CN109659516B - Preparation method of electrode positive electrode material containing graphene - Google Patents
Preparation method of electrode positive electrode material containing graphene Download PDFInfo
- Publication number
- CN109659516B CN109659516B CN201811420596.5A CN201811420596A CN109659516B CN 109659516 B CN109659516 B CN 109659516B CN 201811420596 A CN201811420596 A CN 201811420596A CN 109659516 B CN109659516 B CN 109659516B
- Authority
- CN
- China
- Prior art keywords
- stirring
- graphene
- port
- bottle
- ethyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
A preparation method of a graphene-containing electrode cathode material comprises the following steps: the preparation method comprises the steps of graphene microchip preparation, graphene microchip reduction and preparation of a graphene/nickel hydroxide electrode material. The positive electrode material contains graphene micro-sheets and nickel hydroxide particles, and the weight ratio of the graphene micro-sheets to the nickel hydroxide particles is about 3.85: 1-2.56: 1, more than 85% of nickel hydroxide particles exist by covering the surfaces of the graphene oxide micro-sheets with large radial dimension, and every two graphene oxide micro-sheets with large radial dimension are mutually adjacent, and the surface which is not exposed for the nickel hydroxide particles to adhere to is less than 80%.
Description
Technical Field
The invention relates to the technical field of positive electrode materials containing graphene, in particular to a positive electrode material containing graphene and a preparation method thereof.
Background
Graphene is a two-dimensional material consisting of carbon atoms and having a thickness of only one atom, has very excellent physicochemical properties, such as excellent mechanical properties, high electrical conductivity, good thermal conductivity and the like, and is considered to be one of the most potential nano materials at present. As a one-dimensional carbon nano material, the carbon nano fiber has the advantages of good mechanical property, larger specific surface area, good chemical stability and the like, and the special properties enable the carbon nano fiber to be widely applied to the fields of catalyst carriers, polymer nano composite materials, flexible substrate materials of energy conversion and storage devices and the like. Taking the graphene microchip as an example, the graphene microchip not only has better physical properties and electrical properties, but also can be compounded with other materials to further improve the properties of other materials.
Graphene exists as an electrode material for preparing a positive electrode in the prior art, but has a large distance from the goals of stable structure, uniform dispersion and average electrical properties, and a paper "TiO _2 and graphene _ Ni _ OH _2 electrode material for energy storage" gives Ni (OH)2The electrode material of the composite of particles and reduced graphene has poor properties and very uneven dispersion from the obtained product, and the phenomenon of graphene lamination is very large from the electron microscope picture, Ni (OH)2The particles are more and non-uniform in agglomeration and are dispersed on each surface position of graphene, and generally, the electrode material is only experimental in nature, and the charge and discharge performance and stability cannot be guaranteed when the material with the poor structure is applied in practical application.
Disclosure of Invention
The invention aims to provide an improved preparation method to solve the problems of uneven structure, insufficient performance and difficulty in practicability of an electrode material of a graphene-containing positive electrode in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a graphene-containing electrode positive electrode material is characterized by comprising the following steps.
1) Preparing graphene nanoplatelets: taking a large number of prefabricated expanded graphite sheets as raw materials, and ultrasonically stripping the raw materials in absolute ethyl alcohol for more than 1-2h to generate graphene microchip dispersion liquid; taking out the upper-layer dispersion liquid through low-frequency ultrasound, and leaving the graphite which is not stripped in the container; supplementing the solvent absolute ethyl alcohol of the upper-layer dispersion liquid to more than 200-300ml, carrying out high-intensity ultrasonic oscillation for 3-5min, standing for 5-10s, immediately discarding half of the upper-layer dispersion liquid, supplementing the absolute ethyl alcohol to the volume of more than 200-300ml, and repeating the above processes for at least 10-20 times until the average radial size of the graphene nanoplatelets is confirmed to be more than 5-10um by AFM or SEM; and (4) evaporating all solvents in a rotary manner, and drying at normal temperature to obtain the graphene oxide micro-sheets with large radial sizes.
