CN116443956A - Preparation method of nano nickel oxide/graphene composite electrode material - Google Patents
Preparation method of nano nickel oxide/graphene composite electrode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 34
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 30
- 108010010803 Gelatin Proteins 0.000 claims description 26
- 239000008273 gelatin Substances 0.000 claims description 26
- 229920000159 gelatin Polymers 0.000 claims description 26
- 235000019322 gelatine Nutrition 0.000 claims description 26
- 235000011852 gelatine desserts Nutrition 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000499 gel Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LONQOCRNVIZRSA-UHFFFAOYSA-L nickel(2+);sulfite Chemical compound [Ni+2].[O-]S([O-])=O LONQOCRNVIZRSA-UHFFFAOYSA-L 0.000 claims description 2
- 230000006340 racemization Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
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- 238000011160 research Methods 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
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- 238000002848 electrochemical method Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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Abstract
The invention discloses a preparation method of a nano nickel oxide/graphene composite electrode material, and relates to the technical field of graphene composite batteries. The size and the composite low-rate GO are controlled to achieve high capacity, the prepared NiO-GO composite electrode effectively increases the electrode capacity (the lifting amplitude can be more than 50 percent), and in addition, the composite electrode has better reversibility (the average reversible potential can be increased by 20 mV) and faster charging speed (the charging time can be effectively shortened by more than 20 percent).
Description
Technical Field
The invention relates to the technical field of graphene composite batteries, in particular to a preparation method of a nano nickel oxide/graphene composite electrode material.
Background
Energy is the most important component of the world's continuous technological development. The energy crisis has increased in recent decades due to the high cost and limited supply of fossil fuels and the growing concern about environmental pollution. The increasing demand for energy and the growing concern for global warming and air pollution have prompted intensive research into renewable energy and energy storage devices. Renewable energy sources face challenges that need to be overcome due to their intermittent nature. Therefore, efficient energy storage methods are a technical challenge to ensure energy availability in the 21 st century. Recently, green energy technology has been used for hybrid and electric vehicles, mobile phones, entertainment instruments, and space equipment. Quick charge and discharge, high volume energy density, low cost, legal resources, safety, environmental protection (recoverable), long service life and high efficiency are important factors of new energy storage devices in the future. Among alternative forms of energy storage, electrical energy storage is one of the best technologies, as it can be transported over long distances and is also considered a clean energy source. The positive electrode plays an important role in an energy storage system, and the porosity structure, the specific surface area and the conductivity in the electrochemical reaction are special factors influencing the energy storage capacity.
As an ideal matrix, graphene has many attractive properties such as high conductivity, large specific surface area, high mechanical flexibility, and significant thermal and chemical stability. Extensive research has been conducted in the manufacture of graphene transition metal oxide composites for energy storage applications that can combine the advantages of both components and produce specific properties by mutual reinforcement or modification. Recently the Meryl d.stoller group reported that chemically modified graphene was used as the electrode material for supercapacitors (Nano Lett 2008;8 (10): 3498-502), which has high conductivity and still good performance at a wide voltage sweep rate, but low specific capacitance.
Amorphous hydrous ruthenium oxide is known to be the most promising electrode material of high-power high-energy density super capacitors, but is expensive and resource-deficient, and the used electrolyte pollutes the environment, so that the commercial development of the amorphous hydrous ruthenium oxide is greatly limited. While NiO and other oxide electrode materials have the same properties as RuO 2 ·xH 2 O functions similarly and is inexpensive, but NiO has two very deadly disadvantages as a supercapacitor material: one is poor in conductivity and the other is that the NiO nanomaterial is easily agglomerated. In recent years, gradient porous NiO synthesized by Cheng et al (J Power Sources2008;185 (2): 1563-68.) as an electrode material for supercapacitors by the template method is much better in both capacitance, power density and energy density than commercially available NiO, but is inferior in stability at higher voltages.
