CN115536075A - CoNb 2 O 6 Composite porous graphene composite material and preparation method thereof - Google Patents
CoNb 2 O 6 Composite porous graphene composite material and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 239000010406 cathode material Substances 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 abstract description 3
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 abstract description 3
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- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OMLRJCKUNDGAMS-UHFFFAOYSA-N potassium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[K+].[Nb+5] OMLRJCKUNDGAMS-UHFFFAOYSA-N 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The present disclosure relates to a CoNb 2 O 6 The preparation method of the composite porous graphene composite material comprises the following steps: obtaining graphene oxide dispersion liquid; adding 30% H to the graphene oxide dispersion 2 O 2 Raising the temperature of the solution to 75-95 ℃ for reaction; adding Co into the reacted product 2 O 3 And Nb 2 O 5 Then ball milling is carried out; raising the ball-milled product to 700-900 ℃ in the protective gas atmosphere, and reacting at constant temperature to obtain CoNb 2 O 6 Compound polyA porous graphene composite material. According to the invention, the niobium pentoxide and the cobaltous oxide are combined to prepare the bimetallic oxide composite graphene oxide, so that the conductivity of the bimetallic oxide composite graphene oxide is improved, and the obtained cathode material has high capacity and good cycle stability and can be used as a cathode material of a lithium ion battery.
Description
Technical Field
The disclosure relates to the field of chemical power sources, in particular to a CoNb 2 O 6 A composite porous graphene composite material and a preparation method thereof.
Background
The gas emission generated by fossil fuel causes serious pollution to the air, and also causes rapid global warming, and at the same time, because it is non-renewable, human beings face energy crisis, and therefore, the development of environment-friendly renewable energy is urgently needed. The lithium ion battery is used as a novel chargeable chemical power supply, has the advantages of high energy density, good safety, long cycle life and the like, is widely applied to the fields of portable electronic goods, electric automobiles, military, aerospace and the like, and has a very wide development space.
The negative electrode material affects performance parameters of the battery such as discharge capacity, cycle life, energy density and the like, so research and development of the negative electrode material are very important factors for determining the performance of the battery. Niobium-based oxides have received attention from numerous researchers as the negative electrode of lithium batteries, nb 2 O 5 The bulk phase material has no phase change in the lithium removing/embedding process and small volume change, so that the bulk phase material has a capacitive process and quick response time, and is a lithium ion electrode material capable of realizing quick charge and quick discharge. Meanwhile, composite oxides of Nb and other metals have attracted attention as negative electrode materials, and mainly include titanium niobium oxide, potassium niobium oxide, and the like. Jo and the like prepare ordered mesoporous TiNb by a block copolymer assisted self-assembly method 2 O 7 The material has larger specific surface area, and specific capacity of 289mAh/g under 0.1C multiplying power [ chem.Mater,2014,26 (11): 3508-3514.]Griffith et al prepared micron-sized Nb by solid phase method 16 W 5 O 55 And Nb 18 W 16 O 93 Optimizing the diffusion rate of ions in the cell [ Nature,2018, 559.]However, the niobate material still has the problems of low theoretical capacity and poor conductivity, so further research is needed to obtain a niobate negative electrode material with better performance.
Disclosure of Invention
The present disclosure provides a CoNb 2 O 6 The composite porous graphene composite material and the preparation method thereof can solve the problems of low theoretical capacity and poor conductivity of niobate materials. To solve the above problemsTo solve the technical problem, the present disclosure provides a CoNb 2 O 6 The preparation method of the composite porous graphene composite material comprises the following steps:
obtaining graphene oxide dispersion liquid;
adding 30% H to the graphene oxide dispersion 2 O 2 Raising the temperature of the solution to 75-95 ℃ for reaction;
adding Co into the reacted product 2 O 3 And Nb 2 O 5 Then ball milling is carried out;
raising the ball-milled product to 700-900 ℃ in the protective gas atmosphere, and reacting at constant temperature to obtain CoNb 2 O 6 Disclosed is a composite porous graphene composite material.
