CN116404170B - Modified current collector and preparation method and application thereof - Google Patents
Modified current collector and preparation method and application thereof Download PDFInfo
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- CN116404170B CN116404170B CN202310660991.5A CN202310660991A CN116404170B CN 116404170 B CN116404170 B CN 116404170B CN 202310660991 A CN202310660991 A CN 202310660991A CN 116404170 B CN116404170 B CN 116404170B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 239000011888 foil Substances 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 239000012954 diazonium Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 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
- 238000000034 method Methods 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- -1 amine cations Chemical class 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UEUIKXVPXLWUDU-UHFFFAOYSA-O 4-sulfobenzenediazonium Chemical compound OS(=O)(=O)C1=CC=C([N+]#N)C=C1 UEUIKXVPXLWUDU-UHFFFAOYSA-O 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910010093 LiAlO Inorganic materials 0.000 description 2
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical class [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical class [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
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- 238000004108 freeze drying Methods 0.000 description 2
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- 229920000178 Acrylic resin Polymers 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 239000007767 bonding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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- 230000002269 spontaneous effect Effects 0.000 description 1
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- 238000006277 sulfonation reaction Methods 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
- H01M4/663—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
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
-
- 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
Abstract
The invention discloses a modified current collector and a preparation method and application thereof, and belongs to the technical field of secondary battery materials. The preparation method of the modified current collector comprises the following steps: s1, grafting graphene by diazonium sulfonate, and reacting the obtained product with polyoxyethylene ether quaternary ammonium salt; s2, dispersing the product obtained in the step S1 and the binder in a solvent to obtain slurry with the pH value of 8-9.5; and S3, coating the slurry on the surface of the metal foil. The modified current collector prepared by the preparation method can improve the conductivity of the modified current collector and improve the adhesive strength of the coating of the electrode prepared by the modified current collector. The invention also provides the modified current collector prepared by the preparation method and application of the obtained modified current collector.
Description
Technical Field
The invention relates to the technical field of secondary battery materials, in particular to a modified current collector, a preparation method and application thereof.
Background
In the conventional manufacturing process of the pole piece of the lithium ion battery, an electrode coating comprising a binder and an electrode active material is directly arranged on the surface of a current collector (aluminum foil/copper foil), and the binder in the electrode coating is used for bonding the electrode coating and the current collector. Such a structural design has the following 2 disadvantages: the contact area between the rigid metal current collector and the active material particles is limited, the interface resistance is larger, the internal resistance of the battery is increased, and the battery performance, particularly the performance under the condition of heavy current charge and discharge, is negatively influenced; in addition, the bonding strength of the bonding agent is limited, and in the continuous charge and discharge process, the expansion and separation between the active material and the current collector easily occur, so that the internal resistance of the battery is further increased, and the cycle life and the safety performance of the battery are influenced.
In order to solve the above problems, attempts have been made to provide a conductive layer on the surface of a metal foil. The conductive material in the conductive layer typically includes carbon black, graphene, carbon nanotubes, and the like; the theoretical conductivity of graphene is highest, but is the conductivity in a single-layer and flattened state, which is hardly achieved in practical production.
That is, in the existing current collector having the conductive coating layer, the improvement of the conductivity is not enough and the adhesion between the electrode coating layer and the current collector cannot be significantly increased.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the preparation method of the modified current collector provided by the invention can effectively exert the conductivity of graphene, and finally can improve the conductivity of the obtained modified current collector, and simultaneously comprises the coating adhesion strength of the electrode of the obtained modified current collector.
The invention also provides the modified current collector prepared by the preparation method.
The invention also provides application of the modified current collector.
According to an embodiment of the first aspect of the present invention, there is provided a method for preparing a modified current collector, the method comprising the steps of:
s1, grafting graphene with diazonium sulfonate, and reacting the obtained product with polyoxyethylene ether quaternary ammonium salt to obtain modified graphene; the chemical formula of the polyoxyethylene ether quaternary ammonium salt is C 9 H 19 C 6 H 4 (OCH 2 CH 2 ) n O(CH 2 ) 2 N + (CH 3 ) 3 Cl - The method comprises the steps of carrying out a first treatment on the surface of the Wherein n has a value ranging from 8 to 12 (polyoxyethylene ether quaternary ammonium salt of the chemical formula is commonly referred to as nonylphenol polyoxyethylene ether quaternary ammonium salt);
s2, dispersing the modified graphene and the binder in a solvent to obtain slurry with pH of 8-9.5;
s3, coating the slurry obtained in the step S2 on the surface of the metal foil to obtain the conductive layer.
