CN116565217A - Composite current collector with automatic fire extinguishing function and preparation method thereof - Google Patents
Composite current collector with automatic fire extinguishing function and preparation method thereof Download PDFInfo
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- CN116565217A CN116565217A CN202310632070.8A CN202310632070A CN116565217A CN 116565217 A CN116565217 A CN 116565217A CN 202310632070 A CN202310632070 A CN 202310632070A CN 116565217 A CN116565217 A CN 116565217A
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- current collector
- film substrate
- fire extinguishing
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 20
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- 239000002184 metal Substances 0.000 claims abstract description 44
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
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- WVSNNWIIMPNRDB-UHFFFAOYSA-N 1,1,1,3,3,4,4,5,5,6,6,6-dodecafluorohexan-2-one Chemical compound FC(F)(F)C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WVSNNWIIMPNRDB-UHFFFAOYSA-N 0.000 claims description 9
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- OXZOLXJZTSUDOM-UHFFFAOYSA-N fluoro 2,2,2-trifluoroacetate Chemical compound FOC(=O)C(F)(F)F OXZOLXJZTSUDOM-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
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- 239000004593 Epoxy Substances 0.000 claims 1
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- 230000000052 comparative effect Effects 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 229920002799 BoPET Polymers 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
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- 238000010438 heat treatment Methods 0.000 description 8
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- 239000011248 coating agent Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
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- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
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- 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 description 3
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- 239000003822 epoxy resin Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical class CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
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- 229910052744 lithium 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a composite current collector with an automatic fire extinguishing function and a preparation method thereof, wherein the composite current collector comprises a polymer film substrate and metal layers plated on the upper surface and the lower surface of the polymer film substrate; wherein the polymer film substrate comprises a polymer and a fire extinguishing agent, and the mass of the fire extinguishing agent is 0.3-20% of the mass of the polymer film substrate. According to the composite current collector provided by the invention, the fire extinguishing agent with a lower melting point is doped in the polymer film matrix, so that the composite current collector can be released in time at the initial stage of thermal runaway of a battery, and the release can be realized without the need of waiting for the polymer matrix to be destroyed, thereby having better active fire extinguishing effect and remarkably improving the safety protection capability of the current collector in a battery core.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a composite current collector with an automatic fire extinguishing function and a preparation method thereof.
Background
With the rapid popularization of electric automobiles and the rapid development of new energy in recent years, the installed capacity of lithium ion batteries is in an explosive growth state. 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, however, the improvement of the energy density inevitably increases the potential safety hazard of the lithium ion battery. When the lithium ion battery is damaged by mechanical stress, thermal stress and the like, internal short circuit can occur, so that the battery is in thermal runaway; or when the inconsistency of the batteries is amplified, the battery is easy to fire or even explode when a certain single battery is abused. Improving the safety of lithium ion batteries is therefore a hotspot of current research.
The lithium ion battery cell is generally composed of positive and negative electrode materials, a diaphragm, a current collector, electrolyte and the like. At present, a great deal of research focuses on adding a flame retardant into electrolyte to achieve the aim of timely inhibiting ignition and explosion of a battery, but the electrolyte directly participates in electrochemical reaction in the battery, the flame retardant is often organic molecules, oxidation-reduction side reaction is easy to occur under the potential of an electrode, normal operation of the battery is influenced, and a current collector is used as an auxiliary material which does not directly participate in the electrochemical reaction, so that the flame retardant is a good fire extinguishing carrier. Current collectors do not directly provide capacity and therefore it is desirable to reduce their weight as much as possible to increase the energy density of the cell as a whole. The traditional lithium ion battery current collector is a metal current collector, namely an aluminum foil for a positive electrode and a copper foil for a negative electrode. The pure metal current collector has large mass, the rigid current collector is easy to break, and burrs are easy to generate to pierce the diaphragm so as to generate short circuit.