One of the current research hot spots is to research nickel oxide and graphene composite materials, and the composite materials can play respective advantages, overcome the defect of a single material and expand the application range of the material. Patent CN101733985a discloses a graphene/nickel oxide layered structure composite film and a preparation method thereof, wherein the graphene and nickel oxide are mixed by an ultrasonic method, and then the graphene/nickel oxide layered structure composite film is obtained by high-temperature heat treatment; patent CN102522218A reports a nano nickel oxide/graphene composite electrode material, a preparation method and application thereof, wherein the high conductivity of reduced graphene oxide is mainly utilized to reduce the internal resistance and the high specific surface of the composite electrode, and the characteristics of the composite electrode, namely the composite electrode can be used as an electric double layer capacitor, so that the high-power discharge capacity of the composite capacitor is improved, and the aperture of the nano nickel oxide/graphene composite electrode material is nano nickel oxide with the average particle size of 750nm in the range of 2-65 nm. Although the specific capacitance of the composite material is improved to a certain extent, the nano nickel oxide with the average particle size of 750nm can cause the limit of electrochemical performance.
The electrode prepared by the prior art has low capacity, poor reversibility and the prepared battery charging speed to be further improved, so that the battery is limited to be used in more fields.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a nano nickel oxide/graphene (NiO-GO) composite electrode material, which can improve the capacity and reversibility of an electrode, and the battery prepared from the electrode material prepared by the preparation method has the technical effects of higher charging speed and low battery loss, so as to solve at least one technical problem in the background art, and belongs to the technical field of graphene composite batteries.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect of the present invention, there is provided a method for modifying NiO NPs on Graphene Oxide (GO), in which the NiO NPs are modified on Graphene Oxide (GO) by a sol-gel method, that is, a method for preparing a nano nickel oxide/graphene composite electrode material, comprising the steps of:
(1) Respectively dissolving water-soluble nickel salt, graphene oxide and gelatin in water to form a water-soluble nickel salt solution, a graphene oxide solution and a gelatin solution;
(2) Adding a water-soluble nickel salt solution into a graphene oxide solution to form a mixed solution, adding the mixed solution into a gelatin solution, and heating and stirring to obtain gel;
(3) Drying the gel to obtain the nano nickel oxide/graphene composite electrode material;
wherein the mass ratio of the water-soluble nickel salt to the graphene oxide to the gelatin is 80-200:1:40-125
The particle size of the prior art is about 500nm, the particle size prepared by the method is about 10nm, a reagent is necessary to control the particle size in a sol-gel method, the applicant ensures that the gelatin, the synthesized nano particles have high quality and uniform size, and the gelatin can be removed at 300 ℃.
In an exemplary embodiment of the method for modifying NiO NPs on Graphene Oxide (GO), the water-soluble nickel salt is at least one of nickel nitrate, nickel sulfate, nickel acetate, nickel chloride, and nickel sulfite.
In one exemplary embodiment of the method for modifying NiO NPs on Graphene Oxide (GO), in the step (1), gelatin is dissolved in water by heating in a water bath, and the temperature is kept at 60-80 ℃.
Specifically, the graphene oxide is prepared according to a Hummers method, the Hummers method comprises the following steps: uniformly stirring and mixing 0.1-2M sulfuric acid solution, 0.1-2M phosphoric acid solution, graphite flake and potassium permanganate by magnetic force to obtain a mixed solution, wherein the mass ratio of the sulfuric acid solution to the phosphoric acid solution to the graphite flake to the potassium permanganate is 50-170:10-50:1:2.67-12, and gradually adding H after the color of the mixed solution is changed from dark purple green to dark brown 2 O 2 And (3) carrying out racemization reaction on the solution, reacting for 10-15min, namely obtaining a reaction solution when the color of the mixed solution is changed into bright yellow, and centrifugally washing the supernatant of the reaction solution to obtain the graphene oxide.
The invention obtains the composite low-rate GO, compared with the operation of using Reduced Graphene Oxide (RGO) to reach large capacity at high rate, and RGO is more expensive than GO, and the invention is more suitable for industrial production.
In one exemplary embodiment of the method of modifying NiO NPs on Graphene Oxide (GO) of this invention, the H 2 O 2 The volume concentration of the solution is 30%, H is added 2 O 2 The amount of solution was 30mL.
In an exemplary embodiment of the method for modifying NiO NPs on Graphene Oxide (GO), in the step (2), the mixed solution is added into a gelatin solution, and the temperature is kept at 60-80 ℃ while heating and stirring.
In one exemplary embodiment of the method of modifying NiO NPs on Graphene Oxide (GO) of the present invention, in step (3), the drying conditions are: heating to 300-350deg.C at a rate of 20-30deg.C/min, and maintaining at 300-350deg.C for 1-3 hr.
