CN114195504A - MgAl2O4Preparation method and application of nanowire film - Google Patents
MgAl2O4Preparation method and application of nanowire film Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 229910020068 MgAl Inorganic materials 0.000 claims abstract description 26
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 26
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- 235000011285 magnesium acetate Nutrition 0.000 claims description 6
- 239000011654 magnesium acetate Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
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- 238000010277 constant-current charging Methods 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 3
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- 101150058243 Lipf gene Proteins 0.000 description 2
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- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 description 1
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
- C04B35/443—Magnesium aluminate spinel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H01M2300/00—Electrolytes
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Abstract
The invention belongs to the technical field of nano materials, and discloses MgAl2O4A preparation method and application of the nanowire film. The preparation method comprises the following steps: (1) mixing the lithium-aluminum alloy with alcohol, and reacting to prepare nanowire gel; (2) washing the nanowire gel prepared in the step (1) by adopting alcohol, and then preparing a gel film; (3) pre-calcining the gel film prepared in the step (2), then soaking the gel film subjected to pre-calcination in an organic magnesium salt solution, taking out the gel film, and calcining to obtain MgAl2O4A nanowire film. MgAl prepared by the method2O4The nanowire film has uniform and compact appearance, is applied to battery electrolyte and has good performance. The reaction condition is mild, the reaction is easy to control, long-time high temperature is not needed, and the requirement on equipment is low; and the cost is low, the operation is simple, and the universality is strong.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to MgAl2O4A preparation method and application of the nanowire film.
Background
Nanoscale materials are referred to as nanomaterials. Compared with the traditional bulk material, the one-dimensional nano material has excellent physical, chemical, electrical, thermal, optical and other properties, and has wide application prospects in the aspects of photoelectric devices, energy conversion and storage, structural ceramics, photoelectrocatalysis and the like. Therefore, one-dimensional nanomaterials such as nanowires, nanotubes, nanofibers, nanobelts and nanorods have been widely studied due to their uniqueness. In which, taking nanowires as an example, the growth and preparation of nanowires have been rapidly developed since the bottom-up growth of silicon nanowires was realized in the last 60 years. A hydrothermal/solvothermal method, a coprecipitation method, a sol-gel method, a template method, a self-assembly method, an electrostatic spinning method, an electrochemical deposition method, a selective dealloying method and the like are developed in sequence. Many of these methods have harsh synthesis conditions, such as high temperature and high pressure, or use of catalysts and activators, which are not suitable for mass production of nanowires. In addition, the use of catalysts or surfactants limits the direction of crystal growth in the nanowires, and thus many methods are only suitable for specific synthesis systems and lack of universality.
Magnesium aluminate spinel (MgAl)2O4) Is one of the most promising advanced ceramic materials, and has the characteristics of high melting point, high hardness, chemical corrosion resistance, high strength at high temperature, low dielectric loss and the like. MgAl in powder and block structure2O4Are all widely studied, and the one-dimensional MgAl2O4Nanowires or MgAl2O4The synthesis research of the nanowire film is less, and the synthesis method has certain limitation. If the reaction temperature is high (1350 ℃) and the time is long (the temperature is higher than 3 hours), the synthesis needs to be carried out under the atmosphere of inert argon, the requirements on equipment are high, the preparation cost is improved invisibly, the universality is weak, and the large-scale production is not facilitated.
Therefore, it is highly desirable to provide MgAl2O4The preparation method of the nanowire film has mild reaction conditions and low equipment requirement, and the prepared MgAl2O4The nanowire film is applied to battery electrolyte and has good performance.
Disclosure of Invention
The inventionWhich aims to solve at least one of the technical problems of the prior art. Therefore, the invention provides MgAl2O4The preparation method of the nanowire film has mild reaction conditions, does not need long-time high temperature, and has the calcination temperature not more than 1200 ℃ and the heat preservation time not more than 2.5 hours; low requirement for equipment and the prepared MgAl2O4The nanowire film is applied to battery electrolyte and has good performance.
