CN113206265B - Lithium-carbon dioxide battery anode catalyst and preparation method thereof - Google Patents

Lithium-carbon dioxide battery anode catalyst and preparation method thereof Download PDF

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CN113206265B
CN113206265B CN202110523958.9A CN202110523958A CN113206265B CN 113206265 B CN113206265 B CN 113206265B CN 202110523958 A CN202110523958 A CN 202110523958A CN 113206265 B CN113206265 B CN 113206265B
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lithium
carbon dioxide
dioxide battery
catalyst
anode catalyst
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CN113206265A (en
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谈鹏
肖旭
张卓君
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University of Science and Technology of China USTC
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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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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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    • 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
    • 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
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    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • 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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    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a lithium-carbon dioxide battery anode catalyst, and belongs to the technical field of batteries. The lithium-carbon dioxide battery anode catalyst is a cobalt-doped nickel oxide carbon nanotube material, the aperture of the porous structure material is 2-100 nm, and the size of cobalt-doped nickel oxide nanoparticles is 7-10 nm; when the lithium-carbon dioxide battery is used in a lithium-carbon dioxide battery, the discharge capacity can reach 5848 mAh/g at the current density of 100 mA/g, and the coulombic efficiency is 92.81% when the charge cut-off voltage is 4.5V; when the capacity is limited to 500 mAh/g, the overpotential can be reduced to 1.26V, and the electrode can stabilize the charge-discharge cycle for more than 500 hours without fading. The catalyst of the invention effectively reduces the cost, and the synthesis method is simple and efficient. The nano-particle size of the catalyst is reduced, and the reaction active area is increased; the conductivity and the electrocatalytic activity of the nickel oxide in the anode catalyst are improved, and the solid discharge product is favorably stored, so that the battery capacity is improved.

Description

Lithium-carbon dioxide battery anode catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-efficiency and low-cost lithium-carbon dioxide battery anode catalyst and a preparation method thereof.
Background
Lithium carbon dioxide batteries utilize a redox reaction (4 Li +3 CO) between metallic lithium and carbon dioxide 2 ↔2Li 2 CO 3 + C), has realized the dual function of carbon dioxide cyclic utilization and electrochemical conversion storage. Lithium carbon dioxide batteries are considered to be a promising electrochemical energy storage technology due to their high discharge potential (-2.80V) and theoretical energy density (-1876 Wh/kg). However, the solid discharge product lithium carbonate is relatively stable and difficult to decompose, which causes problems of high charging and discharging overpotential, poor cycle stability and the like, and hinders practical application and popularization of the lithium-carbon dioxide battery. Therefore, it is of great significance to develop a lithium carbon dioxide anode catalyst with high efficiency and low price to accelerate the kinetics of electrochemical reaction, reduce voltage polarization and further improve the cycle performance.
Carbon Nanotube (CNT) positive electrode catalyst: (Chemical Communications. 2015, 51: 14636-14639)) achieved lithium carbon dioxideThe chargeability of the battery is poor, but the catalytic activity of the battery on the oxidation reaction of carbon dioxide is poor, and the charging voltage of the battery is still overhigh (>4.5V). In addition, under a low current density (50 mA/g), the overpotential of the battery is always kept above 2V, and the charging and discharging cycle can be kept for only 29 times. By combining carbon nanotubes with ruthenium dioxide (CNT @ RuO) 2 ) Make up of a composite catalystACS Applied Materials & Interfaces2019, 11: 5146-5151) has the practical charge-discharge cycle life of 25 times under relatively large current (100 mA/g), but ruthenium dioxide is a noble metal oxide, has high economic cost and is not suitable for real application and popularization. Nickel oxide-carbon nanotube (NiO-CNT) transition metal positive electrode catalytic material (NiO-CNT)Journal of Materials Chemistry A .2018, 6: 2792-2796) successfully reduces the charging voltage to 4.30V, and can effectively decompose the main discharge product lithium carbonate in a pure carbon dioxide atmosphere. However, nickel oxide is large (300 nm) in size and poor in conductivity, resulting in poor reduction activity of carbon dioxide. And the battery can only be operated for 25 times of charge-discharge cycles under a large current (100 mA/g).
