CN116706009A - Polyimide composite carbon aerogel lithium battery positive electrode slurry, positive electrode plate and preparation method thereof - Google Patents
Polyimide composite carbon aerogel lithium battery positive electrode slurry, positive electrode plate and preparation method thereof Download PDFInfo
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- CN116706009A CN116706009A CN202310578634.4A CN202310578634A CN116706009A CN 116706009 A CN116706009 A CN 116706009A CN 202310578634 A CN202310578634 A CN 202310578634A CN 116706009 A CN116706009 A CN 116706009A
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- carbon aerogel
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- lithium battery
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 111
- 229920001721 polyimide Polymers 0.000 title claims abstract description 111
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- 239000011267 electrode slurry Substances 0.000 title claims description 58
- 238000002360 preparation method Methods 0.000 title abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 239000006258 conductive agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000006256 anode slurry Substances 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000017 hydrogel Substances 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 239000004964 aerogel Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- -1 benzene tetramethyl anhydride Chemical class 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 9
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 238000001291 vacuum drying Methods 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 9
- 239000002109 single walled nanotube Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 provides a polyimide composite carbon aerogel lithium battery positive plate and a preparation method thereof. According to the method for preparing the positive plate, polyimide particles generated by proper in-situ polymerization are embedded into pores of a carbon aerogel framework, and the novel binary conductive agent compounded by graphene and carbon nanotubes is adopted to replace the traditional conductive carbon black, so that a synergistic effect is achieved among the one-dimensional carbon nanotubes, the two-dimensional flaky graphene and the three-dimensional carbon aerogel in the positive plate of the polyimide composite carbon aerogel lithium battery, and a multiple high-efficiency three-dimensional conductive network is constructed in an omnibearing manner among polyimide particles with extremely poor conductivity, so that the positive plate of the polyimide composite carbon aerogel lithium battery has the advantages of high specific capacity, good multiplying power performance, good structural stability, good cycling stability and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to polyimide composite carbon aerogel lithium battery positive electrode slurry, a positive electrode plate and a preparation method thereof.
Background
In recent years, lithium ion batteries have been developed very rapidly, and have been widely used in electric vehicles, electronic products, and various large-sized energy storage devices. The traditional lithium ion battery anode materials comprise lithium iron phosphate, lithium cobalt oxide, lithium manganate, ternary nickel cobalt manganese materials and the like, but most of the inorganic materials have smaller theoretical capacity, high cost and limited resources. Therefore, it is not easy to find a new electrode material that can replace the conventional inorganic positive electrode material.
Compared with inorganic positive electrode materials, organic polymer positive electrode materials, especially conjugated carbonyl polymers, are considered as one of the novel electrode materials with great prospect due to the advantages of high theoretical capacity, rich raw materials, environmental friendliness, strong structural designability, safety of the system and the like. Among them, conjugated carbonyl compounds represented by polyimide are favored by researchers as a battery positive electrode material because of their high electrochemical activity, excellent mechanical properties, good thermal stability, and the like.
However, polyimide has problems of low carbonyl utilization and poor electron conductivity when used as a positive electrode material for lithium ion batteries. Therefore, modification research on polyimide is mainly performed at present by adding high-conductivity carbon such as graphene, carbon nanotube, carbon black and the like in the preparation process to improve carbonyl utilization rate and electronic conductivity of the material so as to obtain an electrode material with excellent electrochemical performance. Although many reports about polyimide-carbon based composite materials used as anode materials of lithium ion batteries in the prior art exist, the preparation methods are mostly similar, and polyimide is often compounded with one-dimensional (such as carbon nanotubes) or two-dimensional (such as graphene) nano carbon materials by an in-situ polymerization method, such as CN111490233a (a rechargeable magnesium battery anode material based on polyimide and graphene compounding and a preparation method thereof). However, in order to build up a high-efficiency conductive network inside the polyimide electrode, the addition amount of the conductive agent is often required to be high (usually 30-70 wt% of the conductive agent), but the conductive agent itself cannot provide the capacity of inserting and extracting lithium, and the addition amount is relatively high, which can lead to the reduction of specific energy and specific power of the lithium battery and limit the commercialized application prospect of the lithium battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides polyimide composite carbon aerogel lithium battery positive electrode slurry, a positive electrode plate and a preparation method thereof. The specific scheme is as follows:
a polyimide composite carbon aerogel lithium battery positive electrode slurry comprises an active substance, a conductive agent and a binder; the active substance is polyimide composite carbon aerogel, the conductive agent is a combination of graphene and carbon nano tubes, and the mass ratio of the graphene to the carbon nano tubes is 1:2 to 3.