The invention provides MgAl in a first aspect2O4A method for preparing a nanowire film.
In particular to MgAl2O4The preparation method of the nanowire film comprises the following steps:
(1) mixing the lithium-aluminum alloy with alcohol, and reacting to prepare nanowire gel;
(2) washing the nanowire gel prepared in the step (1) by adopting alcohol, and then preparing a gel film;
(3) pre-calcining the gel film prepared in the step (2), then soaking the gel film subjected to pre-calcination in an organic magnesium salt solution, taking out the gel film, and calcining to obtain the MgAl2O4A nanowire film.
Preferably, in the lithium aluminum alloy of step (1), the atomic ratio of aluminum to lithium is 1: (0.5-3); further preferably, in the lithium aluminum alloy of step (1), the atomic ratio of aluminum to lithium is 1: (1-2).
Preferably, in step (1), the purity of the lithium aluminum alloy is greater than 99.0%; further preferably, the purity of the lithium aluminum alloy is greater than 99.5%.
Preferably, in the step (1), the lithium aluminum alloy is prepared by the following method: mixing aluminum powder and lithium blocks, reacting at 600-1000 ℃ for 10-60min, and cooling to obtain the lithium-ion battery.
Preferably, in step (1), the alcohol is ethanol. Ethanol is selected to react with the lithium-aluminum alloy, the prepared nanowire gel has uniform appearance, and the subsequent treatment is convenient; and MgAl finally prepared2O4The diameter of the nano wire is 30-80nm, the diameter is uniform, the nano wire is uniformly cross-linked, and MgAl is formed2O4Nanowire filmsAnd (4) compacting.
The reaction is represented by the following formula: AlLi +4CH3CH2OH→Al(OCH2CH3)3+LiOCH2CH3+2H2。
Preferably, in the step (1), the mass ratio of the alcohol to the lithium aluminum alloy is (50-200): 1; further preferably, the mass ratio of the alcohol to the lithium aluminum alloy is (100- & ltSUB & gt 200-): 1.
preferably, in the step (1), the reaction temperature is 45-70 ℃, and the reaction time is 10-50 h; further preferably, in the step (1), the reaction temperature is 50-70 ℃, and the reaction time is 20-40 h.
Preferably, in step (2), the alcohol is ethanol. And the nanowire gel can be more stable by adopting ethanol for washing.
Preferably, in the step (2), the nanowire gel is prepared into a gel film by a suction filtration method. The suction filtration method is simple and easy to operate, and can recover all solvents.
Preferably, in step (3), the pre-calcination process is carried out at 0.5-2 ℃ for min-1The heating rate is from room temperature (10-35 ℃) to 350-; further preferably, in the step (3), the pre-calcination process is carried out at 0.8-1.5 ℃ for min-1The temperature rising rate is from room temperature (10-35 ℃) to 350-450 ℃, and then the temperature is kept for 8-15 min. The pre-calcination process can stabilize the morphology of the nanogel prior to impregnation. The control of the temperature is the key of pre-calcination, and when the temperature is lower than 350 ℃, the shape of the nanowires in the gel film after impregnation cannot be well maintained; too high temperature also affects the morphology and increases the manufacturing cost.
Preferably, in step (3), the organic magnesium salt is magnesium acetate. Magnesium acetate has good solubility in alcohol (especially ethanol), and is beneficial for impregnation and is complementary to magnesium source.
Preferably, the concentration of the substance of the magnesium acetate solution is 0.5-2mol L-1(ii) a Further preferably, the concentration of the substance of the magnesium acetate solution is 0.5 to 1.5mol L-1。
Preferably, in the step (3), the calcination process is carried out at 0.5-2 ℃ for min-1The temperature rise rate is from room temperature (10-35 ℃) to 500-700 ℃, and then is from 3-8 ℃ for min-1The temperature rise rate is increased to 900-2O4A nanowire film.
