A seawater conductivity sensor electrode material based on copper-nickel based nanostructure and its preparation method

Abstract

The present invention discloses a copper-nickel nanostructure-based seawater conductivity sensor electrode material and preparation method. The electrode material comprises: a substrate having a copper-nickel nanostructure layer formed on its surface; the substrate comprising an insulating composite and a coating applied to the surface of the insulating composite, the insulating composite comprising at least one of high-resistance silicon, silicon oxide, aluminum oxide ceramic, and plastic; the coating comprising a metal coating and / or a semiconductor coating; and the copper-nickel nanostructure layer having a dendritic or clustered morphology. The copper-nickel alloy nanostructure is the core material of the electrode, enabling the electrode material to have a high specific surface area and abundant active sites. This improves the electrode material's measurement accuracy and measurement limit, extends its service life, reduces manufacturing costs, and meets the application requirements of the marine Internet of Things.

Description

Technical Field

[0001] The present invention relates to the technical field of ocean sensors, and in particular to a seawater conductivity sensor electrode material based on a copper-nickel-based nanostructure and a preparation method thereof. Background Art

[0002] Salinity is an important parameter that plays a key role in ocean dynamics and the interaction between the ocean and the atmosphere. Changes in salinity are strongly intrinsically linked to changes in the marine environment and climate. Its precise detection is of great significance to the study of oceanography, monitoring and prediction of the marine environment and climate, military affairs, coastal oil production, and marine fisheries.

[0003] Electrode-based seawater salinity sensors are widely used in ocean salinity monitoring due to their high measurement accuracy and fast response speed. However, the harsh seawater environment in which these sensors are used often damages the electrode material, impacting the sensor's measurement accuracy, reliability, and lifespan. Currently, most electrode-based seawater salinity sensors use platinum black electrodes. In complex marine environments, platinum black electrodes are prone to detachment, causing physical and chemical degradation of the electrode surface. Furthermore, they are susceptible to attachment by marine organisms, significantly reducing detection accuracy, reliability, and lifespan. With the increasing demand for ocean stereoscopic observation and high-density, low-cost sensor deployment, it is crucial to design a new, low-cost sensor electrode material with superior physical and chemical properties to achieve higher measurement accuracy, detection limits, and a longer operating life than traditional platinum black electrodes. Summary of the Invention

[0004] The purpose of the present invention is to provide a seawater conductivity sensor electrode material based on a copper-nickel-based nanostructure. The copper-nickel alloy nanostructure is the core material of the electrode, which can enable the electrode material to have a high specific surface area and abundant active sites, thereby improving the side beam accuracy and measurement limit of the electrode material, extending the service life and reducing manufacturing costs.

[0005] To this end, the present invention provides a seawater conductivity sensor electrode material based on a copper-nickel-based nanostructure, comprising: a substrate, a copper-nickel-based nanostructure layer formed on the surface of the substrate; the substrate comprising an insulating composite and a coating coated on the surface of the insulating composite, the insulating composite comprising at least one of high-resistance silicon, silicon oxide, aluminum oxide ceramics and plastic, the coating comprising a metal coating and / or a semiconductor coating, and the copper-nickel-based nanostructure layer having a dendritic or clustered morphology.

[0006] Preferably, the thickness of the seawater conductivity sensor electrode material is 0.02-100 μm.

[0007] Preferably, the coating includes at least one of a platinum coating, a silicon coating and an alumina ceramic coating.

[0008] Preferably, a titanium vapor-deposited layer is formed on the surface of the copper-nickel alloy nanostructure layer, and the thickness of the titanium vapor-deposited layer is 20-200 nm.

[0009] Preferably, a gold vapor-deposited layer is formed on the surface of the copper-nickel alloy nanostructure layer, and the thickness of the gold vapor-deposited layer is 20-500 nm.

[0010] The present invention also provides a method for preparing the copper-nickel-based nanostructured seawater conductivity sensor electrode material, comprising:

[0011] S1: ultrasonically clean the silicon wafer with acetone, deionized water, and ethanol in sequence;

[0012] S2: depositing a titanium conductive layer and a nickel conductive layer on the surface of the silicon wafer in sequence to obtain a substrate;

[0013] S3: After cleaning, the substrate is subjected to electrochemical deposition with a deposition solution comprising nickel sulfate NiSO4, copper sulfate CuSO4, and boric acid H3BO3. During the deposition process, the B20 white copper alloy serves as the anode and the substrate as the cathode. The cathode surface must be covered with a hydrophilic microporous filter membrane.