The mass ratio of the active substance to the conductive agent to the binder is 80-90:1-5:5-10.
The binder is PTFE or PVDF.
The preparation method of the polyimide composite carbon aerogel lithium battery positive electrode slurry disclosed by any one of the above steps comprises the following steps:
(1) Uniformly mixing polyimide composite carbon aerogel, a conductive agent and a binder;
(2) And then dropwise adding an NMP solvent, and stirring to obtain polyimide composite carbon aerogel positive electrode slurry.
The preparation method of the polyimide composite carbon aerogel in the step (1) comprises the following steps:
s1, weighing a certain amount of dianhydride monomer, carbon aerogel and NMP solvent, uniformly mixing, adding diamine monomer, and heating and refluxing for reaction under the stirring condition;
s2, collecting a reaction product, and then washing and drying;
and S3, finally, carrying out heat treatment on the product in an argon atmosphere to obtain the polyimide composite carbon aerogel.
The molar ratio of the diamine monomer to the dianhydride monomer to the carbon aerogel added in the step S1 is 1:1, the mole ratio of the dianhydride monomer to the carbon aerogel added is 2:1 to 5.
The dianhydride monomer in the step S1 is 1,4,5, 8-naphthalene tetramethyl anhydride monomer, benzene tetramethyl anhydride monomer or 3,4,9, 10-perylene tetracarboxylic dianhydride monomer.
And in the step S1, ethylenediamine, p-phenylenediamine or hexamethylenediamine.
The carbon aerogel in the step S1 is prepared by the following steps:
step 1, mixing resorcinol (R), formaldehyde (F), sodium carbonate (C) and water (W) according to a molar ratio of R/F=1:2, R/C=100-1500 and W/R=4-90, stirring to form a uniform solution, injecting the uniform solution into a cylindrical mold, and standing for 16-24H at normal temperature to obtain sol;
step 2, heating the sol obtained in the step 1 in a water bath at the temperature of 40-60 ℃ for 16-24H, and aging for 16-24H at the temperature of 60-80 ℃ after the sol is gelled to obtain dark red hydrogel;
step 3, soaking the hydrogel sample obtained in the step 2 in an ethanol solvent for 4-6 days, and replacing ethanol every 8H;
step 4, finally, carrying out supercritical drying on the hydrogel obtained in the step 3 to obtain aerogel;
and 5, carbonizing the aerogel under the vacuum condition, controlling the temperature to rise to 800-1000 ℃ at the speed of 2-5 ℃/min, and then preserving the heat for 2H to obtain the carbon aerogel material.
The reagent washed in the step S2 is one or more of NMP solvent and acetone;
the drying temperature in the step S2 is 80-120 ℃ and the drying time is 8-12H.
The temperature of the heat treatment in the step S3 is 250-300 ℃ and the time is 6-10H.
The lithium battery electrode slice comprises a positive current collector and positive electrode slurry coated on the positive current collector, wherein the positive electrode slurry is the polyimide composite carbon aerogel lithium battery positive electrode slurry described in any one of the above.
