CN217007103U - Boundary-limited electrolytic cell device of symmetric four-electrode system - Google Patents
Boundary-limited electrolytic cell device of symmetric four-electrode system Download PDFInfo
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- CN217007103U CN217007103U CN202220432634.4U CN202220432634U CN217007103U CN 217007103 U CN217007103 U CN 217007103U CN 202220432634 U CN202220432634 U CN 202220432634U CN 217007103 U CN217007103 U CN 217007103U
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Abstract
The utility model provides a boundary-limited electrolytic cell device of a symmetrical four-electrode system, which comprises an electrolytic cell body, an electrolytic cell sealing cover, a working electrode, two auxiliary electrodes, a reference electrode and two spacers. The utility model limits the movement space of particles in the electrolytic cell solution to the maximum extent by simply improving the common three-electrode electrolytic cell device, namely symmetrically arranging the auxiliary electrode, the spacer and the like, and forms two symmetrical boundary-limited effective solution areas, thereby ensuring that the thicknesses of the same corresponding positions on the front side and the back side of a deposition layer (or a plating layer and a chemical reaction layer) on a working electrode pole piece are the same, meanwhile, different areas on the same side are also the same, and greatly improving the uniformity of the deposition layer (the plating layer and the chemical reaction layer). The utility model can be used in the fields of electrochemical deposition, electroplating, electrophoretic deposition, electrochemical testing and the like. The device has the characteristics of good repeatability and uniformity of test results, strong operability and wide applicability.
Description
Technical Field
The utility model belongs to the technical field of electrochemical deposition, electroplating, electrophoretic deposition and electrochemical testing, and particularly relates to a boundary-limited electrolytic cell device of a symmetrical four-electrode system.
Background
Electrochemical deposition or electroplating refers to a process in which a metal or alloy or metal compound is deposited on the surface of an electrode from an aqueous solution, a non-aqueous solution or a molten salt of the compound through an oxidation-reduction reaction under the action of an electric field. Electrophoretic deposition refers to the process of dispersing charged colloidal particles in a medium, making directional movement towards a cathode or an anode under the action of electrostatic force of an electric field, and depositing on the surface of an electrode. Deposition from a compound solution is a common material synthesis mode, and electrochemical tests are generally carried out by using a three-electrode (working electrode, auxiliary electrode and reference electrode) system device after the materials are synthesized. The relative position and number of electrodes, the surface condition of the pole pieces, the spatial distribution of particles in the compound solution, the properties of the solution itself, and electrical parameters all contribute to the quality of the deposited product. The electrolytic cell used for deposition is usually found in the common cylindrical glass container, and even the square electrolytic cell made by order has the defects of high cost, fixed size, single function and the like. The reason is that the existing common three-electrode system electrolytic cell device only has one auxiliary electrode on one side, and the electric field intensity of one side of the working electrode, which is just opposite to the auxiliary electrode, is stronger than that of the other side of the working electrode; meanwhile, particles in the solution around the working electrode can be randomly and linearly diffused and transferred, and the particles in the region outside the region just opposite to the surface of the electrode pole piece in the compound solution move to the edge of the pole piece and are closer to the middle of the pole piece than the particles in the region just opposite to the surface of the electrode pole piece.
Disclosure of Invention
In order to solve the problems that one side of a pole piece, which faces an auxiliary electrode, is thicker than a settled layer at the same position of a back-to-back side, and the settled layer is thicker and thicker on each side, which is closer to the edge of the pole piece, in the prior art, the utility model provides a boundary-limited electrolytic cell device of a symmetrical four-electrode system, which can ensure that two symmetrical effective solution areas separated by the device during use are uniform electric fields and symmetrically distributed, can change the material and the size of the pole piece simultaneously, and can perform corresponding electrode setting (four electrodes are used for deposition or electroplating, and three electrodes are used for electrochemical tests) according to the use requirements. The device improves the uniformity of the thickness of the deposited layer and the operability of the device by simply improving the common electrolytic cell.
