CN114314673A - Preparation method of flaky FeOCl nano material - Google Patents
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Abstract
A preparation method of a sheet FeOCl nano material relates to the technical field of preparation of positive electrode materials of chloride ion batteries, and is characterized in that sodium chloride powder is added into molten ferric chloride hexahydrate and heated to 140-250 ℃ under the condition of negative pressure to react to obtain the FeOCl nano material. The invention uses freeze-dried NaCl as a template, and can convert liquid FeCl into FeCl in the reaction process3·6H2O is limited between NaCl layers to limit the growth of FeOCl, and dispersed FeOCl sheets are obtained, so that 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 has good dispersibility, and the product has good stabilityThe active substances are easy to disperse when the material is agglomerated and coated into an electrode, and the volume expansion and contraction influence in the phase change process of FeOCl is small, thereby being beneficial to improving the cycle stability of the chloride ion battery; the product has thin sheet layer, is beneficial to the transmission of chloride ions and can improve the discharge capacity of the chloride ion battery.
Description
Technical Field
The invention relates to the technical field of preparation of anode materials of chloride ion batteries, in particular to a preparation method of a flaky FeOCl nano material.
Background
From the beginning of the 20 th century and the fifties, FeOOL is mainly used as a lithium ion battery cathode material, a chlorine ion battery anode material, an HCl gas detector, a catalyst for degrading pollutants in water and the like, and is widely researched, a chlorine ion battery belongs to a secondary battery based on halogen anion conduction, can use alkali metal, alkaline earth metal elements or rare earth metal with abundant reserves as an electrode material, has the theoretical energy density of 2500Wh/L, is considered as a powerful competitor of a next generation battery, is used as a chlorine ion battery anode material, has abundant resources of the layered FeOOL (the content of iron elements in earth shells is 4.75 percent, the metal elements are arranged in the second place), can stably exist in a chlorine ion battery system taking ionic liquid as electrolyte, has high theoretical capacity (250mAh/g), the operating voltage is high. In the discharging process, the separation of chloride ions from FeOCl is divided into two steps of reactions, firstly, the chloride ions are separated out, the FeOCl structure is kept unchanged (2.8V of a discharging platform), when the separation of the chloride ions reaches 50%, the FeOCl undergoes phase transition to generate FeO (2.2V of the discharging platform), and 141.7% of volume expansion and 58.6% of volume contraction of the FeOCl electrode material can occur in the charging and discharging processes, so that the electrochemical performance of the battery is seriously influenced.
Currently, the preparation methods of FeOCl are mainly divided into two, and the first conventional method is to use FeCl3And Fe2O3Prepared by gas phase transmission method, anhydrous FeCl3And Fe2O3Fully mixing the raw materials according to a molar ratio of 4:3, sealing the mixture in a quartz tube, and preserving the heat for 2-14 days at a temperature of not less than 350 ℃ and not more than 460 ℃ to obtain the purple micron-sized strip FeOCl powder. The product has large particles, needs an activation process (after 20 cycles, the discharge capacity can reach 141mAh/g) when being used as the anode material of the chloride ion battery, and the FeOCl has large particles, large volume expansion and contraction influence in the phase change process and poor battery cycle stability. Meanwhile, the gas phase transmission method has the disadvantages of unsafe high temperature and high pressure and installationThe powder needs to be operated in an anhydrous environment, the reaction time is long, and the like. Anhydrous FeCl3Gasifying at 316 ℃ to form gas and Fe2O3The reaction occurs, the sealed environment has certain pressure bearing capacity, and the requirement on equipment is higher.
The second conventional approach is to use FeCl3·6H2Partial thermal decomposition of O to FeCl3·6H2Placing O in an oven or a furnace (introducing flowing nitrogen), keeping the temperature for 1-4 hours at the temperature of not less than 200 ℃ and not more than 350 ℃ to obtain the aggregated red micro-nano strip-shaped or sheet FeOCl powder, or placing in a microwave oven, and reacting for 2-5min to obtain the aggregated red micro-nano needle-shaped FeOCl powder. FeOOCl nano flaky or needle-shaped materials are agglomerated together in the reaction process and are not well dispersed. Although 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 cycle stability is poor.
