CN114314673B - Preparation method of flaky FeOCl nano material - Google Patents
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- CN114314673B CN114314673B CN202111660299.XA CN202111660299A CN114314673B CN 114314673 B CN114314673 B CN 114314673B CN 202111660299 A CN202111660299 A CN 202111660299A CN 114314673 B CN114314673 B CN 114314673B
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Abstract
A preparation method of a flaky FeOCl nano material relates to the technical field of preparation of positive electrode materials of chloride ion batteries, and sodium chloride powder is added into molten ferric trichloride hexahydrate and heated to 140-250 ℃ for reaction under negative pressure to obtain the FeOCl nano material. The invention uses freeze-dried NaCl as a template, and can make liquid FeCl in the reaction process 3 ·6H 2 O is limited between NaCl layers, and FeOCl growth is limited, so that dispersed FeOCl tablets are obtained, and secondary particles are not formed in the preparation process. The thickness of the product is about 20nm, the length and the width are within 2 mu m, the product dispersibility is good, the agglomeration is avoided, the active substances are easy to disperse when the product is coated into an electrode, the influence of volume expansion and shrinkage in the FeOCl phase change process is small, and the cycle stability of the chloride ion battery is improved; the product sheet layer is thin, which is favorable for chloride ion transmission and can improve the discharge capacity of the chloride ion battery.
Description
Technical Field
The invention relates to the technical field of preparation of a chloride ion battery anode material, in particular to a preparation method of a flaky FeOCl nano material.
Background
The chloride ion battery belongs to a secondary battery based on halogen anion conduction, can use alkali metal, alkaline earth metal element or rare earth metal with abundant storage as electrode materials, can reach 2500Wh/L in theoretical energy density, is regarded as a powerful competitor of the next generation battery, is used as a positive electrode material of the chloride ion battery, has abundant resources of the layered FeOCl material (the content of the iron element in the crust is 4.75 percent, the content of the metal element is the second percent), can stably exist in a chloride ion battery system using ion liquid as electrolyte, has high theoretical capacity (250 mAh/g), has high working voltage, and is separated into two-step reactions in the process of separating the chloride ion from the FeOCl, firstly, the structure of the FeOCl is kept unchanged (2.8V) when the chloride ion is separated from the electrode, and the FeOCl is separated from the electrode by 50 percent, and the FeOCl is severely contracted by the volume percent (62 percent) when the FeOCl is separated from the electrode by the electrochemical compression process, and the FeOCl is severely contracted by the volume of the expansion and the expansion of the FeO 2.38 percent is generated when the FeOCl is discharged by the electrode is greatly changed.
Currently, the preparation methods of FeOCl are mainly divided into two types, and the first conventional method is to use FeCl 3 And Fe (Fe) 2 O 3 Prepared by a gas phase transmission method, anhydrous FeCl 3 And Fe (Fe) 2 O 3 Fully mixing according to the molar ratio of 4:3, sealing in a quartz tube, and preserving heat for 2-14 days at the temperature of not lower than 350 ℃ and not higher than 460 ℃ to obtain the purple micron-sized strip FeOCl powder. The product has large particles, the activation process is needed as a positive electrode material of the chloride ion battery (after 20 cycles, the discharge capacity can reach 141 mAh/g), the FeOCl particles are large, the influence of volume expansion and shrinkage in the phase change process is large, and the battery has poor cycle stability. Meanwhile, the gas phase transmission method has the defects of unsafe high temperature and high pressure, long reaction time and the like because powder filling needs to be operated in an anhydrous environment. Anhydrous FeCl 3 Gasifying at 316 deg.c to form gas and Fe 2 O 3 The reaction occurs, the sealed environment needs to have certain bearing capacity, and the requirement on equipment is relatively high.
