, polyethylene terephthalate, polybutylene terephthalate, and in a preferred embodiment, the second polyolefin material may be polypropylene, and the first polyolefin material is different from the second polyolefin material, but not limited thereto.
The conductive filler is at least one of carbon-based conductive material or metal oxide material, and the mass ratio of the conductive filler in the porous conductive layer 12 is 10% -45%, the mass ratio of the conductive filler is quite important, if the mass ratio exceeds 45%, the extrusion process is affected, so that the porous conductive layer 12 cannot be stretched to form a hole, otherwise, if the mass ratio of the conductive filler is less than 10%, a conductive network cannot be formed.
In an embodiment, the carbon-based conductive material may be surface modified by at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, where the coupling agent added is effective in that when the proportion of the carbon-based conductive material is small, that is, the mass ratio of the carbon-based conductive material in the porous conductive layer 12 is not more than 20%, the added coupling agent can promote the dispersion effect of the carbon-based conductive material in the polymer, whereas when the mass ratio of the carbon-based conductive material in the porous conductive layer 12 is more than 20%, the filler particles are easy to form a conductive network, so that the difference in the effect of the surface modification of the carbon-based conductive material is not large, and at the same time, the other properties of the core layer are not affected by the modification.
In one embodiment, the carbon-based conductive material is at least one of conductive carbon black, graphite, graphene or carbon nanotubes, and when the carbon-based conductive material is carbon nanotubes, the diameter is 5nm to 15nm and the length is 0.1 μm to 2 μm, but not limited thereto, and the metal oxide material includes at least one of Ti, V, sn, zn metal oxide or Ti, V, sn, zn metal oxide doped with metal oxide, and in one embodiment, the metal oxide material is at least one of TiO2, ti4O7, V2O3, VO2, snO2, znO doped whiskers or powders, wherein when the conductive filler is particulate, the particle size is 10nm to 500nm, or when the conductive filler is whisker or fiber, the diameter is 0.005 μm to 2 μm and the length is 0.05 μm to 3 μm.
In one embodiment, the thickness ratio of the insulating support layer 11 to the porous conductive layer 12 is 1:0.2-10, and the insulating support layer and the porous conductive layer are formed by extrusion at one time in a multi-layer coextrusion mode, but not limited thereto.
Please refer to fig. 2, which is a schematic diagram illustrating a current collector according to an embodiment of the present invention. As shown in the drawings, the current collector 2 of the present invention includes the flexible current collector core layer 1 and the conductive metal layer 21, and the conductive metal layer 21 is disposed on two sides of the porous conductive layer 11, wherein the conductive metal layer 21 is made of at least one of aluminum, copper, nickel, titanium, silver, nickel-copper alloy and aluminum-zirconium alloy, and the thickness of the conductive metal layer 21 is 0.5 μm-3 μm, but not limited thereto.
Please refer to fig. 3, which is a schematic diagram of a pole piece according to an embodiment of the present invention. As shown in the drawings, the electrode sheet 3 of the present invention includes the aforementioned current collector 2 and the electrode active material layer 31, wherein the electrode active material layer 31 is formed on the surface of the current collector 2.
Fig. 4 is a schematic structural diagram of a battery according to an embodiment of the invention. As shown in the figure, the battery 4 of the present invention comprises a positive electrode piece 41, a negative electrode piece 42, a diaphragm 43 and an electrolyte 44, wherein the diaphragm 43 is disposed between the positive electrode piece 41 and the negative electrode piece 42, and the electrolyte 44 is filled between the positive electrode piece 41 and the negative electrode piece 42, so that the positive electrode piece 41 and the negative electrode piece 42 are electrically connected, and the following details are provided:
In one implementation, positive electrode tab 41 is the aforementioned tab 3 and has a positive polarity, while negative electrode tab 42 is the same aforementioned tab 3 and has a negative polarity, but is not limited thereto.
In one embodiment, the separator 43 is a microporous and porous film, mainly made of PP and PE, and has the main function of closing or blocking the channels, so as to isolate the positive electrode 41 from the negative electrode 42, and prevent short circuit, but not limited thereto.
In one implementation, the electrolyte 44 primarily functions to transfer the entire electrochemically reactive ions.
