CN113948713A - Method for preparing nano composite cathode material by electrostatic spinning coupling impregnation method - Google Patents
Method for preparing nano composite cathode material by electrostatic spinning coupling impregnation method Download PDFInfo
- Publication number
- CN113948713A CN113948713A CN202111065986.7A CN202111065986A CN113948713A CN 113948713 A CN113948713 A CN 113948713A CN 202111065986 A CN202111065986 A CN 202111065986A CN 113948713 A CN113948713 A CN 113948713A
- Authority
- CN
- China
- Prior art keywords
- bcfzyo
- gco
- nano
- cathode material
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 60
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 50
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000005470 impregnation Methods 0.000 title claims abstract description 16
- 230000008878 coupling Effects 0.000 title claims abstract description 14
- 238000010168 coupling process Methods 0.000 title claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 14
- 239000002121 nanofiber Substances 0.000 claims abstract description 77
- 238000009987 spinning Methods 0.000 claims abstract description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000011833 salt mixture Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000007598 dipping method Methods 0.000 claims description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910009112 xH2O Inorganic materials 0.000 claims description 7
- 229910002768 BaCo0.4Fe0.4Zr0.1Y0.1O3-δ Inorganic materials 0.000 claims description 5
- 229910002767 BaCo0.4Fe0.4Zr0.1Y0.1O3−δ Inorganic materials 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910003101 Y(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 208000012886 Vertigo Diseases 0.000 claims 5
- 238000001523 electrospinning Methods 0.000 claims 3
- 239000000243 solution Substances 0.000 abstract description 52
- 239000002105 nanoparticle Substances 0.000 abstract description 14
- 239000011259 mixed solution Substances 0.000 abstract description 9
- 230000010287 polarization Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a method for preparing a nano composite cathode material by an electrostatic spinning coupling impregnation method, in particular relates to a method for preparing a nano composite cathode material of a proton conductor solid oxide fuel cell by an electrostatic spinning coupling impregnation method, and belongs to the technical field of energy materials. Firstly, preparing a mixed spinning solution comprising a metal salt mixture, N-dimethylformamide and polyvinylpyrrolidone, spinning the mixed solution by using an electrostatic spinning technology to prepare a spinning substance, and calcining the spinning substance in a box-type furnace to obtain the BCFZYO nano-fiber; and then generating nanoparticles GCO on the surface of the BCFZYO nanofibers by an in-situ impregnation method, thereby obtaining the nano composite cathode material GCO-BCFZYO. The nano-composite cathode material GCO-BCFZYO obtained by the invention has higher electrocatalytic activity and specific surface area, has more electrochemical reaction active points, accelerates cathode reaction kinetics, and effectively reduces the polarization resistance of the cathode of the proton conductor solid oxide fuel cell.
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)
1. A method for preparing a nano composite cathode material by an electrostatic spinning coupling dipping method is characterized by comprising 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 mass ratio of the metal salt mixture is as follows: n, N-dimethylformamide: polyvinylpyrrolidone 1:8: 1; preparing composite fiber by an electrostatic spinning method, and calcining the composite fiber to obtain BCFZYO nano-fiber powder;
s2: gd (NO)3)3·xH2O、Ce(NO3)3·6H2Dissolving O, glycine and absolute ethyl alcohol in deionized water together, and uniformly stirring to obtain a GCO solution, wherein Gd (NO) is calculated by mass ratio3)3·xH2O:Ce(NO3)3·6H2Glycine is 1:5.06: 0.729; soaking the BCFZYO nano-fiber powder in the GCO solution for the first time, taking out after the powder is completely wetted, drying, soaking the dried BCFZYO nano-fiber in the GCO solution for the second time, taking out again after the powder is completely wetted for the second time, drying for the second time, soaking the dried BCFZYO nano-fiber in the GCO solution for the third time, taking out after the powder is completely wetted for the third time, and drying to obtain the BCFZYO nano-fiber material with the GCO dipping film;
s3: and calcining the BCFZYO nanofiber material with the GCO impregnated film to obtain the nano composite cathode material GCO-BCFZYO.
2. The method for preparing the nano-composite cathode material by the electrostatic spinning coupling impregnation method according to claim 1, wherein the preparation method of the BCFZYO nano-fiber powder in S1 is as follows:
s1.1: adding the metal salt mixture to deionized water; after the metal salt mixture is completely dissolved, adding the N, N-dimethylformamide, then adding the polyvinylpyrrolidone, and uniformly stirring to obtain a spinning solution;
s1.2: carrying out electrostatic spinning treatment on the spinning solution to obtain spinning; and calcining the obtained spinning at high temperature and preserving heat for 1h to obtain the BCFZYO nano-fiber powder.
3. The method for preparing a nanocomposite cathode material according to claim 2 by electrospinning coupled dipping, wherein the metal salt mixture 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。
4. The method for preparing a nano composite cathode material according to the electrostatic spinning coupling dipping method as claimed in claim 2, wherein the chemical formula of the BCFZYO nano fiber in S1.2 is BaCo0.4Fe0.4Zr0.1Y0.1O3-δ。
5. The method for preparing a nano composite cathode material by an electrospinning coupled dipping method according to claim 1, wherein the calcining conditions in S3 are as follows: and (3) heating to 600 ℃ at the heating rate of 3 ℃/min, and calcining for 1h at constant temperature.
6. The method for preparing a nano composite cathode material by using an electrospinning coupling dipping method according to claim 1, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in S2 is 1: 1.
