CN113725434B - Nickel-based metal organic frame derived composite electrode and preparation method thereof - Google Patents

Nickel-based metal organic frame derived composite electrode and preparation method thereof Download PDF

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CN113725434B
CN113725434B CN202110902068.9A CN202110902068A CN113725434B CN 113725434 B CN113725434 B CN 113725434B CN 202110902068 A CN202110902068 A CN 202110902068A CN 113725434 B CN113725434 B CN 113725434B
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CN113725434A (en
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严平
陈修栋
刘金杭
李振峰
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Jiujiang University
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Abstract

The invention provides a nickel-based metal organic framework derived composite electrode material 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 then placing the mixed solutions in an oven for reaction; (3) Washing the resultant obtained by the reaction, and drying the resultant after centrifugal separation to obtain a precursor material; (4) Heating the precursor material in a tube furnace, and then annealing to obtain a flower-shaped electrode material; (5) Uniformly mixing a flower-shaped electrode material with conductive carbon black and 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 beater to obtain black glue-shaped slurry; (6) And uniformly coating the black glue-like slurry on the copper foil which is treated in advance, and drying in a vacuum drying oven to prepare the composite electrode material.

Description

Nickel-based metal organic frame derived composite electrode and preparation method thereof
Technical Field
The invention relates to the technical field of energy storage devices and new material preparation, in particular to a nickel-based metal organic framework derived composite electrode material and a preparation method thereof.
Background
Currently, the energy density of secondary batteries such as commercial lead-acid batteries and alkaline zinc-manganese batteries has not met the increasing needs of people. Meanwhile, lead-acid batteries and alkaline zinc-manganese batteries have a plurality of problems such as poor portability, high recycling difficulty, and environment friendliness. In order to solve the above problems, researchers have developed many new 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 present problems such as cycle performance and safety performance that need to be further solved, and thus are far from commercialized roads. Lithium ion batteries having excellent properties have been widely used, and have gradually become the mainstream of secondary batteries. However, as the living standard of people increases, lithium ion batteries having more excellent performance are urgently demanded.
Nickel-based metal organic framework 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 morphology are widely studied, especially by regulating reaction conditions. Many documents have reported that structurally uniform, structured nickel-based metal-organic framework-derived materials are capable of excellent electrochemical energy.
The current research of lithium ion anode materials mainly focuses on developing transition metal oxides and transition metal sulfides with different morphologies, and good results are already achieved. However, new nickel-based metal organic framework materials have been less studied, in particular based on flower-like materials derived from nickel-based metal organic framework materials.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a preparation method of a nickel-based metal-organic framework-derived composite electrode material, 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, and transferring to a polytetrafluoroethylene lining reaction kettle to be placed 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 drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) The precursor material obtained in the step (3) is placed in a porcelain boat and is transferred into a tube furnace, and the temperature is firstly increased under the air atmosphere, and then annealing treatment is carried out to obtain a flower-shaped electrode material;
(5) Uniformly mixing the flower-like electrode material obtained in the step (4) with conductive carbon black and PVDF adhesive to form a mixture, adding the mixture into N, N-dimethyl pyrrolidone, and dispersing slurry by using a high-speed internal rotation beater to obtain black glue-like slurry;
(6) And (3) uniformly coating the black glue-like slurry obtained in the step (5) on the copper foil which is treated in advance, and drying in a vacuum drying oven to obtain 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 method comprises the steps of,
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-like electrode material, the conductive carbon black and the PVDF adhesive is 8:1:1,9:1:1.
The mass volume ratio of the 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.
In the step (2), the reaction temperature is 150-200 ℃ and the reaction time is 10-15 h.
Preferably, the method comprises the steps of,
the reaction temperature is 155 ℃,160 ℃,165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃ and 195 ℃;
the reaction time was 11h,12h,13h, and 14h.
In the step (4), the temperature is raised to 450-550 ℃ at a heating rate of 2-5 ℃/min under the air atmosphere, and then annealing treatment is carried out for 1-4 hours to obtain the flower-shaped electrode material.
