CN106119816A - A kind of method preparing metallic cobalt/Graphene composite foam material - Google Patents

A kind of method preparing metallic cobalt/Graphene composite foam material Download PDF

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Publication number
CN106119816A
CN106119816A CN201610486853.XA CN201610486853A CN106119816A CN 106119816 A CN106119816 A CN 106119816A CN 201610486853 A CN201610486853 A CN 201610486853A CN 106119816 A CN106119816 A CN 106119816A
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China
Prior art keywords
solution
concentration
polyurethane foam
cobalt
sodium
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CN201610486853.XA
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Chinese (zh)
Inventor
赵崇军
蔡云霄
张小军
王威
唐小林
邓丽娟
钱秀珍
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SINOMAX (ZHEJIANG) POLYURETHANES HOUSEHOLD ARTICLES CO Ltd
East China University of Science and Technology
Original Assignee
SINOMAX (ZHEJIANG) POLYURETHANES HOUSEHOLD ARTICLES CO Ltd
East China University of Science and Technology
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Priority to CN201610486853.XA priority Critical patent/CN106119816A/en
Publication of CN106119816A publication Critical patent/CN106119816A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • C08J9/40Impregnation
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating
    • C23C18/285Sensitising or activating with tin based compound or composition
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating
    • C23C18/30Activating or accelerating or sensitising with palladium or other noble metal
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

Abstract

The invention discloses a kind of method preparing metallic cobalt/Graphene composite foam material.Using cellular polyurethane as supporter and template, by the method for chemical plating, prepare metallic cobalt/Graphene composite deposite on the surface of polyurethane.This metallic cobalt/Graphene composite foam material all has a wide range of applications at aspects such as energy storage, water process, sound insulations.The method preparation process is simple and easy to control, low cost, synthesis condition gentle, and material size is controlled.

