CN113948713A - A method for preparing nanocomposite cathode material by electrospinning coupled impregnation method - Google Patents
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- 239000010406 cathode material Substances 0.000 title claims abstract description 60
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000005470 impregnation Methods 0.000 title claims abstract description 17
- 238000001523 electrospinning Methods 0.000 title claims abstract 12
- 239000002121 nanofiber Substances 0.000 claims abstract description 77
- 238000009987 spinning Methods 0.000 claims abstract description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 238000002360 preparation method Methods 0.000 claims abstract description 5
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Abstract
本发明提供了一种静电纺丝耦合浸渍法制备纳米复合阴极材料的方法，具体涉及了一种静电纺丝耦合浸渍法制备质子导体固体氧化物燃料电池纳米复合阴极材料的方法，属能源材料技术领域。该制备方法首先配制包括金属盐混合物、N，N‑二甲基甲酰胺、聚乙烯吡咯烷酮的混合纺丝溶液，然后利用静电纺丝技术将以上混合溶液进行纺丝制备纺丝物，再将纺丝物放入箱式炉中煅烧，获得BCFZYO纳米纤维；然后通过原位浸渍法，使得BCFZYO纳米纤维表面产生纳米颗粒GCO，从而得到纳米复合阴极材料GCO‑BCFZYO。本发明得到的纳米复合阴极材料GCO‑BCFZYO具有更高的电催化活性和比表面积，具有更多的电化学反应活性点，加速了阴极反应动力学，有效降低了质子导体固体氧化物燃料电池阴极的极化电阻。
The invention provides a method for preparing a nanocomposite cathode material by an electrospinning coupled impregnation method, in particular to a method for preparing a nanocomposite cathode material for a proton conductor solid oxide fuel cell by an electrospinning coupled impregnation method, which belongs to the technology of energy materials field. The preparation method firstly prepares a mixed spinning solution comprising a metal salt mixture, N,N-dimethylformamide and polyvinylpyrrolidone, then uses the electrospinning technology to spin the above mixed solution to prepare a spinning product, and then spin the spinning solution. The silk material is calcined in a box furnace to obtain BCFZYO nanofibers; and then by in-situ dipping method, nanoparticle GCO is produced on the surface of BCFZYO nanofibers, thereby obtaining nanocomposite cathode material GCO-BCFZYO. The nanocomposite cathode material GCO-BCFZYO obtained by the invention has higher electrocatalytic activity and specific surface area, has more electrochemical reaction active points, accelerates the kinetics of the cathode reaction, and effectively reduces the cathode of the proton conductor solid oxide fuel cell. polarization resistance.
Description
Technical Field
The invention belongs to the technical field of energy materials, and relates to a method for preparing a nano composite cathode material by an electrostatic spinning coupling impregnation method.
Background
Energy shortage and environmental pollution are important challenges facing the rapid development of human society. As an all-solid-state power generation device for converting chemical energy into electric energy, a proton conductor solid oxide fuel cell (H-SOFC) has the advantages of environmental friendliness, high energy efficiency, strong fuel applicability and the like, and is widely concerned at home and abroad. Compared with an oxygen ion solid oxide fuel cell (O-SOFC), the H-SOFC can work in a medium and low temperature range (700 ℃ F.) and 500 ℃ C.) because the electrolyte of the H-SOFC has higher proton conductivity and lower proton conduction activation energy, thereby prolonging the service life of the cell and saving the cost. However, as the operating temperature is lowered, the reaction kinetics of the cathode are more retarded, resulting in an increase in the polarization resistance of the cathode. Currently, low activity cathode materials have become a key issue that restricts the commercial application of H-SOFCs.
Research finds that BaCo with electron-proton-oxygen ion three-phase conduction0.4Fe0.4Zr0.1Y0.1O3-δ. The (BCFZYO) material has good electrochemical performance as a cathode of the H-SOFC. However, the BCFZYO material prepared by the traditional solid phase method has large electrode particles, small specific surface and few reactive active sites.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing a nano composite cathode material by an electrostatic spinning coupling dipping method.