2) And (3) graphene nanoplatelets reduction: taking a four-mouth bottle with the volume of more than 2L, adding 180 parts by weight of double distilled water, inserting a stirring rod from the first mouth of the four-mouth bottle, stirring at 3-10 r/s, and keeping the temperature to be 35-45 ℃ for continuous stirring; slowly adding 0.2-0.4 weight part of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder grinding until the average particle size is below 60um from the second opening of the four-opening bottle; slowly adding 20 parts by weight of graphene oxide micro-sheets with large radial dimension from the second port of the four-port bottle, after all the graphene oxide micro-sheets are added, dissolving 5-10 parts by weight of ascorbic acid with double-distilled water at 35-45 ℃, keeping the solution of ascorbic acid under magnetic stirring at 35-45 ℃, and adding the ascorbic acid solution from the third port of the four-port bottle by using a dropper at the speed of 20-30 drops/min until the addition is finished; stirring for 10-15min, adding dropwise ammonia water from the third port, measuring pH value, and stopping adding ammonia water when pH value is stably higher than 7 and is kept for more than 5 min; and stirring for 10-15min, pouring out the mixture in the four-mouth bottle, removing supernatant, and continuously washing for 6 times by using excess absolute ethyl alcohol, double distilled water, absolute ethyl alcohol and double distilled water at about 40 ℃ to obtain the completely reduced graphene oxide micro-tablets with large radial sizes.
3) Preparing a graphene/nickel hydroxide electrode material: taking a four-mouth bottle with the volume of more than 2L, putting 100-120ml double distilled water, inserting a stirring rod from the first mouth of the four-mouth bottle, stirring at 3-10 r/s, and keeping the temperature to be 35-45 ℃ for continuous stirring; slowly adding 0.5-1g of PVA (polyvinyl acetate) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um from the second opening of the four-opening bottle; slowly adding 10-12g of graphene oxide micro-tablets with large radial dimension from a second port of a four-port bottle, continuously stirring for 5-10min after all the graphene oxide micro-tablets are added, adding 8-10g of NiCl 2.6H2O from a third port of the four-port bottle, continuously stirring for 5-10min, adding 1ml of ammonia water from the third port of the four-port bottle, continuously stirring for 15-20min, and pouring all the mixture into a hydrothermal reaction kettle; hydrothermal circulation reaction: placing the hydrothermal reaction kettle into a thermostat at 90 ℃ for 3h, taking out, placing on a spin coater base, rotating at the speed of 2-5 r/s for 25-35min, placing back into the thermostat at 90 ℃, and repeating the hydrothermal-rotating steps for at least 3 times; and pouring out the mixture in the hydrothermal reaction kettle, removing supernatant, continuously washing with excessive absolute ethyl alcohol, double distilled water, absolute ethyl alcohol and double distilled water at the temperature of about 40 ℃ for 6 times to obtain a filter cake, spreading the filter cake in a container under a flowing nitrogen environment at the temperature of 30-40 ℃, and drying overnight to obtain the cathode material.
The graphene-containing electrode cathode material is prepared by the preparation method of the graphene-containing electrode cathode material, and is characterized in that: the positive electrode material contains graphene micro-sheets with large radial size and Ni (OH)2Particles, the graphene nanoplatelets of large radial dimension and Ni (OH)2The weight ratio of the particles is about 3.85: 1-2.56: 1, more than 85% of Ni (OH)2The particles are present on the surface of the graphene micro-sheet with large radial dimension, and the graphene micro-sheets with large radial dimension are adjacent to each other in pairs and can not expose Ni (OH)2The surface to which the particles are attached is below 80%.
