Electroplating additive solution, preparation method and hard silver graphene electroplating mixed solution

Abstract

The invention discloses an electroplating additive solution, a preparation method and a hard silver graphene electroplating mixed solution. The electroplating additive solution comprises metal oxide, glycerin, alkali metal hydroxide and water. When the electroplating additive disclosed by the invention is used in an electroplating mixed solution, the metal oxide can stably and reliably refine a coating crystal and improve a cathode polarization reaction, so that the hardness of a finally formed coating is increased. The alkali metal hydroxide can react with glycerol, and a product obtained by the reaction can be complexed with the metal oxide, so that the metal oxide cannot precipitate in the electroplating mixed solution, and later electroplating is facilitated. Furthermore, when the electroplating mixed solution is used for manufacturing a plated part, the metal oxide can be uniformly dispersed in a plating layer, so that the overall hardness of the plating layer is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of electroplating, and in particular to an electroplating additive solution and a preparation method thereof, and a hard silver graphene electroplating mixed solution. Background Art

[0002] Traditional connectors are usually plated with a silver layer. With the development of technology, electroplating a silver-graphene mixed coating on the outside of the connector has become a better choice, which can further improve the conductivity of the connector. However, the number of plug-in and unplug times of the connector is high, and the hardness of the existing silver-graphene coating is low, which reduces the life of the connector. There is an urgent need for a silver-graphene coating with high hardness and good conductivity to solve this problem. Summary of the invention

[0003] In view of this, the present invention provides an electroplating additive solution and a preparation method, and a hard silver graphene electroplating mixed solution, aiming to improve the problem of low hardness of the existing silver graphene coating.

[0004] The embodiment of the present invention is implemented as follows: an electroplating additive solution includes metal oxide, glycerol, alkali metal hydroxide, and water;

[0005] The mass ratio of the metal oxide, glycerol, alkali metal hydroxide and water is 1:(1-3):(3-6):(8-15).

[0006] Optionally, in some embodiments, the metal oxide includes one or more of antimony trioxide, bismuth oxide, and manganese oxide.

[0007] Optionally, in some embodiments, the mass ratio of the metal oxide, glycerol, alkali metal hydroxide and water is 1:(1-3):(3-6):(8-15).

[0008] Accordingly, an embodiment of the present invention further provides a method for preparing the electroplating additive solution as described above, comprising:

[0009] mixing an alkali metal hydroxide with glycerol and stirring to obtain a first solution;

[0010] adding a metal oxide and water to the first solution, stirring and heating to obtain a second solution;

[0011] The second solution is allowed to stand, and the upper clear liquid is taken as the electroplating additive solution.

[0012] Optionally, in some embodiments, the stirring time of the first solution is 5-15 minutes;

[0013] The heating time of the second solution is 4-6 hours, and the heating temperature is 70-80° C.;

[0014] The second solution is allowed to stand for 4-6 hours.

[0015] Correspondingly, an embodiment of the present invention further provides a hard silver graphene electroplating mixed solution including the electroplating additive solution as described above, and the electroplating mixed solution also includes a silver salt, a complexing agent, graphene, and a dispersant.

[0016] Optionally, in some embodiments, the silver salt comprises potassium silver cyanide; and / or

[0017] The complexing agent comprises potassium cyanide; and / or

[0018] The dispersant includes one or more of benzenesulfonic acid condensate sodium salt and sulfonic acid sodium salt.

[0019] Optionally, in some embodiments, the sodium salt of benzenesulfonic acid condensate includes one or more of sodium monobenzenesulfonate condensate, sodium o-benzenesulfonate condensate, and sodium tribenzenesulfonate condensate.

[0020] Optionally, in some embodiments, the sodium sulfonate salt includes one or more of sodium 2-2-ethylhexyl sulfonate, sodium diethyl triacetate sulfonate and sodium benzene sulfonate.

[0021] Optionally, in some embodiments, the concentration of the silver salt in the electroplating mixture is 10-30 g / L; and / or

[0022] In the electroplating mixed solution, the concentration of the graphene is 0.5-4 g / L; and / or

[0023] In the electroplating mixed solution, the concentration of the dispersant is 3-7 g / L; and / or

[0024] In the electroplating mixed solution, the concentration of the electroplating additive solution is 3-10 ml / L; and / or

[0025] In the electroplating mixed solution, the concentration of the complexing agent is 155-190 g / L.