The safety of the lithium ion battery is improved by adopting the composite current collector, the high polymer material is used as a substrate, the metal coating layer is plated on the surface to realize the conductive function, and the high polymer has light weight and can improve the energy density of the battery. However, in terms of safety, the polymer substance is often inflammable and serious in smoke generation, the problem is generally solved by adding some flame retardants into the polymer substrate in the prior art, but the method focuses on the flame retardance of the current collector, and does not have an active fire extinguishing function, in addition, the polymer substrate is usually higher in melting point, and the flame retardants can be released only after the polymer substrate is melted, so that the flame retardance effect is achieved in the prior art.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a composite current collector with an automatic fire extinguishing function and a preparation method thereof.
In one aspect, an embodiment of the present invention provides a composite current collector, including a polymer film substrate and metal layers plated on upper and lower surfaces of the polymer film substrate;
wherein the polymeric film substrate comprises a polymer and a fire extinguishing agent; and the mass of the fire extinguishing agent is 0.3-20% of the mass of the polymer film substrate.
According to the composite current collector disclosed by the embodiment of the invention, the fire extinguishing agent is directly doped in the gaps of the polymer molecular structure by doping and modifying the current collector, so that the fire extinguishing agent can spontaneously gasify and rush out of the current collector in the thermal runaway process, and the active fire extinguishing effect is achieved.
In some embodiments of the invention, the mass of the fire extinguishing agent is preferably 10% to 15% of the mass of the polymer film substrate.
In some embodiments of the invention, the fire extinguishing agent is selected from at least one of perfluorohexanone, heptafluoropropane, haloalkanes, preferably perfluorohexanone.
In some embodiments of the invention, the polymeric film substrate has a thickness of 4 to 20 μm; the thickness of the metal layer is 1-3 mu m.
In some embodiments of the invention, the polymer is selected from at least one of polyethylene terephthalate, polyurethane, polycarbonate, polyamide, polyimide, polyvinylidene fluoride, polypropylene, polymethyl methacrylate, epoxy resin, carboxymethyl cellulose, preferably polyethylene terephthalate or polyimide.
In some embodiments of the present invention, the metal layer is made of any one of copper, aluminum, silver or gold.
In some embodiments of the invention, the polymeric film substrate is prepared by steps comprising one of the following steps (1), (2), (3):
(1) Cleaning and vacuum drying the polymer, uniformly mixing the polymer with a fire extinguishing agent, and smelting the mixture at 245-275 ℃ for 30-60 min to obtain composite slurry; and extruding, stretching and cooling the composite slurry to obtain the polymer film substrate.
(2) Cleaning and vacuum drying the polymer, dissolving the polymer in a solvent, and adding a fire extinguishing agent to uniformly mix to obtain composite slurry; then adopting a casting molding process to prepare the polymer film substrate; wherein the solvent is any one of hexafluoroisopropanol, hexafluoroacetic acid, tetrafluoroacetic acid, trifluoroacetic acid or a mixed solution of phenol and tetrachloroethane.
(3) Mixing corresponding monomer molecules of the polymer in proportion, and carrying out polymerization reaction to obtain the polymer; then adding fire extinguishing agent, mixing uniformly to obtain composite slurry, and preparing the polymer film substrate by using a coating process.
On the other hand, the embodiment of the invention also provides a preparation method of the composite current collector, which comprises the following steps:
s1, preparing a polymer film substrate;
s2, respectively carrying out plasma treatment on the upper surface and the lower surface of the polymer film substrate at the temperature of 25-35 ℃;
and S3, plating metal layers on the upper surface and the lower surface of the treated polymer film substrate by magnetron sputtering, and increasing the thickness of the metal layer by vacuum evaporation to enable the thickness of the metal layer to reach 1-3 mu m to prepare the composite current collector.
In some embodiments of the invention, in step S2, the plasma treatment time is 5 to 20 minutes.
The features and advantages described above for the composite current collector are equally applicable to the method for preparing the composite current collector, and are not described here again.
In another aspect, the embodiment of the invention further provides an electrode, which comprises the composite current collector, and the electrode is an anode or a cathode.
The embodiment of the invention also provides a lithium ion battery, which comprises the composite current collector.
