A patch clamp probe for testing material state density and its use method
By designing a patch clamp probe that integrates electrolyte, electrolytic cell and electrode, the problem that traditional tests cannot distinguish the electrochemical contribution of local active sites is solved, the local electrochemical information of micro-nano energy storage on-chip devices can be obtained, the preparation process is simplified and the cost is reduced.
Patent Information
- Application Number
- CN202411827817.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-11
- Publication Date
- 2025-09-09
- Estimated Expiration
- 2044-12-11
AI Technical Summary
Electrochemical testing of traditional micro-nano energy storage on-chip devices cannot distinguish the electrochemical contribution of local active sites, making it difficult to obtain true electrochemical information of local active sites.
A patch clamp probe is designed, which integrates electrolyte, electrolytic cell, counter electrode and reference electrode. A three-dimensional mobile device is used to approach the surface of the micro-nano energy storage chip device to be tested for local electrochemical testing.
The preparation process of micro-nano energy storage on-chip devices has been simplified, and the electrochemical state density characterization of different active sites has been realized, which is low-cost and highly adaptable.
Smart Images
Figure CN119643363B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of micro-nano energy storage devices, and in particular relates to a patch clamp probe for testing material state density and a method for using the same. Background Art
[0002] As a micro-device for electrochemical testing, micro-nano energy storage on-chip devices offer unique advantages. Compared to electrochemical testing of traditional materials, they can measure electrochemical information within the material window region. However, electrochemical testing of traditional micro-nano energy storage on-chip devices can only obtain the average information of the contributions of all active sites within the window region, but cannot understand the true contribution of local active sites. Therefore, it is difficult to distinguish the electrochemical contribution of local active sites in various materials.
[0003] Therefore, we independently designed a patch clamp probe to integrate the electrolyte, electrolytic cell, counter electrode and reference electrode for electrochemical testing of traditional micro-nano energy storage on-chip devices. The patch clamp probe is moved by a three-dimensional mobile device to approach the surface site of the micro-nano energy storage on-chip device to be tested. This not only simplifies the preparation process of micro-nano energy storage on-chip devices, but also realizes the electrochemical state density characterization of different active sites of the same micro-nano energy storage on-chip device. Summary of the Invention
[0004] The present invention aims to provide a patch clamp probe for measuring the density of states of a material. By integrating the electrolyte, electrolytic cell, counter electrode, and reference electrode of a conventional micro-nano energy storage chip device, the electrochemical density of states information at different sites and regions of the chip device can be measured.
[0005] In order to achieve the above-mentioned purpose, the present application provides a patch clamp probe for testing the state density of a material, characterized in that the patch clamp probe includes a patch clamp pipette, a custom polytetrafluoroethylene sleeve, a reference electrode and a counter electrode, the patch clamp pipette is drawn from a glass tube, and a tip structure is formed at one end of the patch clamp pipette by drawing, and both ends of the patch clamp pipette have openings, wherein the inner diameter of the opening on the side with the tip structure is smaller than the inner diameter of the opening on the other side, the middle part of the custom polytetrafluoroethylene sleeve is provided with a through hole adapted to the outer diameter of the pipette, and two blind holes are symmetrically arranged at both ends of the through hole, and the patch clamp pipette is far One side away from the tip structure is fixedly installed in the through hole of the custom polytetrafluoroethylene sleeve, and conductive copper rods are respectively installed in the two blind holes at the upper end of the custom polytetrafluoroethylene sleeve. The conductive copper rods are symmetrically distributed relative to the patch clamp pipette. The patch clamp pipette is filled with electrolyte. The reference electrode and the counter electrode are inserted into the patch clamp pipette from the side with the larger opening of the patch clamp pipette and contact with the electrolyte. The patch clamp probe also includes a sealing rubber cap, which fixes the reference electrode and the counter electrode and seals the opening on the side where the electrode is located. The reference electrode and the counter electrode are respectively conductively connected to the conductive copper rods.
[0006] Furthermore, the inner diameter of the tip of the patch clamp pipette is 200 nm-1000 nm.
[0007] Furthermore, the reference electrode is an Ag / AgCl reference electrode, which is obtained by constant current electrodeposition, specifically by immersing a pure Ag wire as a working electrode in an HCl solution and performing constant current electrodeposition on a commercial Pt electrode as a counter electrode.
[0008] Furthermore, the counter electrode is a Pt counter electrode, and the Pt counter electrode is prepared by Pt metal wire.
[0009] Furthermore, the electrolyte may be one of a 0.5 mol / L sulfuric acid solution, a hydroxymethylferrocene solution or a BMMIBF4 solution.
[0010] Furthermore, the glass tube is made of one of borosilicate glass, lead glass, laminated glass, and ceramic glass.