In order to realize the aim of the utility model, the utility model provides a boundary-limited electrolytic cell device of a symmetrical four-electrode system, which comprises an electrolytic cell body, an electrolytic cell sealing cover, a working electrode, two auxiliary electrodes, a reference electrode and two spacers;
the electrolytic cell sealing cover is arranged at the opening of the electrolytic cell body, and the electrolytic cell body can contain solution;
the working electrode, the two auxiliary electrodes, the reference electrode and the spacer are all positioned in the electrolytic cell body, and the top ends of the working electrode, the two auxiliary electrodes and the reference electrode can penetrate out of the electrolytic cell sealing cover;
the working electrode and the two auxiliary electrodes respectively comprise pole pieces positioned in the electrolytic cell body;
the two spacers are arranged oppositely, the pole pieces of the working electrode and the two auxiliary electrodes are positioned in the two spacers, the pole pieces of the two auxiliary electrodes are symmetrically arranged on two sides of the pole piece of the working electrode, and the side walls on two sides of the pole piece of the working electrode and the two auxiliary electrodes are uniformly contacted with the inner walls of the two spacers respectively, so that two symmetrical solution areas are formed on two sides of the pole piece of the working electrode and are used for forming two electric field areas with equal strength and opposite electric field lines.
Furthermore, the working electrode and the auxiliary electrode both comprise an electrode rod, a conductive metal core, a clamp for fixing the electrode plate and the electrode plate, the conductive metal core is positioned in the electrode rod, and the electrode plate is fixed at the bottom end of the electrode rod through the clamp for fixing the electrode plate.
Furthermore, each pole piece is perpendicular to the two spacers, the distance between the two spacers is equal to the width of the pole piece, the length of the two spacers is larger than the distance between the two auxiliary electrodes, and the height of the two spacers is not smaller than the distance from the bottom of the clamp for fixing the pole piece to the inner wall of the bottom of the electrolytic cell body.
Further, when the device is used, the height of the solution is smaller than the distance from the bottom of the clamp for fixing the pole piece to the bottom of the inner wall of the electrolytic cell.
Furthermore, four through holes are formed in the electrolytic cell sealing cover, wherein a through hole is formed in the center of the electrolytic cell sealing cover, the other two through holes are symmetrically distributed on two sides of the center through hole, the diameter of the fourth through hole is slightly larger than the outer diameter of the electrode rod in the center vertical direction of the line segment connected with the other three through holes. And the electrode rods of the working electrode, the two auxiliary electrodes and the reference electrode are respectively inserted into the four through holes.
Further, working electrode and auxiliary electrode all still include rubber circle for the fixed depth, and the cover is equipped with the rubber circle for the fixed depth that is used for adjusting electrode rod depth of insertion on the every electrode rod outer wall. The depth of insertion is fixed by a rubber ring.
Furthermore, the bottoms of the pole pieces of the working electrode and the two auxiliary electrodes are both contacted with the inner wall of the bottom of the electrolytic cell body. The bottom solution barrier of the pole piece is formed by contact with the bottom.
And the bottom spacers are positioned at the bottoms of the pole pieces of the working electrode and the two auxiliary electrodes and are in contact with the bottoms of the pole pieces. The bottom solution barrier of the pole piece is formed by arranging a bottom spacer which is in contact with the pole piece.
Furthermore, the pole pieces of the working electrode and the two auxiliary electrodes are rectangular, and the size of each pole piece is the same. The pole piece shape is not limited to the rectangle, can be according to actual conditions and decide, nevertheless for convenient follow-up just separate the pole piece to the solution resistance outside the region, form two symmetries with the equal wide cuboid effective electrochemical deposition (electroplating, electrophoresis) solution region of pole piece, through forming the separation of left and right sides with two spacers promptly, form the bottom separation at the bottom of the contact electrolytic bath inner wall below the pole piece, the pole piece top is then realized through the anchor clamps bottom for the control liquid level is no longer than fixed pole piece. Therefore, the cost and precision of the curved surface processing of the diaphragm and the bottom of the inner wall of the electrolytic cell are limited, and the rectangular pole piece is selected to be the simplest and feasible.
Further, the device can be used in the fields of electrochemical deposition, electrophoretic deposition, electroplating and electrochemical testing, when the device is used for the electrochemical deposition and the electrophoretic deposition, the electrode piece of the auxiliary electrode adopts an inert conductive electrode piece, and when the device is used for the electroplating, the electrode piece of the auxiliary electrode adopts the inert conductive electrode piece or a metal piece which is the same as the plating metal to be electroplated. The metal sheet is used for keeping the concentration of the metal ions to be plated in the solution stable within a certain range.