A method for preparing a nano composite cathode material by an electrostatic spinning coupling dipping method mainly comprises the following steps:
s1: dissolving a metal salt mixture and a high molecular polymer in an organic solvent to obtain a spinning solution, wherein the metal salt mixture: n, N-dimethylformamide: the mass ratio of the polyvinylpyrrolidone is 1:8: 1; preparing composite fiber by an electrostatic spinning method, and calcining the composite fiber in a high-temperature furnace to obtain BCFZYO nano-fiber powder;
s2: gd (NO)3)3·xH2O、Ce(NO3)3·6H2Dissolving O, glycine and absolute ethyl alcohol into deionized water to obtain a mixed solution, and uniformly stirring the mixed solution on a magnetic stirrer to obtain a GCO solution, wherein Gd (NO) is calculated according to the mass ratio3)3·xH2O∶Ce(NO3)3·6H2Glycine to 1:5.06:0.729, deionized water: the volume ratio of the absolute ethyl alcohol is 1: 1; soaking the BCFZYO nano-fiber powder in the GCO solution for the first time in S1, taking out the powder after the powder is completely wetted, putting the powder into an oven for drying, soaking the BCFZYO nano-fiber obtained after drying in the GCO solution for the second time after the powder is completely wetted for the second time, taking out the powder after the powder is completely wetted for the second time, putting the powder into the oven for drying for the second time, soaking the BCFZYO nano-fiber obtained after drying in the GCO solution for the third time after the powder is completely wetted for the third time, and putting the powder into the oven for drying for the third time to obtain the BCFZYO nano-fiber material with the GCO dipping film;
s3: and (3) placing the BCFZYO nanofiber material with the GCO impregnated film obtained in the step (S2) into a high-temperature furnace, heating to 600 ℃ at a heating rate of 3 ℃/min, calcining at a constant temperature for 1h, and calcining to obtain the nano composite cathode material GCO-BCFZYO.
Further, the preparation method of the BCFZYO nanofibers in S1 is specifically as follows:
s1.1: adding ionized water into a beaker, placing the beaker on a digital display temperature control magnetic stirrer, heating the beaker to 60 ℃, stirring the beaker, and sequentially adding the metal salt mixture into the beaker to be stirred and dissolved;
s1.2: after the metal salt mixture is completely dissolved, adding the N, N-dimethylformamide, then adding the polyvinylpyrrolidone to obtain a tawny colloidal solution, and stirring the tawny colloidal solution for 24 hours to obtain the spinning solution; in the invention, the density of the N, N-dimethylformamide is 0.945 g/ml;
s1.3: sucking the spinning solution by using a disposable injector, fixing the spinning solution on an electrostatic spinning device, clamping a needle head of the injector by using a voltage end of the electrostatic spinning device, setting the distance between the needle head and a linkage device of the electrostatic spinning device, and wrapping the linkage device of the electrostatic spinning device by using tinfoil to ensure that all the prepared spinning is attached to the tinfoil; wherein the speed of the electrostatic spinning device is 0.05mm/min, and the positive voltage and the negative voltage are respectively 19.50kV and-3.0 kV; after spinning is finished, taking out the tinfoil attached with the spun yarn, and putting the tinfoil into an oven for drying; in the invention, the model of the electrostatic spinning device is ET-2535H;
s1.4: and stripping the dried spinning from the tinfoil, putting the stripped spinning into a high-temperature furnace, and calcining at high temperature for 1h to obtain the BCFZYO nano-fiber powder.
Further, the metal salt mixture in S1.1 is C4H6BaO4、Co(NO3)2·6H2O、 Fe(NO3)3·9H2O、Zr(NO3)2·5H2O and Y (NO)3)3·6H2Mixture of O, in mass ratio, C4H6BaO4∶Co(NO3)2·6H2O∶Fe(NO3)3·9H2O∶Zr(NO3)2·5H2O∶Y(NO3)3·6H2O＝1.2771∶ 0.582∶0.808∶0.21466∶0.1915。
Further, the chemical formula of the BCFZYO nano-fiber in S1.4 is BaCo0.4Fe0.4Zr0.1Y0.1O3-δ。
Further, the application of the nano composite cathode material in the cathode of the battery is provided.