[0026] Optionally, in some embodiments, the dispersant includes a sodium salt of benzenesulfonic acid condensate at a concentration of 1-2 g / L and a sodium salt of sulfonic acid at a concentration of 2-5 g / L.

[0027] The electroplating additive of the present invention comprises metal oxide and glycerol. When the metal oxide is used in the electroplating mixed solution, the metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. The alkali metal hydroxide can react with glycerol, and the product obtained by the reaction can be complexed with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixed solution, which is convenient for later electroplating.

[0028] In addition, the electroplating mixture of the present invention contains graphene and a dispersant. After the aforementioned electroplating additive is added to the electroplating mixture, glycerol can also lubricate the graphene surface to prevent graphene from agglomerating. Glycerol and the dispersant also have a synergistic effect. The two synergistically disperse graphene and metal oxides, which not only reduces the amount of dispersant used, but also enables each ion, metal oxide and graphene to reach an ideal migration rate in the electroplating mixture, thereby facilitating the preparation of a coating with excellent thermal conductivity, electrical conductivity and hardness. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 The present invention provides a flow chart of a method for preparing an electroplating additive solution. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those skilled in the art without creative work belong to the scope of protection of the present invention. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0032] In the description of the present invention, the term "including" means "including but not limited to." The terms first, second, third, etc. are used merely as labels and do not impose numerical requirements or establish a sequence.

[0033] In the present invention, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B may represent: A exists alone, A and B exist at the same time, and B exists alone. A and B may be singular or plural.

[0034] In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0035] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0036] The technical solution of the present invention is as follows:

[0037] In a first aspect, an embodiment of the present invention provides an electroplating additive solution, which is mainly used in a hard silver graphene electroplating mixture to improve the hardness of a coating prepared using the electroplating mixture.

[0038] The electroplating additive solution of the present invention comprises metal oxides, glycerol, alkali metal hydroxides and water. Among them, the metal oxides can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. Optionally, the metal oxides include but are not limited to one or more of antimony trioxide, bismuth oxide, and manganese oxide. Alkali metal hydroxides can react with glycerol, and the product obtained by the reaction will be complexed with the metal oxides, so that the metal oxides will not precipitate in the electroplating mixture, which is convenient for later electroplating. When the electroplating mixture is used to make plated parts, silver ions, metal oxides and graphene can be synchronized and migrated in proportion, and then silver ions, metal oxides and graphene can be evenly dispersed in the coating, thereby improving the overall hardness of the coating. Optionally, alkali metal hydroxides include but are not limited to one or more of sodium hydroxide and potassium hydroxide.

[0039] In the electroplating additive solution, the mass ratio of metal oxide, glycerol, alkali metal hydroxide and water is 1:(1-3):(3-6):(8-15), for example, 1:(1-2.8):(3-5):(8-13), 1:(1-2.4):(4-6):(10-12), 1:(2-2.5):(3-4):(13-15), 1:(2-3):(5-6):(9-11), 1:(1-1.5):(3-6):(8-10), 1:(1.2-2.6):(4-5):(11-13), 1:(1.8-2.2):(3.5-4.5):(10-14), etc. Within the aforementioned ratio range, when the electroplating additive is used in the hard silver graphene electroplating mixture, the reaction product of the alkali metal hydroxide and glycerol can fully prevent the precipitation of metal oxides. Glycerol has good dispersion properties, which is conducive to the dispersion of metal oxides by glycerol and the synchronous migration of silver ions, metal oxides and graphene in proportion. The metal oxides can be evenly distributed in the coating and can stably and reliably refine the crystals of the coating, thereby increasing the hardness of the coating finally formed.

