CN112744873A - Highly dispersed NiCo2O4-porous carbon lithium ion battery cathode material and preparation method thereof - Google Patents
Highly dispersed NiCo2O4-porous carbon lithium ion battery cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries and discloses a high-dispersion NiCo2O4-porous carbon negative electrode material of lithium ion battery, sea urchin-like nano NiCo2O4The microspheres have unique sea urchin-shaped hollow structures, large specific surface area, abundant active sites for lithium removal and lithium insertion, high dispersion and uniform distribution in a porous carbon matrix, reduced agglomeration phenomenon, reduced active sites for lithium ion de-intercalation, and a porous carbon layer capable of supporting to protect NiCo2O4The hollow sea urchin-shaped appearance of the microsphere is not collapsed, the capacity attenuation of the negative electrode material is reduced, the circulation stability is improved, nitrogen-rich cross-linked chitosan microsphere is carbonized to obtain nitrogen-doped porous carbon, the nitrogen doping can pass through the conductivity and adsorption sites of the porous carbon material, the electronic conductivity and the lithium ion diffusion coefficient of the negative electrode material are improved, and the porous carbon material has higher specific capacity and excellent electrochemical circulation stability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-dispersion NiCo2O4-porous carbon negative electrode material for lithium ion battery and its preparation method.
Background
The lithium ion battery is a rechargeable green battery, has the advantages of high energy density, quick charge and discharge, stable cycle performance and the like, is widely applied to an energy storage power supply system, the positive electrode material and the negative electrode material in the lithium ion battery have great influence on the energy density, the cycle performance and other performances of the lithium ion battery, and the current negative electrode material of the lithium ion battery mainly comprises an alloy negative electrode material, a carbon negative electrode material, a silicon negative electrode material and a transition metal oxide electrode material.
Transition metal oxide electrode materials, e.g. MnO2、Co3O4、NiCo2O4、SnO2The NiCo has good lithium removal and insertion active sites, high theoretical specific capacity, rich sources and low cost, is a lithium ion battery cathode material widely researched and applied, but NiCo has high content of lithium ions and lithium ions2O4The problems of low electrical conductivity and poor cycle stability of the cathode material generally exist, in the processes of lithium removal and lithium insertion, agglomeration and expansion are easy to occur to cause electrode active components to be pulverized and fall off, the actual specific capacity and the cycle stability of the cathode material are seriously influenced, the porous carbon material has rich mesoporous structure and ultrahigh specific surface area, the electrochemical performance is excellent, the porous carbon material is widely applied to the electrode materials such as lithium ion batteries and supercapacitors, and NiCo is used as a material for preparing NiCo2O4Combined with porous carbon material, is an improved NiCo2O4An effective strategy for the electrochemical performance of the anode material, but only compounding the anode material and the cathode material by a simple physical blending mode can lead to the nano NiCo2O4The porous carbon is not uniformly dispersed in the porous carbon group, and agglomeration is easily formed, so that the problems of lithium removal, lithium insertion active site reduction and the like are caused.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-dispersion NiCo2O4The negative electrode material of lithium ion battery with porous carbon and its preparation process solve the problem of NiCo2O4The actual specific capacity of the cathode material is not high, and the electrochemical cycling stability is poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: highly dispersed NiCo2O4-porous carbon lithium ion battery negative electrode material, said highly dispersed NiCo2O4The preparation method of the lithium ion battery anode material of porous carbon is as follows:
(1) adding a mixed solvent of distilled water and glycol, cobalt nitrate, nickel nitrate, urea and oleic acid into a reaction bottle, stirring and dissolving, transferring the solution into a reaction kettle, heating to 110-2O4And (3) microspheres.
(2) Adding distilled water solvent and oleic acid modified hollow sea urchin-shaped NiCo into a reaction bottle2O4Adding potassium permanganate into the nano microspheres after uniform ultrasonic dispersion, placing the mixture in an ultrasonic reaction device for ultrasonic reaction for 5 to 10 hours, centrifugally separating to remove the solvent, washing the mixture by using distilled water and ethanol, and drying the washed mixture to prepare the carboxylated NiCo2O4And (4) nano microspheres.