The invention has the advantages and beneficial effects that: according to the composite current collector, the fire extinguishing agent is directly doped in the gaps of the polymer molecular structure, so that no extra coating material exists, and the composite current collector has the characteristics of low release threshold and high speed; the selected fire extinguishing agent has a low melting point, can be released in time at the initial stage of thermal runaway of the battery, can be released without the need of waiting for the polymer film substrate to be destroyed, has a better active fire extinguishing effect, and remarkably improves the safety protection capability of the current collector in the battery core.
Drawings
Fig. 1 is a schematic diagram of a process of releasing a fire extinguishing agent by using a composite current collector according to an embodiment of the invention.
Reference numerals:
1-a polymer film matrix; 2-a metal layer; 3-a fire extinguishing agent; 3' -fire extinguishing agent after being heated and gasified.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without creative efforts, based on the described embodiments of the present invention belong to the protection scope of the present invention.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
In one aspect, the embodiment of the invention provides a composite current collector, which comprises a polymer film substrate and metal layers plated on the upper surface and the lower surface of the polymer film substrate;
wherein the polymer film substrate comprises a polymer and a fire extinguishing agent; and the mass of the fire extinguishing agent is 0.3-20% of the mass of the polymer film substrate.
According to the composite current collector disclosed by the embodiment of the invention, the fire extinguishing agent is directly doped in the gaps of the polymer molecular structure by doping and modifying the current collector, so that the fire extinguishing agent can spontaneously gasify and rush out of the current collector in the thermal runaway process, and the active fire extinguishing effect is achieved.
Fig. 1 is a schematic diagram of a process of releasing fire extinguishing agent by using a composite current collector according to an embodiment of the invention. As can be seen from fig. 1, under normal conditions, the fire extinguishing agent is sealed in the polymer film matrix, but when the temperature of the battery is raised in thermal runaway, molecules of the fire extinguishing agent begin to gasify and the pressure is increased, when the temperature is further raised due to continuous thermal runaway, the gasification condition of the fire extinguishing agent is increased, the internal pressure is further increased, and thus the polymer film matrix and the metal layer are broken through to be released, so that active fire extinguishing is realized.
In some embodiments of the present invention, the mass of the fire extinguishing agent is preferably 10% to 15% of the mass of the polymer film substrate, such as, by way of non-limiting example: 10%, 12%, 15%, etc.
In some embodiments of the present invention, the fire extinguishing agent is selected from at least one of perfluorohexanone, heptafluoropropane, haloalkanes, preferably perfluorohexanone; the selected fire extinguishing agent has a low melting point, can be released in time at the initial stage of thermal runaway of the battery, can be released without the need of waiting for the polymer film substrate to be destroyed, and has better active fire extinguishing effect.
Further, the haloalkane is C 1 -C 3 An organic compound formed by replacing one or more hydrogen atoms in an alkane molecule (methane, ethane or propane) with halogen atoms; wherein halogen is fluorine, chlorine, bromine or iodine.
In some embodiments of the invention, the polymeric film substrate has a thickness of 4 to 20 μm, such as, by way of non-limiting example: 4 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 20 μm, etc.
In some embodiments of the invention, the metal layer has a thickness of 1 to 3 μm, such as, by way of non-limiting example: 1 μm, 1.5 μm, 2 μm, 3 μm, etc.; if the metal layer is too thick, the time of the preparation process is prolonged, the cost is increased, and in addition, the stability of the metal layer is reduced, so that the cycle durability of the composite current collector is affected; if the metal layer is too thin, insufficient conductivity and strength of the metal layer may be caused, thereby affecting the electron conductivity and strength of the composite current collector.
In some embodiments of the invention, the polymer is selected from at least one of polyethylene terephthalate (PET), polyurethane (PU), polycarbonate (PC), polyamide (PA), polyimide (PI), polyvinylidene fluoride (PVDF), polypropylene (PP), polymethyl methacrylate (PMMA), epoxy resin (EP), carboxymethyl cellulose (CMC), preferably polyethylene terephthalate (PET) or Polyimide (PI).
In some embodiments of the present invention, the metal layer is made of any one of copper, aluminum, silver or gold;
further, the composition and thickness of the metal layers on the upper and lower surfaces of the polymer film substrate are the same.
