CN114497569A - Polymer current collector for lithium ion battery and preparation method thereof - Google Patents
Polymer current collector for lithium ion battery and preparation method thereof Download PDFInfo
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- CN114497569A CN114497569A CN202210019535.8A CN202210019535A CN114497569A CN 114497569 A CN114497569 A CN 114497569A CN 202210019535 A CN202210019535 A CN 202210019535A CN 114497569 A CN114497569 A CN 114497569A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 title claims description 17
- 239000000835 fiber Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 56
- 239000006185 dispersion Substances 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 39
- 239000004952 Polyamide Substances 0.000 claims description 27
- 229920002647 polyamide Polymers 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 15
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 4
- -1 polyethylene terephthalate Polymers 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 239000011149 active material Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 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 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- H01M4/663—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a high-molecular current collector for a lithium ion battery and a preparation method thereof, wherein the high-molecular current collector comprises thermoplastic resin fibers and a conductive agent; the conductive agent is carbon nanotube loaded nano copper, the weight of the high-molecular current collector is reduced by more than 50% compared with that of a copper foil current collector, the internal resistance is greatly reduced, and metal burrs are not generated in the manufacturing process of the battery pole piece due to the high-molecular material, so that the safety of the lithium ion battery is greatly improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-molecular current collector for a lithium ion battery and a preparation method thereof.
Background
In recent years, lithium ion batteries gradually become the main power source of new energy automobiles, the specific energy of the lithium ion batteries determines the endurance mileage of electric automobiles, and at the present stage, methods for improving the specific energy of the batteries include: the positive and negative electrode main materials have high specific energy; the battery is large, and the proportion of auxiliary materials such as a shell is reduced; lightweight housings such as aluminum plastic film packaged batteries; the thickness of the current collector and the diaphragm is reduced.
The positive current collector in the lithium ion battery is an aluminum foil, and the negative current collector is a copper foil. The density of copper is 8.9g/cm3. In recent years, the thickness of copper foil of lithium ion batteries is gradually reduced from 12 μm to 6 μm. However, in the battery, the copper foil ratio is still as high as 10%, the use amount of the copper foil can be reduced by reducing the thickness of the copper foil, and the specific energy of the battery is improved. However, the ultra-thin copper foil causes new troubles in the process such as breakage and curling in the lithium electrodeposition process, so that the thickness of the copper foil cannot be reduced all the time, and there is a limit. Thus, it is difficult to improve the specific energy of the battery by reducing the weight of the current collector.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention provides a high-molecular current collector for a lithium ion battery and a preparation method thereof, and the density of the high-molecular current collector is far lower than that of a copper foil, so that the weight of the lithium ion battery can be reduced, and the specific energy of the battery can be improved.
The adopted technical scheme is as follows:
a high molecular current collector for a lithium ion battery comprises thermoplastic resin fibers and a conductive agent;
the conductive agent is carbon nanotube loaded nano copper.
Further, the mass ratio of the thermoplastic resin fibers to the conductive agent is 95-100: 1-5.
Furthermore, the mass ratio of the thermoplastic resin fibers to the conductive agent is 96: 4.
further, the thermoplastic resin fiber is one or more of polyethylene terephthalate fiber, polybutylene terephthalate fiber, polycarbonate fiber, and polyamide fiber, preferably polyamide fiber.
Further, the preparation method of the polyamide fiber comprises the following steps:
s1: soaking polyamide fiber in 80-85 deg.C NaOH solution, holding for 20-40min, filtering, washing with water, oven drying, soaking in formic acid solution for 1-3 hr, filtering, washing with water, and oven drying;
s2: and adding water, adding a mixed solution consisting of hydrochloric acid and an aniline monomer, stirring for 5-10min, adding an ammonium persulfate solution to polymerize the aniline monomer in situ on the surface of the polyamide for 4-6h, filtering, washing with water, and drying.
Further, the preparation method of the carbon nanotube loaded nano-copper comprises the following steps:
dripping a copper nitrate solution into a sodium borohydride solution, adding a carbon nano tube, adjusting the pH value of the solution to 12, heating to 90-95 ℃, stirring for reaction for 1-2h, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 120-130 ℃ for 20-25h, then immersing into an ethanol solution of oleic acid, filtering after 5-10h, and drying.
Further, the concentration of the copper nitrate solution is 0.01-0.02mol/L, and the concentration of the sodium borohydride solution is 0.02-0.04 mol/L.
Further, the ratio of n (cu) in the copper nitrate solution and the sodium borohydride solution: n (b) ═ 2, n (cu): n (B) is the molar ratio of the copper element to the boron element in the copper nitrate solution and the sodium borohydride solution.
