CN111653798A - Metal-air battery cathode, preparation method and application thereof, and battery - Google Patents

Metal-air battery cathode, preparation method and application thereof, and battery Download PDF

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CN111653798A
CN111653798A CN202010574488.4A CN202010574488A CN111653798A CN 111653798 A CN111653798 A CN 111653798A CN 202010574488 A CN202010574488 A CN 202010574488A CN 111653798 A CN111653798 A CN 111653798A
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air battery
cathode
metal
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transition metal
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不公告发明人
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Wuhan Ruikemei New Energy Co ltd
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    • H—ELECTRICITY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
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Abstract

The invention belongs to the technical field of new energy and new materials, and particularly relates to a metal-air battery cathode, a preparation method and application thereof, and a battery. The method comprises the following steps: 1) preparing a carbon nanotube-supported transition metal oxide; 2) preparing composite gel of polyurethane and silicon dioxide; 3) preparing the carbon nano tube-loaded transition metal oxide obtained in the step 1) and the polyurethane-silicon dioxide composite gel obtained in the step 2) into composite slurry, and preparing the metal-air battery cathode by using the composite slurry. The carbon nano tube is compounded with the transition metal oxide, so that the conductivity of the transition metal oxide is improved, the oxygen reduction and oxygen evolution activities of the electrode are improved, and the capacity and the reversibility are improved by improving the catalytic efficiency of the air electrode.

Description

Metal-air battery cathode, preparation method and application thereof, and battery
Technical Field
The invention belongs to the technical field of new energy and new materials, and particularly relates to a metal-air battery cathode, a preparation method and application thereof, and a battery.
Background
With the development of science and technology, the energy density of conventional batteries (such as lithium ion batteries) is increasingly unable to meet the requirements of people (such as electric vehicles, large-scale energy storage power stations and the like). The metal air battery such as the lithium air battery has extremely high energy density which is about 3 to 5 times of that of the lithium ion battery, and is a great direction for the development of the battery in future. Therefore, the research on how to industrialize the metal-air battery has important significance.
However, metal-air batteries are currently still in the laboratory stage. For example, lithium air battery has poor cycle performance, and the actual charge-discharge energy density is difficult to reach an ideal value. To be practical, the following challenges must be overcome: the charge and discharge efficiency is improved, the instability of electrodes and electrolyte is reduced, the current density is improved, the cycle life is prolonged, and the like.
The method for improving the charge and discharge efficiency and the capacity mainly comprises the steps of selecting a proper positive electrode catalyst to reduce the overpotential of electrode reaction; an air anode with rich reaction sites and large specific surface area is constructed, and a storage place is provided for discharge products while the current and the capacity are improved; and the occurrence of side reactions is reduced, and the stability of the composite material is improved. Air electrodes in laboratories today either build three-dimensional electrodes in situ from synthesis or are coated with a slurry by coating. The experiment for constructing the three-dimensional electrode in situ is difficult to repeat, and the selection range of the type of the catalyst is narrow. Coating on the substrate by the slurry may cause uneven distribution of the components or may block oxygen channels of the air electrode. Transition metal oxides are a catalytic material of an air electrode with low cost and excellent catalytic performance, but the conductivity of the transition metal oxides is poor, and the transmission rate of electrons in a reaction interface is influenced, so that the conductivity of the transition metal oxides needs to be improved and then the transition metal oxides are utilized on the electrode.
Disclosure of Invention
Aiming at the defects of the prior art and aiming at solving the problems of low capacity and low charging and discharging efficiency of the lithium-air battery, the invention provides a metal-air battery cathode, a preparation method and application thereof and a battery.
The technical scheme provided by the invention is as follows:
a preparation method of a cathode of a metal-air battery comprises the following steps:
1) preparing a Transition Metal Oxide (TMO) carried by a Carbon Nanotube (CNT);
2) preparing composite gel of polyurethane and silicon dioxide;
3) preparing the carbon nano tube-loaded transition metal oxide obtained in the step 1) and the polyurethane-silicon dioxide composite gel obtained in the step 2) into composite slurry, and preparing the metal-air battery cathode by using the composite slurry.