Description

A kind of method preparing metallic cobalt/Graphene composite foam material
Technical field
The present invention relates to a kind of method preparing metallic cobalt/Graphene composite foam material, particularly relate to polyurethane Foam, as supporter and template, utilizes electroless plating technology to prepare metallic cobalt/Graphene composite foam material, relates generally to energy storage The technical fields such as material, material for water treatment and deadener.
Background technology
Foam metal has good electric conductivity and certain self-supporting ability, has light weight, porosity, compares table The features such as area is big, are the ideal materials preparing various electrode, it is adaptable to various accumulator, fuel cell, air cell box are too Sun can battery and all kinds of electrochemical process electrode.
First technology deposits on nickel foam substrate thus is prepared for foam cobalt: Wang Dianlong, Wang Chong are with nickel foam as base Body is prepared for foam cobalt through rolling, activation, electro-deposition, and has prepared three-dimensional foamed cobalt oxide cathode material by heat treatment Material.But this method is limited to foam nickel fractions, it is impossible to control the performances such as foam cobalt void ratio, diameter more neatly. Additionally, nanotechnology obtains increasingly extensive application, and metal material is after size reaches nanoscale, and its electric conductivity can be by aobvious Write impact, therefore, it is possible to the Material cladding of high conductivity, be beneficial to the application of this kind of nanometer foam cobalt material.
Summary of the invention
Based on the deficiency in first technology, the present invention is selected polyurethane foam as supporter and template, is aoxidized by introducing Graphene, utilizes electroless plating technology to be prepared for metallic cobalt/Graphene composite foam material.
For achieving the above object, the technical solution of the present invention is as follows:
A kind of method preparing metallic cobalt/Graphene composite foam material, comprises the steps:
(1) polyurethane foam is put in the acid potassium permanganate aqueous solution that 45 C concentration are 1g/L immersion 5 minutes, takes out and rush Wash clean;Then, after clean polyurethane foam being put in the oxalic acid aqueous solution that 45 C concentration are 10g/L immersion 5 minutes, take Go out and rinse well;Then, clean polyurethane foam is put into containing 0.1g/L Palladous chloride., 5g/L stannous chloride and 100g/L After 1000 mL aqueous solutions of sodium chloride soak 10 minutes, take out and rinse well, then be put in 3.7% concentrated hydrochloric acid aqueous solution leaching After steeping 5 minutes, take out and rinse well;
(2) weigh a certain amount of cobaltous sulfate, sodium citrate, sodium hypophosphite, boric acid respectively and be dissolved in successively in deionized water, stirring Mix homogeneously, adds graphene oxide solution, and ultrasonic disperse is uniform, prepares plating solution;
(3) weigh a certain amount of sodium hypophosphite and be dissolved in water, add graphene oxide solution, ultrasonic disperse, make prepreg solution;So After extract processing, through step (1), the polyurethane foam that obtains, put into prepreg solution and soak 10min;
(4) polyurethane foam soaked through step (3) is put in again in the plating solution that step (2) prepares, and by dilute hydroxide It is 8.5 ~ 8.8 that sodium solution controls the pH value of plating solution;Then controlling reaction temperature is that 80 C ~ 90 C change in polyurethane foam Learn cobalt plating reaction 30min ~ 120min;Taking-up is rinsed well and dries, and obtains metallic cobalt/Graphene composite foam material.
Further, in the plating solution described in step (2), cobalt sulfate concentration is 10 ~ 25g/L;Sodium hypophosphite concentration is 15 ~ 25g/ L;Boric acid concentration is 25 ~ 35g/L, and sodium citrate concentration is 55 ~ 65g/L, and graphene oxide concentration is 0.1 ~ 1g/L.
Further, in the prepreg solution described in step (3), sodium hypophosphite concentration is 30g/L;Graphene oxide concentration is 0.4 ~ 2g/L。
The present invention utilizes chemical plating method directly growth acquisition metallic cobalt/Graphene compound vacuole on polyurethane foam matrix Foam material.Wherein polyurethane foam serves as foam metal skeleton.Cobalt salt in plating solution is as the cobalt source of formation foam cobalt, in plating solution Graphene oxide as Graphene originate.In plating process, cobalt salt and graphene oxide are reduced and deposit to simultaneously to gather Urethane surface forms metallic cobalt/Graphene composite foam material.The method preparation process is simple and easy to control, low cost, synthesis condition Gentle.
Accompanying drawing explanation
Metallic cobalt/Graphene the composite foam material of Fig. 1 embodiment 1 preparation
Metallic cobalt/Graphene the composite foam material of Fig. 2 embodiment 2 preparation
Metallic cobalt/Graphene the composite foam material of Fig. 3 embodiment 3 preparation
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
Weigh 1.5g CoSO4, 2.1g NaH2PO2, 30g H3BO3, 5.8g sodium citrate, it is dissolved in water successively, mix homogeneously, Being settled to 100mL, take during wherein 10mL puts into small beaker, add 4g/L graphene oxide 2mL, ultrasonic disperse is uniform, as plating Liquid.
Weigh sodium hypophosphite 0.3g, be dissolved in water, add 4g/L graphene oxide 2.5mL, add water to 10mL, ultrasonic place Reason 10min, as prepreg solution.The polyurethane foam that will process through step (1), extracts and puts into prepreg solution, soaks 10min.
By putting into plating solution through the urethane film of preimpregnation, be fixed under liquid level, sodium hydroxide control plating solution pH be 8.5 ~ 8.8, it is 86 C ~ 88 C that oil bath controls bath temperature.After reaction 60min, taking out, deionized water is cleaned, and air-dries, i.e. obtains metal Cobalt/Graphene composite foam material.Result is as shown in Fig. 1 in Figure of description.
Embodiment 2
Weigh 1.5g CoSO4, 2.1g NaH2PO2, 30g H3BO3, 5.8g sodium citrate, it is dissolved in water successively, mix homogeneously, Being settled to 100mL, take during wherein 10mL puts into small beaker, add 4g/L graphene oxide 3.3mL, ultrasonic disperse is uniform, as Plating solution.
Weigh sodium hypophosphite 0.3g, dissolve, add 4g/L graphene oxide 5mL, add water to 10mL, supersound process 10min, As prepreg solution.The polyurethane foam that will process through step (1), extracts and puts into prepreg solution, soaks 10min.
By putting into plating solution through the urethane film of preimpregnation, be fixed under liquid level, sodium hydroxide control plating solution pH be 8.5 ~ 8.8, it is 86 C ~ 88 C that oil bath controls bath temperature.After reaction 60min, taking out, deionized water is cleaned, and air-dries, i.e. obtains metal Cobalt/Graphene composite foam material.Result is as shown in Fig. 2 in Figure of description.
Embodiment 3
Weigh 1.5g CoSO4, 2.1g NaH2PO2, 30g H3BO3, 5.8g sodium citrate, it is dissolved in water successively, mixing is all Even, it is settled to 100mL, takes during wherein 10mL puts into small beaker, add 4g/L graphene oxide 1mL, ultrasonic disperse is uniform, as Plating solution.
Weigh sodium hypophosphite 0.3g, dissolve, add 4g/L graphene oxide 1mL, add water to 10mL, supersound process 10min, As prepreg solution.The polyurethane foam that will process through step (1), extracts and puts into prepreg solution, soaks 10min.
By putting into plating solution through the urethane film of preimpregnation, be fixed under liquid level, sodium hydroxide control plating solution pH be 8.5 ~ 8.8, it is 86 C ~ 88 C that oil bath controls bath temperature.After reaction 60min, taking out, deionized water is cleaned, and air-dries, i.e. obtains metal Cobalt/Graphene composite foam material.Result is as shown in Fig. 3 in Figure of description.
Embodiment 4
Weigh 1.5g CoSO4, 2.1g NaH2PO2, 30g H3BO3, 5.8g sodium citrate, it is dissolved in water successively, mix homogeneously, Being settled to 100mL, take during wherein 10mL puts into small beaker, add 4g/L graphene oxide 2mL, ultrasonic disperse is uniform, as plating Liquid.
Weigh sodium hypophosphite 0.3g, dissolve, add 4g/L graphene oxide 2.5mL, add water to 10mL, supersound process 10min, as prepreg solution.The polyurethane foam that will process through step (1), extracts and puts into prepreg solution, soaks 10min.
By putting into plating solution through the urethane film of preimpregnation, be fixed under liquid level, sodium hydroxide control plating solution pH be 8.5 ~ 8.8, it is 86 C ~ 88 C that oil bath controls bath temperature.After reaction 30min, taking out, deionized water is cleaned, and air-dries, i.e. obtains metal Cobalt/Graphene composite foam material.
Embodiment 5
Weigh 1.5g CoSO4, 2.1g NaH2PO2, 30g H3BO3, 5.8g sodium citrate, it is dissolved in water successively, mix homogeneously, Being settled to 100mL, take during wherein 20mL puts into small beaker, add 4g/L graphene oxide 3mL, ultrasonic disperse is uniform, as plating Liquid.
Weigh sodium hypophosphite 0.3g, dissolve, add 4g/L graphene oxide 2.5mL, add water to 10mL, supersound process 10min, as prepreg solution.The polyurethane foam that will process through step (1), extracts and puts into prepreg solution, soaks 10min.
By putting into plating solution through the urethane film of preimpregnation, be fixed under liquid level, sodium hydroxide control plating solution pH be 8.5 ~ 8.8, it is 86 C ~ 88 C that oil bath controls bath temperature.After reaction 120min, taking out, deionized water is cleaned, and air-dries, i.e. obtains gold Belong to cobalt/Graphene composite foam material.