[0040] Second, see Figure 1 The present invention also provides a method for preparing an electroplating additive solution, comprising the following steps:

[0041] Step S100, mixing 3-6 parts of alkali metal hydroxide with 1-3 parts of glycerol, and stirring for 5-15 minutes to obtain a first solution;

[0042] Step S200, adding 1 part of metal oxide and 8-15 parts of water to the first solution, stirring and heating for 4-6 hours at a heating temperature of 70-80° C. to obtain a second solution;

[0043] Step S300, the second solution is allowed to stand for 4-6 hours, and the upper clear liquid is taken as the electroplating additive solution.

[0044] In this embodiment, after the alkali metal hydroxide and glycerol are mixed and reacted, the reaction product will be complexed with the metal oxide, so that the metal oxide will not be precipitated in the electroplating mixture.

[0045] In a third aspect, an embodiment of the present invention further provides a hard silver graphene electroplating mixed solution, which comprises a silver salt, a complexing agent, graphene, a dispersant and the electroplating additive solution described above.

[0046] Silver salts include, but are not limited to, potassium silver cyanide.

[0047] Complexing agents include, but are not limited to, potassium cyanide.

[0048] The dispersant includes, but is not limited to, one or more of benzenesulfonic acid condensate sodium salt and sulfonic acid sodium salt.

[0049] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of silver salt is 10-30 g / L, for example, 15-25 g / L, 10-18 g / L, 22-30 g / L, 18-23 g / L, 11-14 g / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0050] Optionally, in the electroplating mixed solution of this embodiment, the concentration of the complexing agent is 155-190 g / L, for example, 170-185 g / L, 155-165 g / L, 175-190 g / L, 175-180 g / L, 157-163 g / L, 180-190 g / L, etc. Within the above concentration range, the complexing agent is conducive to obtaining an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refining the crystallization of the coating, and improving the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0051] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of graphene is 0.5-4g / L, such as 1-3g / L, 2-4g / L, 0.5-1.5g / L, 1.8-3g / L, 2.4-3.5g / L, 3.2-4g / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0052] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of the dispersant is 3-7g / L, such as 4-6g / L, 3-4g / L, 6-7g / L, 3.5-4.5g / L, 5-6.5g / L, 3.5-4.8g / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0053] In the hard silver graphene electroplating mixed solution of this embodiment, the concentration of the electroplating additive solution is 3-10ml / L, such as 5-8ml / L, 3-5ml / L, 8-10ml / L, 4-6ml / L, 7-9ml / L, 6-7ml / L, etc. Within the above concentration range, it is beneficial to obtain an electroplating mixed solution with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and improve the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0054] Optionally, in the electroplating mixed solution of the present embodiment, the dispersant includes sodium salt of benzenesulfonic acid condensate and sodium salt of sulfonic acid. The concentration of sodium salt of benzenesulfonic acid condensate is 1-2 g / L, for example, 1-1.5 g / L, 1.5-2 g / L, 1.2-1.8 g / L, 1.4-1.6 g / L, 1.2-1.5 g / L, 1.7-2.0 g / L, etc.; the concentration of sodium salt of sulfonic acid is 2-5 g / L, for example, 3-4 g / L, 2-3 g / L, 4-5 g / L, 2.5-3.5 g / L, 3.5-4.5 g / L, 2.8-3.8 g / L, etc. Within the above concentration range, the sodium salt of benzenesulfonic acid condensate and the sodium salt of sulfonic acid can cooperate synergistically, which is beneficial to obtain a plating mixture with good dispersion of silver ions, graphene and metal oxides, effectively refine the crystallization of the coating, and enhance the cathode polarization reaction, thereby improving the hardness and wear resistance of the coating.

[0055] Optionally, the sodium salt of benzenesulfonic acid condensate includes one or more of sodium monobenzenesulfonate condensate, sodium o-benzenesulfonate condensate, and sodium tribenzenesulfonate condensate; the sodium sulfonate salt includes one or more of sodium 2-2-ethylhexylsulfonate, sodium diethyl triacetate sulfonate, and sodium benzenesulfonate.

