阅读说明：本技术 一种高性能镍铝层状双硫化物／氧化物复合电极材料的制备方法 (Preparation method of high-performance nickel-aluminum layered double sulfide/oxide composite electrode material ) 是由 李磊 付建建 于 2021-09-08 设计创作，主要内容包括：本发明公开了一种高性能镍铝层状双硫化物/氧化物复合电极材料的制备方法,包括以下步骤：步骤一,制备3D花瓣结构的NiAl LDH基础材料,步骤二,制备3D花瓣结构的NiAl LDS/LDO复合材料,步骤三,制备高性能非对称超级电容器器件。本发明通过水热法调控得到的3D纳米结构的NiAlLDH基础材料具有较高的比表面积,可以为电荷存储提供更多的电活性位点。通过高温退火后,原先的NiAl LDH转化为NiAl LDS/LDO复合材料,转化后,先前的3D结构得以保留,且组成结构的纳米片表面变得更加粗糙,使比表面积进一步增大,与此同时,镍铝双氢氧化物转化为双硫化物/氧化物后,材料的导电性大幅提升,更加有利于材料内部电荷的快速转移。(The invention discloses a preparation method of a high-performance nickel-aluminum layered double sulfide/oxide composite electrode material, which comprises the following steps: preparing a 3D petal-structured NiAl LDS base material, preparing a 3D petal-structured NiAl LDS/LDO composite material, and preparing a high-performance asymmetric supercapacitor device. The NiAlLDH base material with the 3D nano structure, which is obtained by regulating and controlling through a hydrothermal method, has a higher specific surface area, and can provide more electroactive sites for charge storage. After high-temperature annealing, the original NiAl LDH is converted into a NiAl LDS/LDO composite material, after conversion, the previous 3D structure is reserved, the surface of the nanosheet forming the structure becomes rougher, the specific surface area is further increased, meanwhile, after the nickel-aluminum double hydroxide is converted into the double sulfide/oxide, the conductivity of the material is greatly improved, and the rapid transfer of charges inside the material is facilitated.)

1. A preparation method of a high-performance nickel-aluminum layered double sulfide/oxide composite electrode material is characterized by comprising the following steps:

step one, preparing a 3D petal-structured NiAl LDH base material: dissolving nickel nitrate hexahydrate, aluminum nitrate nonahydrate and urea in deionized water, stirring, transferring the mixed solution into a hydrothermal reaction kettle, and heating to obtain NiAl LDH;

step two, preparing the NiAl LDS/LDO composite material with the 3D petal structure: mixing and grinding NiAl LDH and sodium thiosulfate, transferring the mixed powder to a tube furnace, and annealing to obtain NiAl LDS/LDO;

step three, preparing a high-performance asymmetric super capacitor device: the asymmetric NiAl LDS/LDO/G supercapacitor device is assembled by adopting a NiAl LDS/LDO composite material as a positive electrode material and high-purity graphene G as a negative electrode material.

2. The preparation method of the high-performance nickel aluminum layered double sulfide/oxide composite electrode material according to claim 1, characterized by comprising the following steps:

step one, preparing a 3D petal-structured NiAl LDH base material: dissolving 0.006mol of nickel nitrate hexahydrate and 0.002mol of aluminum nitrate nonahydrate in 60mL of deionized water, stirring for 15 minutes, adding 0.03mol of urea, stirring for 15 minutes to form a solution, transferring the solution into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene liner, preserving heat at 120 ℃ for 12 hours, naturally cooling the reaction kettle to room temperature, washing with deionized water and ethanol for 3-5 times, and vacuum-drying the product at 80 ℃ for 12 hours;

step two, preparing the NiAl LDS/LDO composite material with the 3D petal structure: mixing the prepared NiAl LDH and sodium thiosulfate according to a molar ratio of 1:2, finely grinding the mixture for 30 minutes, transferring the mixed powder into a quartz tube of a tube furnace, preserving the heat for 12 hours at 500 ℃ under the protection of argon atmosphere, cooling to room temperature, cleaning a black product with ethanol for 3-5 times, and then carrying out vacuum drying for 12 hours at 80 ℃;

step three: preparing a high-performance asymmetric supercapacitor device: the integrated asymmetric super capacitor device is packaged in a button battery case, and in the assembling process of the device, the NiAl LDS/LDO composite material is adopted as a positive electrode material, the high-purity graphene G is adopted as a negative electrode material, and 6M potassium hydroxide solution is adopted as electrolyte, so that the asymmetric NiAl LDS/LDO/G super capacitor device is assembled.

