WO2023016124A1 - 一种层状金属氧化物 / 胺复合材料及其制备方法与在镁离子电池中的应用 - Google Patents

一种层状金属氧化物 / 胺复合材料及其制备方法与在镁离子电池中的应用 Download PDF

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WO2023016124A1
WO2023016124A1 PCT/CN2022/102446 CN2022102446W WO2023016124A1 WO 2023016124 A1 WO2023016124 A1 WO 2023016124A1 CN 2022102446 W CN2022102446 W CN 2022102446W WO 2023016124 A1 WO2023016124 A1 WO 2023016124A1
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oxide
metal oxide
composite material
amine
amine compound
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French (fr)
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耿凤霞
杨金霖
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Suzhou University
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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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of batteries, in particular to a layered metal oxide/amine composite material, a preparation method thereof and an application in magnesium ion batteries.
  • magnesium-ion batteries can obtain high specific capacity and energy density through the two-electron redox process, are cheap and safe, and have important application prospects in large-scale energy storage, electric vehicles and other fields.
  • the high charge density of divalent magnesium ions leads to slow solid-state diffusion, and conventional electrode materials cannot achieve high-performance magnesium ion storage.
  • Transition metal oxides have the advantages of high theoretical capacity, high redox potential, and low cost, and are ideal magnesium storage materials.
  • there are usually problems such as low capacity, poor rate and cycle performance, which limit the development of magnesium-ion batteries.
  • the purpose of the present invention is to disclose a layered metal oxide/amine composite material, and use it as a positive electrode active material for magnesium ion batteries; by designing the layered metal oxide/amine compound composite material, the stacking structure of the material can be regulated , to solve the problem of slow diffusion of highly charged magnesium ions in the material lattice.
  • the technical scheme adopted in the present invention is as follows: a layered metal oxide/amine composite material prepared from anionic metal oxide and amine compound. Specifically, the anionic metal oxide solution and the amine compound solution are mixed to obtain a precipitate; then the precipitate is dried to obtain a layered metal oxide/amine composite material.
  • the anionic metal oxide solution and the amine compound solution are mixed to obtain a precipitate; this is the inventiveness of the present invention.
  • the present invention uses a sheet-shaped anionic metal oxide and an amine compound as raw materials. A layered material is obtained.
  • the drying is freeze-drying, and the water is sublimated to remove.
  • the specific process parameters are not limited, and the conventional powder freeze-drying can be followed.
  • the invention discloses the application of the layered metal oxide/amine composite material in the preparation of metal ion batteries, preferably magnesium ion batteries.
  • the layered metal oxide/amine composite material disclosed for the first time in the invention is used as an active material for the positive electrode of a metal ion battery, and maximizes the high electrochemical activity of the metal oxide material.
  • the anionic metal oxide is one of titanium oxide, manganese oxide, niobium oxide, niobium titanium oxide, molybdenum oxide, tantalum oxide, and tungsten oxide; specifically, the titanium oxide is Ti 1 ⁇ n O 2 4n ⁇ , 0 ⁇ n ⁇ 1; manganese oxide is MnO 2 x ⁇ , 0 ⁇ x ⁇ 1; niobium oxide is Nb 6 O 17 4 ⁇ , Nb 3 O 8 ⁇ , LaNb 2 O 7 ⁇ , Ca 2 Nb 3 O 10 ⁇ ; the niobium titanium oxide is TiNbO 5 ⁇ , TiNb 6 O 5 5- , Ti 2 NbO 7 ⁇ or Ti 5 NbO 14 3 ⁇ ; the molybdenum oxide is MoO 2 - ; the oxide Tantalum is TaO 3 ⁇ ; the tungsten oxide is W 2 O 7 2 ⁇ , Cs 4 W 11 O 36 2 ⁇ .
  • the amine compound is a small molecular amine compound, which is a monoamine or a diamine, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine Amine, isopentylamine, sec-amylamine, tert-amylamine, n-hexylamine, n-heptylamine, n-octylamine, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octyl Diamine etc.
  • a monoamine or a diamine such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutyl
  • the amine compound is an alkylamine, preferably a straight-chain alkylamine, more preferably a straight-chain alkyl monoamine, preferably n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine.
  • both the anionic metal oxide solution and the amine compound solution are aqueous solutions; in the anionic metal oxide aqueous solution, the total concentration of the anionic metal oxide is 1-8 mg/mL; in the amine compound aqueous solution, the amine compound The volume concentration is 0.1-10%. The volume ratio of the anionic metal oxide solution to the amine compound solution is 1: (0.8-1.2).
