CN111573738A - Pure cubic phase Mg2MnO4Spinel material and preparation method and application thereof - Google Patents

Pure cubic phase Mg2MnO4Spinel material and preparation method and application thereof Download PDF

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CN111573738A
CN111573738A CN202010451001.3A CN202010451001A CN111573738A CN 111573738 A CN111573738 A CN 111573738A CN 202010451001 A CN202010451001 A CN 202010451001A CN 111573738 A CN111573738 A CN 111573738A
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cubic phase
spinel material
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段秀兰
王珍彦
艾黎
于法鹏
朱朋飞
丁吉民
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Shandong University
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    • C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
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Abstract

The invention provides pure cubic phase Mg2MnO4The spinel material and the preparation method and application thereof, wherein the preparation method of the spinel material comprises the following steps: dissolving magnesium salt and manganese salt in deionized water according to the molar ratio of 1:2, and fully and uniformly stirring to obtain a mixed solution; adding a polyvinyl alcohol aqueous solution into the obtained mixed solution, fully stirring and mixing to obtain transparent sol, heating the transparent sol to evaporate the solvent to obtain viscous gel, and drying to obtain a dry gel precursor; and grinding the obtained xerogel precursor, performing heat treatment, and cooling to room temperature to obtain the xerogel. The method has simple process and easy operation, and the types of the required raw materialsLess, low cost, synthesis of Mg with pure cubic phase2MnO4And (3) nano materials. Mg prepared by the invention2MnO4The material can be used as a lithium ion battery cathode, has good cycle stability, shows wide application prospect in the field of ion batteries, and expands the application range of the material.

Description

Pure cubic phase Mg2MnO4Spinel material and preparation method and application thereof
Technical Field
The invention relates to pure cubic phase Mg2MnO4Spinel material and preparation method and application thereof, belonging to the technical field of novel battery materials.
Background
With the gradual reduction of fossil energy and the enhancement of awareness of people on environmental protection, the development of a sustainable green energy storage system is promoted. As an environment-friendly energy storage device, research on lithium ion batteries has been greatly advanced in recent years and is widely used. The lithium ion battery generally comprises three parts, namely a positive electrode, electrolyte and a negative electrode, wherein the negative electrode is an important component of the lithium ion battery and plays a decisive role in the performance of the battery. At present, the widely applied graphite-based negative electrode material has the problems of low theoretical capacity, low potential, potential safety hazard and the like. Therefore, the search for a novel anode material with excellent performance becomes one of the research hotspots in the field of lithium ion batteries.
Spinel compounds are important inorganic functional materials, and have the advantages of corrosion resistance, high hardness, good thermal stability and the like, so that the spinel compounds are widely applied to the fields of electronics, ceramics, optics, magnetics, catalysis and the like. Among the numerous spinel systems, manganese-based spinels are of great interest because of their unique properties. Manganese ions have multiple valence states, electrons are easy to transfer, the three-dimensional network structure of spinel is favorable for ion transfer, and the spinel containing manganese is widely applied to the fields of secondary batteries, electro-catalysts and the like, such as the anode material LiMn of lithium ion batteries2O4And the like. In recent years, CoMn2O4，ZnMn2O4The iso-spinel has attracted great research interest as a novel lithium ion battery cathode material.
Manganese spinels used as battery materials have manganese valence states of mainly +2, +3 and +4, and are composed of high content of Mn4+The spinel of the composition is more favorable for the migration of ions. Mg (magnesium)2MnO4The compound has the structureThe cubic spinel structure, Mn exists mainly in +4 valences and occupies octahedral lattice sites of the spinel structure. At present, the synthesis method of the material mainly comprises a solid phase method, a coprecipitation method and a microemulsion method, wherein the first two methods are difficult to obtain pure phases, and although the material prepared by the microemulsion method is relatively pure in phase, the types of the used raw materials are more, and the process is complex and difficult to control. For example: chinese patent document CN106540534A provides a magnesium manganese composite oxide sulfur transfer agent and a preparation method thereof, wherein the magnesium manganese composite oxide is MgAC with a molar ratio of 1:0.3-32·4H2O and MnAC2·4H2O mixing, and then aerobic calcining, wherein MgAC is2·4H2O and MnAC2·4H2When the molar ratio of O is 1:0.3-0.7, the obtained main product is Mg2MnO4. In the above process, the product obtained is Mg2MnO4With MgMn2O4Mixture of (2), Mg of pure phase not being obtained2MnO4. Garg et al with MnCl2·4H2O、MgSO4Taking ammonium oxalate as a raw material, taking CTAB as a surfactant, 1-butanol as a cosurfactant and isooctane as an oil phase, and preparing Mg by adopting microemulsion2MnO4. (see: Journal of Solid State chemistry 197(2013): 392-.