In some embodiments of the invention, the polymeric film substrate is prepared by steps comprising one of the following steps (1), (2), (3):
(1) Cleaning and vacuum drying the polymer, uniformly mixing the polymer with a fire extinguishing agent, and smelting the mixture at 245-275 ℃ for 30-60 min to obtain composite slurry; and extruding, stretching and cooling the composite slurry to obtain the polymer film substrate.
(2) Cleaning and vacuum drying the polymer, dissolving the polymer in a solvent, and adding a fire extinguishing agent to uniformly mix to obtain composite slurry; then preparing a polymer film substrate by adopting a casting molding process; wherein the solvent is any one of hexafluoroisopropanol, hexafluoroacetic acid, tetrafluoroacetic acid, trifluoroacetic acid or a mixed solution of phenol and tetrachloroethane.
(3) Mixing corresponding monomer molecules of the polymer in proportion, and carrying out polymerization reaction to obtain the polymer; then adding fire extinguishing agent, mixing uniformly to obtain composite slurry, and preparing the polymer film substrate by using a coating process.
On the other hand, the embodiment of the invention also provides a preparation method of the composite current collector, which comprises the following steps:
s1, preparing a polymer film substrate;
s2, respectively carrying out plasma treatment on the upper surface and the lower surface of the polymer film substrate at the temperature of 25-35 ℃;
and S3, plating metal layers on the upper surface and the lower surface of the treated polymer film substrate by magnetron sputtering, and increasing the thickness of the metal layer by vacuum evaporation to enable the thickness of the metal layer to reach 1-3 mu m to prepare the composite current collector.
The features and advantages described above for the composite current collector are equally applicable to the method for preparing the composite current collector, and are not described here again.
In some embodiments of the present invention, in step S2, the plasma treatment time is 5 to 20 minutes;
further, the plasma is O 2 、H 2 、N 2 、NH 3 At least one of non-polymerizable gases such as Ar; the polymer film substrate is firstly treated by plasma before being plated with a metal layer, so that the surface of the polymer film substrate can be grafted with-OH, -NH 3 And hydrophilic functional groups, so that the problem of low adhesion between the metal layer and the polymer film substrate is solved, and the stability and the electronic conductivity of the metal layer are improved.
In another aspect, the embodiment of the invention further provides an electrode, which comprises the composite current collector, and the electrode is an anode or a cathode.
The embodiment of the invention also provides a lithium ion battery, which comprises the composite current collector.
The following non-limiting examples and comparative examples of the present invention are described: the solution of the comparative example is not prior art, but is provided for comparison with the solution of the examples only, and is not intended as a limitation of the invention; experimental methods for which specific conditions are not noted in examples and comparative examples are conventional methods and conventional conditions well known in the art.
Example 1
The preparation method of the composite current collector comprises the following steps:
(1) Washing 85 parts of polyethylene terephthalate (PET), drying in vacuum, shearing into fine fragments, uniformly mixing with 15 parts of perfluorinated hexanone, and smelting for 30min at 245 ℃ to obtain composite slurry; extruding and stretching the composite slurry, and cooling to obtain a PET film substrate with the thickness of 20 mu m;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PET film substrate for 10min at 25 ℃;
(3) Firstly, plating copper metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PET film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the copper metal layers by utilizing vacuum evaporation so that the thickness of the copper metal layers reaches 2 mu m, thus obtaining the composite current collector.
According to the conventional preparation process of the lithium ion battery cathode, 97 parts of graphite cathode material, 1 part of acetylene black conductive agent, 1 part of sodium carboxymethylcellulose (CMC) and 1 part of Styrene Butadiene Rubber (SBR) binder are uniformly mixed to prepare slurry, and then the slurry is coated on the composite current collector, dried and cut into a cathode pole piece A.
Example 2
The preparation method of the composite current collector comprises the following steps:
(1) Washing 85 parts of polyethylene terephthalate (PET), drying in vacuum, shearing into fine fragments, uniformly mixing with 15 parts of perfluorinated hexanone, and smelting for 30min at 245 ℃ to obtain composite slurry; extruding and stretching the composite slurry, and cooling to obtain a PET film substrate with the thickness of 20 mu m;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PET film substrate for 10min at 25 ℃;
(3) Firstly, plating aluminum metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PET film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the aluminum metal layers by utilizing vacuum evaporation so that the thickness of the aluminum metal layers reaches 2 mu m, thus obtaining the composite current collector.