The second conventional method is to use FeCl 3 ·6H 2 O is partially thermally decomposed to decompose FeCl 3 ·6H 2 Placing O in the ovenAnd (3) preserving the heat for 1-4 hours in a box or a furnace (flowing nitrogen) at the temperature of not lower than 200 ℃ and not higher than 350 ℃ to obtain agglomerated red micro-nano level long-strip or sheet FeOCl powder, or placing the agglomerated red micro-nano level long-strip or sheet FeOCl powder in a microwave oven to react for 2-5 minutes to obtain the agglomerated red micro-nano level needle-like FeOCl powder. FeOCl nano-sheet or needle-like materials are clustered together in the reaction process, and are not well dispersed. Although the single particles of the product are small, the single particles are easy to agglomerate into secondary particles, the influence of volume expansion and shrinkage in the phase change process is large, and the battery has poor cycling stability.
Disclosure of Invention
In order to overcome a plurality of defects of the traditional FeOCl preparation method, the invention aims to provide a preparation method of a flaky FeOCl nano material, and the growth of a product in the reaction process is limited by taking sodium chloride as a template, so that the flaky FeOCl nano material of the positive electrode material of the chloride ion battery with higher battery performance is prepared.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
preparation method of flaky FeOCl nano material, namely molten ferric trichloride hexahydrate FeCl 3 ·6H 2 Adding sodium chloride NaCl powder into O, heating to 140-250 ℃ under negative pressure to react to obtain FeOCl nano material, and limiting the growth of FeOCl between NaCl layers by using NaCl as a template to obtain dispersed flaky FeOCl nano material.
As a preferable technical scheme of the invention, in the preparation method, the ferric trichloride hexahydrate FeCl 3 ·6H 2 Heating O to 50-70 ℃ to melt, wherein sodium chloride NaCl powder is prepared from Fe: the molar ratio of Na is 1: 4-40, wherein the sodium chloride NaCl powder is subjected to freeze drying pretreatment before adding.
As a preferable technical scheme of the invention, in the preparation method, the molten ferric trichloride hexahydrate FeCl is firstly added 3 ·6H 2 Adding a solvent into O, adding sodium chloride, performing ultrasonic dispersion, heating under a negative pressure condition to remove the solvent, and continuously heating to 140-250 ℃ to start reaction for 0.5-2h.
In the preparation method, the solvent is absolute ethyl alcohol.
In the preparation method, after the reaction is finished, the reaction is cooled to room temperature, then the NaCl template is removed by using ultrapure water, and the product is washed by using ethanol and dried.
Compared with the prior art, the invention has the beneficial effects that:
1. the freeze-dried NaCl is used as a template, and liquid FeCl can be prepared in the reaction process 3 ·6H 2 O is limited between NaCl layers, and FeOCl growth is limited, so that dispersed FeOCl tablets are obtained, and secondary particles are not formed in the preparation process.
2. The reaction under the negative pressure condition is favorable for the generation of FeOCl, influences the growth direction of FeOCl, obtains the growth of FeOCl main crystal planes along (010) and (110) crystal planes, and the square-sheet FeOCl can prolong the phase transition process of the second step and improve the discharge capacity of the material.
3. The thickness of the square FeOCl product is about 20nm, the length and the width are within 2 mu m, the product dispersibility is good, agglomeration is avoided, the active substances are easy to disperse when the electrode is coated, the influence of volume expansion and shrinkage in the FeOCl phase change process is small, and the cyclic stability of the chloride ion battery is improved; the product sheet layer is thin, which is favorable for chloride ion transmission and can improve the discharge capacity of the chloride ion battery.
Drawings
FIG. 1 is an electron micrograph (a, b for low and high magnification, respectively) of the product prepared in example 1.
FIG. 2 is an EDS chart of the energy spectrum analysis of the product prepared in example 1.
Figure 3 is an XRD pattern of the product prepared in example 1.
Fig. 4 shows the results of the cycle performance test (a, b correspond to the charge-discharge curve and the cycle stability curve of the chloride ion battery, respectively) of the assembled battery prepared in example 1.
Figure 5 is an XRD pattern of the comparative example preparation.
FIG. 6 is an electron micrograph of the comparative example preparation (a, b for low and high magnification, respectively).
