CN109585800A - Vanadic acid cobalt and redox graphene composite negative pole material and preparation method - Google Patents

Vanadic acid cobalt and redox graphene composite negative pole material and preparation method Download PDF

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CN109585800A
CN109585800A CN201810462894.4A CN201810462894A CN109585800A CN 109585800 A CN109585800 A CN 109585800A CN 201810462894 A CN201810462894 A CN 201810462894A CN 109585800 A CN109585800 A CN 109585800A
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negative pole
vanadic acid
composite negative
graphene composite
pole material
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李莉萍
张丹
徐兴良
李广社
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Jilin University
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Jilin 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
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    • Y02E60/10—Energy storage using batteries
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Abstract

The invention discloses a kind of vanadic acid cobalts and redox graphene composite negative pole material and preparation method, graphene oxide and ammonium metavanadate are added in deionized water, after ultrasonic disperse, a hydronium(ion) lithia is added under the conditions of 80 DEG C of water-bath and cobalt chloride hexahydrate stirs 10 minutes, obtained mixed solution 180 DEG C hydro-thermal reaction 10 minutes under agitation, centrifugation, drying, the product after drying is calcined under an inert atmosphere obtains product.Vanadic acid cobalt made from preparation method provided by the invention and redox graphene composite negative pole material have good cyclical stability and high rate performance; simple synthetic method is easy to operate; reaction time is very short, and cost is relatively low, is expected to become a kind of novel anode material that scale uses.

