CN113471454A - 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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CN113471454A
CN113471454A CN202110741241.1A CN202110741241A CN113471454A CN 113471454 A CN113471454 A CN 113471454A CN 202110741241 A CN202110741241 A CN 202110741241A CN 113471454 A CN113471454 A CN 113471454A
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lithium
carbon dioxide
dioxide battery
positive electrode
copper
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CN113471454B (en
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赵兰玲
刘晓猛
钱钊
王俊
许浩然
夏青
李德元
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Shandong University
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Abstract

The invention belongs to the technical field of electrochemistry and new energy, and relates to a lithium-carbon dioxide battery anode catalyst and a preparation method thereof. The preparation process of the material is simple and efficient, special experimental equipment is not needed, the prepared iridium copper nanocages are connected with one another to form a wound irregular three-dimensional nanostructure, the specific surface area is large, the conductivity is excellent, the material shows excellent cycling stability when being used as an efficient catalyst for the anode of the lithium-carbon dioxide battery, and the possibility is provided for industrial production and practical application of the lithium-carbon dioxide battery.

Description

Lithium-carbon dioxide battery anode catalyst and preparation method thereof
Technical Field
The disclosure belongs to the technical field of electrochemistry and new energy, and relates to a lithium-carbon dioxide battery anode catalyst and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Carbon dioxide has been recognized as an important greenhouse gas for climate problems such as global warming. Various physical and chemical methods are being developed to capture and store the huge amount of carbon dioxide that is produced every day, and the emission of carbon dioxide is not increased and gradually decreased after reaching the peak value all over the world, so that the produced carbon dioxide is further eliminated in various ways. However, most current capture technologies face the challenge of consuming large amounts of energy for capture fluid or sorbent regeneration, which also greatly increases costs.
In recent years, lithium carbon dioxide batteries using carbon dioxide as the cathode gas have attracted great interest to researchers. It can provide energy source while absorbing and storing carbon dioxide, and has 1876Wh kg-1The theoretical energy density of (2) is an energy storage device with great potential in the future. However, the lithium-carbon dioxide battery has the problems of slow electrode reaction kinetics, high overpotential, low electrolyte decomposition and energy conversion efficiency and the like, so that the development of a high-efficiency anode catalyst for improving the electrocatalysis performance is particularly critical.
Researchers have made many efforts in the research field of lithium carbon dioxide battery anode catalysts, and developed various anode catalysts, such as carbon materials, transition metal oxides, transition metal carbides, noble metals and compounds thereof, and the like. The noble metal has quite good catalytic activity and chemical stability due to the unique electronic structure, and shows good electrocatalytic performance, but the high price limits further development and application. Meanwhile, research on the application of noble metals to the lithium-carbon dioxide battery cathode catalyst is not deep enough, and the catalytic capability needs to be further improved.
Research shows that both iridium and copper can be used as anode catalysts of lithium-carbon dioxide batteries, iridium nanoparticles can induce the formation of discharge products, and copper nanoparticles are beneficial to promoting Li in the charging process2CO3Reaction with amorphous carbon to release Li+And CO2. The Zhou team of southern university (Zhang Zhang, Zongwen Zhang, Peifangliu, et al.identification of cathode stability in Li-CO)2battieres with Cu nanoparticles high density dispersed on N-doped graphene, j. mater. chem.a,2018,6(7),3218) also reported a nitrogen-doped graphene-loaded copper nanoparticle composite material, which when used as a positive electrode of a lithium-carbon dioxide battery, had a current density of 50mA g-1Can realize 14864mAh g-1Specific discharge capacity. Subsequently, Zhou et al (Chengyi Wang, Qinming Zhang, Xin Zhang, et al, Fabiating Ir/C Nanofiber Networks as Free-Standing Air catalysts for Rechargeable Li-CO)2Batteries[J]Small,2018,14(28):1800641) the composite material of carbon nanofiber supported iridium nanoparticles is prepared by an electrospinning method, and iridium is used for a lithium-carbon dioxide battery positive electrode catalyst for the first time. At 50mA g-1The first ring complete discharge specific capacity can reach 21528mAh g under the current density-1At a fixed capacity of 1000mAh g-1And the circulation can be stabilized for 45 circles. Zhou et al (Zhuang, Chao Yang, Shuang Shu Wu, et al. Exploiting Synergistic Effect by Integrating Ruthenium-Copper Nanoparticles high hly Co-Dispersed on Graphene as Efficient Air catalysts for Li-CO2Batteries, adv.energy.mater,2019,9(8),1802805) also report that a graphene-supported ruthenium-copper nanoparticle composite material is used for the positive electrode of a lithium-carbon dioxide battery. The current density of the battery is 200mAg-1The fixed capacity is 1000mAh g-1Can be continuously circulated for 100 circles and can keep lower overpotential. At 200mA g-1When the discharge voltage is 2V under the current density, the specific capacity can reach 13698mAh g-1。
The inventors found that although some studies have been made on the performance of lithium carbon dioxide batteries using noble metal-based catalysts, the catalytic effect is still not satisfactory, and the amount of noble metal used is large. Particularly, the metal active material is supported by conductive carbon materials such as graphene and carbon nanofiber, so that the preparation difficulty is increased, and the cycle stability of the lithium-carbon dioxide battery is still poor. Therefore, how to further improve the structure of the noble metal catalyst is important to further reduce the using amount of the noble metal, reduce the preparation difficulty of the material and improve the electrochemical performance of the lithium-carbon dioxide battery.
