CN115247273A - Method for electrodepositing silver - Google Patents
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- CN115247273A CN115247273A CN202210067561.8A CN202210067561A CN115247273A CN 115247273 A CN115247273 A CN 115247273A CN 202210067561 A CN202210067561 A CN 202210067561A CN 115247273 A CN115247273 A CN 115247273A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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Abstract
The invention relates to the technical field of electrodeposition, in particular to a method for electrodepositing silver. The method for electrodepositing silver comprises: placing the matrix in electrolyte, and performing electrodeposition by adopting a potentiostatic method to obtain a silver coating; wherein the electrolyte comprises a eutectic ionic liquid, an additive and a silver source; the additive comprises at least one of a chloride salt, a nitrogen-containing heterocyclic compound and an amine compound. The method for electrodepositing silver provided by the invention can obviously improve the quality of the prepared silver plating layer by adopting the specific electrolyte, especially adding the specific additive, so that the prepared silver plating layer is silvery white without yellowing, has proper thickness, and can enhance the bonding force and the anti-tarnishing capability of the plating layer.
Description
Technical Field
The invention relates to the technical field of electrodeposition, in particular to a method for electrodepositing silver.
Background
The metal silver has excellent corrosion resistance, lubricity, decoration, bacterial resistance, high conductivity, high catalytic performance, high sensitivity to environment and the like, and is widely applied to the fields of microelectronics, catalysts, sensors and magnetic resistance material preparation.
The nanometer material has become a hot point of research because of its unique physical and chemical properties and wide application prospect. Among them, nano silver is widely used in many fields such as ceramic materials, environmental protection materials and paints as an important functional material. The synthesis method of the nano silver comprises a chemical reduction method, an ultrasonic method, a photoreduction method, an electrochemical reduction method and the like. The electrodeposition method is suitable for a plurality of nanocrystalline materials, the electrodeposition method can be used for fast preparation, and the prepared nanocrystalline materials have stable properties. Wherein the choice of electrolyte plays a crucial role.
With the improvement of environmental protection consciousness and the proposal of green chemical concept, novel Ionic Liquid (ILs) electrolyte is highly concerned by people. The ionic liquid is a molten salt system which is composed of specific organic positive ions and inorganic negative ions and is in a liquid state at room temperature or near room temperature, and is a novel medium and a 'soft' functional material. It is used for the deposition of copper, zinc, chromium, silver and other metals and alloys because of its advantages of low melting point, wide electrochemical window, high stability, selective dissolving power and designability.
In recent years, eutectic ionic liquids (also called eutectic solvents, DESs) have unique advantages of no toxicity, low cost, high purity and the like, and become green substitutes of traditional ILs and aqueous solutions. The most common eutectic ionic liquids are based on a mixture of urea and choline chloride, with a freezing point of 12 ℃ and remain liquid at room temperature. The green and sustainable nature of this new solvent is that both its components are inexpensive, biodegradable, non-toxic, and widely used in nature. They can be easily mixed to form a high purity solvent without the need for expensive labor and equipment.
The electrolyte of the conventional aqueous solution system has complex components and needs to be added with additives such as a brightener, a main complexing agent, an auxiliary complexing agent, a flatting agent and the like. However, these organic additives make the solution components more complicated, make the solution unstable, make recovery and treatment of the plating solution difficult, and pollute the environment.
The silver plating layer obtained by the conventional eutectic ionic liquid deposition often has the problems of yellowing, poor binding force, poor anti-tarnishing capability and the like, and cannot meet the use requirement of the process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first object of the present invention is to provide a method for electrodepositing silver, which can significantly improve the quality of the prepared silver plating layer by adding a specific additive to an electrolyte, so that the prepared silver plating layer has a silver white color without yellowing and a suitable thickness, and can enhance the bonding force and discoloration resistance of the plating layer.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a method for electrodepositing silver, which comprises the following steps:
placing the matrix in electrolyte, and performing electrodeposition by adopting a constant potential method to obtain a silver coating;
wherein the electrolyte comprises a eutectic ionic liquid, an additive and a silver source;
the additive comprises at least one of a chloride salt, a nitrogen-containing heterocyclic compound and an amine compound.
In some specific embodiments of the present invention, the additive may be one selected from a chloride salt, a nitrogen-containing heterocyclic compound and an amine compound, or a mixture of any of the above.
