WO2022127648A1 - Liquid metal-in-carbon nanotube lithium air battery positive electrode and preparation method therefor - Google Patents
Liquid metal-in-carbon nanotube lithium air battery positive electrode and preparation method therefor Download PDFInfo
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- WO2022127648A1 WO2022127648A1 PCT/CN2021/136152 CN2021136152W WO2022127648A1 WO 2022127648 A1 WO2022127648 A1 WO 2022127648A1 CN 2021136152 W CN2021136152 W CN 2021136152W WO 2022127648 A1 WO2022127648 A1 WO 2022127648A1
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- liquid metal
- gallium
- tin
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- carbon nanotube
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 106
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract 3
- 229910052744 lithium Inorganic materials 0.000 title abstract 3
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 173
- YZZNJYQZJKSEER-UHFFFAOYSA-N gallium tin Chemical compound [Ga].[Sn] YZZNJYQZJKSEER-UHFFFAOYSA-N 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052738 indium Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 61
- 229910052733 gallium Inorganic materials 0.000 claims description 61
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- IBWDHWVZWMPSAI-UHFFFAOYSA-N S(=O)(=O)(O)CCC(=O)NS Chemical compound S(=O)(=O)(O)CCC(=O)NS IBWDHWVZWMPSAI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000000523 sample Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910005538 GaSn Inorganic materials 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/96—Carbon-based 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
Definitions
- the invention relates to the field of lithium-air batteries, in particular to a liquid metal@carbon nanotube lithium-air battery positive electrode and a preparation method thereof.
- Lithium-air batteries have a high theoretical specific energy density (11400Wh ⁇ kg -1 ), which is much higher than that of current commercial lithium-ion batteries, and has good development prospects.
- the poor cycle performance of lithium-air batteries caused by the passivation of the positive electrode is one of the important reasons that hinder the development of lithium-air batteries.
- lithium-air battery cathodes loaded with catalysts such as noble metals, transition metal oxides, nitrides, and perovskites have been developed.
- catalysts such as noble metals, transition metal oxides, nitrides, and perovskites.
- the purpose of the present invention is to provide a liquid metal@carbon nanotube lithium-air battery positive electrode and a preparation method thereof, so as to improve the fluidity and self-repairability of the lithium-air battery positive electrode.
- the liquid metal is one of gallium tin liquid metal and gallium indium liquid metal, and the size distribution of the liquid metal is 100nm-800nm; the composite of liquid metal and carbon nanotube
- the method is one of the blending method and the dropping method, and the mass ratio of the liquid metal to the carbon nanotube is 1:1 to 10:1.
- the mass ratio of metal tin to metal gallium in the gallium-tin liquid metal is 88:12.
- the mass ratio of metal tin to metal gallium in the gallium indium liquid metal is 75:25.
- the liquid metal is one of gallium tin liquid metal and gallium indium liquid metal, and the size distribution of the liquid metal is 100-800 nm.
- the compounding method of the liquid metal and the carbon nanotubes is a blending method or a dropping method, and the mass ratio of the liquid metal and the carbon nanotubes is 1:1-10:1.
- the mass ratio of metal tin to metal gallium in the gallium-tin liquid metal is 88:12.
- the mass ratio of metal tin to metal gallium in the gallium indium liquid metal is 75:25.
- the liquid metal@carbon nanotube lithium-air battery cathode further includes carbon paper.
- step (2) Take 0.5-2.0 g of the gallium-tin liquid metal or gallium-indium liquid metal obtained in step (1) and add 3.75 mL of anhydrous ethanol containing 0.25-3 mg of 3-sulfo-N-mercaptopropionamide (surfactant).
- the mass ratio of gallium tin liquid metal or gallium indium liquid metal to 3-sulfo-N-mercaptopropionamide is 1000:0.5-1000:1.5.
- gallium-tin liquid metal powder or gallium-indium liquid metal powder prepared in step (2) Weigh 5-200 mg of gallium-tin liquid metal powder or gallium-indium liquid metal powder prepared in step (2) and mix with 5-20 mg of carbon nanotubes, add 25 mL of absolute ethanol, and ultrasonically disperse for a period of time to obtain a liquid metal@carbon nanotube composite
- the gallium tin liquid metal@carbon nanotube lithium-air battery positive electrode or the gallium indium liquid metal@carbon nanotube lithium-air battery positive electrode was obtained by blending the material and then sprayed onto a 10cm ⁇ 10cm carbon paper current collector.
- step (2) Add 5-200 mg of the gallium tin liquid metal powder or gallium indium liquid metal powder obtained in step (2) into 2 mL of absolute ethanol, and ultrasonically disperse to obtain a gallium tin liquid metal dispersion or a gallium indium liquid metal dispersion.
- Tin liquid metal dispersion or gallium indium liquid metal dispersion is dropped on the carbon paper prepared in step a, vacuum dried, and the composite gallium tin liquid metal@carbon nanotube lithium-air battery cathode or gallium indium liquid metal@ Carbon nanotube lithium-air battery cathode.
- the present invention has no special requirements on the melting atmosphere and time, as long as it can form a uniform liquid metal alloy.
- the present invention has no special requirements on ultrasonic power and ultrasonic time, as long as a uniform mixed solution can be generated.
- the present invention has no special requirements on the drying temperature and time, as long as it can ensure that the moisture of the solids after washing is removed.
- the present invention has no special requirements for the spraying process, as long as a positive electrode with uniform distribution of active materials can be prepared.
- Liquid metal has fluidity and self-healing ability, and can maintain its morphology and structure during charging and discharging, preventing the cathode from being completely blocked by discharge products.
- Carbon nanotubes have high electrical conductivity and high specific surface area, which can further improve the electrical conductivity of liquid metals and increase the active sites of positive electrodes.
- the liquid metal@carbon nanotube lithium-air battery cathode prepared by the invention has better full discharge capacity, rate characteristic, cycle stability and anti-passivation ability.
- Fig. 1 is the SEM image of the liquid metal@carbon nanotube positive electrode of Example 1;
- Fig. 2 is the liquid metal self-healing schematic diagram of embodiment 1;
- Fig. 3 is the element distribution diagram of embodiment 1;
- Fig. 4 is the particle size distribution diagram of embodiment 1;
- Fig. 5 is the XRD pattern of embodiment 1;
- Fig. 6 is the charge-discharge curve diagram comparison diagram of embodiment 2, the dotted line is carbon nanotube, and the solid line is liquid metal@carbon nanotube;
- Table 7 is the full discharge control curve of Example 2, the dotted line is carbon nanotubes, and the solid line is liquid metal@carbon nanotubes;
- Fig. 8 is the ratio characteristic comparison curve of embodiment 2, the virtual frame is carbon nanotubes, and the solid frame is liquid metal@carbon nanotubes;
- Fig. 9 is the SEM image of embodiment 3.
