CN111613453A - Preparation method of porous nickel cobaltate/graphene nano composite electrode material - Google Patents
Preparation method of porous nickel cobaltate/graphene nano composite electrode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 239000007772 electrode material Substances 0.000 title claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 34
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000499 gel Substances 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 239000011240 wet gel Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 38
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 11
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940045136 urea Drugs 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- IEWUUVGDINEFTP-UHFFFAOYSA-J cobalt(2+) nickel(2+) dicarbonate Chemical compound [Co++].[Ni++].[O-]C([O-])=O.[O-]C([O-])=O IEWUUVGDINEFTP-UHFFFAOYSA-J 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention relates to a preparation method of a porous nickel cobaltate/graphene nano composite electrode material, belonging to the field of preparation of new energy materials. Aiming at the defects that the cost of the porous nickel cobaltate prepared by the existing hydrothermal method and the composite material is high and the porous nickel cobaltate is not suitable for large-scale industrial production. The invention takes polymer gel with a three-dimensional network structure synthesized in situ as a template, and obtains the porous nickel cobaltate/graphene nano composite electrode material with the pore diameter and the grain size both in nano level through closed reaction and low-temperature calcination. The basic process is that a reticular polymer formed by in-situ polymerization of micromolecular organic matter under a certain condition is utilized, aqueous slurry containing soluble metal salt, urea and graphene is directly changed into wet gel, the urea is hydrolyzed at a certain temperature, precipitation reaction is carried out in a three-dimensional network, and finally, the porous nano composite electrode material is obtained through drying and calcining and is applied to the high-performance supercapacitor electrode material. The preparation method has the advantages of simple process, energy conservation, environmental protection and easy industrial production.
Description
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a method for preparing a porous nickel cobaltate/graphene nano composite electrode material.
Background
Nickel cobaltate of the formula NiCo2O4The electrode material has the advantages of low toxicity, abundant resources, high theoretical capacity, good redox reversibility and the like, and thus has a very promising prospect. To satisfy NiCo2O4The preparation method is widely applied to the field of super capacitors, and the conductivity, specific capacitance, multiplying power and cycling stability of the super capacitors, particularly the electrochemical properties such as cycling stability and the like, are required to be further improved, so that the preparation cost is further reduced. At present, the nano, porous, special shape and composite are to improve NiCo2O4An efficient method for electrochemical performance of a base electrode material. The comprehensive utilization of several means for improving electrochemical performance is the current porous NiCo2O4The research of the base nanometer composite electrode material is hot. Among a plurality of nano composite electrode materials, the carbon material is an important option of a second phase due to the advantages of rich raw materials, low price, good processing performance, no toxicity, large specific surface area, good conductivity, high chemical stability, wide use temperature range and the like. Graphene is commonly used for improving the performance of different materials due to excellent conductivity and mechanical properties of graphene in recent years, and is no exception as an electrode material of a supercapacitor.
Most commonly used for preparing porous NiCo2O4The method of the/graphene nano composite electrode material is a hydrothermal method, and not only can the morphology of the nano crystal be controlled, but also the size of the hole can be controlled, so that the synergistic effect of the nano crystal and the hole can be exerted, and the electrochemical performance can be improved. However, the hydrothermal method not only needs a special hydrothermal reaction kettle, but also is difficult to produce in large scale, has high preparation cost and is not beneficial to NiCo2O4Practical application of the base electrode material. For this purpose, a porous NiCo with high cycle stability and specific structure is prepared by a method which is low in cost and suitable for industrial production in consideration of comprehensive performance and cost2O4The base nano-composite electrode material isAs necessary.
Disclosure of Invention
In view of the defects and shortcomings of the prior art that the cost is high and the composite material thereof prepared by the hydrothermal method is not suitable for large-scale industrial production, the invention aims to provide the porous nickel cobaltate (NiCo) composed of the nanocrystalline and the mesoporous and having the electrochemical performance with excellent rate capability and cycle life2O4) A preparation method of a Graphene (GO) nano composite electrode material.
