CN111900382A - Preparation method and application of manganese pyrophosphate electrode material - Google Patents
Preparation method and application of manganese pyrophosphate electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a manganese pyrophosphate electrode material, which comprises the steps of firstly stirring sodium sulfide and phosphorus trichloride for reaction to obtain a precursor I, then adding soluble manganous salt for dissolution, adding polyvinylpyrrolidone, continuing stirring for reaction, and finally annealing to obtain the manganese pyrophosphate electrode material. The manganese pyrophosphate electrode material prepared by the preparation method realizes accurate regulation and control of the size of manganese pyrophosphate, and has more excellent electrochemical performance; the preparation method has the advantages of low cost of raw materials, high product yield and simple preparation method, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to preparation and application of a manganese pyrophosphate material for energy storage.
Background
With the rapid development of the world economy and the increase of energy consumption, the global power supply is challenged by the exhaustion of fossil energy and environmental problems. The advent of renewable clean energy sources (e.g., wind, solar, hydro, etc.) has greatly relieved the global energy pressure. However, since these renewable clean energy sources are intermittently generated, the unstable supply is a big problem, which results in irregular power supply to the grid. Therefore, it is a feasible solution today to develop a large-scale energy storage system, which is matched with a smart grid to store unstable energy sources to match the power supply requirements of different time periods and regions.
In energy storage technology, rechargeable batteries have attracted extensive research interest due to their inherently superior characteristics of high round-trip efficiency, long cycle stability, and ease of maintenance. In many battery types, with the rapid development of various power devices, the conventional low-capacity (372mAh/g) graphene negative electrode has difficulty in meeting the requirements, and a new generation of negative electrode material is urgently needed to be developed and researched.
Manganese pyrophosphate (Mn)2P2O7) Researches show that the material has various compositions, crystal structures and properties, and has very wide application in the fields of laser main bodies, phosphate fertilizers, ceramic dyes, catalysis and the like. In recent years, transition metal pyrophosphates have attracted attention in the field of negative electrode materials for batteries. Most of the traditional preparation methods of manganese pyrophosphate need hydrothermal synthesis or pyrolysis of diammonium phosphate, and few researches report the size control synthesis of manganese pyrophosphate. Methods of making manganese pyrophosphate and enabling control of manganese pyrophosphate size remain challenging.
In the existing patent, chinese granted patent CN104934599A provides a lithium ion battery anode material manganese pyrophosphate with a core-shell structure and a preparation method thereof, which is prepared by dissolving an organic manganese source and a phosphorus source in proportion into a mixed aqueous solution, adjusting the pH value, performing water bath to form a gel, drying to obtain a manganese pyrophosphate precursor, and then placing the manganese pyrophosphate precursor in a non-oxidizing atmosphere for sintering and cooling. For example, chinese patent application CN110217771A provides a manganese pyrophosphate polyanionic lithium battery negative electrode material and a preparation method thereof, in which soluble divalent manganese salt and a compound containing pyrophosphate ions are respectively and uniformly dispersed in an aqueous organic solvent to respectively form corresponding solutions, and then the solutions are mixed and stirred to carry out hydrothermal reaction, and the obtained reaction product is filtered, washed and dried to obtain a finished product.
Neither of the two techniques can realize the size control of focusing manganese phosphate, and the electrochemical properties such as cycling stability and the like still have a room for increasing.
In the existing literature, preparation and research of a negative plate material of an acid salt bond ion secondary battery (Wu Tongfu, Nanjing university, 2016), MnSO is adopted4As a source of manganese, NH4H2PO4Mn prepared by conventional solvothermal method for phosphorus source2P2O7The material is used as the negative electrode material of lithium ion secondary battery, and Mn is generated after the cycle number exceeds 202P2O7The discharge capacity was stabilized at 390 mAh/g. In the existing document "Solvothermal synthesis of Mn2P2O7 and its application in lithium-ion battery Shiquan" (Shiquan Wang, Xueya Jiang, et al. materials Letters, 2011, 65: 3265-2S5Mn production by solvothermal method2P2O7The initial specific capacity of the material is 470mAh/g, the material is reduced to 300mAh/g after 10 cycles of circulation, and is reduced to only 160mAh/g after 35 cycles of circulation. The prior art document "immunization of involved Irregenerative Capacity in Mesoporous Tin phosphor Coating" (Eunjin Kim, Yoojin Kim, et al. electrochemical and solid-State Letters, 2006, 9(3): A156-A159) discloses that SnCl is added4And Na2HPO4Obtaining Sn by solvothermal2P2O7At a current density of 65mA/g, the current density remained 467mAh/g after 20 cycles. The electrochemical properties of the electrode materials prepared in these documents have room for improvement, particularly in terms of stability after repeated use.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a manganese pyrophosphate electrode material, which is realized by the following technology.
