Preparation method of intercalation type negative electrode material MoS2-M of rechargeable aqueous zinc ion battery
By preparing MoS2-M materials doped with transition metals, the resource constraints and zinc dendrite problems of lithium-ion batteries were solved, achieving high capacity and improved safety of zinc-ion batteries. This broadened the zinc ion transport path and solved the problems of zinc dendrite growth and low material utilization.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN UNIV
- Filing Date
- 2023-12-06
- Publication Date
- 2026-06-19
AI Technical Summary
Existing lithium-ion batteries suffer from limited lithium resources, high costs, and the high risk of organic electrolytes. The growth of zinc dendrites leads to poor cycle stability and safety of zinc-ion batteries. Pure MoS2 has weak Zn2+ storage capacity and low material utilization.
Intercalated anode materials were prepared by using MoS2-M material doped with transition metal elements through a programmed temperature-controlled hydrothermal reaction, which widened the interlayer spacing and improved zinc ion transport efficiency and storage capacity.
It significantly improves the specific capacity and electrochemical performance of zinc-ion batteries, reduces costs, enhances safety and stability, and widens the interlayer spacing of MoS2 to provide a better transport path for Zn2+.
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Figure CN117658215B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrochemistry and relates to anode materials for aqueous zinc-ion batteries, specifically to a method for preparing MoS2-M, an intercalated anode material for rechargeable aqueous zinc-ion batteries. Background Technology
[0002] Lithium-ion batteries (LIBs) are currently mainly used for large-scale energy storage and energy storage in portable electronic devices. However, as the demand for energy storage batteries continues to increase, the availability of lithium metal in the environment is limited, the cost is high, and the organic electrolytes used in lithium-ion batteries are relatively hazardous. To improve this situation, researchers have begun to search for metals that are low-cost and have good stability. Among them, Zn... 2 + Mg 2+ Al 3+ K + Plasma batteries are increasingly being used in research. Aqueous rechargeable zinc-ion batteries (ARZIBs) are low-cost, and their electrolyte contains zinc. 2+ An aqueous solution of Zn 2+ As a multi-electron ion, it has higher theoretical and volumetric capacity, making it a good alternative to LIB for large-scale energy storage.
[0003] Initially, zinc was used as the negative electrode in zinc-ion batteries (ZIBs), but during the charging and discharging process, Zn... 2+ Uneven deposition of zinc dendrites on the zinc electrode surface not only accelerates the corrosion of zinc in the electrolyte but can also puncture the separator, leading to a short circuit and reducing cycle stability and coulombic efficiency. Accompanying dendrite formation are other side reactions; for example, zinc corrosion in aqueous solution wastes electrolyte, and the hydrogen evolution reaction produces hydrogen gas, further reducing overall device safety and shortening battery life. Although most tests still use zinc as the negative electrode material, the redox reaction only occurs on the zinc surface, resulting in an overall material utilization rate of less than 5%. Researchers have therefore optimized zinc electrodes through structural design and surface optimization. While this avoids zinc dendrite growth and reduces side reactions, increasing the interface layer also affects the electrode's mass transfer efficiency. Consequently, intercalated materials have gained increasing attention due to their high ion and electron transport efficiency, good structural and chemical stability, open layered or porous structures, and numerous active sites to accommodate zinc ions. Among these, molybdenum disulfide (MoS2), with its layered structure, has attracted widespread interest.
[0004] Molybdenum disulfide (MoS2) crystals are composed of multiple molybdenum disulfide atoms, with each Mo atom bonded to two S atoms. The molybdenum disulfide layers are connected by van der Waals forces, allowing them to slide relative to each other, thus making them suitable as a lubricant. Furthermore, due to its two-dimensional layered structure, it can also be used as a substrate for Zn.2+ H + It provides a transport path for Zn, and is therefore often used in the research of electrode materials and supercapacitors. However, pure-phase MoS2 provides a transport path for Zn. 2+ Its storage capacity is relatively weak. Summary of the Invention
[0005] To address the problems existing in the prior art, this invention relates to a novel method for preparing aqueous zinc-ion battery anode materials, specifically molybdenum disulfide (MoS2-M) doped with metallic elements. The technical solution adopted by this invention is as follows:
[0006] A method for preparing MoS2-M, an intercalated anode material for rechargeable aqueous zinc-ion batteries, is described below.
[0007] (1) Weigh the molybdenum source, sulfur source and compound containing doped transition metal element M into a small beaker, so that the molar ratio of molybdenum atoms to sulfur atoms reaches 1:3 to 1:5. Add 30 mL of deionized water to the small beaker and stir for 30 to 60 min until the solution system is stable.
[0008] (2) Transfer the obtained solution to a 50mL hydrothermal reactor, place it in a forced-air drying oven, and react at 140-170℃ for 16-18h. Then raise the temperature to 190-220℃ and react for 4-8h.