Compared with the prior art, the invention has at least the following beneficial effects: 1) select the graphite alkene microchip of big radial dimension, reduced the complex degree that the system mixes, mainly be the granule or the aggregate that adhere to nickel hydroxide on graphite alkene surface like this, and use the graphite alkene of not selecting, because the size of own is not of uniform size, directly strengthened the system complex degree, also make the position and the effect that nickel hydroxide adheres to hardly estimate. 2) The performance of the positive electrode material is guaranteed to be good, the performance of the graphene oxide is not enough, the graphene is required to be changed into a reduction state, the conductivity of the reduction state graphene can meet the requirement of the positive electrode material, the adhesion of nickel hydroxide is easy to realize, how to guarantee the sufficient reduction of the graphene microchip is achieved, the situation that much adhesion and lamination happen is avoided, a small amount of PVA (polyvinyl alcohol) ultrafine powder is used, and due to the fact that the PVA ultrafine powder is an insulator, the excellent effect of promoting the dispersion of the graphene is achieved, and the process of reducing the graphene is sufficient and comprehensive. 3) When the nickel hydroxide is attached to the graphene, the PVA ultrafine powder is continuously used, and the dispersion degree of the graphene is indirectly higher due to the fact that isolated islands are formed in the solution relatively, so that the method has a good technical effect on full dispersion and attachment/recombination of the nickel hydroxide.
Compared with the prior art, the scheme of the application has more directivity, obtains better technical effect and does not suggest.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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 invention.
Example 1
A preparation method of a graphene-containing electrode positive electrode material is characterized by comprising the following steps.
1) Preparing graphene nanoplatelets: taking a large number of prefabricated expanded graphite sheets as raw materials, and ultrasonically stripping the raw materials in absolute ethyl alcohol for more than 1-2h to generate graphene microchip dispersion liquid; taking out the upper-layer dispersion liquid through low-frequency ultrasound, and leaving the graphite which is not stripped in the container; supplementing the solvent absolute ethyl alcohol of the upper-layer dispersion liquid to more than 200-300ml, carrying out high-intensity ultrasonic oscillation for 3-5min, standing for 5-10s, immediately discarding half of the upper-layer dispersion liquid, supplementing the absolute ethyl alcohol to the volume of more than 200-300ml, and repeating the above processes for at least 10-20 times until the average radial size of the graphene nanoplatelets is confirmed to be more than 5-10um by AFM or SEM; and (4) evaporating all solvents in a rotary manner, and drying at normal temperature to obtain the graphene oxide micro-sheets with large radial sizes.
2) And (3) graphene nanoplatelets reduction: taking a four-mouth bottle with the volume of more than 2L, adding 180 parts by weight of double distilled water, inserting a stirring rod from the first mouth of the four-mouth bottle, stirring at 3-10 r/s, and keeping the temperature to be 35-45 ℃ for continuous stirring; slowly adding 0.2-0.4 weight part of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder grinding until the average particle size is below 60um from the second opening of the four-opening bottle; slowly adding 20 parts by weight of graphene oxide micro-sheets with large radial dimension from the second port of the four-port bottle, after all the graphene oxide micro-sheets are added, dissolving 5-10 parts by weight of ascorbic acid with double-distilled water at 35-45 ℃, keeping the solution of ascorbic acid under magnetic stirring at 35-45 ℃, and adding the ascorbic acid solution from the third port of the four-port bottle by using a dropper at the speed of 20-30 drops/min until the addition is finished; stirring for 10-15min, adding dropwise ammonia water from the third port, measuring pH value, and stopping adding ammonia water when pH value is stably higher than 7 and is kept for more than 5 min; and stirring for 10-15min, pouring out the mixture in the four-mouth bottle, removing supernatant, and continuously washing for 6 times by using excess absolute ethyl alcohol, double distilled water, absolute ethyl alcohol and double distilled water at about 40 ℃ to obtain the completely reduced graphene oxide micro-tablets with large radial sizes.