A preparation method of a manganese pyrophosphate electrode material comprises the following steps:
s1, dissolving sodium sulfide nonahydrate in water to prepare a sodium sulfide solution with the concentration of 1.2-3.5 mol/L, dropwise adding 6-7 ml of phosphorus trichloride into the sodium sulfide solution, stirring and reacting at normal temperature for 2-5 hours, taking out crystals, washing, and carrying out vacuum filtration and drying to obtain a precursor I; the precursor I is white powder;
s2, dissolving the precursor I and soluble divalent manganese salt in water, adding polyvinylpyrrolidone, stirring and reacting at normal temperature for 12-24 h, taking out crystals, washing, vacuum-filtering and drying to obtain a precursor II;
and S3, annealing the precursor II at 500-900 ℃ in the atmosphere of nitrogen or inert gas to obtain the manganese pyrophosphate electrode material.
When the manganese pyrophosphate electrode material is prepared by adopting the steps, the reaction principle is as follows: in step S1, phosphorus trichloride PCl3During the process of slowly dripping the sodium sulfide NaS solution, the sodium sulfide NaS solution is firstly mixed with oxygen O in the air2Oxidation reaction is carried out to generate phosphorus oxychloride POCl3Then sodium sulfide reacts with phosphoryl chloride in water to generate Na2HPO4Adding soluble divalent manganese salt (such as manganese chloride, manganese sulfate, manganese acetate, manganese nitrate, etc.), ion-exchanging sodium ion with manganese ion, and pyrolyzing under inert atmosphere to obtain Mn2P2O7(ii) a After polyvinylpyrrolidone (PVP) is added, the strong interaction between PVP and manganese ions can reduce the electrostatic attraction between crystals to achieve the dispersion effect, the crystal size can be obviously reduced in the crystal growth process, and the cycling stability of the battery is improved. Electrochemical tests prove that the manganese pyrophosphate material prepared by the method is used as a negative electrode material of a lithium battery, and the discharge capacitance of the first circle reaches 864.6mAh/g and the discharge capacitance of the lithium battery still reaches 482.5mAh/g after 200 circles of circulation under the condition that the current density is 0.1 mA/g.
When preparing manganese pyrophosphate electrode material, Na is not generated in the reaction2HPO4In addition, Na may be produced by side reactions3HPO4And Na produced2HPO4There are two different crystal forms. Therefore, if the above steps are not followed, for example, the whole raw materials are directly mixed and reacted, more side reactions are generated, the purity of the product is low, the impurity content is higher, and the yield of the electrode material is seriously influenced.
Preferably, in step S1, the ambient temperature of phosphorus trichloride when dropwise adding the sodium sulfide solution is-1 to 5 ℃. The precipitation of white crystals is accelerated at-1 to 5 ℃.
More preferably, in step S1, after stirring and reacting for 2-5h at normal temperature, standing at 0-5 ℃ for 12h, then taking out the crystal, washing, vacuum filtering and drying. The effect of first standing at 0-5 ℃ is also to accelerate the precipitation of white crystals.
More preferably, the washing process of step S1 employs absolute ethanol washing; the washing process of step S2 is performed by first washing with deionized water and then with absolute ethanol. The precursor I is easily dissolved by water, and in order to accelerate drying, the effect is best by using absolute ethyl alcohol.
Preferably, in step S2, the weight ratio of the precursor i, the soluble divalent manganese salt, and the polyvinylpyrrolidone is 0.8:1: 0.5-2.
More preferably, in step S2, the weight ratio of the precursor i, the soluble manganous salt and the polyvinylpyrrolidone is 0.8:1: 1. The more PVP is not added, the better, when PVP is added in a certain dosage range, Mn can be reduced2P2O7The specific capacity of the battery is reduced due to the increase of the carbon content, because the theoretical specific capacity of the carbon is 372mAh/g, the specific capacity of the battery is reduced. If the content of the PVP exceeds the upper limit of the PVP, the specific capacity of manganese pyrophosphate can be seriously reduced in the charging and discharging processes, so that the cycle stability performance is influenced.