Furthermore, the electrolytic cell body and the partition sheet are made of insulating, chemical corrosion resistant, easy-to-machine and low-cost materials. Such as polytetrafluoroethylene, glass, etc.; the electrolytic cell sealing cover needs to be perforated, so that polytetrafluoroethylene materials are mostly selected; transparent glass materials are mostly used for the electrolytic cell body and the partition pieces, and the internal condition of the electrolytic cell device is convenient to observe.
Compared with the prior art, the utility model has the following beneficial effects:
two identical auxiliary electrodes are symmetrically arranged at two sides of the working electrode, so that two electric field areas with equal strength and opposite electric field line directions can be formed; by using three pole pieces, placing spacers on two sides of the pole pieces in a close manner, contacting the bottom of the inner wall of the bottom of the electrolytic cell body by the pole pieces and limiting the height of the liquid level of the solution, an effective solution area with the same width as the pole pieces can be formed. Finally, the thickness of the deposition layers on the two surfaces of the pole piece is ensured to be uniform. Meanwhile, the device can adjust the material and the size of the pole piece according to the use requirement. The quality of the deposition layer is high, the operability of the device is strong, and the applicability is wide.
Drawings
FIG. 1 is a schematic view of the overall construction of the electrolytic cell device of the present invention (solution not shown in the figure);
FIG. 2 is a schematic view of the construction of the working/auxiliary electrodes in the electrolytic cell unit of the present invention;
FIG. 3 is a schematic of a three-dimensional view and the overall structure of the working/auxiliary electrode structure in the electrolytic cell unit of the present invention;
FIG. 4.1 is a schematic three-dimensional view and configuration of the four-electrode, cover-position layout of the cell assembly of the present invention;
FIG. 4.2 is a schematic diagram of the three-dimensional view and the structure of the position layout of the cell body and the partition in the electrolytic cell device of the utility model;
FIG. 5 is a schematic diagram showing the results of pole piece deposition simulation of a conventional three-electrode cell apparatus, wherein (a) shows the overall electrode position layout of the apparatus; (b) the schematic diagram shows the thickness distribution of the deposition layer on the front surface of the working pole piece; (c) the schematic diagram shows the thickness distribution of the deposition layer on the back of the working pole piece; (d) showing a conventional electrolytic cell deposition apparatus (solution shown in figure d);
FIG. 6 is a diagram showing the simulation result of pole piece deposition, wherein (a) shows the layout of the overall electrode position of the device; (b) the schematic diagram shows the thickness distribution of the deposition layer on the front surface of the working pole piece; (c) the schematic diagram shows the thickness distribution of the deposition layer on the back of the working pole piece; (d) showing the electrolytic cell deposition apparatus of the present invention (solution is shown in the figure d);
in the figure: 1 a working electrode; 2 an auxiliary electrode; 3 a reference electrode; 4, sealing the electrolytic cell; 5, a pool body of the electrolytic pool; 6 spacer; 11 a conductive metal core; 12 rubber ring for fixing depth; 13 electrode rods; 14 fixing the pole piece fixture; 15 electrode pieces.
Detailed Description
The technical solution in the embodiment of the present invention is clearly and completely described below with reference to the accompanying drawings of the present invention.
Referring to fig. 1-6, the present invention provides a boundary-limiting type electrolytic cell device with a symmetrical four-electrode system, comprising: the device comprises a working electrode 1, two auxiliary electrodes 2, a reference electrode 3, an electrolytic cell sealing cover 4, an electrolytic cell body 5 and two separation sheets 6.
The electrolytic cell sealing cover 4 is arranged at the opening of the electrolytic cell body 5, and the electrolytic cell body 5 can contain solution therein; the working electrode 1, the two auxiliary electrodes 2, the reference electrode 3 and the spacer 6 are all positioned in the electrolytic cell body 5, and the top ends of the working electrode 1, the two auxiliary electrodes 2 and the reference electrode 3 can penetrate out of the electrolytic cell sealing cover 4; the working electrode 1 and the two auxiliary electrodes 2 both comprise pole pieces positioned in the electrolytic cell body 5; wherein, two spacers 6 set up relatively, and the pole piece of working electrode 1 and two auxiliary electrode 2 is located two spacers 6, and the pole piece symmetry of two auxiliary electrode 2 sets up in the pole piece both sides of working electrode 1, and the lateral wall of the pole piece of working electrode 1 and two auxiliary electrode 2 is equallyd divide and is do not contacted with the inner wall of two spacers 6 to form two symmetrical boundary limit type effective solution regions in the pole piece both sides of working electrode 1.
