CN114156486B - Light flame-retardant current collector, preparation method thereof, electrode and battery - Google Patents
Light flame-retardant current collector, preparation method thereof, electrode and battery Download PDFInfo
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- CN114156486B CN114156486B CN202111274750.4A CN202111274750A CN114156486B CN 114156486 B CN114156486 B CN 114156486B CN 202111274750 A CN202111274750 A CN 202111274750A CN 114156486 B CN114156486 B CN 114156486B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 107
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
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- 238000009832 plasma treatment Methods 0.000 claims abstract description 11
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- 239000002245 particle Substances 0.000 claims description 30
- 229920000307 polymer substrate Polymers 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
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- 239000012510 hollow fiber Substances 0.000 claims description 7
- 239000002923 metal particle Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000005429 filling process Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000005289 physical deposition Methods 0.000 claims description 5
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- 229920005597 polymer membrane Polymers 0.000 claims description 5
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- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 4
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- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000002657 fibrous material Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- MMKLGSAPZRJREQ-UHFFFAOYSA-N butylbenzene phosphoric acid Chemical compound C(CCC)C1=CC=CC=C1.P(O)(O)(O)=O MMKLGSAPZRJREQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 4
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- 238000001755 magnetron sputter deposition Methods 0.000 description 3
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- 230000035882 stress Effects 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- 239000007773 negative electrode material Substances 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/668—Composites of electroconductive material and synthetic resins
-
- 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)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a light flame-retardant current collector, a preparation method thereof, an electrode and a battery. The main flame retardant is introduced into the polymer current collector in a micro-vessel mode, when the battery is subjected to mechanical impact, the outer wall of the micro-vessel flame retardant at the position of the mechanical impact is broken, when the battery is subjected to thermal impact, the outer wall of the micro-vessel flame retardant is heated to be broken, the main flame retardant overflows along with a micro-vessel path to cover the surfaces of the current collector and other components in the battery, and absorbs heat, so that the battery is prevented from firing and exploding, and the safety of the battery is improved; the hydrophilic functional groups are grafted by the plasma treatment technology of the surface of the high polymer material, so that the problem of low adhesion between the metal layer and the polymer film material is solved, and the durability of the current collector is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lightweight flame-retardant current collector, a preparation method thereof, an electrode and a battery.
Background
The lithium ion battery has wide application in the fields of 3C, new energy automobiles and electric power energy storage. With the progress of technology, the energy density, the power density, the environmental adaptability and other characteristics of the lithium ion battery are obviously improved, and the premise is that the lithium ion battery still needs to have excellent safety and reliability for realizing the application of the high-performance lithium ion battery. The lithium ion battery mainly comprises two carrier transportation, namely lithium ion migration and electron transportation. Wherein the transport of electrons takes place mainly through the current collector in the electrode. At present, the traditional current collector for the lithium ion battery is a metal current collector, namely an aluminum foil for a positive electrode and a copper foil for a negative electrode. Lithium ion batteries may suffer from damage such as mechanical stress, thermal stress, or electrical stress, and internal short circuits may occur, resulting in thermal runaway of the battery. In particular, when subjected to mechanical stresses such as, for example, extrusion, needling, impact, etc., rigid current collectors in lithium ion batteries are prone to cracking, forming burrs that pierce the separator, resulting in internal shorting of the battery's positive and negative electrodes. Therefore, improving the safety of lithium ion batteries by improving the mechanical properties of current collectors for lithium ion batteries is a hot spot in current research.