[0009] (3) After the hydrothermal reactor is cooled to room temperature, the obtained product is washed with deionized water and ethanol 2 to 5 times respectively, and the black precipitate is collected by centrifugation at 800 to 1400 rpm.
[0010] (4) The black precipitate was transferred to a vacuum drying oven and dried at 50-70°C for 10-24 hours to obtain the product MoS2-M.
[0011] The electrode sheet was coated using the MoS2-M material prepared above. The preparation process of the electrode sheet is as follows:
[0012] The product MoS2-M, acetylene black, and polyvinylidene fluoride (PVDF) were dissolved in N-methylpyrrolidone (NMP) at a mass ratio of 7:2:1. The mixture was then ground in an agate mortar for 15–60 min to prepare a slurry. The slurry was then uniformly coated onto a copper foil and transferred to a vacuum drying oven. The foil was dried at 50–70 °C for 8–12 h to obtain a negative electrode sheet. After drying, the active material on the electrode sheet reached 2–4 mg.
[0013] The aqueous zinc-ion battery negative electrode sheet prepared above is used to assemble the battery.
[0014] The assembly uses the MoS2-M material prepared above as the negative electrode, a zinc sheet as the counter electrode, and 90–160 μL of 3 mol·L⁻¹ electrolyte.-1 A 2032-type half-cell with zinc trifluoromethanesulfonate (Zn(CF3SO3)2) and a glass fiber diaphragm. The scan rate was 5 mV·s. -1 Cyclic voltammetry tests were performed on the battery at a potential range of 0.2–1.2 V, at a voltage of 0.1 A·g. -1 The battery was then subjected to a constant current charge-discharge test.
[0015] When assembled into a battery, its specific capacity is significantly improved compared to using pure MoS2 as a negative electrode material in zinc-ion batteries.
[0016] Furthermore, in step (1), the molybdenum source is either ammonium molybdate or sodium molybdate.
[0017] Furthermore, in step (1), the sulfur source is either thiourea or thioacetamide.
[0018] Furthermore, in step (1), the transition metal elements M = La, Mn, Co.
[0019] Furthermore, in step (1), the amount of M added is 1% of the molar mass of Mo.
[0020] Compared with existing technologies, the preparation method, materials, and properties of MoS2-M used in this invention have the following advantages:
[0021] (1) Zinc-ion batteries have the advantages of lower cost and safer and more stable electrolyte compared to lithium-ion batteries, providing diversity for energy storage batteries.
[0022] (2) This material is synthesized by a hydrothermal reaction with programmed temperature rise, which is low in cost, simple in synthesis process and highly operable.
[0023] (3) This material is made by doping pure MoS2 with metal element M. Compared with pure MoS2, it has a larger capacity and higher specific capacity, showing excellent electrochemical performance. Attached Figure Description
[0024] Figure 1 This is a comparison of the XRD patterns of MoS2-La and MoS2;
[0025] Figure 2 These are MoS2 and MoS2-LaSEM images; the left side is MoS2, and the right side is MoS2-La.
[0026] Figure 3 It is MoS2-La and MoS2 at 5mV·s -1 The following is a CV diagram;
[0027] Figure 4 It is MoS2-La and MoS2 at 0.1 A·g -1 The following GCD diagram;
[0028] Figure 5 It is the reaction of MoS2-Mn with MoS2 at 5 mV·s -1 The following is a CV diagram;
[0029] Figure 6 It is MoS2-Mn and MoS2 at 0.1 A·g -1 The GCD diagram below. Detailed Implementation
[0030] The following examples are provided to better understand the present invention, but are not intended to limit the invention. Unless otherwise specified, all materials and reagents used in the following examples can be purchased from biological or chemical reagent companies.
[0031] Example 1
[0032] 1.5 g of ammonium molybdate and 2.5 g of thiourea were dissolved in 40 mL of deionized water and stirred for 1 h. The resulting solution was transferred to a 50 mL hydrothermal reactor and placed in a forced-air drying oven, where it was reacted at 180 °C for 24 h. After the hydrothermal reactor cooled to room temperature, the resulting product was washed three times with deionized water and ethanol, respectively, and centrifuged to collect a black precipitate. The product was transferred to a vacuum drying oven and dried at 40 °C for 24 h to obtain MoS2.
