CN111063869A - Graphene electrode material precursor, graphene electrode material, preparation method of graphene electrode material and lithium ion battery - Google Patents

Graphene electrode material precursor, graphene electrode material, preparation method of graphene electrode material and lithium ion battery Download PDF

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CN111063869A
CN111063869A CN201911164075.2A CN201911164075A CN111063869A CN 111063869 A CN111063869 A CN 111063869A CN 201911164075 A CN201911164075 A CN 201911164075A CN 111063869 A CN111063869 A CN 111063869A
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graphene
electrode material
salt
water
soluble
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吕树申
马良
莫冬传
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Sun Yat Sen University
National Sun Yat Sen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application relates to the field of lithium batteries, in particular to a graphene electrode material precursor, a graphene electrode material, a preparation method of the graphene electrode material and a lithium ion battery. The lithium ion battery comprises a lithium electrode, electrolyte and a graphene electrode material. The graphene electrode material comprises a graphene carrier and a load. In the charging and discharging processes, a load reaction generates a binary metal simple substance, and the binary metal simple substance can catalyze the reversible decomposition of the electrolyte. The metal simple substance can release and activate a large number of lithium storage sites for reducing the surface functional groups of the graphene oxide, the utilization rate of active substances is improved, and higher charge-discharge specific capacity is obtained.

Description

Graphene electrode material precursor, graphene electrode material, preparation method of graphene electrode material and lithium ion battery
Technical Field
The application relates to the field of lithium batteries, in particular to a graphene electrode material precursor, a graphene electrode material, a preparation method of the graphene electrode material and a lithium ion battery.
Background
The lithium ion battery, also called lithium secondary battery, has the characteristics of high working voltage, large specific energy, long cycle life, good safety performance, no public hazard, no memory effect, small self-discharge, rapid charge and discharge, wide working temperature range and the like, and is widely applied in the fields of portable electronic equipment, electric automobiles and the like.
At present, carbon materials such as activated carbon, carbon nanotubes, graphene and the like have become one of lithium ion battery electrode materials, wherein graphene oxide of graphene and derivatives thereof with a two-dimensional honeycomb structure composed of single-layer or few-layer carbon atoms has excellent electrical properties, excellent chemical stability and thermodynamic stability, and good physical properties and mechanical properties, and is recognized as a lithium ion battery electrode material with application prospect.
The transition metal oxide lithium ion battery electrode material has the characteristics of large charge-discharge specific capacity, reasonable price, environmental friendliness and the like, and is also paid more and more attention. Although the transition metal oxide lithium ion battery electrode material can obtain considerable reversible capacity, the cycle stability and the reversible degree of electrochemical reaction of the transition metal oxide lithium ion battery electrode material are poor.
The graphene and graphene oxide composite multi-transition metal oxide lithium ion battery electrode material of the graphene derivative and the graphene oxide composite multi-transition metal oxide lithium ion battery electrode material of the graphene which are reported at present are mainly prepared by a hydrothermal method reaction or an electrostatic spinning method. However, these preparation methods are complicated in process or expensive in reaction equipment, which increases the preparation cost of the electrode material and limits large-scale industrial production.
Disclosure of Invention
An object of the embodiments of the present application is to provide a graphene electrode material precursor, a graphene electrode material, a preparation method thereof, and a lithium ion battery, in which a simple preparation method is adopted to improve cycle stability and lithium storage capacity of the lithium ion battery.
In a first aspect, the present application provides a lithium ion battery comprising:
a lithium electrode;
an electrolyte; and
the graphene electrode material comprises a graphene carrier and a load; the load comprises NiO and a second metal oxide; in the charging and discharging processes, a load reaction generates a binary metal simple substance, and the binary metal simple substance can catalyze the reversible decomposition of the electrolyte.
In the charging and discharging process of the lithium ion battery, a load reaction generates a binary metal simple substance, the binary metal simple substance can catalyze the electrolyte to be reversibly decomposed, and the metal simple substance can activate a large number of lithium storage sites of reduced graphene oxide surface functional groups, so that the utilization rate of active substances is improved, and higher charging and discharging specific capacity is obtained.
In a second aspect, the present application provides a method for preparing a graphene electrode material, including:
uniformly mixing a transition metal salt and a dispersion liquid of a graphene material to obtain a first dispersion liquid;
adding a precipitator into the first dispersion liquid to react to prepare a precursor;
and calcining the precursor.
The method comprises the steps of mixing and reacting water-soluble nickel salt, second metal salt, a graphene material and a precipitator, loading nickel ions and the second metal ions on the graphene material, and calcining a precursor to obtain the lithium ion battery electrode material.