[0056] The electroplating mixed solution of the present invention comprises a dispersant and the electroplating additive solution described above, wherein the electroplating additive solution comprises glycerol and a metal oxide. The metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. The alkali metal hydroxide can react with glycerol, and the product obtained by the reaction can be complexed with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixed solution, which is convenient for later electroplating. Furthermore, when the electroplating mixed solution is used to make plated parts, the metal oxide can be uniformly dispersed in the coating, thereby improving the hardness of the coating as a whole. Glycerol can also lubricate the graphene surface to prevent graphene from agglomerating. Glycerol and the dispersant also have a synergistic effect, and the two cooperate to disperse graphene and metal oxide, which not only reduces the amount of the dispersant, but also makes each ion, metal oxide and graphene reach an ideal migration rate in the electroplating mixed solution, thereby facilitating the preparation of a coating with excellent thermal conductivity, electrical conductivity and hardness.

[0057] In a fourth aspect, an embodiment of the present invention further provides a plated component, wherein at least one surface of the plated component is combined with a plating layer, and the plating layer is prepared by electroplating or other methods using the hard silver graphene electroplating mixture described above.

[0058] The present invention will be specifically described below through specific examples. The following examples are only partial embodiments of the present invention and are not intended to limit the present invention.

[0059] Electroplating mixed solution embodiment 1

[0060] Preparation of electroplating additive solution:

[0061] Mix 4.5 parts of potassium hydroxide with 2 parts of glycerol and stir for 5-15 minutes to obtain a first solution;

[0062] Add 1 part of metal oxide and 11 parts of water to the first solution, stir and heat for 4-6 hours at a heating temperature of 70-80° C. to obtain a second solution;

[0063] The second solution is allowed to stand for 4-6 hours, and the upper clear liquid is taken as the electroplating additive solution.

[0064] Among them, 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0065] The hard silver graphene electroplating mixed solution is prepared by using the electroplating additive solution. The hard silver graphene electroplating mixed solution includes 6 ml / L of the electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium monobenzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate.

[0066] Electroplating mixed solution embodiment 2

[0067] The electroplating mixed solution embodiment includes 8 ml / L of electroplating additive solution, 15 g / L of potassium silver cyanide, 185 g / L of potassium cyanide, 3.5 g / L of graphene, 2 g / L of sodium monobenzenesulfonate condensate, and 3 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 5 parts of potassium hydroxide, 3 parts of glycerol, and 10 parts of water, wherein 1 part of metal oxide includes 0.5 parts of antimony trioxide, 0.2 parts of bismuth oxide, and 0.3 parts of manganese oxide.

[0068] Electroplating mixed solution embodiment 3

[0069] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.6 parts of antimony trioxide and 0.4 parts of manganese oxide, and does not contain bismuth oxide.

[0070] Electroplating mixed solution embodiment 4

[0071] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.7 parts of antimony trioxide and 0.3 parts of bismuth oxide, and does not contain manganese oxide.

[0072] Electroplating mixed solution embodiment 5

[0073] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.5 parts of bismuth oxide and 0.5 parts of manganese oxide, and does not contain antimony trioxide.

[0074] Electroplating mixed solution embodiment 6

[0075] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 1 part of antimony trioxide, and does not contain bismuth oxide and manganese oxide.

[0076] Electroplating mixed solution embodiment 7

[0077] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 1 part of bismuth oxide, and does not contain antimony trioxide and manganese oxide.

[0078] Electroplating mixed solution embodiment 8

[0079] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 1 part of manganese oxide, and does not contain antimony trioxide and bismuth oxide.

[0080] Electroplating mixed solution embodiment 9

[0081] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 1 part of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0082] Electroplating mixed solution embodiment 10

[0083] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 1.5 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0084] Electroplating mixed solution embodiment 11

[0085] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2.5 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0086] Electroplating mixed solution embodiment 12

[0087] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 3 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0088] Electroplating mixed solution embodiment 13

[0089] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 6 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0090] Electroplating mixed solution embodiment 14

[0091] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 8 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0092] Electroplating mixed solution embodiment 15

[0093] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 15 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0094] Electroplating mixed solution embodiment 16

[0095] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1 g / L of sodium benzenesulfonate condensate, and 2 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0096] Electroplating mixed solution embodiment 17

[0097] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 2 g / L of sodium benzenesulfonate condensate, and 5 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0098] Electroplating mixed solution comparative example 1

[0099] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium monobenzenesulfonate condensate, and 4 g / L of 2-2 ethylhexyl sodium sulfonate; the electroplating additive solution includes 4.5 parts of potassium hydroxide and 11 parts of water. The electroplating mixed solution does not contain metal oxides and glycerol.