Description

Vanadic acid cobalt and redox graphene composite negative pole material and preparation method
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of vanadic acid cobalts and redox graphene Compound Negative Pole material and preparation method.Wherein, vanadic acid cobalt and redox graphene composite negative pole material are Co1.8V1.2O4With reduction-oxidation Graphene composite negative pole.
Background technique
The advantages that lithium ion battery is due to energy density with higher and longer cycle life, in the modern life Through becoming essential electrochemical energy accumulating device.However, with the development of consumer electrical product and electric car, when Preceding lithium ion battery negative material is no longer satisfied growing requirement.In order to meet the needs of social development, science Family making great efforts to explore advanced substitute to replace graphite cathode.It is worth noting that, the oxide of cobalt due to have compared with High theoretical capacity receives special attention.But significant volume change and poor electronics itself are led in charge and discharge process Electrically seriously hinder their development.
In order to solve these problems, a kind of strategy is synthesis bimetallic oxide as negative electrode material, this can be effectively Improve electron conduction, improve reversible capacity, enhances mechanical stability.And part replaces the higher and toxic cobalt of price can be with The cost of electrode material is reduced, is polluted smaller.Vanadium is successfully formed vanadic acid cobalt in conjunction with cobalt, and illustrates charming electricity Chemical property.Another strategy is to introduce a kind of suitable, flexible matrix in electrode material and carry out commensurate structure to change and mention High electronics and ionic conduction.Graphene is a kind of good ion and electronic conductor, and has excellent mechanical elasticity, thermostabilization Property, chemical stability and big specific surface area, therefore very likely simultaneously by the composite material of graphene and vanadic acid cobalt after compound With high reversible capacity, excellent cyclical stability and good high rate performance.Currently, Co3V2O8,Co2V2O7And CoV2O6Base Negative electrode material be extensively studied and shown excellent chemical property.However, CoxV3-xO4The negative electrode material of base Almost without being reported, it is primarily due to CoxV3-xO4Synthetic method it is considerably less, this causes to simply synthesize CoxV3-xO4Nanometer It is still a huge challenge that particle, which is grown on graphene,.Therefore, a kind of method synthesis Co of simplicity is inventedxV3-xO4Nano particle Become to be even more important as lithium cell negative pole material with the composite material of graphene.
In conclusion problem of the existing technology is:
CoxV3-xO4Synthetic method it is considerably less, the synthesis of only method is difficult, and the period is very long, is unfavorable for large-scale production； CoxV3-xO4Nano particle synthesizes more difficult with the composite material of graphene.
Summary of the invention
The object of the invention is that providing a kind of vanadic acid cobalt and redox graphene is multiple to solve the above-mentioned problems Close negative electrode material and preparation method.
The present invention through the following technical solutions to achieve the above objectives:
The present invention the following steps are included:
(1) graphene oxide and ammonium metavanadate are added in deionized water, it is 30-120 minutes ultrasonic；
(2) under the conditions of 60-90 DEG C of water-bath, a hydronium(ion) lithia and cobalt chloride hexahydrate is added, stirring 10-60 divides Clock；
(3) above-mentioned mixed solution is added in hydrothermal reaction kettle, 180 DEG C are stirred to react 10-40 minutes, it is centrifuged, drying, 1-4 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene Compound Negative to sample after drying under an inert atmosphere Pole material.
Preferably, graphene oxide described in step (1) is 0.06g；The ammonium metavanadate is 0.374g；The deionization Water is 60-80mL；Ultrasound is 30 minutes.
Preferably, bath temperature is 80 DEG C in step (2)；The one hydronium(ion) lithia is 0.08g, the six hydrations chlorine Change cobalt is 0.152g, is stirred 10 minutes.
Preferably, mixing time is 10 minutes in step (3), and calcination time is 1 hour.
As an improvement, graphene oxide is not added in step (1), other conditions are identical, and extra small vanadic acid cobalt nanometer is made Grain.
The vanadic acid cobalt and redox graphene composite negative pole material of preparation method preparation of the invention, which is characterized in that The vanadic acid cobalt and redox graphene composite negative pole material are Co1.8V1.2O4The compound lithium ion with redox graphene Cell negative electrode material.
The method that vanadic acid cobalt of the present invention and redox graphene composite negative pole material prepare lithium battery: by vanadic acid cobalt It is mixed with redox graphene composite negative pole material with 20% conductive agent, then the N- methylpyrrole with the binder containing 10% The mixing of alkanone solution, is coated on copper foil after mixing evenly, is put into 100 DEG C of drying in vacuum drying oven；It then is 14mm's with diameter Slicer cuts out electrode slice, is put into 80 DEG C of dry 6~12h in vacuum drying oven；It is then transferred into the glove box full of argon gas, with Metal lithium sheet is to electrode, and polypropylene porous film is diaphragm, the ethylene carbonate and dimethyl carbonate of 1mol/L lithium hexafluoro phosphate Mixed solution is electrolyte, is assembled into button cell.
Preferably, the mass ratio of the vanadic acid cobalt and redox graphene composite negative pole material and binder is 7:1, institute The mass ratio for stating vanadic acid cobalt and redox graphene composite negative pole material and conductive agent is 7:2.
Preferably, the binder is Kynoar, and solvent is N-Methyl pyrrolidone, and the conductive agent is conductive carbon It is black.
The beneficial effects of the present invention are:
The present invention is a kind of vanadic acid cobalt and redox graphene composite negative pole material and preparation method, with prior art phase Than the present invention provides simple, the quick method of one kind and synthesized Co1.8V1.2O4/ redox graphene composite material, as lithium Cell negative electrode material shows good stability and excellent high rate performance.To the synthesis for pushing vanadic acid cobalt and in lithium The development applied in battery has great importance.
Compared with prior art, the present invention has following income effect:
The present invention passes through simple ultrasound, stirring, hydro-thermal, centrifugation, drying, calcining realization, and whole process is fairly simple, consumption When it is very short, controllability is strong, low in cost, is suitble to industrialized production.
Compared to the synthesis of other most of vanadic acid cobalts, generated time of the invention at least shortens three times or more, greatly Shorten the production cycle.
Novel anode material produced by the present invention is applied to field of lithium ion battery for the first time, and it is steady to show excellent circulation Qualitative energy and and high rate performance.
Detailed description of the invention
Fig. 1 is Co provided in an embodiment of the present invention1.8V1.2O4With the preparation side of redox graphene composite negative pole material Method flow chart.
Fig. 2 is Co provided in an embodiment of the present invention1.8V1.2O4With the XRD of redox graphene composite negative pole material and Raman figure and pure Co1.8V1.2O4XRD diagram.In Fig. 2: (a) being XRD diagram；(b) scheme for Raman.
Fig. 3 is Co provided in an embodiment of the present invention1.8V1.2O4Scheme with the XPS of redox graphene composite negative pole material Spectrum.In Fig. 3: being (a) map in the region C 1s；It (b) is the map in the region Co 2p；It (c) is the map in the region V 2p；It (d) is O The map in the region 1s.
Fig. 4 is Co provided in an embodiment of the present invention1.8V1.2O4With the TEM of redox graphene composite negative pole material, HRTEM and EDS distribution diagram of element.In Fig. 4: (a) scheming for TEM；(b) scheme for HRTEM；It (c) is C element distribution map；It (d) is Co member Plain distribution map；It (e) is O distribution diagram of element；It (f) is V element distribution map.