3. The method for preparing a high performance nickel aluminum layered double sulfide/oxide composite electrode material as claimed in claim 2, wherein in the third step, the active materials acetylene black and polytetrafluoroethylene are mixed with a small amount of ethanol in a ratio of 70:20:5, and uniformly coated on the foamed nickel current collector, and vacuum dried at 80 ℃ for 12 hours.

4. The preparation method of the high-performance nickel aluminum layered double sulfide/oxide composite electrode material as claimed in any one of claims 1 to 3, wherein the selected medicines such as nickel nitrate hexahydrate, aluminum nitrate nonahydrate, urea, sodium thiosulfate and the like are analytically pure, and the purity of the medicines is 99.99%.

5. The method for preparing a high-performance nickel aluminum layered double sulfide/oxide composite electrode material as claimed in any one of claims 1 to 3, wherein the preparation of the NiAl LDS/LDO is performed by a chemical reaction in two stages of decomposition and synthesis, wherein the reaction process comprises:

and (3) decomposition reaction:

Ni(OH)₂→NiO+H₂O

2Al(OH)₃→Al₂O₃+3H₂O

4Na₂S₂O₃→3Na₂SO₄+Na₂S₅

and (3) synthesis reaction:

Technical Field

The invention relates to the field of electrode material preparation, in particular to a preparation method of a high-performance nickel-aluminum layered double sulfide/oxide composite electrode material.

Background

In recent years, along with the pursuit and pursuit of new electronic products by human beings, the development of a high-performance energy storage device matched with the electronic product becomes a wind vane for future scientific and technological development. However, lead-acid batteries, lithium ion batteries, and the like, which are commonly used in the field, have many defects in safety, service life, extreme weather power loss, and the like. Therefore, it is very important to search for a new energy storage device that can compensate the above defects. As a very potential energy storage device, the super capacitor has the advantages of high power density, rapid charging and discharging, long cycle life, safety, environmental protection and the like, becomes the mastery force in the current energy storage research field, and is actively popularized and applied to new energy buses and large-scale hoisting equipment. However, the lower energy density has made it a greater obstacle to further research and application.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of a high-performance nickel-aluminum layered double sulfide/oxide composite electrode material.

In order to solve the technical problems, the invention provides the following technical scheme:

the invention relates to a preparation method of a high-performance nickel-aluminum layered double sulfide/oxide composite electrode material, which comprises the following steps:

step one, preparing a 3D petal-structured NiAl LDH base material: dissolving nickel nitrate hexahydrate, aluminum nitrate nonahydrate and urea in deionized water, stirring, transferring the mixed solution into a hydrothermal reaction kettle, and heating to obtain NiAl LDH;

step two, preparing the NiAl LDS/LDO composite material with the 3D petal structure: mixing and grinding NiAl LDH and sodium thiosulfate, transferring the mixed powder to a tube furnace, and annealing to obtain NiAl LDS/LDO;

step three, preparing a high-performance asymmetric super capacitor device: the asymmetric NiAl LDS/LDO/G supercapacitor device is assembled by adopting a NiAl LDS/LDO composite material as a positive electrode material and high-purity graphene G as a negative electrode material.

As a preferable technical scheme of the invention, the method comprises the following steps:

step one, preparing a 3D petal-structured NiAl LDH base material: dissolving 0.006mol of nickel nitrate hexahydrate and 0.002mol of aluminum nitrate nonahydrate in 60mL of deionized water, stirring for 15 minutes, adding 0.03mol of urea, stirring for 15 minutes to form a solution, transferring the solution into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene liner, preserving heat at 120 ℃ for 12 hours, naturally cooling the reaction kettle to room temperature, washing with deionized water and ethanol for 3-5 times, and vacuum-drying the product at 80 ℃ for 12 hours;

step two, preparing the NiAl LDS/LDO composite material with the 3D petal structure: mixing the prepared NiAl LDH and sodium thiosulfate according to a molar ratio of 1:2, finely grinding the mixture for 30 minutes, transferring the mixed powder into a quartz tube of a tube furnace, preserving the heat for 12 hours at 500 ℃ under the protection of argon atmosphere, cooling to room temperature, cleaning a black product with ethanol for 3-5 times, and then carrying out vacuum drying for 12 hours at 80 ℃;

step three: preparing a high-performance asymmetric supercapacitor device: the integrated asymmetric super capacitor device is packaged in a button battery case, and in the assembling process of the device, the NiAl LDS/LDO composite material is adopted as a positive electrode material, the high-purity graphene G is adopted as a negative electrode material, and 6M potassium hydroxide solution is adopted as electrolyte, so that the asymmetric NiAl LDS/LDO/G super capacitor device is assembled.