[0014] S4: The deposited sample is placed in acetone and / or sodium hydroxide solution to remove the residual hydrophilic microporous filter membrane, and then rinsed with deionized water and dried under nitrogen flow.

[0015] Preferably, the thickness of the titanium conductive layer is 30-50 nm, and the thickness of the nickel conductive layer is 100 nm-50 μm.

[0016] Preferably, the concentration of nickel sulfate NiSO4 is 0.02-1.0M, the concentration of copper sulfate CuSO4 is 0.02-1.0M, and the concentration of boric acid H3BO3 is 0.01-2.0M.

[0017] Preferably, electrochemical deposition is performed in a constant potential mode, with a deposition voltage of -0.5V-5V, a deposition time of 0.1-30 minutes, and a deposition charge density controlled at 0.05-16C / cm².

[0018] Preferably, the thickness of the hydrophilic microporous filter membrane is 5um-30um, and the hydrophilic microporous filter membrane includes a polyethersulfone membrane and / or a polyvinylidene fluoride membrane.

[0019] Compared with the prior art, the advantages and positive effects of the present invention are:

[0020] The present invention provides a seawater conductivity sensor electrode material based on a copper-nickel-based nanostructure. The copper-nickel alloy nanostructure is the core material of the electrode. The copper-nickel alloy nanostructure forms a dendritic branch structure and a multi-level branched structure through a constant potential electrochemical deposition process. The copper-nickel-based nanostructure layer is in a dendritic or clustered form, which significantly increases the contact area between the electrode and the solution and improves the electrochemically active surface area. The copper-nickel alloy nanostructure has excellent surface wettability, can effectively reduce the interfacial contact resistance, and increase the ion migration speed. The nickel element in the copper-nickel alloy nanostructure is distributed at the dendrite edge and growth front to form a protective layer, which significantly improves the corrosion resistance of the electrode. The copper-nickel alloy nanostructure exhibits low signal drift during long-term use, especially under low temperature conditions, with the drift amplitude being less than ±0.10mS / cm.

[0021] The copper-nickel-based nanostructure optimizes the micromorphology (such as dendritic and multi-level branching) and interface properties, increases the contact area between the electrode and seawater, enriches the electrochemically active sites, makes the electrical signal transmission more stable and the response more sensitive, reduces signal fluctuations and errors, and improves the accuracy of seawater conductivity detection.

[0022] The high specific surface area and abundant active sites of the nanostructure allow the electrode to generate recognizable electrical signals even for seawater with extremely low or extremely high conductivity; optimizing the interface characteristics and reducing the contact resistance allow the sensor to detect a wider conductivity range, breaking through the lower limit (capable of measuring lower conductivity) and upper limit (capable of measuring higher conductivity) of traditional electrode detection, and expanding the measurement limit.

[0023] The present invention provides a method for preparing a seawater conductivity sensor electrode material based on a copper-nickel-based nanostructure, which has a simple preparation process, low cost, and good application prospects.

[0024] Other features and advantages of the present invention will become more apparent after reading the detailed description of the present invention in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a SEM image of the copper-nickel-based nanostructure layer of the electrode material prepared in Example 1;

[0026] Figure 2 is a SEM image of the copper-nickel-based nanostructure layer of the electrode material prepared in Example 2;

[0027] Figure 3 is a SEM image of the copper-nickel-based nanostructure layer of the electrode material prepared in Example 3;

[0028] Figure 4 This is an SEM image of the copper-nickel-based nanostructure layer of the electrode material prepared in Example 4. DETAILED DESCRIPTION

[0029] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0030] The copper-nickel-based nanostructured seawater conductivity sensor electrode material of the present application includes: a substrate, and a copper-nickel-based nanostructured layer is formed on the surface of the substrate.