Preferably, in step S3, the temperature increase rate of the annealing treatment is 2 to 5 ℃/min, and the time of the annealing treatment is 4 hours. By adopting the temperature rise rate, the phenomenon that the temperature rises too fast to influence the performance of a reaction product can be prevented.
Preferably, the material is applied to button cells as an electrode material.
Compared with the prior art, the invention has the advantages that:
1. the invention adopts a simple and feasible three-step preparation method, the cost of raw materials required by synthesis preparation is low, the yield of the prepared electrode material is high, and the method is suitable for large-scale production;
2. by adjusting the consumption of the high molecular compound PVP, the size of the manganese pyrophosphate can be accurately regulated and controlled, and the experimental repeatability is high;
3. the manganese pyrophosphate material prepared by the invention has very good electrochemical performance as an electrode material, and the first-circle discharge capacitance and the cycle stability of the manganese pyrophosphate material are far higher than those of other existing manganese pyrophosphate electrode materials. When the lithium battery cathode is used for a lithium battery cathode, electrochemical tests prove that the discharge capacitance of the first circle reaches 864.6mAh/g under the condition that the current density is 0.1mA/g, and the discharge capacitance of the first circle still reaches 482.5mAh/g after 200 cycles.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of a manganese pyrophosphate electrode material prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of the manganese pyrophosphate electrode material prepared in example 1;
FIG. 3 is a CV curve of a manganese pyrophosphate electrode material prepared in example 1;
FIG. 4 is a constant current charge and discharge curve of the manganese pyrophosphate electrode material prepared in example 1;
FIG. 5 is a cycle curve of the manganese pyrophosphate electrode material prepared in example 1;
FIG. 6 is a Nyquist plot for the manganese pyrophosphate electrode material prepared in example 1;
FIG. 7 is a Scanning Electron Microscope (SEM) picture of the manganese pyrophosphate electrode material prepared in example 2;
FIG. 8 is a Scanning Electron Microscope (SEM) picture of the manganese pyrophosphate electrode material prepared in example 3;
FIG. 9 is a Scanning Electron Microscope (SEM) picture of a manganese pyrophosphate electrode material prepared in comparative example 3;
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The manganese pyrophosphate electrode material provided by the embodiment is prepared by the following method:
s1, dissolving 48g of sodium sulfide nonahydrate in 100mL of deionized water to prepare a sodium sulfide solution with the concentration of about 2mol/L, dropwise adding 6.6mL of phosphorus trichloride into the sodium sulfide solution at 5 ℃, stirring and reacting for 2-5h at normal temperature, putting the solution into a refrigerator to accelerate crystallization, taking out crystals, washing, and carrying out vacuum filtration and drying to obtain a white powdery precursor I;
s2, dissolving 0.4g of the precursor I and 0.5g of soluble divalent manganese salt in water, and adding 0.5g of polyvinylpyrrolidone, namely the precursor I and manganese chloride (MnCl)2) The weight ratio of polyvinylpyrrolidone to polyvinylpyrrolidone is 0.8:1:1, stirring and reacting for 12h at normal temperature, taking out crystals, washing, vacuum filtering and drying to obtain a precursor II;
and S3, putting the precursor II into a tube furnace, heating to 700 ℃ at the speed of 3 ℃/min in the nitrogen atmosphere, keeping the temperature for 4h, and annealing to obtain the manganese pyrophosphate electrode material.
Example 2
The manganese pyrophosphate electrode material provided by the embodiment is different from the manganese pyrophosphate electrode material provided by the embodiment 1 in that: in step S2, 0.4g of the precursor I and 0.5g of soluble manganous salt are taken and dissolved in water, and 0.25g of polyvinylpyrrolidone is added, namely the weight ratio of the precursor I to the soluble manganous salt to the polyvinylpyrrolidone is 0.8:1: 0.5.
The other steps are the same as in example 1.
Example 3
The manganese pyrophosphate electrode material provided by the embodiment is different from the manganese pyrophosphate electrode material provided by the embodiment 1 in that: in step S2, 0.4g of the precursor I and 0.5g of soluble manganous salt are taken and dissolved in water, and 1g of polyvinylpyrrolidone is added, namely the weight ratio of the precursor I to the soluble manganous salt to the polyvinylpyrrolidone is 0.8:1:2.
The other steps are the same as in example 1.