The carbon nanotubes are selected from one or more of single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs) and the like.
The transition metal oxide is selected from manganese dioxide MnO2Iron oxide Fe2O3Fe, Fe ferroferric oxide3O4Tricobalt tetraoxide Co3O4Or cobalt oxide, CoO, or the like.
In the above technical scheme:
in step 1), the CNT and TMO can be mixed to achieve the nano-scale dispersion effect suitable for the cathode application of the metal-air battery. After the nanoscale dispersion is formed, both CNT and TMO are present at the same reaction site. The CNT and the TMO on the same reaction site are used as catalysts together, and have catalytic activities of oxygen reduction and oxygen evolution reaction at the same time, and the combination is suitable for the charge and discharge process of the cathode of the metal air battery, but has too strong or too weak catalytic activity or has the opposite effect;
adding PU/SiO into the slurry obtained in step 3)2The gel can realize the ion conduction in the slurry, and the ion conductor can be other energy ion conductors, so that the ion conductivity of the catalyst can be improved, and the performance of the air battery can be improved;
the PTFE emulsion is added into the slurry in the step 3), so that water can be prevented from invading a catalytic interface, and the electrolyte can be resisted to wash the catalyst, so that the stability of the electrode performance is maintained.
According to the technical scheme, the carbon nano tube is compounded with the transition metal oxide, so that the conductivity of the transition metal oxide is improved, and the oxygen reduction and oxygen evolution activities of the electrode are improved; adding an ionic conductor to improve interface contact and improve ionic conductivity; adding a binder to prevent the catalyst from falling off the substrate; the hydrophobic emulsion is added to prevent water from invading the catalytic interface to generate side reaction. According to the technical scheme, the problems that the actual capacity of the lithium-air battery in the air is not enough and the reversibility is not good are solved, and thus the capacity and the reversibility are improved by improving the catalytic efficiency of the air electrode.
Specifically, in the step 1), the carbon nanotube-supported transition metal oxide is prepared by a ball milling method.
Specifically, the step 1) comprises the following steps: firstly, mixing transition metal oxide and carbon nano tubes, then carrying out solid phase dry ball milling on the mixed material, adding N-methyl pyrrolidone into the mixed material, and then continuing ball milling to obtain the carbon nano tube loaded transition metal oxide.
The technical scheme can construct the air anode with rich reaction sites and large specific surface area by a specific ball milling technology. And the carbon nano tube supported transition metal oxide and the transition metal oxide can be simultaneously carried on the same reaction site, so that the conductivity of the transition metal oxide is obviously improved, the oxygen reduction and oxygen evolution activities of the electrode are obviously improved, the catalytic efficiency of the air electrode is obviously improved, and the capacity and the reversibility of the battery are obviously improved.
Specifically, the method comprises the following steps:
the mass ratio of the transition metal oxide to the carbon nano tube is 1: n, n is more than or equal to 0.2 and less than or equal to 5;
the rotating speed of the dry ball milling is 50-2000r/min, and the time of the dry ball milling is more than or equal to 2 hours;
the time for continuing the ball milling is more than or equal to 1 hour.
Specifically, the step 2) comprises the following steps: adding polyurethane into a solvent for forming gel, uniformly stirring, then adding silicon dioxide, and uniformly stirring until the solution is transparent to obtain the composite gel of polyurethane and silicon dioxide.
Specifically, the method comprises the following steps:
the solvent is selected from any one of N-methyl pyrrolidone, N-dimethyl formamide or acetone;
the using ratio of the polyurethane to the silicon dioxide to the solvent is as follows: 4-6 g: 0.8-1.2 g: 40-60 mL.