The technical scheme provided by the invention has the beneficial effects that: the method comprises the steps of firstly preparing a BCFZYO nano-fiber cathode material with high specific surface area and high length-diameter ratio by using an electrostatic spinning technology, then loading GCO nano-particles on the BCFZYO nano-fiber cathode material by using an in-situ impregnation method, and greatly improving the loading rate of the GCO nano-particles by repeated impregnation in the preparation process, so that the BCFZYO nano-fiber cathode material has more electrochemical reaction active points, the cathode reaction kinetics is accelerated, and the polarization resistance of an H-SOFC cathode is effectively reduced.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is an XRD pattern of a nanocomposite cathode material GCO-BCFZYO prepared in three examples of the invention;
FIG. 2a is an SEM image of a spun yarn without calcination treatment at a magnification of 3 ten thousand in three examples of the present invention;
FIG. 2b is an SEM image of a spun yarn without calcination treatment at 1 ten thousand magnification in three examples of the invention;
FIG. 3a is an SEM image of the calcined spun BCFZYO nanofibers enlarged by 3 ten thousand times;
FIG. 3b is an SEM image of the calcined spun BCFZYO nanofibers enlarged by 1 ten thousand times;
FIG. 4a is an SEM image of BCFZYO nanofibers loaded with 0.1mol/L GCO particles after being magnified by 3 ten thousand times in the example of the present invention;
FIG. 4b is an SEM image of BCFZYO nanofibers loaded with 0.1mol/L GCO particles of the example of the invention after being magnified by 1 ten thousand times;
FIG. 5a is an SEM image of BCFZYO nanofibers loaded with 0.2mol/L GCO particles after being magnified by 3 ten thousand times in the example of the present invention;
FIG. 5b is an SEM image of BCFZYO nanofibers loaded with 0.2mol/L GCO particles after being magnified by 1 ten thousand times in the example of the present invention;
FIG. 6a is an SEM image of BCFZYO nanofibers loaded with 0.5mol/L GCO particles after being magnified by 3 ten thousand times in the example of the present invention;
FIG. 6b is an SEM image of the BCFZYO nanofibers loaded with 0.5mol/L GCO particles of the example of the invention after being magnified by 1 ten thousand times;
fig. 7 is an impedance diagram of the nanocomposite cathode material GCO-BCFZYO prepared in three examples of the present invention after electrochemical impedance testing.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that processes not specifically described in detail below are all those skilled in the art to which they pertain having the benefit of the present teachings. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
< example 1>
A method for preparing a nano composite cathode material by an electrostatic spinning coupling dipping method comprises the following steps:
s1, preparing BCFZYO nano-fiber powder, adding 13ml of deionized water into a beaker, placing the beaker on a digital display temperature-control magnetic stirrer, heating the mixture to 60 ℃, stirring the mixture, and adding 1.2771g C4H6BaO4、0.582gCo(NO3)2·6H2O、 0.808gFe(NO3)3·9H2O、0.21466gZr(NO3)2·5H2O and 0.1915gY (NO)3)3·6H2Sequentially adding O into the beaker, stirring and dissolving;
after the metal salt mixture is completely dissolved, adding 12.5ml of N, N-dimethylformamide, then adding 3g of polyvinylpyrrolidone to obtain a tawny colloidal solution, and stirring the tawny colloidal solution for 24 hours to obtain the spinning solution; in the invention, the density of the N, N-dimethylformamide is 0.945 g/ml;
sucking the spinning solution by using a disposable injector, fixing the spinning solution on an electrostatic spinning device, clamping a needle head of the injector by using a voltage end of the electrostatic spinning device, setting the distance between the needle head and a linkage device of the electrostatic spinning device, and wrapping the linkage device of the electrostatic spinning device by using tinfoil to ensure that all the prepared spinning is attached to the tinfoil; wherein the speed of the electrostatic spinning device is 0.05mm/min, and the positive voltage and the negative voltage are respectively 19.50kV and-3.0 kV; and after spinning is finished, taking out the tinfoil attached with the spun yarn, and drying in an oven. In the invention, the model of the electrostatic spinning device is ET-2535H;
