CN117317223B - Preparation method and application of active porous carbon - Google Patents
Preparation method and application of active porous carbon Download PDFInfo
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- CN117317223B CN117317223B CN202311596802.9A CN202311596802A CN117317223B CN 117317223 B CN117317223 B CN 117317223B CN 202311596802 A CN202311596802 A CN 202311596802A CN 117317223 B CN117317223 B CN 117317223B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 64
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 64
- 239000000661 sodium alginate Substances 0.000 claims abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 aldehyde sodium alginate Chemical class 0.000 claims abstract description 28
- 150000003983 crown ethers Chemical group 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 239000003575 carbonaceous material Substances 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003763 carbonization Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CHBDXRNMDNRJJC-UHFFFAOYSA-N 1,2,3-triphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CHBDXRNMDNRJJC-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
-
- 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 relates to the technical field of carbon materials, and discloses a preparation method and application of active porous carbon, wherein dibenzo-18-crown-6, 1,3, 5-tri (4-aminophenyl) benzene and aldehyde sodium alginate are used for cross-linking polymerization to form cross-linked porous sodium alginate with a three-dimensional porous network structure, and the cross-linked porous sodium alginate is carbonized at high temperature to form porous carbon with larger specific surface area and total pore volume. The nickel ions are coordinated and complexed by using crown ether structure in crown ether-containing crosslinked porous sodium alginate, and then reduced by sodium borohydride, so that nickel nano particles are uniformly loaded into a porous carbon matrix, active porous carbon coated with nano nickel is used as an active material of a lithium ion battery negative electrode, agglomeration of the nickel nano particles in the porous carbon is effectively overcome, and the negative electrode material has the advantages of large charge-discharge specific capacity, high coulomb efficiency, good cycle reversibility and high capacity retention rate.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a preparation method and application of active porous carbon.
Background
Sodium alginate is a polysaccharide compound which is widely used in brown algae plants, has rich reserves, has the advantages of environmental protection, no toxicity, no pollution and the like, is widely applied in the fields of food industry, medicine and the like, and is a research hot spot for the practical development and application of the sodium alginate. Patent publication No. CN109637829B discloses a method for preparing nitrogen-doped porous carbon by crosslinking sodium alginate and diamine compound, and super capacitor prepared by using the method as electrode material shows good electrochemical performance; however, the electrochemical performance of the electrode material is poor by simply using porous carbon, and the porous carbon and the transition metal substance are combined to exert the synergistic effect of the porous carbon and the transition metal substance, so that the high-performance new energy electrode material is obtained.
Although the lithium ion battery has the advantages of high energy density, long cycle life, small environmental pollution and the like, the commercial negative electrode material is a graphite carbon material, and has the problems of lower theoretical specific capacity and the like, so that the development of the high-performance negative electrode material applied to the lithium ion battery is urgent. The transition metals such as nickel and the like have high theoretical specific capacity, the reserves of nickel element are very rich, and the method has wide application prospect in lithium ion batteries. The nano nickel particles are combined with porous carbon, so that the method is an effective strategy for preparing the high-performance lithium ion battery anode active material, and sodium alginate has good char formation, so that the sodium alginate can be used as a precursor of the porous carbon material.
Disclosure of Invention
The invention solves the technical problems that: the active porous carbon coated with nano nickel is prepared, and has excellent specific charge and discharge capacity, cycle reversibility and capacity retention rate when being used as a negative electrode material of a lithium ion battery.
A method for preparing active porous carbon, comprising the following steps:
step (1): adding crown ether crosslinked porous sodium alginate into nickel chloride aqueous solution, performing ultrasonic vibration absorption, adding sodium borohydride, reacting for 1-3h, filtering, washing with distilled water, and drying to obtain crosslinked porous sodium alginate coated nano nickel;
step (2): and (3) putting the crosslinked porous sodium alginate coated nano nickel into a tube furnace, introducing argon, heating to 700-850 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-2h, and cooling to obtain the active porous carbon coated with nano nickel.
