WO2018205476A1 - 三电极阵列局部电化学信息测试系统及测试方法 - Google Patents

三电极阵列局部电化学信息测试系统及测试方法 Download PDF

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WO2018205476A1
WO2018205476A1 PCT/CN2017/101319 CN2017101319W WO2018205476A1 WO 2018205476 A1 WO2018205476 A1 WO 2018205476A1 CN 2017101319 W CN2017101319 W CN 2017101319W WO 2018205476 A1 WO2018205476 A1 WO 2018205476A1
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electrode
electrochemical
testing
working electrode
concentric
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PCT/CN2017/101319
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English (en)
French (fr)
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唐晓
李焰
马超然
徐苗苗
吕晓蕾
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中国石油大学(华东)
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Publication of WO2018205476A1 publication Critical patent/WO2018205476A1/zh
Priority to US16/677,705 priority Critical patent/US11333624B2/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
    • G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301—Reference electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

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  • the invention relates to the field of electrochemical testing, in particular to a three-electrode array local electrochemical information testing system and testing method.
  • the local corrosion of metal is related to the electrochemical process of the interface.
  • the distribution characteristics of local electrochemical parameters such as interface potential, current density and impedance are crucial for studying the distribution characteristics and mechanism of local corrosion.
  • Classical corrosion electrochemical methods such as cyclic voltammetry, polarization curves, electrochemical impedance spectroscopy, etc. can only obtain electrochemical information on the surface of the entire sample, giving statistical average data, difficult to electrochemical signals on local regions. Make a distinction.
  • the scanning vibration electrode can test the surface current density distribution of the metal material in the solution; scanning electrochemical microscopy (SECM) can be used to evaluate the local electrochemical redox reaction activity; local electrochemical impedance spectroscopy (LEIS) Not only can the full-frequency electrochemical impedance spectrum of a specific point be studied, but also the scanning surface of the electrode can be studied at a fixed frequency.
  • SECM scanning electrochemical microscopy
  • LEIS local electrochemical impedance spectroscopy
  • the scanning Kelvin probe method SSP
  • SSP scanning Kelvin probe method
  • the application conditions and information obtained by the above test methods have certain limitations, and only information on potentials, currents, impedances, etc. of the electrochemical test system can be obtained, and some of them are indirect information.
  • SVET and LEIS are based on interface yin and yang.
  • the extremely electrochemical reaction leads to the test of the electric field gradient of the electrolyte.
  • the current density distribution and the micro-area impedance obtained are not the reaction information of the base material.
  • SKP is based on the electrode surface work function and directly measures the Kelvin potential. The potential at the electrode/solution interface.
  • the object of the present invention is to provide a three-electrode array local electrochemical information testing system, which is more convenient for obtaining the galvanic current, corrosion potential, corrosion current density, electrochemical impedance spectrum and the like in the electrode coupling/uncoupling state. Surface electrochemical information.
  • the invention also provides a test method for the system.
  • a three-electrode array local electrochemical information testing system comprises a concentric three-electrode array, a high-speed switching switch and an electrochemical workstation electrically connected in sequence, the concentric three-electrode array comprising a plurality of concentric three-electrode units, adjacent concentric
  • the circular three-electrode unit is separated by an insulating material;
  • the concentric three-electrode unit comprises a ring-shaped auxiliary electrode, a solid-state reference electrode and a filament-shaped working electrode, wherein the annular auxiliary electrode and the solid reference electrode are both annular and wire
  • the working electrode is located in the solid reference electrode, and the wire working electrode and the solid reference electrode are separated by an insulating material;
  • the solid reference electrode is located in the annular auxiliary electrode, and the solid reference electrode and the annular auxiliary electrode are insulated Material isolation;
  • the annular auxiliary electrode, the solid reference electrode and the wire working electrode are connected to the high speed switch.
  • the material of the annular auxiliary electrode is selected from a platinum plate, a platinum-plated black platinum plate, a graphite or a Hastelloy; and the solid reference electrode is a solid Ag reference. Electrode, AgCl reference electrode or zinc reference electrode. These three electrodes are solid reference electrodes. The potential is relatively stable and economical in conventional natural environmental corrosion systems.
