CN111342064B - Lanthanum-cobalt-oxygen nano composite fiber membrane and application method thereof - Google Patents

Lanthanum-cobalt-oxygen nano composite fiber membrane and application method thereof Download PDF

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CN111342064B
CN111342064B CN202010146568.XA CN202010146568A CN111342064B CN 111342064 B CN111342064 B CN 111342064B CN 202010146568 A CN202010146568 A CN 202010146568A CN 111342064 B CN111342064 B CN 111342064B
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李双寿
张琦
汤彬
白旭明
韩湛然
陈卓凡
王海燕
姚启明
王健美
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Abstract

The invention adopts the electrostatic spinning technology to prepare the loaded high catalytic activity LaCo1‑xMxO3The polymer fiber membrane of (M ═ V, Cr, Mn, Fe, Ni, Cu) nanocrystal, the uniformly dispersed catalytic material and the interlaced reticular fiber membrane provide a large amount of solid, liquid and gas three-phase reaction sites for the catalytic process, and the conductive material attached to the catalytic material and the polymer fiber membrane enhances the chemical activity of the catalytic material and the transmission capability of carriers. The nano composite fiber membrane has high catalytic activity and high stability, can avoid the use loss and material loss of catalytic materials, and meets the requirements of the fields of flexible energy storage and the like and civil applications of wearable equipment, household facilities and the like.

Description

Lanthanum-cobalt-oxygen nano composite fiber membrane and application method thereof
Technical Field
The invention belongs to the technical field of nano composite catalytic materials and application thereof, and particularly relates to a lanthanum-cobalt-oxygen nano composite fiber membrane with high catalytic activity and an application method thereof.
Background
Currently, the earth on which people live cannot meet the basic requirements of human survival development due to serious waste and pollution caused by the increasing scarcity of resources such as coal, oil, natural gas and the like and the inefficient use of resources. In turn, mankind explores cleaner, efficient and rich energy forms, and new energy sources such as nuclear energy, solar energy, biological energy and the like are deeply researched and widely applied based on the background environment. The form of civil energy storage is also developed from a single-use primary battery to a rechargeable and recyclable secondary battery, and is changed from a lead-acid battery with high toxicity, low energy and heaviness to a lithium ion battery and a nickel-hydrogen battery with low toxicity, high energy and light weight. Particularly, in recent years, development of hybrid batteries and metal-air batteries and increase of requirements of flexible devices such as wearable electronics and the like have completely new changes to application forms of energy and survival ways of human beings, so that scientific researchers have paid extensive attention to and industrialized application and popularization.
The lithium-air battery and the zinc-air battery are taken as representatives, the metal-air battery has the advantages of large capacity, high energy density, low price, long storage/service life, small internal resistance, stable discharge curve, light weight, easy disassembly, assembly and maintenance and the like, particularly oxygen is used as a raw material, the source is rich, the taking is convenient, and the metal-air battery is suitable to be used as an active catalytic electrode of a flexible energy storage device so as to meet the application requirements of civil fields such as wearable equipment and household facilities.
However, although many excellent catalytic materials are reported, a series of problems still face in the industrial application process, especially in the application process of flexible energy storage devices, such as safety problem caused by high toxicity of the nano-structure type material, low catalytic activity caused by factors such as the composition and structure of the catalytic material, reduction of specific surface area of the catalytic material caused by agglomeration, secondary growth and the like, and sharp reduction of catalytic activity caused by use loss. Therefore, the development of a flexible catalytic material with high catalytic activity and high stability to meet the application requirements of flexible energy storage devices is urgent.