[0100] Electroplating mixed solution comparative example 2

[0101] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium monobenzenesulfonate condensate, and 4 g / L of 2-2 ethylhexyl sodium sulfonate; the electroplating additive solution includes 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water. The electroplating mixed solution does not contain metal oxides.

[0102] Electroplating mixed solution comparative example 3

[0103] The present electroplating mixed solution embodiment comprises 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 1.5 g / L of sodium benzenesulfonate condensate, and 4 g / L of 2-2 ethylhexyl sodium sulfonate; the electroplating additive solution comprises 1 part of metal oxide, 4.5 parts of potassium hydroxide, and 11 parts of water, wherein 1 part of metal oxide comprises 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide. The present electroplating mixed solution does not contain glycerol.

[0104] Electroplating mixed solution comparative example 4

[0105] The electroplating mixed solution embodiment includes 6 ml / L of electroplating additive solution, 22 g / L of potassium silver cyanide, 175 g / L of potassium cyanide, 2 g / L of graphene, 3 g / L of sodium benzenesulfonate condensate, and 6 g / L of 2-2-ethylhexyl sodium sulfonate; the electroplating additive solution includes 1 part of metal oxide, 4.5 parts of potassium hydroxide, 2 parts of glycerol, and 11 parts of water, wherein 1 part of metal oxide includes 0.4 parts of antimony trioxide, 0.4 parts of bismuth oxide, and 0.2 parts of manganese oxide.

[0106] Plated Example 1

[0107] At least one surface of the plated part of the present embodiment is provided with a plating layer, and the plating layer is obtained by electroplating the hard silver graphene electroplating mixed solution of the electroplating mixed solution embodiment 1 on the surface of the plated part.

[0108] Plated Parts Examples 2 to 17

[0109] Plated component embodiments 2 to 17 are substantially the same as plated component embodiment 1, except that the plating layers of plated component embodiments 2 to 17 use the hard silver graphene electroplating mixed solution of electroplating mixed solution embodiments 2 to 17.

[0110] Plated Comparative Examples 1 to 4

[0111] The plated comparative examples 1 to 4 are substantially the same as the plated example 1, except that the plated layers of the plated comparative examples 1 to 4 use the hard silver graphene electroplating mixed solution of the electroplating mixed solution comparative examples 1 to 4.

[0112] The coatings of the plated parts of the plated parts of the plated parts examples 1 to 17 and the plated parts comparison examples 1 to 4 were subjected to abrasion resistance test and hardness test, respectively, to obtain the average number of frictions and hardness that the coatings can withstand per micron. The abrasion resistance test was conducted by using a steel wool abrasion resistance tester to test the coatings; the hardness test was conducted by using a hardness tester. The test results are shown in Table 1.

[0113] Table 1:

[0114]

[0115]

[0116] From Table 1 we can see that:

[0117] Compared with the average number of frictions that can be borne per micron of the coating of the plated comparative examples 1 to 4, the average number of frictions that can be borne per micron of the coating of the plated examples 1 to 17 is higher, and the wear resistance is increased by more than 12%. The reason is that the hard silver graphene electroplating mixture used in the preparation of the coating of the plated examples 1 to 17 includes the electroplating additive solution of the present invention, and the electroplating additive solution includes alkali metal hydroxide, glycerol and metal oxide. The metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the wear resistance of the coating finally formed. The alkali metal hydroxide can react with glycerol, and the product obtained by the reaction will complex with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixture, so that the coating has good hardness.

[0118] Compared with the hardness of the coating of the plated comparative examples 1 to 4, the hardness of the coating of the plated examples 1 to 17 is higher, because the hard silver graphene electroplating mixture used in the preparation of the coating of the plated examples 1 to 17 includes the electroplating additive solution of the present invention, and the electroplating additive solution includes glycerol and metal oxide. The metal oxide can stably and reliably refine the crystallization of the coating, improve the cathode polarization reaction, and thus increase the hardness of the coating finally formed. Alkali metal hydroxide can react with glycerol, and the product obtained by the reaction will complex with the metal oxide, so that the metal oxide will not precipitate in the electroplating mixture, so that the coating has good hardness.