The invention also provides the nano nickel oxide/graphene composite electrode material prepared by the preparation method.
The invention also provides application of the nano nickel oxide/graphene composite electrode material in preparation of a composite electrode.
The preparation method of the composite electrode comprises the following steps: niO/GO electrodes were prepared by mixing 60-80wt.% NiO/GO powder with 12-18wt.% acetylene black, slurried with 8-12wt.% polyvinylidene fluoride (PVDF) and 1-methyl-2-pyrrolidone (NMP) as solvents, and then a clean nickel foil (0.125 mm thick, 1cm 2 Area) and dried in air in a horizontal furnace at 80-90 c for 12-16 hours, the mass of NiO/GO composite coated on each electrode is approximately between 1-2 mg.
In one exemplary embodiment of the method of preparing a NiO/GO composite electrode of the invention, the 1-methyl-2-pyrrolidone (NMP) is used in an amount of 20 to 35 parts NMP per 10 parts active material.
The beneficial effects are that:
in summary, the preparation method of the NiO-GO composite electrode material provided by the invention has the beneficial effects that:
1) The size and the composite low-speed GO are controlled to achieve high capacity, so that the capacity of the NiO-graphene oxide composite electrode is effectively improved, and the improvement amplitude can reach more than 50%;
2) The NiO-graphene oxide composite electrode has better reversibility, and the average reversible potential of the NiO-graphene oxide composite electrode can be increased by 20mV;
3) The NiO/GO composite electrode has a faster charging speed, and the charging time can be effectively shortened by more than 20%.
Drawings
FIG. 1 is a diagram of a prefabricated electrode; where a is various materials for preparing an electrode, and b is an electrode material and an electrode pattern coated by using a markopite.
FIG. 2 is a diagram of electrochemical measurement of NiO/GO of a coating performed by a three-electrode system; wherein, (a) is a potentiostat (Versa STAT 3, ametek), and (b) is a three-electrode system electrochemical cell.
Fig. 3 is an XRD pattern after calcination at 300 ℃ of NiO NPs prepared in example 1 and NiO/GO (1%) composites prepared in example 3.
Fig. 4 is raman spectra of NiO prepared in example 1 and NiO/GO prepared in example 3.
Fig. 5 is a FESEM image of NiO/GO morphology prepared in example 3.
FIG. 6 is a HRTEM image of NiO/GO nanoparticle structures prepared in example 3; wherein, (a) is a TEM image of NiO NPs decorated GO sheets and (b) is a Ni map of individual nanoparticles attached to GO sheets.
FIG. 7 is a cyclic voltammogram observed for NiO NPs calcined at 300℃under scan rates of 1, 5, 15, 20 and 30mV/S in 1M KOH for electrochemical testing of NiO/GO composites prepared in example 5.
FIG. 8 is a CV curve of NiO prepared in comparative example 1 and NiO/GO composite prepared in example 5.
Fig. 9 is a graph of charge and discharge tests at different current densities for NiO/GO electrodes prepared in example 5.
Fig. 10 is a charge-discharge test chart of NiO NPs prepared in comparative example 1 and NiO/GO electrodes prepared in example 5.
Detailed Description
Example 1
Preparation of NiO particles
4g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 20mL deionized water and then stirred for 30 minutes. Meanwhile, 2g of gelatin was dissolved in 40mL of deionized water, respectively, and then stirred at 40 ℃ for 45 minutes to obtain a clear gelatin solution. Thereafter, the nickel nitrate solution was added to the gelatin solution and heated in a water bath at 60 ℃ with stirring. Stirring was continued for 15 hours to give a honey-like and bright green gel. The green gel was then placed in an oven. The furnace was heated from room temperature to 300℃at a rate of 25℃per minute. At the final temperatureAfter 2 hours of holding, the furnace was naturally cooled to room temperature to obtain nano nickel oxide (NiO NPs).