[0031] The thickness of the seawater conductivity sensor electrode material is 0.02-100μm, and it has the following excellent technical effects:

[0032] 1. Performance adaptation

[0033] 1.1. Optimizing Electrical Performance: Electrode material thicknesses within the 0.02-100μm range allow the copper-nickel nanostructure to form a suitable conductive pathway, ensuring excellent conductivity for accurate sensing of changes in seawater conductivity without overly thick electrodes that would otherwise cause excessive resistance and affect signal transmission, or overly thin electrodes that would cause unstable conductivity and susceptibility to breakage. For example, when measuring seawater conductivity, the optimal thickness allows the electrode to respond more sensitively and accurately to changes in conductivity.

[0034] 1.2 Structural Stability: Electrode materials with a thickness of 0.02-100μm exhibit excellent mechanical strength and structural integrity, withstanding the impact and pressure of marine environments without deformation or damage, ensuring long-term stable sensor operation. In environments like flowing seawater, electrode materials of this thickness maintain structural stability, ensuring continuous and effective detection.

[0035] 2. Convenient preparation and application

[0036] 2.1. Fabrication Feasibility: This thickness is within the range achievable by existing nanostructure preparation technologies (such as physical deposition and chemical synthesis). It is convenient to precisely control the thickness by adjusting process parameters such as deposition time and solution concentration, which is conducive to industrial production.

[0037] 2.2. Adaptation to the substrate: It can fit well with the substrate (including insulating compound and coating), ensuring the bonding strength with the substrate and the coordination of the overall structure. It will not peel off from the substrate due to being too thick, nor will it be difficult to form an effective functional layer on the substrate due to being too thin. It can work with the substrate to improve the overall performance of the sensor.

[0038] 3. Function Implementation

[0039] Adaptation to seawater environment: Seawater has special physical and chemical properties. This thickness can make the electrode material have a suitable specific surface area and reaction activity in seawater, which is conducive to electrochemical reaction in contact with seawater. At the same time, it can resist the adverse effects of seawater corrosion, biological attachment, etc. to a certain extent, thereby extending the service life.

[0040] The substrate comprises an insulating compound and a coating coated on the surface of the insulating compound, the insulating compound comprises at least one of high-resistance silicon, silicon oxide, aluminum oxide ceramics and plastic, and the coating comprises a metal coating and / or a semiconductor coating.

[0041] Since the insulating composite is non-conductive, the coating on the surface of the insulating composite has conductive or semiconductor properties, which can realize a conductive path, connect the subsequent copper-nickel alloy nanostructure layer with the external circuit, and ensure the transmission of electrical signals.

[0042] The coating can improve the surface properties of the insulating composite, enhance the bonding strength with the copper-nickel alloy nanostructure layer, enable the subsequent nanostructure layer to be deposited and grown more stably, and can also regulate the interface electrical properties and assist in optimizing electrode performance.

[0043] The coating includes at least one of a platinum coating, a silicon coating and an alumina ceramic coating. The platinum coating has good chemical stability and catalytic activity, the silicon coating can regulate the electrical properties, and the alumina ceramic coating can enhance corrosion resistance. It can give the substrate specific properties (such as corrosion resistance, electrochemical activity, etc.) according to needs, and synergistically improve the overall performance of the electrode.

[0044] The copper-nickel-based nanostructure has dendritic and multi-level branching forms (such as tree-like branches and clusters). Compared with conventional flat structures, this complex three-dimensional structure greatly increases the "expanded area" of the electrode material surface, making the electrode material have a high specific surface area.

[0045] The dendrites and branches of the copper-nickel-based nanostructures make the atomic arrangement and electron distribution on the material surface special, forming a large number of active areas that can participate in electrochemical reactions (such as charge exchange with seawater ions), that is, electrochemically active sites; at the same time, different atomic ratios and interfaces in the copper-nickel alloy will also contribute active sites, making the electrode material rich in electrochemical active sites.

[0046] After copper and nickel atoms form an alloy, the addition of nickel can form a dense oxide film (such as a nickel-containing passivation film) on the alloy surface, which hinders further erosion by seawater (containing corrosive ions such as chloride ions); and the interaction between atoms within the alloy changes the electrode potential of electrochemical corrosion, reduces the corrosion rate, and makes the electrode material corrosion-resistant.