Disclosure of Invention
Based on the problems in the background art, the inventionThe invention aims to provide a lanthanum-cobalt-oxygen nano composite fiber membrane with high catalytic activity and high stability, and a loaded LaCo with high catalytic activity is prepared by adopting an electrostatic spinning technology1-xMxO3The polymer fiber membrane of (M ═ V, Cr, Mn, Fe, Ni, Cu) nanocrystal, the uniformly dispersed catalytic material and the interlaced reticular fiber membrane provide a large amount of solid, liquid and gas three-phase reaction sites for the catalytic process, and the conductive material attached to the catalytic material and the polymer fiber membrane enhances the chemical activity of the catalytic material and the transmission capability of carriers. The nano composite fiber membrane has high catalytic activity and high stability, can effectively avoid performance reduction and safety problems caused by use loss and material loss of catalytic materials, and meets the requirements of the field of flexible energy storage (such as metal-air batteries and hybrid power batteries) and civilized applications of wearable equipment, household facilities and the like. The specific technical scheme is as follows:
a lanthanum-cobalt-oxygen nano composite fiber membrane with high catalytic activity and high stability is characterized in that an electrostatic spinning technology is adopted to prepare a loaded LaCo with high catalytic activity1-xMxO3The polymer fiber film of (M ═ V, Cr, Mn, Fe, Ni, Cu) nanocrystal, the uniformly dispersed catalytic material and the interlaced reticular fiber film provide a large amount of solid, liquid and gas three-phase reaction sites for the catalytic process, and the conductive material attached to the catalytic material and the polymer fiber film enhances the chemical activity of the catalytic material and the transmission capability of carriers;
alternatively, the preparation method of the fiber membrane may include using LaCo1-xMxO3Preparing a solution used for electrostatic spinning by a catalytic material, preparing a nano composite fiber film by electrostatic spinning, and passivating at a low temperature after film forming; can be directly sprayed on the surface of a rigid, flexible and curved substrate;
optionally, the LaCo1-xMxO3The catalytic material is prepared by adopting a sol-gel method, and the solution used in the electrostatic spinning comprises the following components:
Figure BDA0002400966420000021
optionally, in the process of preparing the nano composite fiber membrane by electrostatic spinning, the voltage is 10-20kV, and the jet speed is 0.1-5 mm/min; in the low-temperature passivation treatment process after film formation, the temperature is 20-300 ℃, the treatment time is 0.5-12h, and the atmosphere is one of air, argon or nitrogen;
optionally, the preparation method of the fiber membrane may also include preparing a precursor solution for electrostatic spinning containing a La source, a Co source and an M source, preparing a nanofiber membrane by electrostatic spinning, performing low-temperature pretreatment after membrane formation, and preparing loaded LaCo with high catalytic activity by high-temperature sintering1-xMxO3A nanocrystalline nanocomposite fiber film; and promoting the La, Co and M precursors attached to the fiber film to crystallize to obtain the target nano composite material. Can be directly sprayed on the surface of a high-temperature-resistant rigid, flexible and curved substrate.
Optionally, the precursor solution for electrospinning containing a La source, a Co source, and an M source comprises the following components:
Figure BDA0002400966420000031
wherein, the amounts of the components of the La source, the Co source and the M source are configured according to the stoichiometric ratio of La, Co and M;
optionally, the La source is La (NO)3)3、LaCl3、La(CH3COO)3、La2(SO4)3、La2O3One or more of the above; the Co source is Co (NO)3)2、CoCl2、Co(CH3COO)2、CoSO4One or more of CoO and CoO; the M source is M (NO)3)2、MCl2、M(CH3COO)2、MSO4One or more of MO and the other MO;
optionally, in the process of preparing the nanofiber membrane by electrostatic spinning, the voltage is 10-20kV, and the jet speed is 0.1-5 mm/min; after film forming, the temperature is 20-300 ℃, the time is 0.5-12h and the atmosphere is air in the low-temperature pretreatment process; the temperature in the high-temperature sintering process is 500-1000 ℃, the heating rate is 3-10 ℃/min, the time is 2-12h, and the atmosphere is one of argon or nitrogen;
optionally, the conductive material is attached to the catalytic material and the polymer fiber membrane, so that chemical activity of the catalytic material and carrier transport capability can be enhanced. The conductive material comprises one or more of conductive graphite, carbon nanospheres, carbon nanotubes, graphene oxide, reduced graphene oxide, nano silver, nano copper, nano nickel and magnesium-based amorphous alloy;
optionally, the high molecular polymer is one or more of polyacrylonitrile, polypropylene, polytetrafluoroethylene, polyvinylpyrrolidone and polyvinylidene fluoride;
optionally, the solvent comprises at least two of deionized water, absolute ethyl alcohol, ethylene glycol, isopropanol, dimethylformamide, dimethyl sulfoxide, propylene carbonate, dichloromethane and dichloroethane. The use of a single solvent cannot obtain uniform electrospinning solution, and the mixed solvent has the function of adjusting the solubility and spinnability of the electrospinning solution; the spinnability of the single solvent when the nano composite catalytic fiber membrane is prepared by electrostatic spinning and the crystallinity and catalytic activity of the spun particles are not as good as those of the mixed solvent;
optionally, the fiber membrane has excellent catalytic activity, and can meet the requirements of the fields of flexible energy storage and the like, such as an air electrode in a metal-air battery and a pseudo capacitor in a hybrid battery; in addition, the prepared nano composite catalytic fiber membrane is assembled into wearable equipment and household facilities, and the requirement of energy supply is met.
