CN105428081A - Ni3S2 coated MMoO4 composite material grown in-site on metal substrate and application of composite material - Google Patents

Ni3S2 coated MMoO4 composite material grown in-site on metal substrate and application of composite material Download PDF

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CN105428081A
CN105428081A CN201510996638.XA CN201510996638A CN105428081A CN 105428081 A CN105428081 A CN 105428081A CN 201510996638 A CN201510996638 A CN 201510996638A CN 105428081 A CN105428081 A CN 105428081A
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composite material
coated
metallic substrates
mmoo
stick array
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王润伟
张宗弢
蔚艳茹
蒋尚
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Jilin University
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Jilin University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/46—Metal oxides
    • 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
    • Y02E60/13—Energy storage using capacitors

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  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • Chemically Coating (AREA)
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Abstract

The invention relates to a Ni3S2 coated MMoO4 composite material grown in-site on a metal substrate and application of the composite material. The Ni3S2 coated MMoO4 composite material is prepared according to the following steps of dissolving an M salt in deionized water, wherein M is Ni, Co or Mn; adding a molybdenum source; growing an MMoO4 nanorod array on the metal substrate after hydrothermal crystallization, drying and calcination; dissolving a nickel source in the deionized water; adding a sulfur source; and obtaining the Ni3S2 coated MMoO4 nanorod array composite material grown on the metal substrate after hydrothermal crystallization and drying, wherein the M salt is Ni(NO3)2, Ni(CH3COO)2, NiCl2, NiSO4, Co(NO3)2, Co(CH3COO)2, CoCl2, CoSO4, Mn(NO3)2, Mn(CH3COO)2, MnCl2 or MnSO4. The material has relatively high specific capacitance, favorable cyclic stability and rate performance, and can be more widely applied in the field of a supercapacitor.

Description

The Ni of growth in situ in a kind of metallic substrates 3s 2coated MMoO 4composite material and application thereof
Technical field
The invention belongs to electrode material for super capacitor technical field, be specifically related to the Ni that a kind of metallic substrates grows 3s 2coated MMoO 4(M=Ni, Co or Mn) composite material and the application in electrode material for super capacitor thereof.
Background technology
Along with the continuous progress of whole world modernization and automaticity, impel the demand of the energy also increasing.But traditional fossil energy has the trend of progressively approach exhaustion.Therefore, to development and utilization that is sustainable and renewable resource be the effective way of human kind sustainable development.Along with the new forms of energy vehicles are as the fast development in the fields such as electric automobile, Aero-Space and portable electronic equipment, the mechanism of new electrochemical power sources that exploitation has high-energy-density and a power density has simultaneously become one of problem that current people must face and solve.Ultracapacitor, be also referred to as electrochemical capacitor, it is a kind of novel energy-storing element between battery and traditional capacitor, because it has both the advantage higher than the power density of battery and the energy density higher than conventional electrostatic capacitor, also there is long discharge and recharge life-span, wide operating temperature range and the feature such as environmentally friendly simultaneously, be considered to one of new green power of most potentiality in this century.
The electrode material of ultracapacitor is the principal element determining ultracapacitor chemical property, MMoO 4there is because of it characteristics such as excellent chemical property and inexpensive low toxicity receive much concern, and its electron conduction is poor; Ni 3s 2to exist in a large number with mineral forms at nature and have good conductivity, but the electrochemical stability of this material is poor, therefore, the application in the capacitor of these materials is extremely restricted.In Chinese invention patent CN103779105A and CN103811189A, respectively nickel molybdate and cobalt molybdate are carried out compound with Graphene respectively obtain good chemical property.In addition, the coated Ni of carbon of patent of invention CN104240971A announcement 3s 2/ graphene composite material, impels Ni 3s 2the cyclical stability of material is significantly improved.Therefore in order to overcome MMoO 4and Ni 3s 2the shortcoming of material, the present invention is by MMoO 4growth, can the raising material electronics conductivity of high degree and specific area in the substrate of metal, in addition, by Ni 3s 2growth in situ is coated on MMoO 4surface, further improve MMoO 4electron conduction, also improve Ni simultaneously 3s 2cyclical stability, the final MMoO obtained 4ni 3s 2composite material will show more excellent chemical property.Up to the present, bibliographical information is not had to grow MMoO on the metallic substrate 4ni 3s 2composite material.