- Example 10 is a comparison chart of the charge-discharge curve diagram of Example 3, the dotted line is carbon nanotubes, and the solid line is liquid metal@carbon nanotubes;
- Figure 11 is the full-discharge control curve of Example 3, the dotted line is carbon nanotubes, and the solid line is liquid metal@carbon nanotubes;
- FIG. 12 is a comparison curve of the magnification characteristic of Example 3, the dotted frame is carbon nanotubes, and the solid frame is liquid metal@carbon nanotubes.
- step (2) Take 0.9 g of the gallium-tin liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 0.7 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to treat the gallium-tin liquid metal. After the liquid metal is dispersed, it is allowed to stand at room temperature for 3 hours, the supernatant liquid is sucked, and the gallium tin liquid metal powder is obtained after drying.
- surfactant 3-sulfo-N-mercaptopropionamide
- step (3) Weigh 10 mg of the gallium-tin liquid metal powder obtained in step (2) into 2 mL of absolute ethanol, ultrasonically disperse to obtain a gallium-tin liquid metal dispersion, and drop the gallium-tin liquid metal dispersion in step (3) On the prepared carbon paper current collector, vacuum drying is used to obtain a gallium tin liquid metal@carbon nanotube lithium-air battery cathode compounded by dropwise method.
- the prepared gallium tin liquid metal was characterized by self-healing performance characterization, field emission scanning electron microscope, X-ray energy dispersive spectroscopy (SEM/EDS for short), and X-ray diffractometer (XRD for short).
- the test results are shown in Figure 1- Figure 5, respectively. It can be seen from Figure 1 that the gallium tin liquid metal is spread on the carbon nanotubes by dropping. It can be seen from Figure 2 that when the gallium-tin liquid metal is subjected to external force, the contact surface is deformed, and when the external force is removed, the deformation returns to its original state. It is proved that the liquid metal has good deformability and self-healing properties.
- FIG. 3 It can be seen from Figure 3 that the gallium tin liquid metal is dispersed on the carbon paper current collector sprayed with carbon nanotubes. It can be seen from Figure 4 that the average particle size of the gallium tin liquid metal is 210 nm.
- Figure 5 is the XRD pattern of the gallium-tin liquid metal powder, a broad peak appears in the range of 29.6°-49.7°, which indicates grain growth with short-range order, which is a typical feature of liquid metals, Ga 2 O 3 The diffraction peak at 35.2° overlaps with the broad peak.
- step (2) Take 0.9 g of the gallium-tin liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 0.9 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to treat the gallium-tin liquid metal. After the liquid metal is dispersed, it is allowed to stand at room temperature for 4 hours, the supernatant is sucked, and the gallium tin liquid metal powder is obtained after drying.
- surfactant 3-sulfo-N-mercaptopropionamide
- step (2) Weigh 20 mg of the gallium-tin liquid metal powder obtained in step (2) into 2 mL of anhydrous ethanol, and ultrasonically disperse to obtain a gallium-tin liquid metal dispersion.
- the gallium tin liquid metal dispersion is dropwise added on the carbon paper current collector prepared in step (3), and vacuum dried to obtain a gallium tin liquid metal@carbon nanotube lithium-air battery positive electrode compounded by dropwise addition.
- Figure 6 shows the first cycle of charge-discharge curves when carbon nanotubes and gallium tin liquid metal@carbon nanotubes are used as the positive electrode of lithium-air batteries. It can be seen that gallium tin liquid metal@carbon nanotubes have lower overpotential when used as positive electrode . It can be seen from Figure 7 that the full discharge capacity of the battery is about 9 times that of carbon nanotubes when gallium tin liquid metal@carbon nanotubes are used as the positive electrode, and the battery capacity is significantly improved after gallium tin liquid metal composite carbon nanotubes.
- Figure 8 shows the rate performance of Li-air batteries when carbon nanotubes and gallium tin liquid metal@carbon nanotubes are used as cathodes.
- step (2) Take 0.8 g of the gallium tin liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 0.9 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to treat the gallium tin After the liquid metal is dispersed, it is allowed to stand at room temperature for 4 hours, the supernatant is sucked, and the gallium tin liquid metal powder is obtained after drying.
- surfactant 3-sulfo-N-mercaptopropionamide
- step (3) Weigh 30 mg of gallium-tin liquid metal powder prepared in step (2) and mix with 10 mg of carbon nanotubes, add 25 mL of absolute ethanol, and ultrasonically disperse for a period of time to obtain a liquid metal@carbon nanotube composite and spray it to 10cm ⁇ 10cm On the carbon paper current collector, a liquid metal@carbon nanotube lithium-air battery cathode compounded by blending is obtained.
- Figure 9 shows the SEM image of the gallium-tin liquid metal@carbon nanotube lithium-air battery cathode compounded by blending. It can be seen that the surface of the gallium tin liquid metal is wrapped by carbon nanotubes.
- step (2) Take 0.9 g of the gallium indium liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 1.0 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to process the gallium indium After the liquid metal is dispersed, it is allowed to stand at room temperature for 4 hours, the supernatant is sucked, and the gallium indium liquid metal powder is obtained after drying.
- surfactant 3-sulfo-N-mercaptopropionamide
- step (2) Weigh 30 mg of the gallium indium liquid metal powder obtained in step (2) into 2 mL of anhydrous ethanol, and ultrasonically disperse to obtain a gallium indium liquid metal dispersion.
- the gallium indium liquid metal dispersion is dropwise added on the carbon paper current collector prepared in step (3), and vacuum dried to obtain a gallium indium liquid metal@carbon nanotube lithium-air battery cathode compounded by dropwise addition.
- Figure 10 shows the first cycle of charge-discharge curves when carbon nanotubes and gallium indium liquid metal@carbon nanotubes are used as cathodes of lithium-air batteries. It can be seen that the overpotential of gallium indium liquid metal@carbon nanotube as the positive electrode is 0.7V (at 0.05mAh), which is lower than the overpotential of carbon nanotube at 0.05mAh in the first cycle. It can be seen from Figure 11 that when the gallium indium liquid metal@carbon nanotubes and carbon nanotubes are used as the cathode of the lithium-air battery, the full discharge time of the battery is 4.1 hours and 34.2 hours, respectively, and the battery capacity is significantly improved after the gallium indium liquid metal composite carbon nanotubes.
- Figure 12 shows the rate performance of Li-air batteries when carbon nanotubes and GaIn liquid metal@carbon nanotubes are used as cathodes.