  • test methods of the three-electrode array local electrochemical information test system described above include:
  • the wire-shaped working electrode of the plurality of concentric three-electrode unit is in an uncoupled state by controlling the high-speed switching switch, so that the annular auxiliary electrode, the solid reference electrode and the wire-shaped working electrode are connected to the electrochemical workstation;
  • the method of testing the open circuit potential comprising: testing a potential difference between the wire working electrode and the solid reference electrode;
  • the electrochemical behavior of a single filamentary working electrode was obtained by an open circuit potential test, and single-electrode electrochemical, thermodynamic and kinetic information was obtained by data analysis of the electrochemical behavior of a single filamentary working electrode;
  • the data analysis method includes: open circuit potential , polarization curve, electrochemical impedance spectroscopy, cyclic voltammetry, galvanic current, charging curve and other test methods obtained by the test data, data analysis according to the principle of corrosion electrochemical, to obtain the relevant potential distribution, current density distribution, electrochemical impedance Thermodynamic and kinetic parameters such as capacitance and corrosion rate.
  • test method for a three-electrode array local electrochemical information test system, the test method further includes:
  • the wire-shaped working electrode of the plurality of concentric three-electrode unit is in an uncoupled state by controlling the high-speed switching switch, so that the annular auxiliary electrode, the solid reference electrode and the wire-shaped working electrode are connected to the electrochemical workstation;
  • the electrochemical behavior of a single filamentary working electrode was obtained by an open circuit potential test, and single-electrode electrochemical, thermodynamic and kinetic information was obtained by data analysis of the electrochemical behavior of a single filamentary working electrode; the data analysis method includes: specific The data analysis method is based on the cyclic voltammetry curve to obtain the electrode reaction, the reaction reversibility, and the reaction electricity. Bit window, current peak and other related information.
  • test method for a three-electrode array local electrochemical information test system, the test method further includes:
  • the wire-shaped working electrode of the plurality of concentric three-electrode unit is in an uncoupled state by controlling the high-speed switching switch, so that the annular auxiliary electrode, the solid reference electrode and the wire-shaped working electrode are connected to the electrochemical workstation;
  • the electrochemical behavior of a single filamentary working electrode was obtained by an open circuit potential test, and single-electrode electrochemical, thermodynamic and kinetic information was obtained by data analysis of the electrochemical behavior of a single filamentary working electrode; the data analysis method includes: polarization
  • the data analysis methods of the curve include linear fitting, integral curve fitting, Tafel extrapolation and the like.
  • test method for a three-electrode array local electrochemical information test system, the test method further includes:
  • the wire-shaped working electrode of the plurality of concentric three-electrode unit is in an uncoupled state by controlling the high-speed switching switch, so that the annular auxiliary electrode, the solid reference electrode and the wire-shaped working electrode are connected to the electrochemical workstation;
  • the electrochemical behavior of a single filamentary working electrode was obtained by an open circuit potential test, and single-electrode electrochemical, thermodynamic and kinetic information was obtained by data analysis of the electrochemical behavior of a single filamentary working electrode; the data analysis method includes: electrochemical Data analysis methods for impedance spectra include dynamic analysis and equivalent circuit simulation.
  • test method for a three-electrode array local electrochemical information test system, the test method further includes:
  • the wire-shaped working electrode of the plurality of concentric three-electrode unit is in an uncoupled state by controlling the high-speed switching switch, so that the annular auxiliary electrode, the solid reference electrode and the wire-shaped working electrode are connected to the electrochemical workstation;
  • All the electrodes except the electrode to be tested are short-circuited into a whole by a high-speed switching switch, and the current between the electrode to be tested and the other electrodes is tested one by one through the electrochemical workstation (8).
  • test method for a three-electrode array local electrochemical information test system, the test method further includes:
  • Test single-electrode anode reaction current density based on the galvanic current of a single electrode measured in a coupled state, and the self-corrosion current density measured in an uncoupled state, and then algebraically added.
  • the coupling state refers to short-circuiting the respective working electrode wires in the three-electrode array to form a coupling state between the respective electrode reactions.
  • the uncoupled state refers to each set of three-electrode independent working states constituting the array, and the working electrodes in each set of arrays are not short-circuited together.
