CN107732206B - Preparation method of bimetallic oxide composite negative electrode material with multilevel structure - Google Patents
Preparation method of bimetallic oxide composite negative electrode material with multilevel structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a bimetallic oxide composite negative electrode material with a multilevel structure, and belongs to the technical field of lithium ion batteries. The method comprises the following specific steps: dissolving nickel nitrate, cobalt nitrate, ammonium salt and amide in water, stirring, transferring into a polytetrafluoroethylene reaction kettle, adding a proper amount of foam metal, and reacting for 10-15 h. Cooling, drying, transferring into tube furnace, and heating in N2Heat treating for 1-5h in the atmosphere to obtain NiCoO growing on the foam metal2‑Co3O4(ii) a And then putting the mixture into a small beaker, adding an aqueous solution of a surfactant, carrying out ultrasonic treatment and stirring, sequentially adding pyrrole, an acid solution and an oxidant, stirring in an ice-water bath, washing, and drying to obtain a target product. The Co and Ni bimetal oxide composite negative electrode material prepared by the method has the advantages of uniform particle size, stable structure, compactness, considerable reversible capacity of a wide potential window, excellent rate performance and stable cycle life.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, particularly relates to a bimetallic oxide negative electrode material of a lithium ion battery, and particularly relates to a preparation method of a bimetallic oxide composite negative electrode material with a multilevel structure.
Background
The traditional fossil energy is facing the crisis of shortage and even exhaustion, and brings huge pressure to environmental protection, and the novel industrialization development direction of circular economy and low-carbon economy can promote the rapid development of the new energy automobile industry. The lithium ion power battery is used as a new-generation environment-friendly and high-energy battery and has become a mainstream product of the power battery for the new energy automobile at present. However, since the commercialization of lithium ion batteries in the 90's of the 20 th century, the positive electrode materials are continuously updated, and the negative electrode materials are always graphite-based materials, and compared with the continuous increase of the capacity of the positive electrode materials, the capacity of the negative electrode materials is always limited by the lower theoretical capacity (372mAh/g) of graphite, which also hinders the energy density of the lithium ion batteriesFurther improvement, the current lithium ion battery can not fully meet the requirements of users. As an alternative material of graphite negative electrodes, transition metal oxides are one of the hot spots in the research and development of current high-performance lithium ion battery negative electrode materials. Transition metal elements all have more valence states, and their oxides or complexes are easily prepared, but different nanostructures have a significant influence on their electrochemical performance. At the same time, the other unique properties of transition metal oxides have generated great interest to researchers in a number of different fields. However, the actual reversible lithium storage capacity of such materials is much lower than the theoretical capacity, e.g. Co3O4The reversible mass specific capacity of the negative electrode material after 50 weeks of circulation is only 300-400mAh/g, so that the transition metal oxide negative electrode material cannot well meet the social requirements on the negative electrode material with high capacity and long service life.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to solve the technical problem of providing a preparation method of a bimetallic oxide composite anode material with a multilevel structure, and the synthesis method aims to construct a CoNiO2、Co3O4And polypyrrole (PPy) to obtain a composite material with stable structure and high conductivity, so that the obtained cathode material with a multilevel structure has uniform particles, uniform particle size distribution and high electronic conductivity, and the lithium storage performance of the Co and Ni bimetallic oxide cathode material can be effectively improved.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a bimetal oxide composite anode material with a multilevel structure comprises the following steps:
0.001mol of Ni (NO)3)2·6H2O、0.002mol Co(NO3)2·6H2Dissolving O, 0.003mol of ammonium salt and 0.005mol of amide in deionized water, stirring for 1-3h, transferring into a 100mL polytetrafluoroethylene reaction kettle, adding a proper amount of foam metal, and reacting in an oven at 110-130 ℃ for 10-15 h. After cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Is maintained at 400-600 ℃ under the atmosphereHeat treatment is continued for 1-5h to obtain NiCoO growing on the foam metal2-Co3O4The bimetallic cathode material is characterized in that the diameter of the foam metal is 14mm, and the thickness of the foam metal is 1 mm. NiCoO to be grown on the foam metal2-Co3O4Placing the bimetallic negative electrode material in a small beaker, adding 50-70mL of 0.1g/L surfactant aqueous solution, performing ultrasonic treatment for 3-9 minutes, mechanically stirring for 10-15 hours, and sequentially adding 0.03-0.15 mL of pyrrole and 1 mol.L-1And 0.1-0.2g of oxidant, wherein the volume ratio of pyrrole to acid is 0.07:1, stirring for 1-4h in an ice water bath, washing with deionized water for 3-5 times after stirring, washing with acetone for 2-3 times, and drying to obtain the NiCoO with a multi-stage structure2-Co3O4-PPy bimetallic oxide composite negative electrode material.
