CN118954506B - Preparation method and application of porous carbon with dendritic pore structure - Google Patents
Preparation method and application of porous carbon with dendritic pore structure Download PDFInfo
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- CN118954506B CN118954506B CN202411440619.4A CN202411440619A CN118954506B CN 118954506 B CN118954506 B CN 118954506B CN 202411440619 A CN202411440619 A CN 202411440619A CN 118954506 B CN118954506 B CN 118954506B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 239000011148 porous material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 239000004760 aramid Substances 0.000 claims abstract description 27
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 229920000728 polyester Polymers 0.000 claims abstract description 24
- 125000004193 piperazinyl group Chemical group 0.000 claims abstract description 22
- 239000005011 phenolic resin Substances 0.000 claims abstract description 21
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 18
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 18
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000007833 carbon precursor Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- AGZYNVVJQAOVRP-UHFFFAOYSA-N thiophene-3,4-diamine Chemical compound NC1=CSC=C1N AGZYNVVJQAOVRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- KZBSENMHTIDEHV-UHFFFAOYSA-N 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarbonitrile Chemical compound S1C(C#N)=C(N)C2=C1SC(C#N)=C2N KZBSENMHTIDEHV-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 15
- 239000010703 silicon Substances 0.000 abstract description 15
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 238000009826 distribution Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- -1 uses graphite Chemical compound 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 210000004443 dendritic cell Anatomy 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/027—Negative electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of porous carbon with a dendritic pore structure, which comprises the following steps of (S1) dissolving thermoplastic phenolic resin, a sacrificial agent and a curing agent in a solvent together to form a mixed solution, then performing rotary evaporation and crushing to obtain solid particles, wherein the sacrificial agent is polyester polyurethane, polymethyl methacrylate and aromatic polyamide with a piperazine structure according to a mass ratio of (0.6-0.8) to (1.2-1.5), and (S2) performing gradient heat treatment on the solid particles in an inert atmosphere to obtain a porous carbon precursor, and (S3) performing activation reaming on the porous carbon precursor to obtain the porous carbon with the dendritic pore structure. The porous carbon with the dendritic pore canal structure prepared by the invention has good circulation stability and higher capacitance when being used as a silicon-carbon anode of a lithium battery after being coated by chemically deposited silicon and carbon.
Description
Technical Field
The invention belongs to the technical field of battery cathode materials, and particularly relates to a preparation method and application of porous carbon with a dendritic pore structure.
Background
The domestic lithium battery industry is coming to the rapid development period, and the requirements of new energy automobiles and unmanned aerial vehicles drive the pursuit of high-energy-density batteries. This trend has a key role in promoting the popularization of new energy vehicles, realizing energy structure transformation and replacing fossil fuels with electric energy. The battery industry is improving the battery performance and reducing the cost through technical innovation and large-scale production, thereby meeting the high standard requirement of the market. The negative electrode material is one of important raw materials of the lithium ion battery, and has great influence on the energy density, the cycle performance, the charge-discharge multiplying power and the low-temperature performance of the lithium ion battery.
The existing negative electrode material used by lithium ions mainly uses graphite, the theoretical gram capacity of the graphite negative electrode is 372mAh/g only, the theoretical gram capacity of the silicon-based negative electrode can reach 4200mAh/g, but the expansion rate of the pure silicon-based negative electrode material is 300%, and the silicon is powdered in the charge and discharge process, so that the cycle performance of the pure silicon-based negative electrode material is far lower than that of the graphite negative electrode and is only 300-500 times of cycles. In the prior art, the main effort direction is silicon-carbon composite materials, namely, silicon atoms are deposited into a porous carbon material by using a chemical vapor deposition method in the porous carbon material to form the silicon-carbon composite materials, so that the volume expansion of silicon can be effectively reduced. The carbon material and the high-capacity silicon material are compounded, so that the composite material has high capacity and good conductivity, meanwhile, the carbon layer can reduce direct contact between silicon and electrolyte, inhibit growth of SEI film and improve cycle performance of the material.
