CN110931762B - Nano copper oxalate composite three-dimensional graphene anode material and preparation method and application thereof - Google Patents
Nano copper oxalate composite three-dimensional graphene anode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nano copper oxalate composite three-dimensional graphene anode material as well as a preparation method and application thereof, wherein the method comprises the following steps: s1: putting the lithium sheet into a tube furnace, and vacuumizing the tube furnace; s2: carbon dioxide gas is charged into the tube furnace. Heating a tube furnace to obtain a three-dimensional graphene crude product; s3: crushing the three-dimensional graphene crude product into powder; s4: putting the powdery three-dimensional graphene crude product into concentrated nitric acid to be continuously soaked for more than 2 hours; s5: adding copper powder or copper salt into the suspension and fully stirring; s6: slowly dripping absolute ethyl alcohol into the suspension and continuously stirring; s7: and sequentially filtering, washing and drying the product obtained in the step S6 to obtain the nano copper oxalate composite three-dimensional graphene negative electrode material. According to the invention, the nanometer copper oxalate is compounded on the surface of the three-dimensional graphene anode material, so that the coulomb efficiency of the obtained three-dimensional graphene anode material is greatly improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a nano copper oxalate composite three-dimensional graphene negative electrode material as well as a preparation method and application thereof.
Background
Currently, under the new situation that fossil energy is gradually exhausted, the environment is seriously polluted, and the global climate is increasingly warmed. The world energy development trend has shifted from developing new energy sources to developing new energy storage systems. The development of a novel green energy storage device with high energy density and high power density to replace the traditional energy storage and transportation system is the urgent priority of various countries with large energy consumption in the world. Lithium ion batteries have higher energy density, longer cycle life, and better safety in use than conventional batteries. Graphene has many excellent characteristics such as high electrical conductivity, high thermal conductivity, high specific surface area, high strength and rigidity, and is widely applied in many fields such as energy storage, photoelectric devices, chemical catalysis, and the like. The ideal graphene is a real surface solid, all carbon atoms of which are exposed on the surface, and has the unique advantages of being used as a positive and negative electrode material of a lithium ion battery: 1) the graphene has an ultra-large specific surface area, and the increase of the specific surface area can reduce the polarization of the battery and reduce the energy loss of the battery caused by the polarization. 2) Graphene has excellent electrical and thermal conductivity properties, i.e. has good electron transport channels, and good thermal conductivity ensures its stability in use. 3) In the macro electrode material formed by aggregation, the scale of the graphene sheet layer is in the micro-nano order and is far smaller than that of bulk phase graphite, so that the diffusion path of lithium between the graphene sheet layers is short; and the lamella spacing is larger than that of graphite with good crystallinity, so that the lithium diffusion and transmission are facilitated. Therefore, the graphene-based electrode material has good electron transmission channels and ion transmission channels, and is very beneficial to improving the power performance of the lithium ion battery. The theoretical capacity of the graphite negative electrode of the commercial lithium ion battery is 372 mAh/g. In order to realize high power density and high energy density of the lithium ion battery, how to improve the capacity of the lithium ion battery cathode material is a key problem. The thermal reduction graphene material with disorder or high specific surface area has a large number of micropore defects, and can improve reversible lithium storage capacity. Compared with graphite materials, graphene has the following advantages: 1) higher specific capacity: lithium ions are intercalated/deintercalated in the graphene in a non-stoichiometric ratio, and the specific capacity can reach 700-2000 mAh/g and is far more than the theoretical specific capacity of a graphite material; 2) faster charge and discharge rates: the interlayer distance of the multilayer graphene material is obviously larger than the interlayer distance of graphite, so that the multilayer graphene material is more favorable for rapid intercalation and deintercalation of lithium ions. However, the complexity of the microstructure of carbonaceous materials, the relationship between the material structure and the electrochemical performance of the electrodes, have restricted the development of high performance lithium ion batteries. The lithium salt electrolyte forms a passivation film (SEI film) on the surface of the carbon cathode, so that the coulombic efficiency of the three-dimensional graphene electrode in the first charge-discharge process is only 50-70%, and the irreversible specific capacity loss is as high as 30-50%. Therefore, the low coulombic efficiency of the graphene negative electrode material is a bottleneck problem which restricts the practical application of the graphene negative electrode material. Therefore, how to develop a novel graphene anode material capable of improving the coulomb efficiency of the first discharge is a research direction of those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a nano copper oxalate composite three-dimensional graphene negative electrode material, which can improve the coulombic efficiency of the obtained nano copper oxalate composite three-dimensional graphene negative electrode material.