[0119] Compared with the plated comparative example 4, the plated layer of the plated example 1 has a higher hardness, a higher average number of frictions that the plated layer can withstand per micron, and a smaller amount of benzenesulfonic acid condensate sodium salt and sulfonic acid sodium salt is used. The reason is that the hard silver graphene electroplating mixed solution used in the preparation of the plated layer of the plated example 1 includes the electroplating additive solution of the present invention, and the electroplating additive solution includes glycerol. Glycerol and the dispersant have a synergistic effect, and the two cooperate to disperse graphene and metal oxides, which not only reduces the amount of dispersant used, but also enables each ion, metal oxide and graphene to reach an ideal migration rate in the electroplating mixed solution, thereby facilitating the preparation of a coating with excellent thermal conductivity, electrical conductivity and hardness.

[0120] The electroplating additives, electroplating additive solutions and preparation methods, and hard silver graphene electroplating mixed solutions provided in the embodiments of the present invention are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the methods of the present invention and its core ideas. At the same time, for those skilled in the art, according to the ideas of the present invention, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. An electroplating additive solution, characterized in that: The electroplating additive solution includes metal oxide, glycerol, alkali metal hydroxide and water; The mass ratio of the metal oxide, glycerol, alkali metal hydroxide and water is 1:(1-3):(3-6):(8-15).

2. The electroplating additive solution according to claim 1, characterized in that The metal oxide includes one or more of antimony trioxide, bismuth oxide, and manganese oxide.

3. A method for preparing the electroplating additive solution according to any one of claims 1 to 2, characterized in that: The method comprises: mixing an alkali metal hydroxide with glycerol and stirring to obtain a first solution; adding a metal oxide and water to the first solution, stirring and heating to obtain a second solution; The second solution is allowed to stand, and the upper clear liquid is taken as the electroplating additive solution.

4. The method for preparing the electroplating additive solution according to claim 3, characterized in that: The stirring time of the first solution is 5-15 minutes; The heating time of the second solution is 4-6 hours, and the heating temperature is 70-80° C.; The second solution is allowed to stand for 4-6 hours.

5. A hard silver graphene electroplating mixed solution comprising the electroplating additive solution according to any one of claims 1 to 2, characterized in that: The electroplating mixed solution also includes silver salt, complexing agent, graphene and dispersant.

6. The hard silver graphene electroplating mixed solution as claimed in claim 5, characterized in that: The silver salt comprises potassium silver cyanide; and / or The complexing agent comprises potassium cyanide; and / or The dispersant includes one or more of benzenesulfonic acid condensate sodium salt and sulfonic acid sodium salt.

7. The hard silver graphene electroplating mixed solution according to claim 6, characterized in that: The benzenesulfonic acid condensate sodium salt includes one or more of sodium monobenzenesulfonate condensate, sodium o-benzenesulfonate condensate, and sodium tribenzenesulfonate condensate.

8. The hard silver graphene electroplating mixed solution as claimed in claim 6, characterized in that: The sodium sulfonate salt includes one or more of sodium 2-2-ethylhexyl sulfonate, sodium diethyl triacetate sulfonate and sodium benzene sulfonate.

9. The hard silver graphene electroplating mixed solution as claimed in claim 5, characterized in that: In the electroplating mixed solution, the concentration of the silver salt is 10-30 g / L; and / or In the electroplating mixed solution, the concentration of the graphene is 0.5-4 g / L; and / or In the electroplating mixed solution, the concentration of the dispersant is 3-7 g / L; and / or In the electroplating mixed solution, the concentration of the electroplating additive solution is 3-10 ml / L; and / or In the electroplating mixed solution, the concentration of the complexing agent is 155-190 g / L.

10. The hard silver graphene electroplating mixed solution according to claim 9, characterized in that: The dispersant includes benzenesulfonic acid condensate sodium salt with a concentration of 1-2 g / L and sulfonic acid sodium salt with a concentration of 2-5 g / L.

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