For the silicon carbon anode material, the deposition uniformity and deposition amount of silicon nano particles can greatly influence the performance of the anode material, and the pore size distribution uniformity, stability and porosity of the porous carbon material prepared in the traditional active carbon field at present are still to be further improved so as to meet the requirements of a high-standard novel silicon carbon anode material, so that the development and preparation of the porous carbon with a stable structure and high porosity and suitable pore size distribution have great significance.
In the prior art, porous carbon with proper pore size distribution is classified porous carbon, such as Xu Jiankang and the like (carbon, 2018, 1:05-07), cobalt acetate is used as a template, citric acid is used as a carbon source, a rapid temperature-raising and lowering process is adopted, the classified porous carbon is prepared by a one-step template carbonization method, the obtained porous carbon has a typical mesopore-micropore classified pore structure, micropores are concentrated in 0.8 nm, mesopores are concentrated in 4 nm, the specific surface area is 753-890 m 2/g, but the specific surface area of the classified porous carbon is lower, and the porosity is low.
The patent CN 118016879A discloses a graded porous carbon and a preparation method and application thereof, wherein the graded porous carbon is formed by mutually connecting and penetrating macropores, mesopores and micropores to form a three-dimensional interconnected network crosslinked carbon skeleton, and part of carbon in the network crosslinked carbon skeleton is graphitized to form a graphitized carbon network crosslinked skeleton. The pore diameter range of the macropores of the porous carbon prepared by the method is more than 50nm, the pore diameter range of the mesopores is 2-50nm, the pore diameter range of the micropores is less than 2nm, the pore diameter distribution is too wide, the hollows and the macropores are both bigger, and the whole specific surface area is lower.
Disclosure of Invention
In order to achieve the aim of developing porous carbon with stable structure and high porosity and proper pore size distribution, the invention adopts the following technical scheme:
a preparation method of porous carbon with a dendritic pore structure comprises the following steps:
(S1) jointly dissolving thermoplastic phenolic resin, a sacrificial agent and a curing agent in a solvent to form a mixed solution, and then performing rotary evaporation and crushing to obtain solid particles, wherein the sacrificial agent is a compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing a piperazine structure according to the mass ratio of (0.6-0.8) to (1.2-1.5);
(S2) carrying out gradient heat treatment on the solid particles in an inert atmosphere to obtain a porous carbon precursor;
And (S3) activating and reaming the porous carbon precursor to obtain the porous carbon with the dendritic pore structure.
The dendritic cell structure porous carbon provided in the present invention means a porous carbon having a central radial cell structure and having a cell size gradually increasing from the inside of the particle to the surface of the particle. The pore canal structure has good connectivity, when silicon is deposited by chemical vapor deposition, silicon particles can enter the middle inside of the porous carbon, and all adsorption sites are fully utilized, so that the deposition rate of silicon and the dispersion uniformity in the porous carbon can be improved, the stability of the electrode structure is maintained, and the cycle stability of the battery is improved.
In the step (S1), the mass ratio of the thermoplastic phenolic resin to the sacrificial agent to the curing agent is 1 (0.15-0.3), preferably 1 (0.2-0.25), and is 0.03-0.06.
Further, in the step (S1), the sacrificial agent is a compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing piperazine structures according to the mass ratio of (0.7-0.8) to (1.3-1.4).
In the step (S1), the aromatic polyamide containing the piperazine structure is prepared by reacting piperazine with aromatic diacid chloride, wherein the molar ratio of the piperazine to the aromatic diacid chloride is (1.05-1.15): 1, such as 1.1:1. The aromatic binary acyl chloride is at least one of terephthaloyl chloride or isophthaloyl chloride.
Further, the piperazine structure-containing aromatic polyamide is obtained by a preparation method comprising the following steps:
Dissolving anhydrous piperazine and anhydrous carbonate in a solvent to form a solution A, and dissolving dibasic acyl chloride in the solvent to form a solution B;
(L2) mixing the solution B and the solution A, and reacting for 4-8 hours at 3-10 ℃ in an inert atmosphere to obtain a reaction mixture;
(L3) filtering and vacuum drying the reaction mixture to obtain the piperazine-containing aromatic polyamide.