The lithium ion battery with partially improved design adopts a polymer current collector, and solves the safety problems that after the lithium ion battery is subjected to external physical impact, internal short circuit is easy to cause, thermal runaway and the like by utilizing the characteristic of high ductility of a high polymer film. Chinese patent (CN 201710534998.7) discloses a current collector, a pole piece containing the current collector, and a solid-state battery. The current collector is a high-molecular polymer positive temperature coefficient resistor film formed by mixing a high-molecular polymer material and conductive powder according to Curie temperature points of the current collector. However, the disadvantages of inflammable high polymer materials, poor heat conductors and the like cause the current collector to have potential safety hazards. Chinese patent (cn 2015123018. X) discloses a current collector comprising a polymer matrix material, metal particles and a coupling agent, which can effectively reduce the weight of the current collector of a battery so as to increase the energy density of the unit mass of the battery and improve the safety performance under abusive conditions, but the polymer matrix material selected from styrene-butadiene rubber and the like is a flammable material with high smoke yield, so that the current collector has potential safety hazard. (CN 202011092168.1) discloses a composite current collector comprising a conductive polymer fiber film and metal layers arranged on two sides of the conductive polymer fiber film, which has good conductivity and high ductility, and avoids the occurrence of short circuit in a battery, but the adhesion between the metal layers and the polymer layers is poor due to the difference of intrinsic properties of materials, so that contact failure is easy to cause, and the cycle durability is insufficient.
Therefore, it is necessary to develop a current collector that is lightweight, flame retardant, and has high electrical conductivity, and to improve the cycle durability and safety of the battery.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor performs intensive research and provides a light flame-retardant current collector, a preparation method thereof, an electrode and a battery, and the circulation durability and the safety of the battery are improved by selecting materials of the current collector and designing the preparation method, so that the invention is completed.
The technical scheme provided by the invention is as follows:
In a first aspect, a light-weight flame-retardant current collector includes a polymer film and metal layers on both sides of the polymer film, wherein the polymer film includes a polymer base material, conductive particles and a microvascular flame retardant, and the microvascular flame retardant is a fibrous material filled with flame retardant; the mass ratio of the polymer substrate material to the microvascular flame retardant to the conductive particles is (0.3-0.8): (0.01-0.1): (0.2-0.6).
In a second aspect, a method for preparing a lightweight flame retardant current collector includes the steps of:
Step 1: weighing a high polymer base material, conductive particles and a microvascular flame retardant according to a certain mass, wherein the main flame retardant and an outer wall material in the microvascular flame retardant are weighed according to a certain proportion;
Step 2: drawing the outer wall material of the weighed microvascular flame retardant into a hollow fiber shape by adopting fiber manufacturing equipment; mixing and dispersing high molecular polymer substrate materials and conductive particles in a solvent to form mixed slurry; paving a transverse hollow fibrous outer wall material and a longitudinal hollow fibrous outer wall material in a template, introducing mixed slurry, and heating to 50-200 ℃ for curing for 5-36 h to obtain an intermediate membrane containing a hollow pipeline; filling a main flame retardant into an intermediate membrane containing a hollow pipeline by adopting a filling process to obtain a high molecular polymer membrane;
Step 3: carrying out plasma treatment on two sides of the high polymer film, wherein the treatment temperature is 25-40 ℃ and the treatment time is 6-15 min;
step 4: and depositing metal particles on two sides of the treated high polymer film by adopting a physical deposition method to form a metal layer, thereby obtaining the light-weight flame-retardant current collector.
In a third aspect, an electrode comprising the light-weight, flame-retardant current collector of the first aspect, wherein the electrode is a positive electrode or a negative electrode.
In a fourth aspect, a battery comprising the electrode of the third aspect may be a pouch battery, a square aluminum case, a square steel case, a cylindrical aluminum case, or a cylindrical steel case battery.
