CN111426732A - Preparation method of AgX @ Ag core-shell electrode material - Google Patents
Preparation method of AgX @ Ag core-shell electrode material Download PDFInfo
- Publication number
- CN111426732A CN111426732A CN202010259163.7A CN202010259163A CN111426732A CN 111426732 A CN111426732 A CN 111426732A CN 202010259163 A CN202010259163 A CN 202010259163A CN 111426732 A CN111426732 A CN 111426732A
- Authority
- CN
- China
- Prior art keywords
- agx
- solution
- core
- silver halide
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011258 core-shell material Substances 0.000 title claims abstract description 49
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 56
- 239000004332 silver Substances 0.000 claims abstract description 56
- -1 silver ions Chemical class 0.000 claims abstract description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 238000011946 reduction process Methods 0.000 claims abstract description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 14
- 229910021607 Silver chloride Inorganic materials 0.000 description 13
- 230000010287 polarization Effects 0.000 description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
Abstract
The invention belongs to the technical field of electrode preparation, and particularly relates to a preparation method of an AgX @ Ag core-shell electrode material, which comprises the steps of pretreating AgX by utilizing polyethylene glycol, modifying the surface of AgX by utilizing a mercaptosilane coupling agent, enabling AgX nucleation to be uniformly dispersed, having a regular shape and a smaller particle size, not causing agglomeration, having a surface rich in mercapto active sites, slowly reducing a silver ammonia solution by utilizing a weak reducing agent glucose to obtain silver ions, wherein in the silver reduction process, the silver particles can preferentially nucleate in the active sites out of phase, and then the reduced silver crystal nuclei grow directionally on the surface of AgX, so that the AgX @ Ag core-shell material with a compact silver particle coating is formed; the principle is scientific and reliable, the prepared AgX @ Ag core-shell material synthesizes the angle from the liquid phase, the mixing degree of Ag and AgX is improved, the Ag and AgX are in coating contact, the contact degree of the Ag and AgX is greatly higher than that of mechanical mixing, and the electrode material has better contact degree and smaller electrode particles.
Description
The technical field is as follows:
the invention belongs to the technical field of electrode material preparation, and particularly relates to a preparation method of an AgX @ Ag core-shell electrode material.
Background art:
when the actual potential of the metal is measured, a standard potential serving as a reference is required, one end of a potential meter is connected with the metal to be measured, the other end of the potential meter is connected with a standard potential calibration object, the potential value of the metal to be measured can be measured, and in the process, a reference electrode is indispensable.
With the development of science and technology, the requirements on the environmental interference resistance, the monitoring accuracy and other aspects of the reference electrode are continuously improved no matter in a laboratory or engineering application, so that the working environment of the reference electrode is continuously widened, and the laboratory is expanded to various complex working environments in real engineering application, such as various harsh environments, such as a sea mud environment, underground soil, deep sea high pressure and the like. Meanwhile, the performances of the reference electrode such as service life, chemical fouling resistance, high temperature and high pressure resistance and the like are greatly improved, and the application range is expanded to a plurality of fields such as corrosion rate, polarization resistance, electrochemical impedance test, electrochemical noise and component detection and monitoring.
