Nanoparticle assembled mulberry-shaped basic cupric carbonate material and application thereof
Through the preparation method of assembling mulberry-like alkaline copper carbonate materials in nanoparticles, the problem of the existing alkaline copper carbonate materials limiting electrochemical reactions is solved, the high specific surface area and electrical conductivity are improved, and the electrochemical performance of lithium-ion batteries is significantly improved.
Patent Information
- Application Number
- CN202411968807.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-30
- Publication Date
- 2025-05-06
AI Technical Summary
The existing basic copper carbonate materials are mostly blocks, and their limited specific surface area limits the active area of the reaction, making the degree of electrochemical reaction incomplete, and poor conductivity also affects the performance of the material.
The preparation method of assembling mulberry-like alkaline copper carbonate material by nanoparticles, by adding soluble copper salt dropwise to the carbonate solution, stirring at room temperature, and following the steps of centrifugation, washing, and drying, mulberry-like nanoparticles with high specific surface area are synthesized. At the same time, the conductive properties of the material are enhanced by in-situ composite graphene oxide.
It improves the electrochemical performance of the material, has high lithium storage reversibility and ultra-high capacity, provides higher specific capacity, high-strength rate performance and better cycle stability, and is simple in process and low in cost.
Smart Images
Figure CN119929862A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of battery electrode materials, and in particular relates to a nano-particle-assembled mulberry-shaped basic copper carbonate material and an application thereof. Background Art
[0002] Nanostructured metal oxides and semiconductor materials are highly desirable for advanced electronic, magnetic, optoelectronic and sensing applications. The performance of nanoparticles depends largely on their phase, size, shape and dimensions. Developing scalable and facile routes to produce them with controlled size and microstructure is very important for nanotechnology and synthetic chemistry. Transition metal carbonates have attracted much attention as anode materials for LIBs due to their high specific capacity. However, transition metal basic carbonates are rarely used in battery anodes and have higher theoretical specific capacity than transition metal carbonates, which is much higher than commercial carbon anode materials.
[0003] Basic copper carbonate has a wide range of uses. It can be used to make pigments, fireworks, paints, fungicides, and wood preservatives. Further, by improving the morphology of basic copper carbonate, its optical, electrical, and magnetic effects can be improved. By utilizing the valence change of the copper element in basic copper carbonate, a reversible electrochemical reaction can be achieved, thereby preparing a secondary battery of basic copper carbonate with excellent performance. Using basic copper carbonate as an electrode material, using commonly used salts and alkalis as electrolytes, and water as a solvent, it has the advantages of high safety and low cost, and has great application potential in the field of energy storage batteries.
[0004] The existing copper carbonate materials are mostly in bulk form. The limited specific surface area of the bulk material limits the active area of the reaction, making the electrochemical reaction of copper carbonate incomplete. In addition, the poor conductivity of copper carbonate also affects the performance of the material to a certain extent.
[0005] It is of great significance to develop a basic copper carbonate material with a new morphology suitable for battery applications. Summary of the invention
[0006] The purpose of the present invention is to design and synthesize a new type of transition metal basic carbonate as a negative electrode material for lithium ion batteries, and to provide a nanoparticle-assembled mulberry-shaped basic copper carbonate material and its application.
[0007] The technical solution adopted by the present invention is as follows:
[0008] The first aspect of the present invention provides a nanoparticle-assembled mulberry-shaped basic copper carbonate material, and the preparation method thereof comprises the following steps:
[0009] S1: dispersing a soluble copper salt in ultrapure water to obtain solution A, and dispersing a carbonate in ultrapure water to obtain solution B;
[0010] S2: adding the solution A dropwise into the solution B to mix them evenly, and stirring at room temperature for a certain period of time;
[0011] S3: Centrifuge to obtain a solid product, wash and dry to obtain nanoparticles to assemble mulberry-shaped basic copper carbonate material.
[0012] Preferably, in step S1, the soluble copper salt is one or more of copper nitrate, copper sulfate, copper acetate, and copper chloride; and the carbonate is one or more of sodium carbonate and potassium carbonate.
[0013] Preferably, the molar ratio of copper ions in solution A to carbonate ions in solution B is 1:1.0-1.3.
[0014] Preferably, in step S2, the reaction time is 8-14 h and the reaction temperature is 25-45°C.
[0015] Preferably, in step S3, the drying temperature is 80-125° C., and the drying time is 5-12 hours.
[0016] Preferably, in step S1, graphene oxide is also dispersed in solution A.