(3) Distilled water, chitosan and carboxylated NiCo are added into a reaction flask2O4Dispersing the nano-microsphere evenly by ultrasonic, slowly dripping acetic acid until the chitosan is dissolved, adding a condensing agent, slowly dripping sodium sulfate and sodium hydroxide in a nitrogen atmosphere, stirring at a constant speed for reacting for 2-6h, drying in vacuum to remove the solvent, washing by using distilled water and ethanol, and drying to prepare the nano NiCo2O4And (3) grafting chitosan.
(4) Adding distilled water solvent and nano NiCo into a reaction bottle2O4Grafting chitosan and a cross-linking agent glutaraldehyde, addingHeating to 50-80 deg.C, stirring at constant speed for 6-12h, distilling the solution under reduced pressure to remove solvent, washing with distilled water and ethanol, and drying to obtain NiCo2O4Grafted cross-linked chitosan microspheres.
(5) Mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace for carbonization to prepare highly dispersed NiCo2O4Nitrogen doped carbon material.
(6) Mixing highly dispersed NiCo2O4Uniformly mixing the nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:20-35, placing the mixture in an atmosphere furnace, and performing a thermal activation process to prepare highly dispersed NiCo2O4-a lithium ion battery anode material of porous carbon.
Preferably, the mass ratio of the cobalt nitrate, the nickel nitrate, the urea and the oleic acid in the step (1) is 100:50:700-800: 150-250.
Preferably, the oleic acid modified hollow sea urchin-shaped nano NiCo in the step (2)2O4The mass ratio of the microspheres to the potassium permanganate is 100: 50-120.
Preferably, the ultrasonic reaction device in the step (2) comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotary gear is fixedly connected inside the water bath, the rotary gear is movably connected with a screw rod, an objective table is fixedly connected below the screw rod, and a reaction bottle is arranged above the objective table.
Preferably, the condensing agent in the step (3) is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, chitosan or carboxylated NiCo2O4The mass ratio of the nano-microsphere, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the sodium sulfate and the sodium hydroxide is 100:300-500:75-130:1200-1800: 1000-1500.
Preferably, the nano NiCo in the step (4)2O4The mass ratio of the grafted chitosan to the glutaraldehyde is 100: 15-25.
Preferably, the carbonization process in the step (5) is a nitrogen atmosphere, and the carbonization is carried out at 750-800 ℃ for 2-3 h.
Preferably, the thermal activation process in the step (6) is a nitrogen atmosphere, and the thermal activation is performed for 1-2h at 650-750 ℃.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the highly dispersed NiCo2O4In a thermal solvent system of distilled water and ethylene glycol, urea is firstly hydrolyzed to generate ammonia gas and carbon dioxide bubbles, meanwhile, the ammonia gas is hydrolyzed to generate hydroxyl anions, the hydroxyl anions are used as nucleating agents and form nano needle-shaped hydroxide precursor precipitates on the surfaces of the bubbles together with nickel ions and cobalt ions, the Ostwald curing process is further improved, the nano needle-shaped hydroxide precursors are self-assembled into sea urchin-shaped microspheres, the reaction is further carried out through a high-temperature thermal solvent method, and the bubbles in the sea urchin-shaped microspheres escape at high temperature to form sea urchin-shaped nano NiCo2O4The microsphere has a unique sea urchin-shaped hollow structure, has a large specific surface area, has abundant active sites for lithium removal and lithium insertion, promotes the transmission and diffusion of lithium ions, and is favorable for relieving stress generated by bulk expansion so as to improve the nano NiCo2O4Cycling stability of microspheres and sea urchin-like nano NiCo produced in a hot solvent system2O4The surface of the microsphere contains a large amount of hydroxyl, and oleic acid containing active carboxyl is added in the hot solvent reaction process to form NiCo2O4Carrying out esterification modification on hydroxyl on the surface of the microsphere to obtain oleic acid modified hollow sea urchin-shaped nano NiCo2O4And (3) microspheres.