Preferably, in the step (L1), the mass ratio of the anhydrous piperazine to the anhydrous carbonate is 1 (1.5-2), the total concentration of the solution A is 20-30 wt%, and the concentration of the solution B is 10 wt-20 wt%. The dosage of the solution A and the solution B satisfies that the mol ratio of piperazine to aromatic binary acyl chloride is (1.05-1.15): 1.
Preferably, in the step (L1), the anhydrous carbonate is anhydrous K 2CO3 or anhydrous Na 2CO3, and the solvent is at least one of N, N '-Dimethylacetamide (DMAC), N' -Dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
Preferably, in step (L2), the inert atmosphere is at least one of nitrogen or argon.
Preferably, in the step (L3), the vacuum drying is performed at 50-70 ℃ for 12-24 hours.
Further, in the step (S1), the number average molecular weight of the thermoplastic phenolic resin is 1500-5000, the number average molecular weight of the polyester polyurethane is 5000-20000, the number average molecular weight of the polymethyl methacrylate is 5000-15000, and the number average molecular weight of the piperazine-structure-containing aromatic polyamide is 3000-5000.
Further, in the step (S1), the curing agent is at least one of hexamethylenetetramine, trimethylhexamethylenediamine, diethylaminopropylamine, 3, 4-diaminothiophene, 3, 4-diaminothieno [2,3-B ] thiophene-2, 5-dinitrile, and preferably 3, 4-diaminothiophene.
In the step (S1), the solvent is any one of methanol, ethanol and acetone, and the crushing is carried out until the granularity is 100-400 meshes.
Further, in the step (S2), the gradient heat treatment is performed at 150-250 ℃ for 1-3 hours, then at 270-300 ℃ for 2-4 hours, then at 320-400 ℃ for 2-4 hours, and finally at 600-900 ℃ for 1-4 hours.
Further, in the step (S2), the inert atmosphere is nitrogen, argon or helium.
Further, in the step (S3), the activating agent is at least one of water vapor, carbon dioxide, ammonia gas and hydrogen sulfide, and the activating condition is that the temperature is 800-1000 ℃ and the time is 4-8 hours.
In a second aspect, the present invention provides a porous carbon of dendritic pore structure, prepared by the aforementioned preparation method.
In a third aspect, the invention provides a silicon-carbon anode, which is prepared by coating porous carbon with a dendritic pore structure prepared by the preparation method through vapor deposition silicon and carbon. Vapor deposition of silicon and carbon coating processes are well known to those skilled in the art, such as vapor deposition of silicon using a organosilicon source gas selected from at least one of silane, dichlorosilane, trichlorosilane, silicon tetrachloride, silicon tetrafluoride, disilane, and the like, and carbon coating using a carbon source gas selected from at least one of C1-4 alkanes, C2-4 alkenes, C2-4 alkynes.
The mechanism of the invention is described:
The phenolic resin is a heat stable polymer with higher decomposition temperature, the structure of the phenolic resin contains active phenolic hydroxyl and hydroxymethyl, and the carbon residue rate is high, thus the phenolic resin is an ideal carbon forming polymer. The sacrificial agent is a heat-labile polymer, and forms a phase separation structure after being mixed with the phenolic resin, and can be thermally decomposed at a relatively low temperature and released in the form of small molecular gas, so that pores are formed in the mixed system. According to the invention, polyester polyurethane, polymethyl methacrylate and piperazine structure-containing aromatic polyamide are adopted to perform gradient heat treatment with thermoplastic phenolic resin according to the mass ratio of (0.6-0.8) to (1.2-1.5), and the inventor finds that the matching of the polyester polyurethane, polymethyl methacrylate and piperazine structure-containing aromatic polyamide can produce porous carbon with a dendritic pore structure with stable structure. The possible reasons are that the urethane groups on the main chain of the polyester polyurethane are broken from C-O bonds within the temperature range of 150-180 ℃ to generate isocyanate, the isocyanate can be subjected to crosslinking reaction with the thermoplastic phenolic resin within the temperature range to improve the compactness of the isocyanate, the rest groups on the main chain of the polyester polyurethane are decomposed to generate small molecular gases such as CO 2 and olefin and the like to escape from a matrix to leave pores along with the temperature rise to the vicinity of 250 ℃, and the polyester polyurethane can be thermally decomposed to generate more CO 2 relative to the polyether polyurethane, so that the porosity is improved more advantageously. The aromatic polyamide containing piperazine structure has better thermal stability due to the existence of the piperazine structure and the aromatic group, and can decompose at 300-400 ℃ to generate small molecular substances and gas, thereby further generating pores in the matrix. In conclusion, the combined action of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing piperazine structure realizes the graded pore-forming at different temperatures, so as to generate porous carbon with dendritic pore canal structure. Meanwhile, as the decomposition product isocyanate of the polyester polyurethane at 150-180 ℃ and the curing agent can jointly crosslink and cure the thermoplastic phenolic resin, the thermoplastic phenolic resin is formed into a compact crosslinked network structure, and then the porous carbon with a dendritic pore structure with stable structure is formed when the temperature is continuously increased to 600-900 ℃ for carbonization. In addition, the piperazine structure-containing aromatic polyamide has high nitrogen element content, realizes the doping of nitrogen atoms of porous carbon, is beneficial to improving the electrochemical performance and prolonging the cycle life.
