CN111825070B - In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 Preparation method of/C composite material - Google Patents
In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 Preparation method of/C composite material Download PDFInfo
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Abstract
The invention discloses an in-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 Firstly, respectively dissolving phenylphosphonic acid and cobalt nitrate hexahydrate with the mass ratio of 1:1.3 into a mixed solvent with the volume ratio of anhydrous ethanol to ethylene glycol of 2:3, and then, reacting for 12-48 hours at 150 ℃ to prepare a flower-shaped cobalt phenylphosphonate coordination polymer [ Co (PhPO) 3 )]A precursor; 200mg Co (PhPO) was weighed out 3 ) In nitrogen atmosphere at 2 ℃ for min ‑1 The temperature rising speed of the catalyst is increased from normal temperature to the temperature (600-1000 ℃) required by calcination, and the catalyst is kept for two hours, so as to prepare the target product in-situ hybridized coordination polymer-derived porous flower-like Co 2 P 2 O 7 Composite material/C (Co 2 P 2 O 7 C-X; wherein X is the temperature of calcination). The in-situ hybridized coordination polymer derived porous flower-like Co provided by the invention 2 P 2 O 7 Preparation strategy of/C composite material, realizing nano Co 2 P 2 O 7 The in-situ hybridization of the particles and the nano graphitized carbon effectively enhances the conductivity and the circulation stability of the material, and has good application potential of the super capacitor.
Description
Technical Field
The invention belongs to the technical field of new functional materials, and in particular relates to an in-situ hybridization porous flower-shaped Co based on a cobalt phenylphosphonate coordination polymer 2 P 2 O 7 Controllable preparation method of/C composite material and its electrochemical energy storage application.
Background
With the rapid development of electric automobiles and mobile electronic devices, conventional energy storage devices cannot meet the increasing production demands of people, and therefore, the development of safe, efficient and convenient energy storage devices is particularly important. Super capacitor, as an emerging electric energy storage device, has the advantages of long cycle life, fast charge and discharge rate, high safety coefficient, high power density and the like, and is widely focused in the scientific community. It is well known that supercapacitors are largely classified into electric double layer supercapacitors and pseudocapacitance supercapacitors, depending on the charge storage mechanism. The pseudo-capacitor super capacitor realizes charge storage by means of redox reaction between electrode materials and electrolyte solution, so that the redox reaction activity between the electrode materials and the electrolyte solution is improved by designing and adjusting proper electrode materials, and the pseudo-capacitor super capacitor is one of strategies for improving the energy storage performance of the pseudo-capacitor super capacitor.
Transition metal phosphates (TMPs, M) x P y O z M=Co 2+ ,Ni 2+ ,Mn 2+ Et al) is a structurally stable class of materials with an open framework constructed from phosphate/pyrophosphate/phosphorus anions and metal ions. By Co 2 P 2 O 7 For example, the material has the advantages of excellent redox activity, abundant natural reserves, environmental friendliness and the like, and is one of potential candidate electrode materials. However, the electron conductivity of the material itself is low, limiting its energy storage properties. Therefore, designing and constructing a composite material of TMPs and a high-conductivity material, especially nano-scale composite and in-situ doping, is an effective way for solving the intrinsic conductivity defect of the material and improving the performance of the capacitor.
Coordination polymers are polymer network structures formed by mutually connecting metal ions and organic ligands through coordination bonds in a self-assembly mode. The porous ceramic material has the advantages of various structures and compositions, ultrahigh specific surface area, rich pore structures, adjustable pore diameters and the like, and is an ideal precursor for preparing the electrode material of the supercapacitor. In addition, the unique metal-organic hybridization structure of the coordination polymer can realize in-situ hybridization of inorganic nano particles and nano carbon, enhance the electronic conductivity of the composite material and promote the dynamic process of electrochemical reaction. Therefore, the coordination polymer precursor with specific morphology is designed and prepared, and the nano transition metal phosphate doped with in-situ carbon is constructed through a controllable treatment process, so that the intrinsic defect of the transition metal phosphate can be remarkably improved, and the performance of the supercapacitor is improved.