3) Preparing a graphene/nickel hydroxide electrode material: taking a four-mouth bottle with the volume of more than 2L, putting 100-120ml double distilled water, inserting a stirring rod from the first mouth of the four-mouth bottle, stirring at 3-10 r/s, and keeping the temperature to be 35-45 ℃ for continuous stirring; slowly adding 0.5-1g of PVA (polyvinyl acetate) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um from the second opening of the four-opening bottle; slowly adding 10-12g of graphene oxide micro-tablets with large radial dimension from the second opening of a four-opening bottle, continuously stirring for 5-10min after all the graphene oxide micro-tablets are added, and then adding 8-10g of NiCl from the third opening of the four-opening bottle2·6H2Continuously stirring for 5-10min, adding 1ml of ammonia water from a third port of the four-port bottle, continuously stirring for 15-20min, and pouring the whole mixture into a hydrothermal reaction kettle; hydrothermal circulation reaction: placing the hydrothermal reaction kettle into a thermostat at 90 ℃ for 3h, taking out, placing on a spin coater base, rotating at the speed of 2-5 r/s for 25-35min, placing back into the thermostat at 90 ℃, and repeating the hydrothermal-rotating steps for at least 3 times; and pouring out the mixture in the hydrothermal reaction kettle, removing supernatant, continuously washing with excessive absolute ethyl alcohol, double distilled water, absolute ethyl alcohol and double distilled water at the temperature of about 40 ℃ for 6 times to obtain a filter cake, spreading the filter cake in a container under a flowing nitrogen environment at the temperature of 30-40 ℃, and drying overnight to obtain the cathode material.
Example 2
The difference from the method in example 1 is that: in the step (1), graphene is generated through ultrasonic stripping for more than 1.5h in absolute ethyl alcoholA microchip dispersion; and (3) supplementing absolute ethyl alcohol serving as a solvent of the upper-layer dispersion liquid to more than 220ml, carrying out high-intensity ultrasonic oscillation for 4min, standing for 8s, supplementing absolute ethyl alcohol to more than 220ml, and repeating the above processes for at least 15 times until AFM or SEM is used for confirming that the average radial size of the graphene nanoplatelets is more than 5 um. In the step (2), a stirring rod is inserted from the first port of the four-port bottle to stir at 4 revolutions per second, and the stirring is continuously carried out at the temperature of 35-40 ℃; slowly adding 0.2-0.3 weight part of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder grinding until the average particle size is below 60um from the second opening of the four-opening bottle; dissolving 5-7 weight parts of ascorbic acid in double distilled water at 35-40 deg.C, magnetically stirring at 35-40 deg.C, and adding via dropper at 24 drops/min from the third port of the four-port bottle; stirring for 12 min; stirring for another 12 min. In the step (3), 110ml of double distilled water is put in, a stirring rod is inserted from the first port of the four-port bottle to stir at 4 revolutions per second, and the stirring is continued at the temperature of 35-40 ℃. Slowly adding 0.6g of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um from the second opening of the four-opening bottle; taking 11g of graphene oxide micro-tablets with large radial dimension, continuously stirring for 6min, and adding 9g of NiCl from a third port of a four-port bottle2·6H2Continuously stirring for 6min, adding 1ml of ammonia water from a third port of the four-port bottle, continuously stirring for 16min, and pouring the whole mixture into a hydrothermal reaction kettle; hydrothermal circulation reaction: taking out, placing on spin coater base, rotating at speed of 3 r/s for 30min, and repeating above hydrothermal-rotation steps for at least 4 times; the filter cake was spread out in a vessel under a flowing nitrogen atmosphere at 30-35 ℃.
Example 3
The method is the same as the method of the embodiment 1, except that: in the step (1), the graphene microchip dispersion liquid is generated through ultrasonic stripping for more than 2 hours in absolute ethyl alcohol; supplementing absolute ethyl alcohol serving as a solvent of the upper-layer dispersion liquid to more than 270ml, carrying out high-intensity ultrasonic oscillation for 5min, standing for 10s, supplementing absolute ethyl alcohol to more than 270ml, and repeating the above processes for at least 20 times until AFM or SEM is used for confirming that the average radial size of the graphene nanoplatelets is higher than 6 um; in the step (2), a stirring rod is inserted from the first port of the four-port bottle to stir at 5 revolutions per second, and the stirring is continuously carried out at the temperature of 34-45 ℃; take 0.3-0.4 part by weight of PVA (polyvinyl acetate) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um is slowly added from the second opening of the four-opening bottle; dissolving 7-9 weight parts of ascorbic acid in double distilled water at 40-45 deg.C, magnetically stirring at 40-45 deg.C, and adding via dropper at 28 drops/min from the third port of the four-port bottle; stirring for 14 min; stirring for 14 min; in the step (3), 120ml of double distilled water is put in, a stirring rod is inserted from the first port of the four-port bottle to stir at 5 revolutions per second, and the stirring is continuously carried out at the temperature of 40-45 ℃; slowly adding 0.8g of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um from the second opening of the four-opening bottle; taking 12g of graphene oxide micro-tablets with large radial dimension, continuously stirring for 8min, and adding 10g of NiCl from a third port of a four-port bottle2·6H2Continuously stirring for 8min, adding 1ml of ammonia water from a third port of the four-port bottle, continuously stirring for 18min, and pouring the whole mixture into a hydrothermal reaction kettle; hydrothermal circulation reaction: taking out, placing on spin coater base, rotating at 5 rpm for 35min, and repeating the above hydrothermal-rotation steps for at least 5 times; the filter cake was spread out in a vessel under a flowing nitrogen atmosphere at 35-40 ℃.
