CN113371759A - Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material - Google Patents
Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an amorphous transition metal oxide packaged manganese-based oxide composite material. Firstly, obtaining a 2X2 tunnel type manganese-based oxide precursor by a hydrothermal method, and then obtaining a final product, namely the amorphous transition metal oxide packaging manganese-based oxide composite material by a hydrolysis method. The preparation method is simple, the reaction condition is mild, the preparation cost is low, high-temperature calcination is not needed, and the industrial mass production is facilitated.
Description
Technical Field
The invention belongs to the technical field of preparation of advanced secondary battery materials, and particularly relates to a preparation method of an amorphous transition metal oxide packaged manganese-based oxide composite material and application of the amorphous transition metal oxide packaged manganese-based oxide composite material in a water-based zinc ion battery.
Background
The research and development of secondary energy storage materials have an important promoting effect on the development of green renewable resources, and particularly the research and development of secondary battery electrode materials with low cost, high safety and high energy density have very important practical significance and scientific value. Among various secondary batteries, the water-based zinc ion battery (AZIBs) is a new energy storage device, and because the market price of a zinc cathode in the device is low, and the ionic conductivity of the zinc ion battery is higher than that of a lithium ion battery, more importantly, a safer water-based electrolyte is used as the electrolyte, the battery assembly process is simple, and the water-based zinc ion battery has a good application prospect.
Among various zinc ion battery positive electrode materials, manganese-based oxide materials have been widely studied due to their high voltage plateau and high specific capacity. The manganese-based oxide mainly comprises manganese monoxide (MnO) and manganese dioxide (MnO)2) Manganese oxide (Mn)2O3) Manganomanganic oxide (Mn)3O4). Wherein manganese dioxide (MnO) is further used2) The crystal form is the most complex one, such as: alpha-MnO2、β-MnO2、γ-MnO2、δ-MnO2And the like. The manganese-based oxide has good electrochemical energy storage performance when being used as a positive electrode material, is expected to be used for large-scale energy storage, but has limited electrochemical performance due to low inherent conductivity and inevitable manganese dissolution, and directly causes poor rate performance and capacity attenuation. In order to improve the poor zinc storage performance of metal oxides as positive electrode materials, an effective method is to use highly conductive amorphous materials (e.g., highly conductive amorphous materials)Amorphous ZrO2) Encapsulating the transition metal oxide. Selective amorphous state ZrO2The reasons for the coating layer are: (1) amorphous ZrO2After zinc, only a slight volume expansion (≦ 4%) occurs, and the zinc-containing amorphous ZrO is charged and discharged2The conductivity of the electrode can be effectively improved; (2) zinc amorphous ZrO2The layer can improve the safety due to good thermal stability, and inhibit the thermal reaction of the high-zinc metal oxide phase and the electrolyte solution, thereby stabilizing the interface and improving the multiplying power capability.
The invention patent with the application number of 201910580311.2 discloses a water system zinc ion battery anode material, wherein the active substance of the anode material is a manganese dioxide anode material coated by metal oxide, and an oxide coating layer is formed on the surface of the manganese dioxide, so that on one hand, the large volume change of the material in the charging and discharging process can be effectively inhibited, and on the other hand, the direct contact between the electrode material and electrolyte can be prevented, thereby avoiding the dissolution of manganese in the electrode material. The metal oxide coating obviously improves the chemical stability of the manganese dioxide material in the charging and discharging processes. The existence of the metal oxide coating layer can also avoid side reaction on the surface of the electrode material and keep the electrochemical reaction activity on the surface of the manganese oxide material electrode, thereby improving the cycle stability and high-rate charge and discharge performance of the battery. In the coating process described in the document, an aqueous solution is used as a reaction medium, and an oxide coating layer is formed on the surface of manganese dioxide through a hydrolysis reaction, however, a certain space for improvement of the coating layer formed by using water as a medium still exists in the method, and the formation of an amorphous transition metal oxide coating layer can be better realized by changing the reaction medium, so that when the amorphous transition metal oxide-encapsulated manganese-based oxide composite material is used as a cathode material of a water-based zinc ion battery, the manganese-based oxide composite material finally shows relatively more excellent rate performance and cycle stability.