Further, the ultrasonic vibration adsorption process in the step (1) is that ultrasonic vibration is firstly carried out for 10-30min at the temperature of 20-40 ℃, and then stirring and adsorption are carried out for 4-8h.
Further, the ratio of crown ether crosslinked porous sodium alginate to nickel chloride aqueous solution in the step (1) is (1-15) g:1L.
Further, the mass fraction of nickel chloride in the nickel chloride aqueous solution is 0.2-2%.
Further, the preparation method of the crown ether crosslinked porous sodium alginate comprises the following steps: dispersing aldehyde sodium alginate into dimethyl sulfoxide, and adding into a solution with structural formula ofDibenzo-18-crown-6 of the formula +.>Reacting 1,3, 5-tri (4-aminophenyl) benzene at 60-80 ℃ for 6-18h, cooling, filtering, washing filter cake with ethanol, drying to obtain crown ether crosslinked porous seaSodium alginate;
further, the ratio of the aldehyde sodium alginate, dimethyl sulfoxide and dibenzoyl dibenzo-18-crown-6, 1,3, 5-tris (4-aminophenyl) benzene is 1g: (50-100) mL: (0.05-0.2) g: (0.12-0.5) g.
Further, the preparation method of the dibenzoyl dibenzo-18-crown-6 comprises the following steps: adding dibromodibenzo-18-crown-6, 4-aldehyde phenylboronic acid, tetraphenylphosphine palladium and potassium carbonate aqueous solution into tetrahydrofuran, introducing nitrogen, refluxing at 65-75 ℃ for 12-24h, cooling, distilling under reduced pressure, washing with water and diethyl ether in sequence, and drying to obtain the dibenzo-18-crown-6.
Further, the ratio of the aqueous solution of tetrahydrofuran, dibromodibenzo-18-crown-6, 4-aldehyde phenylboronic acid, tetraphenylphosphine palladium and potassium carbonate is (50-80) mL:1g: (0.5-0.7) g: (0.38-0.45) g: (7-12) mL.
Further, the mass fraction of the potassium carbonate in the aqueous potassium carbonate solution is 20-30%.
The active porous carbon obtained by the preparation method is applied to the negative electrode of the lithium ion battery.
The beneficial effects are that: the invention uses dibenzo-18-crown-6, 1,3, 5-tri (4-aminophenyl) benzene and aldehyde sodium alginate to carry out cross-linking polymerization to form cross-linked porous sodium alginate with a three-dimensional porous network structure, and porous carbon is formed by high-temperature carbonization, and the specific surface area and the total pore volume are larger. And the crosslinked porous sodium alginate skeleton contains a rigid high-carbon triphenylbenzene structure, so that the carbon forming performance and the mass residual rate of the sodium alginate can be improved, and the sodium alginate forms porous carbon with stable mechanical structure through high-temperature carbonization.
According to the invention, the crown ether structure in the crown ether-containing crosslinked porous sodium alginate is utilized to carry out coordination complexing on nickel ions, and then sodium borohydride is used for reduction, so that nickel nano particles are uniformly loaded into a porous carbon matrix, active porous carbon coated with nano nickel is used as an active material of a lithium ion battery cathode, the agglomeration of the nickel nano particles in the porous carbon is effectively overcome, and higher charge-discharge specific capacity can be expressed; and the carbon matrix with high specific surface area and high pore volume provides a transmission path for lithium ions and charges in the charge and discharge process of the lithium ion battery, and meanwhile, nickel nano particles are coated by the porous carbon layer, so that the volume expansion phenomenon is relieved, and the negative electrode material has the advantages of large charge and discharge specific capacity, high coulomb efficiency, good cycle reversibility and high capacity retention rate.
Drawings
Fig. 1 is a transmission electron microscope image of active porous carbon coated with nano nickel.
Fig. 2 is a first charge-discharge graph of various embodiments.
Fig. 3 is a first charge-discharge graph of each comparative example.