Fig. 5 is a flowchart of a method for preparing a flexible current collector core layer according to an embodiment of the invention. As shown in the figure, the preparation method of the flexible current collector core layer comprises the following steps:
step S1, an insulating support layer material and a porous conductive layer material are respectively added into an extruder for melting and plasticizing, and an insulating support layer melting raw material and a porous conductive layer melting raw material are generated and extruded to a die head;
s2, synchronously extruding the molten raw materials of the insulating support layer and the molten raw materials of the porous conductive layer through the die head, and drawing to form a casting film, wherein the structure of the casting film comprises an insulating support layer and a porous conductive layer, and the porous conductive layers are respectively arranged on two sides of the insulating support layer; and
And S3, generating a flexible current collector core layer by the casting film through a stretching procedure, wherein the stretching procedure is longitudinal and transverse stretching, the stretching temperature is 90-140 ℃, and the stretching ratio is 1-5 times.
As shown in step S1, the method is a step of mixing, melting and extruding, wherein the insulating support layer material and the porous conductive layer material are respectively added into an extruder for melting and plasticizing, so that the insulating support layer melting raw material and the porous conductive layer melting raw material can be produced and extruded to a die head.
As shown in step S2, which is a casting step, the molten raw materials of the insulating support layer and the porous conductive layer are synchronously extruded through a die head and pulled into a casting film, at this time, the casting film forms a three-layer structure with the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 sequentially, i.e. the porous conductive layers 12 are respectively disposed at two sides of the insulating support layer 11, and in an embodiment, the casting film can be cooled by a cooling roller at 50-130 ℃ to obtain a casting sheet, but not limited thereto.
As shown in step S3, it is a stretching step, where the casting film is stretched longitudinally and transversely at a stretching temperature of 90-140 ℃ and a stretching ratio of 1-5 times, and heat-set after high-temperature stretching, to obtain the flexible current collector core layer 1, and for this purpose, in a preferred embodiment, the melting point of the first polyolefin material of the insulating support layer 11 must be not higher than 135 ℃, and in a preferred embodiment, the melting point of the first polyolefin material of the insulating support layer is not higher than 130 ℃, so that a dense structure of the insulating support layer 11 is ensured, and, under stretching, the surface of the porous conductive layer 12 has a hole structure, that is, the surface of the flexible current collector core layer 1 will have a hole structure.
Referring to fig. 6, a flow chart of a method for preparing a current collector according to an embodiment of the invention is shown. As shown in the figure, the preparation method of the current collector of the invention has the steps different from the preparation method of the flexible current collector core layer in that the preparation method further comprises the step S4.
And S4, forming a conductive metal layer on the surfaces of the porous conductive layers on the two sides of the flexible current collector core layer respectively through a mechanical rolling process, a bonding process, a vapor deposition process or an electroless plating process to generate a current collector.
As shown in step S4, which is a metal plating step, a conductive metal layer 21 of 0.5 μm to 3 μm is formed on both side surfaces of the flexible current collector core layer 1 by means of alkalinity, acid plating or a combination of both processes, to obtain the final current collector 2.
For testing the data related to the flexible current collector core layer 1 of the present invention, the following test methods were provided:
1. volume resistivity measurement:
reference formula:
wherein ρv is the volume resistivity of the sample in Ω·cm;
rv is the volume resistance of the sample in Ω;
s is the cross-sectional area of the sample in the direction perpendicular to the current, and the unit is cm2; and
d is the length of the sample parallel to the current direction in cm.
Because the porous conductive layers 12 of the flexible current collector core layer 1 are disposed on two sides of the insulating support layer 11, the volume resistivity of the flexible current collector core layer 1 cannot be directly tested, and in order to conveniently test the volume resistivity of the porous conductive layers 12, the materials of the porous conductive layers 12 in each embodiment need to be extruded separately, and then cast pieces are collected, and further cut samples are tested.