Disclosure of Invention
Aiming at the problems, the material is simple and efficient in preparation process, special experimental equipment is not needed, the prepared iridium copper nanometer cages are connected with each other to form a wound irregular three-dimensional nanometer structure, the specific surface area is large, the conductivity is excellent, the catalyst shows excellent circulation stability when being used as an efficient catalyst for the anode of the lithium-carbon dioxide battery, and the possibility is provided for industrial production and practical application of the lithium-carbon dioxide battery.
Specifically, the present disclosure is realized by the following technical solutions:
in a first aspect of the disclosure, a lithium carbon dioxide battery positive electrode catalyst comprises an iridium copper hollow nanocage.
In a second aspect of the present disclosure, a lithium-carbon dioxide battery positive electrode is coated with a coating composed of the lithium-carbon dioxide battery positive electrode catalyst, conductive carbon and a binder on a positive electrode substrate.
In a third aspect of the present disclosure, a lithium-carbon dioxide battery is characterized by including the lithium-carbon dioxide battery positive electrode catalyst and/or the lithium-carbon dioxide battery positive electrode.
One or more embodiments of the present disclosure have the following advantageous effects:
(1) the in-situ co-reduction is realized at a lower temperature through a simple water bath method, the hollow iridium copper nanometer cage structure is constructed, the utilization rate of noble metals is improved due to the hollow structure, the consumption of the noble metals is reduced due to the introduction of copper, and the formation of the hollow structure is facilitated. It is worth noting that the element proportion of the iridium-copper alloy can be controlled by adjusting the adding amount of the raw materials, so as to regulate and control the catalytic capability of the material.
(2) The iridium copper bimetallic hydrogel material has ultra-light volume density and large specific surface area, can expose more catalytic active sites, improves catalytic activity, and has a three-dimensional space network structure which is beneficial to storage of a discharge product and increase the specific discharge capacity.
(3) In the specific embodiment, the morphology and the electrochemical performance of the anode catalytic material have good repeatability and high cycle performance stability. In a specific embodiment, the electrode has a current density of 800mA g-1Fixed capacity of 1000mAh g-1The scanning speed is 0.15mV s, and the circulation can be stabilized for 50 circles-1The cyclic voltammogram showed a distinct redox peak.
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The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this disclosure, illustrate embodiment(s) of the disclosure and together with the description serve to explain the disclosure and not to limit the disclosure. Embodiments of the present disclosure are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is Ir synthesized in example 13And (3) a field emission Scanning Electron Microscope (SEM) picture of the Cu hollow nano cage.
FIG. 2 shows Ir synthesized in example 13Transmission electron micrograph of Cu hollow nanocage.
FIG. 3 is Ir synthesized in example 13X-ray diffraction pattern of Cu hollow nanocages.
FIG. 4 shows Ir synthesized in example 13Isothermal nitrogen adsorption and desorption curves and aperture distribution maps of the Cu hollow nanocages.