7. Use of a nanocomposite cathode material according to any one of claims 1 to 6 in a cathode of a battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111065986.7A CN113948713A (en) | 2021-09-10 | 2021-09-10 | Method for preparing nano composite cathode material by electrostatic spinning coupling impregnation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111065986.7A CN113948713A (en) | 2021-09-10 | 2021-09-10 | Method for preparing nano composite cathode material by electrostatic spinning coupling impregnation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113948713A true CN113948713A (en) | 2022-01-18 |
Family
ID=79328300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111065986.7A Pending CN113948713A (en) | 2021-09-10 | 2021-09-10 | Method for preparing nano composite cathode material by electrostatic spinning coupling impregnation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113948713A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326031A (en) * | 2013-06-06 | 2013-09-25 | 哈尔滨工业大学 | One-dimensional SYCO cathode material and preparation method and method to prepare composite cathode by using the cathode material |
| CN106887603A (en) * | 2017-03-21 | 2017-06-23 | 哈尔滨工业大学 | One kind improves SOFC Sm0.5Sr0.5CoO3‑δThe resistance to SO of negative electrode2Method |
| US20180138535A1 (en) * | 2015-06-30 | 2018-05-17 | Lg Chem, Ltd. | Method for manufacturing electrolyte membrane for solid oxide fuel cell, electrolyte membrane for solid oxide fuel cell, solid oxide fuel cell, and fuel cell module |
| CN108448125A (en) * | 2018-04-12 | 2018-08-24 | 中国矿业大学 | A kind of cathode material and preparation method of proton conductor solid oxide fuel cell |
| CN108461759A (en) * | 2018-01-19 | 2018-08-28 | 合肥国轩高科动力能源有限公司 | A kind of method of the nano combined cathode material of infusion process preparation solid oxide fuel cell |
| CN110429288A (en) * | 2019-08-08 | 2019-11-08 | 南京工业大学 | A kind of proton conductor fuel battery cathode material of B defect, electrolyte and preparation method thereof |
-
2021
- 2021-09-10 CN CN202111065986.7A patent/CN113948713A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326031A (en) * | 2013-06-06 | 2013-09-25 | 哈尔滨工业大学 | One-dimensional SYCO cathode material and preparation method and method to prepare composite cathode by using the cathode material |
| US20180138535A1 (en) * | 2015-06-30 | 2018-05-17 | Lg Chem, Ltd. | Method for manufacturing electrolyte membrane for solid oxide fuel cell, electrolyte membrane for solid oxide fuel cell, solid oxide fuel cell, and fuel cell module |
| CN106887603A (en) * | 2017-03-21 | 2017-06-23 | 哈尔滨工业大学 | One kind improves SOFC Sm0.5Sr0.5CoO3‑δThe resistance to SO of negative electrode2Method |
| CN108461759A (en) * | 2018-01-19 | 2018-08-28 | 合肥国轩高科动力能源有限公司 | A kind of method of the nano combined cathode material of infusion process preparation solid oxide fuel cell |
| CN108448125A (en) * | 2018-04-12 | 2018-08-24 | 中国矿业大学 | A kind of cathode material and preparation method of proton conductor solid oxide fuel cell |
| CN110429288A (en) * | 2019-08-08 | 2019-11-08 | 南京工业大学 | A kind of proton conductor fuel battery cathode material of B defect, electrolyte and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108321376A (en) | A kind of N doping porous carbon nanofiber@tin dioxide lithium ion battery negative pole materials and preparation method thereof | |
| CN106784745A (en) | The sodium-ion battery method for manufacturing electric spinning of cobaltosic oxide carbon nano-fiber | |
| CN108682802A (en) | A method of preparing lithium cell negative pole shell-core structure nanofiber | |
| Huang et al. | High-performance flexible supercapacitors based on mesoporous carbon nanofibers/Co 3 O 4/MnO 2 hybrid electrodes | |
| CN108807915B (en) | CoFe2O4Preparation method and application of/graphene composite nanofiber | |
| CN109065808A (en) | A kind of preparation method of the functional interlayer for lithium-sulfur cell | |
| CN112582682A (en) | Lithium ion solid electrolyte with core-shell structure and preparation method thereof | |
| CN108565127B (en) | Electrode material capable of improving specific capacity of supercapacitor, preparation method and application | |
| CN108048955B (en) | Preparation method of strontium iron molybdenum based double perovskite type metal oxide nano fiber | |
| CN110504456A (en) | It is a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application | |
| WO2012115340A1 (en) | Negative electrode material for a secondary battery and method for manufacturing same | |
| CN108198701A (en) | A kind of cobaltosic oxide/carbon composite electrode material, preparation method and applications | |
| CN112786869B (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material | |
| WO2024066186A1 (en) | Binary high-nickel sodium ion battery positive electrode material, preparation method, and application | |
| CN103326031A (en) | One-dimensional SYCO cathode material and preparation method and method to prepare composite cathode by using the cathode material | |
| CN111146443A (en) | Zinc electrode material for zinc battery and preparation method thereof | |
| CN113948713A (en) | Method for preparing nano composite cathode material by electrostatic spinning coupling impregnation method | |
| CN114334484B (en) | Nickel-copper oxide/carbon composite nanofiber electrode material and preparation method thereof | |
| CN115395025A (en) | Solid oxide fuel cell cathode membrane based on electrospun nanofibers and in-situ preparation method thereof | |
| CN115513448A (en) | Battery positive electrode material, preparation method and application | |
| CN114725403A (en) | Microbial fuel cell anode material and preparation method and application thereof | |
| CN115064707A (en) | Multi-phase composite anode material based on SFMO (small form-factor metal oxide) nanofiber framework and preparation method thereof | |
| CN112885616A (en) | Flexible porous nano material and preparation method and application thereof | |
| CN109509880A (en) | A kind of sodium-ion battery cathode preparation method that solid spherical tin electrode material is grown on carbon cloth | |
| CN110010916A (en) | A kind of preparation method of efficient nitrogen-doped carbon nano wire fuel-cell catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220118 |