The invention also provides a preparation method of the polymer current collector for the lithium ion battery, which comprises the following steps:
dispersing a conductive agent in water to prepare a dispersion liquid A, adding thermoplastic resin fibers into the dispersion liquid A to prepare a dispersion liquid B, mixing and shearing the dispersion liquid A and the dispersion liquid B for 1-3h, then performing suction filtration, and drying the obtained flaky high-molecular current collector at 60-80 ℃.
Further, the thickness of the flaky polymer current collector is 2-6 μm.
The invention has the beneficial effects that:
the invention provides a high molecular current collector, thermoplastic resin fiber is used as a carrier of a Carbon Nano Tube (CNTs) conductive network on one hand, and polyaniline is doped on the other hand, so that a polyaniline layer on the surface of the thermoplastic resin fiber generates conductive performance and can be used as a channel for outputting and inputting current, the utilization rate of active substances is improved, the Carbon Nano Tube (CNTs) has high conductivity and large length-diameter ratio and is easy to form the conductive network, so the carbon nano tube is one of lithium ion battery conductive agents with better effect at present, the conductive capability is improved after the nano copper is loaded, the cohesiveness among active materials and between the active materials and the current collector can be improved, the specific surface area is larger, the adsorption capability to electrolyte is strong, and the capacity of the active materials is better exerted, compared with a copper foil current collector, the weight of the high molecular current collector is reduced by more than 50 percent, and the internal resistance is greatly reduced, and metal burrs are not generated in the manufacturing process of the battery pole piece due to the high polymer material, so that the safety of the lithium ion battery is greatly improved.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a polymer current collector for a lithium ion battery comprises a polymer material and a polymer material, wherein the polymer material comprises the following components in a mass ratio of 96: 4, the polyamide fiber and the carbon nano tube load a nano copper conductive agent;
the preparation method of the polyamide fiber comprises the following steps:
soaking polyamide fiber in NaOH solution at 85 ℃ for heat preservation treatment for 30min, filtering, washing, drying, then soaking in formic acid solution with volume concentration of 50% for treatment for 2h, filtering, washing, drying, then adding water, adding mixed solution consisting of hydrochloric acid and aniline monomer, stirring for 10min, adding 1M ammonium persulfate solution for initiating reaction, polymerizing aniline monomer on the surface of polyamide in situ for 5h, filtering, washing, and drying.
The preparation method of the carbon nano tube loaded nano copper comprises the following steps:
dripping 0.01mol/L copper nitrate solution with the volume ratio of 1:1 into 0.02mol/L sodium borohydride solution, adding a carbon nano tube, adjusting the pH value of the solution to 12, heating to 90 ℃, stirring and reacting for 2 hours, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 130 ℃ for 25 hours, immersing into 10 wt% ethanol solution of oleic acid, filtering after 10 hours, and drying.
A preparation method of a high-molecular current collector for a lithium ion battery comprises the following steps:
dispersing a conductive agent in water to prepare a dispersion liquid A, adding polyamide fibers into the dispersion liquid A to prepare a dispersion liquid B, mixing and shearing the dispersion liquid A and the dispersion liquid B for 3 hours, then carrying out suction filtration, and drying the obtained flaky high-molecular current collector at 80 ℃ to obtain the high-molecular current collector with the thickness of 2-6 microns.
Example 2:
a polymer current collector for a lithium ion battery comprises a polymer material and a polymer material, wherein the polymer material comprises the following components in a mass ratio of 96: 4, the polyamide fiber and the carbon nano tube load a nano copper conductive agent;
the preparation method of the carbon nano tube loaded nano copper comprises the following steps:
dripping 0.01mol/L copper nitrate solution with the volume ratio of 1:1 into 0.02mol/L sodium borohydride solution, adding a carbon nano tube, adjusting the pH value of the solution to 12, heating to 90 ℃, stirring and reacting for 2 hours, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 130 ℃ for 25 hours, immersing into 10 wt% ethanol solution of oleic acid, filtering after 10 hours, and drying.
A preparation method of a high-molecular current collector for a lithium ion battery comprises the following steps:
dispersing a conductive agent in water to prepare a dispersion liquid A, adding polyamide fibers into the dispersion liquid A to prepare a dispersion liquid B, mixing and shearing the dispersion liquid A and the dispersion liquid B for 3 hours, then carrying out suction filtration, and drying the obtained flaky high-molecular current collector at 80 ℃ to obtain the high-molecular current collector with the thickness of 2-6 microns.
Example 2 is substantially the same as example 1 except that the polyamide fiber is used as it is.
Example 3:
a polymer current collector for a lithium ion battery comprises a polymer material and a polymer material, wherein the polymer material comprises the following components in a mass ratio of 96: 4, the polycarbonate fiber and the carbon nano tube load a nano copper conductive agent;
the preparation method of the carbon nano tube loaded nano copper comprises the following steps:
dripping 0.01mol/L copper nitrate solution with the volume ratio of 1:1 into 0.02mol/L sodium borohydride solution, adding a carbon nano tube, adjusting the pH value of the solution to 12, heating to 90 ℃, stirring and reacting for 2 hours, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 130 ℃ for 25 hours, immersing into 10 wt% ethanol solution of oleic acid, filtering after 10 hours, and drying.
