CN106953101B - Lithium-oxygen secondary battery positive electrode and preparation method thereof, and lithium-oxygen secondary battery - Google Patents
Lithium-oxygen secondary battery positive electrode and preparation method thereof, and lithium-oxygen secondary battery Download PDFInfo
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- CN106953101B CN106953101B CN201710173467.XA CN201710173467A CN106953101B CN 106953101 B CN106953101 B CN 106953101B CN 201710173467 A CN201710173467 A CN 201710173467A CN 106953101 B CN106953101 B CN 106953101B
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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Abstract
The invention provides a lithium-oxygen secondary battery anode, which comprises a reticular metal material and a nitrogen-doped carbon nanotube compounded on the surface of the metal material; the metallic material comprises one or more of iron, nickel and iron-nickel alloy. According to the invention, the catalyst with the porous structure is grown on the surface of the metal material net through a one-step method, so that the bendable and super-hydrophobic integrated anode material of the lithium-oxygen secondary battery is obtained, the pore utilization rate and the connectivity are high, the mass transfer capacity is strong, and the charge-discharge utilization rate and the cycle number are improved. The preparation method is simple in process, convenient to operate and easy to realize large-scale production, a current collector and a binder are not required to be added, a complex powder electrode preparation process is omitted, and the specific energy, the energy utilization efficiency and the stability of the air anode of the lithium-air battery are greatly improved. Meanwhile, the material has higher mechanical strength and stronger hydrophobic property under the bending condition, and has wide application prospect in the field of wearable electronics.
Description
Technical Field
The invention relates to the technical field of lithium-oxygen secondary batteries, relates to a lithium-oxygen secondary battery anode and a preparation method thereof, and a lithium-oxygen secondary battery, and particularly relates to a flexible and super-hydrophobic lithium-oxygen secondary battery anode and a preparation method thereof, and a lithium-oxygen secondary battery.
Background
An air battery is a kind of chemical battery, and is constructed on the similar principle to a dry battery except that its oxidant is taken from oxygen in the air, and is also called an oxygen battery, and is generally classified into a lithium-air battery, a zinc-air battery, an aluminum-air battery, and the like, i.e., a metal-oxygen battery, according to a positive electrode material. For example, zinc-air batteries use zinc as the cathode, sodium hydroxide as the electrolyte, and porous activated carbon as the anode, so that oxygen in the air can be adsorbed to replace the oxidant in the conventional dry battery.
Among these metal-oxygen batteries, a lithium-oxygen battery is a battery in which lithium is used as a negative electrode and oxygen in the air is used as a positive electrode reactant, and the discharge process is as follows: the lithium of the anode releases electrons to become lithium cations (Li)+)，Li+Through the holeAn electrolyte material which is combined with oxygen gas and electrons from an external circuit at a cathode to generate lithium oxide (Li)2O) or lithium peroxide (Li)2O2) And left at the cathode. Lithium-oxygen batteries have a higher specific energy and are therefore also widely appreciated by researchers in the industry, and have a higher energy density than lithium-ion batteries because their positive electrode materials (mainly porous carbon) are light and oxygen is taken from the environment without being stored in the battery. Theoretically, oxygen as the positive electrode reactant is not limited, and the capacity of the cell depends only on the lithium electrode, which has a specific energy of 5.21kWh/kg (including oxygen mass), or 11.14kWh/kg (excluding oxygen).
However, in order to realize wide application of lithium-oxygen secondary batteries, it is necessary to solve a series of problems such as high overpotential, low discharge capacity, short cycle life, and the like. At present, commercially used porous carbon air anodes are obtained by stacking and pore-forming carbon materials, the pore channel utilization rate is low, the connectivity is poor, the energy transmission capacity is poor, and the discharge product Li is influenced2O2The deposition of (2) results in an increase in the overpotential of the lithium-oxygen secondary battery and a small number of charge-discharge cycles. On the other hand, the load of the oxygen reduction/oxygen precipitation catalyst in the existing porous carbon air anode mainly adopts a mechanical mixing mode, so that the synergistic effect between the carrier and the catalyst cannot be effectively exerted, and the energy conversion efficiency and the rate capability of the lithium-air battery are further deteriorated.
In recent years, flexible energy devices such as lithium ion batteries, supercapacitors and piezoelectric devices lay a foundation for the field of wearable electronics, but the low energy density of the flexible energy devices cannot meet the requirement of long endurance of wearable equipment. However, most of the positive electrodes of the lithium-oxygen secondary batteries are rigid and inflexible, and the assembled lithium-oxygen secondary battery devices are difficult to achieve complex distortion deformation and cannot meet the requirements of wearable equipment.
Therefore, how to obtain a lithium-oxygen secondary battery cathode material with better performance and a lithium-oxygen secondary battery, and simultaneously, how to widen the application of the lithium-oxygen secondary battery in a flexible energy device has become one of the focuses of extensive attention of many prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a lithium-oxygen secondary battery anode, a preparation method thereof, and a lithium-oxygen secondary battery.