According to the conventional preparation process of the positive electrode of the lithium ion battery, 97 parts of lithium iron phosphate positive electrode material, 1.5 parts of acetylene black conductive agent and 1.5 parts of PVDF binder are uniformly mixed to prepare slurry, and then the slurry is coated on the composite current collector, dried and cut into positive electrode sheet B.
Example 3
The preparation method of the composite current collector comprises the following steps:
(1) Adding 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene (6 FAPB) and 4,4' -diaminodiphenyl ether (ODA) into a solvent according to a molar ratio of 1:1, stirring and mixing uniformly, adding pyromellitic dianhydride, heating to 180 ℃, and heating for 2 hours to obtain polyamide acid; then adding acetic anhydride dehydrating agent and ethylenediamine catalyst, adding 15wt% of perfluoro-hexanone, stirring uniformly, and performing chemical dehydration cyclization at 35 ℃ to obtain composite slurry of Polyimide (PI) and perfluoro-hexanone fire extinguishing agent; coating the composite slurry on a glass plate, scraping the composite slurry to be 20 mu m thick by a scraper, and naturally air-drying to obtain a PI film substrate;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PI film substrate for 10min at 25 ℃;
(3) Firstly, plating copper metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PI film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the copper metal layers by utilizing vacuum evaporation so that the thickness of the copper metal layers reaches 2 mu m, thus obtaining the composite current collector.
According to the conventional preparation process of the lithium ion battery cathode, 97 parts of graphite cathode material, 1 part of acetylene black conductive agent, 1 part of sodium carboxymethylcellulose (CMC) and 1 part of Styrene Butadiene Rubber (SBR) binder are uniformly mixed to prepare slurry, and then the slurry is coated on the composite current collector, dried and cut into cathode pole pieces C.
Example 4
The preparation method of the composite current collector comprises the following steps:
(1) Adding 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene (6 FAPB) and 4,4' -diaminodiphenyl ether (ODA) into a solvent according to a molar ratio of 1:1, stirring and mixing uniformly, adding pyromellitic dianhydride, heating to 180 ℃, and heating for 2 hours to obtain polyamide acid; then adding acetic anhydride dehydrating agent and ethylenediamine catalyst, adding 15wt% of perfluoro-hexanone, stirring uniformly, and performing chemical dehydration cyclization at 35 ℃ to obtain composite slurry of Polyimide (PI) and perfluoro-hexanone fire extinguishing agent; coating the composite slurry on a glass plate, scraping the composite slurry to be 20 mu m thick by a scraper, and naturally air-drying to obtain a PI film substrate;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PI film substrate for 10min at 25 ℃;
(3) Firstly, plating aluminum metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PI film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the aluminum metal layers by utilizing vacuum evaporation so that the thickness of the aluminum metal layers reaches 2 mu m, thus obtaining the composite current collector.
According to the conventional preparation process of the positive electrode of the lithium ion battery, 97 parts of lithium iron phosphate positive electrode material, 1.5 parts of acetylene black conductive agent and 1.5 parts of PVDF binder are uniformly mixed to prepare slurry, and then the slurry is coated on the composite current collector, dried and cut into positive electrode sheet D.
Comparative example 1
A method for preparing a current collector, comprising the steps of:
(1) Washing polyethylene terephthalate (PET), vacuum drying, shearing into fine fragments, and smelting at 245 ℃ for 30min to obtain slurry; extruding and stretching the slurry, and cooling to obtain a PET film substrate with the thickness of 20 mu m;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PET film substrate for 10min at 25 ℃;
(3) Firstly, plating copper metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PET film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the copper metal layers by utilizing vacuum evaporation so that the thickness of the copper metal layers reaches 2 mu m, thus obtaining the current collector.