  • the present invention has the following advantages:
  • the organic combination of the array electrode and the three-electrode system is realized, which facilitates comprehensive acquisition of interface electrochemical information such as galvanic current, corrosion potential, corrosion current density and electrochemical impedance spectroscopy in the coupled/uncoupled state of the electrode, and the test information is more comprehensive. rich.
  • the conventional array electrode can only obtain the potential and galvanic current distribution information, and cannot obtain local current and impedance. according to.
  • the short-distance concentric three-electrode array realizes that the auxiliary electrode and the reference electrode 2 are circumferentially distributed around the working electrode at a close distance, and the power line distribution is more uniform during the test; and the resistivity is relatively large and the electrolysis is relatively large.
  • the liquid dispersion system since the distance between the reference electrode and the working electrode is relatively close, the potential test accuracy is high, and the current test is not easy to open.
  • This partial electrochemical test method has certain universality and can be extended to various heterogeneous medium corrosion electrochemical research systems such as atmospheric corrosion, soil corrosion, sediment corrosion, and coating under corrosion, or applied to galvanic couples.
  • Typical local corrosion types such as corrosion, crevice corrosion, and erosion corrosion.
  • FIG. 1 is a schematic structural view of a concentric three-electrode unit
  • FIG. 2 is a schematic structural view of a concentric three-electrode array
  • FIG. 3 is a schematic diagram of a partial electrochemical information testing system based on a concentric circular three-electrode array
  • a three-electrode array partial electrochemical information testing system includes a concentric three-electrode array 5 electrically connected by wires 6 in turn, and a high-speed switch 7 And an electrochemical workstation 8, the concentric three-electrode array 5 comprising a plurality of concentric three-electrode cells, the adjacent concentric three-electrode cells being separated by an insulating material 4; the concentric three-electrode unit comprising a ring-shaped auxiliary electrode 1.
  • the solid reference electrode 2 and the wire working electrode 3 are both connected to the high speed switch 7.
  • the insulating material 4 is made of an insulating epoxy resin.
  • the material of the annular auxiliary electrode is selected from a platinum plate, a platinum-plated black platinum plate, graphite or Hastelloy.
  • the solid reference electrode 2 is a solid Ag reference electrode, an AgCl reference electrode or a zinc reference electrode.
  • test method for the three-electrode array local electrochemical information test system described in the above embodiment includes:
  • the filament-shaped working electrode 3 of the plurality of concentric three-electrode units are in an uncoupled state by controlling the high-speed switching switch 7, and the annular auxiliary electrode 1, the solid reference electrode 2, and the filamentary working electrode 3 are both connected to the electrochemical workstation.
  • the open potential test method comprises: testing the potential difference between the wire working electrode and the solid reference electrode; obtaining the electrochemical behavior of the single wire working electrode 3 by an open circuit potential test, By a single filament
  • the electrochemical behavior of the working electrode 3 is analyzed by data to obtain single-electrode electrochemical, thermodynamic and kinetic information; the data analysis methods include: open circuit potential, polarization curve, electrochemical impedance spectroscopy, cyclic voltammetry, galvanic current, charging
  • the test data obtained by the test methods such as curves are analyzed according to the principle of corrosion electrochemistry, and the thermodynamic and kinetic parameters such as potential distribution, current density distribution, electrochemical impedance, capacitance and corrosion rate are obtained.
  • the test method further includes: firstly, the filament-shaped working electrode 3 of the plurality of concentric three-electrode units is in an uncoupled state by controlling the high-speed switching switch 7, and the annular auxiliary electrode 1, the solid reference electrode 2, and the wire-like operation are performed.
  • the electrodes 3 are all connected to the electrochemical workstation 8; then the cyclic voltammetry curve test is performed; the electrochemical behavior of the single filamentary working electrode 3 is obtained by the open circuit potential test, and the electrochemical behavior of the single filamentary working electrode 3 is obtained by data analysis.
  • Single-electrode electrochemical, thermodynamic and kinetic information; the data analysis method includes: analyzing according to the cyclic voltammetry curve, and obtaining related information such as electrode reaction, reaction reversibility, reaction potential window, current peak and the like.