Further preferably, in the step (3), the calcination process is carried out at 0.8-1.5 ℃ for min-1The temperature rise rate is from room temperature (10-35 ℃) to 550-650 ℃, and then the temperature is increased for 4-6 ℃ min-1The temperature rise rate is increased to 1000-1200 ℃, and the MgAl is prepared after heat preservation for 1-2.5h and cooling2O4A nanowire film. The control of the calcining process is beneficial to the volatilization of water adsorbed in the gel film and the decomposition of organic components; is also beneficial to MgAl2O4The formation of crystal grains in the nanowire film and the maintenance of the shape of the nanowire.
The second aspect of the invention provides the use of the above-mentioned preparation method.
Specifically, the above MgAl2O4The application of the preparation method of the nanowire film in the preparation of batteries.
More specifically, the above MgAl2O4The application of the preparation method of the nanowire film in the preparation of battery electrolyte.
A semi-solid electrolyte, which comprises MgAl prepared by the preparation method2O4A nanowire film.
A method of preparing a semi-solid electrolyte, comprising the steps of: MgAl prepared by the preparation method2O4Soaking the nanowire film in the photocuring precursor solution, and performing photocuring to obtain a composite film; and then soaking the composite membrane in electrolyte for 1-24 h to prepare the semi-solid electrolyte.
A battery of LiFePO4(LFP) is a positive electrode material, Li plate is a negative electrode material, and the semi-solid electrolyte is assembled.
Compared with the prior art, the invention has the following beneficial effects:
(1) the MgAl provided by the invention2O4The preparation method of the nano-wire comprises the steps of firstly adopting lithium aluminum alloy to react with alcohol to prepare aluminum alkoxide nano-wire gel (such as aluminum ethoxide); then the nanowire gel is filtered and dipped in organic magnesium salt solution and then calcined, and the prepared MgAl is prepared by controlling the processes of precalcination and calcination2O4The nanowire film has uniform and compact appearance, and has good performance when being applied to battery electrolyte.
(2) The MgAl provided by the invention2O4The preparation method of the nanowire has mild reaction conditions, is easy to control, does not need long-time high temperature and has low requirement on equipment; and the cost is low, the operation is simple, and the universality is strong.
Drawings
FIG. 1 is a schematic diagram of MgAl prepared in example 12O4Process schematic of nanowire film;
FIG. 2 shows MgAl obtained in example 12O4Scanning electron microscopy images of nanowire films;
FIG. 3 shows MgAl obtained in example 12O4Transmission electron microscopy of individual nanowires in the nanowire film;
FIG. 4 shows the results of the batteries obtained in example 2 and comparative example 1 at 170mA g-1A specific capacity diagram of constant current charging and discharging under current density;
FIG. 5 shows the results of the batteries obtained in example 2 and comparative example 1 at 170mA g-1Coulomb efficiency diagram of constant current charging and discharging at current density.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
Aluminum powder (99.5% pure), Li particles (99.9% pure), magnesium acetate tetrahydrate (99% pure) used in the following examples was obtained from shanghai alading biochem technologies, ltd, and ethanol (99.8% pure, HPLC) was obtained from shanghai mclin biochem technologies, ltd. Other starting materials, reagents or equipment may be obtained from conventional commercial sources or may be obtained by known methods in the art, unless otherwise specified.