[0011] Furthermore, the inner diameter of the glass tube is 0.5-3 mm, and the outer diameter is 1-5 mm.
[0012] Furthermore, the diameter of the Ag / AgCl reference electrode is 0.1-0.3 mm; the diameter of the Pt counter electrode is 0.1-0.3 mm.
[0013] The present invention also provides a method for testing the state density of a material using the patch clamp probe described above, comprising the following steps:
[0014] (1) Place the micro-nano energy storage chip device on a three-dimensional movable micro-probe platform, press the metal probe of the micro-probe platform onto the gold electrode of the chip device as a wire connecting the working electrode to the electrochemical workstation;
[0015] (2) Fix the patch clamp probe on the three-axis movable probe clamp of the scanning electrochemical microscope, and connect the reference electrode and counter electrode of the patch clamp probe to the electrochemical workstation;
[0016] (3) Using a scanning electrochemical microscope, the tip of the patch clamp probe is brought close to the surface site of the micro-nano energy storage chip device to be tested. By adjusting the electrochemical test parameters, electrochemical tests are performed on different sites of the same micro-nano energy storage chip device to obtain the state density information of the material on the micro-nano energy storage chip device.
[0017] Furthermore, the micro-nano energy storage chip device includes a silicon base layer, a silicon dioxide layer on the surface of the silicon base layer, a gold electrode layer with a regular pattern arranged on the surface of the silicon dioxide, and the material to be tested is deposited on the silicon dioxide layer and conductively connected to the regular pattern gold electrode.
[0018] Beneficial effects of the present invention:
[0019] The present invention integrates electrolyte, electrolytic cell, counter electrode and reference electrode by adopting patch clamp probe, and moves the patch clamp probe by three-dimensional moving device to approach the surface of micro-nano energy storage chip device to be tested, which not only simplifies the preparation process of micro-nano energy storage chip device, but also obtains state density information of different sites by testing local electrochemical information of different sites of the same on-chip device, thereby realizing electrochemical state density characterization of different active sites of the same micro-nano energy storage chip device. At the same time, the patch clamp probe of the present application has a simple manufacturing process and low raw material cost. At the same time, different probe systems can be prepared according to different materials and have good adaptability. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] In order to more clearly illustrate the technical solution of the embodiment of the present invention, the structure of the embodiment is briefly described below with reference to the accompanying drawings.
[0021] Figure 1 Schematic diagram of the overall structure of the micro-nano energy storage on-chip device test provided by the embodiment of the present invention
[0022] Figure 2 Schematic flow chart of the preparation of the patch clamp probe provided in the embodiment of the present invention
[0023] Figure 3 Physical flow chart for preparing patch clamp probes provided in an embodiment of the present invention
[0024] Reference numerals: 1 - patch clamp pipette; 2 - electrolyte; 3 - custom polytetrafluoroethylene sleeve; 4 - conductive copper rod; 5 - Pt electrode; 6 - Ag / AgCl electrode; 7 - sealing rubber cap. DETAILED DESCRIPTION
[0025] To make the technical solutions and advantages of the present invention more clear, the present invention and its beneficial effects will be described in further detail below with reference to specific implementation methods and accompanying drawings, but the implementation methods of the present invention are not limited thereto.
[0026] In this disclosure, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b and c" can refer to a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or plural.
[0027] Figure 2 The schematic flow chart of the preparation of the patch clamp probe provided by the embodiment of the present invention is as follows: Figure 2 It can be determined that the patch clamp probe includes a patch clamp pipette and a custom polytetrafluoroethylene sleeve. The patch clamp pipette is drawn from a glass tube. A tip structure is formed at one end of the patch clamp pipette, and both ends have openings, wherein the inner diameter of the opening on the side with the tip structure is smaller than the inner diameter of the opening on the other side. A through hole that matches the outer diameter of the pipette is provided in the middle portion of the custom polytetrafluoroethylene sleeve, and two blind holes are symmetrically arranged at both ends of the through hole. The side of the patch clamp pipette away from the tip structure is fixedly mounted on the through hole of the custom polytetrafluoroethylene sleeve. In the hole, conductive copper rods are respectively installed in the two blind holes at the upper end of the custom polytetrafluoroethylene sleeve. The conductive copper rods are symmetrically distributed relative to the patch clamp pipette. The patch clamp pipette is filled with electrolyte. The Ag / AgCl reference electrode and the Pt counter electrode are inserted into the electrolyte from the opening on the other side of the patch clamp pipette relative to the tip side, and the opening is sealed by a sealing rubber cap. At the same time, the Ag / AgCl reference electrode and the Pt counter electrode are fixed, and the reference electrode and the counter electrode are respectively conductively connected to the conductive copper rods.