According to the invention, the specific electrolyte is adopted, and particularly the specific additive is added, so that the quality of the prepared silver plating layer is obviously improved, the prepared silver plating layer is silvery white, has no yellowing phenomenon, and is proper in thickness; and moreover, the binding force between the plating layer and the substrate and the anti-tarnishing capability of the silver plating layer are obviously enhanced.
Meanwhile, the electrolyte provided by the invention can be repeatedly utilized, and not only can the cost be saved and the resource waste be avoided, but also the problems of complex components, difficult recovery, difficult treatment and the like of the conventional aqueous solution system electrolyte in the prior art are solved.
Specifically, the mechanism of improving the quality of the silver plating layer, enhancing the binding force between the plating layer and the substrate and the anti-tarnishing capability of the plating layer by adding a specific additive through a specific electrolyte is as follows:
the addition of specific additives makes the silver ion exist in the plating solution in the form of complex, thus, when depositing, the electrochemical polarization can be greatly displayed. And the magnitude of the electrochemical polarization is related to the energy change upon ligand conversion around the central ion. The energy change is larger when the silver complex ions mainly existing in the electrolyte are converted into the activated complex, the activation energy required during reduction is higher, the electrochemical polarization is increased, and the quality of the obtained coating is good. In addition, the additive adsorbed on the surface of the cathode and silver complex ions in the solution generate coordination reaction to form surface complex on the metal surface, the formation of the surface complex makes the discharge of the metal ions more difficult, the overvoltage of the reaction is obviously increased, which is beneficial to the formation of new crystal nucleus, and the silver crystal grains precipitated are smaller.
In addition, the silver plating layers with different crystal nucleus sizes can be obtained by adding different types and dosage of additives, so that different deposition effects can be obtained. In particular, due to Ag + Having full d 10 The electronic configuration forms an electrovalence (or external orbital) complex, and lone pair electrons of the ligand can only enter Ag + And so it is active in electron substitution reactions. The electrode reduction reaction is faster in electrode reaction kinetics, and the electrode reaction rate constant value is the highest (more than or equal to 10) value in metal ions -1 s -1 ) To greatly reduce Ag + The invention controls the growth speed and direction of crystal nucleus by adding additive and silver ion to form complex compound, so as to obtain silver plating layers with different crystal nucleus sizes and different deposition effects.
Preferably, the eutectic ionic liquid comprises at least one of a mixture of choline chloride and urea, 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium hexafluorophosphate.
The eutectic ionic liquid, also called eutectic solvent, is a two-component or three-component eutectic mixture formed by combining a hydrogen bond acceptor and a hydrogen bond donor in a certain stoichiometric ratio, and the freezing point of the eutectic ionic liquid is significantly lower than the melting point of pure substances of each component.
The eutectic ionic liquid is used as a solvent, and has the advantages of no toxicity, low cost, easy preparation, biodegradability and the like.
Preferably, the chloride salt comprises ammonium chloride and/or potassium chloride.
The chloride salt is a generic term for salts whose anion is chloride.
The invention forms [ AgCl ] by adding chloride and silver ions 2 ] -1 The complex compound can control the growth speed and direction of crystal nucleus, so as to obtain silver coatings with different crystal nucleus sizes.
And/or the nitrogen-containing heterocyclic compound comprises at least one of 5, 5-dimethylhydantoin, hydantoin and 5-methylhydantoin.
The nitrogen-containing heterocyclic compound refers to a heterocyclic compound containing a nitrogen atom. The heterocyclic compound is an organic compound having a heterocyclic structure in a molecule, and the atoms constituting the ring contain at least one heteroatom in addition to carbon atoms, and is an organic compound having the largest number, and the most common heteroatoms are nitrogen atoms, sulfur atoms and oxygen atoms.
5, 5-dimethylhydantoin of formula C 5 H 8 N 2 O 2 Also known as dimethylhydantoin, 5-dimethylimidazolidinedione, and DMH. It is mainly used as raw materials of a sterilizing disinfectant, epoxy resin and amino acid.
Hydantoin is an organic compound with the molecular formula C 3 H 4 N 2 O 2 It is mainly used in the fields of chemical industry, medicine, textile, biochemistry and the like, and is also called hydantoin and 2, 4-imidazolidinedione.