The technical scheme is as follows:
a preparation method of a nano copper oxalate composite three-dimensional graphene negative electrode material comprises the following steps: s1: putting the lithium sheet into a ceramic boat in an inert gas glove box, putting the ceramic boat into a tube furnace, and vacuumizing the tube furnace until the pressure in the tube furnace is reduced to 10 Pa; s2: filling carbon dioxide gas into the tubular furnace, heating the tubular furnace to 550-600 ℃, and keeping the temperature for 24-48h to obtain a three-dimensional graphene crude product; s3: crushing the three-dimensional graphene crude product obtained in the step S2 to obtain a powdery three-dimensional graphene crude product; s4: soaking the powdery three-dimensional graphene crude product obtained in the step S3 in concentrated nitric acid for more than 2 hours, wherein the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid is more than 1: 2; s5: adding copper powder or copper salt into the suspension obtained in the step S4, and fully stirring to ensure that the mass ratio of the three-dimensional graphene crude product to the copper in the suspension reaches 100: 1-5; s6: continuously magnetically stirring the suspension obtained in the step S5, and slowly dropwise adding absolute ethyl alcohol until the copper and the ethyl alcohol in the suspensionIs divided into Ratio of sub-quantities1, reaching the following steps: 1-2; s7: and sequentially filtering, washing and drying the product obtained in the step S6 to obtain the nano copper oxalate composite three-dimensional graphene negative electrode material.
Preferably, in the preparation method of the nano copper oxalate composite three-dimensional graphene anode material, in step S2: and (3) filling carbon dioxide gas into the tubular furnace until the pressure value in the tubular furnace reaches 0.3-0.5Mpa, heating the tubular furnace to 550-600 ℃ at the temperature rise speed of 5-10 ℃ per minute, and keeping the temperature in the tubular furnace at 550-600 ℃ for 24-48h to obtain the three-dimensional graphene crude product.
Preferably, in the preparation method of the nano copper oxalate composite three-dimensional graphene negative electrode material, the powdery three-dimensional graphene crude product obtained in step S3 is a three-dimensional graphene crude product with a mesh number of 100 meshes or more.
Preferably, in the preparation method of the nano copper oxalate composite three-dimensional graphene anode material, in step S4: and (3) putting the powdery three-dimensional graphene crude product obtained in the step (S3) into concentrated nitric acid with the concentration of 68% to soak for 12 hours, wherein the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid is 1: 4-5.
Preferably, in the preparation method of the nano copper oxalate composite three-dimensional graphene negative electrode material, the copper salt in the step S5 is any one or a combination of any several of copper nitrate, copper carbonate, copper sulfate and copper chloride.
By adopting the technical scheme: firstly, preparing a powdery three-dimensional graphene crude product, and mixing the three-dimensional graphene crude product with concentrated nitric acid to form turbid liquid; then adding copper powder or copper salt into the suspension to react nitric acid in the suspension with the copper powder or copper salt to generate copper nitrate; and then, absolute ethyl alcohol is further added into the turbid liquid, the absolute ethyl alcohol and a copper nitrate solution further react to generate nano copper oxalate, and the nano copper oxalate grows in situ on the surface of the three-dimensional graphene material to change the electrochemical property of the three-dimensional graphene material. And finally, sequentially filtering, washing and drying the turbid liquid containing the nano copper oxalate composite three-dimensional graphene material to obtain a final nano copper oxalate composite three-dimensional graphene negative electrode material product.
The invention also discloses a nano copper oxalate composite three-dimensional graphene anode material which is prepared by adopting the preparation method of the nano copper oxalate composite three-dimensional graphene anode material.
The invention further discloses a lithium ion battery which comprises the nano copper oxalate composite three-dimensional graphene negative electrode material.
The invention achieves the following beneficial effects: the specific capacity of the nano copper oxalate composite three-dimensional graphene anode material is several times higher than that of a graphite material under the same current density, and the nano copper oxalate composite three-dimensional graphene anode material is suitable for quick charge and discharge under the large current density, and can be dozens of times faster than that of the graphite material in the charge and discharge rate. Through detection, the first coulombic efficiency of the nano-copper oxalate composite three-dimensional graphene negative electrode material reaches 87.5%, which is far higher than that of a nano-copper oxalate composite three-dimensional graphene negative electrode material.
Compared with the prior art, the preparation method is simple, copper powder or copper salt and ethanol are added in the pickling and purification process of the three-dimensional graphene crude product, and the nano copper oxalate grows in situ on the surface of the three-dimensional graphene by utilizing the slow reaction of concentrated nitric acid and ethanol, so that the coulomb efficiency of the obtained nano copper oxalate composite three-dimensional graphene negative electrode material can be greatly improved, and the technical bottleneck of the prior art is broken through.