The Ag/AgCl reference electrode preparation method comprises the steps of preparing an Ag/AgCl all-solid-state composite reference electrode disclosed in Chinese patent 201410750796.2, preparing the Ag/AgCl reference electrode and preparing an Ag/AgCl all-solid-state composite reference electrode, wherein the preparation method comprises the steps of preparing the Ag/AgCl reference electrode and preparing an Ag/AgCl all-solid-state composite reference electrode, the preparation method comprises the steps of pretreating a silver wire, taking a silver wire 11cm in diameter of 0.6mm, sequentially polishing the silver wire by 1# to 5# abrasive paper, bending the silver wire into a spiral shape with d being 3mm, sequentially cleaning the silver wire by acetone and secondary distilled water, finally activating a silver wire 355 mol thin silver nitrate solution in 0.84 min, and activating the silver wire 355-silver nitrate thin silver solution in a thin silver wire 353 min-84 minPreparing a silver plating layer: using pretreated ring silver wire as cathode, platinum electrode as anode, and using 3.75mA/cm at room temperature2Electroplating at a current density of 7.5mA/cm for 15min2The current density electroplating is carried out for 30min, the electroplated annular silver wire is sequentially cleaned by potassium iodide solution, ammonia water and secondary distilled water, the electroplating solution is prepared by taking 3g of silver nitrate, 60g of potassium iodide and 7m L of 25 percent ammonia water to be dissolved in 100m L secondary distilled water, the chlorination of the spiral silver wire is carried out by taking the spiral silver wire as an anode, a platinum electrode as a cathode and 1 mol/L hydrochloric acid solution as electrolyte, and 0.75mA/cm is firstly carried out at room temperature2The current density of (2) is electrolyzed and chlorinated for 30min, and then the concentration of the solution is 1.5mA/cm2The Ag/AgCl all-solid-state composite reference electrode is prepared by respectively adding 60g of urea and 142g of 38% formaldehyde solution into a 500m L three-neck flask provided with a stirrer and a reflux condenser, adjusting the pH value of the mixture to 7-8 by using 2 mol/L KOH solution, heating and refluxing for 2h, adding an oil-water separator between the three-neck flask and the reflux condenser, evaporating water of 40m L to obtain slurry urea-formaldehyde resin, preparing the solid-state composite reference electrode by standing the prepared Ag/AgCl electrode at the center of a mold tube (the inner diameter is 12mm), ensuring that the bottom of the Ag/AgCl electrode is separated from the bottom end of the mold tube by l-2 mm, dripping the prepared slurry urea-formaldehyde resin, polyethylene glycol and ground KCl powder into a mixture according to the ratio of 60% urea-formaldehyde resin, 20% polyethylene glycol and 20% potassium chloride powder, fully mixing the urea-formaldehyde resin, the polyethylene glycol and the potassium chloride powder, stirring the mixture uniformly, and dripping the slurry urea-formaldehyde resin, the KCl powder and the KCl powder into a No. 5/NO skeleton material, and stirring the mixture uniformly to obtain an AgCl skeleton material, wherein the AgCl material is mixed with the mixture3After 4 drops of concentrated hydrochloric acid, the solution is quickly poured into a plastic mould tube, the plastic mould tube is placed at room temperature for 12 hours, the plastic mould tube is taken out after natural solidification, and the lower end of the plastic mould tube is polished to be smooth by 5# metallographic abrasive paper to obtain an Ag/AgCl all-solid-state combined type reference electrode; the chinese patent 201910880365.0 discloses a method for preparing a lithium ion battery reference electrode, comprising: s110, providing a lithium-philic reference electrode substrate and a current collector metal sheet adhered with a tab adhesive; s120, welding the lithium-philic reference electrode substrate to the current collector metal sheet far away from the tab glueOne end; s130, placing one end, far away from the tab glue, of the lithium-philic reference electrode substrate in molten liquid lithium for 2-5 seconds in an anhydrous and oxygen-free environment, cooling and drying, and sequentially forming an alloy layer and a lithium metal layer on the surface layer of the lithium-philic reference electrode substrate; s140, placing the lithium-philic reference electrode substrate with the alloy layer and the lithium metal layer in a first electrolyte for soaking for 1.5-2.5 hours, and forming a solid electrolyte interface film layer on the surface of the lithium metal layer, wherein the first electrolyte is a mixed solution of a secondary electrolyte and vinylene carbonate with the volume ratio concentration of 0.3-0.5%; s150, drying the lithium-philic reference electrode substrate with the solid electrolyte interface film layer to form the lithium ion battery reference electrode. However, the presence of Br in a seawater environment-Due to Br-With Cl-Produce a competitive effect, and Br-More easily react with Ag+AgBr with smaller solubility product is generated, thereby influencing the content of the effective component AgCl of the Ag/AgCl electrode and electrode reaction, further leading the potential of the electrode to drift and influencing the accuracy of the test result. In order to overcome the above-mentioned technical problems, the invented product can be mixed with Cl in seawater at the end of 20 th century-And Br-A new thermodynamically balanced solid solution of AgX (X ═ Cl, Br) is established. Experiments show that the Ag/AgX electrode has good potential stability and electrochemical performance response, small potential drift amount and small influence of light on potential, and is more suitable for marine environment.