The mechanism of the preparation method is as follows:
in the step S1, diazo groups in diazosulfonate are grafted to the surface of graphene through a free radical addition reaction, so that sulfonate is introduced into the graphene; and then, combining quaternary amine cations and sulfonate anions in the polyoxyethylene ether quaternary amine salt, and introducing an open polyoxyethylene ether chain into the modified graphene.
In step S3, in the process of drying the slurry, the alkalinity of the slurry is raised, and micro corrosion can be performed on the metal foil.
The control method according to the embodiment of the invention has at least the following beneficial effects:
(1) According to the invention, the modified graphene is prepared by adopting a special method, and due to the action of long-chain polyoxyethylene ether, interlayer recombination can be avoided, the dispersion performance is good, the self-flattening effect is realized, and the conductivity of the graphene can be utilized to the greatest extent. Therefore, the thickness of the conductive layer can be reduced on the basis of obtaining a considerable conductivity as compared with the conventional modified current collector, and finally the energy density of the secondary battery including the modified current collector is improved; if the thickness of the conductive layer is equivalent to that of the conventional technology, the conductivity of the obtained modified current collector is remarkably improved.
Further, polyoxyethylene ether quaternary amine salts within the chemical formula limited range have good dispersion properties and moderate viscosity. Facilitating the reaction.
(2) The sizing agent adopted by the invention has slight alkalinity, so that on one hand, the dispersion uniformity of the modified graphene in the sizing agent can be improved (Zeta potential of the dispersing sizing agent can be reduced under alkaline conditions).
On the other hand, in the drying process of the slurry, as the water content is reduced, the alkalinity is improved, and finally the capability of corroding the metal foil is provided, so that the roughness of the metal foil can be improved to a certain extent, and the adhesion fastness of attachments on the surface of the metal foil is improved. The invention not only avoids damaging the metal foil, but also influences the mechanical strength of the metal foil by controlling the pH value of the slurry; the adhesion is also improved, whereby the amount of binder in the paste can be reduced and the conductive properties of the conductive layer (the binder is typically insulating) are further improved.
(3) The preparation method provided by the invention is simple, easy to realize and convenient for large-scale industrial production.
According to some embodiments of the invention, in step S1, the diazonium sulfonate comprises diazonium benzenesulfonic acid (CAS: 305-80-6).
According to some embodiments of the invention, in step S1, the graphene includes at least one of graphene that has not been subjected to any modification and reduced graphene oxide. Graphene oxide has relatively high defects and relatively poor conductivity, so that the graphene oxide is not generally used for preparing a modified current collector; graphene oxide is reduced, and the dispersibility of graphene in a reaction system can be improved through an oxidation process and a reduction process; in summary, as long as the conductivity is good and the graphene is well dispersed in water, the source and form of the graphene in practical production are not strictly limited.
According to some embodiments of the invention, in step S1, the thickness of the graphene is 0.3-10 nm. For example, the wavelength may be specifically 1 to 5nm.
According to some embodiments of the invention, in step S1, the number of layers of the graphene is equal to or less than 20. For example, the number of layers may be 3 to 6.
According to some embodiments of the invention, in step S1, the specific surface area of the graphene is equal to or greater than 20m 2 And/g. For example, it may be more specifically 28.gtoreq. 28m 2 Per g, or greater than or equal to 45 m 2 /g。
According to some embodiments of the invention, in step S1, the mass ratio of the graphene to the diazonium sulfonate is 1:2-4. For example, the ratio may be specifically 1:2.2 to 2.8. And more specifically may be about 1:2.5.
According to some embodiments of the invention, in step S1, the grafting is performed in an aqueous solution.
According to some embodiments of the invention, in step S1, the concentration of the graphene in the grafted reaction system is 0.5-6 mg/mL. For example, the concentration of graphene may be specifically 1-3 mg/mL.
According to some embodiments of the invention, in step S1, the grafted pH is 9 to 12. For example, the specific value may be 9.5 to 10.5.
The grafting is specifically performed by dispersing the graphene in water, adjusting the pH of the aqueous dispersion, and then adding the diazonium sulfonate. The grafted pH refers to the pH of the aqueous dispersion of graphene.
According to some embodiments of the invention, in step S1, the grafting temperature is 0-5 ℃. At this reaction temperature, the probability of side reactions of the diazo groups in the diazonium sulfonate is relatively low.