In the third step, when preparing the electrode, adding a small amount of ethanol into the active materials acetylene black and polytetrafluoroethylene according to the proportion of 70:20:5, mixing, uniformly coating the mixture on a foamed nickel current collector, and drying in vacuum at 80 ℃ for 12 hours.

As a preferred technical scheme of the invention, the selected medicines such as nickel nitrate hexahydrate, aluminum nitrate nonahydrate, urea, sodium thiosulfate and the like are analytically pure, and the purity of the medicines is 99.99%.

As a preferred technical scheme of the invention, the preparation of the NiAl LDS/LDO is carried out by chemical reactions of two stages of decomposition and synthesis, and the specific reaction process is as follows:

and (3) decomposition reaction:

Ni(OH)₂→NiO+H₂O

2Al(OH)₃→Al₂O₃+3H₂O

4Na₂S₂O₃→3Na₂SO₄+Na₂S₅

and (3) synthesis reaction:

compared with the prior art, the invention has the following beneficial effects:

according to the invention, the NiAl LDH base material with the 3D nano structure obtained by regulation and control through a hydrothermal method has a higher specific surface area, and can provide more electroactive sites for charge storage, after high-temperature annealing, the original NiAl LDH is converted into a NiAl LDS/LDO composite material, after conversion, the previous 3D structure is retained, and the surface of the nanosheet forming the structure becomes rougher, so that the specific surface area is further increased, meanwhile, after the nickel-aluminum double hydroxide is converted into a double sulfide/oxide, the conductivity of the material is greatly improved, the rapid transfer of charges in the material is more facilitated, and finally, the NiAl LDS/LDO and the NiAl LDS/LDO are respectively used as the anode material and the cathode material of a super capacitor to assemble a high-performance energy storage device, and the improvement of the performance of the electrode material is well verified.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is an X-ray diffraction pattern of a composite material of the present invention;

FIG. 2 is a scanning electron microscope image of a composite material of the present invention;

FIG. 3 is a transmission electron microscope photograph of a composite material of the present invention;

FIG. 4 is a cyclic voltammetry test of a composite of the invention;

FIG. 5 is a charge and discharge test of the composite of the present invention;

FIG. 6 is a cycle life test of the composite of the present invention;

FIG. 7 is a capacitance test of an asymmetric supercapacitor device of the present invention;

fig. 8 is a cycle life test of an asymmetric supercapacitor device of the present invention.

Detailed Description

The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.

Example 1

As shown in fig. 1 to 8, the present invention provides a method for preparing a high-performance nickel-aluminum layered double sulfide/oxide composite electrode material, comprising the following steps:

step one, preparing a 3D petal-structured NiAl LDH base material: dissolving 0.006mol of nickel nitrate hexahydrate and 0.002mol of aluminum nitrate nonahydrate in 60mL of deionized water, stirring for 15 minutes, adding 0.03mol of urea, stirring for 15 minutes to form a solution, transferring the solution into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene liner, preserving heat at 120 ℃ for 12 hours, naturally cooling the reaction kettle to room temperature, washing with deionized water and ethanol for 3-5 times, and vacuum-drying the product at 80 ℃ for 12 hours;

step two, preparing the NiAl LDS/LDO composite material with the 3D petal structure: mixing the prepared NiAl LDH and sodium thiosulfate according to a molar ratio of 1:2, finely grinding the mixture for 30 minutes, transferring the mixed powder into a quartz tube of a tube furnace, preserving the heat for 12 hours at 500 ℃ under the protection of argon atmosphere, cooling to room temperature, cleaning a black product with ethanol for 3-5 times, and then carrying out vacuum drying for 12 hours at 80 ℃;

step three: preparing a high-performance asymmetric supercapacitor device: the integral asymmetric super capacitor device is packaged in a CR 2302 button battery case, and in the assembling process of the device, the NiAl LDS/LDO composite material is adopted as a positive electrode material, the high-purity graphene G is adopted as a negative electrode material, and 6M potassium hydroxide solution is adopted as electrolyte, so that the asymmetric NiAl LDS/LDO/G super capacitor device is assembled.