The highly dispersed NiCo2O4The alkenyl of oleic acid breaks the bond to generate carboxyl under the oxidation action of potassium permanganate to obtain the carboxylated hollow sea urchin-shaped nano NiCo2O4Microspheres, then NiCo by activation with 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride2O4The carboxyl modified by the microspheres and the amino of the chitosan are subjected to amidation reaction and further cross-linked by glutaraldehyde,forming NiCo2O4Grafted cross-linked chitosan microsphere, and grafting the hollow sea urchin-shaped nano NiCo by a chemical covalent bond method2O4The microspheres are highly dispersed in the cross-linked chitosan microsphere matrix, and NiCo is reduced2O4The microspheres are agglomerated and then are activated by high-temperature carbonization and potassium hydroxide etching to obtain highly dispersed NiCo2O4And the lithium ion battery cathode material is loaded with porous carbon.
The highly dispersed NiCo2O4-porous carbon negative electrode material of lithium ion battery, hollow sea urchin-like nano NiCo2O4The microspheres are highly dispersed and uniformly distributed in a porous carbon matrix, so that the agglomeration phenomenon is reduced, a large number of active sites for lithium ion deintercalation are reduced, and the porous carbon layer can play a supporting role to protect NiCo2O4The hollow sea urchin-shaped appearance of the microsphere is not collapsed, the capacity attenuation of the negative electrode material is reduced, the circulation stability is improved, nitrogen-doped porous carbon is obtained by carbonizing the crosslinked chitosan microsphere rich in nitrogen, the nitrogen doping can pass through the conductivity and adsorption sites of the porous carbon material, the electronic conductivity and the lithium ion diffusion coefficient of the negative electrode material are improved, and the highly dispersed NiCo is enabled to be2O4The lithium ion battery cathode material of porous carbon has higher specific capacity and excellent electrochemical cycling stability.
Drawings
FIG. 1 is a schematic front view of an ultrasonic reaction apparatus;
fig. 2 is a schematic view of screw adjustment.
Fig. 3 is a schematic view of the structure of the rotary gear and the screw.
1-ultrasonic reaction device; 2-water bath; 3-an ultrasonic generator; 4-a rotating gear; 5-a screw; 6-an objective table; 7-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: highly dispersed NiCo2O4The preparation method of the lithium ion battery anode material with porous carbon is as follows:
(1) is turned to the reverse directionAdding a mixed solvent of distilled water and ethylene glycol, cobalt nitrate, nickel nitrate, urea and oleic acid with the mass ratio of 100:50:700-800:150-250 into a reaction bottle, stirring and dissolving, transferring the solution into a reaction kettle, heating to 110-130 ℃, reacting for 5-8h, heating to 180-200 ℃, reacting for 10-20h, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and drying to prepare the oil acid modified hollow sea urchin-shaped nano NiCo2O4And (3) microspheres.
(2) Adding distilled water solvent and oleic acid modified hollow sea urchin-shaped NiCo into a reaction bottle2O4Adding potassium permanganate with the mass ratio of 100:50-120 after uniform ultrasonic dispersion into nano microspheres, placing the nano microspheres in an ultrasonic reaction device, wherein the ultrasonic reaction device comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotating gear is fixedly connected inside the water bath, the rotating gear is movably connected with a screw, a carrier table is fixedly connected below the screw, a reaction bottle is arranged above the carrier table, carrying out ultrasonic reaction for 5-10h, centrifugally separating to remove a solvent, washing and drying by using distilled water and ethanol, and preparing the carboxylated NiCo2O4And (4) nano microspheres.
(3) Distilled water, chitosan and carboxylated NiCo are added into a reaction flask2O4Dispersing the nano-microsphere uniformly by ultrasonic, slowly dripping acetic acid until the chitosan is dissolved, then adding a condensing agent 1- (3-dimethylamino propyl) -3-ethyl carbodiimide hydrochloride, and slowly dripping sodium sulfate and sodium hydroxide in a nitrogen atmosphere, wherein the chitosan and the carboxylated NiCo2O4The mass ratio of the nano microspheres to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the sodium sulfate to the sodium hydroxide is 100:300-2O4And (3) grafting chitosan.