[0047] The chemical composition and electrical properties of the copper-nickel alloy surface inhibit the attachment of marine organisms (such as microorganisms and shellfish). On the one hand, the copper-nickel alloy surface is not easily adhered to by sticky substances secreted by organisms; on the other hand, its electrochemical environment is not conducive to biofilm formation and biological attachment growth, thereby reducing the impact of biological attachment on electrode performance and endowing the electrode material with anti-biofouling properties.

[0048] The copper-nickel alloy nanostructure forms a dendritic branch structure and a multi-level branch structure through a constant potential electrochemical deposition process. The copper-nickel-based nanostructure layer has a dendritic or clustered morphology, which significantly increases the contact area between the electrode and the solution and improves the electrochemically active surface area; the copper-nickel alloy nanostructure has excellent surface wettability, which can effectively reduce the interfacial contact resistance and increase the ion migration speed; the nickel element in the copper-nickel alloy nanostructure is distributed at the dendrite edge and growth front, forming a protective layer, which significantly improves the corrosion resistance of the electrode; the copper-nickel alloy nanostructure exhibits low signal drift during long-term use, especially under low temperature conditions, with the drift amplitude less than ±0.10mS / cm.

[0049] The atomic ratio of nickel in the copper-nickel-based nanostructured layer is 0.05-0.95. The atomic ratio of nickel can be controlled by adjusting the deposition voltage from (-0.75V) to (-2.5V) and the molar ratio of copper sulfate to nickel sulfate from 1:1 to 1:50.

[0050] The atomic ratio of nickel is 0.05-0.95, which has the following excellent technical effects:

[0051] 1. Impact on material properties

[0052] 1.1 Electrical Properties: Changes in the nickel atomic ratio affect the electrical properties of copper-nickel alloys, including conductivity. For example, a high nickel content may result in relatively low conductivity. However, through proper regulation, in certain applications (such as the production of seawater conductivity sensor electrode materials), a suitable nickel atomic ratio can optimize the electrode's electrical response, enabling it to more accurately sense changes in seawater conductivity.

[0053] 1.2 Mechanical Properties: Different ratios of copper and nickel will change the alloy's mechanical properties, such as hardness, strength, and toughness. Properly increasing the nickel content can enhance the alloy's strength and wear resistance, meeting the requirements of long-term use of electrode materials in complex marine environments and preventing mechanical wear that could affect sensor performance.

[0054] 1.3. Corrosion Resistance: The marine environment is characterized by high salt content and humidity, placing high demands on the corrosion resistance of materials. Copper-nickel alloys inherently exhibit good corrosion resistance. Properly controlling the nickel atomic ratio can further enhance the alloy's corrosion resistance in seawater, extending the service life of the seawater conductivity sensor electrode material.

[0055] 2. From the perspective of preparation process

[0056] 2.1. Deposition Voltage Control: By setting an appropriate deposition voltage range, the deposition rate and structural morphology of the copper-nickel alloy on the electrode material can be effectively controlled. A lower deposition voltage may result in a denser alloy deposition, which helps form a uniform nanostructure and thus affects the overall performance of the material.

[0057] 2.2 Solution Composition Control: Different molar ratios of copper sulfate and nickel sulfate affect the concentration and deposition activity of copper and nickel ions in the solution. A suitable molar ratio ensures the desired deposition of copper and nickel atoms, thereby precisely controlling the atomic ratio of nickel in the alloy and producing electrode materials with specific properties.

[0058] In short, this setting is to achieve precise control of the composition of copper-nickel alloy in the preparation process, and thus obtain materials that meet the electrical, mechanical, corrosion resistance and other performance requirements of seawater conductivity sensor electrode materials.

[0059] A titanium vapor deposition layer is formed on the surface of the copper-nickel alloy nanostructure layer, and the thickness of the titanium vapor deposition layer is 20-200 nm.

[0060] The titanium vapor-deposited layer can enhance the bonding force, improve the adhesion between the copper-nickel alloy nanostructure layer and other layers (such as subsequent possible functional layers or substrate-related structures), optimize the interface performance, and also improve the corrosion resistance and electrical contact characteristics of the electrode to a certain extent.