Specifically, the step 3) comprises the following steps: uniformly mixing the carbon nano tube loaded transition metal oxide obtained in the step 1), polyvinylidene fluoride and the composite gel of polyurethane and silicon dioxide obtained in the step 3) to obtain a premix, adding polytetrafluoroethylene emulsion and N-methyl pyrrolidone into the premix, stirring to prepare a composite slurry, and spraying the composite slurry on a conductive substrate to obtain the metal-air battery cathode.
Alternatively, step 3) comprises the steps of: uniformly mixing the carbon nanotube-loaded transition metal oxide obtained in the step 1) and the polyvinylidene fluoride obtained in the step 3) with the composite gel of the polyurethane and the silicon dioxide to obtain a premix, adding N-methylpyrrolidone into the premix, and stirring to prepare the composite slurry. And spraying the composite slurry on a conductive substrate, and finally hot-pressing a polytetrafluoroethylene film on the conductive substrate to obtain the cathode of the metal-air battery.
Specifically, in step 3):
according to the mass ratio, the using amount ratio of the carbon nano tube loaded transition metal oxide and polyvinylidene fluoride obtained in the step 1) to the polyurethane and silicon dioxide composite gel obtained in the step 3) is 9: m: n, m is less than or equal to 2, and n is less than or equal to 5;
the mass ratio of the premix to the polytetrafluoroethylene emulsion is (95-99.9): 1;
the mass ratio of the premix to the N-methylpyrrolidone added in the step is (20-500) to 1;
the conductive substrate is selected from foamed nickel, carbon cloth or cracked graphite sheet.
Specifically, the preparation method of the cathode of the metal-air battery specifically comprises the following steps:
step (1): preparation of multiwall carbon nanotube (MWCNT) loaded TMO (TMO @ MWCNT)
Firstly, commercial TMO and MWCNTCNT with the mass ratio of 1: n (n is 0.2 and n is less than or equal to 5) are mixed, and solid phase dry ball milling is carried out for more than 2 hours at a certain rotating speed. And scraping the materials attached to the wall of the ball milling tank, adding a proper amount of N-methylpyrrolidone (NMP), and continuously ball milling for more than 1 hour to obtain the TMO @ MWCNT.
Step (2) of PU/SiO2Preparation of the gel
Slowly adding Polyurethane (PU) into appropriate amount of solvent such as (NMP), stirring, and slowly adding certain proportion of silicon dioxide SiO2Uniformly stirring to obtain PU and SiO2Transparent solution to obtain PU/SiO2And (4) gelling.
And (3): preparation of the slurry
According to the mass ratio TMO @ MWCNT: PVDF: PU/SiO2M is 9: n (m is less than or equal to 2 and n is less than or equal to 5), adding a proper amount of Polytetrafluoroethylene (PTFE) emulsion and NMP, and stirring by using a grease homogenizing machine to prepare slurry.
And (4): preparation of air electrode the required amount of slurry was sprayed onto a conductive substrate (which could be foamed nickel, carbon cloth, cracked graphite flakes, etc.) using a 0.1 to 0.5mm bore diameter spray gun, if no PTFE emulsion was added in step (3), the same effect was achieved by hot pressing the PTFE film onto the foamed nickel after spraying the slurry.
The invention also provides the metal-air battery cathode prepared by the preparation method of the metal-air battery cathode.
The specific capacity of the air battery manufactured by the metal air battery cathode provided by the invention is obviously higher than that of the conventional other battery cathodes.
The invention also provides the application of the cathode of the air battery, and the cathode is used as the cathode of the lithium air battery, the zinc air battery and the aluminum air battery or the lithium sulfur battery.
The invention also provides a metal-air battery, which comprises a cathode, wherein the cathode is the cathode of the metal-air battery provided by the invention.
The metal-air battery provided by the invention has the specific capacity which is obviously higher than that of other existing metal-air batteries.