The invention provides a lithium-oxygen secondary battery anode, which comprises a reticular metal material and a nitrogen-doped carbon nanotube compounded on the surface of the metal material;
the metallic material comprises one or more of iron, nickel and iron-nickel alloy.
Preferably, the molar ratio of nitrogen to carbon is 1: (10-20).
Preferably, the nitrogen-doped carbon nanotube has a hollow tube structure;
the length of the carbon nano tube is 5-10 mu m;
the diameter of the carbon nano tube is 50-150 nm.
Preferably, the lithium-oxygen secondary battery positive electrode has a multi-stage pore structure.
Preferably, the nitrogen-doped carbon nanotube is a nitrogen-doped carbon nanotube array;
the metallic material comprises stainless steel.
The invention also provides a preparation method of the lithium-oxygen secondary battery anode, which comprises the following steps:
A) and under a protective atmosphere, placing the reticular metal material above the melamine, and roasting to obtain the anode of the lithium-oxygen secondary battery.
Preferably, the roasting temperature is 600-800 ℃;
the roasting time is 2-4 h;
the temperature rise rate of the roasting is 5-8 ℃/min.
Preferably, the step a) is specifically:
A1) firstly, putting melamine into a square boat of roasting equipment, then covering a breathable porous material on the square boat, and then putting a reticular metal material on the breathable porous material;
A2) and roasting in a protective atmosphere to obtain the lithium-oxygen secondary battery anode.
Preferably, the air-permeable porous material comprises one or more of carbon paper, carbon cloth, glass fiber and asbestos mesh;
the mass ratio of the melamine to the metal material is (1-5): 1.
the invention also provides a lithium-oxygen secondary battery, which comprises the positive electrode of the lithium-oxygen secondary battery in any one of the technical schemes or the positive electrode, the diaphragm and the negative electrode of the lithium-oxygen secondary battery prepared in any one of the technical schemes.
The invention provides a lithium-oxygen secondary battery anode, which comprises a reticular metal material and a nitrogen-doped carbon nanotube compounded on the surface of the metal material; the metallic material comprises one or more of iron, nickel and iron-nickel alloy. Compared with the prior art, the invention aims at the problems of high overpotential, low discharge capacity and less cycle times of the existing lithium-oxygen secondary battery, develops and expands the application in flexible energy devices, and assembles the lithium-oxygen secondary battery which can stably maintain the electrochemical performance under the bending conditions of different degrees. The invention designs a catalyst with a porous structure, and the catalyst grows on the surface of a metal material net through a one-step method to obtain a bendable and super-hydrophobic integrated anode material of a lithium-oxygen secondary battery, namely an integrated anode of a nitrogen-doped carbon nanotube @ metal material net, which has higher pore utilization rate and connectivity, stronger mass transfer capacity and improved charge-discharge utilization rate and cycle times. The preparation method of the lithium-oxygen secondary battery anode provided by the invention has the advantages of simple process, convenience in operation and easiness in realization of large-scale production, does not need to add a current collector and a binder, omits a complex powder electrode preparation process, and greatly improves the specific energy, the energy utilization efficiency and the stability of the air anode of the lithium-air battery.
Meanwhile, the voltage platform of the lithium-oxygen secondary battery anode provided by the invention can be stably maintained under a bending condition, has higher mechanical strength and stronger hydrophobic property, and is beneficial to reducing the performance attenuation and short circuit phenomenon of the air battery caused by water molecule contact in the air, so that the lithium-oxygen secondary battery anode has wide application prospect in the field of wearable electronics.
Experimental results show that the positive electrode and the battery thereof provided by the invention have the structure, the discharge capacity is improved by 1 time compared with that of a commercial carbon nano tube air electrode, the overpotential is reduced by 0.6V, the cycle life is prolonged by 4 times, the positive electrode and the battery thereof can stably work under different deformation conditions, and the positive electrode and the battery thereof have high mechanical strength and super-strong hydrophobicity.