Comparative example 1
The manganese pyrophosphate electrode material provided by the comparative example has the same preparation method as that of example 3, except that the step S2 is: dissolving 0.4g of the precursor I and 0.5g of soluble divalent manganese salt in water, and adding 1.2g of polyvinylpyrrolidone, namely the precursor I and manganese chloride (MnCl)2) And polyvinylpyrrolidone in a weight ratio of 0.8:1:2.4, stirring and reacting for 12 hours at normal temperature, taking out the crystal, washing, vacuum-filtering and drying to obtain a precursor II.
Comparative example 2
The manganese pyrophosphate electrode material provided by the comparative example has the same preparation method as that of example 3, except that the step S2 is: dissolving 0.4g of the precursor I and 0.5g of soluble divalent manganese salt in water, and adding 0.1g of polyvinylpyrrolidone, namely the precursor I and manganese chloride (MnCl)2) And polyvinylpyrrolidone in a weight ratio of 0.8:1:0.2, stirring and reacting for 12 hours at normal temperature, taking out the crystal, washing, vacuum-filtering and drying to obtain a precursor II.
Comparative example 3
The manganese pyrophosphate electrode material provided by the comparative example is prepared by the following method:
s1, dissolving 48g of sodium sulfide nonahydrate in 100mL of deionized water to prepare a sodium sulfide solution with the concentration of about 2mol/L, dropwise adding 6.6mL of phosphorus trichloride into the sodium sulfide solution at 5 ℃, stirring and reacting for 2-5h at normal temperature, putting the solution into a refrigerator to accelerate crystallization, taking out crystals, washing, and carrying out vacuum filtration and drying to obtain a white powdery precursor I;
s2, dissolving 0.4g of the precursor I and 0.5g of soluble divalent manganese salt in water (namely polyvinylpyrrolidone is not added), stirring and reacting at normal temperature for 12 hours (namely PVP is not added), taking out crystals, washing, carrying out vacuum filtration and drying to obtain a precursor II;
and S3, putting the precursor II into a tube furnace, heating to 700 ℃ at the speed of 3 ℃/min in the nitrogen atmosphere, keeping the temperature for 4h, and annealing to obtain the manganese pyrophosphate electrode material.
Application example 1: appearance and electrochemical performance tests of manganese pyrophosphate electrode materials prepared in examples 1-3 and comparative examples 1-3
1. The appearance of the manganese pyrophosphate electrode materials prepared in examples 1 to 3 and comparative example 3 was observed by a Scanning Electron Microscope (SEM). When manganese chloride (MnCl) is changed as shown in FIGS. 1, 7-92) And polyvinylpyrrolidone in a weight ratio to Mn2P2O7Has a significant effect on the size of (A) when manganese chloride (MnCl) is used2) And Mn when the weight ratio of polyvinylpyrrolidone is 1:12P2O7Is the smallest.
2. The manganese pyrophosphate material prepared in examples 1 to 3 was mixed with a conductive agent (Super p) and a binder (polytetrafluoroethylene PVDF) at a mass ratio of 6:3:1, and an appropriate amount of N-methylpyrrolidone (NMP) was added to form a slurry, which was coated on a copper foil using a doctor blade or a four-side coater. The coated copper foil is firstly put into a drying oven to be dried for 2 hours at the temperature of 60 ℃, then is put into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃, then the copper foil coated with the material is cut into small wafers with the diameter of 12mm, the wafers are put into a glove box to be assembled into a button cell, and the electrochemical performance of the button cell is tested.
As shown in fig. 3 to 6, the 4 graphs are used to measure the electrochemical performance of the manganese pyrophosphate electrode material prepared in example 1 as a negative electrode of a lithium battery. The CV diagram of fig. 3 may reveal the chemical reaction that the manganese pyrophosphate material takes part in during the charge and discharge processes. Taking the CV diagram under the sweep rate of 10mv/s as an example, the reduction peak position is 0.9V: mn + xLix+xe-→LixMn; oxidation peak position-1.2V: i.e. ixMn→Mn+xLix+xe-Oxidation peak position 1.9V: lixC→C+xLix+xe-. Fig. 4 shows the specific charge-discharge capacity of the first, second and 200 th circles during the charge-discharge process. Figure 5 shows the performance of the manganese pyrophosphate material after 200 cycles, indicating its stability. Figure 6 may indirectly show the sodium ion transport rate in the manganese pyrophosphate material. The resistance of the sodium ions in the manganese pyrophosphate material can be obtained through the fitting of an equivalent device.