The technical solution of the invention is realized as follows:
a preparation method of a porous nickel cobaltate/graphene nano composite electrode material comprises the steps of taking high molecular polymer gel with a three-dimensional network structure synthesized in situ as a template, carrying out closed heat treatment (reaction), and then calcining at low temperature to obtain the porous nickel cobaltate/graphene nano composite electrode material with the aperture and the grain size being in a nano level. The method comprises the following steps:
(1) adding the monomer and the cross-linking agent into deionized water according to the mass ratio of the monomer to the cross-linking agent of 20:1-10:1, and dissolving under stirring to prepare a mixed solution with the mass concentration of the monomer of 7-10%;
(2) according to the molar ratio of cobalt ions, nickel ions and urea of 2:1:3-6, adding water-soluble cobalt salt, nickel salt and urea into the mixed solution in the step (1), stirring and dissolving to prepare a solution with the total molar concentration of cobalt ions and nickel ions being 0.15-0.45 mol/L;
(3) adding graphene and polyvinylpyrrolidone into the solution obtained in the step (2), and performing ultrasonic dispersion for 15-30 minutes to obtain a suspension slurry; wherein the addition amount of the graphene is 0-10% of the mass of the theoretically synthesized nickel cobaltate; the addition amount of the polyvinylpyrrolidone is 2-5% of the mass of the graphene;
(4) weighing 10-20% ammonium persulfate solution and 10-20% sodium sulfite solution with equal volume, adding into the suspension slurry in the step (3) in the stirring process, uniformly stirring, and standing for reacting for 20-30 minutes under the closed condition of room temperature to obtain wet gel;
wherein, per 100ml of the suspension slurry in the step (3), 0.25-0.5ml of ammonium persulfate solution and 0.25-0.5ml of sodium sulfite solution are added;
(5) sealing the gel obtained in the step (4), and carrying out closed reaction for 10-12 hours at the temperature of 100-110 ℃;
(6) drying the wet gel in the step (5) for 12-24 hours at the temperature of 90-100 ℃ to obtain a dried gel;
(7) and (4) calcining the dried gel obtained in the step (6) for 4-6 hours at the temperature of 400 ℃ under the air atmosphere, so as to obtain black fluffy powder, namely the porous nickel cobaltate/graphene nano composite electrode material.
According to the above technical solution, preferably, the method further includes: (8) and (4) washing, filtering, washing with ethanol and drying the porous nickel cobaltate/graphene nano composite electrode powder in the step (7) to obtain the porous nickel cobaltate or porous nickel cobaltate/graphene composite electrode material.
According to the above technical solution, in step (1), preferably, the monomer is acrylamide, and the crosslinking agent is N, N' -methylenebisacrylamide.
According to the above technical solution, preferably, in the step (1), the concentration of the monomer is 7-8%, and the ratio of the monomer to the crosslinking agent is 19: 1.
According to the above technical solution, preferably, in the step (2), the water-soluble cobalt salt and the water-soluble nickel salt are one or two of nitrate, acetate, sulfate and chloride, preferably nitrate and acetate.
According to the above technical solution, in step (2), the molar ratio of the cobalt ions, the nickel ions and the urea is preferably 2:1:3-6, preferably 2:1: 4.
According to the above technical solution, preferably, in the step (2), the total concentration of the cobalt and nickel ions is 0.24-0.33 mol/L.
According to the above technical solution, preferably, in the step (3), the graphene is single-layer or multi-layer graphene, and is preferably multi-layer graphene; the multilayer graphene is prepared by a mechanical stripping method and is provided by Shenzhen national constant-progress science and technology.
According to the above technical solution, preferably, in the step (4), the ammonium persulfate solution and the sodium sulfite solution are newly prepared, that is, are prepared as they are used.
According to the above technical scheme, preferably, in the step (4), the ammonium persulfate solution and the sodium sulfite solution are added in a volume of 0.5ml of 10% ammonium persulfate solution and 0.5ml of 10% sodium sulfite solution per 100ml of slurry.
According to the above technical solution, preferably, in the step (4), the sealable container used for the reaction under the sealed condition is made of glass or stainless steel lined with polytetrafluoroethylene, and preferably, stainless steel lined with polytetrafluoroethylene.
According to the above technical solution, in step (7), the calcination temperature is preferably 300-350 ℃.
According to the above technical solution, preferably, in the step (8), the drying temperature is 60 to 80 ℃, and the drying time is 3 to 6 hours.