The technical scheme provided by the invention has the beneficial effects that:
the invention combines the transition metal oxide with excellent catalytic performance and the carbon nano tube to ensure that the carbon nano tube has good catalytic performanceGood conductivity and large degree of dispersion; simultaneously adding Pu/SiO into the prepared slurry2The ionic conductivity of the material is improved; and the PTFE emulsion can effectively prevent water from invading a catalytic interface to generate side reaction, and the PTFE is insoluble in electrolyte and can effectively resist the electrolyte to wash the catalyst to maintain the stability of the electrode. Meanwhile, the method provided by the embodiment of the invention can be amplified in production and can be used in the fields of lithium-sulfur batteries, zinc-air batteries and aluminum-air batteries.
Drawings
FIG. 1: co3O4@ CNT.
FIG. 2: SEM spectra of the air electrode of example one.
FIG. 3: charge-discharge curve map of air electrode of example one
FIG. 4: SEM image of air electrode of example two.
FIG. 5: the charge-discharge curve map of the air electrode of example two.
FIG. 6: the charge-discharge curve map of the air electrode of example three.
FIG. 7: example four air electrode charge and discharge curve maps.
FIG. 8: and comparing the specific capacity of the lithium-air battery of the comparative example I.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is further described with reference to the following drawings and specific examples, which are not intended to be limiting.
Example one
The embodiment provides a preparation method of an air electrode of a lithium-air battery, which comprises the following steps:
step (1): MWCNT Co-loaded3O4(Co3O4@ CNT) preparation
Firstly, commercial Co with the mass ratio of 1:23O4And MWCNT is ball milled for about 10 hours at a rotational speed of 600 r/min. Then adding a proper amount of NMP and continuing ball milling for 2 hours. The XRD spectrum is shown in figure 1, and the obtained Co3O4@ Co appearing in CNT3O4Peak and Co3O4The PDF card of (1) is completely matched, the peak of the CNT only comprises (002) surfaces, and the CNT is relatively wide and shows an amorphous state.
Step (2) of PU/SiO2Preparation of the gel
5g of Polyurethane (PU) were slowly added to 50ml of NMP, stirred for 12h and then 1g of SiO were slowly added2Stirring for 12h to obtain a transparent solution of PU and SiO 2. Thus obtaining PU/SiO2Gel
And (3): preparation of the slurry
By mass ratio of Co3O4@ CNT: PVDF: PU/SiO 2: 9: 0.5: and 5.5, adding a proper amount of PTFE emulsion NMP, and stirring by using a grease homogenizing machine to obtain the air electrode slurry.
And (4): preparation of air electrode
The slurry was sprayed on a nickel foam substrate with a spray gun having a pore size of 0.5mm, and dried overnight at 80 ℃ to prepare an air electrode. Under a scanning electron microscope, the morphology of the catalyst on the surface of the electrode is shown in fig. 2, and it can be seen that a microstructure of the carbon nanotube supported transition metal oxide has been formed.
The charge-discharge curve map of the button cell assembled by the air electrode is shown in figure 3.
Example two
The embodiment provides a preparation method of an air electrode of a lithium-air battery, which comprises the following steps:
step (1): MWCNT Co-loaded3O4(Co3O4@ CNT) preparation
Firstly, commercial Co with the mass ratio of 1:23O4And MWCNT is ball milled for about 10 hours at a rotational speed of 600 r/min. Then adding a proper amount of NMP and continuing ball milling for 2 hours.
Step (2) of PU/SiO2Preparation of the gel
Slowly adding 5g of Polyurethane (PU) into 50ml of NMP, stirring for 12h, then slowly adding 1g of SiO2, stirring for 12h to obtain transparent PU and SiO2 solution, and obtaining PU/SiO2And (4) gelling.
And (3): preparation of the slurry
By mass ratio of Co3O4@ CNT: PVDF: PU/SiO 2: 9: 0.5: and 5.5, adding a proper amount of NMP, and stirring by using a grease homogenizing machine to obtain the air electrode slurry.
