CN112928233A - Preparation method and application of NiO-C composite electrode material with core-shell structure - Google Patents
Preparation method and application of NiO-C composite electrode material with core-shell structure Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries and discloses a NiO-C composite electrode material with a core-shell structure2+Under high temperature, nano NiO is grown in situ in the carbon sphere matrix, the problem of agglomeration and accumulation of nano NiO is solved, a large number of lithium ion de-intercalation sites are exposed, the nano NiO generated in situ is used as a core, the porous carbon spheres grown outside are used as a shell, the NiO-C composite electrode material with a unique three-dimensional core-shell structure is generated, and the core-shell structure and rich pore structures are lithium ionsProvides a transmission path, accelerates the transmission of lithium ions, has the coating effect of porous carbon spheres, and provides buffer for the stress generated by the volume expansion of the nano NiO, thereby relieving the phenomenon of volume change of the nano NiO.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method and application of a NiO-C composite electrode material with a core-shell structure.
Background
The lithium ion battery has the advantages of high energy density, long cycle service life, wide working temperature range and the like, and is widely applied to the aspects of portable electronic equipment, electric mopeds, electric automobiles and the like.
The transition metal oxides such as iron oxide, nickel oxide, manganese oxide and the like have high theoretical specific capacity, are rich in reserves, cheap and easily available, and are a class of lithium ion battery cathode materials with development potential, but the transition metal oxides such as NiO and Fe3O4The electronic conductivity of the NiO negative electrode material is poor, so that the rate capability of the negative electrode material is poor, the nano NiO is easy to agglomerate, the de-intercalation sites of lithium ions are reduced, the actual specific capacity of the negative electrode material is reduced, and in the continuous de-intercalation process of the lithium ions, metal oxides such as NiO have the problem of volume expansion, so that the negative electrode material is easy to pulverize and decompose, the cycle stability is seriously reduced, and the specific capacity is rapidly attenuated, so that the rate capability and the cycle stability of the NiO negative electrode material are important and difficult to research.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method and application of a NiO-C composite electrode material with a core-shell structure, and solves the problems of lower actual specific capacity and poorer cycle stability of a NiO negative electrode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a core-shell NiO-C composite electrode material is prepared by the following steps:
(1) adding 5-10% by mass of sodium hydroxide solution into a reaction bottle, adding alkali lignin and polyethyleneimine, dropwise adding glutaraldehyde at 20-40 ℃, stirring for reacting for 2-6h, centrifugally washing with distilled water until the upper layer is clear, and washing the lower layer with distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and an inorganic nickel source into a reaction bottle, performing an adsorption process, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tube furnace for carbonization treatment to obtain the nitrogen-doped carbon-coated NiO with a core-shell structure.
(4) And uniformly mixing the nitrogen-doped carbon-coated NiO and the potassium hydroxide, putting the mixture into a tubular furnace for hole-making activation treatment, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the core-shell NiO-C composite material, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the core-shell NiO-C composite electrode material.
Preferably, the mass ratio of the alkali lignin, the polyethyleneimine and the glutaraldehyde is 100:60-120: 10-30.
Preferably, the inorganic nickel source in the step (2) is any one of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate, and the mass ratio of the inorganic nickel source to the polyethyleneimine grafted lignin microspheres is 8-20: 1.
Preferably, the adsorption process in the step (2) is carried out for 6-12h at 30-60 ℃.
Preferably, the carbonization treatment in the step (3) is carried out in an argon atmosphere, the carbonization temperature is 750-900 ℃, and the carbonization time is 1.5-2.5 h.
Preferably, the mass ratio of the nitrogen-doped carbon-coated NiO to the potassium hydroxide in the step (4) is 100: 15-30.
Preferably, the hole-making activation treatment in the step (4) is carried out in an argon atmosphere, the activation temperature is 600-800 ℃, and the activation time is 1-2 h.
Preferably, the NiO-C composite electrode material with the core-shell structure is applied to a negative electrode material of a lithium ion battery.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
the NiO-C composite electrode material with the core-shell structure has the advantages that the hydrogen atom on the alpha carbon at the ortho position of the phenolic hydroxyl group of the alkali lignin is very active and can easily generate Mannich reaction with aldehyde group of glutaraldehyde and amino group of polyethyleneimine, so that polyethyleneimine grafted lignin microspheres are obtained, and the surfaces of the microspheres are coated with the polyethyleneimine grafted lignin microspheresThe surface and the interior contain a large amount of hydroxyl and amino groups, and the hydroxyl and amino groups are Ni2+Has strong coordination and chelation capacity, thereby leading Ni to be mixed with the water2+Uniformly adsorbing Ni on the surface and inside of the microsphere2+Highly dispersed in the microsphere matrix.