Summary of the invention
The object of the present invention is to provide growth in situ Ni in a kind of metallic substrates 3s 2coated MMoO 4nanometer stick array composite material, this material has higher ratio capacitance, good cyclical stability and high rate performance, and it can be more widely used in ultracapacitor field.
The Ni of growth in situ in a kind of metallic substrates of the present invention 3s 2coated MMoO 4nanometer stick array composite material, it is prepared by following steps:
(1) metallic substrates is used 2 ~ 6molL successively -1hydrochloric acid, acetone, distilled water ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt;
(2) take 0.5 ~ 2mmolM salt (M=Ni, Co or Mn), be dissolved in 20 ~ 50mL deionized water, after stirring 10 ~ 20min, slowly add 0.5 ~ 2mmol molybdenum source, stir 1 ~ 2h, form solution A; Solution A be transferred in teflon-lined reactor, be then immersed in this solution by the metallic substrates cleaned up, at autogenous pressures, hydrothermal crystallizing, naturally cools to room temperature after question response terminates; The metallic substrates deionized water obtained and ethanol are washed repeatedly respectively, after drying, carries out roasting in atmosphere, thus growth there is MMoO on the metallic substrate 4nanometer stick array;
(3) 0.5 ~ 2mmol nickel source is dissolved in 20 ~ 50mL deionized water, after stirring 10 ~ 20min, adds 0.5 ~ 4mmol sulphur source, stir 2 ~ 4h, form B solution; B solution is transferred in teflon-lined reactor, then the growth that step (2) obtains is had MMoO 4the metallic substrates of nanometer stick array is immersed in this solution, and at autogenous pressures, hydrothermal crystallizing, naturally cools to room temperature after question response terminates; The metallic substrates deionized water obtained and ethanol are washed repeatedly respectively, after drying, obtains the Ni that metallic substrates grows 3s 2coated MMoO 4nanometer stick array composite material.
In described step (1), metallic substrates comprises stainless steel substrates, stainless (steel) wire, metal titanium sheet, ti-alloy mesh, metal nickel sheet, nickel foam etc.
Optional Ni (the NO of M salt in described step (2) 3) 2, Ni (CH 3cOO) 2, NiCl 2, NiSO 4; Co (NO 3) 2, Co (CH 3cOO) 2, CoCl 2, CoSO 4; Mn (NO 3) 2, Mn (CH 3cOO) 2, MnCl 2, MnSO 4.
Molybdenum source in described step (2) is Na 2moO 42H 2o, (NH 4) 6mo 7o 244H 2o, MoO 3.
The temperature 100 ~ 180 DEG C of hydrothermal crystallizing in described step (2), crystallization time 3 ~ 18h.
Baking temperature 40 ~ 100 DEG C in described step (2), drying time 6 ~ 12h.
Sintering temperature in described step (2) is 400 ~ 600 DEG C, and roasting time is 60 ~ 240min, and heating rate is 1 ~-3 DEG C/min.
Nickel source in described step (3) is Ni (NO 3) 2, Ni (CH 3cOO) 2, NiCl 2, NiSO 4in one or more mixing.
Sulphur source in described step (3) is thiocarbamide, thioacetamide, Na 2one or more the mixing of S.
The temperature 90 ~ 150 DEG C of hydrothermal crystallizing in described step (3), crystallization time 1 ~ 6h.
Baking temperature 40 ~ 100 DEG C in described step (3), drying time 6 ~ 12h.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of the powder sample scraped from foam nickel base that embodiment 1 obtains, and illustrates that the material that nickel foam grows is curing three nickel (JCPDSNO.44-1418) and nickel molybdate (JCPDSNO.86-0361) crystalline phase;
Fig. 2, in embodiment 1, nickel foam grows Ni 3s 2coated MMoO 4(NiMoO 4ni 3s 2) scanned photograph of composite material, the NiMoO that nickel foam grows 4the length of nanometer rods is 2 ~ 5 μm, and diameter is 80 ~ 100nm.
Fig. 3, in embodiment 1, nickel foam grows Ni 3s 2coated MMoO 4(NiMoO 4ni 3s 2) the high power scanned photograph of composite material, be coated on NiMoO 4the Ni of nanometer rods 3s 2sheet thickness be 10 ~ 20nm.