  • the invention discloses a positive electrode of a metal ion battery, which includes a current collector and a positive electrode material located on the current collector.
  • the positive electrode material includes the above-mentioned layered metal oxide/amine composite material, a conductive agent, and a binder; , Adhesives are existing products.
  • the invention discloses a metal ion battery, which comprises the positive pole of the above metal ion battery, an electrolyte, a diaphragm and a negative pole, wherein the electrolyte, the diaphragm and the negative pole are all existing products.
  • the preparation method of the positive electrode of the metal ion battery and the metal ion battery disclosed in the present invention is a conventional technology, which may include the following steps: mixing the above-mentioned layered metal oxide/amine composite material with a conductive agent and a binder in a solvent, and mixing evenly Apply it on the current collector and dry it to form the positive electrode of the metal ion battery; then combine it with the metal negative electrode, diaphragm and electrolyte to obtain the metal ion battery.
  • Metal ion batteries are magnesium ion batteries, lithium ion batteries, sodium ion batteries, zinc ion batteries, and the like.
  • the invention utilizes the interlayer regulating effect of the amine compound on the metal oxide, maintains the stability of the layered structure, and maximizes the high electrochemical activity of the metal oxide material.
  • this material is applied to magnesium-ion batteries, the performance is greatly improved, and the specific capacity reaches 260 mAh/g, the maximum rate is 5 A/g, the charge and discharge cycle can reach 2000 times, and it can work stably in the temperature range of -15°C ⁇ +55°C.
  • the problem of poor rate and cycle performance of the existing magnesium-ion battery due to slow ion solid-state diffusion is solved.
  • Figure 1 is an AFM image of titanium oxide nanosheets.
  • Fig. 2 is the photograph that the titanium oxide solution is mixed with the aqueous solutions of acrylic, butyl, pentamyl, hexyl, and heptylamine compounds respectively.
  • Fig. 3 is the XRD pattern of the titanium oxide/alkylamine composite material.
  • Figure 4 is the SEM image of the titanium oxide/hexylamine composite material.
  • Fig. 5 is a cross-sectional HRTEM image of the titanium oxide/hexylamine composite material.
  • Fig. 6 is the FTIR and Raman diagram of the titanium oxide/hexylamine composite material.
  • Fig. 7 is a static photo of titanium oxide solution mixed with other amine compound aqueous solutions.
  • FIG. 8 is a graph of the rate performance and cycle performance of the magnesium ion battery of Example 3.
  • FIG. 8 is a graph of the rate performance and cycle performance of the magnesium ion battery of Example 3.
  • FIG. 9 is a performance diagram of the temperature-varying test and the GITT test of the magnesium-ion battery of Example 3.
  • FIG. 9 is a performance diagram of the temperature-varying test and the GITT test of the magnesium-ion battery of Example 3.
  • Figure 10 is a diagram of the electrochemical performance of pristine pure titanium oxide.
  • Figure 11 is a diagram of the rate performance and cycle performance of titanium oxide/propylamine, titanium oxide/butylamine, titanium oxide/pentylamine, titanium oxide/hexylamine, and titanium oxide/heptylamine composite materials.
  • Figure 12 is the XRD and charge-discharge curves of titanium oxide and metal ion flocculation materials.
  • Fig. 13 is a diagram of the electrochemical performance of the manganese oxide/hexylamine composite material.
  • the raw material of the present invention is all commercially available products or the product disclosed in existing literature, and concrete preparation method and test method are all conventional methods in this field;
  • Such as amine compound comes from Aladdin, ⁇ 99%, all liquid.
  • the inventiveness of the present invention lies in the use of small molecular amine compounds and anionic metal oxides as raw materials at room temperature to prepare layered metal oxide/amine composite materials, which are used as active materials for magnesium ion batteries, and the performance is greatly improved.
  • the magnesium-ion battery performance test uses a standard battery test system with a current range of 1 mA to 10 mA.
  • the battery temperature test uses a constant temperature test box, and the temperature range can be set from -30°C to 100°C.
  • Preparation example for the preparation of anionic metal oxides, refer to the inventor’s published patents. Take the preparation of Ti 1.74 O 4 1.04- as an example. Obtained through conventional means such as purchase and gift.