5-methyl hydantoin is a chemical substance with a molecular formula of C 4 H 6 N 2 O 2 . Also known as 5-methylhydantoin.
And/or the amine compound comprises ethylenediamine and/or ethylenediamine tetraacetic acid.
Wherein, ethylenediamine, EDA for short, and the chemical formula is C 2 H 8 N 2 It is a typical aliphatic diamine, and is colorless or yellowish oily or water-like transparent liquid.
Ethylenediaminetetraacetic acid (EDTA) is a derivative of aliphatic diamines having the formula C 10 H 16 N 2 O 8 At normal temperature and pressureAs a white powder.
The applicant unexpectedly found that the concentration of ammonium chloride affects the performance of the coating, and that the coating has good performance when the concentration of ammonium chloride is within a specific range, but the bonding force between the coating and the substrate is poor.
Therefore, the invention adopts specific additives, namely, the specific types of nitrogen-containing heterocyclic compounds and amine compounds, so that the color and the anti-tarnishing capability of the plating layer are ensured, the binding force between the plating layer and the matrix is improved, and the obtained plating layer is not easy to fall off and generate the phenomena of peeling or bubbling.
Preferably, the silver source comprises silver nitrate and/or silver chloride.
Silver nitrate is used as a silver source, and ionized silver ions and silver ions form [ AgCl ] 2 ] -1 A complex compound.
Silver chloride is used as a silver source, is an insoluble substance in an aqueous solution, but can be well dissolved into Ag in an ionic liquid system by heating and stirring + 、Cl - 。
Preferably, in the electrolyte, the molar concentration of the additive is 0.1 to 0.6mol/L.
In the present application, the concentration of the additive affects the growth rate and direction of the crystal nuclei, and thus can affect the deposition effect, such as changing the quality of the silver plating (including color and size of silver), the binding force of the plating to the substrate, and the discoloration resistance of the plating.
The molar concentration within the range is favorable for preparing the silver plating layer with more excellent performance.
Preferably, the potential used by the potentiostatic method is between-1.0 and-0.7V, including but not limited to any one of-0.95V, -0.9V, -0.85V, -0.8V, -0.75V or a range between any two.
The deposition potential can also influence the growth speed and direction of the crystal nucleus, thereby changing the electrodeposition effect.
The potential in the above range is favorable for further improving the performance of the silver plating layer.
Preferably, the time of the electrodeposition is 20-60 min; including but not limited to, a point value of any one of 25min, 30min, 35min, 40min, 45min, 50min, 55min, or a range value between any two.
Preferably, the temperature of the electrolyte during the electrodeposition is 40 to 60 ℃, including but not limited to any one of 42 ℃, 45 ℃, 48 ℃, 50 ℃, 53 ℃, 56 ℃, 59 ℃ or a range between any two.
The electrodeposition time and the temperature of the electrolyte in the electrodeposition process have certain influence on the electrodeposition effect. The performance of the silver plating layer can be further improved by adopting the electrodeposition time and the temperature of the electrolyte.
In addition, the method for electrodepositing silver provided by the invention has the advantages of low temperature of the electrolyte, low energy consumption, energy conservation and cost reduction.
Preferably, the substrate comprises a copper alloy and/or carbon steel;
preferably, the copper alloy comprises brass and/or copper.
The kind of the substrate has a great influence on the electrodeposition effect, especially the bonding force between the coating and the substrate. The substrate of the kind is adopted, which is beneficial to enhancing the binding force of the plating layer and the substrate.
Preferably, during the electrodeposition, a three-electrode system is employed;
the three-electrode system takes a substrate as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode.
The three electrodes refer to a working electrode, a reference electrode and an auxiliary electrode, and the potential difference can be more accurately controlled by adopting a three-electrode system, so that errors are reduced.
Preferably, the silver in the silver plating layer has an average particle diameter D50=0.1 to 2.5 μm, including but not limited to any one of 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.8 μm, 1.0 μm, 1.3 μm, 1.6 μm, 1.9 μm, 2 μm, 2.2 μm, 2.4 μm or a range between any two thereof.
By changing various parameters in the electrodeposition process, particularly the type and the dosage of the additive and the deposition potential, the growth speed and the growth direction of crystal nuclei can be controlled, so that silver coatings with different crystal nucleus sizes can be obtained.
