CN109841810B - Preparation method and application of Ni-NiO/C composite material - Google Patents
Preparation method and application of Ni-NiO/C composite material Download PDFInfo
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Abstract
The invention relates to the technical field of composite materials, in particular to a preparation method and application of a Ni-NiO/C composite material, wherein the preparation method is a new method for synthesizing the Ni-NiO/C composite material through one-step in-situ electrolysis, namely, an alkali carbonate is used as a molten salt electrolyte, metallic nickel is used as an anode and a nickel source to carry out continuous electrolytic reaction, and the Ni-NiO/C composite material is prepared on the surface of the cathode; the Ni improves the conductivity of the material and promotes the dynamics of the electrode material. The invention achieves the effect of reducing the preparation process, and the used carbonate has wide source, easy obtaining and low price; no waste water and waste gas are discharged in the preparation process, and the molten salt can be recycled and is environment-friendly; the method is simple and easy to control, has high efficiency and low cost, and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method and application of a Ni-NiO/C composite material.
Background
Nickel oxide (NiO) is used as a 3d transition metal oxide lithium ion battery cathode material and has the characteristics of rich sources, environmental friendliness, high energy density and the like. However, the main problem of practical application of NiO materials is that the first coulombic efficiency is low, generally 60% to 65%, and the cycle performance is not ideal, and the reaction of NiO and lithium follows the following mechanism: NiO + 2Li+ + 2e-→Ni + Li2O, increasing the Ni content, the first of NiO can be increasedA secondary coulombic efficiency; NiO is compounded with a carbon material, so that the cycle stability and the high rate performance can be improved. Currently, NiO/C composite materials are not synthesized in one step, i.e., NiO materials are synthesized first and then subjected to surface carbon coating or compounding (Guomin Li, Yong Li, Jin Chen, Pingging Zhao, Degang Li, Yunhui Dong, Lipeng Zhang, Synthesis and research of egg shell-yolk NiO/C pore composites as lithium-ion base anode material, electrochemical Acta, 2017, 245, 941-948).
The preparation method of the invention is a new method for synthesizing the Ni-NiO/C composite material by one-step in-situ electrolysis, namely, the Ni-NiO/C composite material is prepared on the surface of a cathode by taking alkali carbonate as molten salt electrolyte and metallic nickel as an anode and a nickel source to carry out continuous electrolytic reaction, and the formation mechanism is shown in figure 1. The carbon material generated by electrolysis is porous carbon, so that rich active points are provided for lithium ions, and Ni and NiO can adapt to the volume change of the porous carbon; the Ni improves the conductivity of the material and promotes the dynamics of the electrode material.
Disclosure of Invention
The invention provides a preparation method of a simple, high-efficiency, low-cost and easy-industrialized-production Ni-NiO/C composite material for overcoming the defects in the prior art, and the preparation method is applied to a negative electrode material of a lithium ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention uses alkali carbonate as molten salt electrolyte, and the carbonate is converted into simple substance carbon and oxygen anions by an electrolytic reduction method; meanwhile, nickel ions generated by the anode diffuse to the cathode to combine with oxygen anions to generate nickel oxide, and partial nickel ions are reduced to generate metallic nickel, so that the Ni-NiO/C composite material is obtained.
A method of making a Ni-NiO/C composite, the method comprising the steps of:
s1, taking a proper amount of alkali metal carbonate, drying, placing in a corundum crucible, and fixing a cathode, an anode and a thermocouple in the corundum crucible;
s2, heating the alkali metal carbonate to 600-900 ℃ at a heating rate of 1-10 ℃/min to obtain molten salt, cooling the molten salt to 400-600 ℃ at a cooling rate of 1-10 ℃/min, and electrifying and electrolyzing the cooled molten salt;
and S3, after the electrolysis is finished, soaking the solid product on the surface of the cathode in dilute hydrochloric acid, and filtering, washing and drying the soaked solid product to obtain the Ni-NiO/C composite material.
Preferably, the alkali metal carbonate is present in a mass ratio of 1: (0-2): (0-2) lithium carbonate, sodium carbonate and potassium carbonate, wherein the alkali metal carbonate is preferably lithium carbonate and sodium carbonate in a mass ratio of 1:1, and the alkali metal carbonate is more preferably lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 1:1: 1.
Preferably, in step S1, the anode is nickel and the cathode is nickel or graphite.
Preferably, the voltage applied in step S2 is 2-7V, more preferably 5-7V, and the electrolysis time is 0.5-5 hours.
Preferably, the distance between the cathode and the anode is 1-4 cm, more preferably 2-4 cm, and most preferably 2.5 cm.
Preferably, in step S2, the metal carbonate is heated to 600-800 ℃ at a heating rate of 2-8 ℃/min to obtain molten salt, and then the molten salt is cooled to 480-600 ℃ at a cooling rate of 2-8 ℃/min.