  • the test method further includes: firstly, the filament-shaped working electrode 3 of the plurality of concentric three-electrode units is in an uncoupled state by controlling the high-speed switching switch 7, and the annular auxiliary electrode 1, the solid reference electrode 2, and the wire-like operation are performed.
  • the electrodes 3 are all connected to the electrochemical workstation 8; then the polarization curve test is performed; the electrochemical behavior of the single filamentary working electrode 3 is obtained by the open circuit potential test, and the electrochemical behavior of the single filamentary working electrode 3 is analyzed by data.
  • Electrode electrochemical, thermodynamic and kinetic information; the data analysis method includes: the data analysis method of the polarization curve includes linear fitting, integral curve fitting, Tafel extrapolation and the like.
  • the test method further includes: firstly, the filament-shaped working electrode 3 of the plurality of concentric three-electrode units is in an uncoupled state by controlling the high-speed switching switch 7, and the annular auxiliary electrode 1, the solid reference electrode 2, and the wire-like operation are performed.
  • the electrodes 3 are connected to the electrochemical workstation 8; then the electrochemical impedance spectroscopy test is performed; the electrochemical behavior of the single filamentary working electrode 3 is obtained by the open circuit potential test, and the electrochemical behavior of the single filamentary working electrode 3 is obtained by data analysis.
  • Single-electrode electrochemical, thermodynamic and kinetic information; the data analysis method includes: data analysis methods of electrochemical impedance spectroscopy including dynamic analysis and equivalent circuit simulation.
  • the testing method further includes: testing galvanic current distribution information between each of the filamentary working electrodes 3 and the annular auxiliary electrode 1 and the solid reference electrode 2: firstly, the plurality of concentric three electrodes are controlled by controlling the high speed switching switch 7.