Disclosure of Invention
The invention provides a lithium-carbon dioxide battery anode catalyst and a preparation method thereof, aiming at reducing the cost of the lithium-air battery anode catalyst and solving the problems of large particle size, poor conductivity, weak electrocatalytic activity of carbon dioxide reduction reaction and the like of nickel oxide (NiO) in the battery anode catalyst.
A lithium-carbon dioxide battery anode catalyst is a porous material with cobalt-doped nickel oxide uniformly growing on a carbon nanotube substrate, wherein the pore diameter of the porous material is 2-100 nm, and the size of cobalt-doped nickel oxide (Co-NiO) nanoparticles is 7-10 nm;
when the lithium-carbon dioxide battery is used in a lithium-carbon dioxide battery, the discharge capacity can reach 5848 mAh/g at the current density of 100 mA/g, and the coulombic efficiency is 92.81% when the charge cut-off voltage is 4.5V; when the capacity is limited to 500 mAh/g, the overpotential can be reduced to 1.26V, and the electrode can be stably charged and discharged for more than 500 hours (50 times) without fading.
The preparation operation steps of the lithium-carbon dioxide battery anode catalyst are as follows:
(1) dissolving 105.1-93.4 mg (0.36-0.32 mmol) of nickel nitrate hexahydrate and 11.65-23.30 mg (0.04-0.08 mmol) of cobalt nitrate hexahydrate in 40 mL of deionized water, stirring for 5 minutes, adding 150 mg of carbon nanotubes, and performing ultrasonic dispersion for 2 hours to obtain a suspension;
(2) suspending the suspension at 50 o C, magnetically stirring for 2 hours under the water bath heating condition, slowly dropping 0.5 mol/L sodium hydroxide solution until the pH value reaches 10, and transferring to a room temperature environment for standing for 1 hour to obtain a black precipitate product;
(3) centrifugally cleaning the black precipitate with deionized water and anhydrous ethanol for 5 times, drying at 80 deg.C for 10 hr, placing in a tube furnace, and drying at 5 deg.C o The temperature rises to 300 ℃ at a temperature rise rate of C/min o And C, calcining the catalyst in nitrogen for 2 hours, and cooling the catalyst to room temperature along with the furnace to obtain the lithium-carbon dioxide battery anode catalyst.
The lithium-carbon dioxide battery anode catalyst is used for assembling and testing the lithium-carbon dioxide battery and comprises the following specific steps:
(1) uniformly mixing the prepared lithium-carbon dioxide battery anode catalyst and a Polytetrafluoroethylene (PTFE) binder, diluting with absolute ethyl alcohol, and uniformly spraying the obtained slurry on a carbon paper current collector to obtain a lithium-carbon dioxide battery anode; wherein the mass ratio of the catalyst to the binder is 9:1, the loading of the catalyst is 0.8 mg/cm 2 。
(2) And assembling the lithium-carbon dioxide battery in a glove box filled with argon, wherein the negative electrode of the battery adopts a lithium sheet with the purity higher than 99% and the thickness of 0.58 mm, the diaphragm adopts glass fiber paper, and the electrolyte adopts 1.0 mol/L bis (trifluoromethane) sulfimide lithium/tetraethylene glycol dimethyl ether solution (LiTFSI/TEGDME). Testing the assembled lithium-carbon dioxide battery in a pure carbon dioxide atmosphere; wherein the water content in the electrolyte is less than or equal to 200 ppm, and the carbon dioxide concentration is more than or equal to 99.99%.
The beneficial technical effects of the invention are embodied in the following aspects:
1) the catalyst prepared by the invention adopts nickel and cobalt metal oxides, so that the cost of the lithium-air battery anode catalyst is effectively reduced, and the synthesis method is simple and efficient. The size of the metal catalyst nano particles is reduced to 7-10 nm, and the reaction active area is increased, so that more reaction active sites are provided. The cobalt-doped nickel oxide improves the conductivity and the electrocatalytic activity of the cathode catalyst NiO. In addition, the carbon nanotube substrate provides a porous space with the aperture of 2-100 nm, so that solid discharge products can be stored conveniently, and the capacity of the battery can be improved.