Disclosure of Invention
The invention provides an in-situ hybridization strategy, which is regulated and controlled by a precise preparation process and is based on flower-like cobalt phenylphosphonate coordination polymer [ Co (PhPO) 3 )]The unique coordination framework structure of the precursor maintains Co (PhPO by the high temperature heat conversion process 3 ) Precursor frame, co is prevented 2 P 2 O 7 Excessive agglomeration of nano particles, realizing nano Co 2 P 2 O 7 The specific capacity and the circulation stability of cobalt pyrophosphate are effectively enhanced by in-situ hybridization of particles and nano graphitized carbon.
The invention provides an in-situ hybridization coordination polymer derived porous flower-shaped Co 2 P 2 O 7 The preparation method of the/C composite material can be realized by the following technical route:
(1)Co(PhPO 3 ) Preparing a precursor: respectively dissolving phenylphosphonic acid and cobalt nitrate hexahydrate with the mass ratio of 1:1.3 into a mixed solvent of absolute ethyl alcohol and ethylene glycol with the volume ratio of 2:3, and carrying out ultrasonic dispersion for 30 minutes to uniformly mix the materials and form a uniform solution. Transferring the mixture into a high-pressure reaction kettle, and reacting for 12-48 hours at 150 ℃; the reaction time is 12 to 48 hours to obtain Co (PhPO 3 ) The material can be fully crystallized and mineralized, the crystallinity and the size of the material are smaller when the reaction time is too short, and the crystallinity and the size of the material are gradually increased when the reaction time is increased.
(2)Co 2 P 2 O 7 Preparation of a hybrid material: 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a tube furnace, and in nitrogen atmosphere, at 2deg.C for min -1 The temperature rising speed of (2) is increased from normal temperature to calcinationThe desired temperature (600-1000 ℃) is maintained for two hours at the temperature, and the target product in-situ hybridized coordination polymer derivative porous flower-shaped Co is prepared 2 P 2 O 7 Composite material/C (Co 2 P 2 O 7 C-X; wherein X is the temperature of calcination); the different calcining temperatures can influence the morphology, crystallinity, phase transition degree and the like of the material, when the temperature is too low, the material cannot be completely converted into cobalt pyrophosphate and graphitized carbon, and when the temperature is too high, the flower-like morphology of the precursor is difficult to maintain, and the nano flower-like structure of the material can be damaged.
As a further feature of the present invention: the solvothermal reaction time of the step (1) is 24 hours, and the obtained Co (PhPO) 3 ) The material presents a flower-like morphology piled up by a layered structure; although Co (PhPO) 3 ) The crystallinity of (c) differs from the nano-size, and the same applies to the subsequent thermal conversion process of the present invention, except that the properties differ.
As a further feature of the present invention: the calcination temperature in the step (2) is 900 ℃, and is named as Co 2 P 2 O 7 /C-900。
As a further feature of the present invention: in-situ hybridized coordination polymer derived porous flower-like Co obtained through step (2) 2 P 2 O 7 the/C composite material has good supercapacitor performance, and under the condition of a three-electrode system, the composite material is 1Ag -1 The specific capacity under the current density of 248.2-349.6F g -1 Wherein the optimal sample Co 2 P 2 O 7 C-900 at 2Ag -1 The capacity retention rate after 3000 cycles is as high as 97.33%, and the cycle stability is excellent.