Drawings
FIG. 1 is a schematic diagram of a calcination reaction process provided by the present invention;
fig. 2 is an electron scanning image of the nitrogen-doped carbon nanotube array of the cathode material prepared in example 1 of the present invention;
fig. 3 is an electron transmission diagram of a nitrogen-doped carbon nanotube array of the cathode material prepared in example 1 of the present invention;
fig. 4 is an electron scanning image of the nitrogen-doped carbon nanotube array of the cathode material prepared in example 2 of the present invention;
fig. 5 is an electron scan of the nitrogen-doped carbon nanotube array of the cathode material prepared in example 3 of the present invention;
FIG. 6 is a discharge product Li of a lithium-oxygen battery prepared in example 4 of the present invention2O2A scanning electron microscope image deposited on the surface of the nitrogen-doped carbon nanotube array @ stainless steel mesh anode;
fig. 7 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of a nitrogen-doped carbon nanotube array in a lithium-oxygen battery prepared in example 4 of the present invention;
fig. 8 is a graph comparing the cycling stability of nitrogen-doped carbon nanotubes @ stainless steel mesh positive electrode in a lithium-oxygen battery prepared in example 4 of the present invention with that of commercial carbon nanotubes;
FIG. 9 is a graph comparing the cycling stability of nitrogen-doped carbon nanotubes @ stainless steel mesh positive electrode in a lithium-oxygen battery prepared in example 4 of the present invention with the commercial carbon nanotube discharge capacity;
fig. 10 is a graph comparing the charge/discharge potential of the positive electrode of the nitrogen-doped carbon nanotube @ stainless steel mesh with the charge/discharge potential of a commercial carbon nanotube in a lithium-oxygen battery prepared in example 4 of the present invention;
FIG. 11 is a digital diagram of the assembled lithium air flexible battery of example 5 of the present invention illuminating LED lamps at different bending angles;
fig. 12 is a graph showing the change in voltage during bending of the assembled lithium-oxygen flexible secondary battery according to example 5 of the present invention;
fig. 13 is a test result of the contact angle between the nitrogen-doped carbon nanotube @ stainless steel mesh air positive electrode and water in the lithium-oxygen battery prepared in example 5 of the present invention;
fig. 14 is an electron scan of the positive electrode material prepared in comparative example 1;
fig. 15 is an electron scan of the positive electrode material prepared in comparative example 2;
FIG. 16 is an electron scan of the N-doped carbon nanotube @ stainless steel mesh prepared in comparative example 3;
fig. 17 is an electron scan of the cathode material prepared in comparative example 4.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytically pure or purity conventional in the field of metal-air batteries.
The invention provides a lithium-oxygen secondary battery anode, which comprises a reticular metal material and a nitrogen-doped carbon nanotube compounded on the surface of the metal material;
the metallic material comprises one or more of iron, nickel and iron-nickel alloy.
The definition of the lithium-oxygen secondary battery of the present invention is not particularly limited, and may be defined as a lithium-oxygen secondary battery or a lithium-air secondary battery well known to those skilled in the art, and the lithium-oxygen secondary battery of the present invention is a metal-air battery in which, in operation, oxygen is first reduced to oxygen on the surface of the positive electrode
Then with Li in the electrolyte+Combined to form the product Li2O2Namely, oxygen is adopted as a circulating raw material, so that the circulating conversion of the oxygen between the anode and the cathode of the battery is realized, and electric energy is stored and released. The definition of the positive electrode of the lithium-oxygen secondary battery according to the present invention is not particularly limited, and may be defined as a positive electrode of a metal-air battery well known to those skilled in the art.
The specific parameters of the reticulated metal material of the present invention are not particularly limited, and the reticulated metal material known to those skilled in the art may be selected and adjusted according to the actual application, raw material conditions and product requirements, and the reticulated metal material of the present invention preferably refers to a metal material having a flexible and gas-permeable shape.
The material of the metal material is not particularly limited, and may be one or more of common iron material, nickel material and iron-nickel alloy material, which are well known to those skilled in the art, and those skilled in the art may select and adjust the material according to the actual application situation, the raw material situation and the product requirement.
The definition of the composite of the present invention is not particularly limited, and the composite concept known to those skilled in the art can be selected and adjusted according to the actual application, raw material condition and product requirement, and the composite of the present invention is preferably one or more of growing, binding, coating, brushing, doping or coating, and more preferably growing.
The composition ratio of the nitrogen-doped carbon nanotube is not particularly limited, and the nitrogen-doped carbon nanotube may be selected and adjusted by those skilled in the art according to the actual application, the raw material condition and the product requirement, and the molar ratio of nitrogen to carbon in the nitrogen-doped carbon nanotube of the present invention is preferably 1: (10-20), more preferably 1: (12-18), most preferably 1: (14-16).
The invention has no particular limitation on the specific structure of the nitrogen-doped carbon nanotube, and the structure of the nitrogen-doped carbon nanotube known to those skilled in the art can be selected and adjusted according to the actual application situation, the raw material situation and the product requirement. The nitrogen-doped carbon nano tubes have the appearance of clusters in the structure, and are mutually loosened and interwoven into a curled hair shape, so that more pores can be formed.
The specific parameters of the nitrogen-doped carbon nanotube are not particularly limited, and the parameters of the nitrogen-doped carbon nanotube known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application situation, the raw material situation and the product requirement, and in order to ensure the performance of the cathode material, the length of the nitrogen-doped carbon nanotube is preferably 5-10 μm, more preferably 6-9 μm, and most preferably 7-8 μm.
The specific parameters of the nitrogen-doped carbon nanotube are not particularly limited, and the parameters of the nitrogen-doped carbon nanotube known to those skilled in the art can be selected and adjusted according to the actual application situation, the raw material situation and the product requirement, and in order to ensure the performance of the cathode material, the diameter of the nitrogen-doped carbon nanotube is preferably 50-150 nm, more preferably 55-150 nm, more preferably 60-140 nm, more preferably 70-130 nm, and most preferably 80-120 nm.
The specific structure of the lithium-oxygen secondary battery anode is not particularly limited, and the structure of the lithium-oxygen secondary battery anode known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application situation, the raw material situation and the product requirement.