According to the core-shell NiO-C composite electrode material, lignin microspheres are used as a carbon source, grafted polyethyleneimine is used as an N source, and N-doped porous carbon spheres and uniformly adsorbed Ni are generated through high-temperature carbonization and pore-making activation2+The nanometer NiO is uniformly grown in situ in the carbon sphere matrix at high temperature, the phenomenon that the nanometer NiO is agglomerated and accumulated is solved, a large number of lithium ion de-intercalation sites are exposed, the nanometer NiO generated in situ is used as a core, the porous carbon spheres grown on the outer side are used as a shell, the NiO-C composite electrode material with a unique three-dimensional structure and a core-shell structure is generated, the core-shell structure and the abundant pore structure provide a transmission path for lithium ions, the transmission of the lithium ions is accelerated, and the actual specific capacity of the cathode material is improved.
According to the core-shell NiO-C composite electrode material, the porous carbon spheres have higher conductivity and electrochemical performance after being doped with N, the pore structure is rich, and the stress generated by the volume expansion of the nano NiO is buffered through the coating effect of the porous carbon spheres, so that the phenomenon of volume change is relieved, the rapid capacity attenuation of the NiO cathode material is avoided, and the capacity retention rate and the cycle stability of the cathode material are improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a core-shell NiO-C composite electrode material is prepared by the following steps:
(1) adding 5-10% of sodium hydroxide solution by mass into a reaction bottle, adding alkali lignin, polyethyleneimine and glutaraldehyde in a mass ratio of 100:60-120:10-30, stirring and reacting for 2-6h at 20-40 ℃, centrifugally washing with distilled water until an upper layer solution is clear, and washing a lower layer product with distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and an inorganic nickel source in a mass ratio of 1:8-20 into a reaction bottle, wherein the inorganic nickel source is any one of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate, performing an adsorption process at 30-60 ℃ for 6-12h, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tube furnace, and carrying out carbonization treatment in an argon atmosphere at the temperature of 750-900 ℃ for 1.5-2.5h to obtain the nitrogen-doped carbon-coated NiO with the core-shell structure.
(4) Uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide in a mass ratio of 100:15-30, putting the mixture into a tubular furnace, carrying out hole-making activation treatment under an argon atmosphere, wherein the activation temperature is 600-800 ℃, the activation time is 1-2h, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the core-shell NiO-C composite material, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the core-shell NiO-C composite electrode material which is applied to a negative electrode material of a lithium ion battery.
A NiO-C composite electrode material with a core-shell structure is used as a negative electrode, a lithium sheet is used as a positive electrode, a Celgard-2300 porous polypropylene film is used as a diaphragm, 1mol/L LiPF6 solution is used as electrolyte to form the button cell, the electrochemical performance of the button cell is tested in a CT2001A cell testing system, and the voltage range is 0.01-3.0V.
Example 1
(1) Adding a sodium hydroxide solution with the mass fraction of 5% into a reaction bottle, adding alkali lignin, polyethyleneimine and glutaraldehyde with the mass ratio of 100:60:10, stirring and reacting for 2 hours at 20 ℃, centrifugally washing with distilled water until an upper layer liquid is clear, and washing a lower layer product with the distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and inorganic nickel source nickel chloride in a mass ratio of 1:8 into a reaction bottle, performing an adsorption process at 30 ℃ for 6 hours, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tube furnace, and carbonizing at 750 ℃ for 1.5h in an argon atmosphere to obtain the nitrogen-doped carbon-coated NiO with a core-shell structure.
(4) Uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide in a mass ratio of 100:15, putting the mixture into a tubular furnace, carrying out hole-making activation treatment under an argon atmosphere, wherein the activation temperature is 600 ℃, the activation time is 1h, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the NiO-C composite material with the core-shell structure, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the NiO-C composite electrode material with the core-shell structure, wherein the current density is 0.1 A.g-1The first reversible specific capacity is 1027.2mAh g-1After 200 cycles, the charge capacity was 854.2mAh g-1。
Example 2
(1) Adding 10% by mass of sodium hydroxide solution into a reaction bottle, adding alkali lignin, polyethyleneimine and glutaraldehyde in a mass ratio of 100:80:15, stirring and reacting for 4 hours at 30 ℃, centrifugally washing with distilled water until an upper layer solution is clear, and washing a lower layer product with distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and inorganic nickel source nickel nitrate in a mass ratio of 1:12 into a reaction bottle, performing an adsorption process at 40 ℃ for 12 hours, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tubular furnace, and carbonizing at 800 ℃ for 2 hours in an argon atmosphere to obtain the core-shell structure nitrogen-doped carbon-coated NiO.