stripping the dried spinning from the tinfoil, putting the stripped spinning into a high-temperature furnace, calcining at high temperature and preserving heat for 1h to obtain BCFZYO nano-fiber powder with the chemical formula of BaCo0.4Fe0.4Zr0.1Y0.1O3-δ。
S2, preparing the nano composite cathode material GCO-BCFZYO, mixing 0.34326g Gd (NO3)3·xH2O、 1.7369g Ce(NO3)3·6H2Dissolving O, 0.25023g of glycine and 25ml of absolute ethyl alcohol into 25ml of deionized water together to obtain a mixed solution; placing the mixed solution on a magnetic stirrer and stirring uniformly to obtain a GCO solution with the concentration of GCO nanoparticles being 0.1 mol/L; 2.4964g of the BCFZYO nano-fiber powder is taken and is firstly soaked in the 0.1mol/L GCO solution, the powder is taken out after being completely wetted and is placed in an oven for drying treatment, in order to enable GCO particles to be better loaded on a cathode material, the BCFZYO nano-fiber obtained after drying treatment is secondly soaked in the GCO solution, the powder is taken out again after being completely wetted for the second time and is placed in the oven for secondary drying treatment, the BCFZYO nano-fiber obtained after secondary drying treatment is soaked in the GCO solution for the third time, the powder is taken out after being completely wetted for the third time and is placed in the oven for tertiary drying treatment, and the BCFZYO nano-fiber material with the GCO impregnated film is obtained, wherein the weight of the BCFZYO nano-fiber material is 2.5452 g;
placing the nanofiber material with the GCO impregnated film in a high-temperature furnace, heating to 600 ℃ at a heating rate of 3 ℃/min, calcining at constant temperature for 1h, and obtaining a nano composite cathode material GCO-BCFZYO with the weight of 2.515g after calcining treatment; comparing the weight (2.4964g) of the BCFZYO nanofiber material which is not subjected to impregnation treatment, the change of the weight indicates that part of GCO particles are successfully loaded on the surface of the BCFZYO nanofiber, and observing the surfaces of the calcined spinning, namely the BCFZYO nanofiber, and the BCFZYO nanofiber loaded with 0.1mol/L of GCO particles by using a scanning electron microscope to obtain SEM images under two different multiples, wherein the attached part of the GCO particles on the surface of the BCFZYO nanofiber can be observed by combining the images of 2, 3 and 4, and the appearance is better.
The nano composite cathode material GCO-BCFZYO obtained in the embodiment is applied to a battery cathode, and the specific application steps are as follows:
(1) mixing the nano composite cathode material GCO-BCFZYO and terpineol according to the mass ratio of 1: 2.5 to obtain a mixed sample, and slightly grinding the mixed sample in an agate mortar for 30min to prevent the appearance of the nano composite cathode material GCO-BCFZYO from being damaged;
(2) coating the ground mixed sample in the step (5) on two sides of the surface of the fired BZCYb electrolyte sheet by adopting a screen printing method, drying each side by using a heater after coating, coating again after drying, and respectively coating the two sides for three times;
(3) coating the surface of the BZCYb electrolyte sheet with a nano composite cathode material GCO-BCFZYO, drying for the last time, putting the BZCYb electrolyte sheet into a muffle furnace, heating to 1000 ℃ at a speed of 3 ℃/min, and calcining for 3 hours at constant temperature;
(4) after the calcination is finished, silver paste is fully coated on two sides of the surface of the BZCYb electrolyte sheet coated with the nano composite cathode material GCO-BCFZYO, and then the BZCYb electrolyte sheet is placed in a muffle furnace to be calcined for 1 hour at the constant temperature of 600 ℃, so that the electrode plate is finally obtained.