Disclosure of Invention
In order to overcome the defects of the traditional FeOCl preparation method, the invention aims to provide a preparation method of a flaky FeOCl nano material, which limits the growth of a product in the reaction process by using sodium chloride as a template, so as to prepare the flaky FeOCl nano material of the positive electrode material of the chloride ion battery with higher battery performance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a process for preparing the flaky FeOCl nano material includes adding FeCl hexahydrate in molten state3·6H2Adding sodium chloride NaCl powder into the O, heating to 140-250 ℃ under the condition of negative pressure, reacting to obtain the FeOCl nano material, and limiting the growth of FeOCl between NaCl layers by using NaCl as a template so as to obtain the dispersed flaky FeOCl nano material.
As a preferred technical scheme of the invention, in the preparation method, the ferric chloride hexahydrate FeCl is adopted3·6H2Heating O to 50-70 ℃ to melt the O, wherein the sodium chloride NaCl powder is prepared by mixing Fe: the Na molar ratio is 1: 4-40, and carrying out freeze drying pretreatment on the sodium chloride NaCl powder before addition.
As a preferred technical scheme of the invention, in the preparation method, firstly molten ferric chloride hexahydrate FeCl is added3·6H2Adding a solvent into the O, adding sodium chloride for ultrasonic dispersion, heating to remove the solvent under the condition of negative pressure, and then continuously heating to 140-250 ℃ to start reaction, wherein the reaction time is 0.5-2 h.
As a preferable technical scheme of the invention, in the preparation method, the solvent is absolute ethyl alcohol.
As a preferred technical scheme of the invention, in the preparation method, after the reaction is finished, the reaction product is cooled to room temperature, then the NaCl template is removed by using ultrapure water, and then the product is cleaned by using ethanol and dried.
Compared with the prior art, the invention has the beneficial effects that:
1. the NaCl which is frozen and dried is used as a template, and the FeCl in liquid state can be used in the reaction process3·6H2O is limited between NaCl layers to limit the growth of FeOCl, and dispersed FeOCl sheets are obtained, so that secondary particles are not formed in the preparation process.
2. The reaction under the negative pressure condition is favorable for generating FeOCl, the FeOCl growth direction is influenced, the main crystal face of the FeOCl grows along the (010) crystal face and the (110) crystal face, the square-sheet FeOCl can prolong the phase transformation process of the second step, and the discharge capacity of the material is improved.
3. The thickness of the square FeOCl product is about 20nm, the length and the width are within 2 mu m, the product has good dispersibility and is not agglomerated, when the product is coated into an electrode, active substances are easy to disperse, the volume expansion and shrinkage influence in the phase change process of the FeOCl is small, and the improvement of the cycling stability of the chloride ion battery is facilitated; the product has thin sheet layer, is beneficial to the transmission of chloride ions and can improve the discharge capacity of the chloride ion battery.
Drawings
FIG. 1 is an electron micrograph of the product prepared in example 1 (a, b correspond to low and high magnifications, respectively).
FIG. 2 is an EDS chart of the spectral 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 cycle performance test results of the assembled battery prepared from the product of example 1 (a and b correspond to the charge-discharge curve and the cycle stability curve of the chloride ion battery, respectively).
Fig. 5 is an XRD pattern of the comparative example preparation product.
FIG. 6 is an electron micrograph of a comparative preparation (a, b for low and high magnifications, respectively).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A preparation method of FeOCl nano material comprises the following steps:
step one, weighing 2.5g ferric chloride hexahydrate (FeCl)3·6H2O) is put into a eggplant-shaped bottle, a water bath is heated to 60 ℃, and then ferric chloride hexahydrate is heated in a water bath until being melted.
And step two, adding 50mL of absolute ethyl alcohol, adding 5g of NaCl powder obtained by freeze drying in advance, and performing ultrasonic dispersion.