  • the preparation of titanium oxide Ti 1.74 O 4 1.04- colloidal aqueous solution is as follows: mix TiO 2 , K 2 CO 3 , and Li 2 CO 3 in a molar ratio of 10.4:2.4:0.8, and place them in a muffle furnace for calcination at 800°C for 20 hours , to obtain a layered titanate precursor; the precursor was dispersed in 0.5 M hydrochloric acid solution and stirred for 72 hours for protonation treatment, during which a new hydrochloric acid solution was replaced every 24 hours; after protonation treatment, it was washed with water, suction filtered, and dried.
  • the filter cake was dispersed in tetramethylammonium hydroxide aqueous solution (25wt%) and shaken for 7 days, and then centrifuged to obtain titanium oxide (Ti 1.74 O 4 1.04- ) colloidal aqueous solution, and the concentration was adjusted to 5.0 mg ml - 1 for the following experiments.
  • the above titanium oxide colloidal aqueous solution was dropped on the silicon substrate, and then naturally dried in the air to obtain a silicon substrate loaded with titanium oxide nanosheets, which was characterized by an atomic force microscope (AFM), as shown in Figure 1.
  • AFM atomic force microscope
  • Example 1 At room temperature, 5 mg/mL Ti 0.87 O 2 0.52- water solution (40mL) and 40mL amine compound aqueous solution (0.2mL amine compound) were stirred and mixed for 20 hours and then allowed to stand for 15 minutes. Obvious separation occurred, as As shown in Figure 2; the lower layer of solid was removed, centrifuged and washed with water, then freeze-dried for 48 hours (cold trap temperature -60°C), to obtain a layered metal oxide/amine composite material, solid powder.
  • amine compounds are n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and the corresponding products are titanium oxide/propylamine composite materials, titanium oxide/butylamine composite materials, titanium oxide/pentylamine composite materials, Titanium oxide/hexylamine composite material, titanium oxide/heptylamine composite material, as active materials.
  • Figure 3 is the X-ray diffraction (XRD) pattern of the composite material, which reflects that the material has a large spacing.
  • Figure 4 is a scanning electron microscope (SEM) image of the titanium oxide/hexylamine composite.
  • Figure 5 is a high-resolution transmission electron microscope (HRTEM) image of the titanium oxide/hexylamine composite material, reflecting that the material has a layered stacked structure.
  • Figure 6 is the infrared spectrum (FTIR) and Raman spectrum (Raman) of the titanium oxide/hexylamine composite material, which proves that titanium oxide and hexylamine are successfully composited. If the above-mentioned lower layer solid is heated and dried instead of freeze-dried, the obtained product will be agglomerated and cannot show the accumulation morphology, that is, no layered composite material is obtained.
  • Example 2 At room temperature, mix 5 mg/mL Ti 0.87 O 2 0.52- water solution (40 mL) with 40 mL of methylamine, ethylamine, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine The amine aqueous solution (0.2 mL of the amine compound) was stirred and mixed for 20 hours and then left to stand for 15 minutes. As shown in Figure 7, no flocculation and stratification occurred, and a layered composite material could not be obtained.
  • Example 3 Mix titanium oxide/hexylamine composite material powder with Super P and PVDF binder in NMP at a mass ratio of 8:1:1, stir evenly, apply on titanium foil, and dry in a vacuum oven at 60°C After 12 hours, a positive electrode sheet was obtained, and the loading amount of the active material on the electrode was controlled at 1 mg/cm 2 .
  • FIG. 8 is the rate performance and cycle performance test chart of the above-mentioned magnesium-ion battery. At a low rate of 0.05 A/g, the specific capacity of the battery can reach 260 mAh/g, and the highest rate can reach 5 A/g, and the capacity can still maintain 100 mAh/g.
  • Fig. 9 is a diagram of the variable temperature test and ion diffusion test of the above-mentioned magnesium-ion battery.
  • the battery can work stably in the temperature range of -15°C to +55°C, and has practical application value.
  • the diffusion calculation of magnesium ions in the composite material can be determined by the galvanostatic intermittent titration technique (GITT).
  • the test results show that the diffusion rate at room temperature reaches 10 -8 ⁇ 10 -10 cm 2 s -1 , even at a low temperature of -15°C
  • the magnitude of 10 -9 ⁇ 10 -11 cm 2 s -1 can still be maintained at a low temperature, which reflects that the prepared composite material can provide a fast transmission path for magnesium ions and ensure the high performance of magnesium ion batteries.