The invention has the beneficial effects that: through designing and preparing a lanthanum-cobalt-oxygen nano composite fiber membrane with high catalytic activity and high stability, the loaded LaCo with high catalytic activity is prepared by adopting an electrostatic spinning technology1-xMxO3The high molecular fiber film of (M ═ V, Cr, Mn, Fe, Ni, Cu) nano crystal, uniformly dispersed catalytic material and interlaced reticular fiber film provide lots of solid, liquid and gas three-phase reaction sites for catalytic process, and are attached on the catalytic material and high molecular fiber filmThe conductive material enhances the chemical activity of the catalytic material and the transport capability of carriers. The nano composite fiber membrane has high catalytic activity and high stability, can effectively avoid performance reduction and safety problems caused by use loss and material loss of catalytic materials, and meets the requirements of the fields of flexible energy storage (such as metal-air batteries and hybrid power batteries) and the like and civilized applications of wearable equipment, household facilities and the like.
Drawings
FIG. 1 is an SEM image of a nanocomposite catalytic fibrous membrane of the present invention;
FIG. 2 shows LaCoO according to an embodiment of the present invention3XRD pattern of the nanocomposite catalytic fibrous membrane;
FIG. 3 shows an embodiment of the invention, LaCo0.8Ni0.2O3XRD pattern of the nanocomposite catalytic fibrous membrane;
FIG. 4 shows an embodiment of the invention, LaCo0.7Ni0.3O3XRD patterns of nanocomposite catalytic fiber membranes.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings and examples, and it is obvious that the described examples are only a part of the embodiments of the present invention, but not all of the embodiments. All other technical solutions obtained by a person skilled in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
In the prior art, the high toxicity of the nano-structure material can cause safety problems, the catalytic activity caused by the factors such as the self component and the structure of the catalytic material is low, the specific surface area of the catalytic material caused by the factors such as agglomeration, secondary growth and the like is reduced, and the catalytic activity is sharply reduced caused by use loss. In order to solve the technical problems, the invention provides a lanthanum-cobalt-oxygen nano composite fiber membrane with high catalytic activity and high stability, and a loaded high-catalytic-activity LaCo is prepared by adopting an electrostatic spinning technology1-xMxO3High molecular fiber film of (M ═ V, Cr, Mn, Fe, Ni, Cu) nano crystal, catalytic material dispersed uniformly and interlaced net fiber film are used as catalystThe process provides a large amount of solid, liquid and gas three-phase reaction sites, and the conductive material attached to the catalytic material and the polymer fiber membrane enhances the chemical activity of the catalytic material and the transmission capability of carriers. The nano composite fiber membrane has high catalytic activity and high stability, can effectively avoid performance reduction and safety problems caused by use loss and material loss of catalytic materials, and meets the requirements of the field of flexible energy storage (such as metal-air batteries and hybrid power batteries) and civilized applications of wearable equipment, household facilities and the like.
The following is a general description of LaCo provided in embodiments of the present invention1-xMxO3A nanocomposite catalytic fiber membrane is illustrated.
FIG. 1 shows LaCo1-xMxO3SEM image of nanocomposite catalytic fiber membrane. High catalytic activity LaCo1-xMxO3The (M ═ V, Cr, Mn, Fe, Ni, Cu) nanocrystals were uniformly dispersed on the interlaced reticular polymer fiber membranes, and the conductive material was attached to the catalytic material and the polymer fiber membranes.