  • the wire-shaped working electrode 3 of the unit is in a non-coupling state, so that the annular auxiliary electrode 1, the solid reference electrode 2 and the wire-shaped working electrode 3 are connected to the electrochemical workstation 8; the high-speed switching switch 7 will be used in addition to the electrode to be tested. All of the electrodes are short-circuited into a single unit, and the current between the electrode to be tested and the other electrodes is tested one by one by the electrochemical workstation 8.
  • the test method further comprises: testing the single electrode anode reaction current density: based on the galvanic current of the single electrode measured in the coupled state, and the self-corrosion current density measured in the uncoupled state, and then performing algebraic addition.

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Abstract

一种三电极阵列局部电化学信息测试系统及测试方法，测试系统包括依次电连接的同心圆三电极阵列（5）、高速切换开关（7）和电化学工作站（8），同心圆三电极阵列（5）包括若干同心圆三电极单元，相邻的同心圆三电极单元之间通过绝缘材料（4）隔离；同心圆三电极单元包括环状辅助电极（1）、固态参比电极（2）和丝状工作电极（3），环状辅助电极（1）和固态参比电极（2）均成环形，丝状工作电极（3）位于固态参比电极（2）内，丝状工作电极（3）和固态参比电极（2）之间通过绝缘材料（4）隔离；固态参比电极（2）位于环状辅助电极（1）内。采用三电极阵列局部电化学信息测试系统更加便于全面获取电极耦合/非耦合状态下电偶电流、腐蚀电位、腐蚀电流密度、电化学阻抗谱等界面电化学信息。

Description

三电极阵列局部电化学信息测试系统及测试方法 技术领域
本发明涉及电化学测试领域，特别是涉及一种三电极阵列局部电化学信息测试系统和测试方法。
背景技术
电化学测试体系中不仅需要研究整个电极表面整体的信息，逐渐扩展到电极表面局部电化学信息的表征。例如金属局部腐蚀与界面进行的电化学过程休戚相关，其界面电位、电流密度、阻抗等局部的电化学参数分布特征对于研究局部腐蚀的分布特性和作用机制显得至关重要。经典的腐蚀电化学方法如循环伏安法、极化曲线、电化学交流阻抗谱等只能获取整个样品表面的电化学信息，给出的是统计平均的数据，难以对局部区域的电化学信号进行区分。
各种微区扫描探针电化学测试技术的发展为局部电化学信息的获取提供了有力的技术支撑。水相环境介质中，扫描振动电极(SVET)能测试溶液中金属材料表面电流密度分布；扫描电化学显微镜(SECM)能用来评价局部电化学氧化还原反应活性；局部电化学交流阻抗谱(LEIS)不仅能够研究具体某一点的全频率电化学阻抗谱，还能在固定频率下进行扫描测试研究电极表面阻抗分布特征。薄液膜电解液体系中，可采用扫描开尔文探针方法(SKP)进行不接触测试电极电位分布。以上测试方法的应用条件和获取的信息存在一定的局限性，只能获取电化学测试体系电位、电流、阻抗等某一方面的信息，而且部分为间接信息，例如，SVET和LEIS是基于界面阴阳极电化学反应导致电解质电场梯度进行的测试，分别获取的电流密度分布和微区阻抗并非基底材料的反应信息，SKP是基于电极表面功函进行的测试，直接测得的是开尔文电位，也不同于电极/溶液界面的电位。
然而，在更为复杂的气、液、固多相不均匀的测试体系中，由于含有固态成分，而无法使用SVET、LEIS等扫描移动微探针类型的微区电化学技术。常规阵列电极技术(EA)只能获得腐蚀电位和电偶电流分布信息，无法获得局部的电流、阻抗等数据，测试信息不够全面、丰富。而且在电阻率相对较大和电解液分散的体系中，阵列电极测得的电位精度还受到腐蚀介质欧姆电位降和电解液分散性的影响。因此，需要发展面向非均相体系综合电化学分布信息测试技术。