The ammonium salt is NH4F, the amide is urea.
The foam metal is foam nickel, the diameter is 14mm, the thickness is 1mm, and the pore diameter is 120PPI, wherein PPI refers to the number of pores per inch.
The water solution of the surfactant is the water solution of sodium dodecyl sulfate.
The acid solution is hydrochloric acid solution.
The oxidant is (NH)4)2S2O8。
The bimetal oxide composite negative electrode material obtained by the preparation method can be used as a negative electrode of a lithium electronic battery.
Compared with the prior art, the invention has the following technical effects:
1. the Co and Ni bimetal oxide composite negative electrode material prepared by the method has uniform particle size, stable structure and compactness. Wherein PPy plays a role of framework support in the composite material, NiCoO2And Co3O4Is filled in a three-dimensional cavity constructed by PPy, perfects NiCoO2And Co3O4The gaps among the particles further ensure that the whole composite material is uniformly and compactly dispersed, and the stability and high conductivity of the electrode structure are maintained。
2. The material synthesized by the method has uniform and consistent particles, good dispersibility and high crystallinity, and the obtained material is in a nano rod shape and is beneficial to improving the electrochemical performance of the material.
3. The material obtained by the invention has considerable reversible capacity of a wide potential window, excellent rate capability and stable cycle life, so that the material has high practical use value and can effectively meet the practical requirements of various applications of lithium ion batteries.
4. The lithium ion battery cathode material prepared by the invention has higher theoretical capacity and rapid charge and discharge performance, and improves the energy density and power density of the lithium ion battery.
Drawings
FIG. 1 shows NiCoO obtained in example 1 of the present invention2-Co3O4SEM image of PPy composite negative electrode material.
FIG. 2 shows NiCoO obtained in example 1 of the present invention2-Co3O4-cycle performance diagram of PPy composite negative electrode material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited to the embodiments.
Example 1
1mmol of Ni (NO)3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol of urea are dissolved in 70mL of deionized water, stirred for 1h, transferred into a 100mL polytetrafluoroethylene reaction kettle, added with a proper amount of foam nickel (the diameter is 14mm, the thickness is 1mm, and the pore diameter is 120PPI), and then reacted in an oven at 120 ℃ for 12 h. After cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Continuously carrying out heat treatment for 2h at 600 ℃ in the atmosphere to obtain NiCoO growing on the foamed nickel2-Co3O4A bimetallic cathode material. NiCoO to be grown on the foamed nickel2-Co3O4The bimetallic negative electrode material is placed in a small beaker, then 50mL of sodium dodecyl sulfate aqueous solution with the concentration of 0.1g/L is added,and sonicated for 9 minutes, then mechanically stirred for 10 hours, then added with 0.035mL of pyrrole, 0.5mL of 1 mol. L-1Hydrochloric acid solution and 0.114g of oxidizing agent (NH)4)2S2O8And simultaneously stirring for 2h in an ice water bath, washing with deionized water for 4 times after stirring, then washing with acetone for 3 times, and drying to obtain the NiCoO with a multi-stage structure2-Co3O4-PPy bimetallic oxide composite negative electrode material. The resulting material was in the shape of a nanorod (FIG. 1). The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium battery is charged and discharged at 2000mA/g, the first lithium removal capacity is 1647.6mAh/g (figure 2), and the reversible lithium removal capacity after 100 cycles is 1203mAh/g (figure 2), so that the lithium battery shows excellent high rate performance and cycle stability.