In some embodiments of the present invention, the working electrode 1 and the auxiliary electrode 2 have the same structure, and each of the working electrode and the auxiliary electrode includes an electrode rod 13, a conductive metal core 11, a pole piece fixing clamp 14, an electrode pole piece 15, and a depth fixing rubber ring 12, the conductive metal core 11 is located in the electrode rod 13, the electrode pole piece 15 is fixed at the bottom end of the electrode rod 13 by the pole piece fixing clamp 14, and the outer wall of each electrode rod 13 is sleeved with the depth fixing rubber ring 12 for adjusting the insertion depth of the electrode rod 13.
In the utility model, four through holes are arranged on the electrolytic cell cover 4, the diameter of each through hole is slightly larger than the outer diameter of the electrode rod 13, in some embodiments of the utility model, one through hole is positioned at the center of the electrolytic cell cover 4, the other two through holes are symmetrically distributed on two sides of the center through hole, the fourth through hole is positioned in the vertical direction of the center of the line segment connected with the other three through holes, the electrode rod of the working electrode 1 penetrates out of the through hole positioned in the center, the electrode rods of the two auxiliary electrodes 2 respectively penetrate out of the two through holes symmetrically distributed on two sides of the center through hole, and the electrode rod of the reference electrode 3 penetrates out of the fourth through hole.
In some embodiments of the utility model, the working electrode 1 and the two auxiliary electrodes 2 are rectangular, and the electrode plates have the same size, equal width and equal height, the distance between the two spacers 6 is equal to the width of the electrode plate, the length is greater than the distance between the two auxiliary electrodes 2, the height is not less than the distance from the bottom of the fixture 14 for fixing the electrode plates to the bottom of the inner wall of the electrolytic cell body 5, the electrode plates are perpendicular to and in contact with the two spacers 6, the electrode plate of the working electrode 1 and the electrode plates of the auxiliary electrodes 2 on the two sides are arranged in parallel and opposite, and the bottoms of the three are in contact with the inner wall of the bottom of the electrolytic cell body 5. The left side barrier and the right side barrier are formed by two spacers 6, the lower part of the pole piece is contacted with the inner wall of the bottom of the electrolytic cell body 5 to form the bottom barrier, the liquid level of the upper part of the pole piece is controlled not to exceed the bottom of the clamp 14 for fixing the pole piece, and therefore two symmetrical cuboid effective electrochemical deposition, electroplating and electrophoretic deposition solution areas which are as wide as the pole piece are formed. In other embodiments, a bottom spacer can be further arranged in the electrolytic cell body 5, and the bottom spacer is positioned at the bottom of the pole pieces of the working electrode 1 and the two auxiliary electrodes 2 and is in contact with the bottom of each pole piece, so that a bottom barrier is formed, and two symmetrical boundary-limited effective solution areas can be finally formed.
In some embodiments of the utility model, the height of the solution when the device is used is smaller than the distance from the bottom of the clamp 14 for fixing the pole piece to the bottom of the inner wall of the electrolytic cell body 5. If the electrode holder is made of a conductive material (such as stainless steel), the liquid level exceeds the bottom of the pole piece fixing clamp 14, so that a deposition layer or a plating layer is also formed on the working electrode holder, and the auxiliary electrode holder is electrolytically corroded; if the electrode holder is made of an insulating material (such as teflon), the liquid level exceeds the bottom of the pole piece fixing clamp 14, after deposition or electroplating, no deposition layer or plating layer is left in the pole piece clamping area, the pole piece area above the bottom of the pole piece fixing clamp 14 has defects, and the pole piece in the area cannot be used, so that the liquid level is controlled not to exceed the bottom of the pole piece fixing clamp 14.
The electrolytic cell cover 4, the electrolytic cell body 5 and the spacers 6 are made of insulating, chemically resistant, easily formed and inexpensive materials. In some embodiments of the present invention, the cover 4 is made of teflon to facilitate the hole drilling, and the body 5 and the spacer 6 are made of transparent glass to facilitate the observation of the internal conditions of the electrolytic cell device, and the cost is lower than that of teflon.
The shapes of the electrolytic cell body and the sealing cover are not limited, as long as the electrolytic cell body and the sealing cover can accommodate the electrodes and the spacers and can contain solution with certain depth, and the electrolytic cell can be cylindrical, square or other various electrolytic cells with indefinite shapes.
In some of the embodiments of the present invention, the electrode rod 13 is a teflon electrode rod or a stainless steel electrode rod. The material of the clamp 14 for fixing the pole piece is polytetrafluoroethylene or stainless steel.