Compared with the prior art, the invention has the following beneficial effects:
1. The invention realizes decomposition and pore-forming at different temperatures by taking the compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing piperazine structure as a sacrificial agent and carrying out gradient heat treatment on the thermoplastic phenolic resin, and simultaneously, the decomposed isocyanate of the polyester polyurethane at low temperature and a curing agent can carry out crosslinking curing on the thermoplastic phenolic resin together, so that the porous carbon with a dendritic pore channel structure with stable structure and high porosity is finally prepared, and a foundation is provided for preparing a silicon-carbon anode by further vapor deposition of silicon.
2. The pore size distribution of the porous carbon with the dendritic pore structure is that the pore size distribution of <2nm is 75-85%, the pore size of 2-10nm is 10-20%, the pore size of more than 10nm is Kong Zhanbi and 3-7%, under the condition of the pore size distribution, the pores with the particle size of more than 10nm are taken as a main trunk, the mesopores with the particle size of 2-10nm are taken as branches, and the micropores with the particle size of <2nm are taken as branches, so that the porous carbon with the dendritic pore structure is formed.
3. When the porous carbon with the dendritic pore canal structure prepared by the invention is used as a silicon-carbon negative electrode of a lithium battery after being coated by chemically deposited silicon and carbon, the porous carbon has good cycle stability and higher capacitance, the first reversible specific capacity of the porous carbon reaches over 1900mAh/g, the first efficiency reaches over 90, and the 100-cycle capacity retention rate at 0.1C can reach over 90%.
Drawings
FIG. 1 is a schematic diagram of pore size structure of porous carbon with dendritic pore structure prepared by the invention;
FIG. 2 is a nitrogen adsorption isotherm curve of the dendritic porous carbon prepared in example 1;
FIG. 3 is a graph showing pore size distribution of the dendritic porous carbon prepared in example 1;
FIG. 4 is a plot of pore size fractions for the dendritic porous carbon prepared in example 1;
fig. 5 is a first charge-discharge curve of a lithium battery assembled from the silicon-carbon negative electrode material of application example 1 at a 0.1C rate.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The experimental methods described in the examples below, unless otherwise indicated, are conventional, and the reagents and materials, unless otherwise indicated, are commercially available.
Thermoplastic phenolic resin, polyester polyurethane and polymethyl methacrylate are all purchased from Ala, wherein the number average molecular weight of the thermoplastic phenolic resin is 3000, the number average molecular weight of the polyester polyurethane is 12000, and the number average molecular weight of the polymethyl propionate is 10000.
Preparation of piperazine structure-containing aromatic polyamide
Preparation example 1
(L1) 94.75g (1.1 mol) of anhydrous piperazine, 150g of anhydrous Na 2CO3, and 700g of N, N' -Dimethylacetamide (DMAC) were dissolved to form a solution A, and 203.02g (1 mol) of terephthaloyl chloride was dissolved in 900g of DMAC to form a solution B;
Slowly dropwise adding the solution B into the mixed solution A within 1-2 h, and stirring and reacting for 6h at 5+/-1 ℃ under the protection of nitrogen to obtain a reaction suspension;
(L3) filtering the reaction suspension, and vacuum drying at 60 ℃ for 12 hours to obtain the piperazine-containing aromatic polyamide.