In some embodiments of the present invention, the silver plating layer prepared by the present invention is micro-nano silver particles in a micro-sphere shape.
In some embodiments of the present invention, the method for preparing the electrolyte comprises: after choline chloride and urea are uniformly mixed, a silver source and an additive are sequentially added into the mixture;
preferably, in the process of uniformly mixing choline chloride and urea, the temperature of the mixed materials is 70-90 ℃; including but not limited to values of any one of 72 ℃, 75 ℃, 77 ℃, 80 ℃, 85 ℃, 88 ℃ or ranges between any two.
Preferably, the choline chloride and the urea are mixed uniformly by stirring.
More preferably, the rotation speed of the stirring is 400-600 r/min, including but not limited to the point value of any one of 450r/min, 500r/min, 550r/min or the range value between any two.
More preferably, the stirring time is 2 to 5 hours, including but not limited to the point value of any one of 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or the range value between any two.
Preferably, in the mixture of choline chloride and urea, the molar ratio of choline chloride to urea is 1; more preferably 1.
In some specific embodiments of the present invention, the substrate is pretreated, and the pretreatment specifically includes: and sequentially polishing, washing and activating the substrate.
Preferably, the grinding specifically comprises: sequentially adopting sand paper with the meshes of 240 meshes, 400 meshes, 1200 meshes and 2000 meshes for polishing;
preferably, the washing is performed with water; more preferably, the water comprises deionized water;
preferably, the activating liquid used for activating is acid liquid;
preferably, the acid solution comprises dilute hydrochloric acid and/or dilute sulfuric acid;
preferably, the time of activation is 20 to 60s, including but not limited to 25s, 30s, 35s, 40s, 45s, 50s, 55s, any one of the point values or any range of values therebetween.
In some specific embodiments of the present invention, after the activating, the method further comprises the following steps: carrying out ultrasonic treatment on the activated working electrode, and then washing with water;
preferably, the frequency of the ultrasonic waves is 20 to 40kHz, including but not limited to the point value of any one of 25kHz, 30kHz, 35kHz, 38kHz or the range value between any two.
Preferably, the time of the ultrasonic treatment is 5 to 30min, including but not limited to a point value of any one of 10min, 15min, 20min, 25min or a range value between any two.
Through the pretreatment of the substrate, impurities on the surface of the substrate can be removed, so that the surface of the substrate is smooth, uniform and clean.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for electrodepositing silver, the electrolyte with a specific composition is adopted, and particularly, the specific additive is added, so that the quality of the prepared silver coating can be obviously improved, the prepared silver coating is silvery white in color and appropriate in thickness, the binding force between the coating and a substrate can be enhanced, and the tarnish resistance of the silver coating is enhanced.
(2) According to the method for electrodepositing silver, the silver coatings with different crystal nucleus sizes can be obtained by changing the types and the use amounts of the additives, and the deposition effect is changed.
(3) The method for electrodepositing silver provided by the invention can change the deposition effect by changing the deposition potential used by the potentiostatic method.
(4) The method for electrodepositing silver, provided by the invention, has the advantages of no toxicity, low cost, easiness in preparation, biodegradability and the like, and can be recycled, so that the preparation cost and the treatment cost are saved, and the resource waste is avoided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of a silver plating layer prepared in example 1 provided by the present invention;
FIG. 2 is an EDX chart of silver plating made in example 1 provided by the present invention;
FIG. 3 is an SEM image of a silver plating prepared in example 1 provided by the invention;
FIG. 4 is an XRD pattern of a silver deposit prepared according to comparative example 1 of the present invention;
FIG. 5 is an EDX chart of a silver plating layer prepared in comparative example 1 according to the present invention;
fig. 6 is an SEM image of the silver plating layer prepared in comparative example 1 provided by the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
The method for electrodepositing silver provided by the embodiment comprises the following steps:
(1) 13.9g of choline chloride and 12g of urinePlacing the element (the mol ratio of choline chloride to urea is 1: 2) in a beaker, uniformly mixing, then placing in a 70 ℃ oil bath kettle, and continuously stirring (the stirring speed is 500 r/min) until the mixture is transparent and clear to obtain eutectic ionic liquid; then 0.82g of silver nitrate and 0.4g of NH were added thereto in this order 4 Cl, and stirring uniformly to obtain an electrolyte (NH in the electrolyte) 4 The molar concentration of Cl is 0.3 mol/L);
(2) Sequentially polishing the brass matrix by using 240-mesh, 400-mesh, 1200-mesh and 2000-mesh sand paper, cleaning by using deionized water, and then putting the brass matrix into a mixed solution of dilute hydrochloric acid and dilute sulfuric acid at room temperature for activation for 30s; then ultrasonically cleaning for 10min (the frequency of the ultrasonic wave is 28 kHz) at room temperature, and then cleaning by using deionized water to obtain a pretreated brass matrix;
(3) Adopting a three-electrode system, taking the preprocessed brass matrix obtained in the step (2) as a working electrode, an Ag/AgCl electrode as a reference electrode, and a platinum electrode as an auxiliary electrode; performing electrodeposition by constant potential method at-0.8V, 50 deg.C and 30min; and after the deposition is finished, obtaining a silver plating layer on the surface of the substrate.