发明内容
本发明的目的在于，提供一种三电极阵列局部电化学信息测试系统，采用本系统更加便于全面获取电极耦合/非耦合状态下电偶电流、腐蚀电位、腐蚀电流密度、电化学阻抗谱等界 面电化学信息。同时，本发明还提供了该系统的测试方法。
为解决上述技术问题，本发明采用如下的技术方案：
一种三电极阵列局部电化学信息测试系统，包括依次电连接的同心圆三电极阵列、高速切换开关和电化学工作站，所述同心圆三电极阵列包括若干同心圆三电极单元，相邻的同心圆三电极单元之间通过绝缘材料隔离；所述同心圆三电极单元包括环状辅助电极、固态参比电极和丝状工作电极，所述环状辅助电极和固态参比电极均成环形，丝状工作电极位于固态参比电极内，丝状工作电极和固态参比电极之间通过绝缘材料隔离；固态参比电极位于环状辅助电极内，固态参比电极和环状辅助电极之间通过绝缘材料隔离；环状辅助电极、固态参比电极和丝状工作电极均和高速切换开关相连。
前述的三电极阵列局部电化学信息测试系统中，所述环状辅助电极的制作材料选用铂片、镀铂黑的铂片、石墨或哈氏合金；所述固态参比电极是固态Ag参比电极、AgCl参比电极或锌参比电极，此三种电极为固态参比电极，在常规自然环境腐蚀体系中电位较为稳定，经济有效。
以上所述三电极阵列局部电化学信息测试系统的测试方法包括：
首先通过控制高速切换开关使所述若干同心圆三电极单元的丝状工作电极处于非耦合状态，使环状辅助电极、固态参比电极和丝状工作电极均和电化学工作站相连；
然后进行开路电位测试，所述开路电位测试的方法包括：测试丝状工作电极与固态参比电极之间的电位差；
通过开路电位测试获得单个丝状工作电极的电化学行为，通过对单个丝状工作电极的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：开路电位，极化曲线，电化学阻抗谱，循环伏安，电偶电流，充电曲线等测试方法获得的测试数据，根据腐蚀电化学原理进行数据分析，获得相关的电位分布、电流密度分布、电化学阻抗、电容、腐蚀速度等热力学及动力学参数。
前述的三电极阵列局部电化学信息测试系统的测试方法中，所述测试方法还包括：
首先通过控制高速切换开关使所述若干同心圆三电极单元的丝状工作电极处于非耦合状态，使环状辅助电极、固态参比电极和丝状工作电极均和电化学工作站相连；
然后进行循环伏安曲线测试；
通过开路电位测试获得单个丝状工作电极的电化学行为，通过对单个丝状工作电极的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：具体的数据解析方法为根据循环伏安曲线进行分析，获得其电极反应、反应可逆性、反应电 位窗口、电流峰值等相关信息。
前述的三电极阵列局部电化学信息测试系统的测试方法中，所述测试方法还包括：
首先通过控制高速切换开关使所述若干同心圆三电极单元的丝状工作电极处于非耦合状态，使环状辅助电极、固态参比电极和丝状工作电极均和电化学工作站相连；
然后进行极化曲线测试；
通过开路电位测试获得单个丝状工作电极的电化学行为，通过对单个丝状工作电极的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：极化曲线的数据解析方法包括线性拟合、整体曲线拟合、Tafel外推等方法。
前述的三电极阵列局部电化学信息测试系统的测试方法中，所述测试方法还包括：
首先通过控制高速切换开关使所述若干同心圆三电极单元的丝状工作电极处于非耦合状态，使环状辅助电极、固态参比电极和丝状工作电极均和电化学工作站相连；
然后进行电化学阻抗谱测试；
通过开路电位测试获得单个丝状工作电极的电化学行为，通过对单个丝状工作电极的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：电化学阻抗谱的数据解析方法包括动力学分析和等效电路模拟两种方法。
前述的三电极阵列局部电化学信息测试系统的测试方法中，所述测试方法还包括：
测试每个丝状工作电极与环状辅助电极和固态参比电极之间电偶电流分布信息：
首先通过控制高速切换开关使所述若干同心圆三电极单元的丝状工作电极处于非耦合状态，使环状辅助电极、固态参比电极和丝状工作电极均和电化学工作站相连；
通过高速切换开关将除待测电极之外的所有电极短路连接成一个整体，通过电化学工作站(8)逐个测试待测电极和其他电极之间的电流。
前述的三电极阵列局部电化学信息测试系统的测试方法中，所述测试方法还包括：
测试单电极阳极反应电流密度：基于耦合状态下测得的单个电极的电偶电流，以及非耦合状态下测得的自腐蚀电流密度，然后进行代数相加。耦合状态指的是将三电极阵列中的各个工作电极导线短路连接在一起，形成各个电极反应之间的耦合状态。非耦合状态指的是组成阵列的每组三电极独立工作状态，未将各组阵列中的工作电极短路连接在一起。
与现有技术相比，本发明具有以下优点：