[0017] Preferably, the ratio of soluble copper salt to graphene oxide is 13-20:1
[0018] Preferably, the method for preparing graphene oxide comprises the following steps:
[0019] (1) adding graphite sheets and sodium nitrate into a container containing concentrated sulfuric acid placed in an ice bath and stirring;
[0020] (2) Add KMnO4 to the container and continue stirring;
[0021] (3) Transfer the container to a water bath and stir at 20-50°C;
[0022] (4) Add ultrapure water dropwise into the container to make the solution temperature below 40°C;
[0023] (5) transferring the container to a 95-100° C. oil bath and maintaining vigorous stirring for 20-40 minutes, and then continuously adding ultrapure water and H 2 O 2 at room temperature to obtain a graphene oxide solution;
[0024] (6) The GO solution is centrifuged and dialyzed until the pH value is close to neutral to obtain a concentrated graphene oxide solution, and the concentrated graphene oxide solution is vacuum dried to obtain graphene oxide.
[0025] The second aspect of the present invention provides the use of the nanoparticle-assembled mulberry-shaped basic copper carbonate material in a battery.
[0026] The third aspect of the present invention provides the use of the nanoparticle-assembled mulberry-shaped basic copper carbonate material as described above in lithium-ion battery anode materials.
[0027] The beneficial effects of the present invention are as follows:
[0028] The present invention synthesizes nanoparticles assembled into mulberry-shaped basic copper carbonate (Cu2(OH)2CO3) by a simple precipitation method, and in-situ composite graphene oxide to make its electrochemical performance have high lithium storage reversibility and ultra-high capacity. This method provides lithium-ion batteries with higher specific capacity, high-strength rate performance and better cycle stability. Compared with existing reports, the preparation method of the present invention has simple process and low cost, and the obtained Cu2(OH)2CO3 / GO composite material has excellent cycle performance and rate performance in lithium-ion batteries.
[0029] Mulberry-shaped basic copper carbonate assembled by nanoparticles was successfully synthesized by precipitation method. The synthesis process is green and environmentally friendly, and can be synthesized at room temperature, which is convenient for commercialization and large-scale production. And the mulberry-shaped nanoparticle structure synthesized by the present invention has unique advantages in the negative electrode material of lithium-ion batteries. The mulberry-shaped structure not only increases the specific surface area of the material, but also provides more lithium ion transmission channels, which greatly improves the electrochemical performance of the battery. In addition, compared with the traditional bulk basic nickel carbonate structure, the mulberry-shaped nanoscale particle structure can more effectively regulate the volume effect in the process of lithium ion insertion and extraction and increase the specific surface area of the material, providing more channels for the transmission of lithium ions, thereby improving the cycle stability and rate performance of the battery.
[0030] The poor conductivity of Cu2(OH)2CO3 limits its application in batteries to a certain extent. The present invention uses a simple one-step hydrothermal method to in-situ composite it with graphene oxide material with excellent conductive properties, which improves the conductivity of the material while also refining the particle size of the material and increasing the specific surface area of the material. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, without paying creative labor, other drawings obtained based on these drawings still belong to the scope of the present invention.
[0032] Figure 1 : X-ray diffraction (XRD) patterns of the two materials prepared in Example 1 and Example 2;
[0033] Figure 2: Scanning electron microscope (SEM) image of mulberry-shaped basic copper carbonate prepared in Example 1;
[0034] Figure 3 : Transmission electron microscope (TEM) image of the mulberry-shaped basic copper carbonate prepared in Example 1;
[0035] Figure 4 : Transmission electron microscope (TEM) image of the nanoparticle-assembled mulberry-shaped basic copper carbonate composite graphene high-performance lithium storage material prepared in Example 2;
[0036] Figure 5 :Examples 1-4 Four materials as lithium-ion batteries at 100mA g -1 Cyclic stability test diagram at current density of ;
[0037] Figure 6 :Examples 1-4 Four materials as lithium-ion batteries at 1000mA g -1 Cyclic stability test diagram at current density of ;
[0038] Figure 7 :Examples 1-4 Four materials as lithium-ion batteries at 2000mA g -1 Cyclic stability test diagram at current density of ;
[0039] Figure 8 : Examples 1-4 are graphs showing the cycling stability of the four materials used as lithium-ion batteries at different current densities. DETAILED DESCRIPTION
[0040] In order to make the objectives, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below with reference to the accompanying drawings.
[0041] Example 1
[0042] S1: In a beaker, add 0.055 mol Cu(NO3)2·3H2O to 50 ml ultrapure water and mix evenly by ultrasonic to obtain solution A. Add 0.065 mol NaCO3 to 130 ml ultrapure water and mix evenly by ultrasonic to obtain solution B.