FIG. 4 is a cyclic voltammogram of example 2.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The preparation method of the aldehyde sodium alginate comprises the following steps: dispersing 5g of sodium alginate into 30mL of ethanol, adding 30mL of aqueous solution containing 2.2g of sodium periodate, stirring in a dark place for reaction for 2h, adding ethylene glycol for stopping the reaction, pouring the solution into the ethanol to separate out precipitate, filtering, and washing a filter cake with the ethanol to obtain aldehyde sodium alginate.
Example 1: adding 2g of dibromodibenzo-18-crown-6, 1.2g of 4-aldehyde phenylboronic acid, 0.82g of tetraphenylphosphine palladium and 18mL of 25% potassium carbonate aqueous solution into 120mL of tetrahydrofuran, introducing nitrogen, refluxing at 65 ℃ for 24 hours, cooling, distilling under reduced pressure, washing with water and diethyl ether in sequence, and drying to obtain dibenzo-18-crown-6;
dispersing 3g of aldehyde sodium alginate into 150mL of dimethyl sulfoxide, adding 0.15g of dibenzoyl dibenzo-18-crown-6 and 0.36g of 1,3, 5-tris (4-aminophenyl) benzene, reacting for 6 hours at the temperature of 70 ℃, cooling, filtering, washing a filter cake by ethanol, and drying to obtain crown ether crosslinked porous sodium alginate;
adding 1g of crown ether crosslinked porous sodium alginate into 1L of nickel chloride aqueous solution with the mass fraction of 0.2%, firstly carrying out ultrasonic oscillation at the temperature of 20 ℃ for 30min, then stirring and adsorbing for 4h, then adding 0.85g of sodium borohydride, reacting for 1h, filtering, washing with distilled water, and drying to obtain crosslinked porous sodium alginate coated nano nickel;
and (3) putting the crosslinked porous sodium alginate coated nano nickel into a tube furnace, introducing argon, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to obtain the active porous carbon coated with nano nickel.
The transmission electron microscope image of the active porous carbon coated with nano nickel in fig. 1 shows that the active porous carbon has a large number of pore structures and a higher specific surface area.
Example 2: adding 2g of dibromodibenzo-18-crown-6, 1.4g of 4-aldehyde phenylboronic acid, 0.9g of tetraphenylphosphine palladium and 24mL of 20% mass fraction potassium carbonate aqueous solution into 160mL of tetrahydrofuran, introducing nitrogen, refluxing at 65 ℃ for 18h, cooling, distilling under reduced pressure, washing with water and diethyl ether in sequence, and drying to obtain dibenzo-18-crown-6;
3g of aldehyde sodium alginate is dispersed into 200mL of dimethyl sulfoxide, then 0.38g of dibenzoyl dibenzo-18-crown-6 and 0.92g of 1,3, 5-tris (4-aminophenyl) benzene are added for reaction for 18 hours at the temperature of 60 ℃, and after cooling, filtration, ethanol washing of filter cakes and drying are carried out, thus obtaining crown ether crosslinked porous sodium alginate;
adding 8g of crown ether crosslinked porous sodium alginate into 1L of nickel chloride aqueous solution with the mass fraction of 1%, carrying out ultrasonic oscillation at the temperature of 30 ℃ for 30min, stirring and adsorbing for 4h, adding 4.5g of sodium borohydride, reacting for 2h, filtering, washing with distilled water, and drying to obtain crosslinked porous sodium alginate coated nano nickel;
and (3) putting the crosslinked porous sodium alginate coated nano nickel into a tube furnace, introducing argon, heating to 800 ℃ at a heating rate of 10 ℃/min, preserving heat for 2 hours, and cooling to obtain the active porous carbon coated with nano nickel.