[0061] The thickness of the titanium vapor-deposited layer is 20-200nm. This thickness range is easy to accurately control in the vapor deposition process, which can ensure good bonding strength and interface performance without increasing excessive costs, weight or generating excessive internal stress due to excessive thickness. At the same time, it can cooperate with the performance of the copper-nickel layer to meet functional requirements (such as adhesion and interface optimization) and maintain the overall lightness of the electrode material.

[0062] A gold vapor deposition layer is formed on the surface of the copper-nickel alloy nanostructure layer, and the thickness of the gold vapor deposition layer is 20-500 nm.

[0063] Gold has excellent electrical conductivity and chemical stability (resistance to seawater corrosion and oxidation, etc.). The gold vapor-deposited layer can improve the electrical properties of the electrode, reduce contact resistance, make electrical signal transmission more stable, enhance the electrode's corrosion resistance and anti-pollution ability in seawater environments, and ensure the long-term stable operation of the sensor.

[0064] The thickness of the gold vapor-deposited layer ranges from 20 to 500 nm, ensuring the gold layer exhibits excellent electrical conductivity and corrosion resistance, while balancing cost and performance. A thinner thickness (starting at 20 nm) allows for the initial formation of an effective functional layer, while increasing thickness (up to 500 nm) further enhances performance. However, excessive thickness increases cost and may adversely affect the properties of gold (e.g., changes in structural rigidity due to excessive thickness). This range can be adjusted through process control to meet different performance requirements.

[0065] The preparation method of the electrode material of the seawater conductivity sensor based on the copper-nickel based nanostructure of the present application includes:

[0066] S1: Ultrasonic cleaning of silicon wafers with acetone, deionized water and ethanol in sequence.

[0067] S2: A titanium conductive layer and a nickel conductive layer are sequentially deposited on the surface of the silicon wafer to obtain a base, ensuring that the subsequent growth of the nanostructure can obtain good adhesion and flatness.

[0068] The titanium conductive layer strengthens the bond between the substrate and the copper-nickel alloy nanostructured layer, improving interfacial conductivity and providing a fundamental pathway for electrical signal transmission. The thickness of the titanium conductive layer is 30-50nm, which ensures good bonding and conductivity, and allows for easy process control.

[0069] The nickel conductive layer, as an intermediate conductive layer, can further optimize the conductive path and work together with the copper-nickel alloy layer to improve the overall electrical properties and corrosion resistance of the electrode.

[0070] The thickness of the nickel conductive layer is 100nm-50μm, which can provide more sufficient conductivity and structural support.

[0071] S3: After cleaning, the substrate is electrochemically deposited with a deposition solution comprising nickel sulfate NiSO4, copper sulfate CuSO4, and boric acid H3BO3. During the deposition process, B20 white copper alloy serves as the anode and the substrate as the cathode. The cathode surface must be covered with a hydrophilic microporous filter membrane.

[0072] In the electrochemical deposition system, copper sulfate and nickel sulfate serve as the sources of copper and nickel ions, respectively, for depositing the copper-nickel alloy nanostructures. The concentration of nickel sulfate (NiSO4) and copper sulfate (CuSO4) ranges from 0.02 to 1.0 M, respectively. The concentrations affect the ion deposition rate and the alloy composition ratio. Within this range, the atomic ratio of copper and nickel can be adjusted to optimize the nanostructure's performance.

[0073] Boric acid acts as a buffer, stabilizing the solution pH and ensuring a stable and uniform deposition process. The concentration of boric acid (H₃BO₃) ranges from 0.01-2.0M, matching the aforementioned metal ion concentrations and effectively stabilizing the solution pH. Too low a concentration will result in insufficient buffering capacity, while too high a concentration may introduce impurities and affect deposition.

[0074] S4: The deposited sample is placed in acetone and / or sodium hydroxide solution to remove the residual hydrophilic microporous filter membrane, and then rinsed with deionized water and dried under nitrogen flow.

[0075] Electrochemical deposition was performed in a constant potential mode with a deposition voltage of -0.5V-5V, a deposition time of 0.1-30 minutes, and a deposition charge density controlled at 0.05-16C / cm².

[0076] The hydrophilic microporous membrane, comprised of polyethersulfone and / or polyvinylidene fluoride, serves as a template for the growth of copper-nickel alloy nanostructures within its pores, enabling the regulation of their morphology and distribution. The hydrophilic microporous membrane also filters impurities, ensuring the purity of the electrode material preparation system.