α-MnO2The zinc oxide is a manganese-based oxide with a 2x2 tunnel structure, and the energy storage mechanism is that hydrated zinc ions can be reversibly embedded and removed in the 2x2 tunnel structure during charging and discharging without damaging the structure of the hydrated zinc ions, so that the stable zinc storage performance of the zinc oxide can be realized。α-MnO2The energy storage mechanism is different from that of beta-MnO2、γ-MnO2、δ-MnO2Iso-manganese based oxides of which beta-MnO is2Is a 1x1 tunnel structure, in which hydrated zinc ions are difficult to be embedded, such as the structure is collapsed and changed if the hydrated zinc ions are embedded, the tunnel is relatively small, the structural stability is relatively poor, the structure is not reversible during charge and discharge, the structure is easy to break, and the like, so that the hydrated zinc ions are rarely selected as the positive electrode material of the zinc ion battery. Gamma-MnO2Is a 1x2 tunnel structure, and also, due to the small tunnel, the structure of the zinc ion can be damaged when the zinc ion is hydrated and hydrated, thereby affecting the zinc storage performance. Delta-MnO2Is a layered structure, and the reversible intercalation/deintercalation of the hydrated zinc ions into/from the layered structure during charge and discharge can destroy the layered structure, and the relatively poor structural stability can lead to relatively poor rate performance. Therefore, alpha-MnO having a large tunnel structure is selected2As the anode material of the zinc ion battery, the zinc ion battery has scientific theoretical basis from theory and can be used for alpha-MnO2The amorphous metal oxide is adopted for further coating, the structure, the interface stability and the zinc storage capacity of the amorphous metal oxide can be further improved, and the method is a novel method for improving the material performance, so that the alpha-MnO of a 2x2 tunnel structure2The research on the coating modification of the amorphous transition metal oxide has important scientific significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of the amorphous transition metal oxide packaging manganese-based oxide composite material, which has the advantages of simple process, mild reaction condition and low cost.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the amorphous transition metal oxide encapsulated manganese-based oxide composite material is characterized by comprising the following specific steps:
step S1: 1-2g K2S2O8、0.5-1.5g MnSO4And 0.5-1.5g K2SO4Grinding, mixing, adding into 10-100mL deionized water, stirring for 30-60min for dissolving, and adding 0.2-1.3mL concentrated H2SO4The solution is stirred and mixed evenly, then the mixed system is transferred to a stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction for 5 to 18 hours at the temperature of 120 ℃ and 150 ℃, the precipitate is collected by centrifugal separation, repeatedly washed by deionized water and ethanol and dried for 8 hours at the temperature of 60 to 80 ℃ to obtain the sea urchin-shaped 2 multiplied by 2 tunnel manganese-based oxide precursor alpha-MnO2；
Step S2: 0.1 to 0.2g of the 2X2 tunnel type manganese-based oxide precursor alpha-MnO obtained in the step S12Adding the mixture into a mixed solution containing 100-300mL of anhydrous ethanol and 0.5-0.7mL of ammonia water solution, carrying out ultrasonic stirring to obtain a uniform dispersion liquid, dropwise adding a zirconium source into the dispersion liquid at the temperature of 30-50 ℃ under the condition of oil bath, carrying out stirring reaction, and carrying out centrifugal separation after the reaction is finished to obtain an intermediate product, wherein the zirconium source is any one or more of tetrabutyl zirconate, zirconium acetylacetonate, zirconium hexafluoroacetylacetonate, zirconium oxychloride octahydrate or zirconium trifluoroacetylacetonate;
step S3: the intermediate product obtained in the step S2 is subjected to high-purity N2Under inert atmosphere, at 1-10 deg.C for min-1Heating up to 50-300 ℃ at the heating rate, and carrying out constant-temperature heat treatment for 2-5h to obtain the target product amorphous transition metal oxide packaged manganese-based oxide composite material alpha-MnO2@a-ZrO2alpha-MnO of the composite material2@a-ZrO2In which a-ZrO2Uniformly wrapping sea urchin-shaped alpha-MnO2Forming a uniform encapsulating layer on the surface, wherein the alpha-MnO2In alpha-MnO2@a-ZrO2The composite material comprises 10-80% by mass and the balance of a-ZrO2，a-ZrO2The thickness of the packaging layer is 4-15 nm.