Example 1
MgAl2O4The preparation method of the nanowire film, the schematic diagram of the preparation process of which is shown in fig. 1, comprises the following steps:
a graphite crucible containing 0.3g of aluminum powder and 0.085g of Li particles (atomic ratio: 1) was heated in a muffle furnace at 800 ℃ for 30 minutes and naturally cooled to obtain a Li-Al alloy sheet. Polishing, reacting the polished Li-Al alloy sheet (0.115g) with ethanol (20mL) at 60 deg.C for 30h to obtain Al (EtO)3Nanowire gels. The nanowire gel was filtered with suction, and the Al (EtO) was washed with ethanol (10ml) during the filtration3Nanowire gels 3 times, removing all lithium ethoxide, leaving a layer of Al (EtO) on the filter paper3Gel film, then natural drying. Al (EtO) described above3The gel film is placed in a muffle furnace at 1 deg.C for min-1The temperature rising rate of (2) is increased from room temperature to 400 ℃, and the temperature is kept for 10min, thus completing the precalcination. Then Al (EtO)3Soaking the gel film in 1.1mol/L Mg (CH)3COO)2In the solution, a Mg source was supplemented. Then Al (EtO)3Placing the gel film in a muffle furnace at 1 deg.C for min-1The temperature rise rate of (1) is from room temperature to 600 ℃, and then the temperature is increased for 5min-1Raising the temperature to 1200 ℃, preserving the temperature for 2 hours, and then naturally cooling to obtain MgAl2O4A nanowire film.
Scanning Electron Microscope (SEM) for MgAl2O4The morphology of the nanowire film was characterized, and FIG. 2 is MgAl2O4Scanning electron microscopy of nanowire films. As can be seen from FIG. 2, MgAl produced by this method2O4Nanowire films containing MgAl in some amount2O4The nano wires are uniformly crosslinked to form a compact film; the diameter of the nano-wires is distributed between 30 nm and 80nm, and the average diameter is 53.7 nm.
Further using Transmission Electron Microscope (TEM) to measure MgAl2O4The morphology of a single nanowire in the nanowire film is characterized, and fig. 3 is a transmission electron microscope image of the single nanowire. As can be seen from FIG. 3, the single MgAl element2O4Calcining the nanowiresPresents a continuous bead shape after being burnt, has good mechanical stability and is MgAl2O4The stable foundation of nanowire membrane structure.
Example 2
MgAl2O4-a process for the preparation of a PEO semi-solid electrolyte comprising the steps of:
2g of PEGDA (polyethylene glycol (diol) diacrylate) and 15mg of photoinitiator 819 were dissolved in electrolyte (1M LiPF)6in EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) ═ 1: 1:1 Vol%), and stirred in a glove box filled with argon for 12 hours in a dark place to prepare a photocuring precursor solution. MgAl is added2O4The nanowire film was immersed in the precursor solution for 10 min. Irradiating under 365nm ultraviolet light for 6min, and curing to obtain MgAl2O4PEO films (PEO is polyethylene oxide, obtained after photocuring polymerization of the monomer PEGDA). Cutting the film into a wafer with the diameter of 16mm, soaking the wafer in the electrolyte for 12 hours, and fully absorbing the electrolyte to obtain MgAl2O4PEO semi-solid electrolyte.
A method of making a battery comprising the steps of:
70 wt.% LFP (lithium iron phosphate), 20 wt.% acetylene black, and 10 wt.% polyvinylidene fluoride were dissolved in n-methyl-2-pyrrolidone to form a slurry. The slurry was stirred for 12 hours, knife coated on aluminum foil, baked at 80 ℃ for 18 hours, and cut into LFP pieces with a diameter of 10 mm. Mixing LFP pole piece and MgAl2O4assembling-PEO semi-solid electrolyte and Li cathode into 2032 type button cell (LFP/MgAl) in glove box2O4-PEO/Li)。
Comparative example 1
Comparative example 1 is different from example 2 in that a semi-solid electrolyte is different and a battery is manufactured in the same manner as in example 2.
Specifically, the preparation method of the semi-solid electrolyte comprises the following steps:
2g of PEGDA (polyethylene glycol (diol) diacrylate) and 15mg of photoinitiator 819 were dissolved in electrolyte (1M LiPF)6in EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) ═ 1: 1:1 Vol%) inAnd stirring in a glove box filled with argon for 12 hours in a dark place to prepare the photocuring precursor solution. Directly curing the light-cured precursor liquid under 365nm ultraviolet light for 6min, and cutting into a wafer with the diameter of 16mm to obtain the PEO (polyethylene oxide) semi-solid electrolyte.