Example 2
This example provides a method for electrodepositing silver that is substantially the same as example 1, except that, in step (1), NH is added 4 The amount of Cl added was replaced with 0.82g, NH in the electrolyte 4 The molar concentration of Cl was 0.6mol/L.
Example 3
This example provides a method of electrodepositing silver that is substantially the same as example 1, except that in step (1), NH is added 4 The amount of Cl added was replaced with 0.13g, namely NH in the electrolyte 4 The molar concentration of Cl was 0.1mol/L.
Example 4
This example provides a method for electrodepositing silver that is substantially the same as that of example 1, except that in step (1), an additive NH is added 4 Cl was replaced with DMH (molar concentration of DMH in electrolyte solution was 0.8 mol/L).
Example 5
This embodiment is carriedThe method for electrodepositing silver was substantially the same as in example 1 except that in step (1), an additive NH was added 4 Cl was replaced with EDTA (molar concentration of EDTA in the electrolyte was 0.075 mol/L).
Example 6
This example provides a method of electrodepositing silver that is substantially the same as that of example 1, except that in step (1), 0.4g of NH was added 4 Cl was replaced with a mixture of 2.56g DMH and 0.18g EDTA.
Example 7
Example the method of electrodepositing silver provided is essentially the same as in example 1, except that in step (1), 0.4g of NH was added 4 Cl was replaced by a mixture of 1.96g hydantoin and 0.037g ethylenediamine.
Comparative example 1
This comparative example provides a method for electrodepositing silver that is essentially the same as example 1, except that in step (1), no NH is added 4 Cl。
Comparative example 2
This comparative example provides a method of electrodepositing silver that is substantially the same as example 6, except that in step (3), the deposition potential is replaced with-0.6V.
Comparative example 3
This comparative example provides a method of electrodepositing silver that is substantially the same as example 6, except that in step (3), the deposition potential is replaced with-1.5V.
Comparative example 4
This comparative example provides a method of electrodepositing silver that is substantially the same as example 6 except that in step (2), the substrate is replaced with a nickel sheet.
Experimental example 1
The silver plating layer obtained in example 1 was examined by XRD, EDX and SEM, and the results are shown in fig. 1, 2 and 3, respectively. Wherein, fig. 1 is an XRD pattern of the silver plating layer prepared in example 1 provided by the present invention (example 1, i.e. example 1, marked in fig. 1); FIG. 2 is an EDX chart of silver plating made by example 1 provided by the present invention (example 1, identified in FIG. 2); FIG. 3 is an SEM image of a silver plating prepared in example 1 provided by the present invention.
As can be seen from FIGS. 1, 2 and 3, in example 1 of the present invention, micro-spherical silver particles were obtained after electrodeposition, and XRD results showed that the plating layer consisted of pure silver and a trace amount of AgO 2 Due to trace water reduction and decomposition of AgOH. The EDX results show that the mass percent of silver is 97%. It can be seen that silver plating having a microspherical shape and high purity was produced in inventive example 1.
The silver plating layer obtained in comparative example 1 was subjected to XRD, EDX and SEM examinations, and the results are shown in fig. 4, 5 and 6, respectively. Wherein, FIG. 4 is an XRD pattern of the silver plating layer prepared in comparative example 1 provided by the present invention; FIG. 5 is an EDX chart of a silver plating prepared by comparative example 1 according to the present invention; fig. 6 is an SEM image of the silver plating layer prepared in comparative example 1 provided by the present invention.