Example 2
8g of NiSO 4 ·6H 2 O was dissolved in 40mL deionized water and then stirred for 45 minutes. Meanwhile, 4g of gelatin was dissolved in 80mL of deionized water, respectively, and then stirred at 60 ℃ for 30 minutes to obtain a clear gelatin solution. Thereafter, the nickel sulphate solution was added to the gelatin solution and heated in a water bath at 80 ℃ with stirring. Stirring was continued for 10 hours to give a honey-like and bright green gel. The green gel was then placed in an oven. The furnace was heated from room temperature to 300℃at a rate of 25℃per minute. After 2 hours of holding at the final temperature, the furnace was naturally cooled to room temperature to obtain nano nickel oxide (NiO NPs).
Example 3
The preparation process of the nano nickel oxide/graphene composite material comprises the following specific steps:
s1: 320ml of H 2 SO 4 (0.1M), 80ml of H 3 PO 4 (0.1M), 3g graphite flake and 18g KMnO 4 Slowly add to the reactor and use a magnetic stirrer to perform the mixing process to oxidize the graphite. The color of the mixture changed from dark purple green to dark brown. Then 30ml of H with a volume concentration of 30% are added 2 O 2 The solution stops the oxidation process and the color of the mixture turns bright yellow. The graphite oxide formed was washed three times with 1M aqueous HCl to pH 4-5 and repeatedly with deionized water. The supernatant is subjected to a washing process by simple decantation by centrifugation techniques. During washing with deionized water, the graphite oxide undergoes exfoliation, resulting in thickening of the graphene solution to form a GO gel.
S2: 4g of Ni (NO) 3 ) 2 ·6H 2 O and 0.04g GO were dissolved in 20mL deionized water, respectively, and then they were stirred for 30 minutes. The nickel nitrate solution was then added very slowly to the GO solution. Meanwhile, 2g of gelatin was dissolved in 40mL of deionized water, respectively, and then stirred at 60 ℃ for 45 minutes to obtain a clear gelatin solution. Thereafter, the nickel nitrate/GO solution was added to the gelatin solution and heated in a water bath at 60 ℃ with stirring. Stirring was continued for 15 hoursWhen this is done, a honey-like and black gel is obtained. The black gel was placed in a furnace, which was heated from room temperature to 300℃at a rate of 25℃per minute. After the final temperature is kept for 2 hours, the furnace is naturally cooled to room temperature, and the nano nickel oxide/graphene (NiO/GO) composite material is obtained.
Example 4
NiO NPs are modified on Graphene Oxide (GO).
S1: 320ml of H 2 SO 4 (2M), 80ml of H 3 PO 4 (2M), 3g graphite flake and 18g KMnO 4 Slowly add to the reactor and use a magnetic stirrer to perform the mixing process to oxidize the graphite. The color of the mixture changed from dark purple green to dark brown. Then 30ml of H with a volume concentration of 30% are added 2 O 2 The solution stopped the oxidation process and the color of the mixture changed to bright yellow, indicating that the oxidation level of graphite was high. The graphite oxide formed was washed three times with 1M aqueous HCl to pH 4-5 and repeatedly with deionized water. The supernatant is subjected to a washing process by simple decantation by centrifugation techniques. During washing with deionized water, the graphite oxide undergoes exfoliation, resulting in thickening of the graphene solution to form a GO gel.
S2: 8g of NiSO 4 ·6H 2 O and 0.08g GO were dissolved in 40mL deionized water, respectively, and then they were stirred for 45 minutes. The nickel sulfate solution was then added very slowly to the GO solution. Simultaneously, 5g of gelatin was dissolved in 40mL of deionized water, respectively, and then stirred at 80℃for 30 minutes to give a clear gelatin solution. Thereafter, the nickel nitrate/GO solution was added to the gelatin solution and heated in a water bath at 80 ℃ with stirring. Stirring was continued for 12 hours to give a honey-like and black gel. The black gel was placed in a furnace, which was heated from room temperature to 350 ℃ at a rate of 25 ℃/min. After the final temperature is kept for 2 hours, the furnace is naturally cooled to room temperature, and the nano nickel oxide/graphene (NiO/GO) composite material is obtained.
Example 5
FIG. 1 is a diagram of a prefabricated electrode; where a is various materials for preparing an electrode, and b is an electrode material and an electrode pattern coated by using a markopite. FIG. 2 is a diagram of electrochemical measurement of NiO/GO of a coating performed by a three-electrode system; wherein, (a) is a potentiostat (Versa STAT 3, ametek), and (b) is a three-electrode system electrochemical cell. The preparation process comprises the following steps:
and (3) preparing the NiO/GO composite electrode.