Drawings
FIG. 1 is a process flow diagram of the present invention;
fig. 2 is a voltage-specific capacity curve of the assembled button cell prepared from the nano copper oxalate composite three-dimensional graphene anode material obtained in example 1 at 0.5C rate for the first charge-discharge cycle.
Fig. 3 is a voltage-specific capacity curve of the button cell assembled by the three-dimensional graphene anode material without the nano copper oxalate composite obtained in the comparative example, in the first charge-discharge cycle at 0.5C rate.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following will further describe various embodiments with reference to fig. 1-3. It is to be understood that the practice of the invention is not limited to the following examples, and that any changes and/or modifications may be made thereto without departing from the scope of the invention. In the following examples, all percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a group of preparation processes of a nano copper oxalate composite three-dimensional graphene anode material are as follows:
s1: weighing 1g of metal lithium in an inert gas glove box, putting the metal lithium into a ceramic boat, quickly putting the ceramic boat into a tube furnace, and vacuumizing the tube furnace to 10 Pa;
s2: filling carbon dioxide gas into the tubular furnace to 0.4Mpa, then heating the tubular furnace to 550 ℃ at the temperature rise speed of 5 ℃ per minute, and keeping the temperature for 24 hours to obtain a three-dimensional graphene crude product;
s3: crushing the three-dimensional graphene crude product obtained in the step S2 to more than 100 meshes;
s4: putting the powdery three-dimensional graphene crude product obtained in the step S3 into concentrated nitric acid with the concentration of 68%, and continuously soaking for 12 hours to enable the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid to reach 1: 5;
s5: adding copper powder into the suspension obtained in the step S4, fully stirring the mixture to enable the mass ratio of the three-dimensional graphene crude product to copper in the suspension to reach 100:1, and reacting the copper powder added into the suspension with concentrated nitric acid to generate a copper nitrate solution;
s6: continuously magnetically stirring the suspension obtained in the step S5, and slowly dropwise adding absolute ethyl alcohol until the copper and the ethyl alcohol in the suspensionRatio of molecular number1, reaching the following steps: 1. reacting absolute ethyl alcohol with a copper nitrate solution to generate nano copper oxalate on the surface of the three-dimensional graphene in situ;
s7: and (3) fully filtering, washing and drying the product obtained in the step (S6) in sequence to obtain 0.43g of the nano copper oxalate composite three-dimensional graphene negative electrode material.
Example 2:
a group of preparation processes of a nano copper oxalate composite three-dimensional graphene anode material are as follows:
s1: weighing 1g of metal lithium in an inert gas glove box, putting the metal lithium into a ceramic boat, quickly putting the ceramic boat into a tube furnace, and vacuumizing the tube furnace to 10 Pa;
s2: filling carbon dioxide gas into the tubular furnace to 0.4Mpa, then heating the tubular furnace to 600 ℃ at the temperature rising speed of 8 ℃ per minute, and keeping the temperature for 36 hours to obtain a three-dimensional graphene crude product;
s3: crushing the three-dimensional graphene crude product obtained in the step S2 to more than 100 meshes;
s4: putting the powdery three-dimensional graphene crude product obtained in the step S3 into concentrated nitric acid with the concentration of 68%, and continuously soaking for 12 hours to enable the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid to reach 1: 4;
s5: adding copper sulfate into the suspension obtained in the step S4, fully stirring to enable the mass ratio of the three-dimensional graphene crude product to copper in the suspension to reach 100:5, and reacting the copper sulfate added into the suspension with concentrated nitric acid to generate a copper nitrate solution;
s6: continuously magnetically stirring the suspension obtained in the step S5, and slowly dropwise adding absolute ethyl alcohol until the copper and the ethyl alcohol in the suspensionRatio of molecular number1, reaching the following steps: 2. reacting absolute ethyl alcohol with a copper nitrate solution to generate nano copper oxalate on the surface of the three-dimensional graphene in situ;
s7: and (4) fully filtering, washing and drying the product obtained in the step (S6) in sequence to obtain 0.45g of the nano copper oxalate composite three-dimensional graphene negative electrode material.