As a further feature of the present invention: coordination polymer-derived porous flower-like Co subjected to in-situ hybridization in step (2) 2 P 2 O 7 the/C composite material can also be assembled with a graphene-based supercapacitor negative electrode material to construct a two-electrode supercapacitor, which is 0.375 kW.kg -1 At a power density of up to 21.9 Wh.kg -1 。
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
porous flower-like Co derived from coordination polymer hybridized in situ prepared by the invention 2 P 2 O 7 A/C composite based on an inorganic 2D [ Co (-PO) coated with an organic benzene ring 3 )(H 2 O) 2 ] n Cobalt phenylphosphonate coordination polymer of flower-like structure of layer composition [ Co (PhPO) 3 )]A precursor. In nitrogen atmosphere, converting the 2D inorganic layer in the precursor into Co through a high-temperature calcination process 2 P 2 O 7 The nano particles, meanwhile, the organic benzene ring on the surface of the 2D inorganic layer is converted into graphitized carbon in situ, and the graphitized carbon is covered on the surface of the inorganic layer to form porous flower-like Co 2 P 2 O 7 and/C composite material. Wherein, calcination is carried out under nitrogen atmosphere, oxygen is isolated, and the organic benzene ring in the material can be protected from oxidation. The formation of in-situ nano graphitized carbon can improve the electronic conductivity and the cycling stability of the material and simultaneously prevent Co 2 P 2 O 7 Excessive agglomeration of the nanoparticles provides more electrochemically active sites, increasing the specific capacity of the material. Therefore, the in situ hybridized coordination polymer derived porous flower-like Co prepared by the method of the invention 2 P 2 O 7 the/C composite material has better super capacitor performance, in particular, in 1A g -1 Its specific capacity can be up to 248.2-349.6F g under the condition of current density -1 Wherein the optimal sample Co 2 P 2 O 7 C-900 at 2Ag -1 The capacity retention rate after 3000 cycles was as high as 97.33%, showing excellent cycle stability.
Description of the drawings:
fig. 1: co (PhPO) in example 1 3 ) Scanning electron microscope images of the precursors;
fig. 2: co (PhPO) in example 1 3 ) Powder X-ray diffraction pattern of precursor;
fig. 3: co in example 1 2 P 2 O 7 Powder X-ray diffraction pattern of/C-900;
fig. 4: co in example 1 2 P 2 O 7 Scanning electron microscope image of/C-900;
fig. 5: co in example 1 2 P 2 O 7 Projection electron microscope of/C-900;
fig. 6: co in example 1 2 P 2 O 7 X-ray photoelectron spectrum of/C-900;
fig. 7: co in example 1 2 P 2 O 7 Constant current charge-discharge curve graph of C-900 at different sweep speeds;
fig. 8: co in example 1 2 P 2 O 7 Cycle stability test curve of/C-900 in a three electrode system;
fig. 9: co in example 2 2 P 2 O 7 -900 constant current charge-discharge curves at different sweep rates;
fig. 10: co in example 3 2 P 2 O 7 Constant current charge-discharge curve graph of/C-600 under different sweep speeds;
fig. 11: co in example 4 2 P 2 O 7 Constant current charge-discharge curve graph of/C-700 under different sweep speeds;
fig. 12: co in example 5 2 P 2 O 7 Constant current charge-discharge curve graph of/C-800 under different sweep speeds;
fig. 13: co in example 6 2 P 2 O 7 Constant current charge-discharge curve graph of/C-1000 under different sweep speeds.
Detailed Description
The technical features of the present invention will be described with reference to the following specific experimental schemes and drawings, but the present invention is not limited thereto. The test methods described in the examples below, unless otherwise specified, are all conventional; the apparatus and materials are commercially available unless otherwise specified.
Example 1
In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 The preparation method of the/C composite material comprises the following steps:
(1) Respectively dissolving phenylphosphonic acid and cobalt nitrate hexahydrate in a mass ratio of 1:1.3Adding the mixture into a mixed solvent of absolute ethyl alcohol and ethylene glycol in a volume ratio of 2:3, and performing ultrasonic dispersion for 30 minutes to uniformly mix the mixture and form a uniform solution. After that, it was transferred to an autoclave and reacted at 150℃for 24 hours. Naturally cooling the high-pressure reaction kettle to room temperature, collecting the obtained precipitate, centrifugally washing the precipitate with absolute ethyl alcohol for 2 to 3 times, and then drying the precipitate in an oven at 70 ℃ for 12 hours to obtain flower-like Co (PhPO) 3 ) A precursor. Co (PhPO) 3 ) The morphology of the precursor is shown in a scanning electron microscope image (figure 1); co (PhPO) 3 ) The crystallinity of the precursor is shown by its powder X-ray diffraction pattern (fig. 2).