In order to further improve the stability of the Ag/AgX electrode, the material is optimized, and the limitation of mechanical mixing is included, from the perspective of liquid phase reaction, the AgX @ Ag core-shell electrode material is prepared, so that the problem of AgX decomposition caused by illumination can be solved, Ag and AgX can be combined to the maximum extent, and the stability and the polarization resistance of the reference electrode are improved.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and develops and designs a preparation method of an AgX @ Ag core-shell electrode material so as to improve the reaction rate and the service performance of an electrode.
In order to achieve the purpose, the invention relates to a preparation method of an AgX @ Ag core-shell electrode material, which comprises the following four steps of preparing silver halide powder, pretreating the silver halide powder, preparing modified silver halide powder and preparing the core-shell material:
(1) preparing silver halide powder: cetyl trimethyl ammonium bromide and AgNO3Dissolving the solution A in deionized water to form a solution A, mixing NaCl, NaBr and deionized water to form a solution B, carrying out ultrasonic treatment on the solution A and the solution B, respectively carrying out magnetic stirring, slowly dropwise adding the solution B into the solution A, reacting for 2 hours at room temperature in a dark place, and carrying out centrifugal drying to obtain silver halide powder;
(2) pretreating silver halide powder: placing the silver halide powder prepared in the step (1) and distilled water in a beaker, performing ultrasonic treatment at room temperature, uniformly dispersing, heating in a water bath to control the temperature, slowly stirring for 10min to form a solution C, adding polyethylene glycol into the solution C, keeping the temperature control, electrically stirring for 1h, finishing the reaction, centrifuging, washing, and performing vacuum drying to finish the pretreatment of the silver halide powder;
(3) preparation of modified silver halide powder: placing the silver halide powder pretreated in the step (2), absolute ethyl alcohol and mercaptosilane coupling agent in a conical flask, performing ultrasonic treatment for 10min, refluxing for 6h under the condition of an oil bath at the temperature of 80 ℃, cooling, washing for 3 times by using ethyl alcohol, and performing vacuum drying to obtain modified silver halide powder;
(4) preparing a core-shell material: and (3) placing the modified silver halide powder prepared in the step (3), polyvinyl pyrrolidone, absolute ethyl alcohol and glucose solution in a beaker, performing ultrasonic dispersion for 10min to form a solution D, heating in a water bath, dropwise adding a silver ammonia solution into the solution D, after the reaction is stopped, respectively washing with water and absolute ethyl alcohol for several times, and performing vacuum drying to obtain the AgX @ Ag core-shell electrode material.
