阅读说明：本技术 一种镍基金属有机框架衍生的复合电极材料及其制备方法 (Composite electrode material derived from nickel-based metal organic framework and preparation method thereof ) 是由 严平 陈修栋 刘金杭 李振峰 于 2021-08-06 设计创作，主要内容包括：本发明提供了一种镍基金属有机框架衍生的复合电极材料及其制备方法,所述制备方法包括以下步骤：(1)将六水合氯化镍和丙二酸分别溶于N,N-二甲基甲酰胺中,搅拌使其完全溶解；(2)将两种溶液混合后置于烘箱内反应；(3)洗涤上述反应得到的生成物,离心分离后将生成物干燥,得到前体材料；(4)将前体材料在管式炉中先升温,再进行退火处理得到花状电极材料；(5)将花状电极材料和导电炭黑、PVDF胶黏剂混合均匀形成混合物,再加入N,N-二甲基吡咯烷酮中,用高速内旋式打浆机分散浆液,得到黑色胶状浆料；(6)将黑色胶状浆料均匀的涂覆在事先处理好的铜箔上,并置于真空干燥箱中干燥,制备得到复合电极材料。(The invention provides a composite electrode material derived from a nickel-based metal organic framework and a preparation method thereof, wherein the preparation method comprises the following steps: (1) respectively dissolving nickel chloride hexahydrate and malonic acid in N, N-dimethylformamide, and stirring to completely dissolve the nickel chloride hexahydrate and the malonic acid; (2) mixing the two solutions and placing the mixture in a drying oven for reaction; (3) washing a product obtained by the reaction, centrifugally separating, and drying the product to obtain a precursor material; (4) heating the precursor material in a tubular furnace, and then annealing to obtain a flower-shaped electrode material; (5) uniformly mixing the flower-shaped electrode material, conductive carbon black and a PVDF adhesive to form a mixture, adding the mixture into N, N-dimethyl pyrrolidone, and dispersing slurry by using a high-speed internal rotation type pulping machine to obtain black colloidal slurry; (6) and uniformly coating the black colloidal slurry on the copper foil which is processed in advance, and drying in a vacuum drying oven to prepare the composite electrode material.)

1. A preparation method of a composite electrode material derived from a nickel-based metal organic framework is characterized by comprising the following steps:

(1) respectively dissolving nickel chloride hexahydrate and malonic acid in N, N-dimethylformamide, and stirring to completely dissolve the nickel chloride hexahydrate and the malonic acid;

(2) mixing the two solutions obtained in the step (1), uniformly stirring, transferring to a polytetrafluoroethylene lining reaction kettle, and placing in an oven for reaction;

(3) washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;

(4) placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat in the air atmosphere, and then annealing the porcelain boat to obtain a flower-shaped electrode material;

(5) uniformly mixing the flower-shaped electrode material obtained in the step (4), conductive carbon black and a PVDF adhesive to form a mixture, adding the mixture into N, N-dimethyl pyrrolidone, and dispersing slurry by using a high-speed internal rotation type pulping machine to obtain black colloidal slurry;

(6) and (5) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, and placing the copper foil in a vacuum drying oven for drying to prepare the composite electrode material.

2. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass ratio of the nickel chloride hexahydrate to the malonic acid is 2-3: 1.

3. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass-to-volume ratio of the nickel chloride hexahydrate to the N, N-dimethylformamide is 3-8: 100 g/mL, and the mass-to-volume ratio of the malonic acid to the N, N-dimethylformamide is 1-5: 100 g/mL.

4. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass ratio of the flower-shaped electrode material to the conductive carbon black to the PVDF adhesive is 7-10: 1: 1.

5. The method for preparing the composite electrode material derived from the nickel-based metal organic framework, according to claim 1, is characterized in that: the mass-volume ratio of a mixture formed by the flower-shaped electrode material, the conductive carbon black and the PVDF adhesive to the N, N-dimethyl pyrrolidone is 0.20-0.24: 100 g/mL.

6. The method for preparing the composite electrode material derived from the nickel-based metal organic framework according to any one of claims 1 to 5, wherein the method comprises the following steps: in the step (2), the reaction temperature is 150-200 ℃ and the reaction time is 10-15 h.

7. The method for preparing the composite electrode material derived from the nickel-based metal organic framework according to any one of claims 1 to 5, wherein the method comprises the following steps: in the step (4), the temperature is raised to 450-550 ℃ at the temperature rise rate of 2-5 ℃/min in the air atmosphere, and then annealing treatment is carried out for 1-4 hours to obtain the flower-shaped electrode material.