And (4): preparation of air electrode
Spraying the slurry on a foam nickel substrate by using a spray gun with the aperture of 0.5mm, drying at 80 ℃ overnight, and carrying out hot pressing on a PTFE membrane with the same area and a prepared electrode to obtain the air electrode. Under a scanning electron microscope, the morphology of the catalyst on the surface of the electrode is shown in fig. 4, and it can be seen that a microstructure of the carbon nanotube supported transition metal oxide has been formed.
The charge-discharge curve map of the button cell assembled by the air electrodes is shown in figure 5.
EXAMPLE III
The embodiment provides a preparation method of an air electrode of a lithium-air battery, which comprises the following steps:
step (1): MWCNT Co-loaded3O4(Co3O4@ CNT) preparation
Firstly, commercial Co with the mass ratio of 2:13O4And MWCNT is ball milled for about 10 hours at a rotational speed of 600 r/min. Then adding a proper amount of NMP and continuing ball milling for 2 hours.
Step (2) of PU/SiO2Preparation of the gel
5g of Polyurethane (PU) were slowly added to 50ml of NMP, stirred for 12h and then 1g of SiO were slowly added2Stirring for 12h to obtain a transparent solution of PU and SiO 2. Thus obtaining PU/SiO2Gel
And (3): preparation of the slurry
By mass ratio of Co3O4@ CNT: PVDF: PU/SiO 2: 9: 0.5: and 5.5, adding a proper amount of PTFE emulsion NMP, and stirring by using a grease homogenizing machine to obtain the air electrode slurry.
And (4): preparation of air electrode
The slurry was sprayed on a nickel foam substrate with a spray gun having a pore size of 0.5mm, and dried overnight at 80 ℃ to prepare an air electrode.
The charge-discharge curve map of the button cell assembled by the air electrodes is shown in figure 6.
Example four
The embodiment provides a preparation method of an air electrode of a lithium-air battery, which comprises the following steps:
step (1): MWCNT MnO Supported on MnO2(MnO2@ CNT) preparation
First, commercial MnO of 2:1 mass ratio2And MWCNT is ball milled for about 10 hours at a rotational speed of 600 r/min. Then adding a proper amount of NMP and continuing ball milling for 2 hours.
Step (2) of PU/SiO2Preparation of the gel
5g of Polyurethane (PU) were slowly added to 50ml of NMP, stirred for 12h and then 1g of SiO were slowly added2Stirring for 12h to obtain a transparent solution of PU and SiO 2. Thus obtaining PU/SiO2Gel
And (3): preparation of the slurry
MnO in mass ratio2@ CNT: PVDF: PU/SiO 2: 9: 0.5: and 5.5, adding a proper amount of PTFE emulsion NMP, and stirring by using a grease homogenizing machine to obtain the air electrode slurry.
And (4): preparation of air electrode
The slurry was sprayed on a nickel foam substrate with a spray gun having a pore size of 0.5mm, and dried overnight at 80 ℃ to prepare an air electrode.
The charge-discharge curve map of the button cell assembled by the air electrode is shown in figure 7.
Comparative example 1
For comparison, commercial Co in a mass ratio of 3:6:0.5 was first used3O4MWCNT and PVDF were dissolved in NMP and stirred, the same mass of PTFE emulsion as in example one was added,a general slurry was obtained, and the air battery was assembled according to the method of example one, and the specific capacity thereof was compared with that of example one, as shown in fig. 8. Co of example one3O4The specific capacity of the @ CNT air battery is greater than 6000mAh/g, the specific capacity of the commercial ingredients which are simply mixed is 2000mAh/g, and the specific capacity is increased to 3 times.
FIG. 8: example one air electrode (black) prepared with commercial Co3O4The specific capacity (red) curve diagram of the lithium-air battery assembled by common slurry consisting of the conductive agent and the binding agent.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of a cathode of a metal-air battery is characterized by comprising the following steps:
1) preparing a carbon nanotube-supported transition metal oxide;
2) preparing composite gel of polyurethane and silicon dioxide;
3) preparing the carbon nano tube-loaded transition metal oxide obtained in the step 1) and the polyurethane-silicon dioxide composite gel obtained in the step 2) into composite slurry, and preparing the metal-air battery cathode by using the composite slurry.