In the step (6), the drying temperature is 50-80 ℃ and the drying time is 10-15 h.
Preferably, the method comprises the steps of,
the drying temperature is 55 ℃,60 ℃,65 ℃,70 ℃ and 75 ℃;
the drying time was 11h,12h,13h,14h.
In a second aspect, the invention provides a nickel-based metal-organic framework-derived composite electrode material prepared according to the method provided in the first aspect.
The invention has the beneficial effects that:
the nickel-based metal organic framework derived composite electrode material prepared by the simple hydrothermal method has higher capacity, is mainly due to a stable porous structure and special morphology, is favorable for electrolyte infiltration and effectively relieves volume expansion and structural pulverization of the electrode material in the charge and discharge process, and thus improves electrochemical performance.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings that need to be 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 other drawings can be obtained according to these drawings without inventive effort to those skilled in the art.
FIG. 1 is an XRD pattern 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 nickel-based metal-organic framework-derived composite electrode materials prepared by the method provided in example 1 of the present invention;
FIG. 4 is a charge-discharge graph of a nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 of the present invention;
FIG. 5 is the presentThe nickel-based organic frame derived composite electrode material prepared by the method provided in the invention example 1 is 0.1A g -1 Cycling profile at current density;
fig. 6 is a graph of the impedance of a nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1.
Description of the embodiments
The following are preferred embodiments of the present invention, and it should be noted that modifications and variations can be made by those skilled in the art without departing from the principle of the present invention, and these modifications and variations are also considered as the protection scope of the present invention.
Example 1
The invention provides a preparation method of a nickel-based metal organic framework derived composite electrode material, 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 polytetrafluoroethylene lining reaction kettle of 50mL, placing in a baking 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 drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) Transferring the precursor material obtained in the step (3) into a tube furnace, heating to 500 ℃ at a heating rate of 2 ℃/min under air atmosphere, and performing annealing treatment 2h to obtain a flower-shaped electrode material;
(5) Weighing the flower-like electrode material obtained in the step (4) of 17.6 and mg, uniformly mixing 2.2 mg of conductive carbon black and 2.2 mg of PVDF adhesive to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing the slurry by using a high-speed internal rotation beater for 1min each time, and repeating for 5 times to obtain black colloidal slurry;
(6) And (3) uniformly coating the black glue-like slurry obtained in the step (5) on the copper foil which is treated in advance, and placing the copper foil in a vacuum drying oven to dry 12h at 60 ℃ to prepare the composite electrode material.
The composite electrode material prepared in example 1 was assembled into a coin cell for evaluation, using a lithium foil as a reference electrode, a polypropylene porous membrane (Celgard 2300) as a separator, and LiPF with an electrolyte of 1mol/L 6 The battery was assembled in a glove box filled with high purity argon, with a mixed solution of ethylene carbonate and diethyl carbonate (w/w, 1/1). On the LAND-CT2001C system, at 0.1A g -1 The battery is subjected to lithium intercalation and deintercalation circulation under the current of 0.1 mV s on the Chenhua 760E electrochemical station -1 The CV test was performed with a test voltage range of 1 mV-3.0V.
FIG. 1 is an XRD pattern of a nickel-based metal-organic framework material prepared by the method provided in example 1, and five different characteristic peaks can be seen from the figure, so that the stable crystal structure of the nickel-based metal-organic framework material can be seen.
Fig. 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, and it can be seen from the figures that the electrode material has a flower-like structure with a diameter of about 200-300 a nm a.
Fig. 4 is a charge-discharge graph of the nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1, and a reaction plateau can be clearly seen from the first circle of graph, and the coulomb efficiency of the nickel-based metal organic framework-derived composite electrode is 68.2%, so that the main reason for capacity loss is the formation of a solid electrolyte interface film.
FIG. 5 is a graph of 0.1A g of a nickel-based metal organic framework-derived composite electrode material prepared by the method provided in example 1 -1 The graph of the cycle at current density shows that 1205 mAh g was reached after the first 10 cycles -1 From this, it can be seen that: the nickel-based metal organic framework-derived composite electrode material is a potential high performance electrode material.