Therefore, there is a need to develop a cubic phase Mg which is simple to prepare and gives a product having high purity2MnO4A method for preparing spinel material. And the currently reported Mg2MnO4The material is mainly used as an adsorbent and an electrocatalyst, and application reports in the aspect of lithium ion batteries are not found. The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides pure cubic phase Mg2MnO4The preparation method of the spinel material is simple to operate, and Mg with pure cubic phase can be synthesized2MnO4The electrochemical test proves that the material can be used as a negative electrode material of a lithium ion battery.
The technical scheme of the invention is as follows:
pure cubic phase Mg2MnO4The spinel material is prepared by using inorganic salts of magnesium and manganese as raw materials and polyvinyl alcohol (PVA) as a complexing agent, preparing a precursor by adopting a sol-gel method, and carrying out heat treatment on the precursor.
According to the invention, the pure cubic phase Mg mentioned above2MnO4The preparation method of the spinel material comprises the following steps:
(1) dissolving magnesium salt and manganese salt in deionized water according to the molar ratio of 1:2, and fully and uniformly stirring to obtain a mixed solution;
(2) adding a polyvinyl alcohol aqueous solution into the mixed solution obtained in the step (1), fully stirring and mixing to obtain transparent sol, heating the transparent sol to evaporate the solvent to obtain viscous gel, and drying to obtain a dry gel precursor;
(3) grinding the xerogel precursor obtained in the step (2), then carrying out heat treatment, and then cooling to room temperature to obtain pure cubic phase Mg2MnO4A spinel material.
According to the present invention, preferably, the magnesium salt in step (1) is magnesium nitrate or magnesium acetate; the manganese salt is manganese nitrate or manganese acetate.
According to the present invention, the total concentration of the magnesium salt and the manganese salt in the mixed solution in the step (1) is preferably 0.7 to 1.1mol/L, and more preferably 1 mol/L.
According to the present invention, the mass fraction of the polyvinyl alcohol aqueous solution in the step (2) is preferably 8 to 12%, and more preferably 10%.
According to the present invention, the weight average molecular weight of the polyvinyl alcohol in step (2) is preferably 90000-120000, more preferably 100000-110000, and most preferably 105000.
According to the present invention, it is preferable that the ratio of the number of moles of the polyvinyl alcohol to the total number of moles of the magnesium salt and the manganese salt in the step (2) is 1-2: 1.
According to the present invention, it is preferable that the drying temperature in step (2) is 100-120 ℃; the drying time is 8 to 12 hours, more preferably 10 to 12 hours.
According to the present invention, the heat treatment temperature in step (3) is preferably 500-700 ℃, and the holding time is preferably 2-5h, and more preferably 2-3 h.
According to the invention, preferably, the temperature rise rate of the heat treatment process in the step (3) is 40-80 ℃/h, and the temperature drop rate of the temperature reduction is 60-100 ℃/h.
The particle size of the spinel material obtained by the invention is 30-70nm, and the prepared Mg-Mn-O spinel material is cubic phase Mg2MnO4。
According to the invention, the pure cubic phase Mg mentioned above2MnO4The spinel material is applied to a lithium ion battery as a negative electrode material.
According to the use of the invention, preferably, said pure cubic phase Mg2MnO4The spinel material is used as a negative electrode material and applied to a lithium ion battery, and the specific application steps are as follows: with the above-mentioned Mg2MnO4And (3) assembling the lithium ion button battery by taking an electrode plate prepared from the spinel material as a negative electrode, a metal lithium plate as a counter electrode, polyethylene as a battery diaphragm and lithium hexafluorophosphate as electrolyte.
The invention has the following technical characteristics and beneficial effects:
1. pure cubic phase Mg of the invention2MnO4The spinel nano material is prepared by taking inorganic salts of magnesium and manganese as raw materials and polyvinyl alcohol (PVA) as a complexing agent by adopting a sol-gel method, and Mg2MnO4The formation of (A) is the result of the synergistic effect among a magnesium source, a manganese source and a complexing agent, firstly, the complexing agent polyvinyl alcohol reacts with two metal ions to form a metal ion complex Mg2Mn[(C2H4O)n]xThen high-temperature sintering is carried out, C, H CO is respectively generated2And H2O escapes to finally obtain Mg2MnO4And (3) obtaining the product. The method has the advantages of simple process, easy operation, few types of required raw materials, simple equipment and low cost, and is beneficial to industrial mass production.