In some embodiments of the present invention, the boundary-limited electrolytic cell device with a symmetric four-electrode system can be applied to the fields of electrochemical deposition, electrophoretic deposition, electroplating and electrochemical testing, when the boundary-limited electrolytic cell device is used for electrochemical deposition and electrophoretic deposition, the auxiliary electrode 2 uses an inert conductive electrode piece as a pole piece, and when the boundary-limited electrolytic cell device is used for electroplating, the auxiliary electrode 2 uses an inert conductive pole piece or a metal piece that is the same as the plating metal to be electroplated as a pole piece. When used in an electrochemical test, the electrochemical test can be performed using three of the electrodes (working electrode, one auxiliary electrode, reference electrode).
Through adopting the device that the aforementioned embodiment provided, the device has improved ordinary three-electrode electrolytic cell device simply, symmetry sets up auxiliary electrode and spacer etc. promptly, restrict the motion of the particle in the electrolytic cell solution to the greatest extent, form two symmetries and the cuboid effective solution area that the pole piece is the same wide, thereby make the thickness of the same corresponding position of positive and negative two sides of sedimentary deposit (or cladding coating, the chemical reaction layer takes place) on the working electrode pole piece the same, different regions on the same face are also the same simultaneously, very big improvement the homogeneity of sedimentary deposit (cladding coating, chemical reaction layer). The utility model can realize the relative fixation of the electrode positions, the rapid assembly and the depth adjustment of four electrodes, and keep the working surfaces of the working electrode pole piece and the auxiliary electrode pole pieces symmetrically arranged at two sides opposite and parallel; the size of the spacer depends on the size and the interval of the electrode pole pieces, the material and the size of the electrode pole pieces are adjustable, and the device can be used in the fields of electrochemical deposition, electroplating, electrophoretic deposition, electrochemical test and the like, and has the characteristics of good repeatability and uniformity of test results, strong operability of the device and wide applicability.
The thickness distribution results of the deposition layers or the plating layers on the front and the back surfaces of the working electrode pole piece are obtained through COMSOL simulation deposition or electroplating process, and after the common three-electrode electrolytic cell device is used for deposition or electroplating, as shown in figure 5 (the upper color and the lower color on the working electrode pole piece are not centrosymmetric, because the device controls the liquid level height when in use, and the rest directions of the pole piece are not isolated with solution). FIG. 5(a) is a general schematic diagram of the positional layout between the working electrode plate and the auxiliary electrode plate of the device (the working electrode plate is shown with a deposition layer or plating layer thereon); FIG. 5(b) is a schematic diagram showing the distribution result of the thickness of the deposition layer or plating layer on the side of the working electrode plate facing the auxiliary electrode plate; the color can be seen to gradually deepen from the center to the edge part, namely the settled layer or the plating layer is proved to be gradually thickened from the center to the edge part, the two corners at the lower end have the deepest color and the largest thickness; FIG. 5(c) is a schematic diagram showing the distribution of the thickness of the deposit layer or plating layer on the side of the working electrode plate opposite to the auxiliary electrode plate; the thickness distribution is the same as that of FIG. 5(b), but in contrast, the color distribution is lighter, i.e., the deposited layer or coating is thinner, in FIG. 5(c) than in the same corresponding position of FIG. 5 (b). FIG. 5(d) is a schematic diagram showing the overall structure of a conventional deposition apparatus for a three-electrode electrolytic cell. The simulation result shows that when a common three-electrode electrolytic cell deposition device is used, two problems that a deposition layer or a plating layer is unevenly distributed between different areas on the same surface of a working electrode pole piece and between the front surface and the back surface of the working electrode pole piece can occur.