(1)实现阵列电极和三电极体系的有机结合，便于全面获取电极耦合/非耦合状态下电偶电流、腐蚀电位、腐蚀电流密度、电化学阻抗谱等界面电化学信息，测试信息更加全面、丰富。而常规阵列电极只能获得电位和电偶电流分布信息，无法获得局部的电流、阻抗等数 据。
(2)本发明提供的近距同心圆三电极阵列，实现了将辅助电极和参比电极2围绕工作电极近距离环状分布，测试时电力线分布更为均匀；而且在电阻率相对较大和电解液分散的体系中，由于参比电极和工作电极距离较近，电位测试精度较高，电流测试不易出现断路。
这种局部电化学测试方法具有一定的普适性，可以推广到大气腐蚀、土壤腐蚀、沉积物下腐蚀、涂层下腐蚀等多种非均相介质腐蚀电化学研究体系，或应用于电偶腐蚀、缝隙腐蚀、冲刷腐蚀等典型局部腐蚀类型研究。
附图说明
图1为同心圆三电极单元结构示意图；
图2为同心圆三电极阵列结构示意图；
图3为基于同心圆型三电极阵列的局部电化学信息测试系统示意图；
附图标记：1-环状辅助电极，2-固态参比电极，3-丝状工作电极，4-绝缘材料，5-同心圆三电极阵列，6-导线，7-高速切换开关，8-电化学工作站。
下面结合附图和具体实施方式对本发明作进一步的说明。
具体实施方式
本发明的实施例1：如图1、图2和图3所示，一种三电极阵列局部电化学信息测试系统，包括依次通过导线6电连接的同心圆三电极阵列5、高速切换开关7和电化学工作站8，所述同心圆三电极阵列5包括若干同心圆三电极单元，相邻的同心圆三电极单元之间通过绝缘材料4隔离；所述同心圆三电极单元包括环状辅助电极1、固态参比电极2和丝状工作电极3，所述环状辅助电极1和固态参比电极2均成环形，丝状工作电极3位于固态参比电极2内，丝状工作电极3和固态参比电极2之间通过绝缘材料4隔离；固态参比电极2位于环状辅助电极1内，固态参比电极2和环状辅助电极1之间通过绝缘材料4隔离；环状辅助电极1、固态参比电极2和丝状工作电极3均和高速切换开关7相连。所述绝缘材料4选用绝缘环氧树脂。所述环状辅助电极的制作材料选用铂片、镀铂黑的铂片、石墨或哈氏合金。所述固态参比电极2是固态Ag参比电极、AgCl参比电极或锌参比电极。
以上实施例所述三电极阵列局部电化学信息测试系统的测试方法，所述测试方法包括：
首先通过控制高速切换开关7使所述若干同心圆三电极单元的丝状工作电极3处于非耦合状态，使环状辅助电极1、固态参比电极2和丝状工作电极3均和电化学工作站8相连；然后进行开路电位测试，所述开路电位测试的方法包括：测试丝状工作电极与固态参比电极之间的电位差；通过开路电位测试获得单个丝状工作电极3的电化学行为，通过对单个丝状 工作电极3的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：开路电位，极化曲线，电化学阻抗谱，循环伏安，电偶电流，充电曲线等测试方法获得的测试数据，根据腐蚀电化学原理进行数据分析，获得相关的电位分布、电流密度分布、电化学阻抗、电容、腐蚀速度等热力学及动力学参数。
所述测试方法还包括：首先通过控制高速切换开关7使所述若干同心圆三电极单元的丝状工作电极3处于非耦合状态，使环状辅助电极1、固态参比电极2和丝状工作电极3均和电化学工作站8相连；然后进行循环伏安曲线测试；通过开路电位测试获得单个丝状工作电极3的电化学行为，通过对单个丝状工作电极3的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：根据循环伏安曲线进行分析，获得其电极反应、反应可逆性、反应电位窗口、电流峰值等相关信息。
所述测试方法还包括：首先通过控制高速切换开关7使所述若干同心圆三电极单元的丝状工作电极3处于非耦合状态，使环状辅助电极1、固态参比电极2和丝状工作电极3均和电化学工作站8相连；然后进行极化曲线测试；通过开路电位测试获得单个丝状工作电极3的电化学行为，通过对单个丝状工作电极3的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：极化曲线的数据解析方法包括线性拟合、整体曲线拟合、Tafel外推等方法。
所述测试方法还包括：首先通过控制高速切换开关7使所述若干同心圆三电极单元的丝状工作电极3处于非耦合状态，使环状辅助电极1、固态参比电极2和丝状工作电极3均和电化学工作站8相连；然后进行电化学阻抗谱测试；通过开路电位测试获得单个丝状工作电极3的电化学行为，通过对单个丝状工作电极3的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息；所述数据解析方法包括：电化学阻抗谱的数据解析方法包括动力学分析和等效电路模拟两种方法。
所述测试方法还包括：测试每个丝状工作电极3与环状辅助电极1和固态参比电极2之间电偶电流分布信息：首先通过控制高速切换开关7使所述若干同心圆三电极单元的丝状工作电极3处于非耦合状态，使环状辅助电极1、固态参比电极2和丝状工作电极3均和电化学工作站8相连；通过高速切换开关7将除待测电极之外的所有电极短路连接成一个整体，通过电化学工作站8逐个测试待测电极和其他电极之间的电流。