< example 2>
A method for preparing a nano composite cathode material by an electrostatic spinning coupling dipping method comprises the following steps:
s1, preparing BCFZYO nano-fiber powder, adding 13ml of deionized water into a beaker, placing the beaker on a digital display temperature-control magnetic stirrer, heating the mixture to 60 ℃, stirring the mixture, and adding 1.2771g C4H6BaO4、0.582gCo(NO3)2·6H2O、 0.808gFe(NO3)3·9H2O、0.21466gZr(NO3)2·5H2O and 0.1915gY (NO)3)3·6H2Sequentially adding O into the beaker, stirring and dissolving;
after the metal salt mixture is completely dissolved, adding 12.5ml of N, N-dimethylformamide, then adding 3g of polyvinylpyrrolidone to obtain a tawny colloidal solution, and stirring the tawny colloidal solution for 24 hours to obtain the spinning solution; in the invention, the density of the N, N-dimethylformamide is 0.945 g/ml;
sucking the spinning solution by using a disposable injector, fixing the spinning solution on an electrostatic spinning device, clamping a needle head of the injector by using a voltage end of the electrostatic spinning device, setting the distance between the needle head and a linkage device of the electrostatic spinning device, and wrapping the linkage device of the electrostatic spinning device by using tinfoil to ensure that all the prepared spinning is attached to the tinfoil; wherein the speed of the electrostatic spinning device is 0.05mm/min, and the positive voltage and the negative voltage are respectively 19.50kV and-3.0 kV; after spinning is finished, taking out the tinfoil attached with the spun yarn, and putting the tinfoil into an oven for drying; in the invention, the model of the electrostatic spinning device is ET-2535H;
stripping the dried spinning from the tinfoil, putting the stripped spinning into a high-temperature furnace, calcining at high temperature and preserving heat for 1h to obtain BCFZYO nano-fiber powder with the chemical formula of BaCo0.4Fe0.4Zr0.1Y0.1O3-δ。
S2, preparing a nano composite cathode material GCO-BCFZYO, mixing 0.68652gGd (NO)3)3·xH2O、 3.47376gCe(NO3)3·6H2Dissolving O, 0.5005g of glycine and 25ml of absolute ethyl alcohol into 25ml of deionized water together to obtain a mixed solution; placing the mixed solution on a magnetic stirrer and stirring uniformly to obtain a GCO solution with the concentration of GCO nanoparticles being 0.2 mol/L; 4.2316g of the BCFZYO nano-fiber powder is taken and firstly soaked in the 0.2mol/L GCO solution, the powder is taken out after being completely wetted and is placed in an oven for drying treatment, in order to enable GCO particles to be better loaded on a cathode material, the BCFZYO nano-fiber obtained after drying treatment is secondly soaked in the GCO solution, the powder is taken out again after being completely wetted for the second time and is placed in the oven for secondary drying treatment, the BCFZYO nano-fiber obtained after secondary drying treatment is soaked in the GCO solution for the third time, the powder is taken out after being completely wetted for the third time and is placed in the oven for tertiary drying treatment, and the BCFZYO nano-fiber material with the GCO dipping film is obtained, and the weight of the powder is 4.2701 g;
placing the nanofiber material with the GCO impregnated film in a high-temperature furnace, heating to 600 ℃ at a heating rate of 3 ℃/min, calcining at constant temperature for 1h, and calcining to obtain a nano composite cathode material GCO-BCFZYO with the weight of 4.2537 g; comparing the weight (4.2316g) of the BCFZYO nanofiber material which is not subjected to impregnation treatment, the change of the weight indicates that part of GCO particles are successfully loaded on the surface of the BCFZYO nanofiber, and observing the surfaces of the calcined spinning, namely the BCFZYO nanofiber, and the BCFZYO nanofiber loaded with 0.2mol/L of GCO particles by using a scanning electron microscope to obtain SEM images under two different multiples, wherein the attached part of the GCO particles on the surface of the BCFZYO nanofiber can be observed by combining the images of 2, 3 and 5, and the appearance is better.
The nanocomposite cathode material GCO-BCFZYO obtained in the example was applied to a battery cathode. The specific application steps are as follows:
(1) mixing the nano composite cathode material GCO-BCFZYO and terpineol according to the mass ratio of 1: 2.5 to obtain a mixed sample, and slightly grinding the mixed sample in an agate mortar for 30min to prevent the appearance of the nano composite cathode material GCO-BCFZYO from being damaged;
(2) coating the ground mixed sample in the step (5) on two sides of the surface of the fired BZCYb electrolyte sheet by adopting a screen printing method, drying each side by using a heater after coating, coating again after drying, and respectively coating the two sides for three times;
(3) coating the surface of the BZCYb electrolyte sheet with a nano composite cathode material GCO-BCFZYO, drying for the last time, putting the BZCYb electrolyte sheet into a muffle furnace, heating to 1000 ℃ at a speed of 3 ℃/min, and calcining for 3 hours at constant temperature;
(4) after the calcination is finished, silver paste is fully coated on two sides of the surface of the BZCYb electrolyte sheet coated with the nano composite cathode material GCO-BCFZYO, and then the BZCYb electrolyte sheet is placed in a muffle furnace to be calcined for 1 hour at the constant temperature of 600 ℃, so that the electrode plate is finally obtained.