After the deposition or electroplating is carried out by using the utility model, as shown in FIG. 6 (the color of the edge part of the working electrode plate is slightly dark, because in the simulation parameter design, in consideration of the assembly precision problem in the actual use process, the ideal strict silk seam contact between the working electrode plate and the three surrounding surfaces is not easy to realize, therefore, a certain gap is preset between the working electrode plate and the three surrounding surfaces, if the gap is not preset, the thickness distribution of the working electrode plate is completely uniform in the simulation result). FIG. 6(a) is a general schematic diagram of the positional layout between the working electrode plate and the auxiliary electrode plate of the device (the deposited layer or plated layer is shown on the working electrode plate); FIG. 6(b) is a schematic diagram showing the distribution result of the thickness of the deposit layer or the plating layer on the side of the working electrode pad facing the right auxiliary electrode pad; it can be seen that the color is more consistent than 5(b), i.e., the thickness distribution is demonstrated to be more uniform; FIG. 6(c) is a schematic diagram showing the distribution of the thickness of the deposit layer or plating layer on the side of the working electrode pad opposite to the left auxiliary electrode pad; the thickness distribution is the same as that in FIG. 6 (b); fig. 6(d) is a schematic view of the overall structure of the present invention. The simulation result shows that the device provided by the utility model can effectively solve the two problems that the distribution of the deposition layer or the plating layer is not uniform between different areas on the same surface of the working electrode pole piece and between the front surface and the back surface.
Meanwhile, the present invention has an additional advantageous effect that, as seen from the comparison of the values of the figures 5(b) and (c) and the figures 6(b) and (c) showing the thickness of the deposition layer or the plating layer in the simulation results, the thickness of the deposition layer or the plating layer using the present invention is about 7 times that of the conventional three-electrode electrolytic cell apparatus under the same deposition or plating time condition, proving that the deposition or plating time can be significantly shortened using the present invention.
When the symmetric four-electrode system boundary-limiting type electrolytic cell device provided by the foregoing embodiment is used in the fields of electrochemical deposition, electroplating and electrophoretic deposition, please refer to fig. 1-3, fig. 4.1 and fig. 4.2.
If the electrode plate needs to be subjected to double-sided electrochemical deposition (or electroplating, or electrophoretic deposition), a rectangular electrode plate 15 with a proper size to be deposited (or electroplated) is fixed on an electrode clamp through a pole plate fixing clamp 14 to assemble the working electrode 1, as shown in fig. 2 and 3; when the electrode is used for electrochemical deposition and electrophoretic deposition, two inert conductive pole pieces with the same width and the same height as a pole piece 15 of a working electrode 1 are selected (when the electrode is used for electroplating, two inert conductive pole pieces with the same width and the same height as the pole piece of the working electrode or a metal piece with the same metal as a plating layer to be electroplated are selected to assemble two auxiliary electrodes 2; a reference electrode 3 (such as an alkaline mercury/mercury oxide electrode; a neutral silver/silver chloride electrode; an acidic mercury/mercurous sulfate electrode and the like) which is adaptive to the pH value of an electrolytic cell solution is selected, a partition 6 with corresponding specification is arranged in an electrolytic cell body 5 according to the width and the height of the pole piece, the two partitions are oppositely parallel, the distance is the same width as the pole piece, the lower bottom surface of the partition 6 is contacted with the bottom surface of the inner wall of the electrolytic cell body 5, the four electrodes are respectively inserted into corresponding through holes in an electrolytic cell sealing cover 4 according to a picture 4.1, a rubber ring 12 for adjusting the fixed depth, the bottoms of the pole pieces of the working electrode 1 and the two auxiliary electrodes 2 are contacted with the bottom surface of the inner wall of the electrolytic cell body 5, the pole pieces are opposite and parallel to each other and just positioned in the area of the middle of the partition 6, each pole piece is contacted and vertical with the inner side surface of the partition 6, corresponding solution is added into the electrolytic cell body 5, and the device shown in figure 6(d) is assembled. The liquid level of the added solution does not exceed the bottom end of the clamp 14 for fixing the pole piece, and the bottom end of the reference electrode 3 is immersed in the solution (the bottom end of the reference electrode 3 needs to be inserted into the solution to play the role of the reference electrode). The output ends of the auxiliary electrode wires in the conventional three-electrode power supply method are divided into two to form four-electrode power supply, the four-electrode power supply is respectively connected to the four electrodes of the device, and the electrochemical deposition (or electroplating and electrophoretic deposition) can be carried out by setting the electrical parameters and other process parameters.
Two identical auxiliary electrodes 2 are symmetrically arranged at two sides of the working electrode 1, so that two electric field areas with equal strength and opposite electric field line directions can be formed; through using the high pole piece of three aequilate, be close to in pole piece both sides and place the spacer, the pole piece contacts the height at the bottom of the electrolytic bath cell body inner wall and restriction solution liquid level, can form the cuboid effective solution region with the aequilate of pole piece, thereby can solve the pole piece that exists among the prior art and just thicker than the sedimentary deposit of back to back of the same position of auxiliary electrode's one side, these two problems of being close to pole piece edge sedimentary deposit layer more can appear on every side, the homogeneity of sedimentary deposit layer thickness and the maneuverability of device have been improved.