AgNO in solution A according to step (1) of the present invention3The mass ratio of the ammonium bromide to the hexadecyl trimethyl ammonium bromide is 2.5: 1; the mass ratio of NaCl to NaBr in the solution B is 3: 1; the ultrasonic time of the solution A and the solution B is 10-20 min; the speed and the time of magnetic stirring are respectively 900-; the process of dropwise adding the solution B into the solution A takes 10 min; the silver halide powder involved in the step (2) had a mass of 0.6g, a volume of distilled water of 100ml and a room temperatureThe ultrasonic time is 10-15min, the water bath heating is carried out to control the temperature to be 50 ℃, polyethylene glycol is polyethylene glycol-4000, the mass ratio of the polyethylene glycol to silver halide powder is 1:1, the vacuum drying temperature is 50-60 ℃, the drying time is 6-8h, the mercaptosilane coupling agent involved in the step (3) is 3-mercaptopropyltrimethoxysilane, the mass ratio of the silver halide powder, absolute ethyl alcohol and the mercaptosilane coupling agent pretreated in the step (2) is 0.5g, 120m L and 0.3m L respectively, the vacuum drying temperature is 50 ℃, the drying time is 6-8h, the mass ratio of the modified silver halide powder involved in the step (4) to polyvinyl pyrrolidone is 1:3, the absolute ethyl alcohol and glucose solutions are 30m L and 0.006 mol/L respectively, the water bath heating is carried out to control the temperature to be 50 ℃, the silver ion concentration in the silver ammonia solution is 0.006 mol/L, the time consumption is 10-20min, the vacuum drying temperature is 50-60 ℃, and the drying time is 6-8 h.
When the AgX @ Ag core-shell electrode material is prepared by the preparation method of the AgX @ Ag core-shell electrode material, firstly, polyethylene glycol is adopted to pretreat AgX powder: the polyethylene glycol molecules with the sawtooth long-chain structure are dissolved in water and then become a zigzag structure, the polyethylene glycol molecules are wound on the surface of the AgX particles, and a large number of polyethylene glycol molecules form a support to be wrapped on the AgX particles: then, mercapto silane coupling agent is adopted to carry out thinning modification on the pretreated silver halide powder: forming hydrogen bonds between one O in polyethylene glycol molecules and silicon hydroxyl in alcoholysis products of mercaptosilane coupling agent molecules; finally carrying out silver coating reaction: AgX after being pretreated by polyethylene glycol and modified by a mercapto silane coupling agent contains rich mercapto active sites, silver particles can be preferentially nucleated out of phase at the active sites in the silver reduction process, and reduced silver crystal nuclei grow directionally on the surface of the AgX, so that an AgX @ Ag core-shell material is formed; the method solves the problem that the AgX surface has no groups, and the metal silver nanoparticles are difficult to directionally deposit on the AgX surface due to the unmatched crystal lattices between the metal and the metal compound in the silver coating process.
Compared with the prior art, the method has the advantages that AgX is pretreated by using polyethylene glycol, surface modification is carried out on AgX by using a mercaptosilane coupling agent, AgX nucleation is uniformly dispersed, the appearance is regular, the granularity is small, agglomeration cannot occur, the surface is rich in mercapto active sites, a silver ammonia solution is slowly reduced by using a weak reducing agent glucose to obtain silver ions, silver particles can be preferentially nucleated out of phase at the active sites in the silver reduction process, and then the reduced silver crystal nucleus directionally grows on the AgX surface, so that a silver particle coated compact AgX @ Ag core-shell material is formed; the principle is scientific and reliable, the prepared AgX @ Ag core-shell material synthesizes the angle from the liquid phase, the mixing degree of Ag and AgX is improved, the Ag and the AgX are in coating contact, the contact degree of the Ag and the AgX is greatly higher than that of mechanical mixing, the Ag core-shell material has better contact degree and smaller electrode particles, the AgX decomposition phenomenon caused by illumination can be effectively reduced in the storage process, and a reference electrode prepared by the AgX @ Ag core-shell material has better long-term stability, smaller temperature coefficient and polarization resistance, and the integral service performance of the reference electrode is improved.
Description of the drawings:
fig. 1 is an SEM spectrum of the silver halide powder prepared in example 1 of the present invention.
FIG. 2 is an SEM spectrum of the AgX @ Ag core-shell electrode material prepared in example 1 of the invention.
Fig. 3 is IR spectra of silver halide powder prepared in example 1 of the present invention before pretreatment (a) and after pretreatment (b).