Example 4
A graphene-containing electrode positive electrode material prepared by the method for preparing a graphene-containing electrode positive electrode material according to example 1, wherein the method comprises the following steps: the positive electrode material contains graphene micro-sheets with large radial size and Ni (OH)2Particles, the graphene nanoplatelets of large radial dimension and Ni (OH)2The weight ratio of the particles is about 3.85: 1-2.56: 1, more than 85% of Ni (OH)2The particles are present on the surface of the graphene micro-sheet with large radial dimension, and the graphene micro-sheets with large radial dimension are adjacent to each other in pairs and can not expose Ni (OH)2The surface to which the particles are attached is below 80%.
The large radial dimension graphene nanoplatelets and Ni (OH)2The weight ratio of the particles is about 3.85: 1 to 2.56:1, calculated on the weight of nickel chloride hexahydrate and graphene added, since the process main components are not lost and all nickel chloride is converted, reflected by weightThe ratio corresponds to the above value.
Through SEM and AFM observation, the material obtained by the method does not contain small graphene fragments, and nickel hydroxide which is not attached to graphene is basically not existed in the observation of an electron microscope, so that the product is determined to be Ni (OH) compounded by more than 85 percent2The particles are present as covering the surface of graphene micro-platelets of large radial dimension. For the graphene nanoplatelets with large radial dimension, the two graphene nanoplatelets are adjacent to each other and can not expose Ni (OH)2The surface to which the particles are attached is 80% or less, and when a large number of 50 or more particles are randomly selected in a visual field and analyzed by electron microscope analysis, the number of the adhered or laminated layers is less than 10 to 15% of the total number, and therefore the above condition is certainly satisfied.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (4)
1. A preparation method of a graphene-containing electrode positive electrode material is characterized by comprising the following steps:
1) preparing graphene nanoplatelets:
taking a large number of prefabricated expanded graphite sheets as raw materials, and ultrasonically stripping the raw materials in absolute ethyl alcohol for more than 1.5 hours to generate graphene microchip dispersion liquid; taking out the upper-layer dispersion liquid through ultrasonic treatment, and keeping the graphite which is not stripped in a container;
supplementing absolute ethyl alcohol serving as a solvent of the upper-layer dispersion liquid to more than 220ml, ultrasonically oscillating for 3-5min, standing for 5-10s, immediately discarding half of the upper-layer dispersion liquid, supplementing absolute ethyl alcohol to more than 220ml, and repeating the above processes for at least 15 times until AFM or SEM is used for confirming that the average radial size of the graphene nanoplatelets is higher than 5 um; all solvents are removed through rotary evaporation, and drying is carried out at normal temperature to obtain the graphene oxide micro-sheets with large radial sizes;
2) and (3) graphene nanoplatelets reduction:
taking a four-mouth bottle with the volume of more than 2L, adding 180 parts by weight of double distilled water, inserting a stirring rod from the first mouth of the four-mouth bottle, stirring at 3-10 r/s, and keeping the temperature to be 35-45 ℃ for continuous stirring;
0.2-0.4 weight part of PVA micropowder which is subjected to repeated freeze-drying powder grinding until the average particle size is below 60um is added from the second opening of the four-opening bottle; taking 20 parts by weight of graphene oxide micro-sheets with large radial dimension, adding the graphene oxide micro-sheets from a second port of a four-port bottle, after all the graphene oxide micro-sheets are added, taking 5-10 parts by weight of ascorbic acid, dissolving the ascorbic acid with double-distilled water at 35-45 ℃, keeping the ascorbic acid solution under magnetic stirring at 35-45 ℃, and adding the ascorbic acid solution from a third port of the four-port bottle by using a dropper at the speed of 20-30 drops/min until the addition is finished;
stirring for 10-15min, adding dropwise ammonia water from the third port, measuring pH value, and stopping adding ammonia water when pH value is stably higher than 7 and is kept for more than 5 min;