In a third aspect, the present application provides a graphene electrode material, which includes a graphene carrier and a load;
wherein the load comprises Cr2O3、CoO、ZnO、Fe2O3、Mn3O4NiO and any one of them.
In a fourth aspect, the present application provides a graphene electrode material precursor, which is prepared by the following steps:
uniformly mixing a transition metal salt and a dispersion liquid of a graphene material to obtain a first dispersion liquid;
adding a precipitator into the first dispersion liquid to react to prepare a precursor;
wherein the transition metal salt comprises water-soluble chromium salt, water-soluble cobalt salt, water-soluble zinc salt, water-soluble iron salt, water-soluble manganese salt and water-soluble nickel salt.
Drawings
In order to more clearly explain the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a charge-discharge cycle performance curve of 100mA/g for a lithium ion battery provided in example 1 of the present application;
fig. 2 is a Scanning Electron Microscope (SEM) image of the graphene electrode material in example 1 of the present application, wherein (b) is a high magnification SEM image of a square dashed box region in (a);
fig. 3 is a dQ/dV curve of a charge/discharge cycle of a lithium ion battery provided in example 1 of the present application, wherein (a) is dQ/dV analysis of a discharge curve at turn 2, turn 20, and turn 50, (b) is dQ/dV analysis of a charge curve at turn 2, turn 20, and turn 50, (c) is dQ/dV analysis of a discharge curve at turn 50, turn 100, and turn 200, and (d) is dQ/dV analysis of a charge curve at turn 50, turn 100, and turn 200;
FIG. 4 is a charge-discharge cycle performance curve of the lithium ion battery provided in example 2 of the present application at 100 mA/g;
fig. 5 is a Scanning Electron Microscope (SEM) image of the graphene electrode material in example 2 of the present application; wherein, the picture (b) is a high-power electron microscope picture of a square dashed frame area in the picture (a);
FIG. 6 is a dQ/dV curve for a charge-discharge cycle of a lithium ion battery provided in example 2 of the present application; wherein, (a) is the dQ/dV analysis of the discharge curves of 10 th turn, 100 th turn, 200 th turn and 300 th turn, and (b) is the dQ/dV analysis of the charge curves of 10 th turn, 100 th turn, 200 th turn and 300 th turn;
FIG. 7 is a charge-discharge cycle performance curve of the lithium ion battery provided in example 3 of the present application at 100 mA/g;
fig. 8 is a Scanning Electron Microscope (SEM) image of the graphene electrode material in example 3 of the present application; wherein, the picture (b) is a high-power electron microscope picture of a square dashed frame area in the picture (a);
fig. 9 is a dQ/dV curve of a charge/discharge cycle of a lithium ion battery provided in example 3 of the present application, wherein (a) is dQ/dV analysis of a discharge curve at turn 20, turn 50, and turn 100, (b) is dQ/dV analysis of a charge curve at turn 20, turn 50, and turn 100, (c) is dQ/dV analysis of a discharge curve at turn 100, turn 200, and turn 300, and (d) is dQ/dV analysis of a charge curve at turn 100, turn 200, and turn 300;
FIG. 10 is a charge-discharge cycle performance curve of 100mA/g for the lithium ion battery provided in example 4 of the present application;
fig. 11 is a Scanning Electron Microscope (SEM) image of the graphene electrode material in example 4 of the present application; wherein, the picture (b) is a high-power electron microscope picture of a square dashed frame area in the picture (a);
fig. 12 is a dQ/dV curve for a charge-discharge cycle of a lithium ion battery provided in example 4 of the present application, wherein (a) is dQ/dV analysis of a discharge curve at 10 th turn, 50 th turn, 100 th turn, and 200 th turn, and (b) is dQ/dV analysis of a charge curve at 10 th turn, 50 th turn, 100 th turn, and 200 th turn;
FIG. 13 is a charge-discharge cycle performance curve of the lithium ion battery provided in example 5 of the present application at 100 mA/g;
fig. 14 is a Scanning Electron Microscope (SEM) image of the graphene electrode material in example 5 of the present application; wherein, the picture (b) is a high-power electron microscope picture of a square dashed frame area in the picture (a);
fig. 15 is a dQ/dV curve of a charge/discharge cycle of a lithium ion battery provided in example 5 of the present application, wherein (a) is dQ/dV analysis of a discharge curve at 50 th turn, 100 th turn, 200 th turn, and 400 th turn, and (b) is dQ/dV analysis of a charge curve at 50 th turn, 100 th turn, 200 th turn, and 400 th turn.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some but not all embodiments of the present application. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
The inventor finds that if a nano metal simple substance generated by the irreversible reaction of the transition metal oxide is used as a catalyst of the electrochemical reaction, the nano transition metal simple substance with catalytic activity for reversible decomposition of the solid electrolyte membrane is generated due to the irreversible reaction in the charging and discharging process, and a large number of lithium storage sites for reducing the surface functional groups of the graphene oxide can be released and activated, so that the utilization rate of active substances is improved, and higher charging and discharging specific capacity is obtained.