2) The anode catalyst prepared by the invention obviously improves the electrochemical performance of the carbon dioxide battery and provides effective reference for the practical application and popularization of the lithium carbon dioxide battery. The discharge capacity of the lithium-carbon dioxide battery using the anode catalyst can reach 5848 mAh/g at the current density of 100 mA/g, and the coulombic efficiency is 92.81% when the charge cut-off voltage is 4.5V. The overpotential when the capacity is limited to 500 mAh/g mode can be reduced to 1.26V, and the electrode can stabilize the charge and discharge cycle for more than 500 hours (50 times) without attenuation.
Drawings
FIG. 1 is an X-ray diffraction pattern of a lithium-carbon dioxide battery anode catalyst prepared according to the present invention;
FIG. 2 is a macroscopic view of the positive electrode catalyst of the lithium-carbon dioxide battery prepared by the invention in a scanning electron microscope;
FIG. 3 is a high-power microscopic morphology diagram of the lithium-carbon dioxide battery anode catalyst prepared by the invention in a scanning electron microscope;
FIG. 4 is a distribution diagram of the porous structure of the lithium-carbon dioxide battery positive electrode catalyst prepared by the invention;
FIG. 5 is a cyclic voltammogram of a lithium carbon dioxide cell with a lithium carbon dioxide cell positive electrode catalyst prepared in accordance with the present invention;
FIG. 6 is a graph showing the charging and discharging voltage curves of a lithium-carbon dioxide battery using the lithium-carbon dioxide battery anode catalyst prepared by the present invention;
fig. 7 is a graph showing the cycle stability of a lithium carbon dioxide battery to which the lithium carbon dioxide battery cathode catalyst prepared according to the present invention is applied, in 50 charge and discharge cycles.
Detailed Description
The invention will now be further described by way of example with reference to the accompanying drawings.
Example 1:
the preparation operation steps of the lithium-carbon dioxide battery anode catalyst with high electrochemical performance are as follows:
(1) 105.1 mg (0.36 mmol) of nickel nitrate hexahydrate and 11.65 mg (0.04 mmol) of cobalt nitrate hexahydrate are dissolved in 40 mL of deionized water, stirred for 5 minutes, 150 mg of carbon nanotubes are added, and ultrasonic dispersion is carried out for 2 hours to obtain a suspension.
(2) And magnetically stirring the suspension for 2 hours under the water bath heating condition of 50 ℃, slowly dropping 0.5 mol/L sodium hydroxide solution until the pH value reaches 10, and transferring to a room temperature environment for standing for 1 hour to obtain a black precipitate product.
(3) Centrifuging and cleaning the black precipitate with deionized water and anhydrous ethanol for 5 times, drying at 80 deg.C for 10 hr, placing in a tubular furnace, and cooling to obtain black precipitate o And (3) heating the anode catalyst to 300 ℃ at the heating rate of C/min, calcining the anode catalyst in nitrogen for 2 hours, and cooling the anode catalyst to room temperature along with the furnace to obtain the lithium-carbon dioxide battery anode catalyst.
Referring to fig. 1, the lithium-carbon dioxide battery positive electrode catalyst obtained in this example 1 is a porous material in which cobalt-doped nickel oxide uniformly grows on a carbon nanotube substrate; referring to fig. 2 and 3, the size of the nano-particles of the porous material is 7-9 nm; referring to fig. 4, the porous material is a mesoporous and macroporous structure with the aperture of 2-100 nm.
