A bending-resistant reference electrode paste

Abstract

The application provides a bending-resistant reference electrode slurry, which adopts a perfluoro organic elastic system, has high bending stability and weather resistance, and realizes good contact between silver powder and AgCl powder through decomposition of silver tetrafluoroborate to generate nano silver rivet points in a forming process, so that the reference potential stability is improved.

Description

Technical Field

[0001] This invention relates to the field of electronic sensor materials, and in particular to a reference electrode paste. Background Technology

[0002] Ag / AgCl reference electrodes are commonly used in IVD (In Vitro Diagnostics) devices, such as those for electrocardiogram (ECG), electroencephalogram (EEG), electromyography (EMG), and blood glucose monitoring. They are characterized by constant potential, low impedance, low polarization, and sensitivity to low-frequency electric fields. Printable Ag / AgCl slurries can be used for miniature solid-state reference electrodes. In many applications, these electrodes require excellent printability, flexibility, conductivity, and low-temperature thermosetting properties, especially stable resistance after integral molding. Furthermore, they need to meet environmental durability testing requirements such as dual 85°C. Therefore, targeted improvements to address these issues are essential. Summary of the Invention

[0003] To address the shortcomings of the prior art, the present invention provides a bend-resistant reference electrode paste to solve the problems of bending stability and long-term service environment stability of the reference electrode paste.

[0004] To achieve the above-mentioned technical objectives, the technical solution of the present invention is prepared from the following components by mass percentage: Silver powder 30-50%; AgCl powder 10~20%; Silver tetrafluoroborate 0.5~2%; Perfluoromethyl vinyl ether 20-25%; 5-10% perfluorophenoxypropyl vinyl ether; Perfluorosulfonyl vinyl ethers: 6-12%; Diluent 5~10%; Crosslinking agent 1~2%; The sum of the mass percentages of the components is 100%.

[0005] Preferably, the silver powder is flake-shaped silver powder with a D50 particle size of 5~15μm and a tap density of 3~4g / cm3.

[0006] Preferably, the AgCl powder D50 has a particle size of 0.5~1 μm.

[0007] Preferably, the crosslinking agent is hexafluorobisphenol A.

[0008] Preferably, the diluent is perfluoropolyether.

[0009] The present invention also provides a method for preparing a flexurally resistant reference electrode paste, wherein silver tetrafluoroborate, perfluoromethyl vinyl ether, perfluorophenoxypropyl vinyl ether, perfluorosulfonyl vinyl ether and a crosslinking agent are dissolved in a diluent, the mixture is mixed using a spin coater, and silver powder and AgCl powder are added and then dispersed and homogenized using a kneader to obtain the flexurally resistant reference electrode paste.

[0010] The bend-resistant reference electrode paste of the present invention adopts a perfluorinated organic elastic system, which has high bending stability and weather resistance. Silver tetrafluoroborate decomposes during the molding process to generate nano-silver welding points, achieving good contact between silver powder and AgCl powder and improving the stability of reference potential. Detailed Implementation

[0011] The technical solution of the present invention will be further described below with reference to specific embodiments, but the present invention is not limited to these embodiments. Those skilled in the art should understand that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations on the present invention.

[0012] This invention provides a flexurally resistant reference electrode paste, which is prepared from the following components: Silver powder 30-50%; AgCl powder 10~20%; Silver tetrafluoroborate 0.5~2%; Perfluoromethyl vinyl ether 20-25%; 5-10% perfluorophenoxypropyl vinyl ether; Perfluorosulfonyl vinyl ethers: 6-12%; Diluent 5~10%; Crosslinking agent 1~2%; The sum of the mass percentages of the components is 100%. The proportions of each component are reasonably distributed within their respective ranges, taking into account conductivity, printability, and curing properties.

[0013] The flexurally resistant reference electrode slurry of the present invention is prepared by the following method: silver tetrafluoroborate, perfluoromethyl vinyl ether, perfluorophenoxypropyl vinyl ether, perfluorosulfonyl vinyl ether, and crosslinking agent hexafluorobisphenol A are dissolved in a diluent of perfluoropolyether. The mixture is then mixed using a spin coater. After adding silver powder and AgCl powder, the mixture is dispersed and homogenized using a kneader to obtain the flexurally resistant reference electrode slurry. The silver powder is flake-shaped with a D50 particle size of 5-15 μm and a tap density of 3-4 g / cm³. The AgCl powder has a D50 particle size of 0.5-1 μm.