The number average molecular weight was approximately 4300 as determined by gel permeation chromatography.
Example 1
(S1) 10kg of thermoplastic phenolic resin, 1.5kg of sacrificial agent and 0.3kg of curing agent hexamethylenetetramine are dissolved in acetone together to form a mixed solution, and then the mixed solution is subjected to rotary evaporation and crushing to 200 meshes to obtain solid particles, wherein the sacrificial agent is a compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing a piperazine structure according to a mass ratio of 1:0.6:1.2;
(S2) placing solid particles into an activation furnace, heating to 170 ℃ at a heating rate of 5 ℃ per min in a nitrogen atmosphere, preserving heat for 2 hours, heating to 280 ℃ and preserving heat for 2 hours, heating to 350 ℃ and preserving heat for 2 hours, and heating to 800 ℃ and preserving heat for 3 hours to obtain a porous carbon precursor;
(S3) closing nitrogen, uniformly introducing 1.4kg of water vapor in 6h, and switching to the nitrogen atmosphere after the water vapor ventilation is finished, so that the temperature of the porous carbon is reduced to room temperature, thereby obtaining the porous carbon with the dendritic pore structure.
Fig. 1 is a schematic diagram of pore size structure of porous carbon with dendritic pore structure prepared by the invention.
Example 2
The rest is the same as in example 1, except that in step (S1), the sacrificial agent is a compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing piperazine structure according to a mass ratio of 1:0.7:1.3.
Example 3
The rest is the same as in example 1, except that in step (S1), the sacrificial agent is a compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing piperazine structure according to a mass ratio of 1:0.8:1.4.
Example 4
The rest is the same as in example 1, except that in step (S1), the sacrificial agent is a compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing piperazine structure according to a mass ratio of 1:0.8:1.5.
Example 5
The remainder was the same as in example 2 except that in step (S1), the amount of the sacrificial agent was 2kg, and 0.4kg of 3, 4-diaminothiophene was used instead of 0.03g of hexamethylenetetramine.
Example 6
The remainder was the same as in example 5 except that in step (S1), the amount of the sacrificial agent was 2.5kg and the amount of the curing agent 3, 4-diaminothiophene was 0.5kg.
Example 7
The remainder was the same as in example 5 except that in step (S1), the amount of the sacrificial agent was 3kg, and the amount of the curing agent 3, 4-diaminothiophene was 0.6kg.
Comparative example 1
The rest is the same as in example 1, except that in step (S1), the sacrificial agent is a compound of polymethyl methacrylate and aromatic polyamide containing piperazine structure according to a mass ratio of 1:2, i.e. the sacrificial agent does not contain polyester polyurethane.
Comparative example 2
The other components are the same as in example 1 except that in the step (S1), the sacrificial agent is a compound of polyester polyurethane and polymethyl methacrylate 1:0.6, namely, the sacrificial agent does not contain piperazine aromatic polyamide.
Comparative example 3
The rest is the same as in example 1, except that in step (S2), the temperature is raised to 800 ℃ at a temperature raising rate of 5 ℃ per minute for 3 hours, i.e., one-step heat treatment is adopted without gradient heat treatment.
Application example 1
The porous carbon with the dendritic pore canal structure prepared in the embodiment 1 is subjected to chemical vapor deposition and carbon coating to form a silicon-carbon negative electrode material, and then the silicon-carbon negative electrode material is applied to a negative electrode of a lithium ion battery to be assembled into the lithium battery, and the electrochemical performance of the lithium battery is tested. The preparation method comprises the steps of mixing a silicon-carbon negative electrode material, super P, a carbon nano tube, carboxymethyl cellulose and a styrene-butadiene rubber composite binder according to a mass ratio of 80:9.8:0.2:10 to prepare slurry (CMC and SBR are 1:1), coating the slurry on a copper foil by using a 200 mu m thick scraper, drying in the air, placing the copper foil in vacuum for drying 12h to prepare a silicon-based negative electrode plate, then taking metallic lithium as a counter electrode, polyolefin as a diaphragm, taking 1mol/L LiPF6 (a mixed solution of ethylene carbonate and dimethyl carbonate with a volume ratio of 1:1) as an electrolyte, adding VC with a volume fraction of 2% and FEC with a volume fraction of 5% into the electrolyte, and assembling the copper foil battery in a German Braun inert gas glove box in an argon atmosphere. And (3) carrying out charge and discharge tests on the assembled battery on a LAND charge and discharge tester, wherein the charge and discharge interval is 50 mV-1.5V, the compaction density is 1.1 g/cm 3, and after three times of charge and discharge under the current density of 0.1C (1C =1500 mA/g), the multiplying power charge and discharge tests are respectively carried out under the current densities of 1C and 5C.