According to the above technical solution, preferably, the raw materials include water-soluble cobalt salt, water-soluble nickel salt, urea, acrylamide monomer, N' -methylene bisacrylamide, ammonium persulfate, and sodium sulfite, all of which have purities of analytical purity or contents of 99% or more.
According to the above technical solution, preferably, when the electrode material is a porous nickel cobaltate electrode material, no graphene is added, and no polyvinylpyrrolidone is added, i.e., step (3) is not performed, and step (2) is directly performed to step (4); when the electrode material is prepared from the porous nickel cobaltate and graphene composite electrode material, the addition amount of the graphene is 0.1-10% of the mass of the theoretically synthesized nickel cobaltate.
The invention has the beneficial effects that:
the invention provides a method for synthesizing a pore by using a high molecular polymer gel with a network structure synthesized in situ under room temperature as a template and combining a sealing reaction and a calcination processPorous NiCo with nano-scale diameter and grain size2O4A method for preparing a graphene nano composite electrode material. The basic process comprises the steps of utilizing acrylamide monomer and N, N' -methylene bisacrylamide micromolecule organic matter, taking ammonium persulfate and sodium sulfite as initiators to polymerize in situ to form a reticular polymer at room temperature, directly changing aqueous slurry containing water-soluble cobalt, nickel salt, urea and graphene into wet gel, hydrolyzing the urea at 100-110 ℃ under a closed condition, generating basic cobalt nickel carbonate precipitate with cobalt and nickel ions in a three-dimensional network, and finally drying and calcining to synthesize the porous NiCo2O4The graphene nano composite electrode material is applied to a high-performance supercapacitor electrode material. Introducing water soluble cobalt and nickel salt into metal ions needed in the final product; the urea is used as a precipitator of the reaction, the molar ratio of the urea to cobalt ions is 1.5-3:1, preferably 2:1, the urea is less, the reaction efficiency is influenced, the gelling time is prolonged too much, the efficiency is influenced, and the cost is increased; acrylamide monomer, N, N' -methylene bisacrylamide as raw material for forming network high polymer; the graphene is used as a second phase for improving the electrochemical performance, and has a synergistic effect; ammonium persulfate and sodium sulfite are used as initiators of room temperature polymerization, so that adverse reactions caused by catalytic initiation and heating initiation can be avoided. The amino group in the acrylamide monomer, N, N' -methylene bisacrylamide crosslinking agent has bonding effect with cobalt and nickel ions, and NiCo is calcined2O4The ultra-thin pore walls are formed by nucleation, growth and polymerization, so that the amino groups play a vital role in the formation of the porous material. The pore diameter of the in-situ generated three-dimensional network structure polymer is nano-scale and can be controlled by the concentration of acrylamide and the ratio of acrylamide to N, N' -methylene-bisacrylamide, so that the pore diameter of the porous polymer can be properly adjusted according to the performance. The calcination temperature is preferably 300-350 ℃ because, on the one hand, the temperature is increased, the particle size is increased, the specific surface area is reduced, and the electrochemical performance is not improved, and on the other hand, NiCo2O4For thermodynamically metastable phases, temperatures above 400 ℃ will decompose into Co3O4And NiO. Sealable containers, preferably lined with polytetrafluoroethyleneStainless steel material, this is because glass material is fragile, is difficult to operate, and stainless steel material has more or less some reactions under acid-base environment, and the iron ion that produces can produce the inhibition polymerization to the in situ polymerization reaction, so the inside polytetrafluoroethylene that is lined with the chemical stability excellence of stainless steel container of choosing for use.
The porous NiCo prepared by the method provided by the invention2O4The graphene nano composite electrode material has the advantages of low synthesis temperature, small aperture, fine crystal grains, large specific surface area, excellent rate performance (the rate is more than 85% when the specific capacity is 1A/g under the current density of 10A/g), large energy and power density and excellent cycle stability (the capacity retention rate is more than 120% after 12000 charging and discharging cycles under 4A/g); meanwhile, the preparation method has the advantages of simple and rapid process, low cost, easy process control, energy conservation, environmental protection, easy industrial production and the like.