The bendable and super-hydrophobic lithium-oxygen secondary battery anode provided by the steps is a nitrogen-doped carbon nanotube array @ metal material mesh integrated electrode with a porous structure and has a mesoporous structure. The nitrogen-doped carbon nano tube with the structural characteristics grows on the surface of the metal material net to form an integrated anode with a multi-stage pore channel structure, so that the nitrogen-doped carbon nano tube has high pore channel utilization rate and connectivity and strong mass transfer capacity, and the carbon nano tube with a hollow structure provides a transmission common channel for oxygen and electrolyte; the loose array structure provides solid discharge product Li2O2The location of deposition/expulsion.
The invention provides a preparation method of a lithium-oxygen secondary battery anode, which comprises the following steps:
A) and under a protective atmosphere, placing the reticular metal material above the melamine, and roasting to obtain the anode of the lithium-oxygen secondary battery.
In order to improve the performance of the manufactured product and the integrity of the whole process route and reduce the influence of impurities and oil stains on the raw material, the reticular metal material is preferably a pretreated reticular metal material. The specific steps of the pretreatment in the present invention are not particularly limited, and may be those of metal materials well known to those skilled in the art, and those skilled in the art may select and adjust the steps according to actual production conditions, raw material conditions and product requirements, and the steps of the pretreatment in the present invention preferably include acid washing and/or organic solvent washing, more preferably acid washing and organic solvent washing, and may specifically be dilute hydrochloric acid washing and anhydrous ethanol washing.
The protective atmosphere is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and is preferably nitrogen and/or inert gas, and more preferably nitrogen or argon.
The specific position above the melamine is not particularly limited in the present invention, and those skilled in the art can select and adjust the specific position according to the actual production conditions, raw material conditions and product requirements. The specific value of the certain distance is not particularly limited in the present invention, and those skilled in the art can select and adjust the value according to the actual production situation, raw material situation and product requirement.
In order to ensure that the nitrogen-doped carbon nanotube can be formed and can stably and uniformly grow on the surface of the mesh-shaped metal material, the step a) is preferably as follows:
A1) firstly, putting melamine into a square boat of roasting equipment, then covering a breathable porous material on the square boat, and then putting a reticular metal material on the breathable porous material;
A2) and roasting in a protective atmosphere to obtain the lithium-oxygen secondary battery anode.
The addition amount of the melamine is not particularly limited, and a person skilled in the art can select and adjust the melamine according to the actual production situation, the raw material situation and the product requirement, wherein the mass ratio of the melamine to the metal material is preferably (1-5): 1, more preferably (1.5 to 4.5): 1, more preferably (2-4): 1, most preferably (2.5-3.5): 1.
the air-permeable porous material is not particularly limited in the present invention, and may be any air-permeable porous material commonly used by those skilled in the art, and those skilled in the art can select and adjust the material according to actual production conditions, raw material conditions and product requirements, and the air-permeable porous material of the present invention is preferably a high temperature-resistant air-permeable porous material, more preferably a high temperature-resistant air-permeable fibrous material, more preferably one or more of carbon paper, carbon cloth, glass fiber and asbestos web, more preferably carbon paper, carbon cloth, glass fiber or asbestos web, and most preferably carbon paper or carbon cloth.
The roasting equipment is not particularly limited by the invention, and can be selected and adjusted by the skilled in the art according to the actual production situation, the raw material situation and the product requirement, and the roasting equipment is preferably a high-temperature tube furnace, and the ark can be a ceramic ark.
The roasting temperature is not particularly limited in the invention, and the roasting temperature of the material is known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, raw material situation and product requirement, and the roasting temperature in the invention is preferably 600-800 ℃, more preferably 620-770 ℃, and most preferably 650-750 ℃.
The roasting time is not particularly limited in the invention, and the roasting time of the material is known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, raw material situation and product requirement, and the roasting time in the invention is preferably 2-4 h, more preferably 2.2-3.8 h, and most preferably 2.5-3.5 h.
The temperature rise rate of the roasting is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the actual production situation, the raw material situation and the product requirement, and the temperature rise rate of the roasting is preferably 5-8 ℃/min, more preferably 5.5-7.5 ℃/min, and most preferably 6-7 ℃/min.
In order to improve the performance of the manufactured product and the integrity of the whole process route, the method preferably further comprises a post-treatment process after roasting. The specific steps of the post-treatment of the invention are not particularly limited, and may be post-treatment steps well known to those skilled in the art, and those skilled in the art can select and adjust the steps according to actual production conditions, raw material conditions and product requirements, and the specific steps of the post-treatment of the invention preferably include one or more of washing with water, washing with an organic solvent and drying, more preferably washing with water, washing with an organic solvent and drying in sequence, and particularly may be washing with distilled water, washing with anhydrous ethanol and drying.