- the number of cycles of the Li-air battery with gallium indium liquid metal@carbon nanotubes as the positive electrode is 5 times that of the carbon nanotubes as the positive electrode.
- the lithium-air battery with gallium indium liquid metal@carbon nanotubes as the positive electrode has cycled 105 cycles, which is much higher than the cycle number of carbon nanotubes at this current.
- the rate performance of the lithium-air battery with gallium indium liquid metal@carbon nanotubes as the positive electrode is significantly improved .
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Abstract
Disclosed in the present invention are a liquid metal-in-carbon nanotube lithium air battery positive electrode and a preparation method therefor. Liquid metal is one selected from gallium-tin liquid metal and gallium-indium liquid metal, and the size distribution of the liquid metal ranges from 100 nm to 800 nm. The compounding mode of the liquid metal and a carbon nanotube is one selected from a blending method and a dropwise adding method, and the mass ratio of the liquid metal to the carbon nanotube is 1:1 to 10:1. The liquid metal-in-carbon nanotube lithium air battery positive electrode prepared by the present invention has good full discharge capacity, rate capability, cycling stability, and passivation prevention capability.
Description
本申请要求于2020年12月14日提交中国专利局、申请号为CN202011478988.4、发明名称为“一种液态金属@碳纳米管锂空气电池正极及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number CN202011478988.4 and the invention titled "A liquid metal@carbon nanotube lithium-air battery cathode and its preparation method" submitted to the China Patent Office on December 14, 2020 , the entire contents of which are incorporated herein by reference.
本发明涉及锂空气电池领域，特别涉及一种液态金属@碳纳米管锂空气电池正极及其制备方法。The invention relates to the field of lithium-air batteries, in particular to a liquid metal@carbon nanotube lithium-air battery positive electrode and a preparation method thereof.
锂空气电池具有较高的理论比能密度(11400Wh·kg
-1)，远高于目前商用化的锂离子电池，具有较好的发展前景。然而，锂空气电池的正极钝化导致的电池循环性能差，是阻碍锂空气电池发展的重要原因之一。
Lithium-air batteries have a high theoretical specific energy density (11400Wh·kg -1 ), which is much higher than that of current commercial lithium-ion batteries, and has good development prospects. However, the poor cycle performance of lithium-air batteries caused by the passivation of the positive electrode is one of the important reasons that hinder the development of lithium-air batteries.
锂空气电池正极发生氧还原反应和析氧反应，伴随着固体产物过氧化锂的形成和分解(2Li
++O
2+2e
-＝Li
2O
2，E
0＝2.96V)。由于过氧化锂绝缘，且不溶于电解液，在充电过程中难以被分解而累积在正极上，使得氧气和锂离子传质、电子传导受阻，最终导致电池正极被完全钝化。
Oxygen reduction reaction and oxygen evolution reaction occur in the positive electrode of lithium-air battery, accompanied by the formation and decomposition of solid product lithium peroxide (2Li + +O 2 +2e − =Li 2 O 2 , E 0 =2.96V). Because lithium peroxide is insulating and insoluble in the electrolyte, it is difficult to be decomposed and accumulated on the positive electrode during the charging process, which hinders the mass transfer of oxygen and lithium ions and the conduction of electrons, resulting in complete passivation of the positive electrode of the battery.
为了提高过氧化锂分解动力学，人们研制了负载有贵金属、过渡金属氧化物、氮化物和钙钛矿等催化剂的锂空气电池正极。但由于放电过程中过氧化锂倾向于在催化剂上生长，充电过程中少量残余的过氧化锂都会削弱催化剂的催化活性，并且催化活性不但不能随着充放电循环的进行而修复反而继续降低，最终完全失效。To improve the decomposition kinetics of lithium peroxide, lithium-air battery cathodes loaded with catalysts such as noble metals, transition metal oxides, nitrides, and perovskites have been developed. However, since lithium peroxide tends to grow on the catalyst during the discharge process, a small amount of residual lithium peroxide during the charge process will weaken the catalytic activity of the catalyst, and the catalytic activity will not be repaired with the progress of the charge-discharge cycle, but will continue to decrease. Completely ineffective.
因此，开发具有流动性、可自修复的锂空气电池正极成为亟待解决的问题。Therefore, the development of a fluid and self-healable cathode for Li-air batteries has become an urgent problem to be solved.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明的目的在于提供一种液态金属@碳纳米管锂空气电池正极及其制备方法，提高锂空气电池正极的流动性和自修复性。In view of this, the purpose of the present invention is to provide a liquid metal@carbon nanotube lithium-air battery positive electrode and a preparation method thereof, so as to improve the fluidity and self-repairability of the lithium-air battery positive electrode.
本发明涉及的液态金属@碳纳米管复合物，所述液态金属为镓锡液态 金属和镓铟液态金属中的一种，液态金属的尺寸分布为100nm～800nm；液态金属与碳纳米管的复合方式为共混法和滴加法中的一种，液态金属与碳纳米管的质量比为1：1～10：1。In the liquid metal@carbon nanotube composite involved in the present invention, the liquid metal is one of gallium tin liquid metal and gallium indium liquid metal, and the size distribution of the liquid metal is 100nm-800nm; the composite of liquid metal and carbon nanotube The method is one of the blending method and the dropping method, and the mass ratio of the liquid metal to the carbon nanotube is 1:1 to 10:1.
优选的，所述镓锡液态金属中金属锡与金属镓的质量比为88：12。Preferably, the mass ratio of metal tin to metal gallium in the gallium-tin liquid metal is 88:12.
优选的，所述镓铟液态金属中金属锡与金属镓的质量比为75：25。Preferably, the mass ratio of metal tin to metal gallium in the gallium indium liquid metal is 75:25.
本发明涉及的液态金属@碳纳米管锂空气电池正极，液态金属为镓锡液态金属和镓铟液态金属中的一种，液态金属的尺寸分布为100～800nm。液态金属与碳纳米管的复合方式为共混法或滴加法，液态金属与碳纳米管的质量比为1：1～10：1。In the liquid metal@carbon nanotube lithium-air battery positive electrode involved in the present invention, the liquid metal is one of gallium tin liquid metal and gallium indium liquid metal, and the size distribution of the liquid metal is 100-800 nm. The compounding method of the liquid metal and the carbon nanotubes is a blending method or a dropping method, and the mass ratio of the liquid metal and the carbon nanotubes is 1:1-10:1.
优选的，所述镓锡液态金属中金属锡与金属镓的质量比为88：12。Preferably, the mass ratio of metal tin to metal gallium in the gallium-tin liquid metal is 88:12.
