Preparation method of tin-silver-copper-aluminum quaternary alloy and its application in secondary battery negative electrode

Abstract

A preparation method of a tin-silver-copper-aluminum quaternary alloy and its application in the negative electrode of a secondary battery belong to the technical field of secondary batteries. The present invention aims to solve the problems of limited materials, high cost, complex preparation process, and unsatisfactory electrochemical performance of alloy negative electrodes in existing secondary batteries. Method: 1. Using tin, silver, copper, and aluminum targets as raw materials, setting the argon gas flow rate; 2. Setting the magnetron sputtering power parameters of the tin target, silver target, copper target, and aluminum target respectively; 3. Setting the magnetron sputtering time and substrate speed, turning on the magnetron sputtering power supply, starting sputtering on the current collector, and ending sputtering to obtain a tin-silver-copper-aluminum quaternary alloy. A tin-silver-copper-aluminum quaternary alloy is used as the negative electrode active material of a secondary battery. The preparation process of the present invention is relatively simple, so the cost is greatly reduced. The present invention solves the shortcomings of limited lithium resource reserves and high cost of existing lithium-ion batteries. In addition, the present invention is simpler, safer, more reliable, and has higher energy density than existing sodium-ion batteries.

Description

Technical Field

[0001] The present invention belongs to the technical field of secondary batteries, and in particular relates to a preparation method of a tin-silver-copper-aluminum quaternary alloy and its application in secondary batteries. Background Art

[0002] Secondary batteries, also known as rechargeable batteries, are batteries that can be repeatedly charged and discharged and used multiple times. Compared to non-reusable primary batteries, secondary batteries have the advantages of low cost and less environmental pollution. The main secondary battery technologies currently include lead-acid batteries, nickel-chromium batteries, nickel-metal hydride batteries, lithium-ion batteries, and sodium-ion batteries. Among them, lithium-ion batteries are the most widely used. As a potential energy storage technology to replace lithium-ion batteries, sodium-ion batteries have also received increasing attention in recent years. The core components of lithium-ion batteries and sodium-ion batteries include positive electrodes, negative electrodes, and electrolytes. They achieve electrical energy storage and release through reactions that separate ion transfer and electron transfer at the interfaces of the positive and negative electrodes and the electrolyte. During charging, the reaction occurring at the negative electrode is that lithium / sodium ions are embedded in the negative electrode active material from the electrolyte, and the reaction occurring at the positive electrode is that lithium / sodium ions are released from the positive electrode active material into the electrolyte or anions are intercalated in the positive electrode active material; during discharging, lithium / sodium ions are released from the negative electrode active material and returned to the electrolyte, and the lithium / sodium ions in the electrolyte are embedded in the positive electrode active material or anions are released from the positive electrode active material and returned to the electrolyte.

[0003] Lithium-ion batteries and sodium-ion batteries use oxides, polyanionic compounds, organic compounds, and the like as positive electrode active materials, and carbon materials, alloy materials, oxides, sulfides, phosphides, organic compounds, and the like as negative electrode active materials. However, the types of positive and negative electrode materials currently developed for lithium-ion and sodium-ion batteries are very limited, and research on new positive and negative electrode materials is essentially limited to batteries for lithium or sodium sheets. The electrochemical performance of lithium-ion and sodium-ion batteries based on the developed new positive and negative electrode materials is not very ideal, and the preparation process is also relatively complex. Research on the preparation of negative electrode materials for sodium-ion batteries (Patent Publication Nos.: CN109817960A, CN103647068A, CN103633310A, CN103553129A) all provide methods for preparing high-capacity negative electrode materials for sodium-ion batteries. However, these high-capacity negative electrode materials all suffer from poor cycle performance during charge and discharge.