< example 3>
A method for preparing a nano composite cathode material by an electrostatic spinning coupling dipping method comprises the following steps:
s1, preparing BCFZYO nano-fiber powder, adding 13ml of deionized water into a beaker, placing the beaker on a digital display temperature-control magnetic stirrer, heating the mixture to 60 ℃, stirring the mixture, and adding 1.2771g C4H6BaO4、0.582gCo(NO3)2·6H2O、 0.808gFe(NO3)3·9H2O、0.21466gZr(NO3)2·5H2O and 0.1915gY (NO)3)3·6H2Sequentially adding O into the beaker, stirring and dissolving;
after the metal salt mixture is completely dissolved, adding 12.5ml of N, N-dimethylformamide, then adding 3g of polyvinylpyrrolidone to obtain a tawny colloidal solution, and stirring the tawny colloidal solution for 24 hours to obtain the spinning solution; in the invention, the density of the N, N-dimethylformamide is 0.945 g/ml;
sucking the spinning solution by using a disposable injector, fixing the spinning solution on an electrostatic spinning device, clamping a needle head of the injector by using a voltage end of the electrostatic spinning device, setting the distance between the needle head and a linkage device of the electrostatic spinning device, and wrapping the linkage device of the electrostatic spinning device by using tinfoil to ensure that all the prepared spinning is attached to the tinfoil; wherein the speed of the electrostatic spinning device is 0.05mm/min, and the positive voltage and the negative voltage are respectively 19.50kV and-3.0 kV; and after spinning is finished, taking out the tinfoil attached with the spun yarn, and drying in an oven. In the invention, the model of the electrostatic spinning device is ET-2535H;
stripping the dried spinning from the tinfoil, putting the stripped spinning into a high-temperature furnace, calcining at high temperature and preserving heat for 1h to obtain BCFZYO nano-fiber powder with the chemical formula of BaCo0.4Fe0.4Zr0.1Y0.1O3-δ。
S2 preparation of nano composite cathode material GCO-BCFZYO, 1.7163gGd (NO3)3·xH2O、 8.6844gCe(NO3)3·6H2Dissolving O, 1.2512g of glycine and 25ml of absolute ethyl alcohol into 25ml of deionized water together to obtain a mixed solution; placing the mixed solution on a magnetic stirrer, and uniformly stirring to obtain a GCO solution with the GCO nanoparticle concentration of 0.5 mol/L; 3.6678g of the BCFZYO nano-fiber powder is taken and putSoaking in the 0.2mol/L GCO solution for the first time, taking out after the GCO solution is completely wetted, putting the GCO solution into an oven for drying treatment, soaking the BCFZYO nanofibers obtained after drying treatment in the GCO solution for the second time in order to enable GCO particles to be better loaded on a cathode material, taking out again after the GCO solution is completely wetted for the second time, putting the GCO solution into the oven for the second time for drying treatment, soaking the BCFZYO nanofibers obtained after the second time of drying treatment in the GCO solution for the third time, taking out after the GCO solution is completely wetted for the third time, putting the GCO solution into the oven for the third time for drying treatment, and obtaining the BCFZYO nanofiber material with the GCO impregnation film, wherein the weight of the BCFZYO nanofiber material is 3.6917 g;
placing the nanofiber material with the GCO impregnated film in a high-temperature furnace, heating to 600 ℃ at a heating rate of 3 ℃/min, calcining at constant temperature for 1h, and calcining to obtain a nano composite cathode material GCO-BCFZYO with the weight of 3.6860 g; comparing the weight (3.6678g) of the BCFZYO nanofiber material which is not subjected to impregnation treatment, wherein the change of the weight indicates that part of GCO particles are successfully loaded on the surface of the BCFZYO nanofiber, observing the surface of the BCFZYO nanofiber which is subjected to calcination treatment, namely the BCFZYO nanofiber after calcination treatment and the BCFZYO nanofiber loaded with 0.5mol/L of GCO particles by using a scanning electron microscope to obtain SEM images under two different multiples, and combining with the images of 2, 3 and 6, observing that a large number of GCO particles are attached to the surface of the BCFZYO nanofiber, and the appearance is better and the distribution is uniform.