FIG. 5 shows Ir synthesized in example 13The Cu hollow nanometer cage is used for a cyclic voltammetry curve of a lithium-carbon dioxide battery test, and the scanning speed is 0.15mV s-1。
FIG. 6 is a drawing showing a structure of example 1Synthesized Ir3The Cu hollow nanometer cage is used for a cycle performance chart of a lithium-carbon dioxide battery test, and the test current is 800mA g-1Fixed capacity of 1000mAh g-1。
FIG. 7 is Ir synthesized in example 13The Cu hollow nano cage is used for a selected cyclic charge-discharge curve of a lithium-carbon dioxide battery test, and the test current is 800mA g-1Fixed capacity of 1000mAh g-1。
FIG. 8 is Ir synthesized in comparative example 1 supported on carbon nanotubes3The Cu hollow nanometer cage is used for a cycle performance chart of a lithium-carbon dioxide battery test, and the test current is 200mA g-1Fixed capacity of 1000mAh g-1。
FIG. 9 is Ir synthesized in comparative example 1 supported on carbon nanotubes3The Cu hollow nano cage is used for a selected cyclic charge-discharge curve of a lithium-carbon dioxide battery test, and the test current is 200mA g-1Fixed capacity of 1000mAh g-1。
Detailed Description
The disclosure is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
At present, the catalytic effect of the lithium-carbon dioxide battery catalyst is not ideal, and the traditional catalyst is usually compounded with graphene, nano-fibers and other materials, so that the problem of falling off of active substances and further reduction of the cycling stability of the battery occurs in the cycling process of the lithium-carbon dioxide battery. Meanwhile, the content of noble metal in the existing catalyst is still high, and the utilization efficiency is low. In order to solve these problems, the present disclosure provides a lithium carbon dioxide battery positive electrode catalyst and a preparation method thereof.
In one or more embodiments of the present disclosure, a lithium carbon dioxide battery positive electrode catalyst includes an iridium copper hollow nanocage. The iridium-copper hollow nano cage has a three-dimensional space network structure, and the three-dimensional network is formed by further twisting and coiling the lines connected with the hollow nano cage.
Compared with the existing lithium-carbon dioxide battery anode catalyst, the iridium-copper hollow nanocage is not supported by graphene, nano fibers and other materials. The research disclosed by the disclosure finds that when the traditional composite bimetallic material taking graphene, nano-fiber, nanotube and the like as carriers is adopted, the active substances fall off to cause the reduction of the cycle stability of the battery in the electrochemical cycle process of the lithium-carbon dioxide battery because the catalytic active substances and the carriers cannot be firmly combined. However, the conventional method is considered that if a composite material is not prepared using graphene, nanofibers, or the like as a carrier, the battery performance of the lithium-carbon dioxide battery is degraded due to poor conductivity. In any case, the present disclosure departs from the conventional thinking and finds that, when the iridium copper hollow nano cage is used as the catalytic active substance as the lithium-carbon dioxide battery anode catalyst, the performance of the battery is not reduced, but the cycling stability of the battery is improved, which cannot be expected by the prior art.
In one or more embodiments of the present disclosure, the iridium to copper molar ratio in the iridium-copper hollow nanocage is 2-4:0.5-1.5, preferably 3:1, and it can be seen that the introduction of copper reduces the amount of noble metal used while facilitating the formation of hollow structures.
In one or more embodiments of the present disclosure, the method for preparing the iridium-copper hollow nanocage comprises: dissolving iridium salt and copper salt in water, adding a reducing agent, performing water bath reaction, and drying to obtain the iridium-copper hollow nano cage. The in-situ co-reduction is realized under the condition of lower temperature by a simple water bath method, a hollow iridium copper nano cage structure is constructed, and the utilization rate of noble metals is improved by the hollow structure.
In one or more embodiments of the present disclosure, the iridium salt is chloroiridic acid; or the copper salt is selected from copper chloride, copper nitrate and copper sulfate. The reducing agent is selected from sodium borohydride, ascorbic acid and citric acid.
In one or more embodiments of the present disclosure, the iridium salt aqueous solution has a concentration of 0.01 to 0.1mol L-1Preferably, it is 0.05mol L-1(ii) a Or the concentration of the copper salt aqueous solution is 0.01-0.1mol L-1Preferably, it is 0.05mol L-1(ii) a Or, the concentration of the reducing agent aqueous solution is 0.01-0.1mol L-1Preferably, it is 0.05mol L-1. Based on the optimal concentration, the prepared iridium copper nanocage structure has the optimal electrochemical catalytic activity.