[0004] Lithium-ion batteries and sodium-ion batteries are considered powerful methods for large-scale energy storage. The performance of their anode materials is a crucial performance indicator for these batteries. Taking sodium-ion batteries as an example, hard carbon and alloy materials are currently the predominant anode materials for sodium-ion batteries. For example, reports in IONICS, 2020, 26:5535-5542, Electrochimica Acta, 2020, 361:1370-41, and JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY, 2020, 91:317-329 use hard carbon materials as anodes. Other reports, such as SMALL METHODS, 2020, 4:2000-218, CHEMICAL ENGINEERING JOURNAL, 2020, 388:124-299, and JOURNAL OF ALLOYS AND COMPOUNDS, 2020, 834:154-304, use alloy materials as anodes. However, in addition to requiring stringent preparation conditions (especially alloys), these materials each suffer from a significant drawback when used in sodium-ion anodes. For hard carbon, its voltage plateau approaches the deposition potential of metallic sodium, making it prone to forming sodium metal dendrites under high-current charging conditions, posing a serious safety concern. For alloy anodes, the drastic volume deformation of these materials causes the solid electrolyte interface film on the metal alloy surface to continuously break down and form during charge and discharge, resulting in low coulombic efficiency and significantly limiting the cycle life of the entire battery.

[0005] According to published literature reports and patents, there is no discovery of the use of magnetron sputtering to prepare tin-silver-copper-aluminum quaternary alloy in the negative electrode of secondary batteries. Summary of the Invention

[0006] In response to the problems raised in the above background technology, the purpose of the present invention is to overcome the shortcomings of the existing technology and aim to solve the problems of limited materials, high costs, complex preparation processes, and unsatisfactory electrochemical performance of alloy negative electrodes in existing secondary batteries. The present invention provides a preparation method of a tin-silver-copper-aluminum quaternary alloy and its application in the negative electrode of a secondary battery.

[0007] The present invention uses a magnetron sputtering method to prepare a quaternary alloy using tin, silver, copper and aluminum targets as raw materials. The preparation process is relatively simple, so the cost is greatly reduced. The present invention solves the shortcomings of existing lithium-ion batteries such as limited lithium resource reserves and high costs. In addition, the present invention is simpler, safer, more reliable and has a higher energy density than existing sodium-ion batteries.

[0008] A method for preparing a tin-silver-copper-aluminum quaternary alloy is specifically completed by the following steps:

[0009] 1. Using tin, silver, copper, or aluminum targets as raw materials, set the argon gas flow rate;

[0010] 2. Set the magnetron sputtering power parameters of tin target, silver target, copper target and aluminum target respectively;

[0011] 3. Set the magnetron sputtering time and substrate speed, turn on the magnetron sputtering power, start sputtering on the collector, and end sputtering to obtain a tin-silver-copper-aluminum quaternary alloy.

[0012] A tin-silver-copper-aluminum quaternary alloy is used as a negative electrode active material for a secondary battery.

[0013] Compared with the prior art, the present invention has the following beneficial effects:

[0014] 1. The present invention uses tin, silver, copper, and aluminum as raw materials to prepare a quaternary alloy using a magnetron sputtering method. The prepared tin-silver-copper-aluminum quaternary alloy is used as the negative electrode material of a secondary battery. The capacity decay during each charge and discharge process is small. Therefore, the secondary battery prepared using the tin-silver-copper-aluminum quaternary alloy prepared by the present invention as the negative electrode of the secondary battery has good cycle stability and the battery life is increased to a certain extent.

[0015] 2. The new secondary battery negative electrode prepared by the present invention has a higher specific capacity and energy density than hard carbon negative electrodes; and has a stronger cycle stability than other alloy material negative electrodes;

[0016] 3. The preparation of the secondary battery negative electrode of the present invention uses a magnetron sputtering method to prepare a quaternary alloy using tin, silver, copper and aluminum as raw materials. The preparation process is relatively simple, so the cost is greatly reduced;

[0017] 4. Compared with existing sodium ion batteries, the electrode materials of the present invention are simple, easily available, environmentally friendly and safe, resulting in a simple production process for the battery, low cost, and relatively excellent electrochemical performance of the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 Schematic diagram of the structure of the secondary battery provided by the present invention, wherein 1 is the battery negative electrode current collector, 2 is the battery negative electrode active material, 3 is the electrolyte, 4 is the separator, 5 is the battery positive electrode active material, and 6 is the positive electrode current collector;

[0019] Figure 2 The Sn prepared in Example 1 66 Ag9Cu 16 Al9 negative electrode assembled sodium ion secondary battery and Sn prepared in Example 2 54 Ag 16 Cu 18 Al 12 Cycling performance curve of sodium-ion secondary battery assembled with negative electrode;