Heating to 80 ℃ on a rotary evaporator (under the negative pressure condition of-0.1 MPa) to volatilize ethanol, then continuing heating, controlling the reaction temperature to be 180 ℃, heating for 1h while rotating, cooling to room temperature after the reaction is finished, removing the NaCl template by using ultrapure water, and cleaning and drying the ethanol.
As a comparative example, the step III was carried out under normal pressure conditions, and the reaction temperature and time were kept constant.
As can be seen from FIG. 1, the product prepared in example 1 is in the form of square plate, the thickness of the plate is about 20nm, the length and width of the plate are within 2 μm, and the product has good dispersibility and no agglomeration phenomenon. As can be seen from a combination of FIGS. 2 and 3, the product prepared in example 1 is FeOCl, and the product purity is high.
From the XRD pattern and electron micrograph of the comparative product prepared by the reaction under normal pressure, it can be seen that the prepared product is pure FeOOCl, is needle-shaped, has a diameter of about 40nm and a length within 1 μm, and has poor product dispersibility and serious agglomeration (shown in FIGS. 5 and 6).
By comparison, under the negative pressure condition, the growth of FeOCl is more facilitated, the growth direction of FeOCl is influenced, and the main crystal plane of FeOCl grows along the (010) and (110) crystal planes (shown in FIG. 3). Meanwhile, the prepared square platy FeOCl can prolong the phase transformation 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 were weighed, and the weight ratio was 6: 1: 3, dissolving PVDF in NMP (N-methyl-2-pyrrolidone), fully and uniformly stirring, putting the prepared active substance material and the conductive agent carbon black into an agate mortar for fully grinding and mixing, and finally dispersing the mixed material in the NMP dissolved with PVDF and fully and uniformly stirring. Coating the graphite paper on the synthesized graphite paper, drying the graphite paper in a vacuum drying oven at the temperature of 80 ℃ overnight, and then punching the graphite paper into an electrode slice.
0.5M PP for chloride ion battery electrolyte14Cl (1-butyl-1-methylpiperidine chloride) in PP14TFSI (1-butyl-1-methylpiperidine bis (trifluoromethanesulfonimide) salt) complex ionic liquid. And (3) assembling the prepared ionic electrolyte, the positive electrode plate and the metal Li sheet into a button cell in a glove box, wherein the diaphragm of the cell uses Celgard3501 polypropylene porous membrane.
A battery tester with model number CT-4008-5V10mA of New Wille electronics Limited in Shenzhen is used. Adopts a two-electrode system, uses metal lithium as an auxiliary electrode and a reference electrode, and has a scanning potential range of 1.6V-3.5V (vs+) The current density was 10 mA/g. Scanning is carried out from the open circuit potential to the negative electrode, and the 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 charge-discharge curve diagram of FeOCl material under current density of 10mA/g in different cycles. The first cycle discharge capacity of the battery is 145mAh/g (58% of theoretical capacity), and the first charge-discharge efficiency is 99%. The first three cycles have two obvious charge and discharge platforms, corresponding to the two-step reaction process of separating chloride ions from FeOCl Materials, the second phase transformation process platform is obvious compared with the micron-sized FeOCl anode material (Materials Research Bulletin 96(2017) 485-type 490). After 50 cycles, the capacity retention rate was 80%, and the charge-discharge coulombic efficiency was maintained at 85% (shown in fig. 4 b).
Therefore, when the FeOCl prepared by the method is used as the anode material, the volume expansion and contraction influence in the phase change process is small, and the improvement of the cycle stability of the chloride ion battery is facilitated; meanwhile, the product has thin sheet layer, 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 one, weighing 2.5g ferric chloride hexahydrate (FeCl)3·6H2O) is put into a eggplant-shaped bottle, a water bath is heated to 60 ℃, and then ferric chloride hexahydrate is heated in a water bath until being melted.
And step two, adding 70mL of absolute ethyl alcohol, adding 12g of NaCl powder obtained by freeze drying in advance, and performing ultrasonic dispersion.
Heating to 80 ℃ on a rotary evaporator (under the negative pressure condition of-0.1 MPa), volatilizing ethanol, continuously heating, controlling the reaction temperature to be 200 ℃, heating for 2 hours while rotating, cooling to room temperature after the reaction is finished, removing the NaCl template by using ultrapure water, washing with ethanol, and drying.