NiO/GO electrodes were prepared by mixing 80wt.% NiO/GO powder (prepared in example 3) with 18wt.% acetylene black, slurried with 12wt.% polyvinylidene fluoride (PVDF) and 1-methyl-2-pyrrolidone (NMP) as solvents, and then a clean nickel foil (0.125 mm thick, 1cm 2 Area) and dried in air at 90 c in a horizontal furnace tube for 16 hours to obtain NiO/GO composite electrodes, the mass of NiO/GO composite coated on each electrode was about 2mg.
The amount of 1-methyl-2-pyrrolidone (NMP) used was 35ml NMP per 10g of active material (NiO+acetylene black+PVDF).
Example 6
And (3) preparing the NiO/GO composite electrode.
NiO/GO electrodes were prepared by mixing 60wt.% NiO/GO powder (prepared in example 4) with 18wt.% acetylene black, slurried with 12wt.% polyvinylidene fluoride (PVDF) and 1-methyl-2-pyrrolidone (NMP) as solvents, and then a clean nickel foil (0.125 mm thick, 1cm 2 Area) and dried in air at 90 c in a horizontal furnace tube for 16 hours to obtain NiO/GO composite electrodes, the mass of NiO/GO composite coated on each electrode was about 2mg.
The amount of 1-methyl-2-pyrrolidone (NMP) used was 35ml NMP per 10g of active material (NiO+acetylene black+PVDF).
Comparative example 1
And (3) preparing the NiO composite electrode.
NiO electrodes were prepared by mixing 80wt.% NiO powder (prepared in example 1) with 12wt.% acetylene black, slurried with 8wt.% polyvinylidene fluoride (PVDF) and 1-methyl-2-pyrrolidone (NMP) as solvents, and then a clean nickel foil (0.125 mm thick, 1cm 2 Area) and drying in air at 80 ℃ for 12 hours in a horizontal furnace tube to obtain the NiO/GO composite electrode,the mass of NiO composite coated on each electrode was approximately 1mg.
The amount of 1-methyl-2-pyrrolidone (NMP) used was 20ml NMP per 10g of active material (NiO+acetylene black+PVDF).
Test example 1
The nano nickel oxide prepared in example 1 and NiO/GO prepared in example 3 were characterized separately. The XRD patterns of the NiO NPs and NiO/GO (1%) composites after calcination are shown in FIG. 3.
The raman spectra of NiO and NiO/GO are shown in fig. 4, with NiO/GO samples having two peaks near 1380 and 1600cm "1, corresponding to the D and G bands of graphene, respectively. Typically, the D/G intensity ratio is related to the sp2/sp3 carbon ratio and is an amorphous state.
The morphology of the NiO/GO composite was studied by recording FESEM and the result is shown in FIG. 5 where NiO NP underwent aggregation by vander-Wals interactions. Most graphene nanoplatelets are rolled and wound together to form a layered structure. The TEM image in fig. 6 (a) shows that nionps are decorated on GO sheets. Further, the TEM image showed that the average particle size of the nanoparticles was about 8.7nm. Fig. 6 (b) shows an HRTEM image of a single nionp. It can be seen that the nanoparticles are single crystals with high crystal quality and that there are no defects caused by stacking faults. Furthermore, HRTEM images show a lattice distance of about 0.21nm.
Test example 2
The enhanced capacity Cyclic Voltammetry (CV) technique was used to study the electrochemical performance of NiO NPs produced with sol-gel method as electrode material. FIG. 7 shows cyclic voltammograms observed for NiO NPs calcined at 300℃at scan rates of 1, 5, 15, 20 and 30 mV/S.
CV plots of NiO/GO electrodes at different scan rates showed increased current density and potential at the oxidation and reduction peaks. The shift in redox peaks is due to the rapid ion/electron diffusion rate and to the enhanced electrical polarization and irreversible reaction at higher scan rates. This is because the reaction is limited by the rate of ion diffusion.
The cyclic voltammetry obtained for the NiO/GO complex was compared to nionp as shown in fig. 8. Redox peaks in CV pattern the potentials are denoted as Ea and Ec, respectively. The NiO/GO electrode was found to exhibit good reversibility in the faraday reaction. Thus, during the reaction, electrolyte ions can diffuse more easily in the porous structure of the NiO/GO composite than nionp.