优选的，所述镓铟液态金属中金属锡与金属镓的质量比为75：25。Preferably, the mass ratio of metal tin to metal gallium in the gallium indium liquid metal is 75:25.
优选的，所述液态金属@碳纳米管锂空气电池正极还包括碳纸。Preferably, the liquid metal@carbon nanotube lithium-air battery cathode further includes carbon paper.
本发明涉及的液态金属@碳纳米管锂空气电池正极的制备方法具体步骤为：The specific steps of the preparation method of the liquid metal@carbon nanotube lithium-air battery positive electrode involved in the present invention are as follows:
(1)将金属锡在氩气保护下300℃熔融与金属镓熔融共混，得到镓锡液态金属，金属锡与金属镓的质量比为88：12；或者将金属铟在氩气保护下200℃熔融与金属镓熔融共混，得到镓铟液态金属，金属锡与金属镓的质量比为75：25。(1) Melt metal tin at 300°C under argon protection and melt and blend metal gallium to obtain gallium-tin liquid metal, and the mass ratio of metal tin to metal gallium is 88:12; ℃ melting and melting and blending of metal gallium to obtain gallium indium liquid metal, and the mass ratio of metal tin to metal gallium is 75:25.
(2)取0.5～2.0g步骤(1)所得的镓锡液态金属或者镓铟液态金属加入含有0.25～3mg的3-磺基-N-巯基丙酰胺(表面活性剂)的3.75mL无水乙醇中，镓锡液态金属或者镓铟液态金属与3-磺基-N-巯基丙酰胺的质量比为1000：0.5～1000：1.5。采用超声探头处理将镓锡液态金属或者镓铟液态金属分散后，在室温下静置3小时，吸取上清液，干燥后得到镓锡液态金属粉末或镓铟液态金属粉末。(2) Take 0.5-2.0 g of the gallium-tin liquid metal or gallium-indium liquid metal obtained in step (1) and add 3.75 mL of anhydrous ethanol containing 0.25-3 mg of 3-sulfo-N-mercaptopropionamide (surfactant). Among them, the mass ratio of gallium tin liquid metal or gallium indium liquid metal to 3-sulfo-N-mercaptopropionamide is 1000:0.5-1000:1.5. After dispersing the gallium tin liquid metal or the gallium indium liquid metal by ultrasonic probe treatment, let it stand at room temperature for 3 hours, suck the supernatant, and dry to obtain the gallium tin liquid metal powder or the gallium indium liquid metal powder.
(3)镓锡液态金属@碳纳米管锂空气电池正极或镓铟液态金属@碳纳米管锂空气电池正极：(3) GaSn liquid metal@carbon nanotube lithium-air battery cathode or GaIn liquid metal@carbon nanotube lithium-air battery cathode:
A：共混方式A: Blending method
称取5～200mg步骤(2)制备的镓锡液态金属粉末或镓铟液态金属粉末与5～20mg碳纳米管混合后加入25mL无水乙醇，超声分散一段时间， 得到液态金属@碳纳米管复合物再喷涂到10cm×10cm碳纸集流体上，通过共混方式得到的镓锡液态金属@碳纳米管锂空气电池正极或镓铟液态金属@碳纳米管锂空气电池正极。Weigh 5-200 mg of gallium-tin liquid metal powder or gallium-indium liquid metal powder prepared in step (2) and mix with 5-20 mg of carbon nanotubes, add 25 mL of absolute ethanol, and ultrasonically disperse for a period of time to obtain a liquid metal@carbon nanotube composite The gallium tin liquid metal@carbon nanotube lithium-air battery positive electrode or the gallium indium liquid metal@carbon nanotube lithium-air battery positive electrode was obtained by blending the material and then sprayed onto a 10cm×10cm carbon paper current collector.
B：滴加方式B: dripping method
a：称取5～20mg碳纳米管加入25mL无水乙醇超声分散，用喷枪将超声分散好的碳纳米管浆料均匀的喷涂在10cm×10cm碳纸上，并在真空干燥箱内干燥；a: Weigh 5-20 mg of carbon nanotubes and add 25 mL of anhydrous ethanol to ultrasonically disperse them. Use a spray gun to uniformly spray the ultrasonically dispersed carbon nanotube slurry on 10cm×10cm carbon paper, and dry it in a vacuum drying box;
b：将5～200mg步骤(2)所得的镓锡液态金属粉末或镓铟液态金属粉末加入到2mL无水乙醇中，超声分散得到镓锡液态金属分散液或镓铟液态金属分散液，将镓锡液态金属分散液或镓铟液态金属分散液滴加在步骤a制备的碳纸上，真空干燥，通过滴加方式复合的镓锡液态金属@碳纳米管锂空气电池正极或镓铟液态金属@碳纳米管锂空气电池正极。b: Add 5-200 mg of the gallium tin liquid metal powder or gallium indium liquid metal powder obtained in step (2) into 2 mL of absolute ethanol, and ultrasonically disperse to obtain a gallium tin liquid metal dispersion or a gallium indium liquid metal dispersion. Tin liquid metal dispersion or gallium indium liquid metal dispersion is dropped on the carbon paper prepared in step a, vacuum dried, and the composite gallium tin liquid metal@carbon nanotube lithium-air battery cathode or gallium indium liquid metal@ Carbon nanotube lithium-air battery cathode.
本发明对熔融的气氛和时间没有特别的要求，能形成均匀液态金属合金即可。The present invention has no special requirements on the melting atmosphere and time, as long as it can form a uniform liquid metal alloy.
本发明对超声功率和超声时间没有特别的要求，能产生均匀的混合液即可。The present invention has no special requirements on ultrasonic power and ultrasonic time, as long as a uniform mixed solution can be generated.
本发明对所述干燥的温度和时间没有特别的要求，能够保证将洗涤后固体物的水分去除即可。The present invention has no special requirements on the drying temperature and time, as long as it can ensure that the moisture of the solids after washing is removed.
本发明对喷涂过程没有特殊的要求，能制备活性物质分布均匀的正极即可。The present invention has no special requirements for the spraying process, as long as a positive electrode with uniform distribution of active materials can be prepared.
液态金属具有流动性和自修复能力，在充放电过程中能够保持其形貌和结构，防止正极被放电产物完全堵塞。碳纳米管具有高导电性和高比表面积，能够进一步提高液态金属的导电性并增加正极的活性位点。本发明制得的液态金属@碳纳米管锂空气电池正极具有更好的全放电容量、倍率特性、循环稳定性和防钝化能力。Liquid metal has fluidity and self-healing ability, and can maintain its morphology and structure during charging and discharging, preventing the cathode from being completely blocked by discharge products. Carbon nanotubes have high electrical conductivity and high specific surface area, which can further improve the electrical conductivity of liquid metals and increase the active sites of positive electrodes. The liquid metal@carbon nanotube lithium-air battery cathode prepared by the invention has better full discharge capacity, rate characteristic, cycle stability and anti-passivation ability.