Example 3: adding 2g of dibromodibenzo-18-crown-6, 1g of 4-aldehyde phenylboronic acid, 0.76g of tetraphenylphosphine palladium and 14mL of 30% potassium carbonate aqueous solution into 100mL of tetrahydrofuran, introducing nitrogen, refluxing at 65 ℃ for 24 hours, cooling, distilling under reduced pressure, washing with water and diethyl ether in sequence, and drying to obtain dibenzo-18-crown-6;
3g of aldehyde sodium alginate is dispersed into 300mL of dimethyl sulfoxide, then 0.6g of dibenzoyl dibenzo-18-crown-6 and 1.5g of 1,3, 5-tris (4-aminophenyl) benzene are added for reaction for 6 hours at the temperature of 80 ℃, and after cooling, filtration, ethanol washing of filter cakes and drying are carried out, thus obtaining crown ether crosslinked porous sodium alginate;
adding 15g of crown ether crosslinked porous sodium alginate into 1L of nickel chloride aqueous solution with mass fraction of 2%, firstly carrying out ultrasonic oscillation at 40 ℃ for 10min, then stirring and adsorbing for 8h, then adding 9.8g of sodium borohydride, reacting for 3h, filtering, washing with distilled water, and drying to obtain crosslinked porous sodium alginate coated nano nickel;
and (3) putting the crosslinked porous sodium alginate coated nano nickel into a tube furnace, introducing argon, heating to 850 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and cooling to obtain the active porous carbon coated with nano nickel.
Comparative example 1: is aldehyde sodium alginate.
Carbon residue and specific surface area test: and (3) respectively placing the crown ether crosslinked porous sodium alginate and the aldehyde sodium alginate with certain mass into a tube furnace, introducing argon, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, cooling to obtain a carbon material, and weighing.
And calculating the mass residual rate W. W=m/m 0 ×100%。
Degassing the carbon material at 100 ℃ for 18 hours, and then testing the specific surface area of the carbon material by adopting a full-automatic specific surface area and micropore physical adsorption analyzer, wherein nitrogen is used as an adsorbate, and the testing temperature is 77K.
Table 1 mass remaining ratio and specific surface area test results of the carbon materials in examples 1 to 3 and comparative example 1
Examples 1 to 3 crosslinked porous sodium alginate with three-dimensional porous network structure formed by cross-linking polymerization of dibenzoyl dibenzo-18-crown-6, 1,3, 5-tris (4-aminophenyl) benzene and aldehyde sodium alginate, and porous carbon formed by high temperature carbonization, and larger specific surface area and total pore volume. And the crosslinked porous sodium alginate skeleton contains a rigid triphenylbenzene structure with high carbon content) The carbon forming performance and the mass residual rate of the sodium alginate can be improved, and the sodium alginate forms porous carbon with stable mechanical structure through high-temperature carbonization.
The comparative example 1 is aldehyde sodium alginate, has no cross-linked structure of a three-dimensional porous network, has very low specific surface area and total pore volume of the carbonized carbon material, has poor carbonizing performance and very low mass residual rate, and is unfavorable for carbonization to form porous carbon with stable mechanical structure.
Comparative example 2: dispersing 3g of aldehyde sodium alginate into 150mL of dimethyl sulfoxide, adding 0.36g of 1,3, 5-tris (4-aminophenyl) benzene, reacting for 6 hours at 70 ℃, cooling, filtering, washing a filter cake with ethanol, and drying to obtain crosslinked sodium alginate;
adding 1g of crosslinked sodium alginate into 1L of nickel chloride aqueous solution with the mass fraction of 0.2%, carrying out ultrasonic oscillation at the temperature of 20 ℃ for 30min, stirring and adsorbing for 4h, adding 0.85g of sodium borohydride, reacting for 1h, filtering, washing with distilled water, and drying to obtain crosslinked sodium alginate coated nano nickel;
and (3) putting the crosslinked sodium alginate coated nano nickel into a tube furnace, introducing argon, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to obtain the active porous carbon coated with nano nickel.
Comparative example 3: crown ether crosslinked porous sodium alginate was prepared as in example 1;
and (3) putting the crown ether crosslinked porous sodium alginate into a tube furnace, introducing argon, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to obtain the active porous carbon.