Specifically, the method comprises the following steps:
the preparation method of the fiber membrane can comprise the use of LaCo1-xMxO3Preparing a solution used for electrostatic spinning by a catalytic material, preparing a nano composite fiber film by electrostatic spinning, and passivating at a low temperature after film forming; can be directly sprayed on the surface of a rigid, flexible and curved substrate;
optionally, the solution used for electrospinning comprises the following components:
Figure BDA0002400966420000051
optionally, in the process of preparing the nano composite fiber membrane by electrostatic spinning, the voltage is 10-20kV, and the jet speed is 0.1-5 mm/min; in the low-temperature passivation treatment process after film formation, the temperature is 20-300 ℃, the treatment time is 0.5-12h, and the atmosphere is one of air, argon or nitrogen;
optionally, the preparation method of the fiber membrane also comprises the configurationPrecursor solution containing La source, Co source and M source for electrostatic spinning, preparation of nanofiber membrane by electrostatic spinning, low-temperature pretreatment after film formation, and preparation of loaded high-catalytic-activity LaCo by high-temperature sintering1-xMxO3A step of preparing a nanocrystalline nano composite fiber film; can be directly sprayed on the surface of a high-temperature-resistant rigid, flexible and curved substrate;
optionally, the precursor solution for electrospinning containing a La source, a Co source, and an M source comprises the following components:
Figure BDA0002400966420000052
Figure BDA0002400966420000061
wherein, the amounts of the components of the La source, the Co source and the M source are configured according to the stoichiometric ratio of La, Co and M;
optionally, the La source is La (NO)3)3、LaCl3、La(CH3COO)3、La2(SO4)3、La2O3One or more of the above; the Co source is Co (NO)3)2、CoCl2、Co(CH3COO)2、CoSO4One or more of CoO and CoO; the M source is M (NO)3)2、MCl2、M(CH3COO)2、MSO4One or more of MO and the other MO;
optionally, in the process of preparing the nanofiber membrane by electrostatic spinning, the voltage is 10-20kV, and the jet speed is 0.1-5 mm/min; after film forming, the temperature is 20-300 ℃, the time is 0.5-12h and the atmosphere is air in the low-temperature pretreatment process; the temperature in the high-temperature sintering process is 500-1000 ℃, the heating rate is 3-10 ℃/min, the time is 2-12h, and the atmosphere is one of argon or nitrogen;
optionally, the conductive material is attached to the catalytic material and the polymer fiber membrane, so that chemical activity of the catalytic material and carrier transport capability can be enhanced. The conductive material comprises one or more of conductive graphite, carbon nanospheres, carbon nanotubes, graphene oxide, reduced graphene oxide, nano silver, nano copper, nano nickel and magnesium-based amorphous alloy;
optionally, the high molecular polymer is one or more of polyacrylonitrile, polypropylene, polytetrafluoroethylene, polyvinylpyrrolidone and polyvinylidene fluoride;
optionally, the solvent comprises at least two of deionized water, absolute ethyl alcohol, ethylene glycol, isopropanol, dimethylformamide, dimethyl sulfoxide, propylene carbonate, dichloromethane and dichloroethane. The use of a single solvent cannot obtain uniform electrospinning solution, and the mixed solvent has the function of adjusting the solubility and spinnability of the electrospinning solution; the spinnability of the single solvent when the nano composite catalytic fiber membrane is prepared by electrostatic spinning and the crystallinity and catalytic activity of the spun particles are not as good as those of the mixed solvent;
the loaded LaCo with high catalytic activity provided by the embodiment of the invention is shown by specific examples and comparative examples1- xMxO3The performance difference of the polymer catalytic fiber membrane of the nanocrystalline is explained in detail.
Example 1
70 parts by weight of LaCo1-xNixO3Preparing an electrospinning solution from a mixed solution of a catalytic material, 7 parts by weight of conductive graphite and 100 parts by weight of polymethyl pyrrolidone dissolved in 350 parts by weight of water and absolute ethyl alcohol by a sol-gel method, and preparing LaCo under the conditions of a voltage of 10kV and a jet speed of 0.1mm/min by adopting an electrospinning technology1-xMxO3Nano composite catalytic fiber membrane, and keeping at 170 deg.C for 6 hr to obtain passivated LaCo1-xMxO3A nano composite catalytic fiber membrane.