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
A preparation method of FeOCl nano material comprises the following steps:
step (1), weighing 2.5g of ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) placing into a eggplant-shaped bottle, heating the water bath kettle to 60 ℃, and then heating the ferric trichloride hexahydrate to be molten in the water bath.
And (2) adding 50mL of absolute ethyl alcohol, adding 5g of NaCl powder obtained by freeze drying in advance, and performing ultrasonic dispersion.
And (3) heating to 80 ℃ on a rotary evaporator (negative pressure condition of minus 0.1 MPa) to volatilize ethanol, continuing heating, controlling the reaction temperature to 180 ℃, heating for 1h while rotating, cooling to room temperature after the reaction is finished, removing a NaCl template by using ultrapure water, and cleaning and drying by using ethanol.
As a comparative example, the step (3) was carried out under normal pressure, and the reaction temperature and time were kept uniform.
As can be seen from FIG. 1, the product prepared in example 1 has a square sheet shape, the thickness of the sheet is about 20nm, the length and width of the sheet are within 2 μm, and the product has good dispersibility and no agglomeration phenomenon. As can be seen in combination with fig. 2 and 3, the product prepared in example 1 is FeOCl, and the purity of the product is high.
As can be seen from XRD patterns and electron micrographs of the comparative products prepared by the reaction under normal pressure, the prepared products were pure FeOCl, needle-like, about 40nm in diameter, less than 1 μm in length, poor in dispersibility and severe in agglomeration (shown in FIGS. 5 and 6).
By comparison, under the condition of negative pressure, the method is more favorable for generating FeOCl, influences the growth direction of the FeOCl, and obtains the growth of the FeOCl main crystal planes along (010) and (110) crystal planes (shown in figure 3). Meanwhile, the prepared square sheet FeOCl can prolong the phase transition process of the second step, thereby improving the discharge capacity of the material.
Electrochemical performance test experiment:
the prepared active material (prepared under the negative pressure condition of example 1), binder PVDF (polyvinylidene fluoride) and conductive agent carbon black are weighed according to the following 6:1:3, dissolving PVDF in NMP (N-methyl-2-pyrrolidone), fully and uniformly stirring, putting the prepared active material and conductive agent carbon black into an agate mortar, fully grinding and mixing, and finally dispersing the mixed material in NMP dissolved with PVDF and fully and uniformly stirring. Coating on synthetic graphite paper, drying in a vacuum drying oven at 80deg.C overnight, and stamping to obtain electrode plate.
PP with chloride ion battery electrolyte of 0.5M 14 Cl (1-butyl-1-methylpiperidine chloride) was dissolved in PP 14 Composite ionic liquid of TFSI (1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt). And assembling the prepared ion electrolyte, the positive electrode plate and the metal Li plate into a button cell in a glove box, wherein a Celgard3501 polypropylene porous membrane is used as a cell diaphragm.
A battery tester of model CT-4008-5V10mA of Shenzhen New wile electronic Co., ltd was used. Adopts a two-electrode system, takes metallic lithium as an auxiliary electrode and a reference electrode, and has a scanning potential range of 1.6V-3.5V (vs. Li/Li) + ) The current density was 10mA/g. Scanning from open circuit potential to negative electrode, scanning potential range is 1.6V-3.5V (vs. Li/Li) + ) The test temperature was 25 ℃.
The test results are shown in FIG. 4, and FIG. 4a is a graph showing the charge and discharge curves of FeOCl materials at different cycles at a current density of 10mA/g. The first cycle discharge capacity of the battery is 145mAh/g (58% of theoretical capacity), and the first charge-discharge efficiency is 99%. The former three cycles have more obvious two sections of charge and discharge platforms, corresponding to two-step reaction processes of chloridion removal FeOCl materials, and the second-step phase transition process platform is obvious compared with micron-sized FeOCl positive electrode materials (documents Materials Research Bulletin and 96 (2017) 485-490). After 50 cycles, the capacity retention was 80% and the charge-discharge coulombic efficiency was 85% (shown in fig. 4 b).