A preparation method of a high-molecular current collector for a lithium ion battery comprises the following steps:
dispersing a conductive agent in water to prepare a dispersion liquid A, adding polycarbonate fibers into the dispersion liquid A to prepare a dispersion liquid B, mixing and shearing the dispersion liquid A and the dispersion liquid B for 3 hours, then carrying out suction filtration, and drying the obtained sheet-shaped high-molecular current collector at 80 ℃ to obtain the high-molecular current collector with the thickness of 2-6 microns.
Example 3 is essentially the same as example 2, except that polycarbonate fibers are used instead of polyamide fibers.
Example 4:
a polymer current collector for a lithium ion battery comprises a polymer material and a polymer material, wherein the polymer material comprises the following components in a mass ratio of 96: 4, the PET fiber and the carbon nano tube load a nano copper conductive agent;
the preparation method of the carbon nano tube loaded nano copper comprises the following steps:
dripping 0.01mol/L copper nitrate solution with the volume ratio of 1:1 into 0.02mol/L sodium borohydride solution, adding a carbon nano tube, adjusting the pH value of the solution to 12, heating to 90 ℃, stirring and reacting for 2 hours, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 130 ℃ for 25 hours, immersing into 10 wt% ethanol solution of oleic acid, filtering after 10 hours, and drying.
A preparation method of a high-molecular current collector for a lithium ion battery comprises the following steps:
dispersing a conductive agent in water to prepare a dispersion liquid A, adding PET fibers into the dispersion liquid A to prepare a dispersion liquid B, mixing and shearing the dispersion liquid A and the dispersion liquid B for 3 hours, then carrying out suction filtration, and drying the obtained flaky high-molecular current collector at 80 ℃ to obtain the high-molecular current collector with the thickness of 2-6 microns.
Example 4 is essentially the same as example 2, except that PET fibers are used instead of polyamide fibers.
Example 5:
a polymer current collector for a lithium ion battery comprises a polymer current collector with a mass ratio of 95: 5, the polyamide fiber and the carbon nano tube load a nano copper conductive agent;
the preparation method of the polyamide fiber comprises the following steps:
soaking polyamide fiber in NaOH solution at 85 ℃ for heat preservation treatment for 30min, filtering, washing, drying, then soaking in formic acid solution with volume concentration of 50% for treatment for 2h, filtering, washing, drying, then adding water, adding mixed solution consisting of hydrochloric acid and aniline monomer, stirring for 10min, adding 1M ammonium persulfate solution for initiating reaction, polymerizing aniline monomer on the surface of polyamide in situ for 5h, filtering, washing, and drying.
The preparation method of the carbon nano tube loaded nano copper comprises the following steps:
dripping 0.01mol/L copper nitrate solution with the volume ratio of 1:1 into 0.02mol/L sodium borohydride solution, adding a carbon nano tube, adjusting the pH value of the solution to 12, heating to 90 ℃, stirring and reacting for 2 hours, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 130 ℃ for 25 hours, immersing into 10 wt% ethanol solution of oleic acid, filtering after 10 hours, and drying.
A preparation method of a high-molecular current collector for a lithium ion battery comprises the following steps:
dispersing a conductive agent in water to prepare a dispersion liquid A, adding polyamide fibers into the dispersion liquid A to prepare a dispersion liquid B, mixing and shearing the dispersion liquid A and the dispersion liquid B for 3 hours, then carrying out suction filtration, and drying the obtained flaky high-molecular current collector at 80 ℃ to obtain the high-molecular current collector with the thickness of 2-6 microns.
Example 5 is substantially the same as example 1 except that the mass ratio of the polyamide fiber to the carbon nanotube-supported nanocopper conductive agent was changed.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that carbon nanotubes and nano-copper are directly mixed as a conductive agent instead of loading nano-copper on the surface of the carbon nanotubes;
a preparation method of a high-molecular current collector for a lithium ion battery comprises the following steps:
dispersing carbon nanotubes and nano copper in water to prepare a dispersion liquid A, adding polyamide fibers into the dispersion liquid A to prepare a dispersion liquid B, mixing and shearing the dispersion liquid A and the dispersion liquid B for 3 hours, then carrying out suction filtration, and drying the obtained flaky high-molecular current collector at 80 ℃ to obtain the high-molecular current collector with the thickness of 2-6 microns.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that carbon nanotubes are directly used as a conductive agent.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that nano-copper is directly used as a conductive agent.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that the carbon nanotube-supported nanocopper was not subjected to the oil immersion treatment and was prepared as follows:
dripping 0.01mol/L copper nitrate solution with the volume ratio of 1:1 into 0.02mol/L sodium borohydride solution, adding carbon nano tubes, adjusting the pH value of the solution to 12, heating to 90 ℃, stirring for reaction for 2 hours, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 130 ℃ for 25 hours, then carrying out ethanol drying, filtering after 10 hours, and drying.