2. The overall pore size and porosity test method of the porous conductive layer 12:
in one embodiment, the pore size and porosity of the porous conductive layer 12 may be measured by a water-pressing method, after the thickness is obtained, the porous conductive layer 12 with specific size and mass is cut, and the porous conductive layer is put into a water-pressing apparatus, the measurement pressure is gradually increased from 0psi to 1500psi, water is extruded into the pore canal under the action of the pressure, and the pressure corresponding to the water extruded into different pore sizes follows the Washburn equation, so that a series of pore size and porosity can be calculated, but not limited thereto.
For further understanding of the present invention, preferred embodiments of the present invention are described below in conjunction with the detailed description so as to facilitate understanding of the present invention to those skilled in the art.
Example 1
The materials were selected as follows:
the insulating and supporting layer 11 is made of high-density polyethylene (HDPE) with a melt index of 2.0g/10min, the melting point of which is 136 ℃ and the melting point of which is 125 ℃, and the HDPE and the LDPE are mixed to obtain a uniform mixture, wherein the HDPE accounts for 60 percent of the total mass of the material of the insulating and supporting layer, and the LDPE accounts for 40 percent.
The porous conductive layer 12 is polypropylene with a melt index of 4.0g/10min-6.0g/10min, and 20 parts by weight of acetylene black surface-modified by a titanate coupling agent is added to 100 parts by weight of polypropylene, wherein the particle size of the acetylene black is 45nm.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE and LDPE uniform mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 20 parts by weight of acetylene black subjected to surface modification by a titanate coupling agent into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:2:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched 4 times along the extrusion direction and 2 times transversely stretched, thereby obtaining a flexible current collector core layer 1 having a thickness of 14 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, a conductive metal layer 21 with the thickness of 1 mu m is formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, so that the current collector 2 with the total thickness of 16 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 20 parts by weight of acetylene black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting through a die head of the extruder, cooling through a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform volume resistivity test.
Example 2
The materials were selected as follows:
the insulating and supporting layer 11 is made of high-density polyethylene (HDPE) with a melt index of 1.0g/10min, the melting point of the HDPE is 136 ℃ and the melting point of the LDPE is 125 ℃, and the HDPE and the LDPE are mixed to obtain a uniform mixture, wherein the HDPE accounts for 70 percent of the total mass of the material of the insulating and supporting layer, and the LDPE accounts for 30 percent.
The porous conductive layer 12 is polypropylene with a melt index of 6.0g/10min-8.0g/10min, and 35 parts by weight of acetylene black surface-modified by a titanate coupling agent is added to 100 parts by weight of polypropylene, wherein the particle size of the acetylene black is 45nm.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE and LDPE uniform mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 35 parts by weight of acetylene black subjected to surface modification by a titanate coupling agent into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:2:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched 4 times along the extrusion direction and 2 times transversely stretched, thereby obtaining a flexible current collector core layer 1 having a thickness of 14 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, a conductive metal layer 21 with the thickness of 1 mu m is formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, so that the current collector 2 with the total thickness of 16 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 35 parts by weight of acetylene black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting by a die head of the extruder, cooling by a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform the volume resistivity test.
Example 3
The materials were selected as follows:
the insulating and supporting layer 11 is made of High Density Polyethylene (HDPE) with a melt index of 0.7g/10min-1.5g/10min and a melting point of 126-130 ℃.
The porous conductive layer 12 is polypropylene with a melt index of 8.0g/10min-10.0g/10min, and 45 parts by weight of acetylene black with a particle size of 45nm is added to 100 parts by weight of polypropylene.
1. And (3) mixing and melting extrusion: adding the HDPE into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 45 parts by weight of acetylene black into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:2:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched 4 times along the extrusion direction and 2 times transversely stretched, thereby obtaining a flexible current collector core layer 1 having a thickness of 14 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, conductive metal layers 21 with the thickness of 1 mu m are formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layers 21 are copper metal layers, so that the current collector 2 with the total thickness of 16 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 45 parts by weight of acetylene black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting by a die head of the extruder, cooling by a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform the volume resistivity test.
Example 4
The materials were selected as follows:
the insulating and supporting layer 11 is made of high-density polyethylene (HDPE) with a melt index of 2.0g/10min, the melting point of the high-density polyethylene (HDPE) is 136 ℃ and the melting point of the low-density polyethylene (LDPE) is 125 ℃, and the HDPE and the LDPE are mixed to obtain a uniform mixture, wherein the HDPE accounts for 60% of the total mass of the material of the insulating and supporting layer, and the LDPE accounts for 40%.