Fig. 4, in embodiment 1, nickel foam grows NiMoO 4and NiMoO 4ni 3s 2the specific capacity curve of composite material respectively under different current density condition;
As shown in Figure 4, nickel foam grows NiMoO 4ni 3s 2composite material 2,5,10,15 and 20Ag -1current density under, obtain corresponding ratio capacitance and be respectively 1319,1177,1073,1019 and 975Fg -1; And nickel foam grows NiMoO 42,5,10,15 and 20Ag -1current density under, obtain corresponding ratio capacitance and be respectively 649,507,426,414 and 408Fg -1, this nickel foam of comparative illustration grows NiMoO 4ni 3s 2composite material exhibits gone out excellent capacitive property.
Metallic substrates of the present invention grows NiMoO 4ni 3s 2composite material be carry out constant current charge-discharge test by three electrode test methods, the discharge time under different current density and electromotive force window can be obtained, (I is constant current charge-discharge current density, and Δ t is discharge time, and m is NiMoO to obtain ratio capacitance C=I Δ t/m Δ V by formula 4ni 3s 2electrode material quality, Δ V is electromotive force window).With NiMoO prepared by the embodiment of the present invention 1 4ni 3s 2the sheet metal of composite material is as work electrode, and electrolyte is 2molL -1kOH solution, with platinum electrode as to electrode, by saturated calomel electrode as reference electrode, electromotive force window 0 to 0.45V, electrochemical workstation Bio-LogicVSPmultichannelpotentiostatic-galvanostaticsyst em.
Embodiment
Embodiment 1
(1) nickel foam (2cm × 4cm) is used 6molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.291gNi (NO is taken 3) 26H 2o, is dissolved in 30mL deionized water, stirs 20min, slowly adds 0.242gNa 2moO 42H 2o, stirs 2h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the nickel foam cleaned up, at autogenous pressures, 160 DEG C of hydrothermal crystallizing 10h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, then at 60 DEG C of dry 12h.Roasting 180min under last 400 DEG C of conditions in atmosphere, and heating rate is 2 DEG C/min, obtaining growth in nickel foam has NiMoO 4nanometer stick array;
(3) by 0.291gNi (NO 3) 26H 2o is dissolved in 30mL deionized water, adds 0.076g thiocarbamide after stirring 20min, stirs 4h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the nickel foam of nanometer stick array is immersed in this solution, and at autogenous pressures, 120 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, and then at 60 DEG C of dry 12h, obtaining growth in nickel foam has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that nickel foam grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.
Embodiment 2
(1) nickel foam (2cm × 4cm) is used 6molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.145gNi (NO is taken 3) 26H 2o, is dissolved in 30mL deionized water, stirs 10min, slowly adds 0.121gNa 2moO 42H 2o, stirs 1h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the nickel foam cleaned up, at autogenous pressures, 100 DEG C of hydrothermal crystallizing 18h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, then at 40 DEG C of dry 12h.Roasting 60min under last 400 DEG C of conditions in atmosphere, and heating rate is 1 DEG C/min, obtaining growth in nickel foam has NiMoO 4nanometer stick array;
(3) by 0.291gNi (NO 3) 26H 2o is dissolved in 30mL deionized water, adds 0.076g thiocarbamide after stirring 20min, stirs 4h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the nickel foam of nanometer stick array is immersed in this solution, and at autogenous pressures, 120 DEG C of hydrothermal crystallizing 2h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, and then at 60 DEG C of dry 12h, obtaining growth in nickel foam has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that nickel foam grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.
Embodiment 3
(1) nickel foam (2cm × 4cm) is used 4molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.145gNi (NO is taken 3) 26H 2o, is dissolved in 30mL deionized water, stirs 10min, slowly adds 0.121gNa 2moO 42H 2o, stirs 1h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the nickel foam cleaned up, at autogenous pressures, 180 DEG C of hydrothermal crystallizing 3h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, then at 80 DEG C of dry 6h.Roasting 120min under last 400 DEG C of conditions in atmosphere, and heating rate is 1 DEG C/min, obtaining growth in nickel foam has NiMoO 4nanometer stick array;
(3) by 0.582gNi (NO 3) 26H 2o is dissolved in 50mL deionized water, adds 0.152g thiocarbamide after stirring 20min, stirs 4h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the nickel foam of nanometer stick array is immersed in this solution, and at autogenous pressures, 150 DEG C of hydrothermal crystallizing 1h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, and then at 100 DEG C of dry 6h, obtaining growth in nickel foam has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that nickel foam grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.