The nano-nickel coated activated porous carbon prepared in examples 1 to 3, the nano-nickel coated activated porous carbon prepared in comparative example 2, and the activated porous carbon prepared in comparative example 3 were mixed with conductive carbon black and polyvinylidene fluoride according to 8:1:1 into N-methyl pyrrolidone, then coating the mixture on the surface of an aluminum foil, drying, cutting the mixture into a wafer under a sheet punching machine to serve as a negative electrode of a lithium ion battery, taking a metal lithium sheet as a counter electrode, taking a polypropylene porous membrane as a diaphragm, and 1mol/L LiPF 6 The solution of + ethylene carbonate + diethyl carbonate + dimethyl carbonate was used as an electrolyte, and a coin cell was assembled in an argon-protected glove box. And a charge and discharge tester is adopted to carry out charge and discharge test, and the voltage range is 0.2-3.0V. The cyclic voltammogram test was performed using an electrochemical workstation at a scan rate of 0.1mV/s.
The initial charge/discharge curve of FIG. 2 shows that the initial specific discharge/charge capacity of example 1 is (956.1 mAg/h)/(1072.2 mAg/h) and the coulomb efficiency is 89.2% at a current density of 0.1A/g.
The initial specific discharge/charge capacity of example 2 was (1091.4 mAg/h)/(1186.9 mAg/h), and the coulombic efficiency was 92.0%.
The initial specific discharge/charge capacity of example 3 was (1141.5 mAg/h)/(1291.0 mAg/h), and the coulombic efficiency was 88.4%.
Examples 1 to 3 crosslinked porous sodium alginate with three-dimensional porous network structure formed by cross-linking polymerization of dibenzoyl dibenzo-18-crown-6, 1,3, 5-tris (4-aminophenyl) benzene and aldehyde sodium alginate, and porous carbon formed by high temperature carbonization, and larger specific surface area and total pore volume. The nickel ions are subjected to coordination complexing by utilizing a crown ether structure in crown ether-containing crosslinked porous sodium alginate, and then the nickel nanoparticles are reduced by sodium borohydride, so that the nickel nanoparticles are uniformly loaded into a porous carbon matrix, active porous carbon coated with nano nickel is used as an active material of a lithium ion battery negative electrode, the agglomeration of the nickel nanoparticles in the porous carbon is effectively overcome, the higher charge-discharge specific capacity is further shown, the carbon matrix with high specific surface area and high pore volume provides a transmission path for lithium ions and charges in the charge-discharge process of the lithium ion battery, and meanwhile, the nickel nanoparticles are coated by a porous carbon layer, so that the volume expansion phenomenon is relieved, and the negative electrode material has higher charge-discharge specific capacity and excellent coulomb efficiency.
The first charge/discharge plot of FIG. 3 shows that comparative example 2 has an initial specific discharge/charge capacity of (528.4 mAg/h)/(819.5 mAg/h) and a coulombic efficiency of only 64.5%. The cross-linked sodium alginate prepared in comparative example 2 does not contain crown ether groups, has lower complexing performance and loading capacity on nickel ions, cannot uniformly load nickel ions and nano nickel particles generated by reduction into a porous carbon matrix, and has lower initial discharge/charge specific capacity and poorer coulombic efficiency as an active material of a lithium ion battery anode.
The initial specific discharge/charge capacity of comparative example 3 was (325.2 mAg/h)/(461.9 mAg/h), and the coulombic efficiency was only 70.4%. Comparative example 3 did not complex nickel ions, and the final active porous carbon did not contain nickel nanoparticles, and was the active material for the negative electrode of a lithium ion battery, which had the lowest initial discharge/charge specific capacity and the worst coulombic efficiency.