The morphology of the product prepared in this example was substantially the same as the product prepared in example 1.
Tests show that constant-current charge and discharge experiments are carried out under the current density of 10mA/g, the first-cycle discharge capacity of the battery is 168mAh/g (67% of theoretical capacity), the first-cycle charge and discharge efficiency is 89%, after 50 cycles, the capacity retention rate is 73%, and the charge and discharge coulombic efficiency is maintained at 88%.
Example 3
A preparation method of FeOCl nano material comprises the following steps:
step one, weighing 2.5g ferric chloride hexahydrate (FeCl)3·6H2O) is put into a eggplant-shaped bottle, a water bath is heated to 50 ℃, and then ferric chloride hexahydrate is heated in a water bath until being melted.
And step two, adding 35mL of absolute ethyl alcohol, adding 3g of NaCl powder obtained by freeze drying in advance, and performing ultrasonic dispersion.
Heating to 80 ℃ on a rotary evaporator (under the negative pressure condition of-0.1 MPa), volatilizing the ethanol, continuously heating, controlling the reaction temperature to be 150 ℃, heating for 0.5h while rotating, cooling to room temperature after the reaction is finished, removing the NaCl template by using ultrapure water, and cleaning and drying the ethanol.
The morphology of the product prepared in this example was substantially the same as the product prepared in example 1.
Tests show that constant-current charge and discharge experiments are carried out under the current density of 10mA/g, the first-cycle discharge capacity of the battery is 142mAh/g (57% of theoretical capacity), the first-cycle charge and discharge efficiency is 83%, after 50 cycles, the capacity retention rate is 79%, and the charge and discharge coulombic efficiency is kept at 86%.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. A preparation method of a sheet FeOCl nano material is characterized in that ferric chloride FeCl hexahydrate is molten3·6H2Adding sodium chloride NaCl powder into the O, heating to 140-250 ℃ under the condition of negative pressure, reacting to obtain the FeOCl nano material, and limiting the growth of FeOCl between NaCl layers by using NaCl as a template so as to obtain the dispersed flaky FeOCl nano material.
2. The method of claim 1, wherein the ferric chloride hexahydrate, FeCl3·6H2Heating O to 50-70 ℃ to melt.
3. The method according to claim 1, wherein the NaCl powder is a sodium chloride powder consisting of Fe: the Na molar ratio is 1: 4-40 of an additive.
4. The method according to claim 1, wherein the NaCl powder is pre-treated by freeze-drying before addition.
5. The process according to claim 1, wherein FeCl is initially charged in molten state as iron trichloride hexahydrate3·6H2And adding a solvent into the O, adding sodium chloride, performing ultrasonic dispersion, heating to remove the solvent under a negative pressure condition, and then continuously heating to 140-250 ℃ to start reaction.
6. The preparation method according to claim 5, wherein the reaction time is 0.5 to 2 hours after the temperature is raised to 140 to 250 ℃.
7. The method of claim 5, wherein the solvent is absolute ethanol.
8. The method according to claim 1, wherein the reaction is cooled to room temperature after the completion of the reaction, and then the NaCl template is removed with ultrapure water, and the product is washed with ethanol and dried.
9. The platy FeOCl nanomaterial prepared by the method according to any one of claims 1 to 8, wherein the platy FeOCl nanomaterial is in the form of dispersed square plates, the thickness of the platy FeOCl nanomaterial is 10-30 nm, and the length and the width of the platy FeOCl nanomaterial are within 2 μm.
10. The application of the sheet FeOCl nano material prepared by the method of any one of claims 1 to 8 as a positive electrode material of a chloride ion battery.
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Cited By (2)
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| CN114848580A (en) * | 2022-04-19 | 2022-08-05 | 南京邮电大学 | Microenvironment response type nano composite material for efficiently removing tumor cells, preparation method and application thereof |
| CN115323493A (en) * | 2022-09-23 | 2022-11-11 | 西北工业大学 | Large-size layered FeOCl single crystal and preparation method thereof |
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