The porous conductive layer 12 is made of polypropylene with a melt index of 4.0g/10min-6.0g/10min, and 25 parts by weight of conductive carbon black with a particle diameter of 33nm is added to 100 parts by weight of polypropylene.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE and LDPE EVA homogeneous mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 25 parts by weight of conductive carbon black into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:2:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched, 4.2 times in the extrusion direction, and 2.2 times in the transverse direction, thereby obtaining a flexible current collector core layer 1 having a thickness of 12 μm.
4. A metal coating step: conductive metal layers 21 of 1 μm are formed on both side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layers 21 are copper metal layers, so that a current collector 2 with a total thickness of 14 μm is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 25 parts by weight of conductive carbon black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting by a die head of the extruder, cooling by a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform the volume resistivity test.
Example 5
The materials were selected as follows:
the insulating and supporting layer 11 was composed of a High Density Polyethylene (HDPE) having a melt index of 2.0g/10min, a melting point of 136℃and a Low Density Polyethylene (LDPE), a melting point of 126℃and an ethylene-vinyl acetate copolymer (EVA) having a melting point of 86℃and the HDPE, LDPE and EVA were mixed to obtain a uniform mixture, wherein the HDPE was 70% of the total mass of the material of the insulating and supporting layer, the LDPE was 20% and the EVA was 10%.
The porous conductive layer 12 is polypropylene with a melt index of 4.0g/10min-6.0g/10min, and 12 parts by weight of carbon nano tubes are added to 100 parts by weight of polypropylene, wherein the diameter of the carbon nano tubes is 5nm-15nm, and the length of the carbon nano tubes is 0.1 mu m-2 mu m.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE, LDPE and EVA homogeneous mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 12 parts by weight of carbon nano tubes into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:1:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched 4.5 times and 2.8 times in the extrusion direction, thereby obtaining a flexible current collector core layer 1 having a thickness of 9 μm.
4. A metal coating step: after a thin metal layer is formed by basicity, a conductive metal layer 21 of 0.75 μm is formed on both side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, thereby obtaining a current collector 2 with a total thickness of 10.5 μm.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 12 parts by weight of carbon nano tubes into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting by a die head of the extruder, cooling by a cooling roller at 50-130 ℃, and cutting the sample on the obtained cast sheet to perform the volume resistivity test.
Example 6
The materials were selected as follows:
the insulating and supporting layer 11 is made of high-density polyethylene (HDPE) with a melt index of 2.0g/10min, the melting point of which is 136 ℃ and the melting point of which is 125 ℃, and the HDPE and the LDPE are mixed to obtain a uniform mixture, wherein the HDPE accounts for 70 percent of the total mass of the material of the insulating and supporting layer, and the LDPE accounts for 30 percent.
The porous conductive layer 12 is made of polypropylene with a melt index of 4.0g/10min-6.0g/10min, and 6 parts by weight of carbon nanotubes and 10 parts by weight of conductive carbon black are added to 100 parts by weight of polypropylene, wherein the carbon nanotubes have a diameter of 5nm-15nm, a length of 0.1 μm-2 μm and a particle diameter of 33nm.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE and LDPE uniform mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene, 6 parts by weight of carbon nano tubes and 10 parts by weight of conductive carbon black into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 2:3:2.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched 4.5 times and 2.8 times in the extrusion direction, thereby obtaining a flexible current collector core layer 1 having a thickness of 9 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, a conductive metal layer 21 with the thickness of 11 mu m is formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, so that the current collector 2 with the total thickness of 11 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene, 6 parts by weight of carbon nano tubes and 10 parts by weight of conductive carbon black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting through a die head of the extruder, cooling through a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform volume resistivity test.
Example 7
The materials were selected as follows:
the insulating and supporting layer 11 is made of high-density polyethylene (HDPE) with a melt index of 2.0g/10min, the melting point of which is 136 ℃ and the melting point of which is 125 ℃, and the HDPE and the LDPE are mixed to obtain a uniform mixture, wherein the HDPE accounts for 75 percent of the total mass of the material of the insulating and supporting layer, and the LDPE accounts for 25 percent.