stirring for 10-15min, pouring out the mixture in the four-mouth bottle, removing supernatant, and continuously washing with excessive 40 ℃ absolute ethyl alcohol, double distilled water, absolute ethyl alcohol and double distilled water for 6 times to obtain fully reduced graphene oxide micro-sheets with large radial sizes;
3) preparation of graphene/nickel hydroxide electrode material
Taking a four-mouth bottle with the volume of more than 2L, putting 100-120ml double distilled water, inserting a stirring rod from the first mouth of the four-mouth bottle, stirring at 3-10 r/s, and keeping the temperature to be 35-45 ℃ for continuous stirring;
0.5-1g of PVA (polyvinyl acetate) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um is added from the second opening of the four-opening bottle;
taking 10-12g of graphene oxide micro-tablets with large radial dimension, adding the graphene oxide micro-tablets from a second port of a four-port bottle, continuously stirring for 5-10min after all the graphene oxide micro-tablets are added, and then adding 8-10g of NiCl from a third port of the four-port bottle2·6H2Continuously stirring for 5-10min, adding 1ml of ammonia water from a third port of the four-port bottle, continuously stirring for 15-20min, and pouring the whole mixture into a hydrothermal reaction kettle;
hydrothermal circulation reaction: placing the hydrothermal reaction kettle into a thermostat at 90 ℃ for 3h, taking out, placing on a spin coater base, rotating at the speed of 2-5 r/s for 25-35min, placing back into the thermostat at 90 ℃, and repeating the hydrothermal-rotating steps for at least 3 times;
and pouring out the mixture in the hydrothermal reaction kettle, removing supernatant, continuously washing with excessive 40 ℃ absolute ethyl alcohol, double distilled water, absolute ethyl alcohol and double distilled water for 6 times to obtain a filter cake, spreading the filter cake in a container under a flowing nitrogen environment at the temperature of 30-40 ℃, and drying overnight to obtain the cathode material.
2. The method for preparing a graphene-containing electrode positive electrode material according to claim 1, wherein:
in the step (1), the graphene microchip dispersion liquid is generated through ultrasonic stripping for more than 1.5h in absolute ethyl alcohol; supplementing absolute ethyl alcohol serving as a solvent of the upper-layer dispersion liquid to more than 220ml, ultrasonically oscillating for 4min, standing for 8s, supplementing absolute ethyl alcohol to the volume of more than 220ml, and repeating the above processes for at least 15 times until AFM or SEM is used for confirming that the average radial size of the graphene nanoplatelets is higher than 5 um;
in the step (2), a stirring rod is inserted from the first port of the four-port bottle to stir at 4 revolutions per second, and the stirring is continuously carried out at the temperature of 35-40 ℃; 0.2-0.3 weight part of PVA (polyvinyl acetate) ultrafine powder which is subjected to repeated freeze-drying powder grinding until the average particle size is below 60um is added from the second opening of the four-opening bottle; dissolving 5-7 weight parts of ascorbic acid in double distilled water at 35-40 deg.C, magnetically stirring at 35-40 deg.C, and adding via dropper at 24 drops/min from the third port of the four-port bottle; stirring for 12 min; stirring for 12 min;
in the step (3), 110ml of double distilled water is put in, a stirring rod is inserted from the first port of the four-port bottle to stir at 4 revolutions per second, and the stirring is continuously carried out at the temperature of 35-40 ℃;
0.6g of PVA (polyvinyl alcohol) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um is added from the second opening of the four-opening bottle;
taking 11g of graphene oxide micro-tablets with large radial dimension, continuously stirring for 6min, and adding 9g of NiCl from a third port of a four-port bottle2·6H2O, continuously stirring for 6min, and then stirring againAdding 1ml of ammonia water into the third port of the mouth bottle, continuously stirring for 16min, and pouring the whole mixture into a hydrothermal reaction kettle;
hydrothermal circulation reaction: taking out, placing on spin coater base, rotating at speed of 3 r/s for 30min, and repeating above hydrothermal-rotation steps for at least 4 times; the filter cake was spread out in a vessel under a flowing nitrogen atmosphere at 30-35 ℃.