Further defined, the α -MnO2@a-ZrO2alpha-MnO in composite materials2In alpha-MnO2@a-ZrO258 percent of a-ZrO in percentage by mass of the composite material2In alpha-MnO2@a-ZrO2The mass percent of the composite material is 42 percent, and the alpha-ZrO2The thickness of the encapsulation layer was 8 nm.
The amorphous transition metal oxide packaging manganese-based oxide composite material prepared by the invention is applied to the anode material of a water-based zinc ion battery.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method is simple, mild in reaction condition and low in cost, and is beneficial to industrial mass production.
2. According to the preparation method, firstly, a manganese-based oxide precursor is obtained by a hydrothermal method, and then the final product amorphous transition metal oxide packaging manganese-based oxide composite material can be obtained by a hydrolysis method without high-temperature calcination.
3. Compared with the existing crystalline transition metal oxide coating strategy, the amorphous transition metal oxide has the following advantages: (1) the amorphous transition metal oxide coating layer can better accommodate the zinc ion intercalation and deintercalation; (2) the amorphous transition metal oxide coating layer has higher conductivity; (3) the amorphous transition metal oxide coating layer can better stabilize the interface of the manganese-based oxide, thereby improving the cycle stability of the manganese-based oxide; (4) the amorphous transition metal oxide coating layer is simple in preparation process, high-temperature calcination is not needed, and the preparation cost of the electrode material is greatly saved; (5) the amorphous transition metal oxide coating layer can be prepared by simple room temperature liquid phase, and the mass production is easy.
4. Amorphous zirconia coated echinoid manganese dioxide (alpha-MnO)2@a-ZrO2，a-ZrO2Amorphous zirconia) and crystalline zirconia coated echinoid manganese dioxide (alpha-MnO)2@c-ZrO2 C is an abbreviation for crystallline, c-ZrO2Crystalline zirconia), uncoated echinoid manganese dioxide (alpha-MnO)2) Compared with the prior art, the multiplying power performance and the cycle performance are obviously improved.
5. In the preparation of amorphous transition metal oxide of the coating layer, the patent uses a mixed solution of absolute ethanol and aqueous ammonia solution as a reaction mediumIt is easy to form an amorphous transition metal oxide coating of uniform thickness, and a good coating will not be formed if water is used as a medium. The invention realizes the oxidation of manganese base into 2 multiplied by 2 tunnel type manganese base oxide alpha-MnO through specific process steps2Coated with amorphous transition metal oxide.
6. The reaction mechanism for forming the amorphous transition metal oxide of the coating layer is as follows: (1) the ethanol has strong polarity, easy filtration and small viscosity, and is easy to cause the agglomeration of transition metal ions; (2) ethanol is used as a solvent, so that metal ions can be well adsorbed, the growth of certain crystal faces can be inhibited, and further amorphous transition metal oxide can be obtained; (3) the ammonia water added into the ethanol solution is used as a catalyst to accelerate the amorphous transition metal oxide to form a coating layer with uniform thickness on the surface of the manganese-based oxide.
Drawings
FIG. 1 shows sea urchin-like α -MnO obtained in example 12@a-ZrO2Scanning electron microscope photograph of the composite material.
FIG. 2 shows sea urchin-like α -MnO obtained in example 12@a-ZrO2Composite X-ray powder diffraction pattern.
FIG. 3 shows sea urchin-like α -MnO obtained in example 12@a-ZrO2Composite material, alpha-MnO2@c-ZrO2And alpha-MnO2And (3) a comparison graph of rate performance when the zinc ion battery positive electrode materials are respectively used.
FIG. 4 shows sea urchin-like α -MnO obtained in example 12@a-ZrO2Composite material, alpha-MnO2@c-ZrO2And alpha-MnO2Respectively used as the anode material of a zinc ion battery with the current density of 0.2A g-1Cyclic performance versus time plot.