2. Mg prepared by the invention2MnO4The spinel material can be used as a lithium ion battery cathode material through tests, has good cycle stability, shows wide application prospect in the field of ion batteries, and expands the application range of the material.
Drawings
FIG. 1 is pure cubic phase Mg prepared in example 12MnO4X-ray powder diffraction pattern of spinel material.
FIG. 2 is pure cubic phase Mg prepared in example 22MnO4X-ray powder diffraction pattern of spinel material.
FIG. 3 is pure cubic phase Mg prepared in example 22MnO4Transmission electron micrograph of spinel material.
FIG. 4 is pure cubic phase Mg prepared in example 32MnO4X-ray powder diffraction pattern of spinel material.
FIG. 5 pure cubic Mg prepared in example 32MnO4Transmission electron micrograph of spinel material.
FIG. 6 pure cubic Mg prepared in example 32MnO4And the spinel material is used as a constant current charge-discharge test chart of the lithium ion battery cathode.
FIG. 7 is cubic phase Mg prepared in comparative example 12MnO4And the spinel material is used as a constant current charge-discharge test chart of the lithium ion battery cathode.
FIG. 8 is an X-ray powder diffraction pattern of the Mg-Mn-O spinel material prepared in comparative example 2.
FIG. 9 is an X-ray powder diffraction pattern of the Mg-Mn-O spinel material prepared in comparative example 3.
FIG. 10 is an X-ray powder diffraction pattern of the Mg-Mn-O spinel material prepared in comparative example 4.
FIG. 11 is an X-ray powder diffraction pattern of the Mg-Mn-O spinel material prepared in comparative example 5.
FIG. 12 is an X-ray powder diffraction pattern of the Mg-Mn-O spinel material prepared in comparative example 6.
FIG. 13 is an X-ray powder diffraction pattern of the Mg-Mn-O spinel material prepared in comparative example 7.
Detailed Description
The invention is further described below with reference to specific examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
The polyvinyl alcohol used in the examples was purchased from national chemical group, chemical Co., Ltd, and had a weight average molecular weight of 105000.
Example 1
Pure cubic phase Mg2MnO4The preparation method of the spinel material comprises the following steps:
(1) 0.02mol of magnesium nitrate and 0.04mol of manganese acetate are dissolved in deionized water, and the mixture is fully and uniformly stirred to prepare a mixed solution with the total concentration of magnesium salt and manganese salt being 1 mol/L.
(2) Adding a polyvinyl alcohol aqueous solution with the mass fraction of 10% into the mixed solution obtained in the step (1), wherein the ratio of the total mole number of magnesium salt and manganese salt to the mole number of polyvinyl alcohol (PVA) is 1:2, fully mixing under magnetic stirring to form transparent sol, and directly heating the transparent sol on a hot plate of a magnetic stirrer to evaporate the solvent to obtain viscous gel; and (3) drying the prepared viscous gel in a drying oven at 100 ℃ for 12h to obtain a dry gel precursor.
(3) Grinding the xerogel precursor obtained in the step (2), then placing the ground xerogel precursor into a sintering furnace, heating to 500 ℃ at a heating rate of 60 ℃/h, preserving heat for 2h at 500 ℃, and then cooling to room temperature at a cooling rate of 80 ℃/h to obtain pure cubic phase Mg2MnO4A spinel material.
The X-ray powder diffraction (XRD) pattern of the cubic spinel material prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that cubic Mg is present at a heat treatment temperature of 500 c by the sol-gel method2MnO4Characteristic peaks, product prepared in this example and Mg2MnO4The standard cards (No.19-0773) are in one-to-one correspondence, the peak appearing about 20 in 2Theta is caused by a silicon dioxide sample table, and meanwhile, other miscellaneous peaks are not seen on an XRD (X-ray diffraction) pattern of the obtained product, which indicates that the method provided by the invention is used for preparing the productMg2MnO4Has high purity.
Example 2
Pure cubic phase Mg2MnO4The spinel material was prepared as described in example 1, except that in step (3) the xerogel precursor was placed in a sintering furnace at a heat treatment temperature of 600 ℃ and held for 2 hours.
The XRD pattern of the cubic phase spinel material prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the product obtained at a heat treatment temperature of 600 c has an increased degree of crystallinity compared to that of example 1; meanwhile, no other miscellaneous peak is found on the XRD pattern of the obtained product, which indicates that the Mg prepared by the method of the invention2MnO4Has high purity.
The transmission electron micrograph of the cubic spinel material prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that the grain size of the product is about 40 nm.