3. The method for preparing a graphene-containing electrode positive electrode material according to claim 1, wherein:
in the step (1), the graphene microchip dispersion liquid is generated through ultrasonic stripping for more than 2 hours in absolute ethyl alcohol; supplementing absolute ethyl alcohol serving as a solvent of the upper-layer dispersion liquid to more than 270ml, ultrasonically oscillating for 5min, standing for 10s, supplementing absolute ethyl alcohol to more than 270ml, and repeating the above processes for at least 20 times until AFM or SEM is used for confirming that the average radial size of the graphene nanoplatelets is higher than 6 um;
in the step (2), a stirring rod is inserted from the first port of the four-port bottle to stir at 5 revolutions per second, and the stirring is continuously carried out at the temperature of 34-45 ℃; 0.3-0.4 weight part of PVA micropowder which is subjected to repeated freeze-drying powder grinding until the average particle size is below 60um is added from the second opening of the four-opening bottle; dissolving 7-9 weight parts of ascorbic acid in double distilled water at 40-45 deg.C, magnetically stirring at 40-45 deg.C, and adding via dropper at 28 drops/min from the third port of the four-port bottle; stirring for 14 min; stirring for 14 min;
in the step (3), 120ml of double distilled water is put in, a stirring rod is inserted from the first port of the four-port bottle to stir at 5 revolutions per second, and the stirring is continuously carried out at the temperature of 40-45 ℃;
0.8g of PVA (polyvinyl acetate) ultrafine powder which is subjected to repeated freeze-drying powder crushing until the average particle size is below 60um is added from the second opening of the four-opening bottle;
taking 12g of graphene oxide micro-tablets with large radial dimension, continuously stirring for 8min, and adding 10g of NiCl from a third port of a four-port bottle2·6H2Continuously stirring for 8min, adding 1ml of ammonia water from a third port of the four-port bottle, continuously stirring for 18min, and pouring the whole mixture into a hydrothermal reaction kettle;
hydrothermal circulation reaction: taking out, placing on spin coater base, rotating at 5 rpm for 35min, and repeating the above hydrothermal-rotation steps for at least 5 times; the filter cake was spread out in a vessel under a flowing nitrogen atmosphere at 35-40 ℃.
4. A graphene-containing electrode positive electrode material produced by the method for producing a graphene-containing electrode positive electrode material according to claim 1, characterized in that:
the positive electrode material contains graphene micro-sheets with large radial size and Ni (OH)2Particles, the graphene nanoplatelets of large radial dimension and Ni (OH)2The weight ratio of the particles is 3.85: 1-2.56: 1, more than 85% of Ni (OH)2The particles are present on the surface of the graphene micro-sheet with large radial dimension, and the graphene micro-sheets with large radial dimension are adjacent to each other in pairs and can not expose Ni (OH)2The surface to which the particles are attached is below 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811420596.5A CN109659516B (en) | 2018-11-26 | 2018-11-26 | Preparation method of electrode positive electrode material containing graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811420596.5A CN109659516B (en) | 2018-11-26 | 2018-11-26 | Preparation method of electrode positive electrode material containing graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109659516A CN109659516A (en) | 2019-04-19 |
| CN109659516B true CN109659516B (en) | 2021-07-23 |
Family
ID=66111897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811420596.5A Active CN109659516B (en) | 2018-11-26 | 2018-11-26 | Preparation method of electrode positive electrode material containing graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109659516B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN106179205A (en) * | 2016-07-13 | 2016-12-07 | 安徽师范大学 | A kind of Ni (OH)2the preparation method of graphene composite nano materials |
| CN106340391A (en) * | 2016-11-07 | 2017-01-18 | 珠海格力电器股份有限公司 | Graphene/nickel hydroxide composite material and preparation method thereof, and electrode material |