The porous conductive layer 12 is made of polypropylene having a melt index of 8.0g/10min-10.0g/10min, and 10 parts by weight of zinc oxide whiskers (ZnOw) having a diameter of 0.05 μm-1 μm and a length of 0.5 μm-3 μm and acetylene black having a particle diameter of 45nm are added to 100 parts by weight of polypropylene.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE and LDPE uniform mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene, 10 parts by weight of zinc oxide whisker (ZnOw) and 10 parts by weight of acetylene black into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:1:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched, 3.8 times in the extrusion direction, and 2 times in the transverse direction, thereby obtaining a flexible current collector core layer 1 having a thickness of 15 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, a conductive metal layer 21 with the thickness of 0.5 mu m is formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, so that the current collector 2 with the total thickness of 16 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene, 10 parts by weight of zinc oxide whisker (ZnOw) and 10 parts by weight of acetylene black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting through a die head of the extruder, cooling through a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet for volume resistivity test.
Example 8
The materials were selected as follows:
the insulating support layer 11 is a High Density Polyethylene (HDPE) having a melt index of 0.7g/10min to 1.5g/10min, a melting point of 126 ℃ to 130 ℃, an ethylene-vinyl acetate copolymer (EVA) having a melting point of 86 ℃ and a silane-coated ammonium polyphosphate, and 90 parts by weight of HDPE, 10 parts by weight of EVA and 40 parts by weight of silane-coated ammonium polyphosphate are mixed to obtain a uniform mixture.
The porous conductive layer 12 is made of polypropylene with a melt index of 4.0g/10min-6.0g/10min, and 25 parts by weight of conductive carbon black with a particle diameter of 33nm is added to 100 parts by weight of polypropylene.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the uniform mixture of 90 parts by weight of HDPE, 10 parts by weight of EVA and 40 parts by weight of silane coated ammonium polyphosphate into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 25 parts by weight of conductive carbon black into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding the molten raw material to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:1:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched, 3.8 times in the extrusion direction, and 2 times in the transverse direction, thereby obtaining a flexible current collector core layer 1 having a thickness of 14 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, a conductive metal layer 21 with the thickness of 1 mu m is formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, so that the current collector 2 with the total thickness of 16 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 25 parts by weight of conductive carbon black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting by a die head of the extruder, cooling by a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform the volume resistivity test.
Example 9
The materials were selected as follows:
the insulating and supporting layer 11 is made of High Density Polyethylene (HDPE) having a melt index of 0.7g/10min to 1.5g/10min, a melting point of 126 ℃ to 130 ℃, an ethylene-vinyl acetate copolymer (EVA) having a melting point of 86 ℃ and ammonium polyphosphate, and 95 parts by weight of HDPE, 5 parts by weight of EVA and 15 parts by weight of ammonium polyphosphate are mixed to obtain a uniform mixture.
The porous conductive layer 12 is made of polypropylene having a melt index of 8.0g/10min-10.0g/10min, and 10 parts by weight of zinc oxide whiskers (ZnOw) having a diameter of 0.05 μm-1 μm and a length of 0.5 μm-3 μm and acetylene black having a particle diameter of 45nm are added to 100 parts by weight of polypropylene.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the uniform mixture of 95 parts by weight of HDPE, 5 parts by weight of EVA and 15 parts by weight of ammonium polyphosphate into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene, 10 parts by weight of zinc oxide whisker (ZnOw) and 10 parts by weight of acetylene black into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding the molten raw material to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:1:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched, 3.8 times in the extrusion direction, and 2 times in the transverse direction, thereby obtaining a flexible current collector core layer 1 having a thickness of 14 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, a conductive metal layer 21 with the thickness of 1 mu m is formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, so that the current collector 2 with the total thickness of 16 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene, 10 parts by weight of zinc oxide whisker (ZnOw) and 10 parts by weight of acetylene black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting through a die head of the extruder, cooling through a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet for volume resistivity test.