Further, the inventors found that the transition metal Ni has an excellent catalytic effect, and further, the binary metal catalyst of Ni — M (M ═ Cr, Mn, Fe, Co, Zn) composite has an effect better than that of the single metal catalyst. Therefore, the inventors creatively proposed that the graphene material is used as the reaction irreversible NiO composite transition metal oxide MxOyThe graphene electrode material is prepared by using Ni-M (M ═ Cr, Mn, Fe, Co and Zn) binary metal nano simple substances in the electrode material to catalyze the reversible reaction of a solid electrolyte and the adsorption of graphene so as to improve the lithium storage capacity of the electrode material.
The embodiment of the application provides a preparation method of a graphene electrode material, which comprises the steps of mixing and reacting a water-soluble nickel salt, a second metal salt, a graphene material and a precipitator to prepare a precursor, and then calcining the precursor.
The method comprises the steps of mixing and reacting water-soluble nickel salt, second metal salt, a graphene material and a precipitator, loading nickel ions and the second metal ions on the graphene material, and calcining a precursor to obtain the lithium ion battery electrode material.
In some embodiments of the present application, a method for preparing a graphene electrode material includes:
and step S1, mixing the water-soluble nickel salt, the second metal salt, the graphene material and the precipitator for reaction to obtain a precursor.
Further, the graphene material may be selected from graphene, graphene oxide, or a graphene derivative.
Illustratively, a dispersion of graphene material is formulated with graphene oxide.
Specifically, graphene oxide is dissolved in deionized water, and ultrasonic dispersion is adopted to obtain a uniform dispersion liquid.
Further optionally, when preparing the dispersion liquid of the graphene material, the ratio of the graphene oxide to the deionized water is as follows:
10-200 parts of graphene material and 20-100 parts of deionized water by volume. Further optionally, the graphene material comprises 20-150 parts by mass of deionized water and 30-90 parts by volume of deionized water. Further optionally, 30-100 parts by mass of graphene material and 40-80 parts by volume of deionized water.
For example, 10-200 mg of graphene material and 20-100 ml of deionized water.
Further, the second metal salt comprises any one of water-soluble chromium salt, water-soluble cobalt salt, water-soluble zinc salt, water-soluble iron salt or water-soluble manganese salt;
the precipitant includes ammonia water.
Optionally, when the water-soluble nickel salt, the second metal salt, the graphene material and the precipitant are mixed, the water-soluble nickel salt is 0.01-10 parts by mole, the second metal salt is 0.01-10 parts by mole, and the precipitant is 5-50 parts by mole.
Further optionally, when the water-soluble nickel salt, the second metal salt, the graphene material and the precipitant are mixed, the water-soluble nickel salt is 2-8 parts by mole, the second metal salt is 2-8 parts by mole, and the precipitant is 10-40 parts by mole.
Further optionally, when the water-soluble nickel salt, the second metal salt, the graphene material and the precipitant are mixed, the water-soluble nickel salt is 3-5 parts by mole, the second metal salt is 3-5 parts by mole and the precipitant is 15-30 parts by mole.
Illustratively, 2-8 mmol of water-soluble nickel salt, 2-8 mmol of second metal salt and 10-40 mmol of precipitating agent.
Further, the method comprises the step of mixing and reacting water-soluble nickel salt, second metal salt, graphene material and precipitant to obtain a precursor, and comprises the following steps:
and adding a precipitating agent into the dispersion liquid of the water-soluble nickel salt, the second metal salt and the graphene material in a dropwise manner, reacting until a precipitate is generated, and then drying the precipitate.
Further optionally, ultrasound and agitation are also employed in the reaction. Further optionally, the stirring speed f is 100-1000 r/min, the ultrasonic power g is 10-1000W, and the stirring and ultrasonic interaction time t1 is 1-10 h.
Further, the precipitate was subjected to vacuum filtration and then freeze-dried.
And step S2, calcining the precursor.
Further, the step of calcining the precursor comprises:
and calcining the precursor at 300-400 ℃ in a nitrogen environment. Further optionally, calcining the precursor at 350-400 ℃ in a nitrogen environment. For example, the calcination temperature is 350 ℃, 360 ℃, 370 ℃, 380 ℃ or 390 ℃.