Different Ni element doped catalytic materials can be configured according to different stoichiometric ratios of Co and Ni, and LaCoO is respectively shown in figures 1-33、LaCo0.8Ni0.2O3And LaCo0.7Ni0.3O3Nanometer compositeXRD pattern of synthetic catalytic fiber membrane. As can be seen from the graph, LaCo increases with the Ni doping content1-xNixO3The crystallinity is obviously enhanced, and the catalytic activity is obviously improved; meanwhile, the ratio of the characteristic peaks at 32.85 degrees and 33.35 degrees is gradually increased, and the prepared LaCo is shown to be1-xNixO3The increase of lattice distortion will increase the crystal defects significantly and increase the catalytic reactivity thereof. The conductive graphite is attached to the catalytic material and the polymer fiber membrane, so that the chemical activity of the catalytic material and the transmission capability of carriers are enhanced.
Example 2
Dissolving 5 parts by weight of La source, Co source and Ni source, 0.3 part by weight of reduced graphene oxide and nano silver, 25 parts by weight of polyacrylonitrile and polyvinylidene fluoride in 400 parts by weight of a mixed solution of dimethylformamide and dichloromethane to prepare a precursor solution for electrostatic spinning; wherein, the La source, the Co source and the M source are prepared according to the stoichiometric ratio of La, Co and Ni of 2:1: 1; the La source is La (NO)3)3The Co source is CoCl2The Ni source is Ni (NO)3)2And Ni (CH)3COO)2. Preparing a nanofiber membrane loaded with La source, Co source and Ni source precursors by adopting an electrostatic spinning technology under the conditions that the voltage is 12kV and the jet speed is 0.5mm/min, pretreating at low temperature of 280 ℃ for 8 hours after membrane formation, continuously sintering at high temperature of 800 ℃ for 4 hours under the condition of argon gas, and preparing the loaded LaCo0.5M0.5O3A polymer nano composite catalytic fiber membrane of nano crystal.
Comparative example
Electrostatic spinning solution without conductive graphite LaCo was prepared according to the method of example 11-xNixO3A nanocatalysted fibrous membrane. The catalytic fiber membrane is low in temperature and does not contain conductive graphite, so that the carrier transport capacity of the fiber membrane is poor, and LaCo1- xNixO3The carrier generated by the nano-catalysis cannot timely react with oxygen in a catalytic manner, so that the catalytic activity of the composite fiber membrane is reduced.
Loaded high-catalytic-activity LaCo based on preparation1-xMxO3The (M ═ V, Cr, Mn, Fe, Ni, Cu) nanocrystalline polymer fiber membrane has high catalytic activity and high stability, and the application direction exploration can realize the diversified application of the nanocomposite catalytic fiber membrane.
In one implementation, the fiber membrane has excellent catalytic activity, and can meet the requirements of fields such as flexible energy storage and the like, such as an air electrode in a metal-air battery and a pseudo capacitor in a hybrid battery; in addition, the prepared nano composite catalytic fiber membrane is assembled into wearable equipment and household facilities, and the requirement of energy supply is met.