[0020] Figure 3 The figure is a cycle performance curve of a sodium ion secondary battery assembled using the tin-silver-copper ternary alloy prepared in Comparative Example 1;

[0021] Figure 4 The figure is a cycle performance curve of a sodium ion secondary battery assembled using the tin-silver-aluminum ternary alloy prepared in Comparative Example 2;

[0022] Figure 5 The figure is a cycle performance curve of a sodium ion secondary battery assembled using the tin-copper-aluminum ternary alloy prepared in Comparative Example 3;

[0023] Figure 6 The figure is a cycle performance curve of a sodium ion secondary battery assembled using the tin-silver binary alloy prepared in Comparative Example 4;

[0024] Figure 7 The figure is a cycle performance curve of a sodium ion secondary battery assembled using the tin-copper binary alloy prepared in Comparative Example 5;

[0025] Figure 8 The figure is a cycle performance curve of a sodium ion secondary battery assembled using the tin-aluminum binary alloy prepared in Comparative Example 6;

[0026] Figure 9 This is a cycle performance curve of a sodium-ion secondary battery assembled using pure tin as the negative electrode. DETAILED DESCRIPTION

[0027] Specific embodiment 1: This embodiment is a method for preparing a tin-silver-copper-aluminum quaternary alloy, which is specifically completed by the following steps:

[0028] 1. Using tin, silver, copper, or aluminum targets as raw materials, set the argon gas flow rate;

[0029] 2. Set the magnetron sputtering power parameters of tin target, silver target, copper target and aluminum target respectively;

[0030] 3. Set the magnetron sputtering time and substrate speed, turn on the magnetron sputtering power, start sputtering on the collector, and end sputtering to obtain a tin-silver-copper-aluminum quaternary alloy.

[0031] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the argon gas flow rate in step 1 is 100 mL / min to 300 mL / min. The other steps are the same as those in specific embodiment 1.

[0032] Specific embodiment 3: This embodiment differs from specific embodiments 1 or 2 in that, in step 2, the magnetron sputtering power parameter for the tin target is set to 120W-180W, the magnetron sputtering power parameter for the silver target is set to 15W-40W, the magnetron sputtering power parameter for the copper target is set to 20W-50W, and the magnetron sputtering power parameter for the aluminum target is set to 20W-100W. The other steps are the same as those in specific embodiments 1 or 2.

[0033] Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that, in step 2, the magnetron sputtering power parameter for the tin target is set to 150 W, the magnetron sputtering power parameter for the silver target is set to 25 W, the magnetron sputtering power parameter for the copper target is set to 30 W, and the magnetron sputtering power parameter for the aluminum target is set to 45 W. The other steps are the same as specific embodiments 1 to 3.

[0034] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that: in step 3, the magnetron sputtering time is set to 1800s to 9000s; the substrate rotation speed is set to 0 r / min to 60 r / min; and the current collector in step 3 is a metal conductive material, which is one of aluminum, copper, tin, zinc, lead, antimony, cadmium, gold, bismuth, and germanium, a composite of any of these metals, or an alloy of any of these metals. The other steps are the same as specific embodiments 1 to 4.

[0035] Specific embodiment 6: This embodiment uses a tin-silver-copper-aluminum quaternary alloy as the negative electrode of a secondary battery.

[0036] Specific embodiment 7: This embodiment differs from specific embodiments 1 to 6 in that the secondary battery comprises a positive electrode, a negative electrode, a separator interposed between the positive and negative electrodes, and an electrolyte; the positive electrode comprises a positive electrode active material and a positive electrode current collector. Other steps are the same as specific embodiments 1 to 6.

[0037] Specific Embodiment 8: This embodiment differs from Specific Embodiments 1 to 7 in that the positive electrode active material is lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium cobalt oxide, sodium vanadium phosphate, Prussian blue, or a layered oxide; and the positive electrode current collector is one of carbon-coated aluminum foil, carbon-coated copper foil, carbon-coated iron foil, carbon-coated tin foil, carbon-coated zinc foil, carbon-coated nickel foil, carbon-coated titanium foil, carbon-coated manganese foil, or a composite of any of these metals or an alloy thereof. Other steps are the same as Specific Embodiments 1 to 7.