FIG. 5 shows sea urchin-like α -MnO obtained in example 12@a-ZrO20.05mV s when the composite material is used as a positive electrode material of a zinc ion battery-1CV curve at sweep speed.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Preparation of alpha-MnO2@a-ZrO2Composite material
1.53g K2S2O8、1.02g MnSO4And 1.05g K2SO4Grinding, mixing, adding into 45mL deionized water, stirring for 30min, dissolving, and adding 1.2mL concentrated H2SO4Stirring and mixing the solution uniformly, transferring the mixed system into a 100mL stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene, heating and reacting for 12h at 140 ℃, collecting precipitates through centrifugal separation, repeatedly washing the precipitates with deionized water and ethanol, and drying for 8h at 60 ℃ to obtain 2X2 tunnel type echinoid alpha-MnO2. Then 0.15g of 2X2 tunnel urchin-like alpha-MnO was added2Adding into a mixed solution containing 200mL of absolute ethyl alcohol and 0.6mL of ammonia water solution (28 wt%), carrying out ultrasonic treatment for 30min, stirring under the condition of 40 ℃ oil bath to obtain a uniformly dispersed solution, then dropwise adding 0.9mL of zirconium acetylacetonate, reacting at 40 ℃ for 40h, finally collecting the precipitate through centrifugal separation, repeatedly washing the precipitate with water and ethanol, and drying at 80 ℃ for 12h to obtain an intermediate product. Finally in high purity N2Under inert atmosphere, the intermediate product is heated in a tube furnace at 3 ℃ for min-1Heating up to 300 ℃ at a heating rate, carrying out constant-temperature heat treatment for 2h, and then cooling to room temperature to obtain sea urchin-shaped alpha-MnO2@a-ZrO2A composite material.
Comparative example 1
Preparation of alpha-MnO2@c-ZrO2Composite material
1.53g K2S2O8、1.02g MnSO4And 1.05g K2SO4Grinding, mixing, adding into 45mL deionized water, stirring for 30min, dissolving, and adding 1.2mL concentrated H2SO4Stirring and mixing the solution uniformly, transferring the mixed system into a 100mL stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene, heating and reacting at 140 ℃ for 12h, collecting precipitate by centrifugal separation, repeatedly washing the precipitate with deionized water and ethanol at 60 DEG CDrying for 8h to obtain 2x2 tunnel sea urchin-shaped alpha-MnO2. Then 0.15g of 2X2 tunnel urchin-like alpha-MnO was added2Adding into 200mL deionized water, performing ultrasonic treatment for 30min, stirring at 40 deg.C in oil bath to obtain uniformly dispersed solution, adding 0.9mL zirconium acetylacetonate dropwise, reacting at 40 deg.C for 40h, centrifuging, collecting precipitate, washing precipitate with water and ethanol repeatedly, and drying at 80 deg.C for 12h to obtain intermediate product. Finally in high purity N2Under inert atmosphere, the intermediate product is heated in a tube furnace at 3 ℃ for min-1Heating up to 600 ℃ at a heating rate, carrying out constant-temperature heat treatment for 2h, and then cooling to room temperature to obtain sea urchin-shaped alpha-MnO2@c-ZrO2A composite material.
Comparative example 2
Preparation of alpha-MnO2Material
1.53g K2S2O8、1.02g MnSO4And 1.05g K2SO4Grinding, mixing, adding into 45mL deionized water, stirring for 30min, dissolving, and adding 1.2mL concentrated H2SO4Stirring and mixing the solution uniformly, transferring the mixed system into a 100mL stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene, heating and reacting for 12h at 140 ℃, collecting precipitates through centrifugal separation, repeatedly washing the precipitates with deionized water and ethanol, and drying for 8h at 60 ℃ to obtain 2X2 tunnel type echinoid alpha-MnO2。
The α -MnO obtained in example 1 was characterized by SEM and XRD2@a-ZrO2Composite material, as shown in fig. 1-2.