(4) Uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide in a mass ratio of 100:20, putting the mixture into a tubular furnace, carrying out hole-making activation treatment under an argon atmosphere, wherein the activation temperature is 700 ℃, the activation time is 2 hours, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the NiO-C composite material with the core-shell structure, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the NiO-C composite electrode material with the core-shell structure, wherein the current density is 0.1 A.g-1The first reversible specific capacity is 1096.5mAh g-1After 200 cycles, the charge capacity was 827.1mAh g-1。
Example 3
(1) Adding 8% by mass of sodium hydroxide solution into a reaction bottle, adding alkali lignin, polyethyleneimine and glutaraldehyde in a mass ratio of 100:100:22, stirring and reacting for 4 hours at 30 ℃, centrifugally washing with distilled water until an upper layer solution is clear, and washing a lower layer product with distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and inorganic nickel source nickel sulfate in a mass ratio of 1:16 into a reaction bottle, performing an adsorption process at 50 ℃ for 8 hours, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tubular furnace, and carbonizing at 800 ℃ for 2 hours in an argon atmosphere to obtain the core-shell structure nitrogen-doped carbon-coated NiO.
(4) Uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide in a mass ratio of 100:25, putting the mixture into a tubular furnace, carrying out hole-making activation treatment under an argon atmosphere, wherein the activation temperature is 700 ℃, the activation time is 1.5h, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the NiO-C composite material with the core-shell structure, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, drying and tablettingTreating to obtain the NiO-C composite electrode material with a core-shell structure, wherein the current density is 0.1 A.g-1The first reversible specific capacity is 1169.2mAh g-1After 200 cycles, the charge capacity was 874.2mAh g-1。
Example 4
(1) Adding 10% by mass of sodium hydroxide solution into a reaction bottle, adding alkali lignin, polyethyleneimine and glutaraldehyde in a mass ratio of 100:120:30, stirring and reacting for 6 hours at 40 ℃, centrifugally washing with distilled water until an upper layer solution is clear, and washing a lower layer product with distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and inorganic nickel source nickel acetate in a mass ratio of 1:20 into a reaction bottle, performing an adsorption process at 60 ℃ for 12 hours, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tubular furnace, and carbonizing at 900 ℃ for 2.5 hours in an argon atmosphere to obtain the nitrogen-doped carbon-coated NiO with the core-shell structure.
(4) Uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide in a mass ratio of 100:30, putting the mixture into a tubular furnace, carrying out hole-making activation treatment under an argon atmosphere, wherein the activation temperature is 800 ℃, the activation time is 2 hours, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the NiO-C composite material with the core-shell structure, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the NiO-C composite electrode material with the core-shell structure, wherein the current density is 0.1 A.g-1The first reversible specific capacity is 971.7 mAh.g-1After 200 cycles, the charge capacity was 724.8mAh g-1。
Comparative example 1
(1) Adding 10% by mass of sodium hydroxide solution into a reaction bottle, adding alkali lignin, polyethyleneimine and glutaraldehyde in a mass ratio of 100:40:4, stirring and reacting for 6 hours at 20 ℃, centrifugally washing with distilled water until an upper layer solution is clear, and washing a lower layer product with distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and inorganic nickel source nickel nitrate in a mass ratio of 1:4 into a reaction bottle, performing an adsorption process at 40 ℃ for 10 hours, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tubular furnace, and carbonizing at 800 ℃ for 2 hours in an argon atmosphere to obtain the core-shell structure nitrogen-doped carbon-coated NiO.
(4) Uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide in a mass ratio of 100:10, putting the mixture into a tubular furnace, carrying out hole-making activation treatment under an argon atmosphere, wherein the activation temperature is 700 ℃, the activation time is 2 hours, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the NiO-C composite material with the core-shell structure, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the NiO-C composite electrode material with the core-shell structure, wherein the current density is 0.1 A.g-1The first reversible specific capacity is 822.0mAh g-1After 200 cycles, the charge capacity was 427.8mAh g-1。
Comparative example 2
(1) Adding 10% by mass of sodium hydroxide solution into a reaction bottle, adding alkali lignin, polyethyleneimine and glutaraldehyde in a mass ratio of 100:150:38, stirring and reacting for 5 hours at 30 ℃, centrifugally washing with distilled water until an upper layer solution is clear, and washing a lower layer product with distilled water to obtain the polyethyleneimine grafted lignin microspheres.