(2) 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a tube furnace, and in nitrogen atmosphere, at 2deg.C for min -1 The temperature rise rate of (2) is increased from normal temperature to 900 ℃ and maintained at 900 ℃ for two hours to prepare Co 2 P 2 O 7 /C-900。Co 2 P 2 O 7 The crystallinity of/C-900 is shown in its powder X-ray diffraction pattern (FIG. 3); co (Co) 2 P 2 O 7 The morphology of the C-900 is shown in a scanning electron microscope image (figure 4), the material maintains the flower-shaped morphology of the precursor, and a porous framework is formed; co (Co) 2 P 2 O 7 The microscopic morphology of the/C-900 is shown as a projection electron microscope image (figure 5), and the porous flower-shaped framework of the material is formed by staggered support of nano branches constructed by some nano particles; co (Co) 2 P 2 O 7 The electron spectrum of the/C-900 is shown in an XPS chart (figure 6), and the material contains Co, P, C, O and other elements, which shows that the carbon element is successfully reserved after high-temperature calcination. Co (Co) 2 P 2 O 7 Constant current charge and discharge of the C-900 under different scanning speeds are shown in figure 7, and Co is obtained through calculation 2 P 2 O 7 C-900 at 1Ag -1 The specific capacity at the current density of (a) reaches 349.6F g -1 At 2Ag -1 The capacity retention was as high as 97.33% after 3000 cycles (fig. 8).
Example 2
In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 Preparation of a composite materialA method comprising the steps of:
(1)Co(PhPO 3 ) The precursor was prepared as in example 1.
(2) 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a muffle furnace, and in air at 2deg.C for min -1 The temperature rise rate of (2) is increased from normal temperature to 900 ℃ and maintained at 900 ℃ for two hours to prepare Co 2 P 2 O 7 -900。Co 2 P 2 O 7 Constant current charge and discharge of-900 under different scanning speeds are shown in figure 9, co is calculated through the graph 2 P 2 O 7 -900 at 1Ag -1 The specific capacity at the current density of (a) reaches 234F g -1 。
Example 3
In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 The preparation method of the/C composite material comprises the following steps:
(1)Co(PhPO 3 ) The precursor was prepared as in example 1.
(2) 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a tube furnace, and in nitrogen atmosphere, at 2deg.C for min -1 The temperature rise rate of (2) is raised from normal temperature to 600 ℃ and kept at 600 ℃ for two hours to prepare Co 2 P 2 O 7 /C-600。Co 2 P 2 O 7 Constant current charge and discharge of the C-600 under different scanning speeds are shown in figure 10, and Co is calculated through the graph 2 P 2 O 7 C-600 at 1A g -1 The specific capacity at the current density of (a) reaches 248.2F g -1 。
Example 4
In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 The preparation method of the/C composite material comprises the following steps:
(1)Co(PhPO 3 ) The precursor was prepared as in example 1.
(2) 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a tube furnace, and in nitrogen atmosphere, at 2deg.C for min -1 The temperature rising speed of (2) is from normalRaising the temperature to 700 ℃ and maintaining the temperature at 700 ℃ for two hours to prepare Co 2 P 2 O 7 /C-700。Co 2 P 2 O 7 Constant current charge and discharge of/C-700 under different scanning speeds are shown in FIG. 11, co is calculated by the graph 2 P 2 O 7 C-700 at 1Ag -1 The specific capacity at the current density of 313.8F g -1 。
Example 5
In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 The preparation method of the/C composite material comprises the following steps:
(1)Co(PhPO 3 ) The precursor was prepared as in example 1.