Preferably, the ball-milled product is heated to 600-1000 ℃ in the protective gas atmosphere and then reacts at constant temperature to obtain CoNb 2 O 6 The method also comprises the following steps before compounding the porous graphene composite material: and (4) freeze-drying and grinding the ball-milled product.
Preferably, said 30% by weight H 2 O 2 The volume ratio of the graphene oxide dispersion to the graphene oxide dispersion is 1.
Preferably, the Co is 2 O 3 And Nb 2 O 5 1.
Preferably, the product after reaction is reacted with said Co 2 O 3 And Nb 2 O 5 The mass ratio of (1) to (3).
Preferably, the mass fraction of the graphene oxide dispersion liquid is 1-5 mg/mL.
Preferably, the graphene oxide dispersion is added with 30% by weight 2 O 2 The solution is heated to 75-95 ℃ for reaction for 2-4 h.
Preferably, the ball-milled product is heated to 700-900 ℃ in the protective gas atmosphere, and then the constant temperature reaction time is 6-12 h.
Preferably, the protective gas is argon, nitrogen or helium.
The invention also provides a CoNb 2 O 6 The porous graphene composite material is compounded, and the porous graphene composite material,is prepared by the method.
According to the novel secondary lithium ion battery cathode material provided by the invention, the niobium pentoxide and the cobaltous oxide are combined to prepare the bimetallic oxide, the advantages of the niobium pentoxide and the cobaltous oxide are combined, the conductivity of the graphene oxide is improved after the graphene oxide is compounded, the obtained cathode material has high capacity and good cycling stability, the capacity is still 250mAh/g after 1000 cycles of cycling at 1A/g, the capacity retention rate is 84.3%, the capacity is still 86.8mAh/g under the condition of 20A/g, and the novel secondary lithium ion battery cathode material has good cycling stability and excellent rate capability; the preparation process is simple, is suitable for industrial large-scale production, and has wide application prospect.
Drawings
FIG. 1 shows CoNb 2 O 6 A flow chart of a preparation method of the composite porous graphene composite material;
FIG. 2 shows CoNb 2 O 6 SEM (scanning Electron microscope) image and TEM (Transmission Electron microscope) image of composite porous graphene composite material, wherein images (a), (b) and (c) are CoNb prepared in example 1, example 2 and example 3 respectively 2 O 6 SEM images of the composite porous graphene composite materials, (d), (e), and (f) are CoNb prepared in examples 1, 2, and 3, respectively 2 O 6 A TEM image of the composite porous graphene composite;
FIG. 3 shows CoNb prepared in examples 1, 2 and 3 2 O 6 An XRD pattern of the composite porous graphene composite material;
FIG. 4 shows CoNb prepared in example 1, example 2, and example 3 2 O 6 A raman spectrum of the composite porous graphene composite material;
FIG. 5 shows CoNb prepared in example 1, example 2 and example 3 2 O 6 A rate performance graph of the composite porous graphene composite material;
FIG. 6 shows CoNb prepared in example 1, example 2, and example 3 2 O 6 And the composite porous graphene composite material has a cycle stability performance diagram under the condition that the current density is 1A/g.
Detailed Description
The technical solutions in the embodiments of the present disclosure will be clearly and completely described below with reference to the drawings in the embodiments of the present disclosure, and it is obvious that the described embodiments are only a part of the embodiments of the present disclosure, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
Example 1
The present embodiment provides a CoNb 2 O 6 Referring to fig. 1, a preparation method of a composite porous graphene composite material includes the following specific steps:
and S100, adding 0.4g of graphene oxide and 200mL of deionized water into a 500mL three-neck flask, stirring for 15min, and performing ultrasonic dispersion for 60min to obtain a graphene oxide dispersion liquid.
S200, 20mL of 30% H 2 O 2 Adding the mixture into graphene oxide dispersion liquid, heating to 95 ℃, reacting for 4 hours, and cooling to room temperature.