  • FIG. 10 is the rate performance and cycle performance test chart of the test. At a low rate of 0.05 A/g, only 35 mAh/g low capacity, and can only cycle 50 times.
  • Embodiment 4 replace the titanium oxide/hexylamine composite material in Embodiment 3 with titanium oxide/propylamine composite material, titanium oxide/butylamine composite material, titanium oxide/amylamine composite material, titanium oxide/heptylamine composite material, With the rest unchanged, magnesium-ion batteries based on different active materials are obtained.
  • Figure 11 is the tested rate performance and cycle performance test chart, and the titanium oxide/hexylamine composite material shows the best performance.
  • Comparative example 5 mg/mL Ti 0.87 O 2 0.52- aqueous solution and 0.1 mol/L nitrate aqueous solution were mixed with 40 mL each to obtain a mixed solution. After standing still, the lower layer of precipitate was freeze-dried to obtain a solid powder of the composite material.
  • the solid powder of the composite material, Super P and PVDF binder were mixed in NMP at a mass ratio of 8:1:1, stirred evenly, coated with titanium foil, and dried in a vacuum oven at 60°C for 12 hours to obtain a positive electrode sheet.
  • a 2032-type button battery was assembled by assembling the positive electrode sheet with the metal magnesium foil as the negative electrode, the separator (Whatman GF/D), and the electrolyte (0.4 M 2PhMgCl-AlCl 3 /THF) to obtain a magnesium-ion battery (reference example 3) , the nitrate is lithium nitrate, sodium nitrate, potassium nitrate or magnesium nitrate.
  • Figure 12 shows the XRD pattern of the above-mentioned composite material and the performance diagram of the magnesium-ion battery. The interlayer spacing is small, and the battery can hardly be charged and discharged normally.
  • Example 5 Stir and mix 5 mg/mL MnO 2 0.4 ⁇ aqueous solution (40mL) and 40mL n-hexylamine aqueous solution (n-hexylamine is 0.2mL) for 20 hours, then let it stand for 15 minutes, remove the lower layer of solid and freeze-dry to obtain the solid of the composite material powder.
  • the material loading was controlled at 1 mg/cm 2 .
  • a 2032-type button battery was assembled by assembling the positive electrode sheet, the metal magnesium foil as the negative electrode, the separator (Whatman GF/D), and the electrolyte (0.4 M 2PhMgCl-AlCl 3 /THF), and a magnesium-ion battery was obtained.
  • Figure 13 is the rate performance and cycle performance test chart of the magnesium ion battery. The specific capacity of the battery reaches 105 mAh/g at a low rate of 0.05 A/g, and the highest rate can reach 0.5 A/g, and the capacity can still maintain 100 mAh/g. . And it can be cycled stably for 100 times at a rate of 0.1 A/g.
  • Example 6 At room temperature, 3mg/mL Ti 0.87 O 2 0.52- water solution (40mL) and 40mL n-hexylamine aqueous solution (0.1mL of the amine compound) were stirred and mixed for 20 hours and then allowed to stand for 15 minutes, and obvious stratification appeared; the lower layer was removed The solid is centrifugally washed with water and then freeze-dried to obtain a layered metal oxide/n-hexylamine composite material as a solid powder.
  • the above powder can be used to prepare positive electrode sheets, and further assembled into a magnesium ion battery.
  • the amine compound is combined with the anionic metal oxide for the first time, and the obtained layered material is used for the positive electrode of metal ions, especially magnesium ions, and has excellent performance as an active material.
  • the test results show that the diffusion rate at room temperature reaches 10 -8 ⁇ 10 -10 cm 2 s -1 , even at a low temperature of -15°C, it can still maintain the order of 10 -9 ⁇ 10 -11 cm 2 s -1 , reflecting The prepared composite material can provide a fast transport path for magnesium ions, ensuring the high-performance work of magnesium-ion batteries.