In order to improve the integrity of the whole process route, the preparation steps specifically comprise:
step (1): taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
step (2): weighing a certain amount of melamine solid powder, filling the melamine solid powder into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and putting the whole body into a high-temperature tube furnace;
and (3): starting a tubular furnace by taking argon as a protective gas, raising the temperature to the reaction temperature at the speed of 5 ℃ per minute, and keeping the temperature for several hours;
and (4): and after heating is finished, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively cleaning the stainless steel mesh for a plurality of times by using distilled water and absolute ethyl alcohol, and after the stainless steel mesh is dried in the air, covering a layer of black substance on the surface of the stainless steel mesh to obtain the nitrogen-doped carbon nanotube @ stainless steel mesh integrated electrode.
The preparation method of the lithium-oxygen secondary battery anode provided by the invention is a one-step method, has the advantages of simple process, convenience in operation and easiness in realization of large-scale production, does not need to add a current collector and a binder, omits a complex powder electrode preparation process, and greatly improves the specific energy, the energy utilization efficiency and the stability of the air anode of the lithium-air battery.
Referring to fig. 1, fig. 1 is a schematic diagram of a roasting reaction process provided by the present invention. Wherein, 1 is a tube furnace, 2 is a quartz furnace tube, 3 is the introduction of Ar gas, 4 is the discharge of Ar gas, 5 is a porcelain boat, 6 is carbon paper, 7 is melamine powder filled in the porcelain boat, and 8 is a stainless steel mesh.
The invention also provides a lithium-oxygen secondary battery, which comprises the positive electrode of the lithium-oxygen secondary battery in any one of the technical schemes or the positive electrode, the diaphragm and the negative electrode of the lithium-oxygen secondary battery prepared in any one of the technical schemes.
The negative electrode of the metal-air battery is not particularly limited, and can be selected and adjusted by those skilled in the art according to practical application, raw material conditions and product requirements, and the negative electrode of the metal-air battery comprises metal lithium or a material containing the metal lithium, and is more preferably the metal lithium.
The shape of the negative electrode is not particularly limited in the present invention, and the negative electrode of the metal-air battery known to those skilled in the art may be selected and adjusted according to the actual application, the raw material condition and the product requirement.
The separator of the present invention is not particularly limited as long as it is a separator for a metal-air battery, which is well known to those skilled in the art, and can be selected and adjusted according to practical use, raw material conditions, and product requirements, and preferably includes a gel film.
The flexible and super-hydrophobic lithium-oxygen secondary battery anode is an integrated electrode with a porous channel structure of a loose staggered nitrogen-doped carbon nanotube array @ metal material net. The carbon nano tube with the hollow structure of the anode material provides a transmission common channel for oxygen and electrolyte, and the loose array structure provides a solid discharge product Li2O2The deposition/desorption site has a mesoporous structure as a whole. The one-step method provided by the invention has simple process, convenient operation and easy realization of large-scale production,and a current collector and a binder are not needed to be added, a complex powder electrode preparation process is omitted, and the specific energy, the energy utilization efficiency and the stability of the air anode of the lithium-air battery are greatly improved. And the assembled flexible lithium-oxygen secondary battery has excellent electrochemical performance under different deformation conditions, and the voltage platform can be stably maintained under the bending condition. This shows that the material can work stably under different deformation conditions and has higher mechanical strength. The prepared electrode material has super-strong hydrophobicity, and the performance is favorable for the performance attenuation and short circuit phenomena of the air battery caused by the contact of water molecules in the air, so that the electrode material has wide application prospect in the field of wearable electronics.
Experimental results show that the positive electrode and the battery thereof provided by the invention have the structure, the discharge capacity is improved by 1 time compared with that of a commercial carbon nano tube air electrode, the overpotential is reduced by 0.6V, the cycle life is prolonged by 4 times, the positive electrode and the battery thereof can stably work under different deformation conditions, and the positive electrode and the battery thereof have high mechanical strength and super-strong hydrophobicity.
In order to further illustrate the present invention, the following will describe a lithium-oxygen secondary battery positive electrode and a method for preparing the same, and a lithium-oxygen secondary battery in detail with reference to the following examples, but it should be understood that the examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
The first step is as follows: taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
the second step is that: weighing 2 g of melamine solid powder, loading the melamine solid powder into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and putting the whole body into a high-temperature tube furnace;
the third step: starting a tubular furnace by taking argon as a protective gas, raising the temperature to 750 ℃ at the speed of 5 ℃ per minute, and keeping the temperature for 2 hours;
the fourth step: after heating, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively washing with distilled water and absolute ethyl alcohol for several times, drying in the air, covering a layer of black substance on the surface of the stainless steel mesh to obtain the nitrogen-doped carbon nanotube @ stainless steel mesh integrated electrode,
the lithium-oxygen secondary battery integrated positive electrode prepared in example 1 of the present invention was characterized.
Referring to fig. 2, fig. 2 is an electron scan of the n-doped carbon nanotube array of the cathode material prepared in example 1 of the present invention. As can be seen from fig. 2, the air cathode material prepared in example 1 of the present invention has a multi-stage pore structure
Referring to fig. 3, fig. 3 is an electron transmission diagram of the n-doped carbon nanotube array of the cathode material prepared in example 1 of the present invention.