Example 2
1mmol of Ni (NO)3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol of urea are dissolved in 70mL of deionized water, stirred for 1h, transferred into a 100mL polytetrafluoroethylene reaction kettle and added with a proper amount of foamed nickel (120PPI), and then reacted in an oven at 110 ℃ for 10 h. After cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Heat treatment was continued at 400 ℃ for 5h under an atmosphere to obtain NiCoO grown on foamed nickel (14 mm diameter, 1mm thickness, 120PPI pore size)2-Co3O4A bimetallic cathode material. NiCoO to be grown on the foamed nickel2-Co3O4Placing the bimetallic negative electrode material in a small beaker, adding 70mL of 0.1g/L sodium dodecyl sulfate aqueous solution, performing ultrasonic treatment for 3 minutes, mechanically stirring for 15 hours, and then sequentially adding 0.03mL of pyrrole and 0.43mL of 1 mol.L-1Hydrochloric acid solution and 0.1g of oxidizing agent (NH)4)2S2O8And simultaneously stirring for 1h in an ice water bath, washing with deionized water for 3 times after stirring, then washing with acetone for 2 times, and drying to obtain the NiCoO with a multi-stage structure2-Co3O4-PPy bimetallic oxide composite negative electrode material. The obtained material is in a nanometer rod shape. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium battery is charged and discharged at 2000mA/g, the first lithium removal capacity is 1620.1mAh/g, and the reversible lithium removal capacity after 100 cycles is 1168.3mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Example 3
1mmol of Ni (NO)3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol of urea are dissolved in 70mL of deionized water, stirred for 3h, transferred into a 100mL polytetrafluoroethylene reaction kettle and added with a proper amount of foamed nickel (120PPI), and then reacted in an oven at 130 ℃ for 10 h. After cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Heat treatment was continued at 600 ℃ for 1h under an atmosphere to obtain NiCoO grown on foamed nickel (14 mm diameter, 1mm thickness, 120PPI pore size)2-Co3O4A bimetallic cathode material. NiCoO to be grown on the foamed nickel2-Co3O4Placing the bimetallic negative electrode material in a small beaker, adding 60mL of 0.1g/L sodium dodecyl sulfate aqueous solution, performing ultrasonic treatment for 9 minutes, mechanically stirring for 10 hours, and then sequentially adding 0.15mL of pyrrole and 2.1mL of 1 mol.L-1Hydrochloric acid solution and 0.2g of an oxidizing agent (NH)4)2S2O8. And simultaneously stirring for 4 hours in an ice water bath, washing with deionized water for 5 times after stirring, then washing with acetone for 3 times, and drying to obtain the NiCoO with a multi-stage structure2-Co3O4-PPy bimetallic oxide composite negative electrode material. The obtained material is in a nanometer rod shape. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium is charged and discharged at 2000mA/g, the first lithium removing capacity is 1601.2mAh/g, and the lithium can be removed reversibly after 100 cyclesThe capacity is 1192.5mAh/g, and the excellent high-rate performance and the excellent cycling stability are shown.
Example 4
1mmol of Ni (NO)3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol of urea are dissolved in 70mL of deionized water, stirred for 2h, transferred into a 100mL polytetrafluoroethylene reaction kettle and added with a proper amount of foamed nickel (120PPI), and then reacted in an oven at 115 ℃ for 14 h. After cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Heat treatment was continued at 500 ℃ for 4h under an atmosphere to obtain NiCoO grown on foamed nickel (14 mm diameter, 1mm thickness, 120PPI pore size)2-Co3O4A bimetallic cathode material. NiCoO to be grown on the foamed nickel2-Co3O4Placing the bimetallic negative electrode material in a small beaker, adding 55mL of sodium dodecyl sulfate aqueous solution with the concentration of 0.1g/L, carrying out ultrasonic treatment for 8 minutes, mechanically stirring for 13 hours, and then sequentially adding 0.01mL of pyrrole and 1.4mL of 1 mol.L-1Hydrochloric acid solution and 0.18g of oxidizing agent (NH)4)2S2O8. And simultaneously stirring for 3h in an ice water bath, washing with deionized water for 4 times after stirring, then washing with acetone for 3 times, and drying to obtain the NiCoO with a multi-stage structure2-Co3O4-PPy bimetallic oxide composite negative electrode material. The obtained material is in a nanometer rod shape. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium battery is charged and discharged at 2000mA/g, the first lithium removal capacity is 1630.7mAh/g, and the reversible lithium removal capacity after 100 cycles is 1168.9mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Example 5