Application examples 2 to 7
Other conditions were the same as in application example 1, except that dendritic porous carbon was prepared in examples 2 to 7, respectively.
Comparative application examples 1 to 3
Other conditions were the same as in application example 1, except that dendritic porous carbons were prepared in comparative examples 1 to 3, respectively.
Testing and analysis
1) Pore size distribution measurement according to GB/T19587-2017 gas adsorption BET method, TRISTAR II 3020 type full-automatic specific area and pore size analyzer manufactured by U.S. Micromeritics Instrument Corporation are adopted to conduct low-temperature nitrogen adsorption experiments on the dendritic porous carbon prepared in examples and comparative examples, and pore size distribution is measured. The data are shown in table 1.
The nitrogen adsorption isothermal curve of the dendritic porous carbon prepared in example 1 is shown in fig. 2, the pore size distribution diagram is shown in fig. 3, and the pore size ratio distribution diagram is shown in fig. 4.
TABLE 1 pore size distribution of dendritic porous carbon
。
As can be seen from Table 1, compared with the comparative example, the specific surface area of the porous carbon prepared by the preparation method of the invention is as high as 1800-m 2/g, the pore size distribution range is that the micropore ratio of <2nm is 75-85%, the pore size of the intermediate Kong Zhanbi of 2-10nm is 10-20%, the pore size of the intermediate Kong Zhanbi of 10nm is 3-7%, under the condition of the ratio, the pores of 10nm are taken as trunks, the mesopores of 2-10nm are taken as branches, and the micropores of <2nm are taken as branches, so that the porous carbon with the dendritic pore channel structure is formed.
In comparative example 1, although the pore ratio of <2nm was relatively high, the pore ratio of 10nm or more was too low to form a dendritic pore structure, and the overall specific surface area was low, indicating that the overall porosity was low.
In comparative example 2, the microporosity of <2nm was low, and the overall specific surface area was low.
In comparative example 3, although the specific surface area is higher, the pores with the diameter of more than 10nm occupy more pores, and the pore diameters of 2-10nm occupy less pores, so that a dendritic pore structure is difficult to form, and the porous carbon with the dendritic pore structure with the high specific surface area can be prepared only by the matched gradient heat treatment of the compounded sacrificial agent.
2) Electrochemical performance test the batteries assembled in the application example and the comparative example were subjected to charge and discharge tests on a LAND charge and discharge tester, the electric interval was 50 mV-1.5V, the compaction density was 1.1 g/cm 3, and the charge and discharge tests were performed three times at a current density of 0.1C (1C =1500 mA/g). The battery performance test data are shown in table 2.
Fig. 5 is a first charge-discharge curve of a lithium battery assembled from the silicon-carbon negative electrode material of application example 1 at a 0.1C rate.
Table 2 electrochemical performance test
。
As can be seen from the data in table 2, when the dendritic porous carbon prepared by the preparation method provided by the invention is used as a negative electrode of a lithium battery, the first reversible capacity of the dendritic porous carbon is above 1900 mAh/g, the first coulomb efficiency is above 90%, and the 100-cycle capacity retention rate at 0.1C is above 90%, which indicates that the assembled lithium battery has good cycle stability and higher capacitance.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (9)
1. The preparation method of the porous carbon with the dendritic pore canal structure is characterized by comprising the following steps of:
(S1) jointly dissolving thermoplastic phenolic resin, a sacrificial agent and a curing agent in a solvent to form a mixed solution, and then performing rotary evaporation and crushing to obtain solid particles, wherein the sacrificial agent is a compound of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing a piperazine structure according to the mass ratio of (0.6-0.8) to (1.2-1.5);
(S2) carrying out gradient heat treatment on the solid particles in an inert atmosphere to obtain a porous carbon precursor;
And (S3) activating and reaming the porous carbon precursor to obtain the porous carbon with the dendritic pore structure.