Fig. 5 is Co provided in an embodiment of the present invention1.8V1.2O4With redox graphene composite negative pole material and pure Co1.8V1.2O4Chemical property figure.In Fig. 5: (a) being CV curve；It (b) is voltage curve；It (c) is to be assembled into lithium ion battery With the current density of 100mA/g, in the cycle performance and coulombic efficiency figure of the voltage range of 3~0.01V；(d) being is different electricity High rate performance figure under current density；(e) for be 2000mA/g current density under cycle performance figure.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings:
The present invention the following steps are included:
(1) graphene oxide and ammonium metavanadate are added in deionized water, it is 30-120 minutes ultrasonic；
(2) under the conditions of 60-90 DEG C of water-bath, a hydronium(ion) lithia and cobalt chloride hexahydrate is added, stirring 10-60 divides Clock；
(3) above-mentioned mixed solution is added in hydrothermal reaction kettle, 180 DEG C are stirred to react 10-40 minutes, it is centrifuged, drying, 1-4 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene Compound Negative to sample after drying under an inert atmosphere Pole material.
Preferably, graphene oxide described in step (1) is 0.06g；The ammonium metavanadate is 0.374g；The deionization Water is 60-80mL；Ultrasound is 30 minutes.
Preferably, bath temperature is 80 DEG C in step (2)；The one hydronium(ion) lithia is 0.08g, the six hydrations chlorine Change cobalt is 0.152g, is stirred 10 minutes.
Preferably, mixing time is 10 minutes in step (3), and calcination time is 1 hour.
As an improvement, graphene oxide is not added in step (1), other conditions are identical, and extra small vanadic acid cobalt nanometer is made Grain.
The vanadic acid cobalt and redox graphene composite negative pole material of preparation method preparation of the invention, which is characterized in that The vanadic acid cobalt and redox graphene composite negative pole material are Co1.8V1.2O4The compound lithium ion with redox graphene Cell negative electrode material.
The method that vanadic acid cobalt of the present invention and redox graphene composite negative pole material prepare lithium battery: by vanadic acid cobalt It is mixed with redox graphene composite negative pole material with 20% conductive agent, then the N- methylpyrrole with the binder containing 10% The mixing of alkanone solution, is coated on copper foil after mixing evenly, is put into 100 DEG C of drying in vacuum drying oven；It then is 14mm's with diameter Slicer cuts out electrode slice, is put into 80 DEG C of dry 6~12h in vacuum drying oven；It is then transferred into the glove box full of argon gas, with Metal lithium sheet is to electrode, and polypropylene porous film is diaphragm, the ethylene carbonate and dimethyl carbonate of 1mol/L lithium hexafluoro phosphate Mixed solution is electrolyte, is assembled into button cell.
Preferably, the mass ratio of the vanadic acid cobalt and redox graphene composite negative pole material and binder is 7:1, institute The mass ratio for stating vanadic acid cobalt and redox graphene composite negative pole material and conductive agent is 7:2.
Preferably, the binder is Kynoar, and solvent is N-Methyl pyrrolidone, and the conductive agent is conductive carbon It is black.
Embodiment 1
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Implementation result: by New Co made from the present embodiment1.8V1.2O4With redox graphene composite negative pole material group It dresses up battery and carries out charge-discharge test, Fig. 5 (c) is the current density for being assembled into lithium ion battery with 100mA/g, in 3~0.01V Voltage range cycle performance figure.It can be seen that discharge capacity is 1199mAh/g for the first time for it, reversible capacity is for the first time 782mAh/g, first circle coulombic efficiency are 65%, and cyclical stability is preferable.Fig. 5 (d) is the high rate performance under different current densities, Under the current density of 2000mA/g, still there is the capacity of 628mAh/g, high rate performance is fine.Fig. 5 (e) is the electricity of 2000mA/g Cycle performance figure under current density, it can be seen that it still shows good cycle performance under high current density.
Embodiment 2
0.374g ammonium metavanadate is weighed, is added in 64mL water, ultrasound 30 minutes is added under the conditions of 80 DEG C of water-bath Mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate stir 10 minutes, it is anti-that above-mentioned mixed solution are added to hydro-thermal Answer in kettle, 180 DEG C are stirred to react 10 minutes, are centrifuged, drying, it is dry after sample 400 DEG C of 1 hours of calcining under an inert atmosphere Obtain vanadic acid cobalt negative electrode material.
Implementation result: being assembled into battery for novel vanadic acid cobalt negative electrode material made from the present embodiment and carry out charge-discharge test, Charge-discharge test is carried out to it with the current density of 100mA/g, discharge capacity is 1701mAh/g for the first time, after 100 circle of circulation Keeping discharge capacity is only 112mAh/g.
Embodiment 3
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g frerrous chloride is added, stirs 10 minutes, by above-mentioned mixed solution Be added in hydrothermal reaction kettle, 180 DEG C are stirred to react 10 minutes, are centrifuged, drying, it is dry after sample under an inert atmosphere 400 DEG C 1 hour of calcining obtains ferric vandate and redox graphene composite material.
Embodiment 4
0.374g ammonium metavanadate is weighed, is added in 64mL water, ultrasound 30 minutes is added under the conditions of 80 DEG C of water-bath Mono- hydronium(ion) lithia of 0.08g and 0.087g zinc chloride stir 10 minutes, above-mentioned mixed solution are added to hydrothermal reaction kettle In, 180 DEG C are stirred to react 10 minutes, are centrifuged, drying, it is dry after sample 400 DEG C of 1 hours of calcining under an inert atmosphere to obtain the final product To vanadic acid Zinc material.
Embodiment 5
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 60 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 6
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 70 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 7
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 90 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 8
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 60mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 9
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 70mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 10
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 80mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 11
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 60 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 12
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 90 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 13
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 120 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 14
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 30 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 15
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 60 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 16
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 20 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 17
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 40 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 1 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 18
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 2 hours of 400 DEG C of calcinings obtain vanadic acid cobalt and redox graphene composite negative pole material.
Embodiment 19
0.06g graphene oxide and 0.374g ammonium metavanadate are weighed, is added in 64mL water, ultrasound 30 minutes, in water-bath Under the conditions of 80 DEG C, mono- hydronium(ion) lithia of 0.08g and 0.152g cobalt chloride hexahydrate is added, stirs 10 minutes, by above-mentioned mixing Solution is added in hydrothermal reaction kettle, and 180 DEG C are stirred to react 10 minutes, is centrifuged, and drying, the sample after drying is under an inert atmosphere 4 hours of 400 DEG C of calcinings obtain vanadic acid cobalt and redox graphene composite negative pole material.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims (9)