The nanocomposite cathode material GCO-BCFZYO obtained in the embodiment is applied to an electrode sheet of a battery. The specific application steps are as follows:
(1) mixing the nano composite cathode material GCO-BCFZYO and terpineol according to the mass ratio of 1: 2.5 to obtain a mixed sample, and slightly grinding the mixed sample in an agate mortar for 30min to prevent the appearance of the nano composite cathode material GCO-BCFZYO from being damaged;
(2) coating the ground mixed sample in the step (5) on two sides of the surface of the fired BZCYb electrolyte sheet by adopting a screen printing method, drying each side by using a heater after coating, coating again after drying, and respectively coating the two sides for three times;
(3) coating the surface of the BZCYb electrolyte sheet with a nano composite cathode material GCO-BCFZYO, drying for the last time, putting the BZCYb electrolyte sheet into a muffle furnace, heating to 1000 ℃ at a speed of 3 ℃/min, and calcining for 3 hours at constant temperature;
(4) after the calcination is finished, silver paste is fully coated on two sides of the surface of the BZCYb electrolyte sheet coated with the nano composite cathode material GCO-BCFZYO, and then the BZCYb electrolyte sheet is placed in a muffle furnace to be calcined for 1 hour at the constant temperature of 600 ℃, so that the electrode plate is finally obtained.
Fig. 1 is an X-ray powder diffraction pattern of the nanocomposite cathode material GCO-BCFZYO prepared in the example of the present invention, and the result shows that the nanocomposite cathode material GCO-BCFZYO impregnated with three GCO solutions of different concentrations (in the figure, BCFZYO-GCO1, BCFZYO-GCO2, and BCFZYO-GCO5 represent the nanocomposite cathode material GCO-BCFZYO impregnated with GCO solutions of 0.1mol/L, 0.2mol/L, and 0.5mol/L, respectively) can correspond well to the standard peaks of the BCFZYO nanofibers and GCO nanoparticles corresponding to the examples, and no other significant miscellaneous peaks appear, which proves that the GCO nanoparticles have been successfully loaded on the surface of the BCFZYO nanofibers.
Fig. 7 is an impedance diagram of the nanocomposite cathode material GCO-BCFZYO prepared in the example of the present invention after electrochemical impedance testing. As can be seen from FIG. 7, the polarization resistance of the nanocomposite cathode material GCO-BCFZYO increased from 3.53. omega. cm with the increase of the concentration of the GCO solution-2Respectively changed to 3.27 omega cm-2、2.87Ω cm-2And 2.527 Ω cm-2The impregnation concentration is 0.1mol/L of GCO solution, 0.2mol/L of GCO solution and 0.5mol/L of GCO solution, which shows that the polarization resistance of the electrode can be effectively reduced after the BCFZYO nano-fiber cathode material is loaded with GCO nano-particles. This is due to the higher electrocatalytic activity and specific surface area of the GCO nanoparticles, which can accelerate the cathode reaction kinetics. Therefore, after GCO nanoparticles are introduced on the surface of the BCFZYO nano-fiber by an in-situ impregnation method, the electrochemical performance of the BCFZYO nano-fiber cathode material can be obviously improved. In addition, the loading amount of the GCO nanoparticles has great influence on the performance of the electrode, and when the BCFZYO nanofiber cathode material is soaked in a low-concentration GCO solution, only a small part of the GCO nanoparticles are attached to the surface of the BCFZYO nanofibers and are not attached to the surface of the BCFZYO nanofibersA continuous conductive phase can be formed resulting in a three-phase reaction interface (TPB) only at the electrode-electrolyte interface. However, as the concentration of the GCO impregnation solution increases, the GCO nanoparticle loading increases, which will allow the TPB to extend from the electrode/electrolyte interface throughout the interior of the electrode. Therefore, the polarization resistance of the electrode gradually decreases as the concentration of the GCO dipping solution increases.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
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