And (3) performance testing:
different polymer current collectors and copper foils prepared in examples 1-5 and comparative examples 1-4 are made into 18650 type lithium ion batteries and the performance of the lithium ion batteries is tested, and the manufacturing process is as follows:
(1) preparation of electrode plate
LiFePO of positive electrode4: binder PVDF: the mass ratio of the conductive agent carbon black (SP) is 92: 3.5: 4.5, the thickness of the coated electrode layer is (210 +/-10) mu m, the coated pole piece is compacted by a rolling mill, and the reduction rate is 28%;
graphite for negative electrode: sodium carboxymethylcellulose (CMC): binder Styrene Butadiene Rubber (SBR): the mass ratio of the conductive agent carbon black (SP) is 95.7: 1.3: 2: 1, the thickness of the coated negative electrode layer is (150 +/-5) mu m. And compacting the coated pole piece through a rolling mill.
(2) Battery assembly
The 18650 battery is manufactured by cutting positive and negative pole pieces, welding pole lugs, automatically winding core cladding, putting into a shell, welding a cover cap, degassing to remove trace moisture, injecting electrolyte into a glove box, sealing and the like.
The test results are shown in table 1 below:
table 1:
as can be seen from table 1 above, the weight of the polymer current collector is reduced by more than 50% compared with the copper foil current collector, and the internal resistance is greatly reduced, because the polymer current collector is made of a polymer material, no metal burr is generated during the manufacturing process of the battery pole piece, and the safety of the lithium ion battery is greatly improved.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A polymer current collector for a lithium ion battery is characterized by comprising thermoplastic resin fibers and a conductive agent;
the conductive agent is carbon nanotube loaded nano copper.
2. The polymeric current collector for lithium ion batteries according to claim 1, wherein the mass ratio of the thermoplastic resin fibers to the conductive agent is 95-100: 1-5.
3. The polymeric current collector for a lithium ion battery according to claim 2, wherein the mass ratio of the thermoplastic resin fibers to the conductive agent is 96: 4.
4. the polymer current collector for lithium ion batteries according to claim 1, wherein the thermoplastic resin fibers are one or more of polyethylene terephthalate fibers, polybutylene terephthalate fibers, polycarbonate fibers, and polyamide fibers, and preferably polyamide fibers.
5. The polymeric current collector for lithium ion batteries according to claim 4, wherein the polyamide fiber is prepared by the following method:
s1: soaking polyamide fiber in 80-85 deg.C NaOH solution, holding for 20-40min, filtering, washing with water, oven drying, soaking in formic acid solution for 1-3 hr, filtering, washing with water, and oven drying;
s2: and adding water, adding a mixed solution consisting of hydrochloric acid and an aniline monomer, stirring for 5-10min, adding an ammonium persulfate solution to polymerize the aniline monomer in situ on the surface of the polyamide for 4-6h, filtering, washing with water, and drying.
6. The polymeric current collector for lithium ion batteries according to claim 1, wherein the preparation method of the carbon nanotube-supported nanocopper comprises the following steps:
dripping a copper nitrate solution into a sodium borohydride solution, adding a carbon nano tube, adjusting the pH value of the solution to 12, heating to 90-95 ℃, stirring for reaction for 1-2h, carrying out suction filtration, washing the obtained solid with water, carrying out vacuum drying at 120-130 ℃ for 20-25h, then immersing into an ethanol solution of oleic acid, filtering after 5-10h, and drying.
7. The polymeric current collector for lithium ion batteries according to claim 6, wherein the concentration of the copper nitrate solution is 0.01 to 0.02mol/L and the concentration of the sodium borohydride solution is 0.02 to 0.04 mol/L.
8. The polymeric current collector for lithium ion batteries according to claim 6, wherein the ratio of n (Cu) in the copper nitrate solution and the sodium borohydride solution: n (b) ═ 2.
9. The preparation method of the polymer current collector for the lithium ion battery according to any one of claims 1 to 8, wherein a conductive agent is dispersed in water to prepare a dispersion liquid A, thermoplastic resin fibers are added and dispersed in water to prepare a dispersion liquid B, the dispersion liquid A and the dispersion liquid B are mixed, sheared for 1 to 3 hours and filtered, and the obtained flaky polymer current collector is dried at 60 to 80 ℃.
10. The method for preparing a polymeric current collector for a lithium ion battery according to claim 9, wherein the thickness of the sheet-shaped polymeric current collector is 2 to 6 μm.
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