Embodiment 4
(1) nickel foam (2cm × 4cm) is used 3molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.291gNi (NO is taken 3) 26H 2o, is dissolved in 50mL deionized water, stirs 10min, slowly adds 0.242gNa 2moO 42H 2o, stirs 1h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the nickel foam cleaned up, at autogenous pressures, 130 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 3 times respectively, then at 80 DEG C of dry 12h.Roasting 120min under last 500 DEG C of conditions in atmosphere, and heating rate is 2 DEG C/min, obtaining growth in nickel foam has NiMoO 4nanometer stick array;
(3) by 0.145gNi (NO 3) 26H 2o is dissolved in 20mL deionized water, adds 0.038g thiocarbamide after stirring 10min, stirs 2h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the nickel foam of nanometer stick array is immersed in this solution, and at autogenous pressures, 90 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 3 times respectively, and then at 60 DEG C of dry 12h, obtaining growth in nickel foam has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that nickel foam grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.
Embodiment 5
(1) nickel foam (2cm × 4cm) is used 4molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.145gNi (NO is taken 3) 26H 2o, is dissolved in 30mL deionized water, stirs 10min, slowly adds 0.121gNa 2moO 42H 2o, stirs 1h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the nickel foam cleaned up, at autogenous pressures, 100 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 5 times respectively, then at 60 DEG C of dry 6h.Roasting 60min under last 400 DEG C of conditions in atmosphere, and heating rate is 1 DEG C/min, obtaining growth in nickel foam has NiMoO 4nanometer stick array;
(3) by 0.145gNi (NO 3) 26H 2o is dissolved in 30mL deionized water, adds 0.038g thiocarbamide after stirring 10min, stirs 2h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the nickel foam of nanometer stick array is immersed in this solution, and at autogenous pressures, 90 DEG C of hydrothermal crystallizing 4h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 5 times respectively, and then at 40 DEG C of dry 12h, obtaining growth in nickel foam has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.
Embodiment 6
(1) nickel foam (2cm × 4cm) is used 4molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.291gNi (NO is taken 3) 26H 2o, is dissolved in 30mL deionized water, stirs 10min, slowly adds 0.242gNa 2moO 42H 2o, stirs 2h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the nickel foam cleaned up, at autogenous pressures, 100 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, then at 60 DEG C of dry 6h.Roasting 240min under last 400 DEG C of conditions in atmosphere, and heating rate is 1 DEG C/min, obtaining growth in nickel foam has NiMoO 4nanometer stick array;
(3) by 0.582gNi (NO 3) 26H 2o is dissolved in 50mL deionized water, adds 0.152g thiocarbamide after stirring 20min, stirs 4h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the nickel foam of nanometer stick array is immersed in this solution, and at autogenous pressures, 150 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Nickel foam deionized water and ethanol wash 4 times respectively, and then at 60 DEG C of dry 12h, obtaining growth in nickel foam has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that nickel foam grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.
Embodiment 7
(1) stainless (steel) wire (2cm × 4cm) is used 6molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.582gNi (NO is taken 3) 26H 2o, is dissolved in 50mL deionized water, stirs 20min, slowly adds 0.484gNa 2moO 42H 2o, stirs 2h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the stainless (steel) wire cleaned up, at autogenous pressures, 180 DEG C of hydrothermal crystallizing 18h, naturally cool to room temperature after question response terminates.Stainless (steel) wire deionized water and ethanol wash 4 times respectively, then at 60 DEG C of dry 6h.Roasting 60min under last 600 DEG C of conditions in atmosphere, and heating rate is 3 DEG C/min, obtaining growth on stainless (steel) wire has NiMoO 4nanometer stick array;
(3) by 0.145gNi (NO 3) 26H 2o is dissolved in 30mL deionized water, adds 0.038g thiocarbamide after stirring 10min, stirs 2h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the stainless (steel) wire of nanometer stick array is immersed in this solution, and at autogenous pressures, 120 DEG C of hydrothermal crystallizing 2h, naturally cool to room temperature after question response terminates.Stainless (steel) wire deionized water and ethanol wash 4 times respectively, and then at 60 DEG C of dry 12h, obtaining growth on stainless (steel) wire has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that stainless (steel) wire grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.