[0043] S2: Add the solution A dropwise into the solution B, stir magnetically for 20 minutes to mix evenly, and react at 30°C for 10 hours;
[0044] S3: centrifugation to obtain a solid product, the solid product is washed with water and ethanol, and dried to obtain a nanoparticle-assembled mulberry-shaped basic copper carbonate material;
[0045] S5: Weigh nanoparticles assembled mulberry-shaped basic copper carbonate, acetylene black and sodium alginate in a mass ratio of 7:2:1, mix evenly, add appropriate amount of ultrapure water, stir continuously into a paste, and apply it on copper foil; dry, press and assemble the copper foil coated with nanoparticles assembled mulberry-shaped basic copper carbonate composite graphene high-performance lithium storage material to obtain a lithium-ion battery.
[0046] Example 2
[0047] S1: In a beaker, 0.055 mol Cu(NO3)2·3H2O and 60 mg of graphene oxide were added to 50 ml of ultrapure water and mixed evenly by ultrasonication to obtain solution A. 0.065 mol NaCO3 was added to 130 ml of ultrapure water and mixed evenly by ultrasonication to obtain solution B.
[0048] S2: Add the solution A dropwise into the solution B, stir magnetically for 20 minutes to mix evenly, and react at 30°C for 10 hours;
[0049] S3: centrifugation to obtain a solid product, the solid product is washed with water and ethanol, and dried to obtain a nanoparticle-assembled mulberry-shaped basic copper carbonate composite graphene high-performance lithium storage material;
[0050] S5: Weigh nanoparticle-assembled mulberry-shaped copper carbonate basic graphene composite, acetylene black and sodium alginate in a mass ratio of 7:2:1, mix evenly, add appropriate amount of ultrapure water, stir continuously into a paste, and apply it on copper foil; dry, press and assemble the copper foil coated with nanoparticle-assembled mulberry-shaped copper carbonate basic graphene high-performance lithium storage material to obtain a lithium-ion battery.
[0051] Among them, graphene oxide was prepared by the following method: a certain amount of graphite sheets and sodium nitrate were added to a beaker containing a certain amount of concentrated sulfuric acid placed in an ice bath, the suspension was stirred for 2 hours by mechanical stirring, a certain amount of KMnO4 was slowly added, and stirred for another 2 hours. Then, the beaker was transferred to a water bath and stirred at 35°C for 1 hour. A certain amount of ultrapure water was dropped into the beaker so that the solution temperature was below 40°C. After that, the beaker was transferred to an oil bath at 98°C and kept stirring vigorously for 30 minutes, and then a certain amount of ultrapure water and H2O2 were continuously added at room temperature. Finally, the GO solution was centrifuged with ultrapure water, and the obtained product was placed in a dialysis bag for dialysis until the pH value was close to neutral, and then stored in a dark brown sealed glass bottle. In the concentrated GO solution obtained, the concentration of GO nanosheets was estimated by the mass of GO nanosheets, that is, after vacuum drying the GO solution at 80°C.
[0052] Example 3
[0053] The preparation process of this embodiment is substantially the same as that of embodiment 2, with the only difference being that in step S2, the reaction is performed at 30° C. for 8 h.
[0054] Example 4
[0055] The preparation process of this embodiment is substantially the same as that of embodiment 2, with the only difference being that in step S2, the reaction is performed at 30° C. for 5 h.
[0056] Material properties
[0057] Figure 1 The X-ray diffraction (XRD) patterns of the two materials prepared in Example 1 and Example 2, wherein the XRD test results of the two materials are consistent with the standard card PDF#41-1390, the peak intensity of the basic copper carbonate composite graphene composite material is lower than that of the basic copper carbonate without graphene composite, and it has a smaller particle size; the XRD patterns of the materials prepared in Examples 3 and 4 are consistent with Figure 1 The above is similar to Example 2, so it is omitted here.
[0058] Microscopic characterization
[0059] Figure 2 and Figure 3 They are scanning electron microscope (SEM) and transmission electron microscope (TEM) images of the mulberry-shaped basic copper carbonate prepared in Example 1; its mulberry-shaped morphology can be clearly observed from the images.
[0060] Figure 4 The transmission electron microscope (TEM) image of the nanoparticle-assembled mulberry-shaped basic copper carbonate composite graphene high-performance lithium storage material prepared in Example 2; it can be clearly seen that the graphene and the mulberry-shaped basic copper carbonate material are successfully composited; the TEM images of the materials prepared in Examples 3 and 4 are as follows: Figure 4 are similar and are therefore omitted here.