According to the light flame-retardant current collector, the preparation method thereof, the electrode and the battery provided by the invention, the light flame-retardant current collector has the following beneficial effects:
(1) According to the lightweight flame-retardant current collector, the preparation method thereof, the electrode and the battery, when the battery is subjected to mechanical impact, the outer wall of the microvascular flame retardant at the mechanical impact position is broken, or the outer wall of the microvascular flame retardant is heated and broken when the battery is subjected to thermal impact, the flame retardant overflows along with a microvascular path to cover the current collector and the surfaces of other components in the battery, so that heat is absorbed, and further, the battery is prevented from firing and exploding, so that the risk is reduced, and the safety of the battery is improved;
(2) According to the lightweight flame-retardant current collector, the preparation method, the electrode and the battery, provided by the invention, the flame retardant is introduced into the polymer current collector in a microvascular mode, so that adverse effects of flame retardant addition on conductivity of the current collector are avoided, and the current collector is ensured to have high conductivity and high flame-retardant property;
(3) According to the lightweight flame-retardant current collector, the preparation method thereof, the electrode and the battery, provided by the invention, the hydrophilic functional groups are grafted through the plasma treatment technology of the surface of the high polymer material, so that the problem of low adhesiveness between the metal layer and the polymer film material is solved, and the stability of the metal layer is improved, so that the durability of the current collector is improved.
Drawings
Fig. 1 is a schematic structural view of a flame retardant current collector provided by the invention.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
According to a first aspect of the present invention, as shown in fig. 1, there is provided a lightweight flame-retardant current collector, including a high polymer film and metal layers on both sides of the high polymer film, wherein the high polymer film includes a high polymer base material, conductive particles and a microvascular flame retardant, and the microvascular flame retardant is a fibrous material filled with a flame retardant; the mass ratio of the polymer substrate material to the microvascular flame retardant to the conductive particles is (0.3-0.8): (0.01-0.1): (0.2-0.6).
In the invention, the microvascular flame retardant comprises a main flame retardant and an outer wall material. Wherein the main flame retardant is at least one of phosphorus flame retardants such as triphenyl phosphate, trimethyl phosphate, tri (2, 3-dichloropropyl) phosphate, triethyl phosphate or butyl benzene phosphate; the outer wall material is at least one selected from polyamide, polyureaaldehyde or polymethyl methacrylate.
Further, the mass ratio of the outer wall material of the micro-vessel type flame retardant to the main flame retardant is 1 (0.2-0.8). If the quality of the outer wall material is too high, the energy for damaging or dissolving the outer wall material is enhanced, and the flame retardant effect is reduced; if the quality of the outer wall material is too low, the main flame retardant can overflow in the normal use process, so that the conductivity of the current collector is affected.
Further, the outer wall material of the microvascular flame retardant is hollow fiber, the hollowness is more than 40%, and the outer diameter is 100-2000 nm. If the hollow is too low or the outer diameter is too small, the space for accommodating the flame retardant is easily reduced, and the flame retardant effect is reduced. If the outer diameter is too large, the degree of dispersion of the conductive particles may be hindered, thereby affecting the conductivity of the current collector.
In the present invention, the high molecular polymer base material is at least one selected from polyethylene, polyurethane, polycarbonate, polyamide, polyimide, polyvinylidene fluoride, polypropylene, polymethyl methacrylate, epoxy resin, carboxymethyl cellulose, and styrene butadiene rubber.
In the invention, the conductive particles are selected from at least one of metal conductive particles such as silver, copper or aluminum, or at least one of conductive carbon black, vapor grown carbon fiber, carbon nanotube or Ketjen black, or a combination of the metal conductive particles and the conductive carbon; the composition of the metal conductive particles and conductive carbon is preferable, and the mass ratio of the metal conductive particles to the conductive carbon is 1 (0.5 to 1).
In the invention, the metal layers on both sides of the high polymer film are at least one of silver, copper or aluminum. The metal layer is prepared by physical deposition methods such as a magnetron sputtering method, a vacuum plating method and the like, and the thickness of the metal layer is 50 nm-1 mu m. Preferably, the composition and thickness of the metal layers on both sides are the same. The thickness of the metal layer is too high, and the stability of the metal deposition layer is reduced, so that the circulation durability of the current collector is affected; the thickness of the metal layer is too low, and the conductivity of the metal deposition layer is insufficient, thereby affecting the electron conductivity of the current collector.