In the same materials and processes of examples 1 to 9, if the melting point of the first polyolefin material of the insulating and supporting layer 11 and the polyolefin material of the flame retardant polyolefin material is higher than 136 ℃, the film breaking phenomenon is easily caused during the stretching step, so the melting point thereof must be in the range of not higher than 136 ℃.
Comparative example 1
The materials were selected as follows:
the insulating and supporting layer 11 is made of high-density polyethylene (HDPE) with a melt index of 2.0g/10min, the melting point of which is 136 ℃ and the melting point of which is 125 ℃, and the HDPE and the LDPE are mixed to obtain a uniform mixture, wherein the HDPE accounts for 60 percent of the total mass of the material of the insulating and supporting layer, and the LDPE accounts for 40 percent.
The porous conductive layer 12 is polypropylene with a melt index of 4.0g/10min-6.0g/10min, and 8 parts by weight of acetylene black is added to 100 parts by weight of polypropylene, wherein the particle size of the acetylene black is 45nm.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE and LDPE uniform mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 8 parts by weight of acetylene black into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:2:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched 4 times along the extrusion direction and 2 times transversely stretched, thereby obtaining a flexible current collector core layer 1 having a thickness of 14 μm.
Comparative example 1 the porous conductive layer on the surface of the flexible current collector core layer had a higher volume resistivity, and thus, the electroplated copper metal layer was not performed.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 8 parts by weight of acetylene black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting by a die head of the extruder, cooling by a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform the volume resistivity test.
Comparative example 2
The materials were selected as follows:
the insulating and supporting layer 11 is made of high-density polyethylene (HDPE) with a melt index of 2.0g/10min, the melting point of which is 136 ℃ and the melting point of which is 125 ℃, and the HDPE and the LDPE are mixed to obtain a uniform mixture, wherein the HDPE accounts for 60 percent of the total mass of the material of the insulating and supporting layer, and the LDPE accounts for 40 percent.
The porous conductive layer 12 is polypropylene with a melt index of 4.0g/10min-6.0g/10min, and 10 parts by weight of acetylene black surface-modified by a titanate coupling agent is added to 100 parts by weight of polypropylene, wherein the particle size of the acetylene black is 45nm.
The preparation method comprises the following steps:
1. and (3) mixing and melting extrusion: adding the HDPE and LDPE uniform mixture into an extruder, melting and plasticizing to obtain a molten raw material of the insulating support layer 11, adding 100 parts by weight of polypropylene and 8 parts by weight of acetylene black subjected to surface modification by a titanate coupling agent into the extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, and extruding to a die head.
2. Casting the sheet: the molten raw materials of the insulating support layer 11 and the porous conductive layer 12 pass through a die head with a three-layer co-extrusion structure, so that a casting film with a three-layer structure of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 can be obtained by extrusion, and a casting sheet is obtained by cooling by a cooling roller at 50-130 ℃, wherein the thickness ratio of the layers of the porous conductive layer 12/the insulating support layer 11/the porous conductive layer 12 is 1:2:1.
3. Stretching: the cast film of the porous conductive layer 12/insulating support layer 11/porous conductive layer 12 three-layer structure obtained above was preheated at 90 ℃, and the preheated cast sheet was put into an oven at 135 ℃ to be longitudinally and transversely stretched 4 times along the extrusion direction and 2 times transversely stretched, thereby obtaining a flexible current collector core layer 1 having a thickness of 14 μm.
4. A metal coating step: after a thin metal layer is formed by alkalinity, a conductive metal layer 21 with the thickness of 1 mu m is formed on the two side surfaces of the flexible current collector core layer 1 by acid plating, and the conductive metal layer 21 is a copper metal layer, so that the current collector 2 with the total thickness of 16 mu m is obtained.
The test method is as follows:
and (3) volume resistivity test, namely adding 100 parts by weight of polypropylene and 10 parts by weight of acetylene black into an extruder, melting and plasticizing to obtain a molten raw material of the porous conductive layer 12, casting by a die head of the extruder, cooling by a cooling roller at 50-130 ℃, and cutting a sample on the obtained cast sheet to perform the volume resistivity test.