2. The method for preparing a cathode for a metal-air battery according to claim 1, wherein the step 1) comprises the steps of: firstly, mixing transition metal oxide and carbon nano tubes, then carrying out solid phase dry ball milling on the mixed material, adding N-methyl pyrrolidone into the mixed material, and then continuing ball milling to obtain the carbon nano tube loaded transition metal oxide.
3. The method of making a metal-air battery cathode of claim 2, characterized in that:
the mass ratio of the transition metal oxide to the carbon nano tube is 1: n, n is more than or equal to 0.2 and less than or equal to 5;
the rotating speed of the dry ball milling is 50-2000r/min, and the time of the dry ball milling is more than or equal to 2 hours;
the time for continuing the ball milling is more than or equal to 1 hour.
4. The method of preparing a cathode for a metal-air battery according to claim 1, wherein the step 2) comprises the steps of: adding polyurethane into a solvent for forming gel, uniformly stirring, then adding silicon dioxide, and uniformly stirring until the solution is transparent to obtain the composite gel of polyurethane and silicon dioxide.
5. The method of making a metal-air battery cathode of claim 4, characterized in that:
the solvent is selected from any one of N-methyl pyrrolidone, N-dimethyl formamide or acetone;
the using ratio of the polyurethane to the silicon dioxide to the solvent is as follows: 4-6 g: 0.8-1.2 g: 40-60 mL.
6. The method of preparing a metal-air battery cathode according to claim 1, wherein step 3) comprises the steps of:
uniformly mixing the carbon nanotube-loaded transition metal oxide obtained in the step 1) and polyvinylidene fluoride with the polyurethane-silicon dioxide composite gel obtained in the step 3) to obtain a premix, adding polytetrafluoroethylene emulsion and N-methyl pyrrolidone into the premix, stirring to prepare a composite slurry, and spraying the composite slurry on a conductive substrate to obtain the metal-air battery cathode;
alternatively, step 3) comprises the steps of: uniformly mixing the carbon nanotube-loaded transition metal oxide obtained in the step 1) and the polyvinylidene fluoride obtained in the step 3) with the composite gel of the polyurethane and the silicon dioxide to obtain a premix, adding N-methylpyrrolidone into the premix, and stirring to prepare the composite slurry. And spraying the composite slurry on a conductive substrate, and finally hot-pressing a polytetrafluoroethylene film on the conductive substrate to obtain the cathode of the metal-air battery.
7. The method for preparing a cathode for a metal-air battery according to claim 6, wherein in step 3):
according to the mass ratio, the using amount ratio of the carbon nano tube loaded transition metal oxide and polyvinylidene fluoride obtained in the step 1) to the polyurethane and silicon dioxide composite gel obtained in the step 3) is 9: m: n, m is less than or equal to 2, and n is less than or equal to 5;
the mass ratio of the premix to the polytetrafluoroethylene emulsion is (95-99.9) to 1;
the mass ratio of the premix to the N-methyl pyrrolidone added in the step is (20-500);
the conductive substrate is selected from foamed nickel, carbon cloth or cracked graphite sheet.
8. A metal-air battery cathode prepared according to the method of preparing a metal-air battery cathode of any one of claims 1 to 7.
9. Use of a metal-air battery cathode according to claim 8, characterized in that: as a cathode in the field of lithium air batteries, zinc air batteries and aluminium air batteries or lithium sulphur batteries.
10. A metal-air cell comprising a cathode, characterized in that: the cathode is the metal-air battery cathode of claim 8.
CN202010574488.4A 2020-06-22 2020-06-22 Metal-air battery cathode, preparation method and application thereof, and battery Pending CN111653798A (en)

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