8. The method for preparing the composite electrode material derived from the nickel-based metal organic framework according to any one of claims 1 to 5, wherein the method comprises the following steps: in the step (6), the drying temperature is 50-80 ℃, and the drying time is 10-15 h.

9. A composite electrode material derived from a nickel-based metal organic framework is characterized in that: the composite electrode material is prepared by the method provided by any one of claims 1-8.

Technical Field

The invention relates to the technical field of energy storage devices and new material preparation, in particular to a composite electrode material derived from a nickel-based metal organic framework and a preparation method thereof.

Background

Currently, the energy density of commercial lead-acid batteries, alkaline zinc-manganese batteries, and other secondary batteries has not met the increasing demand of people. Meanwhile, lead-acid batteries and alkaline zinc-manganese batteries have many problems, such as poor portability, high recycling difficulty, environmental friendliness and the like. In order to solve the above problems, researchers have developed many new types of energy storage devices, such as fuel cells, aluminum ion batteries, lithium air batteries, magnesium ion batteries, lithium sulfur batteries, sodium ion batteries, potassium ion batteries, and the like. However, they also have problems such as cycle performance and safety performance, which require further solution, and thus are far from the commercialized road. Lithium ion batteries having excellent performance have been widely used and gradually become the mainstream of secondary batteries. However, with the improvement of living standard of people, lithium ion batteries with better performance are urgently needed.

Nickel-based metal organic frame materials have been widely used in various fields such as gas separation/storage, sewage treatment, optical devices, energy storage, and the like. Currently, nickel-based metal organic framework derivative materials with regular shapes obtained by regulating and controlling reaction conditions are widely researched. Many documents have reported that nickel-based metal organic framework derivative materials with uniform and regular structures can have excellent electrochemical energy.

Currently, research on lithium ion negative electrode materials mainly focuses on developing transition metal oxides and transition metal sulfides with different morphologies, and has already been carried out with relatively good results. However, research on novel nickel-based metal organic framework materials is still relatively small, especially flower-like materials derived from the nickel-based metal organic framework materials.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:

(1) respectively dissolving nickel chloride hexahydrate and malonic acid in N, N-dimethylformamide, and stirring to completely dissolve the nickel chloride hexahydrate and the malonic acid;

(2) mixing the two solutions obtained in the step (1), uniformly stirring, transferring to a polytetrafluoroethylene lining reaction kettle, and placing in an oven for reaction;

(3) washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;

(4) placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat in the air atmosphere, and then annealing the porcelain boat to obtain a flower-shaped electrode material;

(5) uniformly mixing the flower-shaped electrode material obtained in the step (4), conductive carbon black and a PVDF adhesive to form a mixture, adding the mixture into N, N-dimethyl pyrrolidone, and dispersing slurry by using a high-speed internal rotation type pulping machine to obtain black colloidal slurry;

(6) and (5) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, and placing the copper foil in a vacuum drying oven for drying to prepare the composite electrode material.

Wherein the mass ratio of the nickel chloride hexahydrate to the malonic acid is 2-3: 1.

Preferably, the mass ratio of the nickel chloride hexahydrate to the malonic acid is 2.2:1, 2.4:1, 2.5:1, 2.6:1, 2.8: 1.

The mass-volume ratio of the nickel chloride hexahydrate to the N, N-dimethylformamide is 3-8: 100 g/mL, and the mass-volume ratio of the malonic acid to the N, N-dimethylformamide is 1-5: 100 g/mL.

Preferably, the first and second electrodes are formed of a metal,

the mass-volume ratio of the nickel chloride hexahydrate to the N, N-dimethylformamide is 4:100 g/mL, 5:100 g/mL, 6:100 g/mL and 7:100 g/mL;

the mass-volume ratio of the malonic acid to the N, N-dimethylformamide is 2:100 g/mL, 3:100 g/mL and 4:100 g/mL.

The mass ratio of the flower-shaped electrode material to the conductive carbon black to the PVDF adhesive is 7-10: 1: 1.

Preferably, the mass ratio of the flower-shaped electrode material to the conductive carbon black to the PVDF adhesive is 8:1:1 and 9:1: 1.

The mass-volume ratio of a mixture formed by the flower-shaped electrode material, the conductive carbon black and the PVDF adhesive to the N, N-dimethyl pyrrolidone is 0.20-0.24: 100 g/mL.

Preferably, the mass-to-volume ratio of the mixture to the N, N-dimethylpyrrolidone is 0.21:100 g/mL, 0.22:100 g/mL, 0.23:100 g/mL.