According to some embodiments of the invention, in step S1, the grafting reaction time is 6-12 hours. For example, it may be 7 hours.
According to some embodiments of the invention, in step S1, the resulting grafted product is further purified after said grafting.
According to some embodiments of the invention, the purification of the grafted product comprises solid-liquid separation, washing and drying, which are performed sequentially. Wherein the solid-liquid separation comprises suction filtration (220 nm or 450 nm) by using a microporous filter membrane; wherein the cleaning comprises the steps of sequentially adopting DMF, water, absolute ethyl alcohol and acetone for cleaning; the drying includes at least one of vacuum heat drying and freeze drying.
According to some embodiments of the invention, the value range of n in the polyoxyethylene ether quaternary ammonium salt is 9-10.
According to some embodiments of the invention, in step S1, the mass ratio of the grafted product to the polyoxyethylene ether quaternary ammonium salt is 1:2-4. For example, the ratio may be specifically 1:2.5 to 3.5.
According to some embodiments of the invention, in step S1, the temperature of the reaction is 50 to 80 ℃. For example, the temperature may be 60 to 70 ℃.
According to some embodiments of the invention, in step S1, the reaction time is 12-36 h. For example, the time period may be 13 to 16 hours.
According to some embodiments of the invention, in step S1, purifying the product after the reaction is further included. The purification method comprises solid-liquid separation, water washing and acetone washing which are sequentially carried out.
In order to further remove graphene fragments generated during the reaction, dialysis or the like may be performed after washing with acetone.
According to some embodiments of the invention, in step S2, the pH of the slurry is 8 to 8.5.
According to some embodiments of the invention, in step S2, the pH adjusting agent of the slurry comprises at least one of lithium carbonate and lithium hydroxide.
Whereby, when the metal foil is aluminum foil, the above adjustment is performedEtching metal foil with an etchant to form LiAlO 2 That is, a roughened layer having excellent lithium ion conductivity is produced. When the electrode coating is coated on the surface of the modified current collector and compacted, part of the electrode active material is embedded into the conductive layer, thereby being equivalent to coating LiAlO on a local area of the positive electrode active material 2 The rate capability of the secondary battery including the modified current collector is further improved.
According to some embodiments of the invention, in step S2, the mass ratio of the modified graphene to the binder is 1:0.8-2. For example, it may be about 1:1.
According to some embodiments of the invention, in step S2, the binder comprises at least one of SBR, aqueous polyester resin, aqueous acrylic resin, aqueous polyurethane resin, aqueous acrylonitrile copolymer, aqueous epoxy resin, and PVDF.
Wherein the slurry of the positive electrode coating layer is usually an NMP (oily) solvent, and thus if the modified current collector is used for preparing a positive electrode of a secondary battery, the binder is usually an aqueous binder. In contrast, the slurry of the negative electrode coating is usually an aqueous slurry, and thus if the modified current collector is used for preparing a negative electrode of a secondary battery, the binder should be an oily binder. Thereby avoiding the influence on the conductive layer during the electrode coating preparation process.
According to some embodiments of the invention, in step S2, the solvent comprises at least one of water, DMSO, DMF, NMP and ethyl acetate.
According to some embodiments of the invention, in step S2, the mass concentration of the modified graphene in the slurry is 0.05-5%. For example, the content may be 0.1 to 0.5%, or 1 to 3%.
According to some embodiments of the invention, in step S3, the method of coating comprises at least one of knife coating and spray coating.
According to some embodiments of the invention, in step S3, drying is further included after the coating.
The drying includes at least one of forced air drying and vacuum drying, as long as the removal of the solvent can be performed.
According to some embodiments of the invention, in step S3, the metal foil comprises at least one of copper foil and aluminum foil.
According to an embodiment of the second aspect of the present invention, there is provided a modified current collector manufactured by the manufacturing method, the modified current collector including the metal foil, and the conductive layer provided on at least one side surface of the metal foil; the conductive layer includes the modified graphene and a binder.
The control method according to the embodiment of the invention has at least the following beneficial effects:
in the modified current collector prepared by the preparation method, the modified graphene in the conductive layer is evenly unfolded (almost without wrinkles) and is extremely little agglomerated; namely, the modified current collector is smoothly and orderly spread on the surface of the metal foil, thereby fully improving the conductivity of the conductive layer and finally improving the rate capability and the cycle performance of the secondary battery comprising the modified current collector.
According to some embodiments of the invention, the thickness of the conductive layer is 100-1000 nm. Specifically, the wavelength may be 500 to 800nm.