说明书附图Instruction drawings
图1为实施例1的液态金属@碳纳米管正极的SEM图；Fig. 1 is the SEM image of the liquid metal@carbon nanotube positive electrode of Example 1;
图2为实施例1的液态金属自修复示意图；Fig. 2 is the liquid metal self-healing schematic diagram of embodiment 1;
图3为实施例1的元素分布图；Fig. 3 is the element distribution diagram of embodiment 1;
图4为实施例1的粒径分布图；Fig. 4 is the particle size distribution diagram of embodiment 1;
图5为实施例1的XRD图；Fig. 5 is the XRD pattern of embodiment 1;
图6为实施例2的充放电曲线图对照图，虚线为碳纳米管，实线为液态金属@碳纳米管；Fig. 6 is the charge-discharge curve diagram comparison diagram of embodiment 2, the dotted line is carbon nanotube, and the solid line is liquid metal@carbon nanotube;
表7为实施例2的全放电对照曲线，虚线为碳纳米管，实线为液态金属@碳纳米管；Table 7 is the full discharge control curve of Example 2, the dotted line is carbon nanotubes, and the solid line is liquid metal@carbon nanotubes;
图8为实施例2的倍率特性对照曲线，虚框为碳纳米管，实框为液态金属@碳纳米管；Fig. 8 is the ratio characteristic comparison curve of embodiment 2, the virtual frame is carbon nanotubes, and the solid frame is liquid metal@carbon nanotubes;
图9为实施例3的SEM图；Fig. 9 is the SEM image of embodiment 3;
图10为实施例3的充放电曲线图对照图，虚线为碳纳米管，实线为液态金属@碳纳米管；10 is a comparison chart of the charge-discharge curve diagram of Example 3, the dotted line is carbon nanotubes, and the solid line is liquid metal@carbon nanotubes;
图11为实施例3的全放电对照曲线，虚线为碳纳米管，实线为液态金属@碳纳米管；Figure 11 is the full-discharge control curve of Example 3, the dotted line is carbon nanotubes, and the solid line is liquid metal@carbon nanotubes;
图12为实施例3的倍率特性对照曲线，虚框为碳纳米管，实框为液态金属@碳纳米管。FIG. 12 is a comparison curve of the magnification characteristic of Example 3, the dotted frame is carbon nanotubes, and the solid frame is liquid metal@carbon nanotubes.
下面结合实施例和附图对本发明进一步说明。The present invention will be further described below with reference to the embodiments and accompanying drawings.
实施例1：Example 1:
提供通过滴加方式复合的镓锡液态金属@碳纳米管的制备参数。The preparation parameters of gallium tin liquid metal@carbon nanotubes composited by dropwise method are provided.
(1)将2.27g金属锡在氩气保护下300℃熔融与16.64g金属镓熔融共混，得到镓锡液态金属。(1) Melting and blending 2.27 g of metallic tin at 300° C. under the protection of argon with 16.64 g of metallic gallium to obtain a gallium-tin liquid metal.
(2)取0.9g步骤(1)的镓锡液态金属加入含有0.7mg的3-磺基-N-巯基丙酰胺(表面活性剂)的3.75mL无水乙醇中，采用超声探头处理将镓锡液态金属分散后，在室温下静置3小时，吸取上清液，干燥后得到镓锡液态金属粉末。(2) Take 0.9 g of the gallium-tin liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 0.7 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to treat the gallium-tin liquid metal. After the liquid metal is dispersed, it is allowed to stand at room temperature for 3 hours, the supernatant liquid is sucked, and the gallium tin liquid metal powder is obtained after drying.
(3)称取10mg碳纳米管加入25mL无水乙醇超声分散，得到超声分散好的碳纳米管浆料，准备一张10cm×10cm的碳纸，用喷枪将超声分散好的碳纳米管浆料均匀的喷涂在碳纸上，并在真空干燥箱内干燥。(3) Weigh 10 mg of carbon nanotubes and add 25 mL of absolute ethanol to ultrasonically disperse them to obtain ultrasonically dispersed carbon nanotube slurry. Prepare a 10cm×10cm piece of carbon paper, and use a spray gun to disperse the ultrasonically dispersed carbon nanotube slurry. Spray evenly on carbon paper and dry in a vacuum drying oven.
(4)将步骤(2)所得的镓锡液态金属粉末称取10mg加到2mL无 水乙醇中，超声分散得到镓锡液态金属分散液，将镓锡液态金属分散液滴加在步骤(3)制备的碳纸集流体上，真空干燥得到通过滴加方式复合的镓锡液态金属@碳纳米管锂空气电池正极。(4) Weigh 10 mg of the gallium-tin liquid metal powder obtained in step (2) into 2 mL of absolute ethanol, ultrasonically disperse to obtain a gallium-tin liquid metal dispersion, and drop the gallium-tin liquid metal dispersion in step (3) On the prepared carbon paper current collector, vacuum drying is used to obtain a gallium tin liquid metal@carbon nanotube lithium-air battery cathode compounded by dropwise method.
对所制得的镓锡液态金属通过自修复性能表征、场发射扫描电镜和X射线能谱(简称SEM/EDS)、X-射线衍射仪(简称XRD)进行表征。测试结果分别如图1-图5所示。从图1可以看出，镓锡液态金属通过滴加方式平铺在碳纳米管上。从图2可以看出，当镓锡液态金属受到外力作用时，接触面发生形变，外力去除时，形变恢复原状。证明了液态金属具有良好的变形性和自愈特性。图3可以看出，镓锡液态金属分散在喷涂有碳纳米管的碳纸集流体上。图4可以看出，镓锡液态金属平均粒径尺寸为210nm。图5为镓锡液态金属粉末的XRD图，在29.6°-49.7°的范围内出现一个宽峰，该范围表明具有短程有序的晶粒生长，这是液态金属的典型特征，Ga
2O
3的35.2°处的衍射峰与宽峰重叠。
The prepared gallium tin liquid metal was characterized by self-healing performance characterization, field emission scanning electron microscope, X-ray energy dispersive spectroscopy (SEM/EDS for short), and X-ray diffractometer (XRD for short). The test results are shown in Figure 1-Figure 5, respectively. It can be seen from Figure 1 that the gallium tin liquid metal is spread on the carbon nanotubes by dropping. It can be seen from Figure 2 that when the gallium-tin liquid metal is subjected to external force, the contact surface is deformed, and when the external force is removed, the deformation returns to its original state. It is proved that the liquid metal has good deformability and self-healing properties. It can be seen from Figure 3 that the gallium tin liquid metal is dispersed on the carbon paper current collector sprayed with carbon nanotubes. It can be seen from Figure 4 that the average particle size of the gallium tin liquid metal is 210 nm. Figure 5 is the XRD pattern of the gallium-tin liquid metal powder, a broad peak appears in the range of 29.6°-49.7°, which indicates grain growth with short-range order, which is a typical feature of liquid metals, Ga 2 O 3 The diffraction peak at 35.2° overlaps with the broad peak.