S300, taking 40mL of the product obtained after the reaction in the step S200, adding 96.37mgCo into a ball milling tank 2 O 3 、308.9mgNb 2 O 5 And 10g of ball milling medium is put in a ball milling tank, the ball milling rotating speed is set to be 600rpm, the ball milling time is 7.5 hours, and the medium added during ball milling is stainless steel balls with the diameter of 3-20 mm.
S400, freeze-drying the ball-milled product, grinding to obtain a powdery solid, heating the powdery solid to 700 ℃ at a heating rate of 5 ℃/min in an Ar atmosphere, and keeping the temperature for 9 hours to obtain CoNb 2 O 6 Porous graphene composite materials.
Example 2
The present embodiment provides a CoNb 2 O 6 Referring to fig. 1, a preparation method of a composite porous graphene composite material includes the following specific steps:
and S100, adding 0.4g of graphene oxide and 200mL of deionized water into a 500mL three-neck flask, stirring for 15min, and performing ultrasonic dispersion for 60min to obtain a graphene oxide dispersion liquid.
S200, 20mL of 30% H 2 O 2 Adding the mixture into graphene oxide dispersion liquid, heating to 95 ℃, reacting for 4 hours, and cooling to room temperature.
S300, taking 40mL of the product obtained after the reaction in the step S200, adding 96.37mgCo into a ball milling tank 2 O 3 、308.9mgNb 2 O 5 And 10g of ball milling medium is put in a ball milling tank, the ball milling speed is set to 600rpm, the ball milling time is 7.5 hours, the medium added during ball milling is zirconia balls, the diameter of the medium is 3-20 mm, and the medium and Co are mixed 2 O 3 And Nb 2 O 5 The mass ratio of (1).
S400, freeze-drying the ball-milled product, grinding to obtain a powdery solid, heating the powdery solid to 800 ℃ at a heating rate of 5 ℃/min in an Ar atmosphere, and keeping the temperature for 9 hours to obtain CoNb 2 O 6 Porous graphene composite materials.
Example 3
The present embodiment provides a CoNb 2 O 6 Referring to fig. 1, a preparation method of a composite porous graphene composite material includes the following specific steps:
and S100, adding 0.4g of graphene oxide and 200mL of deionized water into a 500mL three-neck flask, stirring for 15min, and performing ultrasonic dispersion for 60min to obtain a graphene oxide dispersion liquid.
S200, 20mL of 30% H 2 O 2 Adding the mixture into graphene oxide dispersion liquid, heating to 95 ℃, reacting for 4 hours, and cooling to room temperature.
S300, taking 40mL of the product reacted in the step S200, putting the product into a ball milling tank, and adding 96.37mgCo 2 O 3 、308.9mgNb 2 O 5 And 10g of ball milling medium is put in a ball milling tank, the ball milling speed is set to be 600rpm, and the ball milling time is set to be 7.5h;
s400, freeze-drying the ball-milled product, grinding to obtain a powdery solid, heating the powdery solid to 900 ℃ at a heating rate of 5 ℃/min in an Ar atmosphere, and keeping the temperature for 9 hours to obtain CoNb 2 O 6 Porous graphene composite materials.
Example 4
In this example, coNb prepared in example 1/2/3 was added 2 O 6 And (3) performing characterization and performance test on the composite porous graphene composite material.
FIG. 2 shows CoNb 2 O 6 SEM image and TEM image of the composite porous graphene composite material, and it can be seen from the images that CoNb is increased with the increase of the firing temperature 2 O 6 The particle size gradually increases from 20nm to over 100nm, and when the roasting temperature is 900 ℃, the content of the porous graphene is sharply reduced, so that CoNb cannot be inhibited 2 O 6 The growth of the particles, and therefore the size of the particles becomes larger, the size increase can increase the ion migration distance, so that the ion migration speed is slow, and the reduction of the porous graphene can also reduce the conductivity of the composite material, so that the electron migration speed is slow.