Drawings
The invention is illustrated in fig. 4, wherein:
FIG. 1 is an X-ray diffraction (XRD) spectrum of a porous material (without graphene) obtained in example 1 at different temperatures;
FIG. 2 is an X-ray diffraction (XRD) pattern of a porous nanocomposite (graphene content 5%) obtained from example 2 calcined at 300 ℃ for 4 hours;
FIG. 3 is a Scanning Electron Microscope (SEM) of the porous material obtained in example 1 after calcination at 300 ℃ for 4 hours;
FIG. 4 is SEM of a porous nanocomposite (graphene content 5%) obtained by calcining example 2 at 300 ℃ for 4 hours;
FIG. 5 is a Transmission Electron Microscope (TEM) of the pore walls of the porous material (without graphene) obtained in example 1, calcined at 300 ℃ for 4 hours.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The raw materials described in the following examples include water-soluble cobalt salt, water-soluble nickel salt, urea, acrylamide monomer, N' -methylenebisacrylamide, ammonium persulfate, and sodium sulfite, all of which are analytically pure.
The graphene in the following embodiments is multilayer graphene, is prepared by a mechanical exfoliation method, and is provided by Shenzhen national constant technology.
Examples 1 to 3
A preparation method of a porous nano nickel cobaltate and a graphene composite electrode material thereof refers to the following steps:
(1) weighing acrylamide and N, N '-methylene bisacrylamide according to the mass ratio of the acrylamide to the N, N' -methylene bisacrylamide of 19:1, adding deionized water, and dissolving under electric stirring to prepare a mixed solution of the N, N '-methylene bisacrylamide and the acrylamide and the N, N' -methylene bisacrylamide;
(2) according to the molar ratio of cobalt ions, nickel ions and urea of 2:1: weighing cobalt nitrate, nickel nitrate and urea or cobalt acetate, nickel acetate and urea, stirring and dissolving in a mixed solution containing acrylamide and N, N' -methylene bisacrylamide to prepare 1000ml of a solution containing cobalt ions and nickel ions;
(3) then adding a proper amount of graphene or not adding the graphene and PVP (polyvinyl pyrrolidone) which is 3% of the graphene in mass, and performing ultrasonic dispersion for 20 minutes to obtain suspension slurry;
(4) then 5ml of 10 wt% ammonium persulfate solution is firstly dripped in the stirring process, then 5ml of 10 wt% sodium sulfite solution is dripped in the stirring process, the mixture is uniformly stirred for 3 minutes, and then the mixture is transferred into a sealable container with a polytetrafluoroethylene lining, and is placed at room temperature for 10 to 20 minutes to form transparent gel, so as to obtain wet gel;
(5) then sealing the container, putting the container in an oven at 100 ℃ or 110 ℃, preserving heat for 12 or 10 hours, and taking out the wet gel;
(6) cutting the obtained wet gel into a plurality of small blocks, putting the small blocks into an oven, heating to 100 ℃, and drying for 12 hours to obtain dry gel;
(7) and finally, putting the xerogel into a box-type furnace, heating to 300 ℃ or 350 ℃ and calcining for 4h to obtain black porous nano-electrode powder. And washing and filtering the powder with water until no white precipitate can be detected by using a 0.1M barium chloride solution, washing with ethanol once, and finally drying in an oven at 80 ℃ for 4 hours to obtain the porous nickel cobaltate/graphene nano composite electrode material with different graphene contents.
The processes of examples 1 to 3 are the same, and the parameters involved are shown in the following table:
FIG. 1 is an XRD pattern of the product of example 1, showing that spinel nickel cobaltate is formed at 300 ℃ and decomposes to Co above 450 ℃3O4And NiO; FIG. 2 is an XRD pattern of the product of example 2 showing that calcination at 300 ℃ for 4 hours resulted in a product consisting of GO and nickel cobaltate; FIG. 3 is SEM of porous nanomaterial obtained in example 1 by calcining at 300 ℃ for 4 hours, and the pore diameter is 3-100 nm; FIG. 4 is an SEM of a porous nanocomposite obtained in example 2 (containing 5% graphene) calcined at 300 ℃ for 4 hours, with a pore size of 3-150 nm; FIG. 5 is a transmission electron microscope of the pore wall of the porous nanomaterial obtained in example 1 by calcining at 300 ℃ for 4 hours, with the grain size of 10-20nm and the pore size of 3-4 nm.