As can be seen from fig. 3, the nitrogen-doped carbon nanotube of the cathode material prepared in example 1 of the present invention has a hollow structure.
Example 2
The first step is as follows: taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
the second step is that: weighing 2 g of melamine solid powder, loading the melamine solid powder into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and putting the whole body into a high-temperature tube furnace;
the third step: starting a tubular furnace by taking argon as a protective gas, raising the temperature to 800 ℃ at the speed of 5 ℃ per minute, and keeping the temperature for 2 hours;
the fourth step: and after heating is finished, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively cleaning the stainless steel mesh for a plurality of times by using distilled water and absolute ethyl alcohol, and after the stainless steel mesh is dried in the air, covering a layer of black substance on the surface of the stainless steel mesh to obtain the nitrogen-doped carbon nanotube @ stainless steel mesh integrated electrode.
The lithium-oxygen secondary battery integrated positive electrode prepared in example 2 of the present invention was characterized.
Referring to fig. 4, fig. 4 is an electron scan of the n-doped carbon nanotube array of the cathode material prepared in example 2 of the present invention.
As can be seen from fig. 4, the nitrogen-doped carbon nanotubes of the cathode material prepared in embodiment 2 of the present invention have an array structure in a staggered distribution as a whole, and the nitrogen-doped carbon nanotubes are loosely interlaced with each other to form a hair-like cluster.
Example 3
The first step is as follows: taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
the second step is that: weighing 1 g of melamine solid powder, loading the melamine solid powder into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and putting the whole body into a high-temperature tube furnace;
the third step: starting a tubular furnace by taking argon as a protective gas, raising the temperature to 600 ℃ at the speed of 5 ℃ per minute, and keeping the temperature for 2 hours;
the fourth step: and after heating is finished, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively cleaning the stainless steel mesh for a plurality of times by using distilled water and absolute ethyl alcohol, and after the stainless steel mesh is dried in the air, covering a layer of black substance on the surface of the stainless steel mesh to obtain the nitrogen-doped carbon nanotube @ stainless steel mesh integrated electrode.
The lithium-oxygen secondary battery integrated positive electrode prepared in example 3 of the present invention was characterized.
Referring to fig. 5, fig. 5 is an electron scan of the n-doped carbon nanotube array of the cathode material prepared in example 3 of the present invention.
Example 4
Preparation of lithium-air Battery
1. Taking a linear metal lithium rod as a negative electrode;
2. uniformly coating a layer of polyvinylidene fluoride-hexafluoropropylene copolymer electrolyte on a lithium rod;
3. winding the lithium-oxygen flexible electrode prepared in example 1 of the present invention on a lithium rod coated with an electrolyte;
4. then winding a layer of foam nickel on the outside;
5. and finally, packaging the battery by using a heat-shrinkable tube to obtain the lithium-oxygen battery.
The lithium-oxygen battery prepared in example 4 of the present invention was tested.
Referring to fig. 6, fig. 6 is a discharge product Li of a lithium-oxygen battery prepared in example 4 of the present invention2O2And (3) a scanning electron microscope image deposited on the surface of the nitrogen-doped carbon nanotube array @ stainless steel mesh anode. As can be seen from fig. 6, the array structure of the nitrogen-doped carbon nanotube array @ stainless steel mesh anode prepared by the present invention provides a deposition site for the solid discharge product.
Referring to fig. 7, fig. 7 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of the nitrogen-doped carbon nanotube array in the lithium-oxygen battery prepared in example 4 of the present invention. As can be seen from fig. 7, the nitrogen-doped carbon nanotube array @ stainless steel mesh air electrode prepared by the present invention has a mesoporous structure.
Referring to fig. 8, fig. 8 is a graph comparing the cycle stability of the nitrogen-doped carbon nanotube @ stainless steel mesh positive electrode in the lithium-oxygen battery prepared in example 4 of the present invention with that of the commercial carbon nanotube.
Referring to fig. 9, fig. 9 is a graph comparing the cycle stability of the nitrogen-doped carbon nanotube @ stainless steel mesh positive electrode in the lithium-oxygen battery prepared in example 4 of the present invention with the discharge capacity of the commercial carbon nanotube.
Referring to fig. 10, fig. 10 is a graph comparing the charge/discharge potential of the positive electrode of the nitrogen-doped carbon nanotube @ stainless steel mesh with the charge/discharge potential of the commercial carbon nanotube in the lithium-oxygen battery prepared in example 4 of the present invention.
As can be seen from FIGS. 8 to 10, the discharge capacity of the lithium-oxygen battery prepared by the method is improved by about 1 time compared with that of a commercial carbon nanotube air electrode, the overpotential is reduced by 0.6V, and the cycle life is improved by about 4 times.