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Abstract

本发明公开了一种层状金属氧化物/胺复合材料及其制备方法与在镁离子电池中的应用。将阴离子型金属氧化物溶液与胺化合物溶液混合，得到沉淀；再将所述沉淀干燥，得到层状金属氧化物/胺复合材料。通过设计层状金属氧化物/胺类化合物复合材料，调控材料的堆积结构，将其作为正极活性材料用于镁离子电池，解决高电荷镁离子在材料晶格中扩散慢的问题，维持了层状结构的稳定性，最大程度发挥了金属氧化物材料的高电化学活性。

Description

一种层状金属氧化物/胺复合材料及其制备方法与在镁离子电池中的应用 技术领域
本发明涉及电池技术领域，具体涉及一种层状金属氧化物/胺复合材料及其制备方法与在镁离子电池中的应用。
 背景技术
随着全球化石燃料的消耗和环境问题的加剧，髙效的电化学储能装置己成为过去几十年的迫切需求。其中，镁离子电池通过两电子氧化还原过程可获得高比容量和能量密度，价格低廉且安全性高，在规模化储能、电动汽车等领域有重要应用前景。然而高电荷密度的二价镁离子导致固态扩散缓慢，常规的电极材料无法实现高性能镁离子存储。过渡金属氧化物具有高理论容量、高氧化还原电势、低成本等优点，是理想的储镁材料，但由于缺乏有效的结构组装和调控手段，过渡金属氧化物在镁离子电池中的应用仍十分有限，通常存在容量低、倍率和循环性能差等问题，限制了镁离子电池的发展。
 技术问题
本发明的目的是公开一种层状金属氧化物/胺复合材料，并将其作为正极活性材料用于镁离子电池；通过设计层状金属氧化物/胺类化合物复合材料，调控材料的堆积结构，解决高电荷镁离子在材料晶格中扩散慢的问题。
 技术解决方案
为达到上述目的，本发明采用的技术方案如下：一种层状金属氧化物/胺复合材料，由阴离子型金属氧化物、胺化合物制备得到。具体的，将阴离子型金属氧化物溶液与胺化合物溶液混合，得到沉淀；再将所述沉淀干燥，得到层状金属氧化物/胺复合材料。
优选的，室温下，将阴离子型金属氧化物溶液与胺化合物溶液混合，得到沉淀；这是本发明的创造性所在，本发明首次以片状阴离子型金属氧化物与胺化合物为原料，在室温下得到层状材料。
优选的，干燥为冷冻干燥，水升华去除，具体的工艺参数没有限制，遵循常规粉体冷冻干燥即可。
本发明公开了上述层状金属氧化物/胺复合材料在制备金属离子电池中的应用，优选为镁离子电池。本发明首次公开的层状金属氧化物/胺复合材料作为活性材料用于金属离子电池正极，最大程度发挥了金属氧化物材料的高电化学活性。
上述技术方案中，所述阴离子型金属氧化物为氧化钛、氧化锰、氧化铌、氧化铌钛、氧化钼、氧化钽、氧化钨中的一种；具体的，所述氧化钛为Ti 1−nO 2 4n−，0<n<1；氧化锰为MnO 2 x−，0<x<1；所述氧化铌为Nb 6O 17 4−、Nb 3O 8 −、LaNb 2O 7 −、Ca 2Nb 3O 10 −；所述氧化铌钛为TiNbO 5 −、TiNb 6O 5 5-、Ti 2NbO 7 − 或Ti 5NbO 14 3−；所述氧化钼为MoO 2 -；所述氧化钽为TaO 3 −；所述氧化钨为W 2O 7 2−、Cs 4W 11O 36 2−。
上述技术方案中，胺化合物为小分子胺化合物，为一元胺或者二元胺，比如甲胺、乙胺、正丙胺、异丙胺、正丁胺、异丁胺、仲丁胺、叔丁胺、正戊胺、异戊胺、仲戊胺、叔戊胺、正己胺、正庚胺、正辛胺、乙二胺、丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺等。优选的，胺化合物为烷基胺，优选直链烷基胺，更优选为直链烷基一元胺，优选正丙胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺。
上述技术方案中，阴离子型金属氧化物溶液与胺化合物溶液都为水溶液；其中阴离子型金属氧化物水溶液中，阴离子型金属氧化物的总浓度为1～8mg/mL；胺化合物水溶液中，胺化合物的体积浓度为0.1～10%。阴离子型金属氧化物溶液与胺化合物溶液的体积比为1∶（0.8～1.2）。