Therefore, the lanthanum-cobalt-oxygen nano composite fiber membrane with high catalytic activity and high stability is designed and prepared, and the loaded high-catalytic-activity LaCo is prepared by adopting the electrostatic spinning technology1-xMxO3The polymer fiber membrane of (M ═ V, Cr, Mn, Fe, Ni, Cu) nanocrystal, the uniformly dispersed catalytic material and the interlaced reticular fiber membrane provide a large amount of solid, liquid and gas three-phase reaction sites for the catalytic process, and the conductive material attached to the catalytic material and the polymer fiber membrane enhances the chemical activity of the catalytic material and the transmission capability of carriers. The nano composite fiber membrane has high catalytic activity and high stability, can effectively avoid performance reduction and safety problems caused by use loss and material loss of catalytic materials, and meets the requirements of the field of flexible energy storage (such as metal-air batteries and hybrid power batteries) and civilized applications of wearable equipment, household facilities and the like.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (7)

1. The lanthanum-cobalt-oxygen nano composite fiber membrane is characterized in that the fiber membrane is prepared by adopting an electrostatic spinning technology to load LaCo with high catalytic activity1-xMxO3Nanocrystalline polymeric fiber film, wherein M = V, Cr, Mn, Fe, Ni, Cu, said fiber film comprising a homogeneously dispersed catalystThe chemical activity of the catalytic material and the transmission capability of carriers are enhanced by the chemical material and the interlaced reticular fibers and the conductive material attached to the catalytic material and the polymer fiber membrane;
the preparation method of the fiber membrane comprises the step of using LaCo1-xMxO3Preparing a solution for electrostatic spinning by using a catalytic material, preparing a nano composite fiber film by electrostatic spinning, directly spraying the nano composite fiber film on the surface of a rigid, flexible and curved substrate, and performing low-temperature passivation treatment after film formation; the solution used for electrospinning comprises the following components:
LaCo1-xMxO35-100 parts by weight of catalytic material
1-10 parts by weight of conductive material
10-200 parts by weight of high molecular polymer
70-350 parts by weight of a solvent; alternatively, the first and second electrodes may be,
the preparation method of the fiber membrane comprises the steps of preparing a precursor solution containing a La source, a Co source and an M source for electrostatic spinning, preparing a nano fiber membrane by electrostatic spinning, directly spraying the nano fiber membrane on the surface of a high-temperature-resistant rigid, flexible and curved substrate, performing low-temperature pretreatment after membrane formation, and sintering at a high temperature; the precursor solution used for electrostatic spinning containing the La source, the Co source and the M source comprises the following components:
1-10 parts by weight of La source, Co source and M source
0.1-2 parts by weight of conductive material
5-50 parts by weight of high molecular polymer
100 portions of solvent
Wherein, the amounts of the components of the La source, the Co source and the M source are configured according to the stoichiometric ratio of La, Co and M;
the conductive material comprises one or more of conductive graphite, carbon nanospheres, carbon nanotubes, graphene oxide, reduced graphene oxide, nano silver, nano copper, nano nickel and magnesium-based amorphous alloy.
2. The lanthanum-cobalt-oxygen nano composite fiber membrane as claimed in claim 1, wherein the voltage is 10-20kV and the spraying speed is 0.1-5mm/min during the preparation method of the fiber membrane; in the low-temperature passivation treatment process after film formation, the temperature is 20-300 ℃, the treatment time is 0.5-12h, and the atmosphere is one of air, argon or nitrogen.
3. The lanthanum cobalt oxygen-based nanocomposite fiber membrane according to claim 1, wherein the La source in the fiber membrane preparation method is La (NO)3)3、LaCl3、La(CH3COO)3、La2(SO4)3、La2O3One or more of the above; the Co source is Co (NO)3)2、CoCl2、Co(CH3COO)2、CoSO4One or more of CoO and CoO; the M source is M (NO)3)2、MCl2、M(CH3COO)2、MSO4And MO, or a plurality of MO.
4. The lanthanum-cobalt-oxygen nano composite fiber membrane as claimed in claim 1, wherein the voltage is 10-20kV and the spraying speed is 0.1-5mm/min during the preparation method of the fiber membrane; after film forming, the temperature is 20-300 ℃, the time is 0.5-12h and the atmosphere is air in the low-temperature pretreatment process; the temperature in the high-temperature sintering process is 500-1000 ℃, the heating rate is 3-10 ℃/min, the time is 2-12h, and the atmosphere is argon or nitrogen.
5. The lanthanum-cobalt-oxygen nano composite fiber membrane as claimed in claim 1, wherein the high molecular polymer is one or more of polyacrylonitrile, polypropylene, polytetrafluoroethylene, polyvinylpyrrolidone and polyvinylidene fluoride.
6. The lanthanum cobalt oxygen-based nanocomposite fiber membrane according to claim 1, wherein the solvent comprises at least two of deionized water, absolute ethanol, ethylene glycol, isopropanol, dimethylformamide, dimethyl sulfoxide, propylene carbonate, methylene chloride, and ethylene dichloride.
7. The method for applying the lanthanum-cobalt-oxygen nano composite fiber membrane as claimed in claim 1, wherein the fiber membrane is applied to an air electrode in a metal-air battery and a pseudo capacitor in a hybrid battery; or assembled into a wearable device.
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