(4) Adding distilled water solvent and nano NiCo with the mass ratio of 100:15-25 into a reaction bottle2O4Grafting chitosan and cross-linking agent glutaraldehyde, heating to 50-80 deg.C, stirring at uniform speed for reaction for 6-12h, distilling the solution under reduced pressure to remove solvent, and distillingDistilled water and ethanol are washed and dried to prepare NiCo2O4Grafted cross-linked chitosan microspheres.
(5) Mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace, and the carbonization process is carried out for 2-3h at the temperature of 750-2O4Nitrogen doped carbon material.
(6) Mixing highly dispersed NiCo2O4Uniformly mixing the nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:20-35, placing the mixture in an atmosphere furnace, and performing a thermal activation process for 1-2 hours at the temperature of 650-750 ℃ in a nitrogen atmosphere to prepare highly dispersed NiCo2O4-a lithium ion battery anode material of porous carbon.
Example 1
(1) Adding a mixed solvent of distilled water and ethylene glycol, cobalt nitrate, nickel nitrate, urea and oleic acid with the mass ratio of 100:50:700:150 into a reaction bottle, stirring to dissolve, transferring the solution into a reaction kettle, heating to 110 ℃, reacting for 5h, heating to 180 ℃, reacting for 10h, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and drying to prepare the oleic acid modified hollow sea urchin-shaped nano NiCo2O4And (3) microspheres.
(2) Adding distilled water solvent and oleic acid modified hollow sea urchin-shaped NiCo into a reaction bottle2O4Uniformly dispersing nano microspheres by ultrasonic, adding potassium permanganate with the mass ratio of 100:50, placing the mixture into an ultrasonic reaction device, wherein the ultrasonic reaction device comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotating gear is fixedly connected inside the water bath, a screw rod is movably connected with the rotating gear, an objective table is fixedly connected below the screw rod, a reaction bottle is arranged above the objective table, carrying out ultrasonic reaction for 5 hours, centrifugally separating to remove a solvent, washing and drying by using distilled water and ethanol, and preparing the carboxylated NiCo2O4And (4) nano microspheres.
(3) Distilled water, chitosan and carboxylated NiCo are added into a reaction flask2O4Dispersing the nanometer microsphere with ultrasonic wave, and slowly dropping acetic acid until the chitosan is dissolvedDissolving, adding condensing agent 1- (3-dimethylamino propyl) -3-ethyl carbodiimide hydrochloride, and slowly adding sodium sulfate and sodium hydroxide dropwise in nitrogen atmosphere, wherein chitosan and carboxylated NiCo2O4The mass ratio of the nano microspheres to the 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to the sodium sulfate to the sodium hydroxide is 100:300:75:1200:1000, the mixture is stirred at a constant speed for reaction for 2 hours, the solvent is removed by vacuum drying, and the nano NiCo is prepared by washing and drying the mixture by using distilled water and ethanol2O4And (3) grafting chitosan.
(4) Adding distilled water solvent and nano NiCo with the mass ratio of 100:15 into a reaction bottle2O4Grafting chitosan and a cross-linking agent glutaraldehyde, heating to 50 ℃, stirring at a constant speed for reaction for 6 hours, distilling the solution under reduced pressure to remove the solvent, washing with distilled water and ethanol, and drying to prepare NiCo2O4Grafted cross-linked chitosan microspheres.
(5) Mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace, and are carbonized for 2 hours at 750 ℃ in the atmosphere of nitrogen to prepare highly dispersed NiCo2O4Nitrogen doped carbon material.
(6) Mixing highly dispersed NiCo2O4Uniformly mixing a nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:20, placing the mixture in an atmosphere furnace, and performing a thermal activation process for 1h at 650 ℃ in a nitrogen atmosphere to prepare highly dispersed NiCo2O4A lithium ion battery anode material 1 of porous carbon.
Example 2
(1) Adding a mixed solvent of distilled water and ethylene glycol, cobalt nitrate, nickel nitrate, urea and oleic acid with the mass ratio of 100:50:720:180 into a reaction bottle, stirring to dissolve, transferring the solution into a reaction kettle, heating to 110 ℃, reacting for 8h, heating to 200 ℃, reacting for 20h, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and drying to prepare the oleic acid modified hollow sea urchin-shaped nano NiCo2O4And (3) microspheres.