本发明公开了一种金属离子电池正极，包括集流体以及位于集流体上的正极材料，正极材料包括上述层状金属氧化物/胺复合材料、导电剂、粘接剂；其中集流体、导电剂、粘接剂都为现有产品。
本发明公开了一种金属离子电池，包括上述金属离子电池正极、电解液、隔膜、负极，其中电解液、隔膜、负极都为现有产品。
本发明公开的金属离子电池正极以及金属离子电池的制备方法为常规技术，可包括如下步骤：将上述层状金属氧化物/胺复合材料与导电剂、粘结剂混合于溶剂中，混合均匀后涂于集流体上，烘干形成金属离子电池正极；再与金属负极、隔膜、电解液常规组合，得到金属离子电池。金属离子电池为镁离子电池、锂离子电池、钠离子电池、锌离子电池等。
本发明利用了胺类化合物对金属氧化物的层间调控作用，维持了层状结构的稳定性，最大程度发挥了金属氧化物材料的高电化学活性。将该材料应用于镁离子电池时性能获得极大提升，比容量达到260 mAh/g，最大倍率为5 A/g，充放电循环可达2000次，并可在-15℃~+55℃温度范围内稳定工作。解决了现有镁离子电池由于离子固态扩散缓慢而导致倍率和循环性能差的问题。
 附图说明
图1为氧化钛纳米片的AFM图。
图2为氧化钛溶液分别与丙、丁、戊、己、庚胺化合物水溶液混合静置的照片。
图3为氧化钛/烷基胺复合材料的XRD图。
图4为氧化钛/己胺复合材料的SEM图。
图5为氧化钛/己胺复合材料的截面HRTEM图。
图6为氧化钛/己胺复合材料的FTIR和Raman图。
图7为氧化钛溶液与其他胺化合物水溶液混合静置照片。
图8为实施例三的镁离子电池的倍率性能和循环性能图。
图9为实施例三的镁离子电池的变温测试和GITT测试性能图。
图10为原始纯氧化钛的电化学性能图。
图11为氧化钛/丙胺、氧化钛/丁胺、氧化钛/戊胺、氧化钛/己胺、氧化钛/庚胺复合材料的倍率性能和循环性能图。
图12为氧化钛与金属离子絮凝材料的XRD和充放电曲线图。
图13为氧化锰/己胺复合材料的电化学性能图。
 本发明的实施方式
下面结合附图以及实施例对本发明作进一步描述：本发明的原料都是市售产品或者现有文献公开的产品，具体制备方法以及测试方法都为本领域常规方法；比如胺化合物来自Aladdin, ≥ 99%，都是液体。本发明的创造性在于室温下，利用小分子胺化合物与阴离子型金属氧化物为原料，制备层状金属氧化物/胺复合材料，作为活性材料用于镁离子电池，性能获得极大提升。
镁离子电池性能测试使用标准电池测试系统，电流量程为1 mA~10 mA。电池变温测试使用恒温测试箱，可设置温度范围为-30℃~100℃。
制备例：阴离子型金属氧化物的准备可参考发明人已经公开的专利，以Ti 1.74O 4 1.04-的制备为例，其余阴离子型氧化物可参照制备或者根据现有方法制备，也可通过市购、赠予等常规途径获得。
氧化钛Ti 1.74O 4 1.04-胶体水溶液的制备为如下步骤：将TiO 2、K 2CO 3、Li 2CO 3以摩尔比10.4:2.4:0.8混合，放置于马弗炉内800℃煅烧20小时，得到层状钛酸盐前驱体；将该前驱体分散于0.5 M盐酸溶液中搅拌72h进行质子化处理，期间每24小时更换新的盐酸溶液；质子化处理后经过水洗、抽滤、干燥，最后将滤饼分散于四甲基氢氧化铵水溶液（25wt%）中常规震荡7天，再进行离心清洗，得到氧化钛（Ti 1.74O 4 1.04-）胶体水溶液，用水调节浓度为5.0 mg ml -1，用于以下实验。
将上述氧化钛胶体水溶液滴在硅基板上，自然平铺后在空气自然晾干，得到负载氧化钛纳米片的硅基板，使用原子力显微镜（AFM）对其表征，如图1所示。
实施例一：室温下，将5 mg/mL Ti 0.87O 2 0.52-水溶液（40mL）与40mL胺化合物水溶液（胺化合物为0.2mL）搅拌混合20小时后静置15分钟，出现明显分层，如图2所示；取下层固体离心水洗后冷冻干燥48小时（冷阱温度-60℃），得到层状金属氧化物/胺复合材料，固体粉末。