According to the conventional preparation process of the lithium ion battery cathode, 97 parts of graphite cathode material, 1 part of acetylene black conductive agent, 1 part of sodium carboxymethylcellulose (CMC) and 1 part of Styrene Butadiene Rubber (SBR) binder are uniformly mixed to prepare slurry, and then the slurry is coated on the current collector, dried and cut into cathode pole pieces A'.
Comparative example 2
A method for preparing a current collector, comprising the steps of:
(1) Washing polyethylene terephthalate (PET), vacuum drying, shearing into fine fragments, and smelting at 245 ℃ for 30min to obtain slurry; extruding and stretching the slurry, and cooling to obtain a PET film substrate with the thickness of 20 mu m;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PET film substrate for 10min at 25 ℃;
(3) Firstly, plating aluminum metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PET film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the aluminum metal layers by utilizing vacuum evaporation so that the thickness of the aluminum metal layers reaches 2 mu m, thus obtaining the current collector.
According to the conventional preparation process of the positive electrode of the lithium ion battery, 97 parts of lithium iron phosphate positive electrode material, 1.5 parts of acetylene black conductive agent and 1.5 parts of PVDF binder are uniformly mixed to prepare slurry, and then the slurry is coated on the current collector, dried and cut into positive electrode sheet B'.
Comparative example 3
A method for preparing a current collector, comprising the steps of:
(1) Adding 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene (6 FAPB) and 4,4' -diaminodiphenyl ether (ODA) into a solvent according to a molar ratio of 1:1, stirring and mixing uniformly, adding pyromellitic dianhydride, heating to 180 ℃, and heating for 2 hours to obtain polyamide acid; then adding an acetic anhydride dehydrating agent and an ethylenediamine catalyst, uniformly stirring, and performing chemical dehydration cyclization at 35 ℃ to obtain Polyimide (PI) slurry; coating the slurry on a glass plate, scraping the slurry to be 20 mu m thick by a scraper, and naturally air-drying to obtain a PI film substrate;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PI film substrate for 10min at 25 ℃;
(3) Firstly, plating copper metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PI film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the copper metal layers by utilizing vacuum evaporation so that the thickness of the copper metal layers reaches 2 mu m, thus obtaining the current collector.
According to the conventional preparation process of the lithium ion battery cathode, 97 parts of graphite cathode material, 1 part of acetylene black conductive agent, 1 part of sodium carboxymethylcellulose (CMC) and 1 part of Styrene Butadiene Rubber (SBR) binder are uniformly mixed to prepare slurry, and then the slurry is coated on the current collector, dried and cut into cathode pole pieces C'.
Comparative example 4
A method for preparing a current collector, comprising the steps of:
(1) Adding 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene (6 FAPB) and 4,4' -diaminodiphenyl ether (ODA) into a solvent according to a molar ratio of 1:1, stirring and mixing uniformly, adding pyromellitic dianhydride, heating to 180 ℃, and heating for 2 hours to obtain polyamide acid; then adding an acetic anhydride dehydrating agent and an ethylenediamine catalyst, uniformly stirring, and performing chemical dehydration cyclization at 35 ℃ to obtain Polyimide (PI) slurry; coating the slurry on a glass plate, scraping the slurry to be 20 mu m thick by a scraper, and naturally air-drying to obtain a PI film substrate;
(2) Respectively carrying out plasma treatment on the upper surface and the lower surface of the PI film substrate for 10min at 25 ℃;
(3) Firstly, plating aluminum metal layers with the thickness of 500nm on the upper surface and the lower surface of the treated PI film substrate respectively by adopting magnetron sputtering, and then increasing the thickness of the aluminum metal layers by utilizing vacuum evaporation so that the thickness of the aluminum metal layers reaches 2 mu m, thus obtaining the current collector.
According to the conventional preparation process of the positive electrode of the lithium ion battery, 97 parts of lithium iron phosphate positive electrode material, 1.5 parts of acetylene black conductive agent and 1.5 parts of PVDF binder are uniformly mixed to prepare slurry, and then the slurry is coated on the current collector, dried and cut into positive electrode pieces D'.
The pole pieces obtained in examples 1 to 4 and comparative examples 1 to 4 were subjected to an ignition test and a fire extinguishing test, and the test results are shown in Table 1.