Claims (9)
1. A preparation method of a porous nickel cobaltate/graphene nano composite electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) adding the monomer and the cross-linking agent into deionized water according to the mass ratio of the monomer to the cross-linking agent of 20:1-10:1, and dissolving under stirring to prepare a mixed solution with the mass concentration of the monomer of 7-10%;
(2) according to the molar ratio of cobalt ions, nickel ions and urea of 2:1:3-6, adding water-soluble cobalt salt, nickel salt and urea into the mixed solution in the step (1), stirring and dissolving to prepare a solution with the total molar concentration of cobalt ions and nickel ions being 0.15-0.45 mol/L;
(3) adding graphene and polyvinylpyrrolidone into the solution obtained in the step (2), and performing ultrasonic dispersion for 15-30 minutes to obtain suspension slurry; wherein the addition amount of the graphene is 0-10% of the mass of the theoretically synthesized nickel cobaltate; the addition amount of the polyvinylpyrrolidone is 2-5% of the mass of the graphene;
(4) adding 10-20% ammonium persulfate solution and 10-20% sodium sulfite solution with equal volume into the suspension slurry in the step (3) in the stirring process, uniformly stirring, and standing for reaction for 10-30 minutes under the sealing condition of room temperature to obtain wet gel;
wherein, per 100ml of the suspension slurry in the step (3), 0.25-0.5ml of ammonium persulfate solution and 0.25-0.5ml of sodium sulfite solution are added;
(5) sealing the gel obtained in the step (4), and carrying out closed reaction for 10-12 hours at the temperature of 100-110 ℃;
(6) drying the wet gel in the step (5) for 12-24 hours at the temperature of 90-110 ℃ to obtain a dried gel;
(7) and (4) calcining the dried gel in the step (6) for 4-6 hours at the temperature of 300-400 ℃ in the air atmosphere to obtain the porous nickel cobaltate/graphene nano composite electrode powder.
2. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 1, characterized by comprising the following steps: further comprising: (8) and (4) washing, filtering, washing with ethanol and drying the porous nickel cobaltate/graphene nano composite electrode powder in the step (7).
3. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 1, characterized by comprising the following steps: in the step (1), the monomer is acrylamide.
4. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 1, characterized by comprising the following steps: in the step (1), the cross-linking agent is N, N' -methylene bisacrylamide.
5. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 1, characterized by comprising the following steps: in the step (2), the water-soluble cobalt salt and the water-soluble nickel salt are respectively one or two of nitrate, acetate, sulfate and chloride.
6. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 1, characterized by comprising the following steps: in the step (3), the graphene is single-layer or multi-layer graphene.
7. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 1, characterized by comprising the following steps: in the step (4), the reaction container used under the sealing condition is made of glass or stainless steel with polytetrafluoroethylene as a lining.
8. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 1, characterized by comprising the following steps: in the step (4), the ammonium persulfate solution and the sodium sulfite solution are prepared at present.
9. The preparation method of the porous nickel cobaltate/graphene nano composite electrode material according to claim 2, characterized by comprising the following steps: in the step (8), the drying temperature is 60-80 ℃, and the drying time is 3-6 hours.
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| US20170053750A1 (en) * | 2015-08-17 | 2017-02-23 | Research Cooperation Foundation Of Yeungnam University | Three-dimensional composites of nickel cobalt oxide/ graphene on nickel foam for supercapacitor electrodes, and preparation method thereof |
| CN106910647A (en) * | 2017-04-24 | 2017-06-30 | 武汉科技大学 | Compound cobalt acid nickel nano-wire array material of graphene aerogel and preparation method thereof |
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| CN1799990A (en) * | 2005-12-02 | 2006-07-12 | 大连交通大学 | Preparation method of nanometer metal oxide and composite metal oxide |
| US20170053750A1 (en) * | 2015-08-17 | 2017-02-23 | Research Cooperation Foundation Of Yeungnam University | Three-dimensional composites of nickel cobalt oxide/ graphene on nickel foam for supercapacitor electrodes, and preparation method thereof |
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