Preferably, the high molecular polymer film is subjected to plasma treatment before depositing the metal layer, wherein the plasma comprises at least one of non-polymerizable gases such as O 2、H2、N2、NH3, ar and the like. Hydrophilic functional groups such as-COOH, -OH, -NH 3 and the like are grafted on the surface of the high-molecular polymer film through plasma treatment, so that the problem of low adhesion between the metal layer and the polymer film material is solved, and the electron conductivity and the stability of the metal layer are improved.
According to a second aspect of the present invention, there is provided a method for preparing a lightweight flame retardant current collector, comprising the steps of:
step 1: weighing a high molecular polymer substrate material, conductive particles and a microvascular flame retardant according to a certain proportion; wherein, main flame retardant and outer wall material in the micro-vessel flame retardant are weighed according to proportion;
Step 2: drawing the outer wall material of the weighed microvascular flame retardant into a hollow fiber shape by adopting fiber manufacturing equipment; mixing and dispersing the high molecular polymer substrate material and the conductive particles in a solvent such as N-methyl pyrrolidone solvent to form mixed slurry; paving a transverse hollow fibrous outer wall material and a longitudinal hollow fibrous outer wall material in a template, introducing mixed slurry, and heating to 50-200 ℃ for curing for 5-36 h to obtain an intermediate membrane containing a hollow pipeline; filling a main flame retardant into an intermediate membrane containing a hollow pipeline by adopting a filling process to obtain a high molecular polymer membrane;
Step 3: carrying out plasma treatment on two sides of the high polymer film, wherein the treatment temperature is 25-40 ℃ and the treatment time is 6-15 min;
step 4: and depositing metal particles on two sides of the treated high polymer film by adopting a physical deposition method to form a metal layer, thereby obtaining the light-weight flame-retardant current collector.
According to a third aspect of the present invention, there is provided an electrode comprising the lightweight, flame-retardant current collector of the first aspect, the electrode being a positive electrode or a negative electrode.
According to a fourth aspect of the present invention there is provided a battery comprising an electrode according to the third aspect, the battery being a pouch battery, a square aluminium can, a square steel can, a cylindrical aluminium can or a cylindrical steel can battery.
Examples
Example 1
Step 1: polyurethane as a high molecular polymer substrate material, conductive particles and a microvascular flame retardant according to the weight ratio of 0.6:0.32: and weighing and mixing according to a proportion of 0.08, wherein the mass ratio of silver particles to conductive carbon black in the conductive particles is 1:0.8, and the mass ratio of polyamide serving as an outer wall material of the micro-vascular flame retardant to triphenyl phosphate serving as a main flame retardant is 1:0.7. And drawing the weighed flame retardant outer wall material into a hollow fiber shape by adopting fiber manufacturing equipment. The hollowness is 50%, and the outer diameter is 1000nm. The high polymer substrate material polyurethane and the conductive particles are mixed and dispersed in the N-methyl pyrrolidone solvent to form mixed slurry. And paving a transverse hollow fibrous outer wall material and a longitudinal hollow fibrous outer wall material in the template, introducing mixed slurry, heating to 120 ℃ for curing for 20 hours, and obtaining the intermediate membrane containing the hollow pipeline. And filling the main flame retardant into the intermediate membrane containing the hollow pipeline by adopting a filling process to obtain the high-molecular polymer membrane.
Step 2: o 2 plasma treatment is carried out on two sides of the high polymer film, the treatment temperature is 30 ℃, and the treatment time is 8min.