Claims (3)

1. the method preparing metallic cobalt/Graphene composite foam material, it is characterised in that comprise the steps:
(1) polyurethane foam is put in the acid potassium permanganate aqueous solution that 45 C concentration are 1g/L immersion 5 minutes, takes out and rush Wash clean;Then, after clean polyurethane foam being put in the oxalic acid aqueous solution that 45 C concentration are 10g/L immersion 5 minutes, take Go out and rinse well;Then, clean polyurethane foam is put into containing 0.1g/L Palladous chloride., 5g/L stannous chloride and 100g/L After 1000 mL aqueous solutions of sodium chloride soak 10 minutes, take out and rinse well, then be put in 3.7% concentrated hydrochloric acid aqueous solution leaching After steeping 5 minutes, take out and rinse well;
(2) weigh a certain amount of cobaltous sulfate, sodium citrate, sodium hypophosphite, boric acid respectively and be dissolved in successively in deionized water, stirring Mix homogeneously, adds graphene oxide solution, and ultrasonic disperse is uniform, prepares plating solution;
(3) weigh a certain amount of sodium hypophosphite and be dissolved in water, add graphene oxide solution, ultrasonic disperse, make prepreg solution;So After extract processing, through step (1), the polyurethane foam that obtains, put into prepreg solution and soak 10min;
(4) polyurethane foam soaked through step (3) is put in again in the plating solution that step (2) prepares, and by dilute hydroxide The pH value of sodium solution regulation plating solution is 8.5 ~ 8.8;Then controlling reaction temperature is that 80 C ~ 90 C change in polyurethane foam Learn cobalt plating reaction 30min ~ 120min;Taking-up is rinsed well and dries, and obtains metallic cobalt/Graphene composite foam material.
Method the most according to claim 1, it is characterised in that in described plating solution, cobalt sulfate concentration is 10 ~ 25g/L;Secondary Sodium phosphate concentration is 15 ~ 25g/L;Boric acid concentration is 25 ~ 35g/L, and sodium citrate concentration is 55 ~ 65g/L, graphene oxide concentration It is 0.1 ~ 1g/L.
Method the most according to claim 1, it is characterised in that sodium hypophosphite concentration in the predip solution described in step (3) For 30g/L;Graphene oxide concentration is 0.4 ~ 2g/L.
CN201610486853.XA 2016-08-19 2016-08-19 A kind of method preparing metallic cobalt/Graphene composite foam material Pending CN106119816A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108176404A (en) * 2017-12-27 2018-06-19 吉林大学 A kind of chemical nickel plating composite catalyst, preparation method and nickel chemical plating technology
CN108624874A (en) * 2018-04-14 2018-10-09 李艳 One kind preventing the caducous preparation method of graphene on graphene strainer

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108176404A (en) * 2017-12-27 2018-06-19 吉林大学 A kind of chemical nickel plating composite catalyst, preparation method and nickel chemical plating technology
CN108624874A (en) * 2018-04-14 2018-10-09 李艳 One kind preventing the caducous preparation method of graphene on graphene strainer

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