If the electrode plate is to be subjected to single-sided electrochemical deposition (or electroplating, electrophoretic deposition), the embodiment is different from the double-sided electrochemical deposition (or electroplating, electrophoretic deposition) only in two points, and the other points are the same. The two points are: firstly, before assembling a working electrode pole piece, an insulating layer is needed to cover one surface of the pole piece which does not need to be deposited or electroplated (such as an insulating tape), and then the working electrode is assembled subsequently, so that the surface is isolated from a contact solution, the surface cannot be influenced after electrifying, and the insulating layer is torn down after the deposition or electroplating is finished; and secondly, an auxiliary electrode (the auxiliary electrode on the side can be not assembled or power supply is not carried out after the assembly) which is opposite to the side of the working electrode pole piece covered with the insulating layer is not needed, so that when power supply wiring is carried out, the output ends of the two auxiliary electrodes are connected to the auxiliary electrode wiring end on the side opposite to the side of the working electrode pole piece to be deposited or plated.
When the device is used for single-side deposition or electroplating, the device can form a cuboid effective solution area with the same width as the pole piece, thereby ensuring that the thickness of a deposition layer or a plating layer on the side surface is uniform.
When the symmetrical four-electrode system boundary limiting type electrolytic cell device provided by the embodiment is used in the technical field of electrochemical testing, the utility model improves the original common three-electrode electrolytic cell device, namely, the device is modified from a graph shown in a graph 6(d) in a graph 5(d), and is used for solving the two problems that the thicknesses of different areas on the same surface of a deposited layer (or a plated layer) on a working electrode plate are different, and the thicknesses of the same corresponding positions on the front surface and the back surface are different. Since the electrochemical test does not have the above two problems, the conventional three-electrode electrolytic cell can meet the requirement of the electrochemical test, and thus, the electrochemical test can be performed by assembling part of the components of the device together, as shown in fig. 5 (d).
Coating an active substance to be measured on a conductive substrate sheet (the active substance to be measured on a pole piece is not fully paved on the surface of the whole conductive substrate sheet, and a certain area is reserved for contacting with a clamp 14 for fixing the pole piece), assembling into an electrode piece to be measured with a proper size and an indefinite shape, fixing the electrode piece to be measured on an electrode clamp through the clamp 14 for fixing the pole piece, and assembling into a working electrode 1; similarly, an inert conductive pole piece with proper size is selected to assemble an auxiliary electrode 2, and a reference electrode 3 (such as an alkaline mercury/mercury oxide electrode, a neutral silver/silver chloride electrode, an acidic mercury/mercurous sulfate electrode and the like) which is adaptive to the pH value of the solution of the electrolytic cell is selected; according to the scheme shown in fig. 5(d), three electrodes are respectively inserted into three corresponding through holes in an electrolytic cell cover 4, a rubber ring 12 for fixing depth is adjusted, two pole pieces of a working electrode 1 and an auxiliary electrode 2 are parallel, the insertion depths of two electrode rods 13 are the same, corresponding solution is added into the electrolytic cell body 5, the liquid level of the added solution does not exceed the bottom end of a clamp 14 for fixing the pole pieces, but all active substances to be detected on a conductive substrate piece need to be immersed, and the bottom end of a reference electrode 3 needs to be immersed in the solution. The electrochemical test can be carried out by respectively connecting the three electrodes of the device with the previously used three-electrode power supply method and setting electrical parameters and other process parameters.
It is clear that the described embodiments are only some of the preferred embodiments of the utility model, but that the utility model is not limited to the above-described embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Claims (10)
1. A boundary-limited electrolytic cell device of a symmetrical four-electrode system is characterized in that: comprises an electrolytic cell body (5), an electrolytic cell sealing cover (4), a working electrode (1), two auxiliary electrodes (2), a reference electrode (3) and two separation sheets (6);
the electrolytic cell sealing cover (4) is arranged at the opening of the electrolytic cell body (5), and the electrolytic cell body (5) can contain solution;
the working electrode (1), the two auxiliary electrodes (2), the reference electrode (3) and the spacer (6) are all positioned in the electrolytic cell body (5), and the top ends of the working electrode (1), the two auxiliary electrodes (2) and the reference electrode (3) can penetrate out of the electrolytic cell sealing cover (4);
the working electrode (1) and the two auxiliary electrodes (2) both comprise pole pieces positioned in the electrolytic cell body (5);
wherein, two spacers (6) set up relatively, and the pole piece of working electrode (1) and two auxiliary electrode (2) is located two spacers (6), and the pole piece symmetry of two auxiliary electrode (2) sets up the pole piece both sides at working electrode (1), and the lateral wall of the pole piece of working electrode (1) and two auxiliary electrode (2) is equallyd divide and is do not contact with the inner wall of two spacers (6) to form two symmetrical solution regions and be used for forming two electric field regions that the electric field line opposite direction of intensity equals in the pole piece both sides of working electrode (1).