[0014] Example 1: A stretchable conductive paste was prepared using the above preparation method. The proportions of each component were as follows: 40% silver powder, 15% AgCl powder, 1% silver tetrafluoroborate; 20% perfluoromethyl vinyl ether, 8% perfluorophenoxypropyl vinyl ether, 8% perfluorosulfonyl vinyl ether; 1.5% hexafluorobisphenol A, and 6.5% perfluoropolyether.

[0015] Example 2: A stretchable conductive paste was prepared using the above preparation method. The proportions of each component were as follows: 30% silver powder, 10% AgCl powder, 2% silver tetrafluoroborate; 24% perfluoromethyl vinyl ether, 10% perfluorophenoxypropyl vinyl ether, 12% perfluorosulfonyl vinyl ether; 2% hexafluorobisphenol A, and 10% perfluoropolyether.

[0016] Example 3: A stretchable conductive paste was prepared using the above preparation method. The proportions of each component were as follows: 42.5% silver powder, 20% AgCl powder, 0.5% silver tetrafluoroborate; 20% perfluoromethyl vinyl ether, 5% perfluorophenoxypropyl vinyl ether, 6% perfluorosulfonyl vinyl ether; 1% hexafluorobisphenol A, and 5% perfluoropolyether.

[0017] Comparative Example 1: In Example 1, silver tetrafluoroborate was replaced with silver nanoparticles, while other components and processes remained the same.

[0018] Comparative Example 2: The composition and content of silver powder and AgCl were the same as in Example 1, but the bisphenol A epoxy and TPU system was used instead of the fluororesin system.

[0019] The products of the examples and comparative examples were printed on TPU elastic substrates and then cured at 120°C. The test performance results are shown in Table 1.

[0020] Table 1 Molding resistance (Ω) 180° bend 1000 times (Ω) 85℃ 85RH (Ω) Potential change (mV / h) after 200 180° bends Example 1 17.8 18.0 22.4 0.02 Comparative Example 1 18.2 24.1 18.9 0.34 Comparative Example 2 27.6 29.1 38.4 0.22 Example 2 15.3 15.8 15.5 0.04 Example 3 22.8 22.9 22.9 0.02 As shown in Table 1, when using a bend-resistant reference electrode paste, compared to Example 1, replacing silver tetrafluoroborate with nano-silver powder significantly increased the bending resistance and potential drift in Comparative Example 1. Silver tetrafluoroborate acts as an in-situ cold-welding anchor point in the system. Compared to Example 1, Comparative Example 2, by replacing the silver tetrafluoroborate with a bisphenol A epoxy and TPU system, showed increased resistance and potential drift during bending and aging at 85℃ and 85RH.

[0021] In summary, the bend-resistant reference electrode paste of the present invention employs a perfluorinated organic elastic system, exhibiting high bend stability and weather resistance. During the molding process, silver tetrafluoroborate decomposes to generate nano-silver welding points, achieving good contact between the silver powder and AgCl powder and improving reference potential stability. Therefore, the present invention effectively overcomes the shortcomings of existing technologies and possesses high industrial value.

[0022] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A flexurally resistant reference electrode paste, characterized in that, It is prepared from the following components according to the mass percentage: Silver powder 30-50%; AgCl powder 10~20%; Silver tetrafluoroborate 0.5~2%; Perfluoromethyl vinyl ether 20-25%; 5-10% perfluorophenoxypropyl vinyl ether; Perfluorosulfonyl vinyl ethers: 6-12%; Diluent 5~10%; Crosslinking agent 1~2%; The sum of the mass percentages of the components is 100%.

2. The flexurally resistant reference electrode paste according to claim 1, characterized in that, The silver powder is in flake form with a D50 particle size of 5-15 μm and a tap density of 3-4 g / cm³. 3 .

3. The flexurally resistant reference electrode paste according to claim 1, characterized in that, The AgCl powder D50 has a particle size of 0.5~1 μm.

4. The flexurally resistant reference electrode paste according to claim 1, characterized in that, The crosslinking agent is hexafluorobisphenol A.

5. The flexurally resistant reference electrode paste according to claim 1, characterized in that, The diluent is perfluoropolyether.

6. A method for preparing a flexurally resistant reference electrode paste, characterized in that, First, silver tetrafluoroborate, perfluoromethyl vinyl ether, perfluorophenoxypropyl vinyl ether, perfluorosulfonyl vinyl ether and crosslinking agent are dissolved in diluent, and then mixed using a spin coater. After adding silver powder and AgCl powder, the mixture is dispersed and homogenized using a kneader to obtain the bending-resistant reference electrode slurry.