[0033] 1.5 g of ammonium molybdate, 2.5 g of thiourea, and 30 mg of La(NO3)3 were dissolved in 40 mL of deionized water and stirred for 1 h. The resulting solution was transferred to a 50 mL hydrothermal reactor and placed in a forced-air drying oven. The reaction was carried out at 140 °C for 14 h, and then the temperature was increased to 180 °C for 10 h. After the hydrothermal reactor cooled to room temperature, the resulting product was washed three times with deionized water and ethanol, and the black precipitate was collected by centrifugation. The product was transferred to a vacuum drying oven and dried at 40 °C for 24 h to obtain MoS2-La. The XRD images of MoS2 before and after doping in Example 1 are shown below. Figure 1 As shown, the MoS2 image corresponds to the standard card JCPDS#17-0744, indicating that the MoS2 purity is high. The XRD peak shifts to the left after La doping, indicating that the MoS2 unit cell deforms after doping, suggesting that La has entered the MoS2. SEM tests were performed on MoS2 before and after doping, and the images are shown below. Figure 2 As shown, both MoS2 and MoS2-La images exhibit petal-like nanostructures and have similar morphologies before and after doping.
[0034] To prepare the negative electrode, the two products mentioned above, acetylene black, and PVDF were dissolved in NMP at a ratio of 7:2:1. The mixture was then ground in an agate mortar for 30 minutes to prepare a slurry. This slurry was coated onto a copper foil and transferred to a vacuum drying oven. After drying at 40°C for 12 hours, the MoS2-La negative electrode was obtained.
[0035] Using MoS2-La as the negative electrode and a zinc sheet as the counter electrode, the electrolyte was 100 μL of 3 mol·L⁻¹. -1 A 2032 model half-cell was assembled using zinc trifluoromethanesulfonate (Zn(CF3SO3)2) and a glass fiber membrane as the separator. The cell operates at 5 mV·s. -1 CV tests were performed on half-cells using MoS2 and MoS2-La as anode materials at a scan rate, and the results are as follows: Figure 3 As shown, the capacity of MoS2-La is significantly improved compared to pure MoS2. At 0.1 A·g -1 GCD tests were performed on half-cells using MoS2 and MoS2-La as anode materials under current, and the results are as follows: Figure 4 As shown, the battery specific capacity ranges from 35 mAh·g -1 Increased to 130mAh·g -1 This indicates that the presence of La improves the specific capacity of zinc-ion batteries using MoS2 as the negative electrode, by widening the interlayer spacing of MoS2, thus facilitating the formation of Zn. 2+ H + The transfer provides a path and improves Zn 2+ Storage capacity.
[0036] Example 2
[0037] 1.5 g of ammonium molybdate and 2.5 g of thiourea were dissolved in 40 mL of deionized water and stirred for 1 h. The resulting solution was transferred to a 50 mL hydrothermal reactor and placed in a forced-air drying oven, where it was reacted at 180 °C for 24 h. After the hydrothermal reactor cooled to room temperature, the resulting product was washed three times with deionized water and ethanol, respectively, and centrifuged to collect a black precipitate. The product was transferred to a vacuum drying oven and dried at 40 °C for 24 h to obtain MoS2.
[0038] 1.5 g of ammonium molybdate, 2.5 g of thiourea, and 30 mg of MnSO4 were dissolved in 40 mL of deionized water and stirred for 1 h. The resulting solution was transferred to a 50 mL hydrothermal reactor and placed in a forced-air drying oven. The reaction was carried out at 140 °C for 14 h, and then the temperature was increased to 180 °C for 10 h. After the hydrothermal reactor cooled to room temperature, the product was washed three times with deionized water and ethanol, respectively, and the black precipitate was collected by centrifugation. The product was transferred to a vacuum drying oven and dried at 40 °C for 24 h to obtain MoS2-Mn.
[0039] To prepare the negative electrode, the two products mentioned above, acetylene black, and PVDF were dissolved in NMP at a ratio of 7:2:1. The mixture was then ground in an agate mortar for 30 minutes to prepare a slurry. This slurry was coated onto a copper foil and transferred to a vacuum drying oven. After drying at 40°C for 12 hours, the MoS2-Mn negative electrode was obtained.
[0040] Using MoS2-Mn as the negative electrode and zinc sheet as the counter electrode, the electrolyte is 100 μL of 3 mol·L⁻¹. -1 A 2032 model half-cell was assembled using zinc trifluoromethanesulfonate (Zn(CF3SO3)2) and a glass fiber membrane as the separator. The cell operates at 5 mV·s. -1 CV tests were performed on half-cells using MoS2 and MoS2-Mn as anode materials at a scan rate, and the results are as follows: Figure 2 As shown, the capacity of MoS2-Mn is significantly improved compared to pure MoS2. At 0.1 A·g -1 The GCD of half-cells using MoS2 and MoS2-Mn as anode materials was tested under current, and the results are as follows: Figure 6 As shown, the battery specific capacity ranges from 35 mAh·g -1 Increased to 65mAh·g -1 This indicates that the introduction of Mn improves the specific capacity of zinc-ion batteries using MoS2 as the negative electrode, by widening the interlayer spacing of MoS2, thus facilitating the addition of Zn. 2+ H + The transfer provides a path and improves Zn 2+ Storage capacity.