Preferably, in step S2, the metal carbonate is heated to 650-750 ℃ at a heating rate of 4-8 ℃/min to obtain a molten salt, and then the molten salt is cooled to 480-520 ℃ at a cooling rate of 4-8 ℃/min.
More preferably, in step S2, the metal carbonate is heated to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, and then the molten salt is cooled to 500 ℃ at a cooling rate of 5 ℃/min.
Preferably, the drying method in step S3 is freeze drying.
Preferably, the preparation method of the Ni-NiO/C composite material comprises the following steps:
s1, uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 1:1:1 to obtain powder, drying at 200 ℃ for 24 hours, placing the dried powder in a corundum crucible, fixing a cathode, an anode and a thermocouple in the corundum crucible, and keeping the distance between the cathode and the anode at 2.5 cm;
s2, heating the alkali metal carbonate to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, cooling the molten salt to 500 ℃ at a cooling rate of 5 ℃/min, and applying a voltage of 5-7V between the two electrodes for electrolysis for 2 h;
and S3, after the electrolysis is finished, putting the solid product on the surface of the cathode into 1mol/L hydrochloric acid for ultrasonic treatment for 2 hours, stirring for 6 hours, filtering, washing with clear water, and freeze-drying to obtain the Ni-NiO/C composite material.
The invention also provides application of the Ni-NiO/C composite material prepared by the method as a lithium ion battery cathode material, wherein the lithium ion battery is prepared by a conventional method.
The invention has the beneficial effects that:
(1) in the invention, the Ni-NiO/C composite material is generated in situ by one step by utilizing an alkali metal molten carbonate electrolysis method, so that the preparation process is greatly reduced, and the used carbonate has wide sources, is easy to obtain and has low cost; no waste water and waste gas are discharged in the preparation process, and the molten salt can be recycled and is environment-friendly;
(2) the method is simple and easy to control, has high efficiency and low cost, and is easy to realize industrial production;
(3) according to the Ni-NiO/C composite material prepared by the method, Ni can promote an electrochemical reaction, NiO is used as an active substance to mainly provide capacity, and the carbon material prepared by electrolysis is porous carbon and can effectively inhibit the capacity attenuation problem caused by the drastic change of the volume of NiO, so that the obtained Ni-NiO/C composite material has the characteristics of high capacity, good cycling stability and the like and can be used as a lithium ion battery cathode material.
Drawings
FIG. 1 is a schematic diagram of the mechanism for preparing Ni-NiO/C composite material according to the present application;
FIG. 2 is an XRD pattern of the Ni-NiO/C composite material prepared in example 1 of the present application;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the Ni-NiO/C composite material prepared in example 1 of the present application;
FIG. 4 is a graph of the cycle performance of a simulated lithium ion battery prepared in example 1 of the present application;
fig. 5 is a graph of rate performance of a simulated lithium ion battery prepared in example 1 of the present application.
Detailed Description
The technical solution of the present invention is further illustrated by the following embodiments in conjunction with the accompanying drawings.
Example 1:
the first step is as follows: preparation of Ni-NiO/C composite material
S1, uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 1:1:1 to obtain powder, drying at 200 ℃ for 24 hours, placing the dried powder in a corundum crucible, fixing a cathode, an anode and a thermocouple in the corundum crucible, and keeping the distance between the cathode and the anode at 2.5 cm;
s2, heating the alkali metal carbonate to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, cooling the molten salt to 500 ℃ at a cooling rate of 5 ℃/min, and applying a voltage of 6V between the two electrodes for electrolysis for 1h, as shown in figure 1;
and S3, after the electrolysis is finished, putting the solid product on the surface of the cathode into 1mol/L hydrochloric acid for ultrasonic treatment for 2 hours, stirring for 6 hours, filtering, washing with clear water, and freeze-drying to obtain the Ni-NiO/C composite material.
Figure 2 is an XRD diffractogram of this material against a standard card with Ni, NiO and amorphous carbon.
FIG. 3 is an SEM image of the material, which shows that the material has a porous morphology.
The second step is that: preparation of simulated lithium ion battery
The Ni-NiO/C composite material and the polyvinylidene fluoride are respectively weighed according to the mass ratio of 85:15, ground and pressed into a sheet to serve as a negative electrode, a metal lithium sheet serves as a positive electrode, an electrolyte is 1mol/L LiTFSI/DOL-DME (1:1), and a polypropylene microporous film serves as a diaphragm, so that the simulated lithium ion battery is assembled.
FIG. 4 is a graph of cycle performance of the lithium ion battery simulated in the embodiment in the voltage range of 0.4A/g and 0.01-3.0V, and the material has a discharge capacity of more than 510 mAh/g after 100 cycles, a capacity retention rate close to 100%, and excellent cycle performance.