(2) Adding distilled water solvent and oleic acid modified hollow sea urchin-shaped NiCo into a reaction bottle2O4Uniformly dispersing nano microspheres by ultrasonic, adding potassium permanganate with the mass ratio of 100:70, placing the mixture into an ultrasonic reaction device, wherein the ultrasonic reaction device comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotating gear is fixedly connected inside the water bath, a screw rod is movably connected with the rotating gear, an objective table is fixedly connected below the screw rod, a reaction bottle is arranged above the objective table, carrying out ultrasonic reaction for 10 hours, centrifugally separating to remove a solvent, washing and drying by using distilled water and ethanol, and preparing the carboxylated NiCo2O4And (4) nano microspheres.
(3) Distilled water, chitosan and carboxylated NiCo are added into a reaction flask2O4Dispersing the nano-microsphere uniformly by ultrasonic, slowly dripping acetic acid until the chitosan is dissolved, then adding a condensing agent 1- (3-dimethylamino propyl) -3-ethyl carbodiimide hydrochloride, and slowly dripping sodium sulfate and sodium hydroxide in a nitrogen atmosphere, wherein the chitosan and the carboxylated NiCo2O4The mass ratio of the nano microspheres to the 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to the sodium sulfate to the sodium hydroxide is 100:350:90:1400:1200, the mixture is stirred at a constant speed for reaction for 6 hours, the solvent is removed by vacuum drying, and the nano NiCo is prepared by washing and drying the mixture by using distilled water and ethanol2O4And (3) grafting chitosan.
(4) Adding distilled water solvent and nano NiCo with the mass ratio of 100:18 into a reaction bottle2O4Grafting chitosan and a cross-linking agent glutaraldehyde, heating to 60 ℃, stirring at a constant speed for reaction for 10 hours, distilling the solution under reduced pressure to remove the solvent, washing with distilled water and ethanol, and drying to prepare NiCo2O4Grafted cross-linked chitosan microspheres.
(5) Mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace, and the carbonization process is carried out for 2.5h at 750 ℃ in the atmosphere of nitrogen, so as to prepare the highly dispersed NiCo2O4Nitrogen doped carbon material.
(6) Mixing highly dispersed NiCo2O4Uniformly mixing the nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:25, placing the mixture in an atmosphere furnace in a nitrogen atmosphere at 650 DEG CThen the thermal activation process is carried out for 2 hours to prepare highly dispersed NiCo2O4A lithium ion battery anode material 2 of porous carbon.
Example 3
(1) Adding a mixed solvent of distilled water and ethylene glycol, cobalt nitrate, nickel nitrate, urea and oleic acid with the mass ratio of 100:50:760:220 into a reaction bottle, stirring to dissolve, transferring the solution into a reaction kettle, heating to 120 ℃, reacting for 6h, heating to 190 ℃, reacting for 15h, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and drying to prepare the oleic acid modified hollow sea urchin-shaped nano NiCo2O4And (3) microspheres.
(2) Adding distilled water solvent and oleic acid modified hollow sea urchin-shaped NiCo into a reaction bottle2O4Uniformly dispersing nano microspheres by ultrasonic, adding potassium permanganate with the mass ratio of 100:95, placing the mixture into an ultrasonic reaction device, wherein the ultrasonic reaction device comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotating gear is fixedly connected inside the water bath, a screw rod is movably connected with the rotating gear, an objective table is fixedly connected below the screw rod, a reaction bottle is arranged above the objective table, carrying out ultrasonic reaction for 8 hours, centrifugally separating to remove a solvent, washing and drying by using distilled water and ethanol, and preparing the carboxylated NiCo2O4And (4) nano microspheres.