实施例2：Example 2:
提供通过滴加方式复合的镓锡液态金属@碳纳米管的制备参数。The preparation parameters of gallium tin liquid metal@carbon nanotubes composited by dropwise method are provided.
(1)将2.27g金属锡在氩气保护下300℃熔融与16.64g金属镓熔融共混，得到镓锡液态金属。(1) Melting and blending 2.27 g of metallic tin at 300° C. under the protection of argon with 16.64 g of metallic gallium to obtain a gallium-tin liquid metal.
(2)取0.9g步骤(1)的镓锡液态金属加入含有0.9mg的3-磺基-N-巯基丙酰胺(表面活性剂)的3.75mL无水乙醇中，采用超声探头处理将镓锡液态金属分散后，在室温下静置4小时，吸取上清液，干燥后得到镓锡液态金属粉末。(2) Take 0.9 g of the gallium-tin liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 0.9 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to treat the gallium-tin liquid metal. After the liquid metal is dispersed, it is allowed to stand at room temperature for 4 hours, the supernatant is sucked, and the gallium tin liquid metal powder is obtained after drying.
(3)称取15mg碳纳米管加入25mL无水乙醇超声分散，得到超声分散好的碳纳米管浆料，准备一张10cm×10cm的碳纸，用喷枪将超声分散好的碳纳米管浆料均匀的喷涂在碳纸上，并在真空干燥箱内干燥。(3) Weigh 15 mg of carbon nanotubes and add 25 mL of absolute ethanol to ultrasonically disperse them to obtain ultrasonically dispersed carbon nanotube slurry. Prepare a 10cm×10cm piece of carbon paper, and use a spray gun to disperse the ultrasonically dispersed carbon nanotube slurry. Spray evenly on carbon paper and dry in a vacuum drying oven.
(4)将步骤(2)所得的镓锡液态金属粉末称取20mg加到2mL无水乙醇中，超声分散得到镓锡液态金属分散液。将镓锡液态金属分散液滴加在步骤(3)制备的碳纸集流体上，真空干燥得到通过滴加方式复合的镓锡液态金属@碳纳米管锂空气电池正极。(4) Weigh 20 mg of the gallium-tin liquid metal powder obtained in step (2) into 2 mL of anhydrous ethanol, and ultrasonically disperse to obtain a gallium-tin liquid metal dispersion. The gallium tin liquid metal dispersion is dropwise added on the carbon paper current collector prepared in step (3), and vacuum dried to obtain a gallium tin liquid metal@carbon nanotube lithium-air battery positive electrode compounded by dropwise addition.
图6所示为碳纳米管和镓锡液态金属@碳纳米管作为锂空气电池正 极时，首圈充放电曲线，可以看出镓锡液态金属@碳纳米管作为正极时有较低的过电位。图7可以看出，镓锡液态金属@碳纳米管作为正极时电池全放电容量约为碳纳米管的9倍，镓锡液态金属复合碳纳米管后电池容量显著提高。图8为碳纳米管和镓锡液态金属@碳纳米管作为正极时锂空气电池倍率性能。在电流增加到0.3mA·cm
-2和0.5mA·cm
-2时，镓锡液态金属@碳纳米管作为正极的锂空气电池循环圈数为138圈和102圈，相比碳纳米管作为正极倍率性能都有所提高。
Figure 6 shows the first cycle of charge-discharge curves when carbon nanotubes and gallium tin liquid metal@carbon nanotubes are used as the positive electrode of lithium-air batteries. It can be seen that gallium tin liquid metal@carbon nanotubes have lower overpotential when used as positive electrode . It can be seen from Figure 7 that the full discharge capacity of the battery is about 9 times that of carbon nanotubes when gallium tin liquid metal@carbon nanotubes are used as the positive electrode, and the battery capacity is significantly improved after gallium tin liquid metal composite carbon nanotubes. Figure 8 shows the rate performance of Li-air batteries when carbon nanotubes and gallium tin liquid metal@carbon nanotubes are used as cathodes. When the current was increased to 0.3 mA·cm -2 and 0.5 mA·cm -2 , the cycle times of Li-air batteries with GaSn liquid metal@carbon nanotubes as cathodes were 138 and 102 cycles, compared with CNTs as cathodes. The magnification performance has been improved.
实施例3：Example 3:
提供通过共混方式复合的镓锡液态金属@碳纳米管的制备参数。The preparation parameters of gallium tin liquid metal@carbon nanotubes composited by blending are provided.
(1)将2.27g金属锡在氩气保护下300℃熔融与16.64g金属镓熔融共混，得到镓锡液态金属。(1) Melting and blending 2.27 g of metallic tin at 300° C. under the protection of argon with 16.64 g of metallic gallium to obtain a gallium-tin liquid metal.
(2)取0.8g步骤(1)的镓锡液态金属加入含有0.9mg的3-磺基-N-巯基丙酰胺(表面活性剂)的3.75mL无水乙醇中，采用超声探头处理将镓锡液态金属分散后，在室温下静置4小时，吸取上清液，干燥后得到镓锡液态金属粉末。(2) Take 0.8 g of the gallium tin liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 0.9 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to treat the gallium tin After the liquid metal is dispersed, it is allowed to stand at room temperature for 4 hours, the supernatant is sucked, and the gallium tin liquid metal powder is obtained after drying.
(3)称取步骤(2)制备的30mg镓锡液态金属粉末与10mg碳纳米管混合后加入25mL无水乙醇，超声分散一段时间，得到液态金属@碳纳米管复合物再喷涂到10cm×10cm碳纸集流体上，得到通过共混方式复合的液态金属@碳纳米管锂空气电池正极。(3) Weigh 30 mg of gallium-tin liquid metal powder prepared in step (2) and mix with 10 mg of carbon nanotubes, add 25 mL of absolute ethanol, and ultrasonically disperse for a period of time to obtain a liquid metal@carbon nanotube composite and spray it to 10cm×10cm On the carbon paper current collector, a liquid metal@carbon nanotube lithium-air battery cathode compounded by blending is obtained.