FIG. 3 shows CoNb obtained at different calcination temperatures 2 O 6 The XRD pattern of the porous graphene composite material has diffraction peaks at 12.2 degrees, 15.1 degrees, 15.6 degrees, 17.8 degrees, 18.1 degrees, 21.8 degrees, 25.9 degrees and 26.8 degrees corresponding to crystal faces of (130), (131), (200), (002), (201), (132), (330) and (261) respectively, and is consistent with an orthorhombic system CoNb 2 O 6 The standard spectrum of (JCPDS 32-0304) is consistent. The diffraction peak becomes stronger with the increase of the firing temperature, which indicates that CoNb is 2 O 6 The crystallinity of (a) is better and better, and the size is larger and larger.
FIG. 4 shows CoNb obtained at different calcination temperatures 2 O 6 Porous graphene composite materials. In the range of 0-1000cm -1 Corresponding to the characteristic peak between the two is CoNb 2 O 6 . At 1340cm -1 And 1585cm -1 The characteristic peaks of the porous graphene respectively correspond to a D peak and a G peak of the porous graphene, and the peak strength is the highest when the roasting temperature is 800 ℃, which indicates that the conductivity is better.
FIGS. 5 and 6 are CoNb 2 O 6 The porous graphene composite material has rate capability and cycle performance when being used as a lithium battery negative electrode material, and when the roasting temperature is 800 ℃, the specific capacity is higher, and the cycle stability is the best.
Although embodiments of the present disclosure have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations may be made in these embodiments without departing from the principles and spirit of the disclosure, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. CoNb 2 O 6 The preparation method of the composite porous graphene composite material is characterized by comprising the following steps:
obtaining graphene oxide dispersion liquid;
adding 30% H to the graphene oxide dispersion 2 O 2 Raising the temperature of the solution to 75-95 ℃ for reaction;
adding Co into the reacted product 2 O 3 And Nb 2 O 5 Then ball milling is carried out;
raising the ball-milled product to 700-900 ℃ in the protective gas atmosphere, and reacting at constant temperature to obtain CoNb 2 O 6 Disclosed is a composite porous graphene composite material.
2. The CoNb of claim 1 2 O 6 The preparation method of the composite porous graphene composite material is characterized in that a ball-milled product is heated to 600-1000 ℃ in a protective gas atmosphere and then reacts at a constant temperature to obtain CoNb 2 O 6 The method also comprises the following steps before compounding the porous graphene composite material: and (4) freeze-drying and grinding the ball-milled product.
3. The CoNb of claim 1 2 O 6 The preparation method of the composite porous graphene composite material is characterized in that the mass fraction of the graphene oxide dispersion liquid is 1-5 mg/mL.
4. The CoNb of claim 1 2 O 6 A method for preparing a composite porous graphene composite material, characterized in that the content is 30% by weight 2 O 2 And the volume ratio of the graphene oxide dispersion liquid to the graphene oxide dispersion liquid is 1.
5. The CoNb of claim 1 2 O 6 The preparation method of the composite porous graphene composite material is characterized in that the Co is 2 O 3 And Nb 2 O 5 In a molar ratio of 1.
6. The CoNb of claim 1 or 3 2 O 6 The preparation method of the composite porous graphene composite material is characterized in that a product after reaction and the Co 2 O 3 And Nb 2 O 5 The mass ratio of (A) to (B) is 3.
7. The CoNb of claim 1 2 O 6 A method for producing a composite porous graphene composite material, characterized in that a graphene oxide dispersion liquid is added by 30% H 2 O 2 The solution is heated to 75-95 ℃ for 2-4 h.
8. The CoNb of claim 1 2 O 6 The preparation method of the composite porous graphene composite material is characterized in that a product after ball milling is heated to 700-900 ℃ in a protective gas atmosphere, and then the constant temperature reaction time is 6-12 h.
9. The CoNb of claim 1 2 O 6 The preparation method of the composite porous graphene composite material is characterized in that the protective gas is argon, nitrogen or helium.
10. CoNb 2 O 6 A composite porous graphene composite material, characterized by being obtained by the method of any one of claims 1 to 9.
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