(3) Distilled water, chitosan and carboxylated NiCo are added into a reaction flask2O4Dispersing the nano-microsphere uniformly by ultrasonic, slowly dripping acetic acid until the chitosan is dissolved, then adding a condensing agent 1- (3-dimethylamino propyl) -3-ethyl carbodiimide hydrochloride, and slowly dripping sodium sulfate and sodium hydroxide in a nitrogen atmosphere, wherein the chitosan and the carboxylated NiCo2O4The mass ratio of the nano microspheres to the 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to the sodium sulfate to the sodium hydroxide is 100:430:110:1600:1300, the mixture is stirred at a constant speed for reaction for 4 hours, the solvent is removed by vacuum drying, and the nano NiCo is prepared by washing and drying the mixture by using distilled water and ethanol2O4And (3) grafting chitosan.
(4) Adding distilled water solvent into a reaction bottle in a mass ratio of 100:22 nano NiCo2O4Grafting chitosan and a cross-linking agent glutaraldehyde, heating to 60 ℃, stirring at a constant speed for reaction for 10 hours, distilling the solution under reduced pressure to remove the solvent, washing with distilled water and ethanol, and drying to prepare NiCo2O4Grafted cross-linked chitosan microspheres.
(5) Mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace, and the carbonization process is carried out for 2.5h at 780 ℃ in the atmosphere of nitrogen, so as to prepare the highly dispersed NiCo2O4Nitrogen doped carbon material.
(6) Mixing highly dispersed NiCo2O4Uniformly mixing a nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:30, placing the mixture in an atmosphere furnace, and performing a thermal activation process at 720 ℃ for 1.5 hours in a nitrogen atmosphere to prepare highly dispersed NiCo2O4A lithium ion battery negative electrode material 3 of porous carbon.
Example 4
(1) Adding a mixed solvent of distilled water and ethylene glycol, cobalt nitrate, nickel nitrate, urea and oleic acid with the mass ratio of 100:50:800:250 into a reaction bottle, stirring to dissolve, transferring the solution into a reaction kettle, heating to 130 ℃, reacting for 8h, heating to 200 ℃, reacting for 20h, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and drying to prepare the oleic acid modified hollow sea urchin-shaped nano NiCo2O4And (3) microspheres.
(2) Adding distilled water solvent and oleic acid modified hollow sea urchin-shaped NiCo into a reaction bottle2O4Uniformly dispersing nano microspheres by ultrasonic, adding potassium permanganate with the mass ratio of 100:120, placing the mixture into an ultrasonic reaction device, wherein the ultrasonic reaction device comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotating gear is fixedly connected inside the water bath, a screw rod is movably connected with the rotating gear, an objective table is fixedly connected below the screw rod, a reaction bottle is arranged above the objective table, carrying out ultrasonic reaction for 10 hours, centrifugally separating to remove a solvent, washing and drying by using distilled water and ethanol, and preparing the carboxylated NiCo2O4And (4) nano microspheres.
(3) To the direction ofDistilled water, chitosan and carboxylated NiCo are added into a reaction flask2O4Dispersing the nano-microsphere uniformly by ultrasonic, slowly dripping acetic acid until the chitosan is dissolved, then adding a condensing agent 1- (3-dimethylamino propyl) -3-ethyl carbodiimide hydrochloride, and slowly dripping sodium sulfate and sodium hydroxide in a nitrogen atmosphere, wherein the chitosan and the carboxylated NiCo2O4The mass ratio of the nano microspheres to the 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to the sodium sulfate to the sodium hydroxide is 100:500:130:1800:1500, the mixture is stirred at a constant speed for reaction for 6 hours, the solvent is removed by vacuum drying, and the nano NiCo is prepared by washing and drying the mixture by using distilled water and ethanol2O4And (3) grafting chitosan.
(4) Adding distilled water solvent and nano NiCo with the mass ratio of 100:25 into a reaction bottle2O4Grafting chitosan and a cross-linking agent glutaraldehyde, heating to 80 ℃, stirring at a constant speed for reaction for 12 hours, distilling the solution under reduced pressure to remove the solvent, washing with distilled water and ethanol, and drying to prepare NiCo2O4Grafted cross-linked chitosan microspheres.