[0038] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that: the separator is a porous polymer film or an inorganic porous film; the porous polymer film is a porous polypropylene film, a porous polyethylene film, or a composite film of porous polypropylene and porous polyethylene; the inorganic porous film is a glass fiber paper or a porous ceramic separator; the electrolyte comprises an electrolyte and a solvent, the electrolyte being a lithium salt or sodium salt electrolyte, and the solvent being selected from one or more organic solvents such as esters, sulfones, ethers, nitriles, and ionic liquids; and the concentration of the electrolyte is 0.1 mol / L to 10 mol / L. Other steps are the same as those of specific embodiments 1 to 8.

[0039] Specific embodiment ten: This embodiment differs from specific embodiments one to nine in that the electrolyte includes lithium hexafluorophosphate, lithium chloride, lithium fluoride, lithium sulfate, lithium carbonate, lithium phosphate, lithium nitrate, lithium difluorooxalatoborate, lithium pyrophosphate, lithium dodecylbenzenesulfonate, lithium dodecyl sulfate, trilithium citrate, lithium metaborate, lithium borate, lithium molybdate, lithium tungstate, lithium bromide, lithium nitrite, lithium iodate, lithium iodide, lithium silicate, lithium ligninsulfonate, lithium oxalate, lithium aluminate, lithium methanesulfonate, lithium acetate, lithium dichromate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonyl imide, sodium hexafluorophosphate, chloride Sodium, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalatoborate, sodium pyrophosphate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium silicate, sodium ligninsulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonimide, sodium trifluoromethanesulfonate and sodium bistrifluoromethanesulfonimide; the solvent includes propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N,N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxymethane, 1,2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, crown ether (12-crown-4), 1-ethyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide, 1-propyl-3-methylimidazole hexafluorophosphate One or more of: 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bis(trifluoromethanesulfonyl)imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bis(trifluoromethanesulfonyl)imide salt, N-butyl-N-methylpyrrolidine-bis(trifluoromethanesulfonyl)imide salt, 1-butyl-1-methylpyrrolidine-bis(trifluoromethanesulfonyl)imide salt, N-methyl-N-propylpyrrolidine-bis(trifluoromethanesulfonyl)imide salt, N-methyl-propylpiperidine-bis(trifluoromethanesulfonyl)imide salt, and N-butyl-N-methylpiperidine-bis(trifluoromethanesulfonyl)imide salt. Other steps are the same as those in specific embodiments one to nine.

[0040] The following examples are used to verify the beneficial effects of the present invention:

[0041] Example 1: A method for preparing a tin-silver-copper-aluminum quaternary alloy is specifically completed by the following steps:

[0042] 1. Using tin, silver, copper, or aluminum targets as raw materials, set the argon gas flow rate;

[0043] The argon gas flow rate in step 1 is 300 mL / min;

[0044] 2. Set the magnetron sputtering power parameters of tin target, silver target, copper target and aluminum target respectively;

[0045] In step 2, the magnetron sputtering power parameter of the tin target is set to 150W, the magnetron sputtering power parameter of the silver target is set to 25W, the magnetron sputtering power parameter of the copper target is set to 30W, and the magnetron sputtering power parameter of the aluminum target is set to 45W;

[0046] 3. Set the time and substrate speed of magnetron sputtering, turn on the power of magnetron sputtering, start sputtering on the collector, and end sputtering to obtain Sn 66 Ag9Cu 16 Al9 tin-silver-copper-aluminum quaternary alloy;

[0047] In step 3, the magnetron sputtering time was set to 5400 s; in step 4, the substrate speed was set to 60 r / min;

[0048] The current collector described in step three is copper foil.

[0049] Example 2: The difference between this example and Example 1 is that in step 2, the magnetron sputtering power parameter of the tin target is set to 140W, the magnetron sputtering power parameter of the silver target is set to 25W, the magnetron sputtering power parameter of the copper target is set to 30W, and the magnetron sputtering power parameter of the aluminum target is set to 45W; in step 3, Sn is obtained. 54 Ag 16 Cu 18 Al 12 Sn-Ag-Cu-Aluminum quaternary alloy. Other steps and parameters are the same as those in Example 1.