The lithium battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is the positive plate of the lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method, polyimide particles generated by proper in-situ polymerization are embedded into the pores of the carbon aerogel framework to form complete filling, so that the close contact between the carbon aerogel and polyimide is realized, and the rapid transmission of electrons is effectively promoted by wrapping the carbon aerogel three-dimensional conductive network outside the polyimide particles; polyimide particles with limited domains in the 3D nano holes communicated with each other are beneficial to realizing uniform dispersion of the polyimide particles and reducing agglomeration so as to expose more reactive sites and improve the circulation stability;
(2) In addition, the novel binary conductive agent compounded by graphene and the carbon nano tube is adopted to replace the traditional conductive carbon black, and compared with a 'point-point' contact model of the conductive carbon black, the 'line-point' contact model of the carbon nano tube and a 'face-point' contact model of the graphene jointly enable active material particles (polyimide composite carbon aerogel) to construct a 'short-range' and 'long-range' complementary conductive network structure on a current collector, so that the contact resistance among electrode material particles is effectively reduced, the conductivity of an integral electrode can be effectively improved, good conductivity can be maintained even under the condition of low conductive agent addition (less than or equal to 5 wt%), the proportion of active materials is further increased, and the volume energy density of a lithium ion battery can be improved;
(3) The one-dimensional carbon nanotube, the two-dimensional flaky graphene and the three-dimensional carbon aerogel in the polyimide composite carbon aerogel lithium battery positive plate have a synergistic effect, and a multiple high-efficiency three-dimensional conductive network is successfully built in an omnibearing manner among polyimide particles with extremely poor conductivity, so that the prepared polyimide composite carbon aerogel lithium battery positive plate has the advantages of high specific capacity, good rate capability, good structural stability, good cycling stability and the like;
(4) The polyimide composite carbon aerogel is prepared by in-situ polymerization in the three-dimensional conductive network of the carbon aerogel framework, and the preparation method is simple and efficient and has no side reaction.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
(1) Preparation of carbon aerogel
a. Preparing sol: 0.2mol of resorcinol (R), 0.4mol of formaldehyde (F), 4mmol of sodium carbonate (C) and 18mol of water (W) are mixed. Stirring the mixed solution until the mixed solution is completely dissolved, injecting the mixed solution into a cylindrical mold, and standing for 1 day at normal temperature to form RF sol;
b. gel aging: placing the RF sol into a water bath, carrying out water bath at 50 ℃ for 1 day, solidifying the sol into gel, and then heating to 75 ℃ for continuous aging for 1 day to obtain dark red hydrogel;
c. solvent replacement: soaking the dark red hydrogel sample in ethanol solvent for 5 days, and replacing ethanol every 8 hours;
d. supercritical drying: placing the hydrogel subjected to solvent replacement into an autoclave, heating to a set temperature of 50-60 ℃ according to a heating rate of 1 ℃/min after sealing, keeping the temperature for 2H under a set pressure of 14-20 MPa, and slowly discharging the supercritical fluid to obtain an RF aerogel material;
e. and (3) placing the RF aerogel into a carbonization furnace, vacuumizing, heating to 1000 ℃ at 2 ℃/min under flowing argon atmosphere, preserving heat for 2H, and cooling along with the furnace to obtain the carbon aerogel material.
(2) Preparation of polyimide composite carbon aerogel
a. Weighing 5.36g of 1,4,5, 8-naphthalene tetramethyl anhydride monomer and 0.31g of carbon aerogel, putting into 0.1LNMP solvent, mixing, carrying out ultrasonic treatment for 20min to uniformly disperse the mixture, transferring the mixture into a three-necked flask, adding 1.34mL of ethylenediamine monomer into a reaction system, and heating and refluxing for 4H under the stirring condition;
b. after centrifugation of the product, washing with NMP and acetone solution, drying at 120℃for 12H;
c. and after drying, carrying out heat treatment on the product at 300 ℃ for 8H (under argon atmosphere) to thoroughly complete the reaction, thus obtaining the polyimide composite carbon aerogel.
(3) Polyimide composite carbon aerogel lithium battery positive electrode slurry and preparation of positive plate
a. 8.5g of polyimide composite carbon aerogel, 0.125g of graphene, 0.375g of single-walled carbon nanotube and 1g of PTFE are sequentially added into a small beaker, a proper amount of NMP solvent is added dropwise, then magnetic constant-temperature stirring is carried out for 8H, and polyimide composite carbon aerogel anode slurry is obtained after uniform mixing;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10H to obtain the polyimide composite carbon aerogel lithium battery positive electrode plate.
Example 2
The embodiment relates to a preparation method of a polyimide composite carbon aerogel lithium battery positive plate, which comprises the following steps.
(1) Preparation of carbon aerogel
A carbon aerogel material was produced in the same manner as in example 1.
(2) Preparation of polyimide composite carbon aerogel
The preparation method of the polyimide composite carbon aerogel in the embodiment 1 is adopted.