[0077] The thickness of the hydrophilic microporous membrane is 5um-30um, and it has the following excellent technical effects:

[0078] Template function adaptation: This thickness can provide appropriate micropore density and depth to allow the smooth growth of nanostructures. If it is too thin, the micropores will be few and easy to break. If it is too thick, the micropores will be deep, the growth will be difficult to control, and the overall thickness and cost of the material will increase.

[0079] Balance between performance and process: On the basis of ensuring the template function (nanostructure growth guidance, filtration), the thickness of the hydrophilic microporous filter membrane is 5um-30um, which is easy to achieve through conventional membrane preparation processes (such as phase inversion method, etc.), and can balance the overall performance of the electrode material (such as flexibility, mechanical strength) and preparation cost.

[0080] The electrode material of the seawater conductivity sensor based on the copper-nickel-based nanostructure of the present application also includes an electrode wire, which is welded to the copper-nickel alloy nanostructure layer, and the welding points are encapsulated with epoxy resin.

[0081] The performance indicators of the electrode material of the present application include: salinity measurement range of 0-60ppt, temperature application range of -2-60°C, and initial conductivity measurement accuracy of not less than ±0.05mS / cm.

[0082] The electrode material used in this application to detect seawater conductivity operates as follows: an electrode array within a conductivity cell acquires conductivity data by monitoring changes in resistance caused by variations in seawater salinity. During actual measurements, as seawater flows through the cell, an electrochemical interface is formed between the electrode array and the seawater, where ion migration and charge transfer occur. Using AC impedance spectroscopy, the resistance change is converted into a frequency signal, and the oscillation frequency is detected by a frequency detection circuit. The relationship between the oscillation frequency and conductivity is calculated using a pre-calibrated mathematical model. Combined with temperature and pressure data provided by temperature and pressure probes, the salinity of the seawater is ultimately calculated.

[0083] The electrode material of this application was tested using electrochemically active surface area (EASA). The results showed that the EASA was maximum at a deposition voltage of -1.35V, indicating that the dendritic structure formed under this condition significantly increased the contact area between the electrode and the solution. Secondly, the sensor's conductivity measurement accuracy was tested. Furthermore, long-term stability testing of the sensor in complex marine environments revealed that its signal drift was less than ±0.10mS / cm, meeting practical application requirements.

[0084] Example 1: The method for preparing the electrode material of the seawater conductivity sensor based on the copper-nickel based nanostructure of this embodiment includes:

[0085] S1: Ultrasonic cleaning of silicon wafers with acetone, deionized water and ethanol in sequence.

[0086] S2: A titanium conductive layer and a nickel conductive layer are sequentially deposited on the surface of the silicon wafer to obtain a substrate; the thickness of the nickel conductive layer is 0.5 μm, and the thickness of the titanium conductive layer is 50 nm.

[0087] S3: After cleaning, the substrate is subjected to electrochemical deposition with a deposition solution, where the deposition solution includes nickel sulfate NiSO4, copper sulfate CuSO4, and boric acid H3BO3; the concentration of nickel sulfate NiSO4 is 0.02M, the concentration of copper sulfate CuSO4 is 0.02M, and the concentration of boric acid H3BO3 is 0.02M.

[0088] During the deposition process, B20 white copper alloy serves as the anode and the substrate serves as the cathode, and the cathode surface needs to be covered with a hydrophilic microporous filter membrane.

[0089] Electrochemical deposition was performed in constant potential mode with a deposition voltage of -1.05 V, a deposition time of 20 minutes, and a deposition charge density of 13.3 C / cm².

[0090] S4: The deposited sample is placed in acetone and / or sodium hydroxide solution to remove the remaining hydrophilic microporous filter membrane, and then rinsed with deionized water and dried under a nitrogen stream. The hydrophilic microporous filter membrane has a thickness of 30 μm and is a polyvinylidene fluoride membrane.

[0091] Example 2: The method for preparing the electrode material of the seawater conductivity sensor based on the copper-nickel based nanostructure of this embodiment includes:

[0092] S1: Ultrasonic cleaning of silicon wafers with acetone, deionized water and ethanol in sequence.