[0050] Comparative Example 1: This example differs from Example 1 in that, in step 2, the magnetron sputtering power parameters for the tin target were set to 140 W, the magnetron sputtering power parameters for the silver target were set to 25 W, the magnetron sputtering power parameters for the copper target were set to 30 W, and the magnetron sputtering power parameters for the aluminum target were set to 0 W. In step 3, a tin-silver-copper ternary alloy was obtained. All other steps and parameters were the same as in Example 1.

[0051] Comparative Example 2: This example differs from Example 1 in that, in step 2, the magnetron sputtering power parameters for the tin target were set to 140 W, the magnetron sputtering power parameters for the silver target were set to 25 W, the magnetron sputtering power parameters for the copper target were set to 0 W, and the magnetron sputtering power parameters for the aluminum target were set to 45 W. In step 3, a ternary tin-silver-aluminum alloy was obtained. All other steps and parameters were the same as in Example 1.

[0052] Comparative Example 3: This example differs from Example 1 in that, in step 2, the magnetron sputtering power parameters for the tin target were set to 140 W, the magnetron sputtering power parameters for the silver target were set to 0 W, the magnetron sputtering power parameters for the copper target were set to 30 W, and the magnetron sputtering power parameters for the aluminum target were set to 45 W. In step 3, a ternary tin-copper-aluminum alloy was obtained. All other steps and parameters were the same as in Example 1.

[0053] Comparative Example 4: This example differs from Example 1 in that, in step 2, the magnetron sputtering power parameters for the tin target were set to 140 W, the magnetron sputtering power parameters for the silver target were set to 25 W, the magnetron sputtering power parameters for the copper target were set to 0 W, and the magnetron sputtering power parameters for the aluminum target were set to 0 W. In step 3, a tin-silver binary alloy was obtained. All other steps and parameters were the same as in Example 1.

[0054] Comparative Example 5: This example differs from Example 1 in that, in step 2, the magnetron sputtering power parameter for the tin target is set to 140 W, the magnetron sputtering power parameter for the silver target is set to 0 W, the magnetron sputtering power parameter for the copper target is set to 30 W, and the magnetron sputtering power parameter for the aluminum target is set to 0 W; and in step 3, a tin-copper binary alloy is obtained. All other steps and parameters are the same as in Example 1.

[0055] Comparative Example 6: This example differs from Example 1 in that, in step 2, the magnetron sputtering power parameter for the tin target is set to 140 W, the magnetron sputtering power parameter for the silver target is set to 0 W, the magnetron sputtering power parameter for the copper target is set to 0 W, and the magnetron sputtering power parameter for the aluminum target is set to 45 W; and in step 3, a tin-aluminum binary alloy is obtained. All other steps and parameters are the same as in Example 1.

[0056] Application Example 1: Using the Sn prepared in Example 1 66 Ag9Cu 16 The sodium ion secondary battery assembled with Al9 tin-silver-copper-aluminum quaternary alloy is specifically completed in the following steps:

[0057] 1) Preparation of battery negative electrode: Sn prepared in Example 1 66 Ag9Cu 16 Al9 tin-silver-copper-aluminum quaternary alloy is cut into 12mm diameter discs and compacted to serve as the battery negative electrode.

[0058] 2) Prepare the electrolyte: Weigh 6.7 g of sodium hexafluorophosphate and add it to 10 mL of a mixed solvent of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate (the volume ratio of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate is 1:1:1). Stir until the sodium hexafluorophosphate is completely dissolved. Stir thoroughly and use it as the electrolyte for later use.

[0059] 3) Preparation of diaphragm: Cut the glass fiber film into 16 mm diameter discs and use them as diaphragms;

[0060] 4) Prepare the positive electrode: Add 0.8g sodium vanadium phosphate, 0.1g carbon black, and 0.1g polytetrafluoroethylene to 4mL of nitrogen-methyl pyrrolidone and grind thoroughly to obtain a uniform slurry. Then, apply the slurry evenly to the surface of carbon-coated aluminum foil (i.e., the positive electrode current collector) and vacuum dry. Cut the dried electrode sheet into 10mm diameter discs for use as the positive electrode.