(3) Polyimide composite carbon aerogel lithium battery positive electrode slurry and preparation of positive plate
a. Weighing 8.5g of polyimide composite carbon aerogel, 0.025g of graphene, 0.075g of single-walled carbon nanotube and 1g of PTFE, sequentially adding into a small beaker, dropwise adding a proper amount of NMP solvent, magnetically stirring at constant temperature for 8H, and uniformly mixing to obtain polyimide composite carbon aerogel anode slurry;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10H to obtain the polyimide composite carbon aerogel lithium battery positive electrode plate.
Example 3
The embodiment relates to a preparation method of a polyimide composite carbon aerogel lithium battery positive plate, which comprises the following steps.
(1) Preparation of carbon aerogel
A carbon aerogel material was produced in the same manner as in example 1.
(2) Preparation of polyimide composite carbon aerogel
The preparation method of the polyimide composite carbon aerogel in the embodiment 1 is adopted.
(3) Polyimide composite carbon aerogel lithium battery positive electrode slurry and preparation of positive plate
a. 8.5g of polyimide composite carbon aerogel, 0.1g of graphene, 0.2g of single-walled carbon nanotube and 1g of PTFE are sequentially added into a small beaker, a proper amount of NMP solvent is added dropwise, then magnetic constant-temperature stirring is carried out for 8H, and polyimide composite carbon aerogel anode slurry is obtained after uniform mixing;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10H to obtain the polyimide composite carbon aerogel lithium battery positive electrode plate.
Example 4
The embodiment relates to a preparation method of a polyimide composite carbon aerogel lithium battery positive plate, which comprises the following steps.
(1) Preparation of carbon aerogel
A carbon aerogel material was produced in the same manner as in example 1.
(2) Preparation of polyimide composite carbon aerogel
The preparation method of the polyimide composite carbon aerogel in the embodiment 1 is adopted.
(3) Polyimide composite carbon aerogel lithium battery positive electrode slurry and preparation of positive plate
a. Weighing 9g of polyimide composite carbon aerogel, 0.125g of graphene, 0.375g of single-walled carbon nanotube and 1g of PTFE, sequentially adding into a small beaker, dropwise adding a proper amount of NMP solvent, magnetically stirring at constant temperature for 8H, and uniformly mixing to obtain polyimide composite carbon aerogel anode slurry;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10 hours to obtain the polyimide composite carbon aerogel lithium battery positive electrode plate.
Example 5
The embodiment relates to a preparation method of a polyimide composite carbon aerogel lithium battery positive plate, which comprises the following steps.
(1) Preparation of carbon aerogel
A carbon aerogel material was produced in the same manner as in example 1.
(2) Preparation of polyimide composite carbon aerogel
The preparation method of the polyimide composite carbon aerogel in the embodiment 1 is adopted.
(3) Polyimide composite carbon aerogel lithium battery positive electrode slurry and preparation of positive plate
a. 8g of polyimide composite carbon aerogel, 0.125g of graphene, 0.375g of single-walled carbon nanotube and 1g of PTFE are sequentially added into a small beaker, a proper amount of NMP solvent is added dropwise, then magnetic constant-temperature stirring is carried out for 8H, and the polyimide composite carbon aerogel anode slurry is obtained after uniform mixing;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10 hours to obtain the polyimide composite carbon aerogel lithium battery positive electrode plate.
Example 6
The embodiment relates to a preparation method of a polyimide composite carbon aerogel lithium battery positive plate, which comprises the following steps.
(1) Preparation of carbon aerogel
A carbon aerogel material was produced in the same manner as in example 1.
(2) Preparation of polyimide composite carbon aerogel
The preparation method of the polyimide composite carbon aerogel in the embodiment 1 is adopted.
(3) Polyimide composite carbon aerogel lithium battery positive electrode slurry and preparation of positive plate
a. 8.5g of polyimide composite carbon aerogel, 0.125g of graphene, 0.375g of single-walled carbon nanotube and 0.5g of PTFE are sequentially added into a small beaker, a proper amount of NMP solvent is added dropwise, then magnetic constant-temperature stirring is carried out for 8H, and polyimide composite carbon aerogel anode slurry is obtained after uniform mixing;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10 hours to obtain the polyimide composite carbon aerogel lithium battery positive electrode plate.