Step 3: and (3) depositing copper metal particles on two sides of the treated high polymer film by adopting a magnetron sputtering method, wherein the thickness of the copper deposited layers is 500nm, so as to form the light-weight flame-retardant negative electrode current collector. And (3) depositing aluminum metal particles on two sides of the treated high polymer film by adopting a magnetron sputtering method, wherein the thickness of the two sides of the aluminum deposition layer is 800nm, so as to form the lightweight flame-retardant anode current collector. Fig. 1 shows a structure of a flame-retardant current collector, wherein reference numeral 1 is a metal layer, reference numeral 2 is a microvascular flame retardant, reference numeral 3 is a high molecular polymer film, reference numeral 4 is metal conductive particles, and reference numeral 5 is conductive carbon.
And respectively coating the obtained positive electrode current collector and negative electrode current collector with a positive electrode active material nickel cobalt lithium manganate ternary material and a negative electrode active material graphite, assembling the materials into a soft-package lithium ion battery, and performing safety performance tests such as needling, extrusion, thermal shock and the like.
Example 2
In this example, a lightweight flame retardant current collector was prepared in substantially the same manner and conditions as in example 1. The difference is that in this embodiment: the main flame retardant in the microvascular flame retardant adopts tri (2, 3-dichloropropyl) phosphate.
Example 3
In this example, a lightweight flame retardant current collector was prepared in substantially the same manner and conditions as in example 1. The difference is that in this embodiment: o 2 plasma treatment is carried out on two sides of the high polymer film, the treatment temperature is 40 ℃, and the treatment time is 10min.
Example 4
In this example, a lightweight flame retardant current collector was prepared in substantially the same manner and conditions as in example 1. The difference is that in this embodiment: the outer wall material of the microvascular flame retardant is polymethyl methacrylate.
Comparative example 1
This comparative example differs from example 1 only in that: the hollow fiber-like outer wall material had a hollowness of 10% and an outer diameter of 80nm.
Comparative example 2
This comparative example differs from example 1 only in that: the mass ratio of the outer wall material to the main flame retardant material is 1:0.1.
Comparative example 3
This comparative example differs from example 1 only in that: the copper metal layer had a thickness of 3 μm and the aluminum metal layer had a thickness of 2. Mu.m.
Comparative example 4
This comparative example differs from example 1 only in that: the high molecular polymer film was not subjected to plasma treatment.
Performance testing
Electrode conductivity test: and (5) conducting electrode conductivity test by adopting a four-probe resistance tester.
Cycle stability test: the battery was charged and discharged at normal temperature at a rate of 0.5C, and the capacity retention rate was calculated after 100 cycles.
Needling test: test methods refer to the GJB 2374A-2013 standard.
Thermal shock test: test methods refer to the GJB 2374A-2013 standard.
The lithium ion batteries prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to electrode conductivity, needling test, and thermal shock test, respectively, according to the above-mentioned test standards. The results of the above test are shown in Table 1.
TABLE 1 physical Property parameters of Polymer lithium ion Battery electrode and various test results
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
What is not described in detail in the present specification is a well known technology to those skilled in the art.
Claims (10)
1. The light flame-retardant current collector is characterized by comprising a high-molecular polymer film and metal layers on two sides of the high-molecular polymer film, wherein the high-molecular polymer film comprises a high-molecular polymer substrate material, conductive particles and a microvascular flame retardant, the microvascular flame retardant is a fibrous material filled with the flame retardant, and the outer wall material of the microvascular flame retardant is hollow fiber; the mass ratio of the polymer substrate material to the microvascular flame retardant to the conductive particles is (0.3-0.8): (0.01 to 0.1): (0.2 to 0.6); the conductive particles are a composition of metal conductive particles and conductive carbon, and the mass ratio of the metal conductive particles to the conductive carbon is 1 (0.5-1);
The preparation method of the light flame-retardant current collector comprises the following steps:
step 1: weighing a high molecular polymer substrate material, conductive particles and a microvascular flame retardant according to a proportion; wherein, main flame retardant and outer wall material in the micro-vessel flame retardant are weighed according to proportion;
Step 2: drawing the outer wall material of the weighed microvascular flame retardant into a hollow fiber shape by adopting fiber manufacturing equipment; mixing and dispersing high molecular polymer substrate materials and conductive particles in a solvent to form mixed slurry; paving a transverse hollow fibrous outer wall material and a longitudinal hollow fibrous outer wall material in a template, introducing mixed slurry, and heating to 50-200 ℃ for curing for 5-36 hours to obtain an intermediate membrane containing a hollow pipeline; filling a main flame retardant into an intermediate membrane containing a hollow pipeline by adopting a filling process to obtain a high molecular polymer membrane;
step 3: carrying out plasma treatment on two sides of the high polymer film, wherein the treatment temperature is 25-40 ℃ and the treatment time is 6-15 min;
step 4: and depositing metal particles on two sides of the treated high polymer film by adopting a physical deposition method to form a metal layer, thereby obtaining the light-weight flame-retardant current collector.