Therefore, when FeOCl prepared by the method is used as a positive electrode material, the influence of volume expansion and shrinkage in the phase change process is small, and the cycle stability of the chloride ion battery is improved; meanwhile, the product sheet layer is thin, which is more beneficial to chloride ion transmission and can improve the discharge capacity of the chloride ion battery.
Example 2
A preparation method of FeOCl nano material comprises the following steps:
step (1), weighing 2.5g of ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) placing into a eggplant-shaped bottle, heating the water bath kettle to 60 ℃, and then heating the ferric trichloride hexahydrate to be molten in the water bath.
And (2) adding 70mL of absolute ethyl alcohol, adding 12g of NaCl powder obtained by freeze drying in advance, and performing ultrasonic dispersion.
And (3) heating to 80 ℃ on a rotary evaporator (negative pressure condition of minus 0.1 MPa) to volatilize ethanol, continuing heating, controlling the reaction temperature to 200 ℃, heating for 2 hours while rotating, cooling to room temperature after the reaction is finished, removing a NaCl template by using ultrapure water, and cleaning and drying by using ethanol.
The morphology of the product prepared in this example was essentially the same as that of the product prepared in example 1.
Tests show that when a constant-current charge-discharge experiment is carried out under the current density of 10mA/g, the first-time cycle discharge capacity of the battery is 168mAh/g (67% of theoretical capacity), the first-time charge-discharge efficiency is 89%, the capacity retention rate is 73% after 50 cycles, and the charge-discharge coulomb efficiency is 88%.
Example 3
A preparation method of FeOCl nano material comprises the following steps:
step (1), weighing 2.5g of ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) placing into a eggplant-shaped bottle, heating the water bath kettle to 50 ℃, and then heating the ferric trichloride hexahydrate to be molten in the water bath.
And (2) adding 35mL of absolute ethyl alcohol, adding 3g of NaCl powder obtained by freeze drying in advance, and performing ultrasonic dispersion.
And (3) heating to 80 ℃ on a rotary evaporator (negative pressure condition of minus 0.1 MPa) to volatilize ethanol, continuing heating, controlling the reaction temperature to 150 ℃, heating for 0.5h while rotating, cooling to room temperature after the reaction is finished, removing a NaCl template by using ultrapure water, cleaning by using ethanol, and drying.
The morphology of the product prepared in this example was essentially the same as that of the product prepared in example 1.
Tests show that when a constant-current charge-discharge experiment is carried out under the current density of 10mA/g, the first-time cycle discharge capacity of the battery is 142mAh/g (57% of theoretical capacity), the first-time charge-discharge efficiency is 83%, the capacity retention rate is 79% after 50 cycles, and the charge-discharge coulomb efficiency is 86%.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (4)
1. A process for preparing the flaky FeOCl nano material includes such steps as preparing molten FeCl hexahydrate 3 ·6H 2 Absolute ethyl alcohol is added into O, and then Fe: the molar ratio of Na is 1: 4-40, adding sodium chloride pretreated by freeze drying, performing ultrasonic dispersion, heating under a negative pressure condition to remove absolute ethyl alcohol, then continuously heating to 140-250 ℃ to start reaction for 0.5-2h to obtain FeOCl nano material, and limiting the growth of FeOCl between NaCl layers by taking NaCl as a template to obtain dispersed Fang Pianzhuang FeOCl nano material with the thickness of 10-30 nm and the length and width of less than 2 mu m.
2. The process according to claim 1, wherein the iron trichloride hexahydrate FeCl 3 ·6H 2 O is heated to 50-70 ℃ to melt the alloy.
3. The preparation method according to claim 1, wherein after the completion of the reaction, the reaction mixture is cooled to room temperature, then the NaCl template is removed by using ultra-pure water, and the product is washed with ethanol and dried.
4. The application of the flaky FeOCl nano material prepared by the method according to any one of claims 1-3 as a positive electrode material of a chloride ion battery.
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