Wherein in the step (2), the reaction temperature is 150-200 ℃ and the reaction time is 10-15 h.

Preferably, the first and second electrodes are formed of a metal,

the reaction temperature is 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ and 195 ℃;

the reaction time is 11h, 12h, 13h and 14 h.

In the step (4), the temperature is raised to 450-550 ℃ at a heating rate of 2-5 ℃/min in the air atmosphere, and then annealing treatment is carried out for 1-4 hours to obtain the flower-shaped electrode material.

Wherein in the step (6), the drying temperature is 50-80 ℃ and the drying time is 10-15 h.

Preferably, the first and second electrodes are formed of a metal,

the drying temperature is 55 ℃, 60 ℃, 65 ℃, 70 ℃ and 75 ℃;

the drying time is 11h, 12h, 13h and 14 h.

In a second aspect, the invention provides a nickel-based metal organic framework-derived composite electrode material, which is prepared according to the method provided by the first aspect of the invention.

The invention has the beneficial effects that:

the composite electrode material derived from the nickel-based metal organic framework prepared by the simple hydrothermal method has higher capacity mainly due to the stable porous structure and the special morphology, is favorable for the infiltration of electrolyte and effectively relieves the volume expansion and structural pulverization of the electrode material in the charging and discharging processes, thereby improving the electrochemical performance.

Drawings

In order to more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it should be obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is an XRD spectrum of a nickel-based metal organic framework material prepared by the method provided in example 1 of the present invention;

FIGS. 2 and 3 are SEM images of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 of the present invention;

FIG. 4 is a charge-discharge curve diagram of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 of the present invention;

FIG. 5 shows that the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 of the present invention is 0.1A g^-1A plot of the cycle at current density;

FIG. 6 is a graph of the impedance of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1.

Detailed Description

The following is a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention.

Example 1

The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:

(1) weighing 0.5 g of nickel chloride hexahydrate and 0.2 g of malonic acid, respectively dissolving in 10mL of N, N-dimethylformamide, and stirring for 10 min to completely dissolve the nickel chloride hexahydrate and the malonic acid;

(2) mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting at 180 ℃ for 12 h;

(3) washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;

(4) placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat to 500 ℃ at a heating rate of 2 ℃/min in the air atmosphere, and then annealing for 2 hours to obtain a flower-shaped electrode material;

(5) weighing 17.6 mg of the flower-shaped electrode material obtained in the step (4), 2.2 mg of conductive carbon black and 2.2 mg of PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, and repeating for 5 times for 1min each time to obtain black colloidal slurry;

(6) and (3) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, placing the copper foil in a vacuum drying oven, and drying the copper foil for 12 hours at the temperature of 60 ℃ to prepare the composite electrode material.

The composite electrode material prepared in example 1 was assembled into button cells for evaluation, and LiPF with lithium foil as a reference electrode, a polypropylene porous membrane (Celgard 2300) as a separator, and 1mol/L electrolyte was used₆The cells were assembled with a mixed solution of ethylene carbonate and diethyl carbonate (w/w, 1/1) in a glove box filled with high-purity argon gas. On the LAND-CT2001C system, at 0.1A g^-1The battery is subjected to lithium intercalation and lithium deintercalation circulation at 0.1 mV s on a Chenghua 760E electrochemical station^-1And the test voltage range is 1 mV-3.0V, and CV test is carried out.

Fig. 1 is an XRD spectrum of the ni-based metal organic framework material prepared by the method provided in example 1, and it can be seen that there are five different characteristic peaks, from which it can be seen that the ni-based metal organic framework material has a stable crystal structure.

FIGS. 2 and 3 are SEM images of the composite electrode material derived from the Ni-based metal organic framework prepared by the method provided in example 1, and it can be seen that the electrode material has a flower-like structure with a diameter of about 200-300 nm.

Fig. 4 is a charge-discharge curve diagram of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1, and the platform of the reaction can be clearly seen from the curve in the first circle in the figure, and meanwhile, the coulombic efficiency of the nickel-based metal organic framework-derived composite electrode is 68.2%, and the main reason for the capacity loss is the formation of a solid electrolyte interface film.

FIG. 5 shows that the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 is 0.1A g^-1The graph of the cycle at current density shows that 1205mAh g is reached after the first 10 cycles^-1From this, it can be seen that: the composite electrode material derived from the nickel-based metal organic framework is a potential high-performance electrode material.

Fig. 6 is a resistance curve diagram of the composite electrode material derived from the nickel-based metal organic framework prepared by the method provided in example 1, and it can be seen from the impedance curve diagram that the resistance of the flower-shaped electrode material is only 130 Ω after one cycle, and thus it can be seen that the composite electrode material derived from the nickel-based metal organic framework has high electrical conductivity.