[0061] 5) Battery assembly: In an inert gas-protected glove box, the prepared battery positive electrode, separator, and battery negative electrode are tightly stacked in sequence, and the electrolyte is added dropwise to completely soak the separator. The stacked part is then encapsulated in a button-type battery casing to complete the battery assembly and obtain a sodium-ion secondary battery.

[0062] At room temperature, the sodium ion secondary battery assembled in Example 1 was subjected to constant current charge and discharge tests using a Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The cycle performance curve is shown in FIG. Figure 2 Sn 66 Ag9Cu 16 As shown in part A19. Figure 2 Sn 66 Ag9Cu 16 As can be seen from the Al9 part, the Sn prepared in Example 1 66 Ag9Cu 16 After several charge and discharge cycles, the sodium ion secondary battery made of Al9 tin-silver-copper-aluminum quaternary alloy has a coulombic efficiency greater than 99%, a charge and discharge capacity of about 600 mAh / g, and a capacity retention rate greater than 90% after about 100 cycles.

[0063] Application Example 2: The difference between this application example and application example 1 is that the Sn prepared in Example 2 is used. 54 Ag 16 Cu 18 Al 12 A sodium ion secondary battery assembled with a tin-silver-copper-aluminum quaternary alloy, that is, the Sn prepared in Example 2 54 Ag 16 Cu 18 Al 12The tin-silver-copper-aluminum quaternary alloy was cut into 12 mm diameter discs and compacted to serve as the battery negative electrode. Other steps and parameters were the same as those in Application Example 1.

[0064] At room temperature, the sodium ion secondary battery assembled in Example 2 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The cycle performance curve is shown in FIG. Figure 2 Sn 66 Ag9Cu 16 As shown in part A19. Figure 2 Sn 66 Ag9Cu 16 As can be seen from the Al9 part, the Sn prepared in Example 2 is used in Example 2. 54 Ag 16 Cu 18 Al 12 After 100 charge and discharge cycles, the charge and discharge capacity of a sodium ion secondary battery assembled from a tin-silver-copper-aluminum quaternary alloy is only about 350 mAh / g, and the capacity retention rate is less than 70%.

[0065] Application Example 3: This application example differs from Application Example 1 in that a sodium-ion secondary battery is assembled using the tin-silver-copper ternary alloy prepared in Comparative Example 1. Specifically, the tin-silver-copper ternary alloy prepared in Comparative Example 1 is cut into 12 mm diameter discs, compacted, and used as the battery's negative electrode. All other steps and parameters are the same as in Application Example 1.

[0066] At room temperature, the sodium ion secondary battery assembled in Example 3 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The test results are as follows: Figure 3 As shown in Example 3, the sodium ion secondary battery assembled with the tin-silver-copper ternary alloy prepared in Comparative Example 1 has a charge and discharge capacity of only about 300 mAh / g after 100 charge and discharge cycles, and a capacity retention rate of less than 55%.

[0067] Application Example 4: This application example differs from Application Example 1 in that a sodium-ion secondary battery is assembled using the tin-silver-aluminum ternary alloy prepared in Comparative Example 2. Specifically, the tin-silver-aluminum ternary alloy prepared in Comparative Example 2 is cut into 12 mm diameter discs, compacted, and used as the battery's negative electrode. All other steps and parameters are the same as in Application Example 1.

[0068] At room temperature, the sodium ion secondary battery assembled in Example 4 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The test results are as follows: Figure 4As shown in Example 4, the sodium ion secondary battery assembled with the tin-silver-aluminum ternary alloy prepared in Comparative Example 2 has a charge and discharge capacity of only about 230 mAh / g after 100 charge and discharge cycles, and a capacity retention rate of less than 40%.

[0069] Application Example 5: This application example differs from Application Example 1 in that a sodium-ion secondary battery is assembled using the tin-copper-aluminum ternary alloy prepared in Comparative Example 3. Specifically, the tin-copper-aluminum ternary alloy prepared in Comparative Example 3 is cut into 12 mm diameter discs, compacted, and used as the battery's negative electrode. All other steps and parameters are the same as in Application Example 1.