According to an embodiment of the third aspect of the present invention, there is provided the use of the modified current collector in the preparation of a secondary battery positive electrode, a secondary battery negative electrode or a supercapacitor.
The secondary battery anode, the secondary battery cathode or the super capacitor adopt all the technical schemes of the modified current collector of the embodiment, so that the modified current collector has at least all the beneficial effects brought by the technical schemes of the embodiment.
According to some embodiments of the invention, the secondary battery positive electrode includes the modified current collector and a positive electrode coating layer covering at least one side surface of the modified current collector.
According to some embodiments of the invention, the positive electrode coating comprises a positive electrode active material.
According to some embodiments of the invention, the positive electrode active material is at least one of a layered positive electrode material, a spinel positive electrode material, and a polyanionic positive electrode material. Wherein the layered cathode material comprises at least one of unmodified lithium cobalt oxide, modified lithium cobalt oxide, unmodified lithium nickel cobalt manganese oxide and modified lithium nickel cobalt manganese oxide. The polyanionic cathode material includes at least one of lithium iron phosphate, lithium manganese phosphate, and lithium manganese iron phosphate.
According to some embodiments of the invention, the secondary battery anode includes the modified current collector and an anode coating layer covering at least one side surface of the modified current collector.
According to some embodiments of the invention, the negative electrode coating comprises a negative electrode active material.
According to some embodiments of the invention, the negative electrode active material comprises at least one of graphite and a silicon-based material. Wherein the silicon-based material comprises at least one of a silicon oxygen material and a silicon carbon material.
According to an embodiment of the fourth aspect of the present invention, there is provided a lithium ion battery, wherein a preparation raw material of the lithium ion battery includes the modified current collector.
The lithium ion battery adopts all the technical schemes of the modified current collector of the embodiment, so that the lithium ion battery has at least all the beneficial effects brought by the technical schemes of the embodiment.
The term "about" as used herein, unless otherwise specified, means that the tolerance is within + -2%, for example, about 100 is actually 100 + -2%. Times.100.
Unless otherwise specified, the term "between … …" in the present invention includes the present number, for example "between 2 and 3" includes the end values of 2 and 3.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 is a morphology diagram of graphene used in example 1 of the present invention.
Fig. 2 is a morphology diagram of the modified graphene obtained in step S1 of embodiment 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The embodiment prepares a modified current collector, which comprises the following specific steps:
s1, preparing modified graphene:
s1a, grafting sulfonation:
graphene (model JY-GP01 from Hunan Jinyang-based carbon New material Co., ltd., the number of layers is 3-6, and the specific surface is about 28 m) 2 /g) in aqueous sodium hydroxide at a pH of about 10 at a concentration of about 1mg/mL;
and (3) carrying out ice-water bath (the temperature is 0-2 ℃) on the obtained graphene dispersion liquid, and then adding diazobenzene sulfonic acid into the graphene dispersion liquid. Wherein the mass ratio of the diazobenzenesulfonic acid to the graphene is 2.5:1.
In the process, the temperature of the reaction system is ensured to be less than or equal to 5 ℃, and diazobenzene sulfonic acid can be added for multiple times to meet the temperature requirement.
After the addition is completed, the temperature is maintained to be less than or equal to 5 ℃ for reaction for 6 hours.
And (3) carrying out solid-liquid separation on the reacted mixture by adopting a filter membrane with the diameter of 0.22 mu m, washing the obtained filter cake by using DMF, water, absolute ethyl alcohol and acetone in sequence (filtering after dispersing), and freeze-drying the finally obtained solid product to obtain the sulfonated graphene.
S1b, ion exchange reaction:
forming an aqueous dispersion with the concentration of 1mg/mL by the sulfonated graphene obtained in the step S1, and heating the aqueous dispersion in a water bath with the temperature of about 60 ℃;
then adding nonylphenol polyoxyethylene ether quaternary ammonium salt (C) 9 H 19 C 6 H 4 (OCH 2 CH 2 ) 10 O(CH 2 ) 2 N + (CH 3 ) 3 Cl - Purchased from Puyang Tenghui chemical Co., ltd.). After the addition was completed, the reaction was continued for 15 hours. The mass ratio of the nonylphenol polyoxyethylene ether quaternary ammonium salt to the sulfonated graphene is 2.5:1.
And after the reaction is finished, adopting a filter membrane with the diameter of 0.22 mu m to carry out solid-liquid separation, and cleaning with water and acetone in sequence to obtain the modified graphene.