(5) Mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace, and the carbonization process is carried out for 3 hours at 800 ℃ in the nitrogen atmosphere to prepare highly dispersed NiCo2O4Nitrogen doped carbon material.
(6) Mixing highly dispersed NiCo2O4Uniformly mixing a nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:35, placing the mixture in an atmosphere furnace, and performing thermal activation for 2 hours at 750 ℃ in a nitrogen atmosphere to prepare highly dispersed NiCo2O4A lithium ion battery negative electrode material 4 of porous carbon.
Comparative example 1
(1) Adding a mixed solvent of distilled water and ethylene glycol, cobalt nitrate, nickel nitrate, urea and oleic acid with the mass ratio of 100:50:670:130 into a reaction bottle, stirring to dissolve, transferring the solution into a reaction kettle, heating to 130 ℃, reacting for 5h, heating to 200 ℃, reacting for 20h, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and drying to prepare the oleic acid modified hollow sea urchin-shaped nano-meterNiCo2O4And (3) microspheres.
(2) Adding distilled water solvent and oleic acid modified hollow sea urchin-shaped NiCo into a reaction bottle2O4Uniformly dispersing nano microspheres by ultrasonic, adding potassium permanganate with the mass ratio of 100:30, placing the mixture into an ultrasonic reaction device, wherein the ultrasonic reaction device comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotating gear is fixedly connected inside the water bath, a screw rod is movably connected with the rotating gear, an objective table is fixedly connected below the screw rod, a reaction bottle is arranged above the objective table, carrying out ultrasonic reaction for 10 hours, centrifugally separating to remove a solvent, washing and drying by using distilled water and ethanol, and preparing the carboxylated NiCo2O4And (4) nano microspheres.
(3) Distilled water, chitosan and carboxylated NiCo are added into a reaction flask2O4Dispersing the nano-microsphere uniformly by ultrasonic, slowly dripping acetic acid until the chitosan is dissolved, then adding a condensing agent 1- (3-dimethylamino propyl) -3-ethyl carbodiimide hydrochloride, and slowly dripping sodium sulfate and sodium hydroxide in a nitrogen atmosphere, wherein the chitosan and the carboxylated NiCo2O4The mass ratio of the nano microspheres to the 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to the sodium sulfate to the sodium hydroxide is 100:250:50:1000:800, the mixture is stirred at a constant speed for reaction for 6 hours, the solvent is removed by vacuum drying, and the nano NiCo is prepared by washing and drying the mixture by using distilled water and ethanol2O4And (3) grafting chitosan.
(4) Adding distilled water solvent and nano NiCo with the mass ratio of 100:18 into a reaction bottle2O4Grafting chitosan and a cross-linking agent glutaraldehyde, heating to 80 ℃, stirring at a constant speed for reaction for 10 hours, distilling the solution under reduced pressure to remove the solvent, washing with distilled water and ethanol, and drying to prepare NiCo2O4Grafted cross-linked chitosan microspheres.
(5) Mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace, and the carbonization process is carried out for 2 hours at 800 ℃ in the nitrogen atmosphere to prepare highly dispersed NiCo2O4Nitrogen doped carbon material.
(6) Divide the height intoDispersed NiCo2O4Uniformly mixing a nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:15, placing the mixture in an atmosphere furnace, and performing a thermal activation process at 700 ℃ for 1.5 hours in a nitrogen atmosphere to prepare highly dispersed NiCo2O4Lithium ion battery negative electrode material of porous carbon comparative 1.
Assembling a button battery: the highly dispersed NiCo of the examples and comparative examples were separately prepared2O4Uniformly mixing a porous carbon lithium ion battery negative electrode material with acetylene black, polyvinylidene fluoride and an N-methyl pyrrolidone solvent, coating the mixture on the surface of copper foil, drying, performing circular punching and stamping to obtain a lithium ion battery working negative electrode, taking a lithium sheet as a positive electrode, taking a polypropylene film as a diaphragm, and containing 1mol/L LiPF6The solution is used as an electrolyte and assembled into a button cell in an argon glove box.
And (3) carrying out cyclic voltammetry test on the assembled button cell in a VMP3 electrochemical workstation, and carrying out constant current charge-discharge performance test in a CT2001A cell test system, wherein the test standard is GB/T36276-.