Further, when preparing the electrode, a small amount of ethanol is added into the active materials acetylene black and polytetrafluoroethylene according to the proportion of 70:20:5 for mixing, and the active materials are uniformly coated on a foam nickel current collector and dried for 12 hours in vacuum at 80 ℃.

Furthermore, the selected medicines such as nickel nitrate hexahydrate, aluminum nitrate nonahydrate, urea, sodium thiosulfate and the like are analytically pure, and the purity of the medicines is 99.99%.

Further, the preparation of the NiAl LDS/LD0 is carried out by chemical reaction of two stages of decomposition and synthesis, and the specific reaction process is as follows:

and (3) decomposition reaction:

Ni(OH)₂→NiO+H₂O

2Al(OH)₃→Al₂O₃+3H₂O

4Na₂S₂O₃→3Na₂SO₄+Na₂S₅

and (3) synthesis reaction:

specifically, when the composite material prepared in example 1 was subjected to X-ray examination, as shown in FIG. 1, it was observed that the diffraction peak included Ni at the same time₃S₂NiO and Al₂S₃The diffraction peak of the NiAl LDS/LDO composite material shows that the NiAl LDS/LDO composite material is successfully prepared.

Referring to fig. 2 and 3, the 3D petal-like structure of the NiAl LDS/LD0 composite material was clearly observed by scanning electron microscopy and transmission electron microscopy, respectively.

Referring to fig. 4, in order to perform cyclic voltammetry on the prepared NiAl LDS/LDO composite material, it can be found in the graph that the curve area is gradually increased along with the continuous increase of the sweep rate in the range of 5-100 mV/s, and no obvious deformation and polarization exist, indicating the superior rate characteristics.

Referring to fig. 5, in order to perform charge and discharge tests on the prepared NiAl LDS/LDO composite material, it was calculated that the composite material exhibited a high capacitance capacity of 2250.5F/g at a current density of 1A/g, and the capacitance did not decrease greatly with the increase of the current density, indicating its superior rate characteristics.

Referring to fig. 6, for the cycle life test of the prepared NiAl LDS/LDO composite material, the capacitance capacity is still maintained at 88.9% after 5000 charge-discharge cycles at a current density of 5A/g, which indicates that the material has a longer service life.

Referring to FIG. 7, for the capacitance test of the prepared NiAl LDS/LDO// G asymmetric supercapacitor device, the device exhibits a capacitance capacity of 153.3F/G at a current density of 1A/G.

Referring to fig. 8, for the cycle life test of the prepared NiAl LDS/LDO// G asymmetric supercapacitor device, after 5000 charge-discharge cycles, the capacitance capacity of the device is kept at 95.68%, and the device is proved to have strong attenuation resistance.

The prepared composite material can be found to present a 3D petal-shaped structure through observation of a scanning electron microscope, and is formed by combining a plurality of two-dimensional nano sheets in a staggered manner, and the nano sheets are mutually communicated, so that surface charges can be rapidly transferred; meanwhile, the porous structure between the materials is beneficial to the rapid diffusion of the electrolyte, so that the electrode material is fully contacted with the electrolyte, and the energy storage utilization rate of the internal active sites is increased; the currently prepared NiAl LDS/LDO composite electrode material shows 2250.5F/g high capacitance capacity when the current density is 1A/g, the curve shape is kept good along with the gradual increase of the current density, the high-rate performance is proved, and meanwhile, under the condition that the current density is 5A/g, after 5000 charge-discharge cycles, the capacitance capacity is still kept at 88.9%, which shows that the material has longer service life

According to the invention, the NiAl LDH base material with the 3D nano structure obtained by regulation and control through a hydrothermal method has a higher specific surface area, and can provide more electroactive sites for charge storage, after high-temperature annealing, the original NiAl LDH is converted into a NiAl LDS/LDO composite material, after conversion, the previous 3D structure is retained, and the surface of the nanosheet forming the structure becomes rougher, so that the specific surface area is further increased, meanwhile, after the nickel-aluminum double hydroxide is converted into a double sulfide/oxide, the conductivity of the material is greatly improved, the rapid transfer of charges in the material is more facilitated, and finally, the NiAl LDS/LDO and the NiAl LDS/LDO are respectively used as the anode material and the cathode material of a super capacitor to assemble a high-performance energy storage device, and the improvement of the performance of the electrode material is well verified.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.