S2, preparing slurry:
dispersing the modified graphene obtained in the step S1 and a binder (SBR) in water according to a mass ratio of 1:1, and regulating the pH value by using a 1M lithium hydroxide aqueous solution to obtain slurry with the concentration of the modified graphene being 1.5wt% and the pH value being 8.
S3, coating the slurry obtained in the step S2 on one side surface of an aluminum foil (double-side smooth surface, average thickness is 12 mu m), and drying to obtain the conductive layer. The thickness of the conductive layer was 500nm.
Example 2
This example produced a modified current collector, which differs from example 1 in the following specific points:
in the step S2, the adopted binder is PVDF, the solvent is NMP, and lithium hydroxide solid powder is directly added for pH adjustment, so that the pH of the obtained slurry is 8.2. And since the amount of lithium hydroxide added is small, the binder will not fail.
In step S3, the metal foil used was copper foil (double-sided smooth surface, average thickness of 8 μm).
Comparative example 1
This comparative example produced a modified current collector, which differs from example 1 in particular in that:
in step S2, the graphene raw material used in example 1 was directly used for slurry preparation without step S1.
Comparative example 2
This comparative example produced a modified current collector, which differs from example 1 in particular in that:
and (3) adjusting the sequence of the step S1 and the step S2, namely, firstly reacting graphene with polyoxyethylene ether quaternary ammonium salt, and then reacting with diazonium sulfonate.
Comparative example 3
This comparative example produced a modified current collector, which differs from example 1 in particular in that:
in step S2, the pH of the slurry was not adjusted, specifically 6.9.
Comparative example 4
This comparative example produced a modified current collector, which differs from example 1 in particular in that:
in step S2, the graphene raw material used in example 2 was directly used for slurry preparation without step S1.
Application example
This example provides 8 kinds of lithium ion battery pole pieces, and is specific:
the first is a positive electrode of a lithium ion battery, specifically comprising the modified current collector provided in example 1, and a positive electrode coating (average thickness of 125 μm) provided on the surface of the modified current collector; the positive electrode coating comprises a positive electrode active material, in particular lithium iron phosphate purchased from BIDIY; the preparation method comprises the steps of dispersing lithium iron phosphate, PVDF and SP in NMP according to the mass ratio of 92:3:5 to form positive electrode slurry with the solid content of 45%, coating the positive electrode slurry on the surface of one side of the modified current collector with the conductive layer, drying in vacuum, and rolling.
The second is a lithium ion battery anode, specifically comprising the modified current collector provided in example 2, and an anode coating (average thickness of 125 μm) provided on the surface of the modified current collector; the negative electrode coating comprises a negative electrode active material, specifically graphite purchased from a fir negative electrode. The preparation method comprises dispersing graphite, SBR, CMC and SP in water according to the mass ratio of 95:2:2:1 to form anode slurry with solid content of 45%, coating the anode slurry on the surface of the side of the modified current collector with the conductive layer, vacuum drying and rolling to obtain the final product.
The third is a positive electrode of a lithium ion battery, and the difference from the first is that:
the positive electrode current collector was a modified current collector obtained in comparative example 1.
The fourth is a positive electrode of a lithium ion battery, and the difference from the first is that:
the positive electrode current collector was a modified current collector obtained in comparative example 2.
The fifth is a positive electrode of a lithium ion battery, and is different from the first in that:
the positive electrode current collector was a modified current collector obtained in comparative example 3.
The sixth is a positive electrode of a lithium ion battery, and is different from the first in that:
the positive electrode current collector was an aluminum foil used in example 1.
The seventh is a negative electrode of a lithium ion battery, and the second is different in that:
the negative electrode current collector was the copper foil used in example 2.
The eighth is a negative electrode of a lithium ion battery, and the second is different in that:
the negative electrode current collector was a modified current collector obtained in comparative example 4.
Test case
The morphology of the graphene raw material used in the embodiment and the morphology of the modified graphene obtained in the step S1 are tested first. The test method is transmission electron microscope. The results show that the raw graphene is very thin, but during the preparation of the electron microscope sample (dispersed droplets on the copper mesh), the graphene tends to twist, fold, and be in a non-flattened state. The modified graphene obtained in step S1 of embodiment 1 will spontaneously flatten to form a flattened and wrinkle-free morphology, and the graphene in the flattened state is expected to better exert its conductivity. The specific morphology is shown in figures 1-2.
The resistivity and the peel strength of each lithium ion battery electrode of the application example are also tested, and the testing method comprises the following steps:
resistivity test the resistivity of the pole pieces was tested using a Suzhou lattice electronics Co Ltd ST2253 digital four-probe tester.