2. The symmetric four-electrode system boundary-bound electrolyzer unit of claim 1 characterized in that: working electrode (1) and auxiliary electrode (2) all include electrode pole (13), electrically conductive metal core (11), anchor clamps (14) and electrode sheet (15) for the fixed pole piece, and electrically conductive metal core (11) are located electrode pole (13), and electrode sheet (15) are fixed in the bottom of electrode pole (13) through anchor clamps (14) for the fixed pole piece.
3. The symmetrical four-electrode system boundary-confining electrolytic cell device as claimed in claim 2, wherein: each pole piece all equals with two spacer (6) mutually perpendicular, and the interval and the pole piece width of two spacer (6) are equal, and length is greater than the distance between two auxiliary electrode (2), highly is not less than the distance of fixed anchor clamps (14) for the pole piece bottom to electrolysis cell body (5) bottom inner wall.
4. The symmetrical four-electrode system boundary-confining electrolytic cell device as claimed in claim 2, wherein: when the device is used, the height of the solution is smaller than the distance from the bottom of the clamp (14) for fixing the pole piece to the inner wall of the bottom of the electrolytic cell body (5).
5. The symmetrical four-electrode system boundary-confining electrolytic cell device as claimed in claim 2, wherein: four through holes are formed in the electrolytic cell sealing cover (4), wherein a through hole is formed in the center of the electrolytic cell sealing cover, the other two through holes are symmetrically distributed on two sides of the center through hole, the diameter of the fourth through hole is larger than the outer diameter of the electrode rod (13) in the center vertical direction of the line segment connected with the other three through holes.
6. The symmetrical four-electrode system boundary-confining electrolytic cell device as claimed in claim 5, wherein: working electrode (1) and auxiliary electrode (2) all still include rubber circle (12) for the fixed degree of depth, and the cover is equipped with rubber circle (12) for the fixed degree of depth that is used for adjusting electrode pole (13) depth of insertion on every electrode pole (13) outer wall.
7. The symmetrical four-electrode system boundary-confining electrolytic cell device as claimed in claim 1, wherein: the bottoms of the pole pieces of the working electrode (1) and the two auxiliary electrodes (2) are both contacted with the inner wall of the bottom of the electrolytic cell body (5).
8. The symmetric four-electrode system boundary-bound electrolyzer unit of claim 1 characterized in that: the electrolytic cell is characterized by further comprising bottom spacers (6) arranged on the inner wall bottom of the electrolytic cell body (5), wherein the bottom spacers (6) are located at the bottoms of the pole pieces of the working electrode (1) and the two auxiliary electrodes (2) and are in contact with the bottoms of the pole pieces.
9. The symmetrical four-electrode system boundary-confining electrolytic cell device as claimed in claim 1, wherein: the pole pieces of the working electrode (1) and the two auxiliary electrodes (2) are rectangular, and the size of each pole piece is the same.
10. A symmetrical four-electrode system boundary-confining electrolytic cell assembly as claimed in any one of claims 1-9 wherein: the device can be used in the fields of electrochemical deposition, electrophoretic deposition, electroplating and electrochemical testing, when the device is used for the electrochemical deposition and the electrophoretic deposition, the pole piece of the auxiliary electrode (2) adopts an inert conductive pole piece, and when the device is used for the electroplating, the pole piece of the auxiliary electrode (2) adopts an inert conductive pole piece or a metal piece which is the same as the plating metal to be electroplated.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116660335A (en) * | 2023-07-31 | 2023-08-29 | 北京航天试验技术研究所 | Electrochemical test device for dinitrogen tetroxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116660335A (en) * | 2023-07-31 | 2023-08-29 | 北京航天试验技术研究所 | Electrochemical test device for dinitrogen tetroxide |
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