Comparative example 1 provides a battery using a PEO semi-solid electrolyte to replace MgAl in example 22O4PEO semi-solid electrolyte, the rest of the preparation method was the same as example 2.
Product effectiveness testing
The batteries prepared in example 2 and comparative example 1 were subjected to cycle performance testing, and the batteries were charged with 1C (1C 170mA g) within a voltage window of 2.8-3.2V-1) Constant current charging and discharging are carried out. FIG. 4 shows the results of the batteries obtained in example 2 and comparative example 1 at 170mA g-1In fig. 4, the abscissa represents the number of cycles (Cycle number) and the ordinate represents the Specific capacity (Specific capacity). As can be seen from fig. 4, the specific capacity of the battery prepared in example 2 was 115mAh g after 100 cycles-1While the specific capacity of the battery prepared in comparative example 1 was attenuated to 85mAh g-1。
FIG. 5 shows the results of the batteries obtained in example 2 and comparative example 1 at 170mA g-1Coulomb efficiency diagram of constant current charging and discharging at current density. In fig. 5, the abscissa is the Cycle number (Cycle number) and the ordinate is the Coulombic efficiency (Coulombic efficiency), and it can be seen from fig. 5 that the Coulombic efficiency of the battery prepared in example 2 is always higher than that of the battery prepared in comparative example 1, indicating that MgAl provided by the present invention is used2O4The semi-solid electrolyte prepared by the nanowire film is applied to a battery, and the charge and discharge performance of the battery is better. This is because of the LFP/MgAl composition2O4Homogeneously crosslinked MgAl in PEO/Li cells2O4On one hand, the nanowire film is used as a ceramic filler to inhibit crystallization of polymer PEO, so that amorphous areas of the PEO are increased, chain segment relaxation is good for conducting lithium ions, and high capacity of the battery is kept; on the other hand, the good mechanical stability of the nanowire film is beneficial to inhibiting the formation of lithium dendrites and avoiding the battery short circuit caused by the fact that the dendrites penetrate through the diaphragm.
Claims (10)
1. MgAl2O4The preparation method of the nanowire film is characterized by comprising the following steps of:
(1) mixing the lithium-aluminum alloy with alcohol, and reacting to prepare nanowire gel;
(2) washing the nanowire gel prepared in the step (1) by adopting alcohol, and then preparing a gel film;
(3) pre-calcining the gel film prepared in the step (2), then soaking the gel film subjected to pre-calcination in an organic magnesium salt solution, taking out the gel film, and calcining to obtain the MgAl2O4A nanowire film.
2. The method according to claim 1, wherein in the lithium aluminum alloy of step (1), the aluminum to lithium atomic ratio is 1: (0.5-3).
3. The method according to claim 1, wherein in the step (1), the reaction temperature is 45 to 70 ℃ and the reaction time is 10 to 50 hours.
4. The production method according to claim 1, wherein in the step (1) and the step (2), the alcohol is ethanol.
5. The method according to claim 1, wherein in the step (2), the nanowire gel is formed into a gel film by a suction filtration method.
6. The method according to claim 1, wherein in the step (3), the pre-calcination is performed at 0.5-2 ℃ for min-1The temperature rising rate is from room temperature to 350-500 ℃, and then the temperature is kept for 5-20 min.
7. The method according to claim 1, wherein in the step (3), the organic magnesium salt solution is magnesium acetate, and the magnesium acetate solution is magnesium acetateIn an amount of 0.5 to 2mol L-1。
8. The method according to claim 1, wherein in the step (3), the calcination is performed at 0.5-2 ℃ for min-1The temperature rise rate is from room temperature to 500-700 ℃, and then is 3-8 ℃ for min-1The temperature rise rate is increased to 900 ℃ and 1200 ℃, and the temperature is kept for 1-2.5 h.
9. An MgAl of any one of claims 1 to 82O4The application of the preparation method of the nanowire film in the preparation of batteries.
10. An MgAl of any one of claims 1 to 82O4The application of the preparation method of the nanowire film in the preparation of battery electrolyte.
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