Example 3
Pure cubic phase Mg2MnO4The spinel material was prepared as described in example 1, except that in step (3) the xerogel precursor was placed in a sintering furnace at a heat treatment temperature of 700 ℃ and held for 2 hours.
The XRD pattern of the cubic phase spinel material prepared in this example is shown in fig. 4, and it can be seen from fig. 4 that the degree of crystallinity of the product obtained at the heat treatment temperature of 700 c is further enhanced as compared with example 1 and example 2; meanwhile, no other miscellaneous peak is found on the XRD pattern of the obtained product, which indicates that the Mg prepared by the method of the invention2MnO4Has high purity.
The transmission electron micrograph of the cubic spinel material prepared in this example is shown in FIG. 5. it can be seen from FIG. 5 that the grain size of the product is 50-70 nm.
Pure cubic phase Mg prepared in this example2MnO4Assembling and electrochemically testing the lithium ion battery by using the spinel material:
pure cubic phase Mg obtained in this example2MnO4The spinel material is an active substance, and is mixed with acetylene black and PVDF according to the mass ratio of 8:1:1Mixing, mixing with NMP solvent to obtain slurry, uniformly coating on copper foil, drying the obtained electrode plate in a vacuum drying oven at 120 ℃ for 12 hours, naturally cooling, and cutting into electrode plates with proper sizes. A button cell is assembled in a glove box filled with Ar gas by taking a lithium sheet as a counter electrode, polyethylene as a battery diaphragm and lithium hexafluorophosphate as electrolyte.
The assembled button cell was subjected to constant current charge and discharge test on a blue light test system, and the test results are shown in fig. 6. As can be seen from FIG. 6, the first charge-discharge specific capacity of the battery is 85.4mAh/g and 346.1mAh/g respectively, except for the first circle, the capacity tends to be stable along with the circulation, and the circulation efficiency is stable over 98%. Mg prepared by the invention2MnO4The spinel material has a specific three-dimensional frame structure and good stability, and has higher cycling stability when being used for a lithium ion battery cathode.
Comparative example 1
Cubic phase Mg2MnO4The spinel material was prepared as described in example 1, except that in step (3) the xerogel precursor was placed in a sintering furnace at a heat treatment temperature of 800 ℃ and held for 2 hours.
Mg prepared by this comparative example2MnO4The particle size of the spinel material is increased, and the constant current charge-discharge test result is shown in fig. 7, and the specific capacity is reduced compared with the product subjected to heat treatment at the temperature of 700 ℃.
Comparative example 2
A Mg-Mn-O spinel material was prepared as described in example 3, except that citric acid was added simultaneously with the addition of the aqueous polyvinyl alcohol (PVA) solution in step (2), and the added citric acid: the molar ratio of the magnesium salt to the manganese salt is 2: 1.
the XRD pattern of the product prepared by the comparative example is shown in FIG. 8, and it can be seen from FIG. 8 that MgMn with tetragonal main phase is obtained after the polyvinyl alcohol/citric acid composite complexing agent is added2O4(Standard card No.23-0392) only a trace amount of cubic Mg was obtained2MnO4(*)。
Comparative example 3
A Mg-Mn-O spinel material is prepared as described in example 3, except that in step (2), an aqueous solution of 40% by weight of sucrose is added simultaneously with the addition of the aqueous solution of polyvinyl alcohol (PVA), the mixed solution is stirred uniformly, and then nitric acid is added to adjust the pH of the solution to 1, wherein the ratio of sucrose: magnesium salt + manganese salt: the molar ratio of polyvinyl alcohol is 4: 1: 1.
the XRD pattern of the product prepared in this comparative example is shown in FIG. 9, and it can be seen from FIG. 9 that the resulting product is mainly tetragonal MgMn2O4Only trace amount of cubic phase Mg is obtained2MnO4(*)。
Comparative example 4
A Mg-Mn-O spinel material was prepared as described in example 3, except that in step (2) the aqueous polyvinyl alcohol (PVA) solution was replaced with citric acid: the molar ratio of the magnesium salt to the manganese salt is 2: 1.
the XRD pattern of the product prepared in this comparative example is shown in FIG. 10, and it can be seen from FIG. 10 that the resulting product is mainly tetragonal MgMn2O4Only a small amount of cubic phase Mg is obtained2MnO4(*)。
Comparative example 5
A Mg-Mn-O spinel material was prepared as described in example 3, except that in step (2), the polyvinyl alcohol (PVA) aqueous solution was replaced with 40% by mass of sucrose aqueous solution, the mixed solution was stirred uniformly, and then nitric acid was added to adjust the pH of the solution to 1, the ratio of sucrose: the molar ratio of the magnesium salt to the manganese salt is 4: 1.
the XRD pattern of the product prepared in this comparative example is shown in FIG. 11, and it can be seen from FIG. 11 that the resulting product is mainly tetragonal MgMn2O4Only a small amount of cubic phase Mg is obtained2MnO4(*)。
Comparative example 6
A Mg-Mn-O spinel material was prepared as described in example 3, except that an aqueous solution of polyvinyl alcohol (PVA) was not added in step (2).