Fig. 4 is a comparison graph of the potential stability of a core-shell material electrode prepared by soaking a common powder tablet electrode and the novel core-shell material electrode prepared by the AgX @ Ag core-shell electrode material in seawater for 200 days according to the present invention in example 1.
FIG. 5 is a graph comparing the linear polarization curves of a conventional powder tablet electrode and a novel core-shell electrode prepared from the AgX @ Ag core-shell electrode material of example 1 of the present invention.
The specific implementation mode is as follows:
the invention is further described by way of example with reference to the accompanying drawings.
Example 1:
the specific process of the preparation method of the AgX @ Ag core-shell electrode material comprises four steps of preparing silver halide powder, pretreating the silver halide powder, preparing modified silver halide powder and preparing the core-shell electrode material:
(1) preparation of silver halide powder 20ml of 0.025 mol/L AgNO were added3Mixing with 0.034g of hexadecyl trimethyl ammonium bromide to form a solution A, mixing 0.03g of NaCl, 0.01g of NaBr and 20ml of deionized water to form a solution B, carrying out ultrasonic treatment on the solution A and the solution B for 10min, then respectively carrying out magnetic stirring at the speed of 900r/m for 10min, slowly dropwise adding the solution B into the solution A by using a rubber head dropper, keeping the dropwise adding process for 10min, reacting for 2 hours under the condition of keeping out of the sun at 25 ℃, and carrying out centrifugal drying to obtain silver halide powder;
(2) pre-treating silver halide powder, namely putting 0.6g of the silver halide powder prepared in the step (1) and 100m L of distilled water into a 250m L beaker, performing ultrasonic treatment at room temperature for 10min, uniformly dispersing, heating in a water bath to control the temperature to be 50 ℃, slowly stirring for 10min to form a solution C, adding 0.6g of polyethylene glycol-4000 into the solution C, keeping the temperature at 50 ℃, electrically stirring for 1h, after the reaction is finished, centrifuging, washing with water for 3 times, and performing vacuum drying at 50 ℃ to finish the pre-treatment of the silver halide powder;
(3) preparation of modified silver halide powder: placing 0.5g of the silver halide powder pretreated in the step (2), 120ml of absolute ethyl alcohol and 0.3ml of 3-mercaptopropyltrimethoxysilane into a conical flask, performing ultrasonic treatment for 10min, refluxing for 6h under the condition of an oil bath at 80 ℃, cooling, washing for 3 times by using ethyl alcohol, and performing vacuum drying at 50 ℃ to obtain modified silver halide powder;
(4) preparing a core-shell electrode material, namely putting 0.15g of the modified silver halide powder prepared in the step (3), 0.45g of polyethylene pyrrolidone, 30m L absolute ethyl alcohol and 30ml of 0.006 mol/L glucose solution into a 250ml polyethylene beaker, ultrasonically dispersing for 10min to form a solution D, heating in a water bath to control the temperature to be 50 ℃, dropwise adding 10ml of silver ammonia solution with silver ion concentration of 0.006 mol/L into the solution D, continuing the dropwise adding process for 10min, after the reaction is stopped, respectively washing with water and absolute ethyl alcohol for a plurality of times, and carrying out vacuum drying at 50 ℃ to obtain the AgX @ Ag core-shell electrode material.
The AgX @ Ag core-shell electrode material prepared in this example is prepared by a powder tabletting method to prepare a novel core-shell electrode, and is subjected to a long-term stability test in seawater together with a common powder tabletting electrode to obtain a potential stability contrast diagram as shown in fig. 4, wherein the potential range of the novel core-shell electrode is less than 3mV, and the potential range of the common powder tabletting electrode is less than 6mV, which indicates that: the stability of the novel core-shell material electrode is superior to that of a common powder pressed electrode, and the novel core-shell material electrode is more suitable for completing a long-term corrosion monitoring task in a marine environment.