| CN106587035A (en) * | 2016-11-23 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Eco-friendly safe reducing agent-based graphene and its preparation and application |
-
2018
- 2018-11-26 CN CN201811420596.5A patent/CN109659516B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN106179205A (en) * | 2016-07-13 | 2016-12-07 | 安徽师范大学 | A kind of Ni (OH)2the preparation method of graphene composite nano materials |
| CN106340391A (en) * | 2016-11-07 | 2017-01-18 | 珠海格力电器股份有限公司 | Graphene/nickel hydroxide composite material and preparation method thereof, and electrode material |
| CN106587035A (en) * | 2016-11-23 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Eco-friendly safe reducing agent-based graphene and its preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| One-pot hydrothermal synthesis of reduced graphene oxide/Ni(OH)2 films on nickel foam for high performance supercapacitors;Shudi Min et al.;《Electrochimica Acta》;20131102;155-164 * |
| 少层石墨及其复合材料制备和电化学性能研究;董伟等;《非金属矿》;20151130;第38卷(第6期);15-18 * |
| 能源储存用TiO2与石墨烯/Ni(OH)2电极材料;张颂;《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》;20130915(第09期);C042-58 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109659516A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201126796A (en) | Dispersant for use in a carbon filler | |
| TW201230466A (en) | Nano-size particle used for negative electrode for lithium ion secondary battery and method for manfacturing the same | |
| CN108390014B (en) | Preparation method of foam nickel loaded cobalt monoxide nano material with different morphologies | |
| CN104108700B (en) | A kind of grapheme material powder and preparation method | |
| CN106966443B (en) | A kind of preparation method of transition metal oxide/sulfide nanocomposite | |
| CN1765749A (en) | Mix metal hydroxide, their preparation and use | |
| CN109266165A (en) | A kind of epoxy composite coating and preparation method thereof | |
| CN105968777B (en) | A kind of antistatic composite nano materials film and preparation method thereof | |
| CN108889959B (en) | rGO/Cu composite material and preparation method thereof | |
| CN105280890B (en) | A kind of core shell structure silicon-carbon composite cathode material and preparation method thereof | |
| CN1800094A (en) | Silicon/charcoal core-shell structure nanometer composite material and its preparation method and uses | |
| CN106947994A (en) | A kind of coat of metal based on cupric oxide nano line | |
| CN106430295A (en) | Micro-nano hierarchy BaTiO3 crystal and preparation method thereof | |
| CN106905743A (en) | Graphene/carbon nano-tube/iron containing compoundses/polymer coating type absorbing material | |
| CN108314092A (en) | A kind of foamed nickel supported nano bar-shape cobalt molybdate and its preparation method and application | |
| CN109686580A (en) | A kind of ultra-thin Ni of 3D structure (OH)2Nanometer sheet/Ni nanoparticle@rGO combination electrode material preparation method and application | |
| CN101062958A (en) | Composite material formed of organic polymer and mesoporous molecular sieve and its interface structure and preparation method thereof | |
| CN109659516B (en) | Preparation method of electrode positive electrode material containing graphene | |
| CN111792669A (en) | TiO 22Nano-rod/multilayer graphene composite material and preparation method thereof | |
| TWI487661B (en) | Method of modifying carbon-based electrode material and carbon-based electrode material formed thereby | |
| CN107611252B (en) | ZnO/BaTiO3Composite material preparation method and ZnO/BaTiO3Composite material and application | |
| KR101254425B1 (en) | Graphene film having graphene oxide/poly vinyl alcohol composite and manufacturing method of the same | |
| CN105198004B (en) | A kind of Fe3O4‑SnO2Nano composite material and preparation method thereof | |
| CN109638238B (en) | Preparation method of electrode negative electrode material containing graphene | |
| CN108470631A (en) | Nickel cobalt iron sulphur multi-element metal oxygen（Sulphur）Compound nano core-shell shape composite material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230329 Granted publication date: 20210723 |
|
| PP01 | Preservation of patent right |