Fig. 5 is a rate performance graph of the lithium ion battery simulated in the embodiment, and as can be seen from the rate performance graph of fig. 5, the rate performance of the material is very good.
Example 2:
the first step is as follows: preparation of Ni-NiO/C composite material
S1, uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 1:1:1 to obtain powder, drying at 200 ℃ for 24 hours, placing the dried powder in a corundum crucible, fixing a cathode, an anode and a thermocouple in the corundum crucible, and keeping the distance between the cathode and the anode at 2.5 cm;
s2, heating the alkali metal carbonate to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, cooling the molten salt to 500 ℃ at a cooling rate of 5 ℃/min, and applying a voltage of 5V between the two electrodes for electrolysis for 1h, as shown in figure 1;
and S3, after the electrolysis is finished, putting the solid product on the surface of the cathode into 1mol/L hydrochloric acid for ultrasonic treatment for 2 hours, stirring for 6 hours, filtering, washing with clear water, and freeze-drying to obtain the Ni-NiO/C composite material.
The second step is that: preparation of simulated lithium ion battery
The Ni-NiO/C composite material and the polyvinylidene fluoride are respectively weighed according to the mass ratio of 85:15, ground and pressed into a sheet to serve as a negative electrode, a metal lithium sheet serves as a positive electrode, an electrolyte is 1mol/L LiTFSI/DOL-DME (1:1), and a polypropylene microporous film serves as a diaphragm, so that the simulated lithium ion battery is assembled.
The capacity of the simulated lithium ion battery assembled in the embodiment of the application is close to 450 mAh/g after the circulation of 0.4A/g for 100 times, the capacity retention rate is close to 97%, and the cycle performance and the reversibility are good.
Example 3:
the first step is as follows: preparation of Ni-NiO/C composite material
S1, uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 1:1:1 to obtain powder, drying at 200 ℃ for 24 hours, placing the dried powder in a corundum crucible, fixing a cathode, an anode and a thermocouple in the corundum crucible, and keeping the distance between the cathode and the anode at 2.5 cm;
s2, heating the alkali metal carbonate to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, cooling the molten salt to 500 ℃ at a cooling rate of 5 ℃/min, and applying a voltage of 7V between the two electrodes for electrolysis for 1h, as shown in figure 1;
and S3, after the electrolysis is finished, putting the solid product on the surface of the cathode into 1mol/L hydrochloric acid for ultrasonic treatment for 2 hours, stirring for 6 hours, filtering, washing with clear water, and freeze-drying to obtain the Ni-NiO/C composite material.
The second step is that: preparation of simulated lithium ion battery
The Ni-NiO/C composite material and the polyvinylidene fluoride are respectively weighed according to the mass ratio of 85:15, ground and pressed into a sheet to serve as a negative electrode, a metal lithium sheet serves as a positive electrode, an electrolyte is 1mol/L LiTFSI/DOL-DME (1:1), and a polypropylene microporous film serves as a diaphragm, so that the simulated lithium ion battery is assembled.
The capacity of the simulated lithium ion battery assembled in the embodiment of the application is close to 427mAh/g after 100 times of 0.4A/g circulation, and the capacity retention rate is close to 95%.
Example 4:
the first step is as follows: preparation of Ni-NiO/C composite material
S1, uniformly mixing lithium carbonate and sodium carbonate in a mass ratio of 1:1 to obtain powder, drying at 200 ℃ for 24 hours, placing the dried powder in a corundum crucible, fixing a cathode, an anode and a thermocouple in the corundum crucible, and keeping the distance between the cathode and the anode at 2.5 cm;
s2, heating the alkali metal carbonate to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, cooling the molten salt to 500 ℃ at a cooling rate of 5 ℃/min, and applying a voltage of 6V between the two electrodes for electrolysis for 1h, as shown in figure 1;
and S3, after the electrolysis is finished, putting the solid product on the surface of the cathode into 1mol/L hydrochloric acid for ultrasonic treatment for 2 hours, stirring for 6 hours, filtering, washing with clear water, and freeze-drying to obtain the Ni-NiO/C composite material.
The second step is that: preparation of simulated lithium ion battery
The Ni-NiO/C composite material and the polyvinylidene fluoride are respectively weighed according to the mass ratio of 85:15, ground and pressed into a sheet to serve as a negative electrode, a metal lithium sheet serves as a positive electrode, an electrolyte is 1mol/L LiTFSI/DOL-DME (1:1), and a polypropylene microporous film serves as a diaphragm, so that the simulated lithium ion battery is assembled.
The capacity of the simulated lithium ion battery assembled in the embodiment of the application is close to 480mAh/g after 0.4A/g circulation for 100 times, and the capacity retention rate is close to 97%.