As shown in FIGS. 3 to 6, when the manganese pyrophosphate electrode material prepared in example 1 is used, the first cycle of discharge capacitance reaches 864.6mAh/g, the discharge capacitance after 200 cycles still reaches 482.5mAh/g, and the resistance is 83.6 Ω under the condition of 0.1A/g of current density. Tests show that the manganese pyrophosphate electrode material prepared in the embodiment 2 has a first-turn discharge capacitance of 879.1mAh/g and a discharge capacitance of 454.9mAh/g after 200 cycles, and the manganese pyrophosphate electrode material prepared in the embodiment 3 has a first-turn discharge capacitance of 819.5mAh/g and a discharge capacitance of 437.3mAh/g after 200 cycles, which are inferior to those of the embodiment 1; the manganese pyrophosphate electrode material prepared in the comparative example 1 has the discharge capacitance of 738.4mAh/g in the first circle and only 359.8mAh/g after 200 cycles under the same test condition, which indicates that the PVP consumption is too high and has adverse effect on the performance of the battery; the manganese pyrophosphate electrode material prepared in the comparative example 2 has the first circle discharge capacitance of 898.7mAh/g and the discharge capacitance of only 322.6mAh/g after 200 cycles under the same test conditions; the manganese pyrophosphate electrode material prepared in the comparative example 3 has the discharge capacity of only 893.2mAh/g in the first circle under the same test condition, and the discharge capacity is reduced to 275.4mAh/g after 200 cycles. This shows that when PVP is not added, not only the size of the manganese pyrophosphate electrode material is affected, but also the conductivity of the electrode material can be seriously affected. Only when the soluble divalent manganese salt and the polyvinylpyrrolidone are used, the manganese pyrophosphate electrode material with the best electrochemical performance can be prepared.
Through analysis, generally, an electrode material is coated on an electrode made of a conductive metal material (copper foil), when the size of the electrode material is too large (several micrometers), the electrode material is easy to generate volume deformation in the use process of a battery and further fall off from the electrode, and the smaller the size is, the more the electrode material is not easy to fall off; in addition, the smaller the size of the electrode material, the more beneficial the transmission of metal ions and electrons, the shorter the travel path of the electrons, and the better the conductivity.
Claims (8)
1. The preparation method of the manganese pyrophosphate electrode material is characterized by comprising the following steps of:
s1, dissolving sodium sulfide nonahydrate in water to prepare a sodium sulfide solution with the concentration of 1.2-3.5 mol/L, dropwise adding 6-7 ml of phosphorus trichloride into the sodium sulfide solution, stirring and reacting at normal temperature for 2-5 hours, taking out crystals, washing, and carrying out vacuum filtration and drying to obtain a precursor I;
s2, dissolving the precursor I and soluble divalent manganese salt in water, adding polyvinylpyrrolidone, stirring and reacting at normal temperature for 12-24 h, taking out crystals, washing, vacuum-filtering and drying to obtain a precursor II;
and S3, annealing the precursor II at 500-900 ℃ in the atmosphere of nitrogen or inert gas to obtain the manganese pyrophosphate electrode material.
2. The method for preparing a manganese pyrophosphate electrode material as claimed in claim 1, wherein in step S1, the ambient temperature of phosphorus trichloride when dropping dropwise into the sodium sulfide solution is-1 to 5 ℃.
3. The method for preparing a manganese pyrophosphate electrode material according to claim 1 or 2, wherein in step S1, after stirring and reacting for 2-5 hours at normal temperature, the reaction product is allowed to stand at 0-5 ℃ for 12 hours, and then the crystal is taken out, washed, vacuum filtered and dried.
4. The method for preparing a manganese pyrophosphate electrode material according to claim 1 or 2, wherein the washing process of step S1 is washing with absolute ethanol; the washing process of step S2 is performed by first washing with deionized water and then with absolute ethanol.
5. The method for preparing a manganese pyrophosphate electrode material according to claim 1, wherein in step S2, the weight ratio of the precursor i, the soluble manganous salt and the polyvinylpyrrolidone is 0.8:1: 0.5-2.
6. The method for preparing a manganese pyrophosphate electrode material according to claim 5, wherein in step S2, the weight ratio of the precursor I, the soluble manganous salt and the polyvinylpyrrolidone is 0.8:1: 1.
7. The method for preparing a manganese pyrophosphate electrode material according to claim 1, wherein in step S3, the temperature rise rate of the annealing treatment is 2 to 5 ℃/min, and the time of the annealing treatment is 4 hours.
8. The application of the manganese pyrophosphate electrode material prepared by the preparation method of claim 1 is characterized in that the manganese pyrophosphate electrode material is applied to button cells as an electrode material.
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