Example 5
Preparation of lithium-air Battery
1. Taking a linear metal lithium rod as a negative electrode;
2. uniformly coating a layer of polyvinylidene fluoride-hexafluoropropylene copolymer electrolyte on a lithium rod;
3. winding the lithium-oxygen flexible electrode prepared in example 2 of the present invention on a lithium rod coated with an electrolyte;
4. then winding a layer of foam nickel on the outside;
5. and finally, packaging the battery by using a heat-shrinkable tube to obtain the lithium-oxygen battery.
The lithium-oxygen battery prepared in example 5 of the present invention was subjected to deformation test.
1) Bending the prepared flexible battery into various shapes by hands, and observing the working state of the battery;
2) and (3) placing the prepared flexible battery on a vertical mechanical property tester, and repeatedly carrying out deformation detection such as pushing, pulling, bending and the like.
Referring to fig. 11, fig. 11 is a digital diagram of the assembled lithium air flexible battery of example 5 of the present invention for lighting the LED lamp under different bending angles.
Referring to fig. 12, fig. 12 is a graph showing the change of voltage during the bending of the assembled lithium-oxygen flexible secondary battery according to example 5 of the present invention.
As can be seen from fig. 11 and 12, the voltage plateau of the lithium-oxygen battery prepared according to the present invention can be stably maintained under the bending condition. This shows that the material can work stably under different deformation conditions and has higher mechanical strength.
The lithium-oxygen battery prepared in example 5 of the present invention was subjected to hydrophobic property detection.
Referring to fig. 13, fig. 13 is a graph showing the contact angle between the nitrogen-doped carbon nanotube @ stainless steel mesh air positive electrode and water in the lithium-oxygen battery prepared in example 5 of the present invention.
As can be seen from FIG. 13, the electrode material of the lithium-oxygen battery prepared by the invention has super-strong hydrophobic property, and the property is beneficial to the performance attenuation and short circuit phenomenon of the air battery caused by the contact of water molecules in the air, so that the lithium-oxygen battery has wide application prospect in the field of wearable electronics.
Comparative example 1
The first step is as follows: taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
the second step is that: weighing 1 g of melamine solid powder, loading the melamine solid powder into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and putting the whole body into a high-temperature tube furnace;
the third step: starting a tubular furnace by taking argon as a protective gas, raising the temperature to 500 ℃ at the speed of 5 ℃ per minute, and keeping the temperature for 2 hours;
the fourth step: and (3) after heating is finished, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively cleaning the stainless steel mesh for a plurality of times by using distilled water and absolute ethyl alcohol, and covering a layer of black substance on the surface of the stainless steel mesh after the stainless steel mesh is dried in the air to obtain the composite cathode material.
The composite positive electrode material prepared in comparative example 1 of the present invention was examined.
Referring to fig. 14, fig. 14 is an electron scan of the cathode material prepared in comparative example 1.
As can be seen from fig. 14, since the reaction temperature is too low, nanoparticles are mainly formed on the surface of the stainless steel mesh, and most of the tubular morphology disappears.
Comparative example 2
The first step is as follows: taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
the second step is that: weighing 0.5 g of melamine solid powder, loading into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and placing the whole into a high-temperature tube furnace;
the third step: starting a tubular furnace by taking argon as a protective gas, raising the temperature to 750 ℃ at the speed of 5 ℃ per minute, and keeping the temperature for 2 hours;
the fourth step: and (3) after heating is finished, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively cleaning the stainless steel mesh for a plurality of times by using distilled water and absolute ethyl alcohol, and covering a layer of black substance on the surface of the stainless steel mesh after the stainless steel mesh is dried in the air to obtain the composite cathode material.
The composite positive electrode material prepared in comparative example 2 of the present invention was examined.
Referring to fig. 15, fig. 15 is an electron scan of the cathode material prepared in comparative example 2.
As can be seen from fig. 15, since the solid melamine powder was reduced and the reactant was insufficient, the carbon nanostructure was not formed on the surface of the stainless steel mesh.
Comparative example 3
The first step is as follows: taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
the second step is that: weighing 2 g of melamine solid powder, loading the melamine solid powder into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and putting the whole body into a high-temperature tube furnace;
the third step: starting a tubular furnace by taking argon as a protective gas, raising the temperature to 750 ℃ at the speed of 5 ℃ per minute, and keeping the temperature for 4 hours;
the fourth step: and (3) after heating is finished, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively cleaning the stainless steel mesh for a plurality of times by using distilled water and absolute ethyl alcohol, and covering a layer of black substance on the surface of the stainless steel mesh after the stainless steel mesh is dried in the air to obtain the composite cathode material.
The nitrogen-doped carbon nanotube @ stainless steel mesh positive electrode material prepared in comparative example 3 of the present invention was tested.
Referring to fig. 16, fig. 16 is an electron scan of the nitrogen doped carbon nanotube @ stainless steel mesh prepared in comparative example 3.
As can be seen from fig. 16, the length of the nitrogen-doped nanotubes increased due to the increase in the reaction time.