Embodiment 8
(1) stainless (steel) wire (2cm × 4cm) is used 6molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.582gNi (NO is taken 3) 26H 2o, is dissolved in 30mL deionized water, stirs 20min, slowly adds 0.484gNa 2moO 42H 2o, stirs 2h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the stainless (steel) wire cleaned up, at autogenous pressures, 180 DEG C of hydrothermal crystallizing 12h, naturally cool to room temperature after question response terminates.Stainless (steel) wire deionized water and ethanol wash 4 times respectively, then at 60 DEG C of dry 6h.Roasting 240min under last 600 DEG C of conditions in atmosphere, and heating rate is 3 DEG C/min, obtaining growth on stainless (steel) wire has NiMoO 4nanometer stick array;
(3) by 0.582gNi (NO 3) 26H 2o is dissolved in 30mL deionized water, adds 0.152g thiocarbamide after stirring 20min, stirs 4h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the stainless (steel) wire of nanometer stick array is immersed in this solution, and at autogenous pressures, 150 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Stainless (steel) wire deionized water and ethanol wash 4 times respectively, and then at 80 DEG C of dry 12h, obtaining growth on stainless (steel) wire has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that stainless (steel) wire grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.
Embodiment 9
(1) metal titanium sheet (2cm × 4cm) is used 2molL successively -1hydrochloric acid, acetone, distilled water carries out ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt, for subsequent use.
(2) 0.582gNi (NO is taken 3) 26H 2o, is dissolved in 20mL deionized water, stirs 20min, slowly adds 0.484gNa 2moO 42H 2o, stirs 2h, and form solution A, solution A be transferred in teflon-lined reactor, be then immersed in this solution by the metal titanium sheet cleaned up, at autogenous pressures, 180 DEG C of hydrothermal crystallizing 12h, naturally cool to room temperature after question response terminates.Metal titanium sheet deionized water and ethanol wash 4 times respectively, then at 100 DEG C of dry 6h.Roasting 60min under last 400 DEG C of conditions in atmosphere, and heating rate is 1 DEG C/min, obtaining growth in metal titanium sheet has NiMoO 4nanometer stick array;
(3) by 0.291gNi (NO 3) 26H 2o is dissolved in 20mL deionized water, adds 0.304g thiocarbamide after stirring 10min, stirs 2h, forms B solution, B solution is transferred in teflon-lined reactor, and then step (2) being obtained length has NiMoO 4the metal titanium sheet of nanometer stick array is immersed in this solution, and at autogenous pressures, 120 DEG C of hydrothermal crystallizing 6h, naturally cool to room temperature after question response terminates.Metal titanium sheet deionized water and ethanol wash 4 times respectively, and then at 60 DEG C of dry 12h, obtaining growth in metal titanium sheet has Ni 3s 2coated NiMoO 4the composite material of nanometer stick array.Characterized by XRD, find that the material that titanium sheet grows is curing three nickel and nickel molybdate two kinds of crystalline phases, can be seen by high power scanned photograph and grow Ni on the nanometer stick array of nickel molybdate 3s 2ultrathin nanometer laminated structure.

Claims (9)

1. the Ni of growth in situ in a metallic substrates 3s 2coated MMoO 4nanometer stick array composite material, it is prepared by following steps:
(1) metallic substrates is used 2 ~ 6molL successively -1hydrochloric acid, acetone, distilled water ultrasonic cleaning, in order to remove surface oxide skin(coating) and greasy dirt;
(2) take 0.5 ~ 2mmolM salt (M=Ni, Co or Mn), be dissolved in 20 ~ 50mL deionized water, after stirring 10 ~ 20min, slowly add 0.5 ~ 2mmol molybdenum source, stir 1 ~ 2h, form solution A; Solution A be transferred in teflon-lined reactor, be then immersed in this solution by the metallic substrates cleaned up, at autogenous pressures, hydrothermal crystallizing, naturally cools to room temperature after question response terminates; The metallic substrates deionized water obtained and ethanol are washed repeatedly respectively, after drying, carries out roasting in atmosphere, thus growth there is MMoO on the metallic substrate 4nanometer stick array;
(3) 0.5 ~ 2mmol nickel source is dissolved in 20 ~ 50mL deionized water, after stirring 10 ~ 20min, adds 0.5 ~ 4mmol sulphur source, stir 2 ~ 4h, form B solution; B solution is transferred in teflon-lined reactor, then the growth that step (2) obtains is had MMoO 4the metallic substrates of nanometer stick array is immersed in this solution, and at autogenous pressures, hydrothermal crystallizing, naturally cools to room temperature after question response terminates; The metallic substrates deionized water obtained and ethanol are washed repeatedly respectively, after drying, obtains the Ni that metallic substrates grows 3s 2coated MMoO 4nanometer stick array composite material.