Further optionally, the calcination time is 1-10 h. Further optionally, the calcination time is 2-8 h. For example, the calcination time is 3h, 4h, 5h or 6 h.
Some embodiments of the present application also provide a graphene electrode material comprising a graphene support and a load;
wherein the load comprises Cr2O3、CoO、ZnO、Fe2O3、Mn3O4Any ofOne and NiO.
The graphene electrode material can be prepared by the preparation method of the graphene electrode material provided by the embodiment.
Some embodiments of the present application further provide a graphene electrode material precursor, which is prepared by mainly using the following steps:
mixing and reacting water-soluble nickel salt, second metal salt, a graphene material and a precipitator to prepare a precursor;
wherein the second metal salt comprises any one of water-soluble chromium salt, water-soluble cobalt salt, water-soluble zinc salt, water-soluble iron salt or water-soluble manganese salt.
The step of preparing the graphene electrode material precursor is the same as step S1 of preparing the graphene electrode material in the foregoing embodiment.
Some embodiments of the present application also provide a lithium ion battery comprising: a lithium electrode; an electrolyte; and a graphene electrode material. The graphene electrode material comprises a graphene carrier and a load; the load comprises NiO and a second metal oxide; in the charging and discharging process, a binary metal simple substance is generated through a load reaction, and the binary metal simple substance can catalyze the reversible decomposition of the electrolyte.
The metal simple substance can release and activate a large number of lithium storage sites for reducing the surface functional groups of the graphene oxide, the utilization rate of active substances is improved, and higher charge-discharge specific capacity is obtained.
Further, the second metal oxide includes Cr2O3、CoO、ZnO、Fe2O3Or Mn3O4Any one of them.
Further, both NiO and the second metal oxide are in a nanometer scale.
Further, the graphene support includes any one of graphene, graphene oxide, or a graphene derivative.
The graphene electrode material of the lithium ion battery is prepared by the preparation method of the graphene electrode material provided by the embodiment. The lithium electrode can adopt a metal lithium sheet, and the electrolyte can be selected from lithium hexafluorophosphate and the like. The lithium electrode, the graphene electrode material and the electrolyte can be assembled into a lithium ion button battery and the like.
The features and properties of the present application are described in further detail below with reference to examples:
example 1
The preparation process of the lithium ion battery is as follows:
1) preparation of water-soluble nickel salt/chromium salt and graphene oxide dispersion liquid
Dissolving 120mg of graphene oxide in 60mL of deionized water, performing ultrasonic dispersion for 45min at 100W power, adding 2.5mmol of nickel nitrate hexahydrate and 7.5mmol of chromium nitrate nonahydrate into the graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a dispersion liquid of water-soluble nickel salt, chromium salt and graphene oxide.
2) Preparation of graphene electrode material precursor
And slowly dripping 12ml of ammonia water serving as a precipitator into the dispersion liquid of the water-soluble nickel salt, the chromium salt and the graphene oxide, performing ultrasonic power 320W action for 5 hours at a stirring speed of 750r/min, performing vacuum filtration, and performing freeze drying to obtain the precursor of the graphene electrode material.
3) Preparation of graphene electrode material
Calcining the prepared precursor of the graphene electrode material for 4h at 400 ℃ in a nitrogen environment to obtain a Ni-Cr binary metal nano simple substance catalytic reaction mechanism-based graphene electrode material A (NiO-Cr)2O3/RGO)。
4) Assembly of lithium ion batteries
And (3) assembling the lithium ion battery with the prepared graphene electrode material by taking a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte.