所述测试方法还包括：测试单电极阳极反应电流密度：基于耦合状态下测得的单个电极的电偶电流，以及非耦合状态下测得的自腐蚀电流密度，然后进行代数相加。

Claims (9)

  1. 一种三电极阵列局部电化学信息测试系统，其特征在于，包括依次电连接的同心圆三电极阵列(5)、高速切换开关(7)和电化学工作站(8)，所述同心圆三电极阵列(5)包括若干同心圆三电极单元，相邻的同心圆三电极单元之间通过绝缘材料(4)隔离；所述同心圆三电极单元包括环状辅助电极(1)、固态参比电极(2)和丝状工作电极(3)，所述环状辅助电极(1)和固态参比电极(2)均成环形，丝状工作电极(3)位于固态参比电极(2)内，丝状工作电极(3)和固态参比电极(2)之间通过绝缘材料(4)隔离；固态参比电极(2)位于环状辅助电极(1)内，固态参比电极(2)和环状辅助电极(1)之间通过绝缘材料(4)隔离；环状辅助电极(1)、固态参比电极(2)和丝状工作电极(3)均和高速切换开关(7)相连。
  2. 根据权利要求1所述的三电极阵列局部电化学信息测试系统，其特征在于，所述环状辅助电极(1)的制作材料选用铂片、镀铂黑的铂片、石墨或哈氏合金。
  3. 根据权利要求1所述的三电极阵列局部电化学信息测试系统，其特征在于，所述固态参比电极(2)是固态Ag参比电极、AgCl参比电极或锌参比电极。
  4. 权利要求1至3任一项所述三电极阵列局部电化学信息测试系统的测试方法，其特征在于，所述测试方法包括：
    首先通过控制高速切换开关(7)使所述若干同心圆三电极单元的丝状工作电极(3)处于非耦合状态，使环状辅助电极(1)、固态参比电极(2)和丝状工作电极(3)均和电化学工作站(8)相连；
    然后进行开路电位测试，所述开路电位测试的方法包括：测试丝状工作电极与固态参比电极之间的电位差；
    通过开路电位测试获得单个丝状工作电极(3)的电化学行为，通过对单个丝状工作电极(3)的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息。
  5. 根据权利要求4所述的三电极阵列局部电化学信息测试系统的测试方法，其特征在于，所述测试方法还包括：
    首先通过控制高速切换开关(7)使所述若干同心圆三电极单元的丝状工作电极(3)处于非耦合状态，使环状辅助电极(1)、固态参比电极(2)和丝状工作电极(3)均和电化学工作站(8)相连；然后进行循环伏安曲线测试；
    通过开路电位测试获得单个丝状工作电极(3)的电化学行为，通过对单个丝状工作电极(3)的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息。
  6. 根据权利要求4所述的三电极阵列局部电化学信息测试系统的测试方法，其特征在 于，所述测试方法还包括：
    首先通过控制高速切换开关(7)使所述若干同心圆三电极单元的丝状工作电极(3)处于非耦合状态，使环状辅助电极(1)、固态参比电极(2)和丝状工作电极(3)均和电化学工作站(8)相连；然后进行极化曲线测试；
    通过开路电位测试获得单个丝状工作电极(3)的电化学行为，通过对单个丝状工作电极(3)的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息。
  7. 根据权利要求4所述的三电极阵列局部电化学信息测试系统的测试方法，其特征在于，所述测试方法还包括：
    首先通过控制高速切换开关(7)使所述若干同心圆三电极单元的丝状工作电极(3)处于非耦合状态，使环状辅助电极(1)、固态参比电极(2)和丝状工作电极(3)均和电化学工作站(8)相连；然后进行电化学阻抗谱测试；
    通过开路电位测试获得单个丝状工作电极(3)的电化学行为，通过对单个丝状工作电极(3)的电化学行为进行数据解析获得单电极电化学、热力学及动力学信息。
  8. 根据权利要求4所述的三电极阵列局部电化学信息测试系统的测试方法，其特征在于，所述测试方法还包括：测试每个丝状工作电极(3)与环状辅助电极(1)和固态参比电极(2)之间电偶电流分布信息：
    首先通过控制高速切换开关(7)使所述若干同心圆三电极单元的丝状工作电极(3)处于非耦合状态，使环状辅助电极(1)、固态参比电极(2)和丝状工作电极(3)均和电化学工作站(8)相连；
    通过高速切换开关(7)将除待测电极之外的所有电极短路连接成一个整体，通过电化学工作站(8)逐个测试待测电极和其他电极之间的电流。
  9. 根据权利要求4所述的三电极阵列局部电化学信息测试系统的测试方法，其特征在于，所述测试方法还包括：
    测试单电极阳极反应电流密度：基于耦合状态下测得的单个电极的电偶电流，以及非耦合状态下测得的自腐蚀电流密度，然后进行代数相加。
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