1. a kind of vanadic acid cobalt and redox graphene composite negative pole material and preparation method, which is characterized in that including following step It is rapid:
(1) graphene oxide and ammonium metavanadate are added in deionized water, it is 30-120 minutes ultrasonic；
(2) under the conditions of 60-90 DEG C of water-bath, a hydronium(ion) lithia and cobalt chloride hexahydrate is added, stirs 10-60 minutes；
(3) above-mentioned mixed solution is added in hydrothermal reaction kettle, 180 DEG C are stirred to react 10-40 minutes, are centrifuged, and dry, dry 1-4 hour of 400 DEG C of calcinings obtains vanadic acid cobalt and redox graphene composite negative pole material to sample afterwards under an inert atmosphere Material.
2. vanadic acid cobalt as described in claim 1 and redox graphene composite negative pole material and preparation method, feature exist In: graphene oxide described in step (1) is 0.06g；The ammonium metavanadate is 0.374g；The deionized water is 60-80mL； Ultrasound is 30 minutes.
3. vanadic acid cobalt as described in claim 1 and redox graphene composite negative pole material and preparation method, feature exist In: bath temperature is 80 DEG C in step (2)；The one hydronium(ion) lithia is 0.08g, and the cobalt chloride hexahydrate is 0.152g is stirred 10 minutes.
4. vanadic acid cobalt as described in claim 1 and redox graphene composite negative pole material and preparation method, feature exist In: mixing time is 10 minutes in step (3), and calcination time is 1 hour.
5. vanadic acid cobalt as described in claim 1 and redox graphene composite negative pole material and preparation method, feature exist In: graphene oxide is not added in (1) in step, and other conditions are identical, and extra small vanadic acid cobalt nano-particle is made.
6. a kind of vanadic acid cobalt and redox graphene composite negative pole material using preparation method described in claim 1 preparation Material, which is characterized in that the vanadic acid cobalt is Co with reduced graphene composite negative pole material1.8V1.2O4It is multiple with redox graphene The lithium ion battery negative material of conjunction.
7. a kind of side for preparing lithium battery using vanadic acid cobalt described in claim 4 and redox graphene composite negative pole material Method, it is characterised in that: vanadic acid cobalt is mixed with redox graphene composite negative pole material with 20% conductive agent, then with contain The N-Methyl pyrrolidone solution of 10% binder mixes, and is coated on copper foil after mixing evenly, is put into vacuum drying oven 100 DEG C Drying；Then electrode slice is cut out with the slicer that diameter is 14mm, is put into 80 DEG C of dry 6~12h in vacuum drying oven；Then it shifts It is to electrode with metal lithium sheet, polypropylene porous film is diaphragm, 1mol/L lithium hexafluoro phosphate into the glove box full of argon gas Ethylene carbonate and dimethyl carbonate mixed solution are electrolyte, are assembled into button cell.
8. the method that vanadic acid cobalt as claimed in claim 7 and redox graphene composite negative pole material prepare lithium battery, special Sign is that the vanadic acid cobalt is 7:1, the vanadic acid cobalt with the mass ratio of redox graphene composite negative pole material and binder It is 7:2 with the mass ratio of redox graphene composite negative pole material and conductive agent.
9. the method that vanadic acid cobalt as claimed in claim 7 and redox graphene composite negative pole material prepare lithium battery, special Sign is that the binder is Kynoar, and solvent is N-Methyl pyrrolidone, and the conductive agent is conductive carbon black.
CN201810462894.4A 2018-09-26 2018-09-26 Vanadic acid cobalt and redox graphene composite negative pole material and preparation method Pending CN109585800A (en)