And carrying out constant current cyclic voltammetry test on the lithium ion battery. When the lithium ion battery is tested for 200 circles under the condition of 100mA/g, the discharge specific capacity can reach 907 mAh/g. FIG. 1 is a charge-discharge cycle performance curve of a graphene electrode material A at 100mA/g based on a Ni-Cr binary metal nano elemental catalytic reaction mechanism; FIG. 2 is a Scanning Electron Micrograph (SEM) thereof; FIG. 3 is a dQ/dV curve of a charge-discharge cycle thereof. From FIG. 3, it can be seen that Ni is present during the cycleO-Cr2O3the/RGO electrode A has obvious 3 pairs of broad peaks of lithium intercalation/lithium deintercalation (oxidation/reduction) electrochemical reaction, the broad peak at 1.2-0.5/1.5-2.5V in the discharging/charging process corresponds to the oxidation reduction process of NiO, and the broad peak at 2.5-1.5/2.0-3.0V in the discharging/charging process corresponds to Cr3+In the reduction oxidation process, the broad peak at 1.0-0.3/0.3-1.5V corresponds to Cr in the discharging/charging process2+And (3) reversible decomposition of the redox process and the solid electrolyte colloidal membrane in the charge-discharge process, wherein the lower potential of 0.5-0V and the higher potential of 2.5-3.0V in the subsequent cycle correspond to the processes of reducing graphite intercalation of graphene oxide RGO and absorbing lithium by surface active functional groups. As can be seen from the figure, as the charging and discharging progresses, Cr in the first 50 circles2+And the wide peaks corresponding to NiO are reduced in different ranges, and the solid electrolyte colloidal film is reversibly decomposed in the charging and discharging processes and Cr is contained under the high voltage of 2.5-3.0V3+The redox process of (a) is enhanced. Cr in the subsequent 100-turn charge-discharge cycle2O3And the broad peaks corresponding to NiO all show a reduced trend, and the reversible decomposition process of the solid electrolyte colloidal membrane in the charging and discharging process and the lithium adsorption process of reducing the RGO surface functional groups of the graphene oxide under the high voltage of 2.5-3.0V are continuously enhanced. These enhanced electrochemical processes are NiO-Cr2O3The charge-discharge specific capacity of the/RGO electrode A can be maintained and even increased. The reason why the electrochemical reaction of the solid electrolyte membrane and the process that the RGO surface active functional group adsorbs lithium under the high voltage of 2.5-3.0V are enhanced is further analyzed to be NiO-Cr2O3The Ni/Cr bimetallic nanoparticles generated by the irreversible reduction of the transition metal oxide of the/RGO electrode A show that the highly dispersed Ni/Cr bimetallic nanoparticles have important promotion effects on the decomposition of the solid electrolyte and the release of RGO surface active functional groups.
Example 2
The preparation process of the lithium ion battery is as follows:
1) preparation of water-soluble nickel salt/manganese salt and graphene oxide dispersion liquid
Dissolving 120mg of graphene oxide in 60mL of deionized water, performing ultrasonic dispersion for 45min at the power of 100W, adding 7.5mmol of nickel nitrate hexahydrate and 2.5mmol of manganese acetate into the graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a dispersion liquid of water-soluble nickel salt, manganese salt and graphene oxide.
2) Preparation of graphene electrode material precursor
And slowly dripping 12ml of ammonia water serving as a precipitator into the dispersion liquid of the water-soluble nickel salt, the manganese salt and the graphene oxide, performing ultrasonic power 320W action for 5 hours at a stirring speed of 750r/min, performing vacuum filtration, and performing freeze drying to obtain the precursor of the graphene electrode material.
3) Preparation of graphene electrode material
Calcining the prepared precursor of the graphene electrode material for 4h at 400 ℃ in a nitrogen environment to obtain a graphene electrode material B (NiO-Mn) based on a Ni-Mn binary metal nano simple substance catalytic reaction mechanism3O4/RGO)。
4) Assembly of lithium ion batteries
And (3) assembling the lithium ion battery with the prepared graphene electrode material by taking a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte.
And carrying out constant current cyclic voltammetry test on the lithium ion battery. When the lithium ion battery is tested for 400 circles under the condition of 500mA/g, the discharge specific capacity can reach 516 mAh/g. FIG. 4 is a charge-discharge cycle performance curve of a graphene electrode material B at 500mA/g based on a Ni-Mn binary metal nano simple substance catalytic reaction mechanism; FIG. 5 is a Scanning Electron Micrograph (SEM) thereof; FIG. 6 is a dQ/dV curve of a charge-discharge cycle thereof. From FIG. 6, it can be seen that NiO-Mn3O was present during the cycle4the/RGO electrode B has obvious 3(4) broad peak for lithium intercalation/lithium deintercalation (oxidation/reduction) electrochemical reaction, the broad peak at 1.5-0.7/1.5-2.2V in the discharging/charging process corresponds to NiO oxidation reduction, Mn3+And higher valence Mnn+In the reduction oxidation process, a broad peak at 1.0-0.3/0.3-1.5V corresponds to Mn in the discharging/charging process2+The redox process and the reversible decomposition of the solid electrolyte colloidal film during the charge and discharge processes, and the lower potential of 0.3-0V and the higher potential of 2.5-3V correspond toThe process of reducing graphite intercalation of graphene oxide RGO and the adsorption of lithium by surface active functional groups. The data of the previous 100 circles show that the graphite lithium intercalation process of reduced graphene oxide RGO with lower potential of 0.3-0V and Mn corresponding to a broad peak at 1.5-1.0/1.5-2.2V3+And higher valence Mnn +The process of reduction and oxidation of (1) shows a continuously enhanced trend in the process of lithium adsorption by RGO surface active functional groups corresponding to a higher potential of 2.5-3V, and Mn corresponding to a broad peak at 1.0-0.3/0.3-1.5V2+The redox process tends to be somewhat attenuated. As charging and discharging continues, the reversible decomposition process of the solid electrolyte colloidal film observed earlier in the latter several hundred cycles, Mn3+And higher valence Mnn+The processes of reducing and oxidizing, namely the processes of adsorbing lithium by RGO surface active functional groups corresponding to 2.5-3V at higher potential all show a continuously increasing trend, and the continuously enhanced reactions are NiO-Mn3O4the/RGO electrode B still has the important reason of 484mAh/g of specific discharge capacity after 300 cycles. Through further analysis, the bimetallic Ni/Mn nano simple substance with high catalytic activity generated by irreversible decomposition of the transition metal oxide in the previous 100-cycle process can be obtained, so that Mn with higher valence state is catalyzedn+And also plays an important role in promoting the reversible decomposition of the solid electrolyte membrane and the lithium adsorption process of the RGO surface active functional groups.