In one or more embodiments of the present disclosure, the temperature of the water bath reaction is 60-70 ℃; preferably, it is 65 ℃; or the water bath reaction time is 2-3h, preferably 3h, and the in-situ co-reduction can be realized at low temperature to obtain the iridium-copper nano cage structure with better appearance and electrochemical performance.
In one or more embodiments of the present disclosure, the bimetallic nanocage is washed with water prior to drying; or, the drying is a freeze-drying mode; furthermore, the freeze drying temperature is-60 to-40 ℃, the freeze drying time is 10-24 hours, and the shape of the iridium copper nanocage structure is favorably maintained based on the optimal freeze drying condition.
In one or more embodiments of the present disclosure, the coating material composed of the lithium carbon dioxide battery positive electrode catalyst, conductive carbon and binder is coated on the positive electrode substrate.
In one or more embodiments of the present disclosure, the conductive carbon is selected from one or more of ketjen black, acetylene black, conductive carbon black, super P, conductive graphite, activated carbon; or the binder is selected from one or more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylate, butyl acrylate-acrylonitrile copolymer, polyacrylonitrile, polytetrafluoroethylene and ethylene-acrylic acid copolymer.
In one or more embodiments of the present disclosure, a lithium carbon dioxide battery includes the lithium carbon dioxide battery positive electrode catalyst and/or the lithium carbon dioxide battery positive electrode; further, the negative electrode of the lithium-carbon dioxide battery is metallic lithium, preferably metallic lithium; further, the electrolyte of the lithium-carbon dioxide battery is bis (trifluoromethyl) imide lithium sulfonate/tetraethylene glycol dimethyl ether, lithium trifluoro-methylsulfonate/tetraethylene glycol dimethyl ether, bis (trifluoromethyl) imide lithium sulfonate/dimethyl sulfoxide and lithium nitrate/dimethyl sulfoxide, preferably, bis (trifluoromethyl) imide lithium sulfonate/tetraethylene glycol dimethyl ether; further, the separator of the lithium carbon dioxide battery is selected from glass fibers.
When lithium bistrifluoromethylsulfonate imine lithium/tetraglyme is used as electrolyte, metal lithium is used as a negative electrode, and glass fiber is used as a diaphragm, the electrochemical cycling stability of the assembled lithium-carbon dioxide battery is poor, however, the cycling stability of the battery can be greatly improved by adopting the iridium-copper nanocage positive electrode catalyst disclosed by the invention.
The present disclosure is described in further detail below with reference to specific examples, which are intended to be illustrative of the disclosure and not limiting.
Example 1
Ir3The Cu hollow nano cage is prepared by the following steps:
(1) adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 0.75mL of solution A and 0.25mL of solution B are added to 35mL of water and stirred well, 3mL of newly prepared solution C are added and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 70 ℃ and is kept warm for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample which is Ir3A Cu hollow nanocage.
From FIG. 1,2, the material synthesized in example 1 has a three-dimensional space network structure, the three-dimensional network is formed by further twisting and coiling the connected lines of hollow nanocages, and the size of the nanocages is about 5 nm. FIG. 3 is Ir3The XRD spectrogram of the Cu hollow nanocage is compared with a standard JCPDS card, so that the formation of the copper-iridium alloy can be confirmed without other impurities. FIG. 4 is a curve of isothermal nitrogen adsorption and desorption, and the specific surface area of the curve is large and can reach 36.66m2 g-1。
Using Ir as obtained in example 13The Cu hollow nano cage is prepared into the anode by the following method:
and (3) adding the following components in percentage by weight of 4: 4: 2 Ir is weighed respectively3Adding Cu, Ketjen black and polytetrafluoroethylene suspension into 3mL of isopropanol, performing ultrasonic treatment for 20 minutes to uniformly disperse and mix the mixture, uniformly spraying the obtained slurry on carbon paper by using an air spray gun, and performing vacuum drying at 120 ℃ for 12 hours to obtain the anode.