The application of the lithium-carbon dioxide battery anode catalyst is used for the assembly and test of the lithium-carbon dioxide battery and comprises the following specific steps:
(1) uniformly mixing the prepared lithium-carbon dioxide battery anode catalyst and a Polytetrafluoroethylene (PTFE) binder, diluting with absolute ethyl alcohol, and uniformly spraying the obtained slurry on a carbon paper current collector to obtain a lithium-carbon dioxide battery anode; wherein the mass ratio of the catalyst to the binder is 9:1, the loading of the catalyst is 0.8 mg/cm 2 。
(2) And assembling the self-made lithium carbon dioxide battery in a glove box filled with argon, wherein the cathode of the battery adopts a lithium sheet with the purity higher than 99% and the thickness of 0.58 mm, the diaphragm adopts glass fiber paper, and the electrolyte adopts 1.0 mol/L bis (trifluoromethanesulfonylimide)/tetraethylene glycol dimethyl ether solution. Testing the assembled lithium-carbon dioxide battery in a pure carbon dioxide atmosphere; wherein the water content in the electrolyte is less than or equal to 200 ppm, and the carbon dioxide concentration is more than or equal to 99.99%.
Setting the voltage window to 2.0-4.5V, at a scan rate of 0.1 mV/s, it can be seen from FIG. 5 that the anodic peak and cathodic peak appear at the positions of potentials of 2.2V and 4.3V, respectively. As shown in FIG. 6, the battery can discharge at a current of 50-200 mA/g, the discharge capacity of the battery can reach 5848 mAh/g at a current density of 100 mA/g, and the coulombic efficiency is 92.81% at a charge cut-off voltage of 4.5V. When the capacity is limited to 500 mAh/g, it can be seen from FIG. 7 that the overpotential can be reduced to 1.26V at a current density of 100 mA/g, and the battery can be stably charged and discharged without degradation over 50 cycles (500 hours).
Example 2
The preparation operation steps of the lithium-carbon dioxide battery anode catalyst with high electrochemical performance are as follows:
(1) 93.4 mg (0.32 mmol) of nickel nitrate hexahydrate and 23.30 mg (0.08 mmol) of cobalt nitrate hexahydrate are dissolved in 40 mL of deionized water, stirred for 5 minutes, 150 mg of carbon nanotubes are added, and ultrasonic dispersion is carried out for 2 hours to obtain a suspension.
(2) And magnetically stirring the suspension for 2 hours under the water bath heating condition of 50 ℃, slowly dropping 0.5 mol/L sodium hydroxide solution until the pH value reaches 10, and transferring to a room temperature environment for standing for 1 hour to obtain a black precipitate product.
(3) Centrifuging and cleaning the black precipitate with deionized water and anhydrous ethanol for 5 times, drying at 80 deg.C for 10 hr, placing in a tubular furnace, and cooling to obtain black precipitate o And (3) heating the anode catalyst to 300 ℃ at the heating rate of C/min, calcining the anode catalyst in nitrogen for 2 hours, and cooling the anode catalyst to room temperature along with the furnace to obtain the lithium-carbon dioxide battery anode catalyst.
Referring to fig. 1, the lithium-carbon dioxide battery positive electrode catalyst obtained in this example 2 is a porous material in which cobalt-doped nickel oxide uniformly grows on a carbon nanotube substrate; the pore diameter of the porous material is 2-100 nm, wherein the size of the cobalt-doped nickel oxide (Co-NiO) nano particles is 8-10 nm.
The application of the lithium-carbon dioxide battery anode catalyst is used for the assembly and test of the lithium-carbon dioxide battery and comprises the following specific steps:
(1) uniformly mixing the prepared lithium-carbon dioxide battery anode catalyst and a Polytetrafluoroethylene (PTFE) binder, diluting with absolute ethyl alcohol, and uniformly spraying the obtained slurry on a carbon paper current collector to obtain a lithium-carbon dioxide battery anode; wherein the mass ratio of the catalyst to the binder is 9:1, the loading of the catalyst is 0.8 mg/cm 2 。
(2) And assembling the self-made lithium carbon dioxide battery in a glove box filled with argon, wherein the negative electrode of the battery adopts a lithium sheet with the purity higher than 99 percent and the thickness of 0.58 mm, the diaphragm adopts glass fiber paper, and the electrolyte adopts 1.0 mol/L bis (trifluoromethane sulfonyl imide) lithium/tetraethyleneglycol dimethyl ether solution. Testing the assembled lithium-carbon dioxide battery in a pure carbon dioxide atmosphere; wherein the water content in the electrolyte is less than or equal to 200 ppm, and the carbon dioxide concentration is more than or equal to 99.99 percent.