The XRD pattern of the product prepared in this comparative example is shown in FIG. 12, and it can be seen from FIG. 12 that the resulting product is mainly tetragonal MgMn2O4Only, isA small amount of cubic phase Mg is obtained2MnO4(*)。
Comparative example 7
A Mg-Mn-O spinel material was prepared as described in example 3, except that in step (2) the aqueous polyvinyl alcohol (PVA) solution was replaced with citric acid and ethylene glycol, the citric acid: ethylene glycol: the molar ratio of the magnesium salt to the manganese salt is 2: 6: 1.
the XRD pattern of the product prepared in this comparative example is shown in FIG. 13, and as can be seen from FIG. 13, the resulting product is tetragonal MgMn2O4And Mn2O3The two phases coexist and no cubic phase Mg appears2MnO4Characteristic peak of (2).

Claims (10)

1. Pure cubic phase Mg2MnO4The spinel material is characterized in that the spinel material is obtained by using inorganic salts of magnesium and manganese as raw materials and polyvinyl alcohol as a complexing agent, preparing a precursor by a sol-gel method, and carrying out heat treatment on the precursor.
2. Pure cubic phase Mg of claim 12MnO4The preparation method of the spinel material comprises the following steps:
(1) dissolving magnesium salt and manganese salt in deionized water according to the molar ratio of 1:2, and fully and uniformly stirring to obtain a mixed solution;
(2) adding a polyvinyl alcohol aqueous solution into the mixed solution obtained in the step (1), fully stirring and mixing to obtain transparent sol, heating the transparent sol to evaporate the solvent to obtain viscous gel, and drying to obtain a dry gel precursor;
(3) grinding the xerogel precursor obtained in the step (2), then carrying out heat treatment, and then cooling to room temperature to obtain pure cubic phase Mg2MnO4A spinel material.
3. Pure cubic phase Mg of claim 22MnO4The preparation method of the spinel material is characterized in that the magnesium salt in the step (1) is magnesium nitrate or magnesium acetate; the above-mentionedThe manganese salt of (1) is manganese nitrate or manganese acetate; the total concentration of the magnesium salt and the manganese salt in the mixed solution is 0.7-1.1mol/L, and preferably 1 mol/L.
4. Pure cubic phase Mg of claim 22MnO4The preparation method of the spinel material is characterized in that the mass fraction of the polyvinyl alcohol aqueous solution in the step (2) is 8-12%, preferably 10%; the weight average molecular weight of the polyvinyl alcohol is 90000-120000, preferably 100000-110000, and more preferably 105000.
5. Pure cubic phase Mg of claim 22MnO4The preparation method of the spinel material is characterized in that the ratio of the mole number of the polyvinyl alcohol to the total mole number of the magnesium salt and the manganese salt in the step (2) is 1-2: 1.
6. Pure cubic phase Mg of claim 22MnO4The preparation method of the spinel material is characterized in that the drying temperature in the step (2) is 100-120 ℃; the drying time is 8-12h, preferably 10-12 h.
7. Pure cubic phase Mg of claim 22MnO4The preparation method of the spinel material is characterized in that the heat treatment temperature in the step (3) is 500-700 ℃, and the heat preservation time is 2-5h, preferably 2-3 h.
8. Pure cubic phase Mg of claim 22MnO4The preparation method of the spinel material is characterized in that the heating rate of the heat treatment process in the step (3) is 40-80 ℃/h, and the cooling rate of the cooling process is 60-100 ℃/h.
9. Pure cubic phase Mg of claim 12MnO4The spinel material is applied to a lithium ion battery as a negative electrode material.
10. Use according to claim 9, characterized in that said pure cubic phase Mg2MnO4The spinel material is used as a negative electrode material and applied to a lithium ion battery, and the specific application steps are as follows: with the above-mentioned Mg2MnO4And (3) assembling the lithium ion button battery by taking an electrode plate prepared from the spinel material as a negative electrode, a metal lithium plate as a counter electrode, polyethylene as a battery diaphragm and lithium hexafluorophosphate as electrolyte.
CN202010451001.3A 2020-05-25 2020-05-25 Pure cubic phase Mg2MnO4Spinel material and preparation method and application thereof Pending CN111573738A (en)

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