Using metallic lithium as a negative electrode, 1mol L-1The lithium bistrifluoromethylsulfonimide/tetraglyme is used as electrolyte, and the glass fiber is used as a diaphragm, so that the lithium-carbon dioxide battery is assembled and tested.
FIG. 5 shows the signal at a scan rate of 0.15mV s-1Cyclic voltammogram of (5) and the results show that Ir3The Cu hollow nano cage electrode shows a very obvious oxidation-reduction current peak, which indicates the excellent catalytic performance of the material. FIGS. 6 and 7 show the test current density of 800mA g-1Fixed capacity of 1000mAh g-1Time cycle performance diagram, the results show that Ir3The Cu hollow nano cage electrode can stably circulate for 60 circles.
Example 2
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 7.5mL of solution A and 2.5mL of solution B are added to 350mL of water, stirred well, 30mL of newly prepared solution C are added, and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept warm for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample which is Ir3A Cu hollow nanocage.
Example 3
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 0.5mL of solution A and 0.5mL of solution B are added to 35mL of water, stirred well, 3mL of newly prepared solution C are added, and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept warm for 3 hours.
(3) And washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample, namely the IrCu hollow nano cage.
Example 4
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 0.25mL of solution A and 0.75mL of solution B are added to 35mL of water and stirred well, 3mL of newly prepared solution C are added and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept warm for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample, namely IrCu3A hollow nanocage.
Example 5
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of the aqueous solution A-1Aqueous solution B of (2), 5mmol of borohydrideSodium was added to ice in 100mL deionized water to give 0.05mol L-1The aqueous solution C of (1).
(2) 5mL of the solution A and 5mL of the solution B are added to 350mL of water, stirred well, 30mL of the newly prepared solution C is added, and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept warm for 3 hours.
(3) And washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample, namely the IrCu hollow nano cage.
Example 6
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 2.5mL of solution A and 7.5mL of solution B are added to 350mL of water, stirred well, 30mL of newly prepared solution C are added, and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept warm for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample, namely IrCu3A hollow nanocage.
Example 7
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 0.75mL of solution A and 0.25mL of solution B are added to 35mL of water and stirred well, 3mL of newly prepared solution C are added and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 55 ℃ and is kept for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample which is Ir3A Cu hollow nanocage.
Example 8
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 0.75mL of solution A and 0.25mL of solution B are added to 35mL of water and stirred well, 3mL of newly prepared solution C are added and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 65 ℃ and is kept warm for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample which is Ir3A Cu hollow nanocage.
Example 9
(1) Adding 5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain L with the concentration of 0.1mol-1Adding 5mmol of anhydrous copper chloride into 50mL of deionized water to obtain 0.1mol L of aqueous solution A-1Adding 5mmol of sodium borohydride into 50mL of ice deionized water to obtain 0.1mol L of the aqueous solution B-1The aqueous solution C of (1).
(2) 0.75mL of solution A and 0.25mL of solution B are added to 35mL of water and stirred well, 3mL of newly prepared solution C are added and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept warm for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample which is Ir3Cu hollow nanocage.
Example 10
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 0.75mL of solution A and 0.25mL of solution B are added to 35mL of water and stirred well, 3mL of newly prepared solution C are added and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept for 2 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain a black light block sample which is Ir3A Cu hollow nanocage.
Example 11
(1) Adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-1Solution C of (1).
(2) 0.75mL of solution A and 0.25mL of solution B are added to 35mL of water and stirred well, 3mL of newly prepared solution C are added and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 60 ℃ and is kept for 2 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 15 hours to obtain a black light block sample which is Ir3A Cu hollow nanocage.
Comparative example 1:
the difference from example 1 is that: carbon nanotubes are used as a carrier. The specific implementation method comprises the following steps:
(1) adding 2.5mmol of chloroiridic acid hexahydrate into 50mL of deionized water to obtain a solution with a concentration of 0.05mol L-12.5mmol of anhydrous cupric chloride is added into 50mL of deionized water to obtain 0.05mol L of solution A-1Adding 5mmol of sodium borohydride into 100mL of ice deionized water to obtain 0.05mol L of solution B-15mg of carbon nanotubes were uniformly dispersed in 35ml of water to obtain a suspension D.