Example 3
The preparation process of the lithium ion battery is as follows:
1) preparation of water-soluble nickel salt/iron salt and graphene oxide dispersion liquid
Dissolving 120mg of graphene oxide in 60mL of deionized water, performing ultrasonic dispersion for 45min at the power of 100W, adding 2.5mmol of nickel nitrate hexahydrate and 7.5mmol of ferric nitrate nonahydrate into the graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a dispersion liquid of water-soluble nickel salt, iron salt and graphene oxide.
2) Preparation of graphene electrode material precursor
And slowly dripping 12ml of ammonia water serving as a precipitator into the dispersion liquid of the water-soluble nickel salt, the iron salt and the graphene oxide, performing ultrasonic power 320W for 5 hours at a stirring speed of 750r/min, performing vacuum filtration, and performing freeze drying to obtain the precursor of the graphene electrode material.
3) Preparation of graphene electrode material
Calcining the prepared precursor of the graphene electrode material for 4h at 350 ℃ in a nitrogen environment to obtain the graphene electrode material C (NiO-Fe) based on a Ni-Fe binary metal nano simple substance catalytic reaction mechanism2O3/RGO)。
4) Assembly of lithium ion batteries
And (3) assembling the lithium ion battery with the prepared graphene electrode material by taking a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte.
And carrying out constant current cyclic voltammetry test on the lithium ion battery. When the lithium ion battery is tested for 300 circles under the condition of 100mA/g, the discharge specific capacity can reach 652 mAh/g. FIG. 7 is a charge-discharge cycle performance curve of a graphene electrode material C at 100mA/g based on a Ni-Fe binary metal nano simple substance catalytic reaction mechanism; FIG. 8 is a Scanning Electron Micrograph (SEM) thereof; FIG. 9 is a dQ/dV curve of a charge-discharge cycle thereof. From FIG. 9, it can be seen that NiO-Fe was present during the first 20 cycles2O3the/RGO electrode C has obvious 3 pairs of wide peaks of lithium intercalation/lithium deintercalation (oxidation/reduction) electrochemical reaction, and the wide peaks at 1.5-0.8/1.3-2.2V correspond to Fe in the discharging/charging process2O3And the oxidation-reduction process of NiO, wherein a broad peak at 0.8-0.1/0.1-1.5V in the discharging/charging process corresponds to reversible decomposition of the solid electrolyte colloidal film in the charging and discharging processes. The corresponding Fe at 1.5-0.8/1.3-2.2V can be observed2O3And the NiO redox process was always in a decreasing trend during the first 20 charge-discharge cycles. In the subsequent charge-discharge cycle process in fig. 9, it can be clearly observed that the reversible decomposition process of the solid electrolyte colloidal film corresponding to 0.8-0.1/0.1-1.5V is continuously enhanced, especially the lithium adsorption process of the reduced graphene oxide RGO surface active functional group occurs at a high voltage of 2.5-3V, and the increased reaction delays NiO-Fe2O3The trend of C discharge specific capacity of the/RGO electrode is reduced, and NiO-Fe is illustrated2O3The electrochemical reaction process of the Ni/Fe bimetallic nanoparticle catalyzed solid electrolyte colloidal membrane in the/RGO electrode C and the lithium adsorption process of releasing and activating RGO surface active functional groups play a main role in maintaining the system capacity.
Example 4
The preparation process of the lithium ion battery is as follows:
1) preparation of water-soluble nickel salt/cobalt salt and graphene oxide dispersion liquid
Dissolving 120mg of graphene oxide in 60mL of deionized water, performing ultrasonic dispersion for 45min at the power of 100W, adding 1.875mmol of nickel nitrate hexahydrate and 5.625mmol of cobalt nitrate hexahydrate into the graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a dispersion liquid of water-soluble nickel salt, cobalt salt and graphene oxide.