[0093] S2: A titanium conductive layer and a nickel conductive layer are sequentially deposited on the surface of the silicon wafer to obtain a substrate; the thickness of the nickel conductive layer is 300 nm, and the thickness of the titanium conductive layer is 30 nm.

[0094] S3: After cleaning, the substrate is subjected to electrochemical deposition with a deposition solution, where the deposition solution includes nickel sulfate NiSO4, copper sulfate CuSO4, and boric acid H3BO3; the concentration of nickel sulfate NiSO4 is 1.0M, the concentration of copper sulfate CuSO4 is 1.0M, and the concentration of boric acid H3BO3 is 1.0M.

[0095] During the deposition process, B20 white copper alloy serves as the anode and the substrate serves as the cathode, and the cathode surface needs to be covered with a hydrophilic microporous filter membrane.

[0096] Electrochemical deposition was performed in constant potential mode with a deposition voltage of -1.2 V, a deposition time of 8 minutes, and a deposition charge density of 13.3 C / cm².

[0097] S4: The deposited sample is placed in acetone and / or sodium hydroxide solution to remove the remaining hydrophilic microporous filter membrane, and then rinsed with deionized water and dried under a nitrogen stream. The hydrophilic microporous filter membrane has a thickness of 30 μm and is a polyvinylidene fluoride membrane.

[0098] Example 3: The preparation method of the electrode material of the seawater conductivity sensor based on the copper-nickel based nanostructure of this embodiment includes:

[0099] S1: Ultrasonic cleaning of silicon wafers with acetone, deionized water and ethanol in sequence.

[0100] S2: A titanium conductive layer and a nickel conductive layer are sequentially deposited on the surface of the silicon wafer to obtain a substrate; the thickness of the nickel conductive layer is 0.5 μm, and the thickness of the titanium conductive layer is 50 nm.

[0101] S3: After cleaning, the substrate is subjected to electrochemical deposition with a deposition solution, where the deposition solution includes nickel sulfate NiSO4, copper sulfate CuSO4, and boric acid H3BO3; the concentration of nickel sulfate NiSO4 is 0.02M, the concentration of copper sulfate CuSO4 is 0.02M, and the concentration of boric acid H3BO3 is 0.02M.

[0102] During the deposition process, B20 white copper alloy serves as the anode and the substrate serves as the cathode, and the cathode surface needs to be covered with a hydrophilic microporous filter membrane.

[0103] Electrochemical deposition was performed in constant potential mode with a deposition voltage of -1.35 V, a deposition time of 4 minutes, and a deposition charge density of 13.3 C / cm².

[0104] S4: The deposited sample is placed in acetone and / or sodium hydroxide solution to remove the remaining hydrophilic microporous filter membrane, and then rinsed with deionized water and dried under a nitrogen stream. The hydrophilic microporous filter membrane has a thickness of 5 μm and is a polyethersulfone membrane.

[0105] Example 4: The method for preparing the electrode material of the seawater conductivity sensor based on the copper-nickel based nanostructure of this embodiment includes:

[0106] S1: Ultrasonic cleaning of silicon wafers with acetone, deionized water and ethanol in sequence.

[0107] S2: A titanium conductive layer and a nickel conductive layer are sequentially deposited on the surface of the silicon wafer to obtain a substrate; the thickness of the nickel conductive layer is 0.5 μm, and the thickness of the titanium conductive layer is 50 nm.

[0108] S3: After cleaning, the substrate is subjected to electrochemical deposition with a deposition solution, where the deposition solution includes nickel sulfate NiSO4, copper sulfate CuSO4, and boric acid H3BO3; the concentration of nickel sulfate NiSO4 is 0.02M, the concentration of copper sulfate CuSO4 is 0.02M, and the concentration of boric acid H3BO3 is 0.02M.

[0109] During the deposition process, B20 white copper alloy serves as the anode and the substrate serves as the cathode, and the cathode surface needs to be covered with a hydrophilic microporous filter membrane.

[0110] Electrochemical deposition was performed in constant potential mode with a deposition voltage of -1.5 V, a deposition time of 3 minutes, and a deposition charge density of 13.3 C / cm².