As can be seen from fig. 4, 5 and 6, the dendritic silver is obtained by electrodeposition in comparative example 1, and the bonding force of the plating layer is deteriorated and the plating layer is not uniform due to the dispersed structural characteristics of the dendritic silver. Meanwhile, the XRD result of comparative example 1 shows that the plating layer is composed of pure silver; EDX results show that the silver mass percentage is 84% due to the thinner plating. It can be seen that the silver plating obtained in comparative example 1 is not only of low purity but also dendritic.
Experimental example 2
The appearance (including color and thickness), discoloration resistance, and bonding force between the plating layer and the substrate of the silver plating layers prepared in the above examples and comparative examples were measured and counted, and the results are respectively shown in table 1 below.
TABLE 1 test results of appearance, discoloration resistance, and bonding force of silver plating layers of each group
It can be seen by comparing example 1 with comparative example 1 in table 1 that the addition of ammonium chloride increases the thickness of the plating layer and the discoloration resistance is enhanced. It can be seen by comparing examples 1, 2 and 3 that the concentration of ammonium chloride has an influence on the performance of the plating layer, and when the concentration of ammonium chloride is 0.3mol/L, the plating layer has the best performance, but the bonding force of the plating layer and the substrate is poor.
In contrast, in examples 4, 5, 6 and 7, the bonding force between the plating layer and the substrate is improved to some extent after the types of the additives are changed, and the performance of the plating layer is improved. In particular, in example 6, DMH is used as a main complexing agent, and EDTA is used as an auxiliary complexing agent, so that the performance of the plating layer can be improved to the greatest extent.
However, when example 6 is compared with comparative examples 2, 3 and 4, it can be seen that the plating performance is reduced at high or low potential, and no plating layer is formed when nickel sheet is used as a deposition substrate. It can be seen that both the deposition potential and the type of substrate have an effect on the properties of the coating. The adoption of the deposition potential and the matrix provided by the invention is beneficial to further improving the performance of the plating layer.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (10)
1. A method of electrodepositing silver comprising the steps of:
placing the matrix in electrolyte, and performing electrodeposition by adopting a potentiostatic method to obtain a silver coating;
wherein the electrolyte comprises a eutectic ionic liquid, an additive and a silver source;
the additive comprises at least one of a chloride salt, a nitrogen-containing heterocyclic compound and an amine compound.
2. The method of electrodepositing silver according to claim 1, wherein the eutectic ionic liquid comprises at least one of a mixture of choline chloride and urea, 1-ethyl-3-methylimidazolium tetrafluoroborate, and 1-ethyl-3-methylimidazolium hexafluorophosphate.
3. The method of electrodepositing silver according to claim 1, wherein the chloride salt comprises ammonium chloride and/or potassium chloride;
and/or the nitrogen-containing heterocyclic compound comprises at least one of 5, 5-dimethylhydantoin, hydantoin, and 5-methylhydantoin;
and/or the amine compound comprises ethylenediamine and/or ethylenediamine tetraacetic acid.
4. The method of electrodepositing silver of claim 1, wherein the silver source comprises silver nitrate and/or silver chloride.
5. The method of electrodepositing silver according to claim 1, wherein the additive is present in the electrolyte at a molar concentration of 0.1 to 0.6mol/L.
6. The method of electrodepositing silver according to any one of claims 1 to 5, wherein the potentiostatic method uses a potential of from-1.0 to-0.7V.
7. The method of electrodepositing silver according to any one of claims 1 to 5, wherein the time of electrodeposition is 20 to 60min;
preferably, the temperature of the electrolyte during the electrodeposition is 40 to 60 ℃.
8. The method of electrodepositing silver according to any one of claims 1 to 5, wherein the substrate comprises a copper alloy and/or carbon steel;
preferably, the copper alloy comprises brass and/or copper.
9. The method of electrodepositing silver according to any one of claims 1 to 5, wherein during the electrodeposition, a three electrode system is employed;
the three-electrode system takes a substrate as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode.
10. The method for electrodepositing silver according to any one of claims 1 to 5, wherein the silver in the silver plating layer has an average particle diameter D50=0.1 to 2.5 μm.
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