Claims (8)
1. Highly dispersed NiCo2O4-a porous carbon lithium ion battery negative electrode material, characterized in that: said highly dispersed NiCo2O4The preparation method of the lithium ion battery anode material of porous carbon is as follows:
(1) adding a mixed solvent of distilled water and glycol, cobalt nitrate, nickel nitrate, urea and oleic acid into a reaction kettle, heating to 110-2O4Microspheres;
(2) adding oleic acid modified hollow sea urchin-shaped NiCo into distilled water solvent2O4The nano-microspheres are added with potassium permanganate after being dispersed uniformly by ultrasonic, and are placed in an ultrasonic reaction device for carrying outUltrasonic reaction is carried out for 5 to 10 hours to prepare carboxylated NiCo2O4Nano-microspheres;
(3) adding chitosan and carboxylated NiCo into distilled water solvent2O4Dispersing the nano microspheres uniformly by ultrasonic, slowly dripping acetic acid until the chitosan is dissolved, adding a condensing agent, adding sodium sulfate and sodium hydroxide in a nitrogen atmosphere, reacting for 2-6h, and preparing to obtain the nano NiCo2O4Grafting chitosan;
(4) adding nano NiCo into distilled water solvent2O4Grafting chitosan and a cross-linking agent glutaraldehyde, heating to 50-80 ℃, reacting for 6-12h, and preparing to obtain NiCo2O4Grafted cross-linked chitosan microspheres;
(5) mixing NiCo2O4The grafted cross-linked chitosan microspheres are placed in an atmosphere furnace for carbonization to prepare highly dispersed NiCo2O4-a nitrogen doped carbon material;
(6) mixing highly dispersed NiCo2O4Uniformly mixing the nitrogen-doped carbon material and potassium hydroxide in a mass ratio of 10:20-35, placing the mixture in an atmosphere furnace, and performing a thermal activation process to prepare highly dispersed NiCo2O4-a lithium ion battery anode material of porous carbon.
2. A highly dispersed NiCo according to claim 12O4-a porous carbon lithium ion battery negative electrode material, characterized in that: the mass ratio of the cobalt nitrate, the nickel nitrate, the urea and the oleic acid in the step (1) is 100:50:700-800: 150-250.
3. A highly dispersed NiCo according to claim 12O4-a porous carbon lithium ion battery negative electrode material, characterized in that: the oleic acid modified hollow sea urchin-shaped nano NiCo in the step (2)2O4The mass ratio of the microspheres to the potassium permanganate is 100: 50-120.
4. A highly dispersed NiCo according to claim 12O4-a porous carbon lithium ion battery negative electrode material, characterized in that: the ultrasonic reaction device in the step (2) comprises a water bath, ultrasonic generators are arranged on two sides of the water bath, a rotary gear is fixedly connected inside the water bath, the rotary gear is movably connected with a screw, an objective table is fixedly connected below the screw, and a reaction bottle is arranged above the objective table.
5. A highly dispersed NiCo according to claim 12O4-a porous carbon lithium ion battery negative electrode material, characterized in that: the condensing agent in the step (3) is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, chitosan and carboxylated NiCo2O4The mass ratio of the nano-microsphere, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the sodium sulfate and the sodium hydroxide is 100: 300-.
6. A highly dispersed NiCo according to claim 12O4-a porous carbon lithium ion battery negative electrode material, characterized in that: the nano NiCo in the step (4)2O4The mass ratio of the grafted chitosan to the glutaraldehyde is 100: 15-25.
7. A highly dispersed NiCo according to claim 12O4-a porous carbon lithium ion battery negative electrode material, characterized in that: the carbonization process in the step (5) is a nitrogen atmosphere, and the carbonization is carried out for 2-3h at the temperature of 750-.
8. A highly dispersed NiCo according to claim 12O4-a porous carbon lithium ion battery negative electrode material, characterized in that: the thermal activation process in the step (6) is a nitrogen atmosphere, and the thermal activation is carried out for 1-2h at 650-750 ℃.
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