Comparative example 1
(1) Preparation of polyimide material
a. Weighing 5.36g of 1,4,5, 8-naphthalene tetramethyl anhydride monomer, putting into 1L of NMP solvent for mixing, carrying out ultrasonic treatment for 20min to uniformly disperse the monomer, transferring the mixture into a three-necked flask, adding 1.34mL of ethylenediamine monomer into a reaction system, and carrying out heating reflux for 4H under the condition of stirring;
b. after centrifugation of the product, washing with NMP and acetone solution, drying at 120℃for 12H;
c. after drying, the product was subjected to heat treatment at 300℃for 8H (under argon atmosphere) to complete the reaction thoroughly, to obtain a polyimide material.
(2) Polyimide lithium battery positive electrode slurry and preparation of positive plate
a. 8.5g of polyimide material, 0.125g of graphene, 0.375g of single-walled carbon nanotube and 1g of PTFE are weighed and sequentially added into a small beaker, a proper amount of NMP solvent is added dropwise, then magnetic constant temperature stirring is carried out for 8H, and polyimide anode slurry is obtained after uniform mixing;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10H to obtain the polyimide lithium battery positive electrode plate.
Comparative example 2
(1) Preparation of polyimide material
Polyimide material was produced in the same manner as in comparative example 1.
(2) Polyimide lithium battery positive electrode slurry and preparation of positive plate
a. 8.5g of polyimide material, 0.5g of conductive carbon black Super P and 1g of PTFE are weighed and sequentially added into a small beaker, a proper amount of NMP solvent is added dropwise, then magnetic constant temperature stirring is carried out for 8H, and polyimide anode slurry is obtained after uniform mixing;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10H to obtain the polyimide lithium battery positive electrode plate.
Comparative example 3
(1) Preparation of polyimide material composite carbon aerogel
A polyimide material composite carbon aerogel was prepared in the same manner as in example 1.
(2) Preparation of polyimide lithium battery positive electrode slurry and positive electrode plate:
a. weighing 8.5g of polyimide material composite carbon aerogel, 0.5g of flaky graphene and 1g of PTFE, sequentially adding into a small beaker, dropwise adding a proper amount of NMP solvent, magnetically stirring at constant temperature for 8H, and uniformly mixing to obtain polyimide anode slurry;
b. and d, uniformly coating the positive electrode slurry prepared in the step a on an aluminum foil, regulating the coating thickness to 200 mu m by using a scraper, and finally transferring the positive electrode slurry into a vacuum drying oven and drying the positive electrode slurry at 100 ℃ for 10H to obtain the polyimide lithium battery positive electrode plate.
Comparative example 4
(1) Adding 0.25g of graphene into a certain amount of N-methylpyrrolidone solution, and performing ultrasonic treatment for half an hour to obtain graphene dispersion;
(2) 5.36g of 1,4,5, 8-naphthalene tetracarboxylic dianhydride was added to the mixed solution of (1), followed by 1.34mL of ethylenediamine, at N 2 Reflux for 8h under protection;
(2) Cooling to room temperature, filtering the product, washing 3 times with NMP, and vacuum drying at 100deg.C for 12H;
(3) Finally, at N 2 Sintering for 8 hours at 300 ℃ in the atmosphere to obtain a polyimide/graphene compound;
(4) Uniformly grinding 8.5g of the prepared polyimide/graphene composite, 0.5g of single-walled carbon nanotube and 1g of PTFE, and adding a proper amount of N-methylpyrrolidone to prepare anode slurry;
(5) Coating the obtained positive electrode slurry on aluminum foil, vacuum drying at 60 ℃ for 12 hours, and cutting into wafers with the diameter of 1.4cm to obtain the positive electrode plate of the battery.
Test results
According to the embodiment of the invention, the polyimide composite carbon aerogel lithium battery positive electrode slurry and the positive electrode plate are prepared by adopting the method provided by the invention, and the test results show that the polyimide composite carbon aerogel lithium battery positive electrode plate prepared by the method provided by the invention has good charge and discharge performance and has great potential when being applied as a battery positive electrode plate in a battery.
Claims (10)
1. The polyimide composite carbon aerogel lithium battery anode slurry is characterized by comprising an active substance, a conductive agent and a binder; the active substance is polyimide composite carbon aerogel, the conductive agent is a combination of graphene and carbon nano tubes, and the mass ratio of the graphene to the carbon nano tubes is 1:2 to 3.