Example 3:
a group of preparation processes of a nano copper oxalate composite three-dimensional graphene anode material are as follows:
s1: weighing 1g of metal lithium in an inert gas glove box, putting the metal lithium into a ceramic boat, quickly putting the ceramic boat into a tube furnace, and vacuumizing the tube furnace to 10 Pa;
s2: filling carbon dioxide gas into the tubular furnace to 0.5Mpa, then heating the tubular furnace to 575 ℃ at a heating rate of 10 ℃ per minute, and keeping the temperature for 48 hours to obtain a three-dimensional graphene crude product;
s3: crushing the three-dimensional graphene crude product obtained in the step S2 to more than 100 meshes;
s4: putting the powdery three-dimensional graphene crude product obtained in the step S3 into concentrated nitric acid with the concentration of 68%, and continuously soaking for 12 hours to enable the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid to reach 1: 4.5;
s5: adding copper carbonate into the suspension obtained in the step S4, fully stirring the mixture to enable the mass ratio of the three-dimensional graphene crude product to copper in the suspension to reach 100:3, and reacting the copper carbonate added into the suspension with concentrated nitric acid to generate a copper nitrate solution;
s6: continuously magnetically stirring the suspension obtained in the step S5, and slowly dropwise adding absolute ethyl alcohol until the copper and the ethyl alcohol in the suspensionRatio of molecular number1, reaching the following steps: 1.5, reacting absolute ethyl alcohol with a copper nitrate solution to generate nano copper oxalate on the surface of the three-dimensional graphene in situ;
s7: and (3) fully filtering, washing and drying the product obtained in the step (S6) in sequence to obtain 0.44g of the nano copper oxalate composite three-dimensional graphene negative electrode material.
Example 4
A group of preparation processes of a nano copper oxalate composite three-dimensional graphene anode material are as follows:
s1: weighing 1g of metal lithium in an inert gas glove box, putting the metal lithium into a ceramic boat, quickly putting the ceramic boat into a tube furnace, and vacuumizing the tube furnace to 10 Pa;
s2: filling carbon dioxide gas into the tubular furnace to 0.3Mpa, then heating the tubular furnace to 575 ℃ at a heating rate of 10 ℃ per minute, and keeping the temperature for 48 hours to obtain a three-dimensional graphene crude product;
s3: crushing the three-dimensional graphene crude product obtained in the step S2 to more than 100 meshes;
s4: putting the powdery three-dimensional graphene crude product obtained in the step S3 into concentrated nitric acid with the concentration of 68%, and continuously soaking for 12 hours to enable the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid to reach 1: 4.5;
s5: adding copper chloride into the suspension obtained in the step S4, fully stirring the mixture to enable the mass ratio of the three-dimensional graphene crude product to copper in the suspension to reach 100:4, and reacting the copper chloride added into the suspension with concentrated nitric acid to generate a copper nitrate solution;
s6: continuously magnetically stirring the suspension obtained in the step S5, and slowly dropwise adding absolute ethyl alcohol until the copper and the ethyl alcohol in the suspensionRatio of molecular number1, reaching the following steps: 1.5, reacting absolute ethyl alcohol with a copper nitrate solution to generate nano copper oxalate on the surface of the three-dimensional graphene in situ;
s7: and (3) fully filtering, washing and drying the product obtained in the step (S6) in sequence to obtain 0.44g of the nano copper oxalate composite three-dimensional graphene negative electrode material.
A comparative example, a group of preparation processes of three-dimensional graphene anode materials without nano copper oxalate composition:
s1: weighing 1g of metal lithium in an inert gas glove box, putting the metal lithium into a ceramic boat, quickly putting the ceramic boat into a tube furnace, and vacuumizing the tube furnace to 10 Pa;
s2: filling carbon dioxide gas into the tubular furnace to 0.4Mpa, then heating the tubular furnace to 550 ℃ at the temperature rise speed of 5 ℃ per minute, and keeping the temperature for 24 hours to obtain a three-dimensional graphene crude product;
s3: crushing the three-dimensional graphene crude product obtained in the step S2 to more than 100 meshes;
s4: putting the powdery three-dimensional graphene crude product obtained in the step S3 into concentrated nitric acid with the concentration of 68%, and continuously soaking for 12 hours to enable the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid to reach 1: 5;
s5: and (3) fully filtering, washing and drying the product obtained in the step (S4) in sequence to obtain 0.42g of the three-dimensional graphene negative electrode material which is not compounded by the nano copper oxalate.