2. The lightweight, flame retardant current collector of claim 1, wherein said microvascular flame retardant comprises a primary flame retardant and an outer wall material; wherein the main flame retardant is at least one selected from triphenyl phosphate, trimethyl phosphate, tri (2, 3-dichloropropyl) phosphate, triethyl phosphate and butyl benzene phosphate; the outer wall material is at least one selected from polyamide, polyureaaldehyde or polymethyl methacrylate.
3. The light-weight flame-retardant current collector according to claim 2, wherein the mass ratio of the main flame retardant to the outer wall material is (0.2 to 0.8): 1.
4. The light-weight flame-retardant current collector according to claim 1, wherein the hollow degree of the outer wall material of the microvascular flame retardant is more than 40%, and the outer diameter is 100 nm-2000 nm.
5. The lightweight, flame retardant current collector of claim 1, wherein said polymeric substrate material is selected from at least one of polyethylene, polyurethane, polycarbonate, polyamide, polyimide, polyvinylidene fluoride, polypropylene, polymethyl methacrylate, epoxy resin, carboxymethyl cellulose, or styrene butadiene rubber.
6. The light weight, flame retardant current collector of claim 1, wherein the conductive particles are selected from at least one of silver, copper or aluminum, or at least one of conductive carbon black, vapor grown carbon fiber, carbon nanotubes or ketjen black, or a combination of the above metal conductive particles and conductive carbon.
7. The light-weight flame-retardant current collector according to claim 1, wherein the metal layers on two sides of the high-molecular polymer film are at least one of silver, copper and aluminum, and the thickness of the metal layers is 50 nm-1 μm.
8. A method for preparing the lightweight flame retardant current collector of claim 1, comprising the steps of:
step 1: weighing a high molecular polymer substrate material, conductive particles and a microvascular flame retardant according to a proportion; wherein, main flame retardant and outer wall material in the micro-vessel flame retardant are weighed according to proportion;
Step 2: drawing the outer wall material of the weighed microvascular flame retardant into a hollow fiber shape by adopting fiber manufacturing equipment; mixing and dispersing high molecular polymer substrate materials and conductive particles in a solvent to form mixed slurry; paving a transverse hollow fibrous outer wall material and a longitudinal hollow fibrous outer wall material in a template, introducing mixed slurry, and heating to 50-200 ℃ for curing for 5-36 hours to obtain an intermediate membrane containing a hollow pipeline; filling a main flame retardant into an intermediate membrane containing a hollow pipeline by adopting a filling process to obtain a high molecular polymer membrane;
step 3: carrying out plasma treatment on two sides of the high polymer film, wherein the treatment temperature is 25-40 ℃ and the treatment time is 6-15 min;
step 4: and depositing metal particles on two sides of the treated high polymer film by adopting a physical deposition method to form a metal layer, thereby obtaining the light-weight flame-retardant current collector.
9. An electrode comprising the lightweight, flame-retardant current collector of any one of claims 1 to 7, wherein the electrode is a positive electrode or a negative electrode.
10. A battery comprising the electrode of claim 9.
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