2. The polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 1, wherein the mass ratio of the active substance to the conductive agent to the binder is 80-90:1-5:5-10.
3. The polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 1, wherein the binder is PTFE or PVDF.
4. A method for preparing the polyimide composite carbon aerogel lithium battery positive electrode slurry according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) Uniformly mixing polyimide composite carbon aerogel, a conductive agent and a binder;
(2) And then dropwise adding an NMP solvent, and stirring to obtain polyimide composite carbon aerogel positive electrode slurry.
5. The method for preparing the polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 4, wherein the method for preparing the polyimide composite carbon aerogel in the step (1) comprises the following steps:
s1, weighing a certain amount of dianhydride monomer, carbon aerogel and NMP solvent, uniformly mixing, adding diamine monomer, and heating and refluxing for reaction under the stirring condition;
s2, collecting a reaction product, and then washing and drying;
and S3, finally, carrying out heat treatment on the product in an argon atmosphere to obtain the polyimide composite carbon aerogel.
6. The method for preparing the polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 5, wherein the molar ratio of the diamine monomer to the dianhydride monomer to the carbon aerogel added in the step S1 is 1:1, the molar ratio of the dianhydride monomer to the carbon aerogel added is 2:1 to 5.
7. The method for preparing the polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 5, wherein the carbon aerogel in the step S1 is prepared by the following steps:
step 1, mixing resorcinol (R), formaldehyde (F), sodium carbonate (C) and water (W) according to a molar ratio of R/F=1:2, wherein R/C=100-1500 and W/R=4-90, stirring to form a uniform solution, injecting the uniform solution into a cylindrical mold, and standing for 16-24H at normal temperature to obtain sol;
step 2, heating the sol in water bath at 40-60 ℃ for 16-24H, and aging the sol at 60-80 ℃ for 16-24H after the sol is gel to obtain dark red hydrogel;
step 3, soaking the hydrogel sample obtained in the step 2 in an ethanol solvent for 4-6 days, and replacing ethanol every 8H;
step 4, finally, carrying out supercritical drying on the hydrogel obtained in the step 3 to obtain aerogel;
and 5, carbonizing the aerogel under the vacuum condition, controlling the temperature to rise to 800-1000 ℃ at the speed of 2-5 ℃/min, and then preserving the heat for 2H to obtain the carbon aerogel material.
8. The method for preparing the polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 5, wherein the dianhydride monomer in the step S1 is 1,4,5, 8-naphthalene tetramethyl anhydride monomer, benzene tetramethyl anhydride monomer or 3,4,9, 10-perylene tetracarboxylic dianhydride monomer.
9. The method for preparing the polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 5, wherein the drying temperature in the step S2 is 80-120 ℃ and the drying time is 8-12H.
10. The method for preparing the polyimide composite carbon aerogel lithium battery positive electrode slurry according to claim 5, wherein the temperature of the heat treatment in the step S3 is 250-300 ℃ and the time is 6-10H.
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| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
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| CN107732242A (en) * | 2017-08-16 | 2018-02-23 | 深圳市沃特玛电池有限公司 | A kind of preparation method of lithium ion battery anode glue size |
| CN109546137A (en) * | 2018-12-14 | 2019-03-29 | 中南民族大学 | Carbon-based supporting polyimide array and preparation method thereof and stored energy application |
| CN111446448A (en) * | 2020-03-09 | 2020-07-24 | 武汉理工大学 | Preparation method of polyimide/graphene composite lithium ion battery cathode material based on conjugated carbonyl |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
| CN107464934A (en) * | 2016-06-06 | 2017-12-12 | 深圳格林德能源有限公司 | One kind is based on graphene/carbon nano-tube combined conductive agent anode sizing agent preparation method |
| CN107732242A (en) * | 2017-08-16 | 2018-02-23 | 深圳市沃特玛电池有限公司 | A kind of preparation method of lithium ion battery anode glue size |
| CN109546137A (en) * | 2018-12-14 | 2019-03-29 | 中南民族大学 | Carbon-based supporting polyimide array and preparation method thereof and stored energy application |
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