Peel strength test 3M HVB double faced adhesive tape (19 mm. Times.60 mm) was attached to one end of the steel plate, after which the pole piece was cut into 20 mm. Times.200 mm strips, and the positive active layer side was attached to the double faced adhesive tape. The peel strength was determined by measuring the peel strength of an aluminum foil at a speed of 100mm/min in a direction of 180℃under an atmosphere of 50% relative humidity at 25 ℃.
The test results are shown in Table 1.
Table 1 resistivity and peel strength of working electrode in application example
Comparing the first, sixth, and second and seventh, it is known that the modified current collector provided by the invention can significantly improve the conductivity and adhesion of the electrode.
Comparing the first and third, it is known that if graphene is not modified, graphene tends to be bent and wrinkled during formation of the conductive layer, and thus conductivity thereof cannot be sufficiently exhibited, and resistivity of the obtained electrode is improved.
Comparing the first and fourth, it can be seen that if graphene and quaternary ammonium salt are reacted first, the quaternary ammonium salt has a certain intercalation stripping effect at this time, so that the degree of graphene agglomeration is lighter than that of the third, and the conductivity is better than that of the third. But may not be capable of the same spontaneous flattening behavior of the modified graphene as the present invention and thus is inferior to the first one in conductivity.
Comparing the first and fifth, it is known that if the pH of the slurry is not adjusted, corrosion of the aluminum foil cannot be caused during the preparation of conductivity, and thus the peel strength is lowered.
In combination with the first and third to fifth, it is known that, although pH adjustment and modification of graphene each have an emphasis, there is still a certain synergistic effect between the two. For example, the peel strength of the third and fourth types is slightly reduced, and the conductivity of the fifth type is slightly reduced.
As is clear from comparison of the second and eighth, the conductive layer has an effect equivalent to that of the positive electrode surface on the negative electrode surface with respect to the performance of the conductive layer.
According to the results and analysis, the modified current collector provided by the invention can cooperatively improve the conductivity and the adhesive strength of an electrode comprising the modified current collector by means of the self-flattening effect of the modified graphene and the etching effect of the conductive paste on the metal foil in the preparation process of the conductive layer; it is expected that secondary batteries, particularly lithium ion secondary batteries, comprising the modified current collector provided by the invention have good rate capability and cycle performance, and that secondary batteries with excellent performance are expected to be widely applied in the 3C field, the energy storage field and the power battery field.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (9)
1. A method for preparing a modified current collector, comprising the steps of:
s1, grafting graphene with diazonium sulfonate, and reacting the obtained product with polyoxyethylene ether quaternary ammonium salt according to a mass ratio of 1:2-4 to obtain modified graphene; the mass ratio of the graphene to the diazonium sulfonate is 1:2-4; the chemical formula of the polyoxyethylene ether quaternary ammonium salt is C 9 H 19 C 6 H 4 (OCH 2 CH 2 ) n O(CH 2 ) 2 N + (CH 3 ) 3 Cl - The method comprises the steps of carrying out a first treatment on the surface of the Wherein the value range of n is 8-12;
s2, dispersing the modified graphene and the binder in a solvent to obtain slurry with pH of 8-9.5;
s3, coating the slurry obtained in the step S2 on the surface of the metal foil to obtain the conductive layer.
2. The method of claim 1, wherein in step S1, the diazonium sulfonate comprises diazonium benzenesulfonic acid.
3. The method according to claim 1, wherein in step S2, the pH adjusting agent of the slurry includes at least one of lithium carbonate and lithium hydroxide.
4. The preparation method of claim 1, wherein in the step S2, the mass ratio of the modified graphene to the binder is 1:0.8-2.
5. The preparation method according to claim 1, wherein in step S2, the concentration of the modified graphene in the slurry is 0.05-5%.
6. A modified current collector manufactured by the manufacturing method according to any one of claims 1 to 5, wherein the modified current collector comprises the metal foil and the conductive layer provided on at least one side surface of the metal foil; the conductive layer includes the modified graphene and a binder.
7. The modified current collector of claim 6, wherein the conductive layer has a thickness of 100 to 1000nm.
8. Use of the modified current collector of claim 6 or 7 for the preparation of a secondary battery positive electrode, a secondary battery negative electrode or a supercapacitor.
9. A lithium ion battery, characterized in that the preparation raw material of the lithium ion battery comprises the modified current collector as claimed in claim 6 or 7.
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