1mmol of Ni (NO)3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol of urea are dissolved in 70mL of deionized water, stirred for 1.5h, and transferred into 100mL of polytetrafluoroethyleneThe mixture was put into a kettle and added with a suitable amount of nickel foam (120PPI), and then reacted in an oven at 125 ℃ for 13 hours. After cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Heat treatment was continued at 550 ℃ for 3h under an atmosphere to obtain NiCoO grown on foamed nickel (14 mm diameter, 1mm thickness, 120PPI pore size)2-Co3O4A bimetallic cathode material. NiCoO to be grown on the foamed nickel2-Co3O4The bimetallic negative electrode material is placed in a small beaker, then an aqueous solution of sodium dodecyl sulfate with the concentration of 0.1g/L is added, ultrasonic treatment is carried out for 7 minutes, mechanical stirring is carried out for 13 hours, and then a hydrochloric acid solution of pyrrole is sequentially added. Wherein the concentration of the hydrochloric acid is 1 mol.L-1The volume ratio of pyrrole to hydrochloric acid is 0.12: 1. Then 65mL of 0.1g/L sodium dodecyl sulfate aqueous solution is added, ultrasonic treatment is carried out for 7 minutes, mechanical stirring is carried out for 14 hours, and then 0.14mL of pyrrole and 2mL of 1 mol.L are added in sequence-1Hydrochloric acid solution and 0.19g of oxidizing agent (NH)4)2S2O8. And simultaneously stirring for 3 hours in an ice water bath, washing for 3 times by using deionized water after stirring is finished, then washing for 3 times by using acetone, and drying to obtain the NiCoO with the multilevel structure2-Co3O4-PPy bimetallic oxide composite negative electrode material. The obtained material is in a nanometer rod shape. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium battery is charged and discharged at 2000mA/g, the first lithium removal capacity is 1608.9mAh/g, and the reversible lithium removal capacity after 100 cycles is 1155.2mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Example 6
1mmol of Ni (NO)3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol of urea are dissolved in 70mL of deionized water, stirred for 2.5h, transferred into a 100mL polytetrafluoroethylene reaction kettle, added with a proper amount of foamed nickel (the diameter is 14mm, the thickness is 1mm, and the pore diameter is 120PPI), and then reacted in an oven at 115 ℃ for 11 h. After the mixture is cooled to the room temperature,filtered, washed and dried, and then transferred to a tube furnace in N2Continuously carrying out heat treatment for 3 hours at 550 ℃ in the atmosphere to obtain NiCoO growing on the foamed nickel2-Co3O4A bimetallic cathode material. NiCoO to be grown on the foamed nickel2-Co3O4The bimetallic negative electrode material is placed in a small beaker, then an aqueous solution of sodium dodecyl sulfate with the concentration of 0.1g/L is added, ultrasonic treatment is carried out for 4 minutes, mechanical stirring is carried out for 14 hours, and then a hydrochloric acid solution of pyrrole is sequentially added. Wherein the concentration of the hydrochloric acid is 1 mol.L-1The volume ratio of pyrrole to hydrochloric acid is 0.09: 1. Then 52mL of 0.1g/L sodium dodecyl sulfate aqueous solution is added, ultrasonic treatment is carried out for 4 minutes, mechanical stirring is carried out for 13 hours, and then 0.03mL of pyrrole and 0.43mL of 1 mol.L are added in sequence-1And 0.1g of an oxidizing agent (NH)4)2S2O8. And simultaneously stirring for 3 hours in an ice water bath, washing for 3 times by using deionized water after stirring is finished, then washing for 3 times by using acetone, and drying to obtain the NiCoO with the multilevel structure2-Co3O4-PPy bimetallic oxide composite negative electrode material. The obtained material is in a nanometer rod shape. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium battery is charged and discharged at 2000mA/g, the first lithium removal capacity is 1599.8mAh/g, and the reversible lithium removal capacity after 100 cycles is 1156.8mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Example 7