Table 1 results of performance testing of the pole pieces of examples 1-4 and comparative examples 1-4
| Ignition experiment | Fire extinguishing experiment | Temperature range of releasable fire extinguishing agent | ||
| Example 1 | Negative pole piece A | Smoking and no fire | Successful fire extinguishment | 77～98℃ |
| Example 2 | Positive electrode sheet B | Smoking and no fire | Successful fire extinguishment | 74～84℃ |
| Example 3 | Negative pole piece C | No smoke and fire | Successful fire extinguishment | 93～108℃ |
| Example 4 | Positive pole piece D | No smoke and fire | Successful fire extinguishment | 89～103℃ |
| Comparative example 1 | Negative electrode sheet A' | Firing on fire | Failure to extinguish fire | / |
| Comparative example 2 | Positive electrode sheet B' | Firing on fire | Failure to extinguish fire | / |
| Comparative example 3 | Negative electrode sheet C' | Firing on fire | Failure to extinguish fire | / |
| Comparative example 4 | Positive electrode sheet D' | Firing on fire | Failure to extinguish fire | / |
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. The composite current collector is characterized by comprising a polymer film substrate and metal layers plated on the upper surface and the lower surface of the polymer film substrate;
wherein the polymeric film substrate comprises a polymer and a fire extinguishing agent; and the mass of the fire extinguishing agent is 0.3-20% of the mass of the polymer film substrate.
2. The composite current collector of claim 1 wherein the mass of said fire extinguishing agent is 10% to 15% of the mass of said polymer film substrate.
3. The composite current collector of claim 1 wherein said fire extinguishing agent is selected from at least one of perfluorohexanone, heptafluoropropane, haloalkanes.
4. The composite current collector of claim 1, wherein the polymer film substrate has a thickness of 4 to 20 μm; the thickness of the metal layer is 1-3 mu m.
5. The composite current collector of claim 1 wherein said polymer is selected from at least one of polyethylene terephthalate, polyurethane, polycarbonate, polyamide, polyimide, polyvinylidene fluoride, polypropylene, polymethyl methacrylate, epoxy, carboxymethyl cellulose.
6. The composite current collector of claim 1 wherein said metal layer is any one of copper, aluminum, silver or gold.
7. The composite current collector of claim 1, wherein said polymer film substrate is prepared by steps comprising one of the following (1), (2), (3):
(1) Cleaning and vacuum drying the polymer, uniformly mixing the polymer with a fire extinguishing agent, and smelting the mixture at 245-275 ℃ for 30-60 min to obtain composite slurry; extruding, stretching and cooling the composite slurry to obtain the polymer film substrate;
(2) Cleaning and vacuum drying the polymer, dissolving the polymer in a solvent, and adding a fire extinguishing agent to uniformly mix to obtain composite slurry; then adopting a casting molding process to prepare the polymer film substrate; wherein the solvent is any one of hexafluoroisopropanol, hexafluoroacetic acid, tetrafluoroacetic acid, trifluoroacetic acid or a mixed solution composed of phenol and tetrachloroethane;
(3) Mixing corresponding monomer molecules of the polymer in proportion, and carrying out polymerization reaction to obtain the polymer; then adding fire extinguishing agent, mixing uniformly to obtain composite slurry, and preparing the polymer film substrate by using a coating process.
8. A method of preparing a composite current collector according to any one of claims 1 to 7, comprising the steps of:
s1, preparing a polymer film substrate;
s2, respectively carrying out plasma treatment on the upper surface and the lower surface of the polymer film substrate at the temperature of 25-35 ℃;
and S3, plating metal layers on the upper surface and the lower surface of the treated polymer film substrate by magnetron sputtering, and increasing the thickness of the metal layer by vacuum evaporation to enable the thickness of the metal layer to reach 1-3 mu m to prepare the composite current collector.
9. The method for preparing a composite current collector according to claim 8, wherein in the step S2, the plasma treatment time is 5 to 20 minutes.
10. An electrode, lithium ion battery comprising the composite current collector of any one of claims 1-7.
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