[0070] At room temperature, the sodium ion secondary battery assembled in Example 5 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The test results are as follows: Figure 5 As shown in Example 5, the sodium ion secondary battery assembled with the tin-copper-aluminum ternary alloy prepared in Comparative Example 3 has a charge and discharge capacity of only about 420 mAh / g after 100 charge and discharge cycles, and a capacity retention rate of less than 65%.

[0071] Application Example 6: This application example differs from Application Example 1 in that a sodium-ion secondary battery is assembled using the tin-copper-aluminum ternary alloy prepared in Comparative Example 4. Specifically, the tin-silver binary alloy prepared in Comparative Example 4 is cut into 12 mm diameter discs, compacted, and used as the battery's negative electrode. All other steps and parameters are the same as in Application Example 1.

[0072] At room temperature, the sodium ion secondary battery assembled in Example 6 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The test results are as follows: Figure 6 As shown in Example 6, the sodium ion secondary battery assembled with the tin-silver binary alloy prepared in Comparative Example 4 has a charge and discharge capacity of only about 110 mAh / g after 100 charge and discharge cycles, and a capacity retention rate of less than 20%.

[0073] Application Example 7: This application example differs from Application Example 1 in that a sodium-ion secondary battery is assembled using the tin-copper binary alloy prepared in Comparative Example 5. Specifically, the tin-copper binary alloy prepared in Comparative Example 5 is cut into 12 mm diameter discs, compacted, and used as the battery's negative electrode. All other steps and parameters are the same as in Application Example 1.

[0074] At room temperature, the sodium ion secondary battery assembled in Example 7 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The test results are as follows: Figure 7As shown in Example 7, the sodium ion secondary battery assembled with the tin-copper binary alloy prepared in Comparative Example 5 has a charge and discharge capacity of only about 340 mAh / g after 100 charge and discharge cycles, and a capacity retention rate of less than 50%.

[0075] Application Example 8: This application example differs from Application Example 1 in that a sodium-ion secondary battery is assembled using the tin-aluminum binary alloy prepared in Comparative Example 6. Specifically, the tin-aluminum binary alloy prepared in Comparative Example 6 is cut into 12 mm diameter discs, compacted, and used as the battery's negative electrode. All other steps and parameters are the same as in Application Example 1.

[0076] At room temperature, the sodium ion secondary battery assembled in Example 8 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The test results are as follows: Figure 8 As shown in Example 8, the sodium ion secondary battery assembled with the tin-aluminum binary alloy prepared in Comparative Example 6 has a charge and discharge capacity of only about 240 mAh / g after 100 charge and discharge cycles, and a capacity retention rate of less than 35%.

[0077] Application Example 9: This application example differs from Application Example 1 in that a sodium-ion secondary battery is assembled using pure tin as the negative electrode. Specifically, the pure tin is cut into 12 mm diameter discs and compacted to serve as the battery negative electrode. All other steps and parameters are the same as those in Application Example 1.

[0078] At room temperature, the sodium ion secondary battery assembled in Example 9 was subjected to constant current charge and discharge tests using the Shenzhen Xinweier battery test system. The charge and discharge current was 500 mA / g, and the charge and discharge voltage range was 2 to 3.8 V. The test results are as follows: Figure 9 As shown in Application Example 9, the sodium ion secondary battery assembled using pure tin as the negative electrode has a charge and discharge capacity of less than 10 mAh / g after 32 charge and discharge cycles, and a capacity retention rate of less than 1% after 100 cycles.

Claims

1. A method for preparing a tin-silver-copper-aluminum quaternary alloy, characterized in that The preparation method is specifically completed according to the following steps:

1. Using tin, silver, copper, or aluminum targets as raw materials, set the argon gas flow rate; 2. Set the magnetron sputtering power parameters of tin target, silver target, copper target and aluminum target respectively; 3. Set the time and substrate speed of magnetron sputtering, turn on the power of magnetron sputtering, start sputtering on the collector, and end sputtering to obtain Sn 54 Ag 16 Cu 18 Al 12 or Sn 66 Ag9Cu 16 Al9 quaternary alloy.