(2) 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a tube furnace, and in nitrogen atmosphere, at 2deg.C for min -1 The temperature rise rate of (2) is increased from normal temperature to 800 ℃, and the mixture is kept at 800 ℃ for two hours to prepare Co 2 P 2 O 7 /C-800。Co 2 P 2 O 7 Constant current charge and discharge of/C-800 under different scanning speeds are shown in FIG. 12, co is calculated by the graph 2 P 2 O 7 C-800 at 1A g -1 The specific capacity at the current density of (a) reaches 334.6F g -1 。
Example 6
In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 The preparation method of the/C composite material comprises the following steps:
(1)Co(PhPO 3 ) The precursor was prepared as in example 1.
(2) 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a tube furnace, and in nitrogen atmosphere, at 2deg.C for min -1 The temperature rise rate of (2) is raised from normal temperature to 1000 ℃ and kept at 1000 ℃ for two hours to prepare Co 2 P 2 O 7 /C-1000。Co 2 P 2 O 7 Constant current charge and discharge of/C-1000 under different scanning speeds is shown in FIG. 13, co is calculated by the graph 2 P 2 O 7 C-1000 at 1A g -1 The specific capacity at current density of 281F g -1 。
The description of the embodiments disclosed in the present invention is not intended to limit the scope of the present invention, but is used to describe the present invention. Accordingly, the scope of the invention is not limited by the above embodiments, but is defined by the claims or equivalents thereof.
Claims (5)
1. In-situ hybridized coordination polymer derived porous flower-like Co 2 P 2 O 7 The preparation method of the/C composite material is characterized by comprising the following steps:
(1)Co(PhPO 3 ) Preparing a precursor: respectively dissolving phenylphosphonic acid and cobalt nitrate hexahydrate with the mass ratio of 1:1.3 into a mixed solvent of absolute ethyl alcohol and ethylene glycol with the volume ratio of 2:3, and carrying out ultrasonic dispersion for 30 minutes to uniformly mix the materials and form a uniform solution. Then transferring the mixture into an autoclave, and reacting for 12-48 hours at 150 ℃.
(2)Co 2 P 2 O 7 Preparation of a hybrid material: 200mg Co (PhPO) was weighed out 3 ) Placing the precursor in a porcelain boat, placing the porcelain boat in a tube furnace, and in nitrogen atmosphere, at 2deg.C for min -1 The temperature rising speed of the catalyst is increased from normal temperature to the temperature (600-1000 ℃) required by calcination, and the catalyst is kept at the temperature for two hours, so as to prepare the target product in-situ hybridized coordination polymer-derived porous flower-like Co 2 P 2 O 7 Composite material/C, porous material obtained at 1Ag -1 The specific capacity under the current density of 248.2-349.6F g -1 。
2. The method of claim 1, wherein: the solvothermal reaction time of the step (1) is 24 hours
3. The method of claim 1, wherein: the calcination temperature in the step (2) is 900 ℃.
4. The process according to claim 1,the method is characterized in that: the step (2) is to obtain Co when the calcination temperature is 900 DEG C 2 P 2 O 7 composite/C2A g -1 The capacity retention rate is as high as 97.33% after 3000 cycles at a current density of (c).
5. The method of claim 1, wherein: in-situ hybridized coordination polymer derived porous flower-like Co obtained through step (2) 2 P 2 O 7 the/C composite material can also be assembled with a graphene-based supercapacitor negative electrode material to construct a two-electrode supercapacitor, which is 0.375 kW.kg -1 At a power density of up to 21.9 Wh.kg -1 。
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CN110707336A (en) * | 2019-08-30 | 2020-01-17 | 南京理工大学 | Cobalt metaphosphate/nitrogen carbon oxygen reduction catalyst and preparation method and application thereof |
CN113036101A (en) * | 2021-02-26 | 2021-06-25 | 中国科学院宁波材料技术与工程研究所 | Carbon-coated pyrophosphate and preparation method and application thereof |
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