The AgX @ Ag core-shell electrode material prepared in this example was prepared into a novel core-shell electrode by a powder tableting method, and was subjected to a linear polarization test with a conventional powder tableting electrode, respectively, to obtain a linear polarization curve contrast diagram as shown in fig. 5, where the polarization resistance of the novel core-shell electrode is 300 Ω · cm2Is obviously less than the polarization resistance 8454 omega cm of the common powder tabletting electrode2In the description: the novel core-shell material electrode has small polarization resistance, large exchange current density and difficult polarization, and has better polarization resistance compared with the common powder pressed sheet electrode.
Claims (6)
1. A preparation method of an AgX @ Ag core-shell electrode material is characterized in that the specific technological process comprises four steps of preparing silver halide powder, pretreating the silver halide powder, preparing modified silver halide powder and preparing the core-shell material:
(1) preparing silver halide powder: cetyl trimethyl ammonium bromide and AgNO3Dissolving the solution A in deionized water to form a solution A, mixing NaCl, NaBr and deionized water to form a solution B, carrying out ultrasonic treatment on the solution A and the solution B, respectively carrying out magnetic stirring, slowly dropwise adding the solution B into the solution A, reacting for 2 hours at room temperature in a dark place, and carrying out centrifugal drying to obtain silver halide powder;
(2) pretreating silver halide powder: placing the silver halide powder prepared in the step (1) and distilled water in a beaker, performing ultrasonic treatment at room temperature, uniformly dispersing, heating in a water bath to control the temperature, slowly stirring for 10min to form a solution C, adding polyethylene glycol into the solution C, keeping the temperature control, electrically stirring for 1h, finishing the reaction, centrifuging, washing, and performing vacuum drying to finish the pretreatment of the silver halide powder;
(3) preparation of modified silver halide powder: placing the silver halide powder pretreated in the step (2), absolute ethyl alcohol and mercaptosilane coupling agent in a conical flask, performing ultrasonic treatment for 10min, refluxing for 6h under the condition of an oil bath at the temperature of 80 ℃, cooling, washing for 3 times by using ethyl alcohol, and performing vacuum drying to obtain modified silver halide powder;
(4) preparing a core-shell material: and (3) placing the modified silver halide powder prepared in the step (3), polyvinyl pyrrolidone, absolute ethyl alcohol and glucose solution in a beaker, performing ultrasonic dispersion for 10min to form a solution D, heating in a water bath, dropwise adding a silver ammonia solution into the solution D, after the reaction is stopped, respectively washing with water and absolute ethyl alcohol for several times, and performing vacuum drying to obtain the AgX @ Ag core-shell electrode material.
2. The method for preparing AgX @ Ag core-shell electrode material according to claim 1, wherein AgNO in the solution A involved in the step (1)3The mass ratio of the ammonium bromide to the hexadecyl trimethyl ammonium bromide is 2.5: 1; the mass ratio of NaCl to NaBr in the solution B is 3: 1; the ultrasonic time of the solution A and the solution B is 10-20 min; the speed and the time of magnetic stirring are respectively 900-; the process of dropwise adding the solution B to the solution A took 10 min.
3. The preparation method of the AgX @ Ag core-shell electrode material according to claim 1, wherein the mass of the silver halide powder involved in the step (2) is 0.6g, the volume of distilled water is 100ml, the ultrasonic time at room temperature is 10-15min, the water bath heating is carried out to control the temperature at 50 ℃, the polyethylene glycol is polyethylene glycol-4000, the mass ratio of the polyethylene glycol to the silver halide powder is 1:1, the vacuum drying temperature is 50-60 ℃, and the drying time is 6-8 h.
4. The preparation method of the AgX @ Ag core-shell electrode material according to claim 1, wherein the mercaptosilane coupling agent involved in the step (3) is 3-mercaptopropyltrimethoxysilane, the silver halide powder pretreated in the step (2), the absolute ethyl alcohol and the mercaptosilane coupling agent are 0.5g, 120m L and 0.3m L respectively, the temperature of vacuum drying is 50 ℃, and the drying time is 6-8 hours.