2. The method for preparing a tin-silver-copper-aluminum quaternary alloy according to claim 1, characterized in that Sn 66 Ag9Cu 16 The magnetron sputtering power parameters set in step 2 corresponding to the Al9 quaternary alloy are: setting the magnetron sputtering power parameter of the tin target to 150W, setting the magnetron sputtering power parameter of the silver target to 25W, setting the magnetron sputtering power parameter of the copper target to 30W, and setting the magnetron sputtering power parameter of the aluminum target to 45W.

3. The method for preparing a tin-silver-copper-aluminum quaternary alloy according to claim 1, characterized in that The current collector in step three is a metal conductive material, and the metal conductive material is aluminum or copper.

4. Application of a tin-silver-copper-aluminum quaternary alloy prepared by the preparation method according to claim 1, characterized in that A tin-silver-copper-aluminum quaternary alloy is used as the negative electrode of a secondary battery.

5. The use of a tin-silver-copper-aluminum quaternary alloy according to claim 4, characterized in that The secondary battery comprises a positive electrode, a negative electrode, a separator between the positive electrode and the negative electrode, and an electrolyte; the positive electrode comprises a positive electrode active material and a positive electrode current collector.

6. The use of a tin-silver-copper-aluminum quaternary alloy according to claim 5, characterized in that The positive electrode active material is lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium cobalt oxide, sodium vanadium phosphate, Prussian blue or layered oxide; the positive electrode current collector is one of carbon-coated aluminum foil, carbon-coated copper foil, carbon-coated iron foil, carbon-coated tin foil, carbon-coated zinc foil, carbon-coated nickel foil, carbon-coated titanium foil, carbon-coated manganese foil, a composite of any one of these metals, or an alloy of any one of these metals.

7. The use of a tin-silver-copper-aluminum quaternary alloy according to claim 5, characterized in that The diaphragm is a porous polymer film or an inorganic porous film; the porous polymer film is a porous polypropylene film, a porous polyethylene film or a composite film of porous polypropylene and porous polyethylene; the inorganic porous film is a glass fiber paper or a porous ceramic diaphragm; the electrolyte includes an electrolyte and a solvent, the electrolyte is a lithium salt or sodium salt electrolyte, and the solvent is selected from one or more of esters, sulfones, ethers, nitriles and ionic liquid organic solvents; the concentration of the electrolyte is 0.1 mol / L~10 mol / L.

8. The use of a tin-silver-copper-aluminum quaternary alloy according to claim 7, characterized in that The electrolyte includes lithium hexafluorophosphate, lithium chloride, lithium fluoride, lithium sulfate, lithium carbonate, lithium phosphate, lithium nitrate, lithium difluorooxalatoborate, lithium pyrophosphate, lithium dodecylbenzenesulfonate, lithium dodecyl sulfate, trilithium citrate, lithium metaborate, lithium borate, lithium molybdate, lithium tungstate, lithium bromide, lithium nitrite, lithium iodate, lithium iodide, lithium silicate, lithium ligninsulfonate, lithium oxalate, lithium aluminate, lithium methanesulfonate, lithium acetate, lithium dichromate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonyl imide, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalatoborate, sodium pyrophosphate, dodecylbenzenesulfonate Sodium, sodium lauryl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium silicate, sodium ligninsulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium perchlorate, sodium trifluoromethanesulfonimide, sodium trifluoromethanesulfonate and sodium bistrifluoromethanesulfonimide; the solvent includes propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N,N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-Dioxolane, 4-methyl-1,3-dioxolane, dimethoxymethane, 1,2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, crown ether (12-crown-4), 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bis(trifluoromethylsulfonyl)imide, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3 One or more of 1-butyl-1-methylimidazole-bis(trifluoromethylsulfonyl)imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bis(trifluoromethylsulfonyl)imide salt, N-butyl-N-methylpyrrolidine-bis(trifluoromethylsulfonyl)imide salt, 1-butyl-1-methylpyrrolidine-bis(trifluoromethylsulfonyl)imide salt, N-methyl-N-propylpyrrolidine-bis(trifluoromethylsulfonyl)imide salt, N-methylpropylpiperidine-bis(trifluoromethylsulfonyl)imide salt and N-butyl-N-methylpiperidine-bis(trifluoromethanesulfonyl)imide salt.

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