The battery can be discharged under the current of 50-200 mA/g. When the capacity is limited to 500 mAh/g, the battery can stabilize charge and discharge cycles for more than 50 times (500 hours) without fading under the current density of 100 mA/g.
Comparative example:
dissolving 116.8 mg (0.40 mmol) of nickel nitrate hexahydrate in 40 mL of deionized water, adding 150 mg of carbon nano tube, dropwise adding 0.5 mol/L sodium hydroxide solution until the pH value reaches 10, and carrying out standing, precipitation, centrifugation, washing, drying, calcination and other steps to obtain the nickel oxide carbon nano tube catalyst for comparison. Uniformly mixing a lithium carbon dioxide anode catalyst and a binder according to a mass ratio of 9:1, diluting with absolute ethyl alcohol, uniformly spraying the obtained slurry on a carbon paper current collector to obtain a lithium carbon dioxide battery anode, assembling a self-made lithium carbon dioxide battery in a glove box filled with argon, wherein a battery cathode adopts a metal lithium sheet, a diaphragm adopts glass fiber paper, an electrolyte adopts 1.0 mol/L lithium bistrifluoromethanesulfonimide/tetraethyleneglycol dimethyl ether solution, and testing the assembled lithium carbon dioxide battery in a pure carbon dioxide atmosphere; the specific operation steps are the same as the embodiment. The lithium-carbon dioxide battery adopting the comparative catalyst can only discharge under the current of 50-100 mA/g, the discharge capacity of the battery under the current density of 100 mA/g is only 3250 mAh/g, and the coulombic efficiency is 84.13%. When the capacity was limited to 500 mAh/g, the overpotential was 1.32V at a current density of 100 mA/g, and the electrode was able to be charged and discharged only 34 times (340 hours).
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (1)

1. A lithium-carbon dioxide battery positive electrode catalyst is characterized in that: the lithium-carbon dioxide battery anode catalyst is a porous material with cobalt-doped nickel oxide uniformly growing on a carbon nanotube substrate, the pore diameter of the porous material is 2-100 nm, and the size of cobalt-doped nickel oxide (Co-NiO) nanoparticles is 7-10 nm;
when the lithium-carbon dioxide battery is used in a lithium-carbon dioxide battery, the discharge capacity can reach 5848 mAh/g at the current density of 100 mA/g, and the coulombic efficiency is 92.81% when the charge cut-off voltage is 4.5V; when the capacity is limited in a mode of 500 mAh/g, the overpotential can be reduced to 1.26V, and the electrode can be stably charged and discharged and can not be attenuated after the charge and discharge cycle exceeds 500 hours;
the preparation operation steps of the lithium-carbon dioxide battery anode catalyst are as follows:
(1) dissolving 105.1-93.4 mg of nickel nitrate hexahydrate and 11.65-23.30 mg of cobalt nitrate hexahydrate in 40 mL of deionized water, stirring for 5 minutes, adding 150 mg of carbon nanotubes, and performing ultrasonic dispersion for 2 hours to obtain a suspension;
(2) suspending the suspension at 50 o C, magnetically stirring for 2 hours under the water bath heating condition, slowly dropping 0.5 mol/L sodium hydroxide solution until the pH value reaches 10, and transferring to a room temperature environment for standing for 1 hour to obtain a black precipitate product;
(3) centrifugally cleaning the black precipitate with deionized water and anhydrous ethanol for 5 times, drying at 80 deg.C for 10 hr, placing in a tube furnace, and drying at 5 deg.C o The temperature rises to 300 ℃ at a temperature rise rate of C/min o And C, calcining the catalyst in nitrogen for 2 hours, and cooling the catalyst to room temperature along with the furnace to obtain the lithium-carbon dioxide battery anode catalyst.
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