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CN111292969A (en) * 2020-02-21 2020-06-16 山东大学 Co2V2O7Hollow nanocage/graphene composite material, preparation method thereof and application of composite material in super capacitor
CN113428897A (en) * 2021-06-25 2021-09-24 湘潭大学 Preparation method of vanadium-based cathode material based on surface modification for enhancing cycle stability
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Cited By (7)

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Publication number Priority date Publication date Assignee Title
US11542614B2 (en) 2019-10-22 2023-01-03 King Fahd University Of Petroleum And Minerals Fabrication of CoVOx composite thin film electrode via single step AACVD
US11746429B2 (en) 2019-10-22 2023-09-05 King Fahd University Of Petroleum And Minerals Method for decomposing water into H2 and O2
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CN110943213A (en) * 2019-12-17 2020-03-31 济南大学 MOF-derived porous carbon box loaded with Co3V2O8Composite negative electrode material and preparation method and application thereof
CN110943213B (en) * 2019-12-17 2023-01-24 济南大学 MOF-derived porous carbon box loaded with Co 3 V 2 O 8 Composite negative electrode material and preparation method and application thereof
CN111292969A (en) * 2020-02-21 2020-06-16 山东大学 Co2V2O7Hollow nanocage/graphene composite material, preparation method thereof and application of composite material in super capacitor
CN113428897A (en) * 2021-06-25 2021-09-24 湘潭大学 Preparation method of vanadium-based cathode material based on surface modification for enhancing cycle stability

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