[0111] S4: The deposited sample is placed in acetone and / or sodium hydroxide solution to remove residual hydrophilic microporous filter membrane, and then rinsed with deionized water and dried under a nitrogen stream. The hydrophilic microporous filter membrane has a thickness of 25 μm and includes a polyethersulfone membrane.

[0112] The morphology changes of the Cu-Ni alloy nanostructures were observed by scanning electron microscopy. Figure 1 As shown in Figure 2, when the deposition voltage is -1.05 V, the electrode surface is mainly composed of nanoscale equiaxed grains. Figure 2 As shown in Figure 2, when the deposition voltage increases to -1.2 V, the grain size decreases and the cluster structure gradually becomes finer. Figure 3 As shown in Figure 2, when the deposition voltage is further increased to -1.35 V, the CuNi structure transforms into a finer dendritic structure, with the main trunk composed of dense nanoparticles and secondary metal dendrites distributed around it. Figure 4 As shown in the figure, when the deposition voltage reaches -1.5 V, the dendritic structure becomes more obvious, showing a multi-level branching morphology, and the size of the main trunk and secondary dendrites increases slightly. These morphological features indicate that the microstructure of the Cu-Ni alloy nanostructure can be precisely controlled by adjusting the deposition voltage.

[0113] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for a person skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to replace some of the technical features therein with equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions claimed to be protected by the present invention.

Claims

1. A seawater conductivity sensor electrode material based on a copper-nickel based nanostructure, characterized in that: include: A substrate, wherein a copper-nickel-based nanostructure layer is formed on the surface of the substrate; The copper-nickel based nanostructured layer is in a dendritic or clustered form; The method for preparing the electrode material for the seawater conductivity sensor based on the copper-nickel based nanostructure comprises: S1: ultrasonically clean the silicon wafer with acetone, deionized water, and ethanol in sequence; S2: depositing a titanium conductive layer and a nickel conductive layer on the surface of the silicon wafer in sequence to obtain a substrate; S3: After cleaning, the substrate is subjected to electrochemical deposition with a deposition solution, the deposition solution including nickel sulfate NiSO4, copper sulfate CuSO4 and boric acid H3BO3; During the deposition process, the B20 white copper alloy serves as the anode and the substrate as the cathode, and the cathode surface needs to be covered with a hydrophilic microporous filter membrane; S4: placing the deposited sample in acetone and / or sodium hydroxide solution to remove the residual hydrophilic microporous filter membrane, and then rinsing with deionized water and drying under nitrogen flow; The concentration of nickel sulfate NiSO4 is 0.02-1.0M, the concentration of copper sulfate CuSO4 is 0.02-1.0M, and the concentration of boric acid H3BO3 is 0.01-2.0M; Electrochemical deposition was performed in a constant potential mode with a deposition voltage of -0.5V-5V, a deposition time of 0.1-30 minutes, and a deposition charge density controlled at 0.05-16C / cm².

2. The seawater conductivity sensor electrode material based on copper-nickel based nanostructures according to claim 1, characterized in that: The thickness of the seawater conductivity sensor electrode material is 0.02-100 μm.

3. The seawater conductivity sensor electrode material based on copper-nickel based nanostructures according to claim 1, characterized in that: A titanium vapor deposition layer is formed on the surface of the copper-nickel-based nanostructure layer, and the thickness of the titanium vapor deposition layer is 20-200 nm.

4. The seawater conductivity sensor electrode material based on copper-nickel based nanostructures according to claim 1, characterized in that: A gold vapor deposition layer is formed on the surface of the copper-nickel-based nanostructure layer, and the thickness of the gold vapor deposition layer is 20-500 nm.

5. The method for preparing the electrode material for seawater conductivity sensor based on copper-nickel based nanostructures according to claim 1, characterized in that: The thickness of the titanium conductive layer is 30-50 nm, and the thickness of the nickel conductive layer is 100 nm-50 μm.

6. The method for preparing a seawater conductivity sensor electrode material based on a copper-nickel based nanostructure according to claim 1, wherein: The thickness of the hydrophilic microporous filter membrane is 5um-30um, and the hydrophilic microporous filter membrane includes a polyethersulfone membrane and / or a polyvinylidene fluoride membrane.

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