5. The preparation method of the AgX @ Ag core-shell electrode material according to claim 1, wherein the mass ratio of the modified silver halide powder to the polyethylene pyrrolidone in the step (4) is 1:3, the mass ratio of the anhydrous ethanol solution to the glucose solution is 30m L and the mass ratio of the anhydrous ethanol solution to the glucose solution is 0.006 mol/L, the temperature is controlled to be 50 ℃ by heating in a water bath, the concentration of silver ions in the silver ammonia solution is 0.006 mol/L, the process of dropping the silver ammonia solution into the solution D takes 10-20min, the temperature of vacuum drying is 50-60 ℃, and the drying time is 6-8 h.
6. The preparation method of the AgX @ Ag core-shell electrode material according to any one of claims 1 to 5, characterized in that when preparing the AgX @ Ag core-shell material, firstly, polyethylene glycol is adopted to pretreat AgX powder: the polyethylene glycol molecules with the sawtooth long-chain structure are dissolved in water and then become a zigzag structure, the polyethylene glycol molecules are wound on the surface of the AgX particles to form a support, and the support is wrapped on the AgX particles: then, mercapto silane coupling agent is adopted to carry out thinning modification on the pretreated silver halide powder: forming hydrogen bonds between one O in polyethylene glycol molecules and silicon hydroxyl in alcoholysis products of mercaptosilane coupling agent molecules; finally carrying out silver coating reaction: AgX after being pretreated by polyethylene glycol and modified by a mercapto silane coupling agent contains rich mercapto active sites, silver particles can be preferentially nucleated out of phase at the active sites in the silver reduction process, and reduced silver crystal nuclei grow directionally on the surface of the AgX to form the AgX @ Ag core-shell material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010259163.7A CN111426732A (en) | 2020-04-03 | 2020-04-03 | Preparation method of AgX @ Ag core-shell electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010259163.7A CN111426732A (en) | 2020-04-03 | 2020-04-03 | Preparation method of AgX @ Ag core-shell electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111426732A true CN111426732A (en) | 2020-07-17 |
Family
ID=71556585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010259163.7A Pending CN111426732A (en) | 2020-04-03 | 2020-04-03 | Preparation method of AgX @ Ag core-shell electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111426732A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116549840A (en) * | 2023-07-07 | 2023-08-08 | 苏州医疗用品厂有限公司 | Processing technology for auditory vagus nerve electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1520428A (en) * | 2001-06-29 | 2004-08-11 | 陶氏环球技术公司 | Water-absorbent carboxyl-contg. polymers with low monomer content |
| CN103223488A (en) * | 2013-05-08 | 2013-07-31 | 宁波大学 | Preparation method for silver-coated silicon dioxide composite microsphere particles |
| CN104043826A (en) * | 2014-07-02 | 2014-09-17 | 广东新劲刚新材料科技股份有限公司 | Aluminum powder surface hydration processing method and application of aluminum powder in preparing Al@Ag nuclear shell composite particle conductive and electromagnetic shielding filler |
| CN108767274A (en) * | 2018-05-14 | 2018-11-06 | 东莞理工学院 | A kind of Ag/C catalyst and preparation method thereof |
-
2020
- 2020-04-03 CN CN202010259163.7A patent/CN111426732A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1520428A (en) * | 2001-06-29 | 2004-08-11 | 陶氏环球技术公司 | Water-absorbent carboxyl-contg. polymers with low monomer content |
| CN103223488A (en) * | 2013-05-08 | 2013-07-31 | 宁波大学 | Preparation method for silver-coated silicon dioxide composite microsphere particles |
| CN104043826A (en) * | 2014-07-02 | 2014-09-17 | 广东新劲刚新材料科技股份有限公司 | Aluminum powder surface hydration processing method and application of aluminum powder in preparing Al@Ag nuclear shell composite particle conductive and electromagnetic shielding filler |