图9所示为通过共混方式复合的镓锡液态金属@碳纳米管锂空气电池正极的SEM图。图中可以看出镓锡液态金属表面被碳纳米管包裹。Figure 9 shows the SEM image of the gallium-tin liquid metal@carbon nanotube lithium-air battery cathode compounded by blending. It can be seen that the surface of the gallium tin liquid metal is wrapped by carbon nanotubes.
实施例4：Example 4:
提供滴加方式复合的镓铟液态金属@碳纳米管的制备参数。The preparation parameters of gallium indium liquid metal@carbon nanotubes composited by dropwise method are provided.
(1)将6.25g金属铟在氩气保护下200℃熔融与18.75g金属镓熔融共混，得到镓铟液态金属。(1) Melting and blending 6.25 g of metal indium at 200° C. under the protection of argon gas with 18.75 g of metal gallium to obtain a gallium indium liquid metal.
(2)取0.9g步骤(1)的镓铟液态金属加入含有1.0mg的3-磺基-N-巯基丙酰胺(表面活性剂)的3.75mL无水乙醇中，采用超声探头处理将镓铟液态金属分散后，在室温下静置4小时，吸取上清液，干燥后得到镓铟液态金属粉末。(2) Take 0.9 g of the gallium indium liquid metal in step (1) and add it to 3.75 mL of absolute ethanol containing 1.0 mg of 3-sulfo-N-mercaptopropionamide (surfactant), and use an ultrasonic probe to process the gallium indium After the liquid metal is dispersed, it is allowed to stand at room temperature for 4 hours, the supernatant is sucked, and the gallium indium liquid metal powder is obtained after drying.
(3)称取10mg碳纳米管加入25mL无水乙醇超声分散，准备一张10cm×10cm的碳纸，用喷枪将超声分散好的碳纳米管浆料均匀的喷涂在碳纸上，并在真空干燥箱内干燥。(3) Weigh 10mg of carbon nanotubes and add 25mL of absolute ethanol to ultrasonically disperse them. Prepare a 10cm×10cm piece of carbon paper. Use a spray gun to evenly spray the ultrasonically dispersed carbon nanotube slurry on the carbon paper. Dry in a dry box.
(4)将步骤(2)所得的镓铟液态金属粉末称取30mg加到2mL无水乙醇中，超声分散得到镓铟液态金属分散液。将镓铟液态金属分散液滴加在步骤(3)制备的碳纸集流体上，真空干燥得到通过滴加方式复合的镓铟液态金属@碳纳米管锂空气电池正极。(4) Weigh 30 mg of the gallium indium liquid metal powder obtained in step (2) into 2 mL of anhydrous ethanol, and ultrasonically disperse to obtain a gallium indium liquid metal dispersion. The gallium indium liquid metal dispersion is dropwise added on the carbon paper current collector prepared in step (3), and vacuum dried to obtain a gallium indium liquid metal@carbon nanotube lithium-air battery cathode compounded by dropwise addition.
图10所示为碳纳米管和镓铟液态金属@碳纳米管作为锂空气电池正极时，首圈充放电曲线。可以看出镓铟液态金属@碳纳米管作为正极时过电位为0.7V(0.05mAh时)，低于碳纳米管在0.05mAh时首圈过电位。图11可以看出，镓铟液态金属@碳纳米管和碳纳米管作为锂空气电池正极时电池全放电时间分别为4.1小时和34.2小时，镓铟液态金属复合碳纳米管后电池容量显著提高。图12为碳纳米管和镓铟液态金属@碳纳米管作为正极时锂空气电池倍率性能。在电流为0.3mA·cm
-2速率下镓铟液态金属@碳纳米管作为正极的锂空气电池循环圈数为碳纳米管作为正极时的5倍，在电流为0.5mA·cm
-2速率下镓铟液态金属@碳纳米管作为正极的锂空气电池循环105圈，远高于此电流下碳纳米管的循环圈数，镓铟液态金属@碳纳米管作为正极的锂空气电池倍率性能显著提高。
Figure 10 shows the first cycle of charge-discharge curves when carbon nanotubes and gallium indium liquid metal@carbon nanotubes are used as cathodes of lithium-air batteries. It can be seen that the overpotential of gallium indium liquid metal@carbon nanotube as the positive electrode is 0.7V (at 0.05mAh), which is lower than the overpotential of carbon nanotube at 0.05mAh in the first cycle. It can be seen from Figure 11 that when the gallium indium liquid metal@carbon nanotubes and carbon nanotubes are used as the cathode of the lithium-air battery, the full discharge time of the battery is 4.1 hours and 34.2 hours, respectively, and the battery capacity is significantly improved after the gallium indium liquid metal composite carbon nanotubes. Figure 12 shows the rate performance of Li-air batteries when carbon nanotubes and GaIn liquid metal@carbon nanotubes are used as cathodes. At the current rate of 0.3 mA·cm -2 , the number of cycles of the Li-air battery with gallium indium liquid metal@carbon nanotubes as the positive electrode is 5 times that of the carbon nanotubes as the positive electrode. At the current rate of 0.5 mA·cm -2 The lithium-air battery with gallium indium liquid metal@carbon nanotubes as the positive electrode has cycled 105 cycles, which is much higher than the cycle number of carbon nanotubes at this current. The rate performance of the lithium-air battery with gallium indium liquid metal@carbon nanotubes as the positive electrode is significantly improved .
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The descriptions of the above embodiments are only used to help understand the method and the core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can also be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
- 一种液态金属@碳纳米管复合物，其特征在于，所述液态金属为镓锡液态金属和镓铟液态金属中的一种，液态金属的尺寸分布为100nm～800nm；液态金属与碳纳米管的复合方式为共混法和滴加法中的一种，液态金属与碳纳米管的质量比为1：1～10：1。A liquid metal@carbon nanotube composite, characterized in that the liquid metal is one of gallium tin liquid metal and gallium indium liquid metal, and the size distribution of the liquid metal is 100nm-800nm; The composite method is one of the blending method and the dropping method, and the mass ratio of the liquid metal to the carbon nanotube is 1:1 to 10:1.
- 根据权利要求1所述的液态金属@碳纳米管复合物，其特征在于，所述镓锡液态金属中金属锡与金属镓的质量比为88：12。The liquid metal@carbon nanotube composite according to claim 1, wherein the mass ratio of metal tin to metal gallium in the gallium-tin liquid metal is 88:12.