[0028] The patch clamp pipette was drawn using a needle puller (HL-1000). The glass tube used was made of borosilicate. The glass tube was 10 cm long, 1.5 mm in outer diameter, 1.0 mm in inner diameter, and 0.25 mm in wall thickness. The tip of the pipette obtained by drawing had an outer diameter of 600 nm, an inner diameter of 500 nm, and a wall thickness of 100 nm.
[0029] The Ag / AgCl reference electrode was obtained by constant current electrodeposition. A pure Ag wire with a diameter of 0.1 mm was used as a working electrode and immersed in a 0.1 mol / L HCl solution. A commercial Pt electrode was used as a counter electrode for constant current electrodeposition. The electrodeposition current was 0.0003 mA and the deposition time was 10 mins.
[0030] The Pt counter electrode is a Pt metal wire with a diameter of 0.1 mm.
[0031] The custom polytetrafluoroethylene sleeve is a cylinder with a diameter of 10 mm and a height of 8 mm, a through hole with a diameter of 1.5 mm in the middle, and two blind holes with a side length of 2 mm at both ends.
[0032] The conductive copper rod is a T2 copper rod with a side length of 2 mm and a length of 3 cm.
[0033] The sealing rubber is a black rubber cap with a diameter of 1.3 mm.
[0034] Furthermore, in a preferred embodiment of the present invention, the electrolyte may be 0.5 mol / L sulfuric acid, hydroxymethylferrocene solution, BMMIBF4 or other solutions.
[0035] Figure 3 The structural assembly diagram of the patch clamp probe for testing the material state density is as follows:
[0036] Step 1: Place a borosilicate glass tube with an outer diameter of 1.5 mm and an inner diameter of 1.0 mm on a needle puller (HL-1000) and pull it to obtain a patch clamp pipette with a tip outer diameter of 600 nm and an inner diameter of 500 nm.
[0037] Step 2: Use a micro syringe to slowly inject the electrolyte into the patch clamp pipette. Apply pressure and blow air at the end of the pipette to expel bubbles and ensure that the electrolyte is fully conductive in the pipette.
[0038] Step 3: Fix the two conductive copper rods to the blind holes at both ends of the custom polytetrafluoroethylene sleeve, and then fix the sleeve to the appropriate position at the end of the patch clamp pipette.
[0039] Step 4: Place the homemade 0.1mm diameter Ag / AgCl electrode and Pt electrode in appropriate positions of the patch clamp pipette.
[0040] Step 5: Seal the base of the patch clamp pipette with a rubber cap to prevent the electrolyte from evaporating.
[0041] Step 6: Use solder to connect the 0.1 mm Ag / AgCl electrode and Pt electrode to the conductive copper rods at both ends of the custom PTFE sleeve.
[0042] Figure 1 This is a schematic diagram of the overall structure of the micro-nano energy storage chip device test. The method of using a patch clamp probe to test the material state density includes the following steps:
[0043] (1) Place the micro-nano energy storage chip device on a three-dimensional movable micro-probe platform, press the metal probe of the micro-probe platform onto the gold electrode of the chip device as a wire connecting the working electrode to the electrochemical workstation;
[0044] (2) Fix the patch clamp probe on the three-axis movable probe clamp of the Chenhua scanning electrochemical microscope, and connect the Ag / AgCl metal wire and Pt wire of the patch clamp probe to the electrochemical workstation as the reference electrode and counter electrode respectively;
[0045] (3) Using a scanning electrochemical microscope, the tip of the patch clamp probe is brought close to the surface site of the micro-nano energy storage chip device to be tested. By adjusting the electrochemical test parameters, electrochemical tests are performed on different sites of the same micro-nano energy storage chip device to obtain the state density information of the material on the micro-nano energy storage chip device.
[0046] The micro-nano energy storage on-chip device includes a silicon base layer, a silicon dioxide layer on the surface of the silicon base layer, and a gold electrode layer with a regular pattern on the silicon dioxide surface. The material to be tested is deposited on the silicon dioxide layer and conductively connected to the regularly patterned gold electrode.
[0047] By using a patch clamp probe to integrate the electrolyte, electrolytic cell, counter electrode and reference electrode, and moving the patch clamp probe through a three-dimensional moving device to approach the surface of the micro-nano energy storage chip device to be tested, not only can the preparation process of the micro-nano energy storage chip device be simplified, but also by testing the local electrochemical information of different sites of the same on-chip device, the state density information of different sites can be obtained, and the electrochemical state density characterization of different active sites of the same micro-nano energy storage chip device can be realized. At the same time, the patch clamp probe of the present application has a simple manufacturing process and low raw material cost. At the same time, different probe systems can be prepared according to different materials and have good adaptability.