| CN108767274A (en) * | 2018-05-14 | 2018-11-06 | 东莞理工学院 | A kind of Ag/C catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| VIVIANA DABOIN ET AL: "Effect of the dispersing agent on the structural and magnetic properties of CoFe2O4/SiO2 nanocomposites", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 * |
| 张宇 等: "Ag／AgX（X＝Cl，Br）核壳复合粒子的制备及表征", 《化工新型材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116549840A (en) * | 2023-07-07 | 2023-08-08 | 苏州医疗用品厂有限公司 | Processing technology for auditory vagus nerve electrode |
| CN116549840B (en) * | 2023-07-07 | 2023-10-31 | 江苏鱼跃医疗设备股份有限公司 | Processing technology for auditory vagus nerve electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Revisiting the electroplating process for lithium‐metal anodes for lithium‐metal batteries | |
| Su et al. | Printing‐scalable Ti3C2Tx MXene‐decorated Janus separator with expedited Zn2+ flux toward stabilized Zn anodes | |
| CN108130574A (en) | A kind of method of oxygen auxiliary cathode deposited metal organic framework material | |
| US9812700B2 (en) | Method for producing porous aluminum foil, porous aluminum foil, positive electrode current collector for electrical storage devices, electrode for electrical storage devices, and electrical storage device | |
| Eisenmann | Kinetics of the electrochemical reduction of dicyanoaurate | |
| CN111426732A (en) | Preparation method of AgX @ Ag core-shell electrode material | |
| CN105633180A (en) | Graphene-assisted silicon wafer wet-process texturing method | |
| CN110316715A (en) | A method of metal derived carbon photonic crystal is prepared in situ | |
| CN110048104A (en) | A kind of water system battery and preparation method thereof based on cyaniding frame material | |
| CN113013418A (en) | Alloy framework supported zinc metal cathode and preparation method and application thereof | |
| CN101525760A (en) | Electrodeposition technology for preparing electrode material of RuO2 of super capacitor | |
| CN106987871A (en) | A kind of production method of three-dimensional porous electrolytic copper foil applied to gel polymer lithium ion battery | |
| Wu et al. | Bifunctional electrolyte additive for stable Zn anode: Reconstructing solvated structure and guiding oriented growth of Zn | |
| CN110484944B (en) | Composite electrolyte for preparing corrosion-resistant surface of petroleum pipeline and preparation method for ultrasonically-assisted electro-deposition petroleum pipeline corrosion-resistant layer | |
| Majidzade et al. | Electrodeposition and Growth of Iron from an Ethylene Glycol Solution. | |
| Ding et al. | Electrochemical deposition and mechanism investigation of Prussian blue on graphic carbon paste electrode from an acidic ferricyanide solution | |
| CN113445097B (en) | Fiber mesh-shaped magnesium oxide film and preparation method and application thereof | |
| CN106337275B (en) | A kind of spherical Cu on activated carbon fibre surface2O crystal films and preparation method thereof | |
| JPH08260175A (en) | Production of zinc oxide film | |
| CN108034968A (en) | A kind of preparation method for the nano bowl noble coatings for suppressing Multipactor | |
| Jiang et al. | Temperature dependence of deposition behavior and corrosion resistance of zinc coatings electroplated on copper substrates from ethaline electrolyte | |
| US4060419A (en) | Method of forming silver halide grains by electrolysis | |
| CN108031480A (en) | BiOI optoelectronic poles prepared by a kind of step infusion process and preparation method thereof | |
| CN110714212B (en) | Method for preparing super-hydrophobic nickel film in aqueous solution system by nickel chloride one-step method | |
| Sun et al. | Preparation of highly reflective silver metallized PVC film by autocatalytic deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200717 |