2) Preparation of graphene electrode material precursor
And slowly dripping 12ml of ammonia water serving as a precipitator into the dispersion liquid of the water-soluble nickel salt, cobalt salt and graphene oxide, performing ultrasonic power 320W action for 5 hours at a stirring speed of 750r/min, performing vacuum filtration, and performing freeze drying to obtain the precursor of the graphene electrode material.
3) Preparation of graphene electrode material
And calcining the prepared graphene electrode material precursor for 4h at 350 ℃ in a nitrogen environment to obtain the graphene electrode material D (NiO-CoO/RGO) based on the Ni-Co binary metal nano simple substance catalytic reaction mechanism.
4) Assembly of lithium ion batteries
And (3) assembling the lithium ion battery with the prepared graphene electrode material by taking a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte.
And carrying out constant current cyclic voltammetry test on the lithium ion battery. When the lithium ion battery is tested for 400 circles under the condition of 500mA/g, the specific discharge capacity can reach 419 mAh/g. FIG. 10 is a graph of the charge and discharge performance of a graphene electrode material D at 500mA/g based on a Ni-Co binary metal nano elemental catalysis reaction mechanism; FIG. 11 is a Scanning Electron Micrograph (SEM) thereof; FIG. 12 shows a dQ/dV curve of a charge/discharge cycle. As can be seen from FIG. 12, in the cycle process, the NiO-CoO/RGO electrode D has 3 pairs of broad peaks in the lithium intercalation/lithium deintercalation (oxidation/reduction) electrochemical reaction, the broad peak at 1.5-0.7/1.5-2.5V in the discharging/charging process corresponds to the oxidation-reduction process of CoO and NiO, the broad peak at 1.0-0.1/0.2-1.5V in the discharging/charging process corresponds to the reversible decomposition of the solid electrolyte colloidal film in the charging/discharging process, and the lower potential of 0.5-0V and the higher potential of 2.5-3V correspond to the process of reducing the graphite intercalation of graphene oxide RGO and adsorbing lithium by the surface active functional groups. It can be clearly observed in the figure that the broad peaks corresponding to CoO and NiO redox processes at 1.5-0.7/1.5-2.5V in the discharging/charging process have been greatly reduced, while the peak of electrochemical reaction of the solid electrolyte colloidal film and the process of lithium adsorption by the surface active functional group of reduced graphene oxide RGO have been enhanced to different degrees. It can also be observed that after 200 cycles of the cycle process, the voltage is 1.5-0.7/1.5-2.5V in the discharging/charging process
Example 5
The preparation process of the lithium ion battery is as follows:
1) preparation of water-soluble nickel salt/zinc salt and graphene oxide dispersion liquid
Dissolving 120mg of graphene oxide in 60mL of deionized water, performing ultrasonic dispersion for 45min at the power of 100W, adding 5mmol of nickel nitrate hexahydrate and 5mmol of zinc nitrate hexahydrate into the graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a dispersion liquid of water-soluble nickel salt, zinc salt and graphene oxide.
2) Preparation of graphene electrode material precursor
Slowly dripping 2ml of ammonia water serving as a precipitator into the dispersion liquid of the water-soluble nickel salt, the zinc salt and the graphene oxide, performing ultrasonic power 320W for 5 hours at a stirring speed of 750r/min, performing vacuum filtration, and performing freeze drying to obtain the graphene electrode material precursor based on the Ni-Zn binary metal nano simple substance catalytic reaction mechanism.
3) Preparation of graphene electrode material
And calcining the prepared graphene electrode material precursor for 4h at 350 ℃ in a nitrogen environment to obtain the graphene electrode material E (NiO-ZnO/RGO) based on the Ni-Zn binary metal nano simple substance catalytic reaction mechanism.
4) Assembly of lithium ion batteries
And (3) assembling the lithium ion battery with the prepared graphene electrode material by taking a lithium sheet as a counter electrode and lithium hexafluorophosphate as an electrolyte.