上述胺化合物分别为正丙胺、正丁胺、正戊胺、正己胺、正庚胺，对应的产品为氧化钛/丙胺复合材料、氧化钛/丁胺复合材料、氧化钛/戊胺复合材料、氧化钛/己胺复合材料、氧化钛/庚胺复合材料，作为活性材料。图3为复合材料的X射线衍射（XRD）图，反映材料具有较大间距。
图4为氧化钛/己胺复合材料的扫描电子显微镜（SEM）图。图5为氧化钛/己胺复合材料的高分辨透射电镜（HRTEM）图，反映材料具有层状堆叠结构。图6为氧化钛/己胺复合材料的红外光谱（FTIR）和拉曼光谱（Raman）图，证明氧化钛与己胺成功复合。如果取上述下层固体加热烘干，而非冷冻干燥，得到的产品会团聚，不能显示出堆积形貌，即没有得到层状复合材料。
实施例二：室温下，将5 mg/mL Ti 0.87O 2 0.52-水溶液（40mL）分别与40mL的甲胺、乙胺、乙二胺、丙二胺、丁二胺、戊二胺、己二胺水溶液（胺化合物为0.2mL）搅拌混合20小时后静置15分钟，如图7所示，没有出现絮凝分层现象，无法得到层状复合材料。
实施例三：将氧化钛/己胺复合材料粉末与Super P和PVDF粘结剂按照8:1:1的质量比混合于NMP中，搅拌均匀后涂抹在钛箔上，于真空烘箱60℃干燥12小时，得到正极电极片，电极上活性材料负载量控制在1mg/cm 2。
采用常规方法，将上述正极电极片与作为负极的金属镁箔、隔膜（Whatman GF/D）、电解液（0.4 M 2PhMgCl-AlCl 3/THF）组装成2032型扣式电池，得到镁离子电池，进行常规测试。图8为上述镁离子电池的倍率性能和循环性能测试图，在0.05 A/g低倍率下该电池比容量达到260 mAh/g，最高倍率可达到5 A/g，容量仍可保持100 mAh/g；并且该电池可在室温下稳定循环长达2000次，说明具有非常优异的储镁性能。图9为上述镁离子电池的变温测试和离子扩散测试图，该电池可在-15℃～+55℃温度范围内稳定工作，具备实际应用价值。通过恒电流间歇滴定技术（GITT）可测定镁离子在复合材料内的扩散计算，测试结果表明在室温下的扩散率达到10 -8～10 -10 cm 2 s -1，即使在低温-15℃下仍可保持10 -9～10 -11 cm 2 s -1的量级，反映所制备的复合材料可提供镁离子的快速传输路径，保障了镁离子电池的高性能工作。
以纯氧化钛替换氧化钛/己胺复合材料粉末进行同样的实验作为对比，相比较，原始纯氧化钛作为正极材料所得到的镁离子电池显示极差的电化学性能。图10为测试的倍率性能和循环性能测试图，在0.05 A/g低倍率下仅可获得35 mAh/g低容量，且仅可循环50次。
实施例四：将实施例三中的氧化钛/己胺复合材料更换为氧化钛/丙胺复合材料、氧化钛/丁胺复合材料、氧化钛/戊胺复合材料、氧化钛/庚胺复合材料，其余不变，得到基于不同活性材料的镁离子电池。图11为测试的倍率性能和循环性能测试图，氧化钛/己胺复合材料显示最优性能。
对比例：将5 mg/mL Ti 0.87O 2 0.52-水溶液与0.1 mol/L硝酸盐水溶液各取40 mL混合后得到混合溶液，静置后取下层沉淀冷冻干燥，得到复合材料的固体粉末。将复合材料的固体粉末与Super P和PVDF粘结剂按照8:1:1的质量比混合于NMP中，搅拌均匀后涂抹与钛箔，于真空烘箱60℃干燥12小时，得到正极电极片。将正极电极片与作为负极的金属镁箔、隔膜（Whatman GF/D）、电解液（0.4 M 2PhMgCl-AlCl 3/THF）组装成2032型扣式电池，得到镁离子电池（参考实施例三），硝酸盐为硝酸锂、硝酸钠、硝酸钾或者硝酸镁。图12为上述复合材料的XRD图与镁离子电池性能图，层间距较小，电池几乎无法正常充放电。