[0061] Electrochemical performance characterization
[0062] Figure 5 The two lithium-ion batteries prepared in Example 1 and Example 2 were subjected to 100 mA g -1 Cyclic stability test diagram at current density of 100 mA g -1 After 50 cycles at a current density of 1.34 W, the capacity is 1171 mAh g -1 , Example 1 at 100mA g -1 After 50 cycles at a current density of 1.34 W, the capacity is 954 mAh g -1 , Example 3 at 100mA g -1 After 50 cycles at a current density of 1.34 W, the capacity is 645 mAh g-1 , Example 4 at 100mA g -1 After 50 cycles at a current density of 1.34 W, the capacity is 498 mAh g -1 ;
[0063] Figure 6 The two lithium-ion batteries of Example 1 and Example 2 are at 1000 mA g -1 Cyclic stability test diagram at current density of 1000 mA g -1 After 200 cycles at a current density of 1.34 W, the capacity is 1081 mAh g -1 , Example 1 at 1000mA g -1 After 200 cycles at a current density of 1.34 W, the capacity is 797 mAh g -1 , Example 3 at 1000mA g -1 After 200 cycles at a current density of 5.38 mAh g -1 , Example 4 at 1000mA g -1 After 200 cycles at a current density of 1.34 W, the capacity is 104 mAh g -1 ,
[0064] Figure 7 The two lithium-ion batteries of Example 1 and Example 2 are charged at 2000 mA g -1 Cyclic stability test diagram at a current density of 2000 mA g -1 After 400 cycles at a current density of -1 , Example 1 at 2000mA g -1 After 400 cycles at a current density of 1.34 W, the capacity is 937 mAh g -1 , Example 3 at 2000mA g -1 After 400 cycles at a current density of 1.34 W, the capacity is 414 mAh g -1 , Example 4 at 2000mA g -1 After 400 cycles at a current density of 1.34 W, the capacity is 44 mAh g -1 ;
[0065] Figure 8 The graphs are cycle stability test diagrams of two lithium-ion batteries of Example 1 and Example 2 at different current densities; the capacity of Example 2 is significantly higher than that of Examples 1, 3, and 4 at various current densities.
[0066] The above disclosure is only the preferred embodiment of the present invention, which certainly cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention are still within the scope of the present invention.
Claims
1. A nanoparticle-assembled mulberry-shaped basic copper carbonate material, characterized in that: The preparation method thereof comprises the following steps: S1: dispersing a soluble copper salt in ultrapure water to obtain solution A, and dispersing a carbonate in ultrapure water to obtain solution B; S2: adding the solution A dropwise into the solution B to mix them evenly, and stirring at room temperature for a certain period of time; S3: Centrifuge to obtain a solid product, wash and dry to obtain nanoparticles to assemble mulberry-shaped basic copper carbonate material.
2. The nanoparticle-assembled mulberry-shaped basic copper carbonate material according to claim 1, characterized in that: In step S1, the soluble copper salt is one or more of copper nitrate, copper sulfate, copper acetate, and copper chloride; the carbonate is one or more of sodium carbonate and potassium carbonate.
3. The nanoparticle-assembled mulberry-shaped basic copper carbonate material according to claim 1, characterized in that: The molar ratio of copper ions in solution A to carbonate ions in solution B is 1:1.0-1.
3.
4. The nanoparticle-assembled mulberry-shaped basic copper carbonate material according to claim 1, characterized in that: In step S2, the reaction time is 8-14 hours and the reaction temperature is 25-45°C.
5. The nanoparticle-assembled mulberry-shaped basic copper carbonate material according to claim 1, characterized in that: In step S3, the drying temperature is 80-125° C. and the drying time is 5-12 hours.
6. The nanoparticle-assembled mulberry-shaped basic copper carbonate material according to claim 1, characterized in that: In step S1, graphene oxide is also dispersed in solution A.
7. The nanoparticle-assembled mulberry-shaped basic copper carbonate material according to claim 6, characterized in that: The ratio of soluble copper salt to graphene oxide is 13-20:
1.
8. The nanoparticle-assembled mulberry-shaped basic copper carbonate material according to claim 6, characterized in that: The preparation method of graphene oxide comprises the following steps: (1) adding graphite sheets and sodium nitrate into a container containing concentrated sulfuric acid placed in an ice bath and stirring; (2) Add KMnO4 to the container and continue stirring; (3) Transfer the container to a water bath and stir at 20-50°C; (4) Add ultrapure water dropwise into the container to make the solution temperature below 40°C; (5) transferring the container to a 95-100° C. oil bath and maintaining vigorous stirring for 20-40 minutes, and then continuously adding ultrapure water and H 2 O 2 at room temperature to obtain a graphene oxide solution; (6) The GO solution is centrifuged and dialyzed until the pH value is close to neutral to obtain a concentrated graphene oxide solution, and the concentrated graphene oxide solution is vacuum dried to obtain graphene oxide.
9. Use of the nanoparticle-assembled mulberry-shaped basic copper carbonate material according to any one of claims 1 to 8 in a battery.
10. Use of the nanoparticle-assembled mulberry-shaped basic copper carbonate material according to any one of claims 1 to 8 in lithium-ion battery anode materials.