Table 1, detailed data of various embodiments
In summary, the volume resistivity is the resistance of the porous conductive layer 12 per unit volume to the current, and is used to represent the electrical property of the porous conductive layer 12, and for this reason, generally, the higher the volume resistivity, the lower the conductive performance, and as can be seen from the table one, the volume resistivity of the comparative examples 1-2 is much higher than that of the examples 1-9, i.e., the conductive performance of the porous conductive layer 12 of the comparative examples 1-2 is lower.
In comparative examples 1 to 2, the difference is that the ratio of acetylene black to the porous conductive layer 12 is lower than 20%, and the acetylene black used in comparative example 2 is surface-modified with a titanate coupling agent, and it is seen that the volume resistivity of the conductive layer in comparative example 2 is reduced by about 95% compared with that in comparative example 1 under the modification, and in example 1, the ratio of acetylene black is just 20%, and the acetylene black is surface-modified with a titanate coupling agent, and at this time, the volume resistivity of the conductive layer is reduced by about 98% compared with that in comparative example 1, and the effect of the surface modification of the coupling agent on the conductive performance is very great when the ratio of acetylene black to the porous conductive layer 12 is not higher than 20%.
In examples 8-9, the insulating support layer 11 was added with a flame retardant polyolefin material, so that the porous conductive layer 12 has a good flame retardant effect and a high conductive performance, and the object of the present invention can be achieved.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the concept of the present invention, and are intended to be comprehended within the scope of the present invention.

Claims (28)

1. A flexible current collector core layer, comprising:
an insulating support layer; and
The porous conducting layers are arranged on two sides of the insulating supporting layer;
the insulating support layer comprises a first polyolefin material and/or a flame-retardant polyolefin material, wherein the melting points of the first polyolefin material and the polyolefin material in the flame-retardant polyolefin material are not higher than 136 ℃;
wherein the porous conductive layer comprises a second polyolefin material and a conductive filler;
wherein, the insulating supporting layer is a dense structure without holes;
wherein, the insulating support layer and the porous conducting layer are formed by one-step extrusion in a multilayer coextrusion mode.
2. The flexible current collector core layer of claim 1, wherein the first polyolefin material and the second polyolefin material are at least one of polyethylene, polypropylene, ethylene-vinyl acetate, ethylene-propylene copolymer, ethylene-octene copolymer, polyethylene terephthalate, polybutylene terephthalate, and wherein the first polyolefin material is different from the second polyolefin material.
3. The flexible current collector core of claim 2, wherein the polyethylene is at least one of high density polyethylene, low density polyethylene, and linear low density polyethylene.
4. The flexible current collector core layer of claim 2, wherein the second polyolefin material is the polypropylene.
5. The flexible current collector core layer of claim 1, wherein the flame retardant filled in the flame retardant polyolefin material is at least one of a halogen-based flame retardant, a phosphorus-nitrogen-based flame retardant, and an inorganic flame retardant.
6. The flexible current collector core of claim 1, wherein the material of the insulating support layer further comprises an ethylene vinyl acetate copolymer.
7. A flexible current collector core layer as in claim 1, wherein the first polyolefin material has a melting point of no greater than 130 ℃.
8. A flexible current collector core layer as in claim 1 wherein the porous conductive layer has a porosity of 10% to 80%.
9. The flexible current collector core layer of claim 1, wherein the porous conductive layer has a pore size of 0.02 μm to 1 μm.
10. The flexible current collector core layer of claim 1, wherein the porous conductive layer has a surface roughness of 0.025 μm to 2 μm.
11. The flexible current collector core layer of claim 1, wherein the conductive filler is at least one of a carbon-based conductive material or a metal oxide material.
12. The flexible current collector core layer of claim 11, wherein the carbon-based conductive material is at least one of conductive carbon black, graphite, graphene, or carbon nanotubes.
13. The flexible current collector core of claim 12, wherein the carbon-based conductive material is carbon nanotubes having a diameter of 5nm to 15nm and a length of 0.1 μm to 2 μm.
14. The flexible current collector core of claim 11, wherein the metal oxide material comprises at least one of a metal oxide of Ti, V, sn, zn or a metal oxide of Ti, V, sn, zn doped with a metal oxide.
15. The flexible current collector core of claim 11, wherein the metal oxide material is at least one of TiO2, ti4O7, V2O3, VO2, snO2, znO doped whiskers, or powders.