Example 5:
the first step is as follows: preparation of Ni-NiO/C composite material
S1, uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 1:1:1 to obtain powder, drying at 200 ℃ for 24 hours, placing the dried powder in a corundum crucible, fixing a cathode, an anode and a thermocouple in the corundum crucible, and keeping the distance between the cathode and the anode at 2.5 cm;
s2, heating the alkali metal carbonate to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, cooling the molten salt to 600 ℃ at a cooling rate of 5 ℃/min, and applying a voltage of 6V between the two electrodes for electrolysis for 1h, as shown in figure 1;
and S3, after the electrolysis is finished, putting the solid product on the surface of the cathode into 1mol/L hydrochloric acid for ultrasonic treatment for 2 hours, stirring for 6 hours, filtering, washing with clear water, and freeze-drying to obtain the Ni-NiO/C composite material.
The second step is that: preparation of simulated lithium ion battery
The Ni-NiO/C composite material and the polyvinylidene fluoride are respectively weighed according to the mass ratio of 85:15, ground and pressed into a sheet to serve as a negative electrode, a metal lithium sheet serves as a positive electrode, an electrolyte is 1mol/L LiTFSI/DOL-DME (1:1), and a polypropylene microporous film serves as a diaphragm, so that the simulated lithium ion battery is assembled.
The capacity of the simulated lithium ion battery assembled in the embodiment of the application is close to 440mAh/g after 100 times of 0.4A/g circulation, and the capacity retention rate is close to 98%.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (9)
1. A preparation method of a Ni-NiO/C composite material is characterized by comprising the following steps:
s1, taking a proper amount of alkali metal carbonate, drying, placing the dried alkali metal carbonate in a corundum crucible, and fixing a cathode, an anode and a thermocouple in the corundum crucible;
s2, heating the alkali metal carbonate to 600-900 ℃ at a heating rate of 1-10 ℃/min to obtain molten salt, cooling the molten salt to 400-600 ℃ at a cooling rate of 1-10 ℃/min, and electrifying and electrolyzing the cooled molten salt;
s3, after the electrolysis is finished, soaking the solid product on the surface of the cathode in dilute hydrochloric acid, and filtering, washing and drying the soaked solid product to obtain the Ni-NiO/C composite material;
in step S1, the anode material is nickel, and the cathode material is nickel or graphite.
2. The method of preparing the Ni-NiO/C composite of claim 1, wherein the alkali metal carbonate is formed by mixing the following materials in a mass ratio of 1: (0-2): (0-2) lithium carbonate, sodium carbonate and potassium carbonate.
3. The method for preparing the Ni-NiO/C composite material according to claim 1, wherein the energizing voltage in step S2 is 2-7V, and the electrolysis time is 0.5-5 hours.
4. The method for preparing the Ni-NiO/C composite material according to claim 1, wherein the distance between the cathode and the anode is 1-4 cm.
5. The method for preparing the Ni-NiO/C composite material according to claim 1, wherein the metal carbonate is heated to 600-800 ℃ at a temperature rising rate of 2-8 ℃/min to obtain a molten salt in step S2, and then the molten salt is cooled to 480-600 ℃ at a temperature lowering rate of 2-8 ℃/min.
6. The method for preparing the Ni-NiO/C composite material according to claim 5, wherein the metal carbonate is heated to 650-750 ℃ at a heating rate of 4-8 ℃/min to obtain a molten salt in step S2, and then the molten salt is cooled to 480-520 ℃ at a cooling rate of 4-8 ℃/min.
7. The method of preparing the Ni-NiO/C composite material of claim 1, wherein the drying means of step S3 is freeze-drying.
8. The method of preparing the Ni-NiO/C composite of claim 1, comprising the steps of:
s1, uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 1:1:1 to obtain powder, drying at 200 ℃ for 24 hours, placing the dried powder in a corundum crucible, fixing a cathode, an anode and a thermocouple in the corundum crucible, and keeping the distance between the cathode and the anode at 2.5 cm;
s2, heating the alkali metal carbonate to 700 ℃ at a heating rate of 5 ℃/min to obtain molten salt, cooling the molten salt to 500 ℃ at a cooling rate of 5 ℃/min, and applying a voltage of 5-7V between the two electrodes for electrolysis for 2 h;
and S3, after the electrolysis is finished, putting the solid product on the surface of the cathode into 1mol/L hydrochloric acid for ultrasonic treatment for 2 hours, stirring for 6 hours, filtering, washing with clear water, and freeze-drying to obtain the Ni-NiO/C composite material.
9. The application of the Ni-NiO/C composite material prepared by the method of any one of claims 1 to 8 as a negative electrode material of a lithium ion battery.
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