Example 2

The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:

(1) weighing 0.4 g of nickel chloride hexahydrate and 0.2 g of malonic acid, respectively dissolving in 10mL of N, N-dimethylformamide, and stirring for 10 min to completely dissolve the nickel chloride hexahydrate and the malonic acid;

(2) mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene-lined reaction kettle, placing in an oven, and reacting for 14h at 160 ℃;

(3) washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;

(4) placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating to 480 ℃ at a heating rate of 4 ℃/min in an air atmosphere, and then annealing for 3 hours to obtain a flower-shaped electrode material;

(5) weighing 16.0 mg of the flower-shaped electrode material obtained in the step (4), 2.0 mg of conductive carbon black and 2.0 mg of PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, 1min each time, and repeating for 6 times to obtain black colloidal slurry;

(6) and (3) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, placing the copper foil in a vacuum drying oven, and drying for 14 hours at the temperature of 55 ℃ to prepare the composite electrode material.

Example 3

The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:

(1) weighing 0.6 g of nickel chloride hexahydrate and 0.2 g of malonic acid, respectively dissolving in 10mL of N, N-dimethylformamide, and stirring for 10 min to completely dissolve the nickel chloride hexahydrate and the malonic acid;

(2) mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting for 10 h at 200 ℃;

(3) washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;

(4) placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tube furnace, heating to 520 ℃ at a heating rate of 3 ℃/min in an air atmosphere, and then annealing for 1.5 h to obtain a flower-shaped electrode material;

(5) weighing 17.5 mg of the flower-shaped electrode material obtained in the step (4), 2.5 mg of conductive carbon black and 2.5 mg of PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, 1min each time, and repeating for 5 times to obtain black colloidal slurry;

(6) and (3) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, placing the copper foil in a vacuum drying oven, and drying the copper foil for 15 hours at the temperature of 50 ℃ to prepare the composite electrode material.

Example 4

The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:

(1) weighing 0.5 g of nickel chloride hexahydrate and 0.2 g of malonic acid, respectively dissolving in 10mL of N, N-dimethylformamide, and stirring for 10 min to completely dissolve the nickel chloride hexahydrate and the malonic acid;

(2) mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting for 13h at 170 ℃;

(3) washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;

(4) placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat to 450 ℃ at a heating rate of 5 ℃/min in the air atmosphere, and then annealing for 4 hours to obtain a flower-shaped electrode material;

(5) weighing 20.0 mg of the flower-shaped electrode material obtained in the step (4), 2.0 mg of conductive carbon black and 2.0 mg of PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, 1min each time, and repeating for 6 times to obtain black colloidal slurry;

(6) and (3) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, placing the copper foil in a vacuum drying oven, and drying for 11 hours at the temperature of 75 ℃ to prepare the composite electrode material.

Example 5

The invention provides a preparation method of a composite electrode material derived from a nickel-based metal organic framework, which comprises the following steps:

(1) weighing 0.6 g of nickel chloride hexahydrate and 0.2 g of malonic acid, respectively dissolving in 10mL of N, N-dimethylformamide, and stirring for 10 min to completely dissolve the nickel chloride hexahydrate and the malonic acid;

(2) mixing the two solutions obtained in the step (1), stirring for 20 min, uniformly mixing, transferring to a 50mL polytetrafluoroethylene lining reaction kettle, placing in an oven, and reacting for 15h at 150 ℃;

(3) washing the product obtained by the reaction in the step (2) with water, N-dimethylformamide and ethanol in sequence, removing unreacted ions in the product, and placing the product obtained by centrifugal separation into a vacuum drying oven for drying to obtain a precursor material;

(4) placing the precursor material obtained in the step (3) in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the porcelain boat to 550 ℃ at a heating rate of 3 ℃/min in an air atmosphere, and then annealing for 1h to obtain a flower-shaped electrode material;

(5) weighing 20.0 mg of the flower-shaped electrode material obtained in the step (4), 2.0 mg of conductive carbon black and 2.0 mg of PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing slurry by using a high-speed internal rotation type pulping machine, and repeating for 5 times for 1min each time to obtain black colloidal slurry;

(6) and (3) uniformly coating the black colloidal slurry obtained in the step (5) on the copper foil which is processed in advance, placing the copper foil in a vacuum drying oven, and drying the copper foil for 12 hours at the temperature of 65 ℃ to prepare the composite electrode material.

The above examples only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the spirit of the present invention, and these changes and modifications are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.