alpha-MnO prepared in example 12@a-ZrO2The composite material, conductive carbon (SuperP) and a binder (CMC)) are mixed and prepared into slurry according to the mass ratio of 6:3:1, the slurry is uniformly coated on a stainless steel mesh current collector to obtain a working electrode, zinc metal is used as a counter electrode, a glass fiber microporous filter membrane GF/D is used as a diaphragm, and 2mol L of the working electrode is obtained-1 ZnSO4 +0.1mol L-1 MnSO4As an electrolyte, the battery was assembled in air. And (3) carrying out charge and discharge tests on the assembled battery on a charge and discharge tester, wherein the tested charge and discharge interval is 0.9-1.8V. At 0.03A g-1、0.05A g-1、0.1A g-1、0.2A g-1、0.5A g-1、0.8A g-1And 1A g-1The rate performance of the assembled cell was tested at current density of (d). Then at 0.2A g-1The cycle performance of the assembled battery was tested under the current density conditions of (1). As can be seen from FIG. 3, the α -MnO2@a-ZrO2The composite material is 0.03A g-1Under the current density, the first reversible specific capacity reaches 298mA h g-1And alpha-MnO2@c-ZrO2And alpha-MnO2The first reversible specific capacity is only 226mA h g-1And 114mA h g-1. The alpha-MnO can be seen from FIG. 42@a-ZrO2Composite material at 0.2A g-1The discharge specific capacity under the condition is 181mA h g-1After 500 cycles, the voltage can still be maintained at 171mA h g-1The capacity retention rate can still reach 94.5 percent. Sea urchin-like alpha-MnO without coating layer2At 0.2A g-1The specific discharge capacity under the condition is only 118mA h g-1After 500 cycles, the specific discharge capacity is only 43mA h g-1；α-MnO2@c-ZrO2Composite material at 0.2A g-1The discharge specific capacity under the condition is 134mA h g-1The capacity is 148mA h g after 500 cycles-1Significantly lower than alpha-MnO2@a-ZrO2. Indicating the alpha-MnO2@a-ZrO2The composite material is superior to alpha-MnO when being used as a positive electrode material of a zinc ion battery2@c-ZrO2And alpha-MnO2Rate capability and cycle capability of (a).
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (3)
1. The preparation method of the amorphous transition metal oxide encapsulated manganese-based oxide composite material is characterized by comprising the following specific steps of:
step S1: 1-2g K2S2O8、0.5-1.5g MnSO4And 0.5-1.5g K2SO4Grinding, mixing, adding into 10-100mL deionized water, stirring for 30-60min for dissolving, and adding 0.2-1.3mL concentrated H2SO4The solution is stirred and mixed evenly, then the mixed system is transferred to a stainless steel high-pressure reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction for 5 to 18 hours at the temperature of 120 ℃ and 150 ℃, the precipitate is collected by centrifugal separation, repeatedly washed by deionized water and ethanol and dried for 8 hours at the temperature of 60 to 80 ℃ to obtain the sea urchin-shaped 2 multiplied by 2 tunnel manganese-based oxide precursor alpha-MnO2；
Step S2: 0.1 to 0.2g of the 2X2 tunnel type manganese-based oxide precursor alpha-MnO obtained in the step S12Adding the mixture into a mixed solution containing 100-300mL of anhydrous ethanol and 0.5-0.7mL of ammonia water solution, carrying out ultrasonic stirring to obtain a uniform dispersion liquid, dropwise adding a zirconium source into the dispersion liquid at the temperature of 30-50 ℃ under the condition of oil bath, carrying out stirring reaction, and carrying out centrifugal separation after the reaction is finished to obtain an intermediate product, wherein the zirconium source is any one or more of tetrabutyl zirconate, zirconium acetylacetonate, zirconium hexafluoroacetylacetonate, zirconium oxychloride octahydrate or zirconium trifluoroacetylacetonate;
step S3: the intermediate product obtained in the step S2 is subjected to high-purity N2Under inert atmosphere, at 1-10 deg.C for min-1Heating up to 50-300 ℃ at the heating rate, and carrying out constant-temperature heat treatment for 2-5h to obtain the target product amorphous transition metal oxide packaged manganese-based oxide composite material alpha-MnO2@a-ZrO2alpha-MnO of the composite material2@a-ZrO2In which a-ZrO2Uniformly wrapping sea urchin-shaped alpha-MnO2Forming a uniform encapsulating layer on the surface, wherein the alpha-MnO2In alpha-MnO2@a-ZrO2The composite material comprises 10-80% by mass and the balance of a-ZrO2，a-ZrO2The thickness of the packaging layer is 4-15 nm.
2. The method of preparing an amorphous transition metal oxide encapsulated manganese-based oxide composite material of claim 1, wherein: the alpha-MnO2@a-ZrO2Composite materialIn-feed alpha-MnO2In alpha-MnO2@a-ZrO258 percent of a-ZrO in percentage by mass of the composite material2In alpha-MnO2@a-ZrO2The mass percent of the composite material is 42 percent, and the alpha-ZrO2The thickness of the encapsulation layer was 8 nm.
3. Use of the amorphous transition metal oxide encapsulated manganese-based oxide composite material prepared according to the method of any one of claims 1-2 in a positive electrode material of an aqueous zinc-ion battery.
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