Fig. 6 is a graph showing the impedance of the nickel-based metal organic frame-derived composite electrode material prepared by the method provided in example 1, and it can be seen from the graph that the impedance of the flower-shaped electrode material is only 130 Ω after one cycle, so that the nickel-based metal organic frame-derived composite electrode material has high conductivity.
Example 2
The invention provides a preparation method of a nickel-based metal organic framework derived composite electrode material, 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 polytetrafluoroethylene lining reaction kettle of 50mL, placing in a baking oven, and reacting at 160 ℃ for 14 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 drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) Transferring the precursor material obtained in the step (3) into a tube furnace, heating to 480 ℃ at a heating rate of 4 ℃/min under air atmosphere, and then carrying out annealing treatment 3h to obtain a flower-shaped electrode material;
(5) Weighing the flower-like electrode material obtained in the step (4) of 16.0 mg, 2.0 mg conductive carbon black and 2.0 mg PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing the slurry by using a high-speed internal rotation beater for 1min each time, and repeating for 6 times to obtain black colloidal slurry;
(6) And (3) uniformly coating the black glue-like slurry obtained in the step (5) on the copper foil which is treated in advance, and placing the copper foil in a vacuum drying oven to dry 14 and h at 55 ℃ to prepare the composite electrode material.
Example 3
The invention provides a preparation method of a nickel-based metal organic framework derived composite electrode material, 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 polytetrafluoroethylene lining reaction kettle of 50mL, placing in a baking oven, and reacting at 200 ℃ for 10 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 drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) Transferring the precursor material obtained in the step (3) into a tube furnace, heating to 520 ℃ at a heating rate of 3 ℃/min under air atmosphere, and then carrying out annealing treatment of 1.5 h to obtain a flower-shaped electrode material;
(5) Weighing the flower-like electrode material obtained in the step (4) of 17.5 mg, 2.5 mg conductive carbon black and 2.5 mg PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing the slurry by using a high-speed internal rotation beater for 1min each time, and repeating for 5 times to obtain black colloidal slurry;
(6) And (3) uniformly coating the black glue-like slurry obtained in the step (5) on the copper foil which is treated in advance, and placing the copper foil in a vacuum drying oven to dry 15h at 50 ℃ to prepare the composite electrode material.
Example 4
The invention provides a preparation method of a nickel-based metal organic framework derived composite electrode material, 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 polytetrafluoroethylene lining reaction kettle of 50mL, placing in a baking oven, and reacting at 170 ℃ to obtain 13 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 drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) Transferring the precursor material obtained in the step (3) into a tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under air atmosphere, and performing annealing treatment for 4 hours to obtain a flower-shaped electrode material;
(5) Weighing the flower-like electrode material obtained in the step (4) of 20.0 mg, 2.0 mg conductive carbon black and 2.0 mg PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing the slurry by using a high-speed internal rotation beater for 1min each time, and repeating for 6 times to obtain black colloidal slurry;
(6) And (3) uniformly coating the black glue-like slurry obtained in the step (5) on the copper foil which is treated in advance, and placing the copper foil in a vacuum drying oven to dry 11h at 75 ℃ to prepare the composite electrode material.
Example 5
The invention provides a preparation method of a nickel-based metal organic framework derived composite electrode material, 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 into a 50mL polytetrafluoroethylene lining reaction kettle, and placing into a baking oven for reaction at 150 ℃ to obtain 15h;
(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 drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) Transferring the precursor material obtained in the step (3) into a tube furnace, heating to 550 ℃ at a heating rate of 3 ℃/min under air atmosphere, and then carrying out annealing treatment 1h to obtain a flower-shaped electrode material;
(5) Weighing the flower-like electrode material obtained in the step (4) of 20.0 mg, 2.0 mg conductive carbon black and 2.0 mg PVDF adhesive, uniformly mixing to form a mixture, adding the mixture into 10mL of N, N-dimethyl pyrrolidone, dispersing the slurry by using a high-speed internal rotation beater for 1min each time, and repeating for 5 times to obtain black colloidal slurry;
(6) And (3) uniformly coating the black glue-like slurry obtained in the step (5) on the copper foil which is treated in advance, and placing the copper foil in a vacuum drying oven to dry 12h at 65 ℃ to prepare the composite electrode material.
The foregoing examples merely illustrate specific embodiments of the invention, which are described in greater detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (5)