(2) Adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and inorganic nickel source nickel chloride in a mass ratio of 1:25 into a reaction bottle, performing an adsorption process at 40 ℃ for 12 hours, and performing vacuum drying to remove the solvent to obtain the nickel-based polyethyleneimine grafted lignin microspheres.
(3) Putting the nickel-based polyethyleneimine grafted lignin microspheres into a tubular furnace, and carbonizing at 900 ℃ for 1.5h in an argon atmosphere to obtain the nitrogen-doped carbon-coated NiO with the core-shell structure.
(4) Uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide in a mass ratio of 100:35, putting the mixture into a tubular furnace, carrying out hole-making activation treatment under an argon atmosphere, wherein the activation temperature is 800 ℃, the activation time is 2 hours, and washing a product to be neutral by distilled water to obtain the core-shell NiO-C composite material.
(5) Putting the NiO-C composite material with the core-shell structure, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the NiO-C composite electrode material with the core-shell structure, wherein the current density is 0.1 A.g-1The first reversible specific capacity is 701.7mAh g-1After 200 cycles, the charge capacity was 428.9mAh g-1。
Claims (8)
1. A NiO-C composite electrode material with a core-shell structure is characterized in that: the preparation method of the core-shell NiO-C composite electrode material is as follows:
(1) adding a sodium hydroxide solution with the mass fraction of 5-10% into a reaction bottle, adding alkali lignin and polyethyleneimine, dropwise adding glutaraldehyde at the temperature of 20-40 ℃, and stirring for reacting for 2-6h to obtain polyethyleneimine grafted lignin microspheres;
(2) adding a distilled water solvent, polyethyleneimine grafted lignin microspheres and an inorganic nickel source into a reaction bottle, and performing an adsorption process to obtain nickel-based polyethyleneimine grafted lignin microspheres;
(3) putting the nickel-based polyethyleneimine grafted lignin microspheres into a tube furnace for carbonization treatment to obtain nitrogen-doped carbon-coated NiO with a core-shell structure;
(4) uniformly mixing nitrogen-doped carbon-coated NiO and potassium hydroxide, and putting the mixture into a tubular furnace for hole-making and activating treatment to obtain a core-shell NiO-C composite material;
(5) putting the core-shell NiO-C composite material, polyvinylidene fluoride and conductive carbon black into an N-methyl pyrrolidone solvent according to the mass ratio of 8:1:1, coating the slurry on a copper foil current collector, and drying and tabletting to obtain the core-shell NiO-C composite electrode material.
2. The core-shell structured NiO-C composite electrode material of claim 1, wherein: the mass ratio of the alkali lignin, the polyethyleneimine and the glutaraldehyde is 100:60-120: 10-30.
3. The core-shell structured NiO-C composite electrode material of claim 1, wherein: the inorganic nickel source in the step (2) is any one of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate, and the mass ratio of the inorganic nickel source to the polyethyleneimine grafted lignin microspheres is 8-20: 1.
4. The core-shell structured NiO-C composite electrode material of claim 1, wherein: the adsorption process in the step (2) is carried out for 6-12h at the temperature of 30-60 ℃.
5. The core-shell structured NiO-C composite electrode material of claim 1, wherein: the carbonization treatment in the step (3) is carried out in an argon atmosphere, the carbonization temperature is 750-900 ℃, and the carbonization time is 1.5-2.5 h.
6. The core-shell structured NiO-C composite electrode material of claim 1, wherein: the mass ratio of the nitrogen-doped carbon-coated NiO to the potassium hydroxide in the step (4) is 100: 15-30.
7. The core-shell structured NiO-C composite electrode material of claim 1, wherein: and (4) carrying out hole-making activation treatment in an argon atmosphere at the activation temperature of 600-800 ℃ for 1-2 h.
8. A NiO-C composite electrode material with a core-shell structure is characterized in that: the NiO-C composite electrode material with the core-shell structure is applied to a negative electrode material of a lithium ion battery.
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| CN114649516A (en) * | 2022-02-28 | 2022-06-21 | 华南理工大学 | A kind of lignin carbon/nickel oxide nanocomposite material and its preparation method and application |
| CN116081619A (en) * | 2023-02-10 | 2023-05-09 | 珠海科创能源技术有限公司 | A kind of carbon-based negative electrode material of sodium ion battery and its preparation process |
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