2. The preparation method of claim 1, wherein in the step (S1), the mass ratio of the thermoplastic phenolic resin to the sacrificial agent to the curing agent is 1 (0.15-0.3): 0.03-0.06.
3. The preparation method according to claim 1 or 2, wherein in the step (S1), the mass ratio of the thermoplastic phenolic resin, the sacrificial agent and the curing agent is 1 (0.2-0.25): 0.03-0.06.
4. The preparation method of the anti-aging agent for the automobile is characterized in that in the step (S1), the sacrificial agent is compounded of polyester polyurethane, polymethyl methacrylate and aromatic polyamide containing a piperazine structure according to the mass ratio of 1 (0.7-0.8) to 1.3-1.4.
5. The method of claim 1, wherein in the step (S1), the aromatic polyamide containing the piperazine structure is prepared by reacting piperazine with aromatic diacid chloride, the molar ratio of the piperazine to the aromatic diacid chloride is (1.05-1.15): 1, and the aromatic diacid chloride is at least one of terephthaloyl chloride or isophthaloyl chloride.
6. The preparation method according to claim 1, wherein the piperazine-containing aromatic polyamide is obtained by a preparation method comprising the steps of:
Dissolving anhydrous piperazine and anhydrous carbonate in a solvent to form a solution A, and dissolving dibasic acyl chloride in the solvent to form a solution B;
(L2) mixing the solution B and the solution A, and reacting for 4-8 hours at 3-10 ℃ in an inert atmosphere to obtain a reaction mixture;
(L3) filtering and vacuum drying the reaction mixture to obtain the piperazine-containing aromatic polyamide.
7. The method according to claim 6, wherein in the step (L1), the mass ratio of the anhydrous piperazine to the anhydrous carbonate is 1 (1.5-2), the total concentration of the solution A is 20-30 wt%, the concentration of the solution B is 10-20 wt%, the amounts of the solution A and the solution B are such that the molar ratio of the piperazine to the aromatic diacid chloride is 1.05-1.15:1, and/or
In the step (L1), the anhydrous carbonate is anhydrous K 2CO3 or anhydrous Na 2CO3, the solvent is at least one of N, N '-Dimethylacetamide (DMAC), N' -Dimethylformamide (DMF), N-methylpyrrolidone (NMP), and/or
In the step (L2), the inert atmosphere is at least one of nitrogen or argon, and/or
In the step (L3), the vacuum drying is performed for 12-24 hours at 50-70 ℃.
8. The method according to claim 1, wherein in the step (S1), the thermoplastic phenol resin has a number average molecular weight of 1500 to 5000, the polyester polyurethane has a number average molecular weight of 5000 to 20000, the polymethyl methacrylate has a number average molecular weight of 5000 to 15000, the aromatic polyamide having a piperazine structure has a number average molecular weight of 3000 to 5000, and/or
In the step (S1), the curing agent is at least one of hexamethylenetetramine, trimethylhexamethylenediamine, diethylaminopropylamine, 3, 4-diaminothiophene and 3, 4-diaminothieno [2,3-B ] thiophene-2, 5-dinitrile, the solvent is any one of methanol, ethanol and acetone, and the crushing is carried out until the granularity is 100-400 meshes.
9. The method according to claim 1, wherein in the step (S2), the gradient heat treatment is performed by heat treatment at 150 to 250 ℃ for 1 to 3 hours, heat treatment at 270 to 300 ℃ for 2 to 4 hours, heat treatment at 320 to 400 ℃ for 2 to 4 hours, and heat treatment at 600 to 900 ℃ for 1 to 4 hours, and/or
In the step (S3), the agent for activating and reaming is at least one of water vapor, carbon dioxide, ammonia gas and hydrogen sulfide, and the activating condition is that the temperature is 800-1000 ℃ and the time is 4-8 hours.
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