(2) 0.75mL of solution A and 0.25mL of solution B were added to 35mL of suspension D, stirred well, 3mL of newly prepared solution C was added, and stirred well again. Then the mixture is put into a water bath kettle with the temperature of 70 ℃ and is kept warm for 3 hours.
(3) Washing the obtained product with deionized water for 3 times, and freeze-drying for 24 hours to obtain Ir loaded on the carbon nano tube3A Cu hollow nanocage.
Lithium carbon dioxide batteries were assembled based on the material of comparative example 1 (the assembly process was the same as in example 1), the cycle performance was measured, and the current density was measuredIs 200mA g-1Fixed capacity of 1000mAh g-1The cycle performance chart of the time can only cycle 28 cycles as shown in fig. 8 and 9.
Although the present disclosure has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the disclosure. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.

Claims (10)

1. The lithium-carbon dioxide battery positive electrode catalyst is characterized by comprising an iridium-copper hollow nanocage.
2. The lithium-carbon dioxide battery positive electrode catalyst as claimed in claim 1, wherein the molar ratio of iridium to copper in the iridium-copper hollow nanocage is 2-4:0.5-1.5, preferably 3: 1.
3. The lithium-carbon dioxide battery positive electrode catalyst as claimed in claim 1, wherein the preparation method of the iridium-copper hollow nanocage comprises the following steps: dissolving iridium salt and copper salt in water, adding a reducing agent, performing water bath reaction, and drying to obtain the iridium-copper hollow nano cage.
4. The lithium carbon dioxide battery positive electrode catalyst as claimed in claim 3, wherein the iridium salt is selected from chloroiridic acid; or, the copper salt is selected from copper chloride, copper nitrate and copper sulfate; or, the reducing agent is selected from sodium borohydride, ascorbic acid and citric acid.
5. The positive electrode catalyst for a lithium-carbon dioxide battery as claimed in claim 3, wherein the iridium salt aqueous solution has a concentration of 0.01 to 0.1mol L-1Preferably, it is 0.05mol L-1(ii) a Or, concentration of said aqueous copper salt solutionThe degree is 0.01-0.1mol L-1Preferably, it is 0.05mol L-1(ii) a Or, the concentration of the reducing agent aqueous solution is 0.01-0.1mol L-1Preferably, it is 0.05mol L-1。
6. The lithium-carbon dioxide battery positive electrode catalyst as claimed in claim 3, wherein the temperature of the water bath reaction is 60-70 ℃; preferably, it is 65 ℃; or the time of the water bath reaction is 2-3h, preferably 3 h.
7. The lithium carbon dioxide battery positive electrode catalyst according to claim 3, wherein the bimetallic nanocage is washed with water before being dried; or, the drying is a freeze-drying mode; furthermore, the freeze drying temperature is-60 to-40 ℃, and the freeze drying time is 10-24 h.
8. A positive electrode for a lithium-carbon dioxide battery, wherein a coating material comprising the positive electrode catalyst for a lithium-carbon dioxide battery according to any one of claims 1 to 7, conductive carbon and a binder is coated on the positive electrode substrate.
9. The positive electrode of claim 8, wherein the conductive carbon is one or more selected from the group consisting of ketjen black, acetylene black, conductive carbon black, super P, conductive graphite, and activated carbon; or the binder is selected from one or more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylate, butyl acrylate-acrylonitrile copolymer, polyacrylonitrile, polytetrafluoroethylene and ethylene-acrylic acid copolymer.
10. A lithium carbon dioxide battery comprising the lithium carbon dioxide battery positive electrode catalyst according to any one of claims 1 to 7 and/or the lithium carbon dioxide battery positive electrode according to claim 8 or 9; further, the negative electrode of the lithium-carbon dioxide battery is metal lithium; further, the electrolyte of the lithium-carbon dioxide battery is bis (trifluoromethyl) imide lithium sulfonate/tetraethylene glycol dimethyl ether, lithium trifluoro-methylsulfonate/tetraethylene glycol dimethyl ether, bis (trifluoromethyl) imide lithium sulfonate/dimethyl sulfoxide and lithium nitrate/dimethyl sulfoxide, preferably, bis (trifluoromethyl) imide lithium sulfonate/tetraethylene glycol dimethyl ether; further, the separator of the lithium carbon dioxide battery is selected from glass fibers.
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