2. the Ni of growth in situ in a kind of metallic substrates as claimed in claim 1 3s 2coated MMoO 4nanometer stick array composite material, is characterized in that: in step (1), metallic substrates is stainless steel substrates, stainless (steel) wire, metal titanium sheet, ti-alloy mesh, metal nickel sheet or nickel foam.
3. the Ni of growth in situ in a kind of metallic substrates as claimed in claim 1 3s 2coated MMoO 4nanometer stick array composite material, is characterized in that: the M salt in step (2) is Ni (NO 3) 2, Ni (CH 3cOO) 2, NiCl 2, NiSO 4, Co (NO 3) 2, Co (CH 3cOO) 2, CoCl 2, CoSO 4, Mn (NO 3) 2, Mn (CH 3cOO) 2, MnCl 2or MnSO 4.
4. the Ni of growth in situ in a kind of metallic substrates as claimed in claim 1 3s 2coated MMoO 4nanometer stick array composite material, is characterized in that: the molybdenum source in step (2) is Na 2moO 42H 2o, (NH 4) 6mo 7o 244H 2o, MoO 3.
5. the Ni of growth in situ in a kind of metallic substrates as claimed in claim 1 3s 2coated MMoO 4nanometer stick array composite material, is characterized in that: the temperature 100 ~ 180 DEG C of hydrothermal crystallizing in step (2), crystallization time 3 ~ 18h; Baking temperature 40 ~ 100 DEG C, drying time 6 ~ 12h; Sintering temperature is 400 ~ 600 DEG C, and roasting time is 60 ~ 240min, and heating rate is 1 ~-3 DEG C/min.
6. the Ni of growth in situ in a kind of metallic substrates as claimed in claim 1 3s 2coated MMoO 4nanometer stick array composite material, is characterized in that: the nickel source in step (3) is Ni (NO 3) 2, Ni (CH 3cOO) 2, NiCl 2, NiSO 4in one or more mixing.
7. the Ni of growth in situ in a kind of metallic substrates as claimed in claim 1 3s 2coated MMoO 4nanometer stick array composite material, is characterized in that: the sulphur source in step (3) is thiocarbamide, thioacetamide, Na 2one or more the mixing of S.
8. the Ni of growth in situ in a kind of metallic substrates as claimed in claim 1 3s 2coated MMoO 4nanometer stick array composite material, is characterized in that: the temperature 90 ~ 150 DEG C of hydrothermal crystallizing in step (3), crystallization time 1 ~ 6h; Baking temperature 40 ~ 100 DEG C, drying time 6 ~ 12h.
9. the Ni of growth in situ in a kind of metallic substrates of claim 1 ~ 8 described in any one 3s 2coated MMoO 4the application of nanometer stick array composite material in electrode material for super capacitor.
CN201510996638.XA 2015-12-28 2015-12-28 Ni3S2 coated MMoO4 composite material grown in-site on metal substrate and application of composite material Pending CN105428081A (en)

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CN108597893A (en) * 2018-05-28 2018-09-28 江苏大学 A kind of preparation method based on the composite electrode material for super capacitor in nickel foam
CN108816250A (en) * 2018-06-06 2018-11-16 北京师范大学 A kind of nanometer stick array composite material and preparation method and application
CN109628951A (en) * 2018-10-31 2019-04-16 中山大学 A kind of nickel sulfide Electrocatalytic Activity for Hydrogen Evolution Reaction agent and the preparation method and application thereof
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CN111111680B (en) * 2020-02-11 2022-11-18 湘潭大学 Rodlike Ni-MoO 3-x Preparation method and application of catalyst
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CN111540609B (en) * 2020-05-07 2021-04-30 电子科技大学 Crystalline-amorphous MoO for super capacitor3@Ni3S2Method for producing a material

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