The cyclic voltammogram of fig. 4 shows that the cyclic voltammogram of the 2 nd cycle and the 3 rd cycle of the active porous carbon coated with nano nickel prepared in example 2 is almost coincident with each other, which indicates that the negative electrode material has good cycle reversibility and maintains a higher capacity retention rate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A method for preparing active porous carbon, which is characterized by comprising the following steps:
step (1): adding crown ether crosslinked porous sodium alginate into nickel chloride aqueous solution, performing ultrasonic vibration absorption, adding sodium borohydride, reacting for 1-3h, filtering, washing with distilled water, and drying to obtain crosslinked porous sodium alginate coated nano nickel;
step (2): putting the crosslinked porous sodium alginate coated nano nickel into a tube furnace, introducing argon, heating to 700-850 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-2h, and cooling to obtain active porous carbon coated with nano nickel;
the preparation method of the crown ether crosslinked porous sodium alginate comprises the following steps: dispersing aldehyde sodium alginate into dimethyl sulfoxide, and adding dibenzoyl dibenzo-18-crown-6, 1,3, 5-tri (4-aminophenyl) benzene, wherein the proportion of aldehyde sodium alginate, dimethyl sulfoxide and dibenzo-18-crown-6, 1,3, 5-tri (4-aminophenyl) benzene is 1g:50-100mL:0.05-0.2g: reacting at 60-80 ℃ for 6-18h at 0.12-0.5g, cooling, filtering, washing filter cake with ethanol, and drying to obtain crown ether crosslinked porous sodium alginate.
2. The method for preparing activated porous carbon according to claim 1, wherein the ultrasonic vibration adsorption in the step (1) is carried out by ultrasonic vibration for 10-30min at 20-40 ℃ and then stirring for adsorption for 4-8h.
3. The method for preparing activated porous carbon according to claim 1, wherein the ratio of crown ether cross-linked porous sodium alginate to nickel chloride aqueous solution in step (1) is 1-15g:1L.
4. The method for producing an activated porous carbon according to claim 1, wherein the mass fraction of nickel chloride in the nickel chloride aqueous solution is 0.2-2%.
5. The method for preparing activated porous carbon according to claim 1, wherein the method for preparing dibenzoyl-18-crown-6 comprises the steps of: adding dibromodibenzo-18-crown-6, 4-aldehyde phenylboronic acid, tetraphenylphosphine palladium and potassium carbonate aqueous solution into tetrahydrofuran, introducing nitrogen, refluxing at 65-75 ℃ for 12-24h, cooling, distilling under reduced pressure, washing with water and diethyl ether in sequence, and drying to obtain the dibenzo-18-crown-6.
6. The method for preparing activated porous carbon according to claim 5, wherein the ratio of tetrahydrofuran, dibromodibenzo-18-crown-6, 4-aldehyde phenylboronic acid, tetraphenylphosphine palladium, potassium carbonate aqueous solution is 50-80mL:1g:0.5-0.7g:0.38-0.45g:7-12mL.
7. The method for producing an activated porous carbon according to claim 5, wherein the mass fraction of potassium carbonate in the aqueous potassium carbonate solution is 20 to 30%.
8. Use of the activated porous carbon obtained by the preparation method according to any one of claims 1 to 7 in a negative electrode of a lithium ion battery.
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| CN104347856A (en) * | 2014-10-14 | 2015-02-11 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN105609704A (en) * | 2013-09-30 | 2016-05-25 | 通用汽车环球科技运作有限责任公司 | Lithium ion battery electrodes |
| CN105944758A (en) * | 2016-06-03 | 2016-09-21 | 河北大学 | Novel nickel/sodium alginate inorganic/organic hybrid material and preparation method and application thereof |
| WO2023134234A1 (en) * | 2022-01-13 | 2023-07-20 | 株式会社村田制作所 | Positive electrode composite material, preparation method therefor, positive electrode, and lithium ion secondary battery |
| CN116885121A (en) * | 2023-06-30 | 2023-10-13 | 中北大学 | Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof |
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| CN105609704A (en) * | 2013-09-30 | 2016-05-25 | 通用汽车环球科技运作有限责任公司 | Lithium ion battery electrodes |
| CN104347856A (en) * | 2014-10-14 | 2015-02-11 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN105944758A (en) * | 2016-06-03 | 2016-09-21 | 河北大学 | Novel nickel/sodium alginate inorganic/organic hybrid material and preparation method and application thereof |
| WO2023134234A1 (en) * | 2022-01-13 | 2023-07-20 | 株式会社村田制作所 | Positive electrode composite material, preparation method therefor, positive electrode, and lithium ion secondary battery |
| CN116885121A (en) * | 2023-06-30 | 2023-10-13 | 中北大学 | Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof |
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