1. A method for preparing a nickel-based metal organic frame-derived composite electrode, which 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, and transferring to a polytetrafluoroethylene lining reaction kettle to be placed 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 drying the product obtained by centrifugal separation in a vacuum drying oven to obtain a precursor material;
(4) The precursor material obtained in the step (3) is placed in a porcelain boat and is transferred into a tube furnace, and the temperature is firstly increased under the air atmosphere, and then annealing treatment is carried out to obtain a flower-shaped electrode material;
(5) Uniformly mixing the flower-like electrode material obtained in the step (4) with conductive carbon black and PVDF adhesive to form a mixture, adding the mixture into N, N-dimethyl pyrrolidone, and dispersing slurry by using a high-speed internal rotation beater to obtain black glue-like slurry;
(6) Uniformly coating the black glue-like slurry obtained in the step (5) on a copper foil which is treated in advance, and drying in a vacuum drying oven to prepare a composite electrode;
the mass ratio of the nickel chloride hexahydrate to the malonic acid is 2-3:1;
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;
in the step (2), the reaction temperature is 150-200 ℃ and the reaction time is 10-15 h;
in the step (4), the temperature is firstly increased to 450-550 ℃ at the temperature increasing rate of 2-5 ℃/min under the air atmosphere, and then annealing treatment is carried out for 1-4 hours to obtain the flower-shaped electrode material.
2. The method for preparing the nickel-based metal organic framework-derived composite electrode according to claim 1, wherein the method comprises the following steps: the mass ratio of the flower-shaped electrode material to the conductive carbon black to the PVDF adhesive is 7-10:1:1.
3. The method for preparing the nickel-based metal organic framework-derived composite electrode according to claim 1, wherein the method comprises the following steps: the mass volume ratio of the 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.
4. A method for preparing a nickel-based metal organic framework-derived composite electrode according to any one of claims 1 to 3, wherein the method comprises the steps of: in the step (6), the drying temperature is 50-80 ℃ and the drying time is 10-15 h.
5. A nickel-based metal organic framework-derived composite electrode characterized by: the composite electrode is prepared by the preparation method according to any one of claims 1-4.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028989A1 (en) * 2010-09-01 2012-03-08 Basf Se Process for producing carbon-comprising composite
CN102962037A (en) * 2012-11-01 2013-03-13 中国科学院大连化学物理研究所 Metal-organic framework material for methane adsorption separation and preparation method thereof
CN103086867A (en) * 2011-10-27 2013-05-08 中国科学院大连化学物理研究所 Nickel base micropore material and preparation method thereof
CN111204822A (en) * 2020-01-08 2020-05-29 九江学院 Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure
CN112893858A (en) * 2019-11-19 2021-06-04 中国科学院大连化学物理研究所 Preparation method of nickel-carbon-based material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012028989A1 (en) * 2010-09-01 2012-03-08 Basf Se Process for producing carbon-comprising composite
CN103086867A (en) * 2011-10-27 2013-05-08 中国科学院大连化学物理研究所 Nickel base micropore material and preparation method thereof
CN102962037A (en) * 2012-11-01 2013-03-13 中国科学院大连化学物理研究所 Metal-organic framework material for methane adsorption separation and preparation method thereof
CN112893858A (en) * 2019-11-19 2021-06-04 中国科学院大连化学物理研究所 Preparation method of nickel-carbon-based material
CN111204822A (en) * 2020-01-08 2020-05-29 九江学院 Preparation method of NiO-ZnO/S lithium-sulfur battery positive electrode material with flower-like structure

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