FIG. 9 is a graph of the current density at different levels and 1M KOH charge/discharge measurements of NiO/GO electrodes were made. It can be seen from the figure that by increasing the current density, the charge/discharge time will decrease and the potential window will increase. The nonlinear charge-discharge curve demonstrates pseudocapacitive behavior of the NiO/GO electrode, consistent with CV results.
To investigate the effect of graphene oxide and NiO NPs, nionp and NiO/GO electrodes were charged/discharged under the same conditions. As a result, as shown in fig. 10, the charge time in NiO/GO was shorter than that of NiO NPs electrode, and the discharge time of NiO/GO was longer than that of nionp electrode. The short charging time of the NiO/GO electrode is due to the existence of graphene, and the graphene improves the conductivity of the electrode material, wherein ions can diffuse on the surfaces of the inner pores and the outer pores of the NiO/GO more rapidly than the NiO-NPs electrode.
Claims (10)
1. The preparation method of the nano nickel oxide/graphene composite electrode material is characterized by comprising the following steps of:
(1) Respectively dissolving water-soluble nickel salt, graphene oxide and gelatin in water to form a water-soluble nickel salt solution, a graphene oxide solution and a gelatin solution;
(2) Adding a water-soluble nickel salt solution into a graphene oxide solution to form a mixed solution, adding the mixed solution into a gelatin solution, and heating and stirring to obtain gel;
(3) Drying the gel to obtain the nano nickel oxide/graphene composite electrode material;
wherein the mass ratio of the water-soluble nickel salt to the graphene oxide to the gelatin is 80-200:1:40-125.
2. The method for preparing the nano nickel oxide/graphene composite electrode material according to claim 1, wherein the water-soluble nickel salt is at least one of nickel nitrate, nickel sulfate, nickel acetate, nickel chloride and nickel sulfite.
3. The method for preparing a nano nickel oxide/graphene composite electrode material according to claim 1, wherein in the step (1), gelatin is dissolved in water by heating in a water bath, and the temperature is kept at 60-80 ℃.
4. The method for preparing the nano nickel oxide/graphene composite electrode material according to claim 1, wherein the graphene oxide is prepared according to a Hummers method, and the Hummers method comprises the following steps: uniformly stirring and mixing 0.1-2M sulfuric acid solution, 0.1-2M phosphoric acid solution, graphite flake and potassium permanganate by magnetic force to obtain a mixed solution, wherein the mass ratio of the sulfuric acid solution to the phosphoric acid solution to the graphite flake to the potassium permanganate is 50-170:10-50:1:2.67-12, and gradually adding H 2 O 2 And (3) carrying out racemization reaction on the solution, reacting for 10-15min to obtain a reaction solution, and centrifugally washing supernatant of the reaction solution to obtain the graphene oxide.
5. The method for preparing nano nickel oxide/graphene composite electrode material according to claim 4, wherein the H is a metal oxide 2 O 2 The volume concentration of the solution is 30%, H is added 2 O 2 The amount of solution was 30mL.
6. The method for preparing a nano nickel oxide/graphene composite electrode material according to claim 1, wherein in the step (2), the mixed solution is added into a gelatin solution, and the temperature is kept at 60-80 ℃ while heating and stirring.
7. The method for preparing the nano nickel oxide/graphene composite electrode material according to claim 1, wherein in the step (3), the drying condition is as follows: heating to 300-350deg.C at a rate of 20-30deg.C/min, and maintaining at 300-350deg.C for 1-3 hr.
8. The nano nickel oxide/graphene composite electrode material prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the nano nickel oxide/graphene composite electrode material according to claim 8 for preparing a composite electrode.
10. The use according to claim 9, wherein the composite electrode is prepared by the following method: uniformly mixing 60-80wt.% of the nano nickel oxide/graphene composite electrode material with 12-18wt.% of acetylene black to obtain a mixture, mixing the mixture with a solvent to prepare a slurry, coating one side of a nickel foil with the slurry, and drying in air at 80-90 ℃ in a horizontal furnace tube for 12-16 hours to prepare the composite electrode, wherein the solvent is polyvinylidene fluoride and 1-methyl-2-pyrrolidone.
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