实施例五：将5 mg/mL MnO 2 0.4−水溶液（40mL）与40mL正己胺水溶液（正己胺为0.2mL）搅拌混合20小时后静置15分钟，取下层固体冷冻干燥，得到复合材料的固体粉末。将复合材料的固体粉末与Super P和PVDF粘结剂按照8:1:1质量比混合于NMP中，搅拌均匀后涂抹与钛箔，于真空烘箱60℃干燥12小时，得到正极电极片，活性材料负载量控制在1mg/cm 2。将正极电极片与作为负极的金属镁箔、隔膜（Whatman GF/D）、电解液（0.4 M 2PhMgCl-AlCl 3/THF）组装成2032型扣式电池，得到镁离子电池。图13为镁离子电池的倍率性能和循环性能测试图，在0.05 A/g低倍率下该电池比容量达到105 mAh/g，最高倍率可达到0.5 A/g，容量仍可保持100 mAh/g。并可在0.1 A/g倍率下稳定循环100次。
实施例六：室温下，将3mg/mL Ti 0.87O 2 0.52-水溶液（40mL）与40mL正己胺水溶液（胺化合物为0.1mL）搅拌混合20小时后静置15分钟，出现明显分层；取下层固体离心水洗后冷冻干燥，得到层状金属氧化物/正己胺复合材料，固体粉末。
室温下，将4mg/mL MnO 2 0.4−水溶液（40mL）与40mL正丁胺水溶液（胺化合物为0.15mL）搅拌混合20小时后静置15分钟，出现明显分层；取下层固体离心水洗后冷冻干燥，得到层状金属氧化物/正丁胺复合材料，固体粉末。
室温下，将2mg/mL Nb 6O 17 4−水溶液（40mL）与40mL正戊胺水溶液（胺化合物为0.2mL）搅拌混合20小时后静置15分钟，出现明显分层；取下层固体离心水洗后冷冻干燥，得到层状金属氧化物/正戊胺复合材料，固体粉末。
参考实施例三的方法，以上粉末可制备正极电极片，并进一步组装成镁离子电池。
本发明首次将胺化合物与阴离子型金属氧化物复合，得到的层状材料用于金属离子尤其是镁离子正极，作为活性材料，具有优异的性能。测试结果表明在室温下的扩散率达到10 -8～10 -10 cm 2 s -1，即使在低温-15℃下仍可保持10 -9～10 -11 cm 2 s -1的量级，反映所制备的复合材料可提供镁离子的快速传输路径，保障了镁离子电池的高性能工作。

Claims (10)

  1. 一种层状金属氧化物/胺复合材料，其特征在于，由阴离子型金属氧化物、胺化合物制备得到。
  2. 根据权利要求1所述层状金属氧化物/胺复合材料，其特征在于，所述阴离子型金属氧化物为氧化钛、氧化锰、氧化铌、氧化铌钛、氧化钼、氧化钽、氧化钨中的一种；所述胺化合物为小分子胺化合物。
  3. 根据权利要求2所述层状金属氧化物/胺复合材料，其特征在于，所述氧化钛为Ti 1−nO 2 4n−，0<n<1；氧化锰为MnO 2 x−，0<x<1；所述氧化铌为Nb 6O 17 4−、Nb 3O 8 −、LaNb 2O 7 −或Ca 2Nb 3O 10 −；所述氧化铌钛为TiNbO 5 −、TiNb 6O 5 5-、Ti 2NbO 7 −或Ti 5NbO 14 3−；所述氧化钼为MoO 2 -；所述氧化钽为TaO 3 −；所述氧化钨为W 2O 7 2−或Cs 4W 11O 36 2−；所述胺化合物为烷基胺。
  4. 根据权利要求3所述层状金属氧化物/胺复合材料，其特征在于，所述胺化合物为直链烷基胺。
  5. 权利要求1所述层状金属氧化物/胺复合材料的制备方法，其特征在于，将阴离子型金属氧化物溶液与胺化合物溶液混合，得到沉淀；再将所述沉淀干燥，得到层状金属氧化物/胺复合材料。
  6. 根据权利要求5所述层状金属氧化物/胺复合材料的制备方法，其特征在于，阴离子型金属氧化物溶液与胺化合物溶液都为水溶液；其中阴离子型金属氧化物水溶液中，阴离子型金属氧化物的浓度为1～8mg/mL；胺化合物水溶液中，胺化合物的体积浓度为0.1～10%。
  7. 一种金属离子电池正极，其特征在于，包括集流体以及位于集流体上的正极材料；所述正极材料包括权利要求1所述层状金属氧化物/胺复合材料、导电剂、粘接剂。
  8. 一种金属离子电池，其特征在于，包括权利要求7所述金属离子电池正极、电解液、隔膜、负极。
  9. 胺化合物在制备权利要求1所述层状金属氧化物/胺复合材料中的应用。
  10. 权利要求1所述层状金属氧化物/胺复合材料在制备金属离子电池中的应用。
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