Comparative example 4
The first step is as follows: taking a piece of stainless steel mesh, and cleaning the stainless steel mesh for a plurality of times by respectively using dilute hydrochloric acid and absolute ethyl alcohol;
the second step is that: weighing 2 g of melamine solid powder, loading the melamine solid powder into a ceramic square boat, covering a piece of carbon paper on the ceramic square boat, placing a cleaned stainless steel mesh on the carbon paper, and putting the whole body into a high-temperature tube furnace;
the third step: starting a tubular furnace by taking argon as a protective gas, raising the temperature to 850 ℃ at the speed of 5 ℃ per minute, and keeping the temperature for 2 hours;
the fourth step: and (3) after heating is finished, cooling the reactant to room temperature, taking out the stainless steel mesh, respectively cleaning the stainless steel mesh for a plurality of times by using distilled water and absolute ethyl alcohol, and covering a layer of black substance on the surface of the stainless steel mesh after the stainless steel mesh is dried in the air to obtain the composite cathode material.
The composite positive electrode material prepared in comparative example 4 of the present invention was examined.
Referring to fig. 17, fig. 17 is an electron scan of the cathode material prepared in comparative example 4.
As is clear from fig. 17, the nanotube structure is destroyed and a particulate substance is generated due to the excessively high reaction temperature.
The foregoing detailed description of the flexible, superhydrophobic lithium-oxygen secondary battery positive electrode and method of making the same, and lithium-oxygen secondary battery provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to facilitate an understanding of the methods of the present invention and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (5)
1. A method for manufacturing a lithium-oxygen secondary battery, comprising the steps of:
(1) taking a linear metal lithium rod as a negative electrode;
(2) uniformly coating a layer of polyvinylidene fluoride-hexafluoropropylene copolymer electrolyte on a lithium rod;
(3) preparing a lithium-oxygen secondary battery anode and winding the anode on a lithium rod coated with an electrolyte;
(4) then winding a layer of foam nickel on the outside;
(5) finally, packaging the battery by using a heat-shrinkable tube to obtain the lithium-oxygen battery;
the preparation method of the lithium-oxygen secondary battery anode comprises the following steps:
A) under a protective atmosphere, placing a net-shaped metal material above melamine, and roasting to obtain the anode of the lithium-oxygen secondary battery;
the step A) is specifically as follows:
A1) firstly, putting melamine into a square boat of roasting equipment, then covering a breathable porous material on the square boat, and then putting a reticular metal material on the breathable porous material;
the mass ratio of the melamine to the metal material is (2.5-3.5): 1;
A2) roasting in a protective atmosphere to obtain the anode of the lithium-oxygen secondary battery;
the roasting temperature is 750-800 ℃;
the roasting time is 2.5-3.5 h;
the temperature rise rate of the roasting is 5-8 ℃/min;
the anode of the lithium-oxygen secondary battery comprises a reticular metal material and nitrogen-doped carbon nanotubes uniformly compounded on the surface of the metal material;
the nitrogen-doped carbon nanotube is a nitrogen-doped carbon nanotube array;
the nitrogen-doped carbon nanotube array has a loose array structure;
the length of the carbon nano tube is 7-8 mu m;
the diameter of the carbon nano tube is 80-120 nm;
the metallic material comprises one or more of iron, nickel and iron-nickel alloy.
2. The production method according to claim 1, wherein the nitrogen-doped carbon nanotube has a hollow tube structure.
3. The production method according to claim 1, wherein the lithium-oxygen secondary battery positive electrode has a multi-stage pore structure.
4. The production method according to any one of claims 1 to 3, wherein the metal material includes stainless steel.
5. The method of claim 1, wherein the air-permeable porous material comprises one or more of carbon paper, carbon cloth, glass fiber, and asbestos wool.
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| CN103915632A (en) * | 2014-03-24 | 2014-07-09 | 复旦大学 | Self-supporting nitrogen-doped carbon nanotube lithium air cell cathode and preparation method thereof |
| CN104176724A (en) * | 2014-08-14 | 2014-12-03 | 浙江大学 | Preparation method and product of nitrogen-doped carbon nano-tube |
| CN104600307A (en) * | 2015-01-13 | 2015-05-06 | 上海交通大学 | Preparation method of multiwalled carbon nanotube for lithium air battery positive electrode |
| CN106048650A (en) * | 2016-08-04 | 2016-10-26 | 浙江大学 | 3D porous electrode preparation method and use of 3D porous electrode in electrochemical hydrogen evolution |
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| CN103915632A (en) * | 2014-03-24 | 2014-07-09 | 复旦大学 | Self-supporting nitrogen-doped carbon nanotube lithium air cell cathode and preparation method thereof |
| CN104176724A (en) * | 2014-08-14 | 2014-12-03 | 浙江大学 | Preparation method and product of nitrogen-doped carbon nano-tube |
| CN104600307A (en) * | 2015-01-13 | 2015-05-06 | 上海交通大学 | Preparation method of multiwalled carbon nanotube for lithium air battery positive electrode |
| CN106048650A (en) * | 2016-08-04 | 2016-10-26 | 浙江大学 | 3D porous electrode preparation method and use of 3D porous electrode in electrochemical hydrogen evolution |
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