And (3) alignment experiment:
mixing and size mixing the nano copper oxalate composite three-dimensional graphene negative electrode material powder obtained in the embodiment 1 and the three-dimensional graphene negative electrode material powder obtained in the comparative example according to the mass ratio of 8:1:1, uniformly coating the mixture on a copper foil current collector, drying the coated copper foil at constant temperature of 120 ℃ for 720min under vacuum, cutting the dried copper foil into round pieces with the same size and diameter of 12mm by using a mold to obtain electrode plates to be tested, assembling the electrode plates by using a metal lithium foil into a CR2032 type button cell in a glove box filled with argon, and performing a charge-discharge performance test on the assembled button cell at room temperature by using a Han blue cell CT2001A test system, wherein the voltage range is 0.001-3V.
As shown in fig. 2-3:
in the first charge-discharge cycle of 0.5C, the first charge specific capacity of the three-dimensional graphene negative electrode material battery obtained by adopting the comparative example is 720mAh/g, the first discharge specific capacity is 303mAh/g, and the coulomb efficiency of the first circle is 42%. Under the condition of the same current density (0.5C), the first-circle charging specific capacity of the nano copper oxalate composite three-dimensional graphene negative electrode material battery prepared in the embodiment 1 is 766mAh/g, the first-circle discharging specific capacity is 670mAh/g, and the first-circle coulombic efficiency reaches 87.5%. Obviously, the coulombic efficiency of the first circle of the nano copper oxalate composite three-dimensional graphene anode material battery prepared in example 1 is greatly improved compared with that of a comparative example.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. The protection scope of the present invention is subject to the protection scope of the claims.
Claims (7)
1. A preparation method of a nano copper oxalate composite three-dimensional graphene anode material is characterized by comprising the following steps:
s1: putting the lithium sheet into a ceramic boat in an inert gas glove box, putting the ceramic boat into a tube furnace, and vacuumizing the tube furnace until the pressure in the tube furnace is reduced to 10 Pa;
s2: filling carbon dioxide gas into the tubular furnace, heating the tubular furnace to 550-600 ℃, and keeping the temperature for 24-48h to obtain a three-dimensional graphene crude product;
s3: crushing the three-dimensional graphene crude product obtained in the step S2 to obtain a powdery three-dimensional graphene crude product;
s4: soaking the powdery three-dimensional graphene crude product obtained in the step S3 in concentrated nitric acid for more than 2 hours, wherein the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid is more than 1: 2;
s5: adding copper powder or copper salt into the suspension obtained in the step S4, and fully stirring to ensure that the mass ratio of the three-dimensional graphene crude product to the copper in the suspension reaches 100: 1-5;
s6: continuously magnetically stirring the turbid liquid obtained in the step S5, slowly dropwise adding absolute ethyl alcohol, further reacting the absolute ethyl alcohol with copper nitrate to generate nano copper oxalate, and growing the nano copper oxalate on the surface of the three-dimensional graphene material in situ;
s7: and sequentially filtering, washing and drying the product obtained in the step S6 to obtain the nano copper oxalate composite three-dimensional graphene negative electrode material.
2. The method for preparing a nano copper oxalate composite three-dimensional graphene anode material according to claim 1, wherein in step S2: and (3) filling carbon dioxide gas into the tubular furnace until the pressure value in the tubular furnace reaches 0.3-0.5Mpa, heating the tubular furnace to 550-600 ℃ at the temperature rise speed of 5-10 ℃ per minute, and keeping the temperature in the tubular furnace at 550-600 ℃ for 24-48h to obtain the three-dimensional graphene crude product.
3. The method for preparing a nano copper oxalate composite three-dimensional graphene anode material according to claim 1, wherein the powdery three-dimensional graphene crude product obtained in step S3 is a three-dimensional graphene crude product with a mesh number of 100 meshes or more.
4. The method for preparing a nano copper oxalate composite three-dimensional graphene anode material according to claim 1, wherein in step S4: and (3) putting the powdery three-dimensional graphene crude product obtained in the step (S3) into concentrated nitric acid with the concentration of 68% to soak for 12 hours, wherein the mass ratio of the three-dimensional graphene crude product to the concentrated nitric acid is up to 1: 4-5.
5. The preparation method of the nano copper oxalate composite three-dimensional graphene anode material according to claim 1, characterized by comprising the following steps: the copper salt in the step S5 is any one of copper nitrate, copper carbonate, copper sulfate and copper chloride or a combination of any several of them.
6. The nano copper oxalate composite three-dimensional graphene anode material is characterized in that: the nano copper oxalate composite three-dimensional graphene negative electrode material is prepared by the preparation method of the nano copper oxalate composite three-dimensional graphene negative electrode material as claimed in any one of claims 1 to 5.
7. A lithium ion battery, characterized by: the negative electrode material containing the nano copper oxalate composite three-dimensional graphene as claimed in claim 6.
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