1mmol of Ni (NO)3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol of urea are dissolved in 70mL of deionized water, stirred for 2h, transferred into a 100mL polytetrafluoroethylene reaction kettle, added with a proper amount of foam nickel (the diameter is 14mm, the thickness is 1mm, and the pore diameter is 120PPI), and then reacted in an oven at 120 ℃ for 12 h. After cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Continuously heat treating for 2h at 500 ℃ in the atmosphere to obtain NiCoO growing on the foamed nickel2-Co3O4A bimetallic cathode material. NiCoO to be grown on the foamed nickel2-Co3O4The bimetallic negative electrode material is placed in a small beaker, then an aqueous solution of sodium dodecyl sulfate with the concentration of 0.1g/L is added, ultrasonic treatment is carried out for 7 minutes, mechanical stirring is carried out for 12 hours, and then a hydrochloric acid solution of pyrrole is added. Wherein the concentration of the hydrochloric acid is 1 mol.L-1The volume ratio of pyrrole to hydrochloric acid is 0.12: 1. Then 54mL of 0.1g/L sodium dodecyl sulfate aqueous solution is added, ultrasonic treatment is carried out for 7 minutes, mechanical stirring is carried out for 12 hours, and then 0.05mL of pyrrole and 0.7mL of 1 mol.L are added in sequence-1Hydrochloric acid solution and 0.15g of oxidizing agent (NH)4)2S2O8. And simultaneously stirring for 2h in an ice water bath, washing with deionized water for 4 times after stirring, then washing with acetone for 3 times, and drying to obtain the NiCoO with a multi-stage structure2-Co3O4-PPy bimetallic oxide composite negative electrode material. The obtained material is in a nanometer rod shape. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium battery is charged and discharged at 2000mA/g, the first lithium removal capacity is 1604.1mAh/g, and the reversible lithium removal capacity after 100 cycles is 1175.8mAh/g, so that the lithium battery shows excellent high rate performance and cycle stability.
Claims (7)
1. A preparation method of a bimetal oxide composite negative electrode material with a multilevel structure is characterized by comprising the following steps:
(1) 0.001mol of Ni (NO)3)2·6H2O、0.002mol Co(NO3)2·6H2Dissolving O, 0.003mol of ammonium salt and 0.005mol of amide in deionized water, stirring for 1-3h, transferring into a 100mL polytetrafluoroethylene reaction kettle, adding a proper amount of foam metal, and reacting in an oven at 110-130 ℃ for 10-15 h; after cooling to room temperature, filtration, washing and drying, the product was transferred to a tube furnace in N2Continuously carrying out heat treatment for 1-5h at 400-600 ℃ in the atmosphere to obtain NiCoO growing on the foam metal2-Co3O4A bimetallic negative electrode material;
(2) the NiCoO obtained in the step (1) is treated2-Co3O4Placing the bimetallic negative electrode material in a small beaker, adding 50-70mL of 0.1g/L surfactant aqueous solution, performing ultrasonic treatment for 3-9 minutes, mechanically stirring for 10-15 hours, and sequentially adding 0.03-0.15 mL of pyrrole and 1 mol.L-1And 0.1-0.2g of oxidant, wherein the volume ratio of pyrrole to acid solution is 0.07:1, stirring is carried out for 1-4 hours in ice water bath, deionized water is used for washing for 3-5 times after stirring is finished, acetone is used for washing for 2-3 times, and NiCoO with a multilevel structure is obtained after drying2-Co3O4-PPy bimetallic oxide composite negative electrode material.
2. The method for preparing a bimetal oxide composite anode material with a multilevel structure according to claim 1, wherein the method comprises the following steps: the ammonium salt in the step (1) is NH4F, the amide is urea.
3. The method for preparing a bimetal oxide composite anode material with a multilevel structure according to claim 1, wherein the method comprises the following steps: the foam metal in the step (1) is foam nickel, the diameter is 14mm, the thickness is 1mm, and the pore diameter is 120 PPI.
4. The method for preparing a bimetal oxide composite anode material with a multilevel structure according to claim 1, wherein the method comprises the following steps: the surfactant in the step (2) is sodium dodecyl sulfate.
5. The method for preparing a bimetal oxide composite anode material with a multilevel structure according to claim 1, wherein the method comprises the following steps: the acid solution in the step (2) is hydrochloric acid solution.
6. The method for preparing a bimetal oxide composite anode material with a multilevel structure according to claim 1, wherein the method comprises the following steps: the oxidant in the step (2) is (NH)4)2S2O8。
7. The use of the bimetallic oxide composite negative electrode material obtained by the preparation method according to claim 1 as a negative electrode of a lithium ion battery.
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