- 根据权利要求1所述的液态金属@碳纳米管复合物，其特征在于，所述镓铟液态金属中金属锡与金属镓的质量比为75：25。The liquid metal@carbon nanotube composite according to claim 1, wherein the mass ratio of metal tin to metal gallium in the gallium indium liquid metal is 75:25.
- 一种液态金属@碳纳米管锂空气电池正极，其特征在于，所述液态金属为镓锡液态金属和镓铟液态金属中的一种，液态金属的尺寸分布为100nm～800nm；液态金属与碳纳米管的复合方式为共混法和滴加法中的一种，液态金属与碳纳米管的质量比为1：1～10：1。A liquid metal@carbon nanotube lithium-air battery positive electrode, characterized in that the liquid metal is one of gallium tin liquid metal and gallium indium liquid metal, and the size distribution of the liquid metal is 100nm-800nm; The composite method of the nanotubes is one of a blending method and a dropping method, and the mass ratio of the liquid metal to the carbon nanotubes is 1:1 to 10:1.
- 根据权利要求5所述的液态金属@碳纳米管锂空气电池正极，其特征在于，所述镓锡液态金属中金属锡与金属镓的质量比为88：12。The liquid metal@carbon nanotube lithium-air battery cathode of claim 5, wherein the mass ratio of metal tin to metal gallium in the gallium-tin liquid metal is 88:12.
- 根据权利要求5所述的液态金属@碳纳米管锂空气电池正极，其特征在于，所述镓铟液态金属中金属锡与金属镓的质量比为75：25。The liquid metal@carbon nanotube lithium-air battery cathode according to claim 5, wherein the mass ratio of metal tin to metal gallium in the gallium indium liquid metal is 75:25.
- 根据权利要求5所述的液态金属@碳纳米管锂空气电池正极，其特征在于，所述液态金属@碳纳米管锂空气电池正极还包括碳纸。The liquid metal@carbon nanotube lithium-air battery positive electrode of claim 5, wherein the liquid metal@carbon nanotube lithium-air battery positive electrode further comprises carbon paper.
- 权利要求5所述的液态金属@碳纳米管锂空气电池正极的制备方法，其特征在于，具体步骤为：The method for preparing a positive electrode of a liquid metal@carbon nanotube lithium-air battery according to claim 5, wherein the specific steps are:(1)将金属锡在氩气保护下300℃熔融与金属镓熔融共混，得到镓锡液态金属，金属锡与金属镓的质量比为88：12；或者将金属铟在氩气保护下200℃熔融与金属镓熔融共混，得到镓铟液态金属，金属锡与金属镓的质量比为75：25；(1) Melt metal tin at 300°C under argon protection and melt and blend metal gallium to obtain gallium-tin liquid metal, and the mass ratio of metal tin to metal gallium is 88:12; ℃ melting and melting and blending of metal gallium to obtain gallium indium liquid metal, and the mass ratio of metal tin to metal gallium is 75:25;(2)取0.5～2.0g步骤(1)所得的镓锡液态金属或者镓铟液态金属加入含有0.25～3mg的3-磺基-N-巯基丙酰胺的3.75mL无水乙醇中，镓锡液态金属或者镓铟液态金属与3-磺基-N-巯基丙酰胺的质量比为1000：0.5～1000：1.5；采用超声探头处理将液态金属分散后，在室温下静置3 小时，吸取上清液，干燥后得到镓锡液态金属粉末或镓铟液态金属粉末；(2) Add 0.5-2.0 g of the gallium-tin liquid metal or gallium-indium liquid metal obtained in step (1) into 3.75 mL of absolute ethanol containing 0.25-3 mg of 3-sulfo-N-mercaptopropionamide, and the gallium-tin liquid metal The mass ratio of metal or gallium indium liquid metal to 3-sulfo-N-mercaptopropionamide is 1000:0.5~1000:1.5; after dispersing the liquid metal by ultrasonic probe treatment, let it stand at room temperature for 3 hours, and absorb the supernatant liquid, and dried to obtain gallium tin liquid metal powder or gallium indium liquid metal powder;(3)镓锡液态金属@碳纳米管锂空气电池正极：(3) GaSn liquid metal@carbon nanotube lithium-air battery cathode:A：共混方式A: Blending method称取5～200mg步骤(2)制备的镓锡液态金属粉末或镓铟液态金属粉末与5～20mg碳纳米管混合后加入25mL无水乙醇，超声分散，得到液态金属@碳纳米管复合物，再喷涂到10cm×10cm碳纸集流体上，通过共混方式得到的镓锡液态金属@碳纳米管锂空气电池正极或镓铟液态金属@碳纳米管锂空气电池正极；Weigh 5-200 mg of the gallium-tin liquid metal powder or gallium-indium liquid metal powder prepared in step (2) and mix with 5-20 mg of carbon nanotubes, add 25 mL of absolute ethanol, and ultrasonically disperse to obtain a liquid metal@carbon nanotube composite, Then sprayed on the 10cm×10cm carbon paper current collector, and obtained the positive electrode of gallium tin liquid metal@carbon nanotube lithium-air battery or the positive electrode of gallium indium liquid metal@carbon nanotube lithium-air battery by blending;B：滴加方式B: dripping methoda：称取5～20mg碳纳米管加入25mL无水乙醇超声分散，用喷枪将超声分散好的碳纳米管浆料均匀的喷涂在10cm×10cm碳纸上，并在真空干燥箱内干燥；a: Weigh 5-20 mg of carbon nanotubes and add 25 mL of anhydrous ethanol to ultrasonically disperse them. Use a spray gun to uniformly spray the ultrasonically dispersed carbon nanotube slurry on 10cm×10cm carbon paper, and dry it in a vacuum drying box;b：将5～200mg步骤(2)所得的镓锡液态金属粉末或镓铟液态金属粉末加入到2mL无水乙醇中，超声分散得到镓锡液态金属分散液或镓铟液态金属分散液，将镓锡液态金属分散液或镓铟液态金属分散液滴加在步骤a制备的碳纸上，真空干燥，通过滴加方式复合的镓锡液态金属@碳纳米管锂空气电池正极或镓铟液态金属@碳纳米管锂空气电池正极。b: Add 5-200 mg of the gallium tin liquid metal powder or gallium indium liquid metal powder obtained in step (2) into 2 mL of absolute ethanol, and ultrasonically disperse to obtain a gallium tin liquid metal dispersion or a gallium indium liquid metal dispersion. Tin liquid metal dispersion or gallium indium liquid metal dispersion is dropped on the carbon paper prepared in step a, vacuum dried, and the composite gallium tin liquid metal@carbon nanotube lithium-air battery cathode or gallium indium liquid metal@ Carbon nanotube lithium-air battery cathode.
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