[0048] The above are merely exemplary embodiments of the present disclosure and are not intended to limit the scope of the present disclosure. That is, any equivalent changes and modifications made in accordance with the teachings of the present disclosure are still within the scope of the present disclosure. After considering the disclosure of the specification and the truth of practice, those skilled in the art will easily think of other embodiments of the present disclosure. This application is intended to cover any variations, uses, or adaptive changes of the present disclosure, which follow the general principles of the present disclosure and include common knowledge or customary techniques in the art that are not described in the present disclosure.
Claims
1. A patch clamp probe for measuring the state density of a material, characterized in that: The patch clamp probe includes a patch clamp pipette, a custom polytetrafluoroethylene sleeve, a reference electrode and a counter electrode. The patch clamp pipette is drawn from a glass tube, and a tip structure is formed at one end of the patch clamp pipette by drawing. Both ends of the patch clamp pipette have openings, wherein the inner diameter of the opening on the side with the tip structure is smaller than the inner diameter of the opening on the other side. The middle part of the custom polytetrafluoroethylene sleeve is provided with a through hole adapted to the outer diameter of the pipette, and two blind holes are symmetrically arranged at both ends of the through hole. The side of the patch clamp pipette away from the tip structure is fixedly mounted on the polytetrafluoroethylene. Conductive copper rods are respectively installed in the through hole of the customized polytetrafluoroethylene sleeve and the two blind holes at the upper end of the customized polytetrafluoroethylene sleeve, and the conductive copper rods are symmetrically distributed relative to the patch clamp pipette. The patch clamp pipette is filled with electrolyte, and the reference electrode and the counter electrode are inserted into the patch clamp pipette from the side with the larger opening of the patch clamp pipette and contact with the electrolyte. The patch clamp probe also includes a sealing rubber cap, which fixes the reference electrode and the counter electrode and seals the opening on the side where the electrode is located. The reference electrode and the counter electrode are respectively conductively connected to the conductive copper rods.
2. The patch clamp probe according to claim 1, wherein The inner diameter of the patch clamp pipette tip is 200 nm-1000 nm.
3. The patch clamp probe for testing material state density according to claim 1, characterized in that: The reference electrode is an Ag / AgCl reference electrode, which is obtained by constant current electrodeposition. Specifically, a pure Ag wire is used as a working electrode and immersed in an HCl solution, and a commercial Pt electrode is used as a counter electrode and prepared by constant current electrodeposition.
4. The patch clamp probe for testing material state density according to claim 3, characterized in that: The counter electrode is a Pt counter electrode, and the Pt counter electrode is prepared by Pt metal wire.
5. The patch clamp probe for testing material state density according to claim 1, wherein: The electrolyte is one of a hydroxymethylferrocene solution, a BMMIBF4 solution or a 0.5 mol / L sulfuric acid solution.
6. The patch clamp probe for testing material state density according to claim 1, characterized in that: The glass tube is made of one of borosilicate glass, lead glass, laminated glass and ceramic glass.
7. The patch clamp probe for measuring material state density according to claim 1, wherein: The inner diameter of the glass tube is 0.5-3 mm, and the outer diameter is 1-5 mm.
8. The patch clamp probe for testing material state density according to claim 4, wherein: The diameter of the Ag / AgCl reference electrode is 0.1-0.3 mm; the diameter of the Pt counter electrode is 0.1-0.3 mm.
9. A method for measuring the state density of a material using the patch clamp probe according to any one of claims 1 to 8, comprising the following steps: (1) Place the micro-nano energy storage chip device on a three-dimensional movable micro-probe platform, press the metal probe of the micro-probe platform onto the gold electrode of the chip device as a wire connecting the working electrode to the electrochemical workstation; (2) Fix the patch clamp probe on the three-axis movable probe clamp of the scanning electrochemical microscope, and connect the reference electrode and counter electrode of the patch clamp probe to the electrochemical workstation; (3) Using a scanning electrochemical microscope, the tip of the patch clamp probe is brought close to the surface site of the micro-nano energy storage chip device to be tested. By adjusting the electrochemical test parameters, electrochemical tests are performed on different sites of the same micro-nano energy storage chip device to obtain the state density information of the material on the micro-nano energy storage chip device.
10. The method according to claim 9, characterized in that The micro-nano energy storage on-chip device includes a silicon base layer, a silicon dioxide layer on the surface of the silicon base layer, and a gold electrode layer with a regular pattern on the silicon dioxide surface. The material to be tested is deposited on the silicon dioxide layer and conductively connected to the gold electrode with a regular pattern.