And carrying out constant current cyclic voltammetry test on the lithium ion battery. When the discharge specific capacity of the lithium ion battery is tested for 700 circles under the condition of 500mA/g, the discharge specific capacity can reach 477 mAh/g. FIG. 13 is a graph of the charge and discharge performance of the graphene electrode material E at 500mA/g based on the Ni-Zn binary metal nano-elemental catalysis reaction mechanism; FIG. 14 is a Scanning Electron Micrograph (SEM) thereof; FIG. 15 is a dQ/dV curve of charge/discharge cycles. As can be seen from FIG. 15, the NiO-ZnO/RGO electrode has 3 obvious pairs of lithium intercalation/lithium deintercalation (oxidation/reduction) electrochemical reactions, 2.0-0.7/2.0-2.5V in the discharging/charging process corresponds to the process of oxidation and reduction of NiO, 1.5-0.8/1.0-1.5V and 0.8-0.3/0.5-1.0V in the discharging/charging process correspond to the processes of oxidation and reduction of ZnO and alloying of ZnLi respectively, and the other 2 overlapping broad peaks (1.0-0.3/1.0-1.4V and 0.5-0/0.2-0.7V) correspond to the processes of reversible decomposition of the solid electrolyte colloidal film in the charging and discharging processes and reduction of graphene oxide RGO graphite intercalation. With the progress of charging and discharging, except for the rule that the peak value at 0.5-0/0.2-0.7V is increased and then decreased, the rest peaks are rapidly and greatly reduced, particularly the oxidation reduction process of NiO at 2.0-0.7/2.0-2.5V is reduced more obviously, which shows that a large amount of metal nano particles are generated in the NiO-ZnO/RGO electrode after 50 cycles of irreversible cycle. Under the catalytic action of the large amount of binary Ni/Zn nano transition metal simple substances with catalytic activity, the reversible decomposition process of the solid electrolyte colloidal film at 1.2-0/1.0-2.0V can be continuously enhanced in the following hundreds of cycles of charge and discharge circulation, so that the specific discharge capacity of the solid electrolyte colloidal film at 300 th cycle is still 867mAh/g under the condition that no transition metal oxide participates in the reaction basically, the specific discharge capacity is equivalent to the specific discharge capacity (894 mAh/g) of the solid electrolyte colloidal film at 2 nd cycle when the transition metal oxide participates in the reaction, and the reversible decomposition of the large amount of binary Ni/Zn nano transition metal simple substances on the solid electrolyte colloidal film has a strong catalytic effect.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. A lithium ion battery, comprising:
a lithium electrode;
an electrolyte; and
a graphene electrode material comprising a graphene carrier and a load; the load comprises NiO and a second metal oxide; in the charging and discharging processes, the load reaction generates a binary metal simple substance, and the binary metal simple substance can catalyze the reversible decomposition of the electrolyte.
2. The lithium ion battery according to claim 1,
the second metal oxide comprises Cr2O3、CoO、ZnO、Fe2O3Or Mn3O4Any one of them.
3. The lithium ion battery according to claim 2,
the NiO and the second metal oxide are both on a nanometer scale.
4. The lithium ion battery according to any one of claims 1 to 3,
the graphene carrier includes any one of graphene, graphene oxide, or a graphene derivative.
5. A preparation method of a graphene electrode material is characterized by comprising the following steps:
mixing and reacting water-soluble nickel salt, second metal salt, a graphene material and a precipitator to prepare a precursor;
calcining the precursor.
6. The method for producing a graphene electrode material according to claim 5,
the second metal salt comprises any one of water-soluble chromium salt, water-soluble cobalt salt, water-soluble zinc salt, water-soluble iron salt or water-soluble manganese salt;
the precipitant comprises ammonia water;
optionally, when the water-soluble nickel salt, the second metal salt, the graphene material and the precipitant are mixed, the water-soluble nickel salt is 0.01-10 parts by mole, the second metal salt is 0.01-10 parts by mole, and the precipitant is 5-50 parts by mole.
7. The method for producing a graphene electrode material according to claim 5,
the step of mixing and reacting the water-soluble nickel salt, the second metal salt, the graphene material and the precipitator to prepare the precursor comprises the following steps:
and adding the precipitant into the dispersion of the water-soluble nickel salt, the second metal salt and the graphene material in a dropwise manner, reacting until a precipitate is generated, and then drying the precipitate.
8. The method for producing a graphene electrode material according to claim 5,
the step of calcining the precursor comprises:
and calcining the precursor at 300-400 ℃ in a nitrogen environment.
9. A graphene electrode material, comprising a graphene support and a load;
wherein the load comprises Cr2O3、CoO、ZnO、Fe2O3、Mn3O4NiO and any one of them.
10. A graphene electrode material precursor is characterized by being prepared by mainly adopting the following steps:
mixing and reacting water-soluble nickel salt, second metal salt, a graphene material and a precipitator to prepare a precursor;
wherein the second metal salt comprises any one of water-soluble chromium salt, water-soluble cobalt salt, water-soluble zinc salt, water-soluble iron salt or water-soluble manganese salt.
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