[0041] Example 3
[0042] 1.5 g of ammonium molybdate and 2.5 g of thiourea were dissolved in 40 mL of deionized water and stirred for 1 h. The resulting solution was transferred to a 50 mL hydrothermal reactor and placed in a forced-air drying oven, where it was reacted at 180 °C for 24 h. After the hydrothermal reactor cooled to room temperature, the resulting product was washed three times with deionized water and ethanol, respectively, and centrifuged to collect a black precipitate. The product was transferred to a vacuum drying oven and dried at 40 °C for 24 h to obtain MoS2.
[0043] 1.5 g of ammonium molybdate, 2.5 g of thiourea, and 30 mg of Co(NO3)2 were dissolved in 40 mL of deionized water and stirred for 1 h. The resulting solution was transferred to a 50 mL hydrothermal reactor and placed in a forced-air drying oven. The reaction was carried out at 140 °C for 14 h, and then the temperature was increased to 180 °C for 10 h. After the hydrothermal reactor cooled to room temperature, the product was washed three times with deionized water and ethanol, respectively, and the black precipitate was collected by centrifugation. The product was transferred to a vacuum drying oven and dried at 40 °C for 24 h to obtain MoS2-Co.
[0044] To prepare the negative electrode, the two products mentioned above, acetylene black, and PVDF were dissolved in NMP at a ratio of 7:2:1. The mixture was then ground in an agate mortar for 30 minutes to prepare a slurry. This slurry was coated onto a copper foil and transferred to a vacuum drying oven. After drying at 40°C for 12 hours, the MoS2-Co negative electrode was obtained.
[0045] Using MoS2-Co as the negative electrode and zinc sheet as the counter electrode, the electrolyte was 100 μL of 3 mol·L⁻¹. -1 Zinc trifluoromethanesulfonate (Zn(CF3SO3)2), with a glass fiber diaphragm, is used to assemble a 2032 model half-cell.
[0046] The metallic elements applicable to this invention are not limited to the several mentioned in the above embodiments, as will be readily understood by those skilled in the art. However, the scope of protection of this invention is not limited thereto. Any modifications, equivalent substitutions, and improvements made within the technical scope of this invention should be included within the scope of protection of this invention.
Claims
1. A method for preparing an intercalation type anode material MoS2-M of a rechargeable aqueous zinc ion battery, characterized in that, Includes the following steps: (1) Weigh the molybdenum source, sulfur source and compound containing doped transition metal element M into a small beaker, so that the molar ratio of molybdenum atoms to sulfur atoms reaches 1:3~1:
5. Add 30 mL of deionized water to the small beaker and stir for 30~60 min until the solution system is stable; transition metal element M = La or Mn or Co; (2) Transfer the obtained solution to a 50 mL hydrothermal reactor, place it in a forced-air drying oven, and react at 140~170 ℃ for 16~18 h, then raise the temperature to 190~220 ℃ and react for 4~8 h; (3) After the hydrothermal reactor is cooled to room temperature, the obtained product is washed with deionized water and ethanol 2 to 5 times respectively, and the black precipitate is collected by centrifugation at 800 to 1400 rpm. (4) The black precipitate was transferred to a vacuum drying oven and dried at 50-70 °C for 10-24 h to obtain the product MoS2-M; The electrode sheet was coated using MoS2-M, and the preparation process of the electrode sheet is as follows: The product MoS2-M, acetylene black and polyvinylidene fluoride were dissolved in N-methylpyrrolidone in a mass ratio of 7:2:1 and ground for 15-60 min to prepare a slurry. The slurry was uniformly coated onto copper foil and dried at 50-70 ℃ for 8-12 h to obtain a negative electrode sheet. After drying, the active material on the electrode sheet reached 2-4 mg. The electrode sheet was assembled into a battery with MoS2-M material as the negative electrode, zinc sheet as the counter electrode, and 90-160 μL of 3 mol·L -1 Zinc trifluoromethanesulfonate, 2032 type half battery with glass fiber diaphragm as diaphragm.
2. The preparation method of the intercalation type anode material MoS2-M of the rechargeable aqueous zinc ion battery according to claim 1, characterized in that, In step (1), the molybdenum source is either ammonium molybdate or sodium molybdate.
3. The method for preparing the intercalated negative electrode material MoS2-M for a rechargeable aqueous zinc-ion battery according to claim 1, characterized in that, In step (1), the sulfur source is either thiourea or thioacetamide.
4. The preparation method of the intercalation type anode material MoS2-M of the rechargeable aqueous zinc ion battery according to claim 1, characterized in that, In step (1), the amount of M added is 1% of the molar mass of Mo.