16. The flexible current collector core of claim 1, wherein the conductive filler is particulate and has a particle size of from 10nm to 500nm.
17. A flexible current collector core layer as claimed in claim 1, wherein the conductive filler is whiskers or fibers having a diameter of 0.005 μm to 2 μm and a length of 0.05 μm to 3 μm.
18. A flexible current collector core layer as claimed in claim 1 wherein the mass fraction of the conductive filler in the porous conductive layer is from 10% to 45%.
19. The flexible current collector core layer of claim 1, wherein the thickness of the flexible current collector core layer is from 5 μm to 20 μm.
20. The flexible current collector core layer of claim 1, wherein the thickness ratio of the insulating support layer to the porous conductive layer is 1:0.2-10.
21. A current collector, comprising:
the flexible current collector core layer of any of claims 1-20; and
And the conductive metal layers are arranged on two sides of the porous conductive layer.
22. The current collector of claim 21, wherein the conductive metal layer is at least one of aluminum, copper, nickel, titanium, silver, nickel-copper alloy, aluminum-zirconium alloy.
23. The current collector of claim 21, wherein the conductive metal layer has a thickness of 0.5 μm to 3 μm.
24. A pole piece, comprising:
the current collector of any one of claims 21-23; and
And an electrode active material layer formed on the surface of the current collector.
25. A battery, comprising:
a positive electrode sheet as claimed in claim 24, and having a positive polarity;
a negative electrode sheet as in claim 24, and said sheet having a negative polarity;
the diaphragm is arranged between the positive pole piece and the negative pole piece to isolate the positive pole piece from the negative pole piece; and
And the electrolyte is filled between the positive pole piece and the negative pole piece, so that the positive pole piece is electrically connected with the negative pole piece.
26. The preparation method of the flexible current collector core layer is characterized by comprising the following steps:
respectively adding an insulating support layer material and a porous conductive layer material into an extruder for melting and plasticizing to generate and extrude an insulating support layer melting raw material and a porous conductive layer melting raw material to a die head;
The insulating supporting layer melting raw material and the porous conducting layer melting raw material are synchronously extruded through the die head and are drawn into a casting film, the structure of the casting film comprises an insulating supporting layer and a porous conducting layer, and the porous conducting layers are respectively arranged on two sides of the insulating supporting layer; and
The casting film is subjected to a stretching procedure to generate a flexible current collector core layer, wherein the stretching procedure is longitudinal and transverse stretching, the stretching temperature is 90-140 ℃, and the stretching ratio is 1-5 times, wherein the flexible current collector core layer comprises an insulating supporting layer and a porous conducting layer, and the insulating supporting layer is of a pore-free compact structure.
27. The preparation method of the current collector is characterized by comprising the following steps:
respectively adding an insulating support layer material and a porous conductive layer material into an extruder for melting and plasticizing to generate and extrude an insulating support layer melting raw material and a porous conductive layer melting raw material to a die head;
the insulating supporting layer melting raw material and the porous conducting layer melting raw material are synchronously extruded through the die head and are drawn into a casting film, the structure of the casting film comprises an insulating supporting layer and a porous conducting layer, and the porous conducting layers are respectively arranged on two sides of the insulating supporting layer;
The casting film is subjected to a stretching procedure to generate a flexible current collector core layer, wherein the stretching procedure is longitudinal and transverse stretching, the stretching temperature is 90-140 ℃, and the stretching ratio is 1-5 times, wherein the flexible current collector core layer comprises the insulating supporting layer and the porous conducting layer, and the insulating supporting layer is of a pore-free compact structure; and
And forming a conductive metal layer on the surfaces of the porous conductive layers on the two sides of the flexible current collector core layer respectively through a mechanical rolling process, a bonding process, a vapor deposition process or an electroless plating process to generate a current collector.
28. The method of manufacturing a current collector according to claim 27, wherein the electroless plating comprises at least one of alkaline plating and acid plating.
CN202210020852.1A 2022-01-10 2022-01-10 Flexible current collector core layer, current collector, pole piece, battery and preparation method of battery Active CN114361461B (en)

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