Nickel electrode slurry and preparation method and application thereof

Abstract

The invention relates to the technical field of materials, and particularly discloses nickel electrode slurry and a preparation method and application thereof. According to the application, nickel metal is taken as a main body, potassium sodium niobate mixed zirconium oxide is taken as a core layer, and MnO and CuO are used for coating treatment, so that the sintering shrinkage temperature and shrinkage rate of the nickel paste are adjusted, and good matching with lead-free low-temperature sintered piezoelectric ceramic is provided through co-firing; and the problems of cracking, discontinuity and the like caused by volatilization of potassium and sodium in the ceramic matrix due to over-high temperature and over-large shrinkage are avoided. The nickel electrode slurry provided by the invention can realize conversion of an electrode material in a piezoelectric ceramic element from noble metal to base metal, and can reduce the sintering temperature in a reduction sintering atmosphere to form good co-firing with a lead-free low-temperature sintered piezoelectric ceramic material.

Description

Technical Field

[0001] This application relates to the field of materials technology, and in particular to a nickel electrode paste, its preparation method and application, and even more particularly to a nickel electrode paste co-fired with piezoelectric ceramics and its preparation method. Background Technology

[0002] With increasingly stringent environmental regulations, piezoelectric ceramic materials are gradually shifting from PZT (lead zirconate titanate)-based to KNN (potassium sodium niobate)-based low-temperature lead-free materials. Currently, Pd / Ag is primarily used as the internal electrode material. As the number of layers increases, the high cost becomes particularly pronounced, leading to a gradual shift in industry trends from precious metals to base metals. Base metals, primarily copper, nickel, and aluminum, present the following challenges compared to precious metals: ① Debinding and sintering require a reducing atmosphere, which can create oxygen vacancies in the matrix ceramic material, affecting its performance; ② High shrinkage matching requirements are necessary. Firstly, the sintering temperature of the matrix ceramic material cannot be too high, as excessively high temperatures can cause the volatilization of some core components. Secondly, good co-firing characteristics are required to avoid cracking caused by shrinkage mismatch. Summary of the Invention

[0003] The purpose of this application is to overcome the shortcomings of the prior art and provide a nickel electrode paste, its preparation method, and its application. The nickel electrode paste provided by this application has good dispersibility, can be matched with lead-free low-temperature piezoelectric ceramics to prepare piezoelectric elements, has good co-firing properties, and a low sintering temperature.

[0004] To achieve the above objectives, the technical solution adopted in this application is as follows: This application provides a nickel electrode paste, which includes a core layer and a coating layer covering the core layer; The core layer is made of nickel metal, potassium sodium niobate, and zirconium oxide. The coating material includes MnO and CuO.

[0005] In the technical solution of this application, nickel metal is used as the main body, potassium sodium niobate (KNN) mixed with zirconium oxide is used as the core layer and MnO and CuO are used for coating treatment to complete the adjustment of the shrinkage temperature and shrinkage rate of nickel paste sintering, so as to achieve good matching with lead-free low-temperature sintering piezoelectric ceramics and avoid cracking, discontinuity and other abnormalities caused by excessive potassium and sodium volatilization and excessive shrinkage in the ceramic matrix due to excessive temperature.

[0006] Among them, the co-fired phase of the nickel electrode slurry is treated by coating potassium sodium niobate with MnO and CuO, which effectively reduces the sintering temperature of pure nickel slurry and the resulting electrode has good continuity. At the same time, it can reduce the formation of oxygen vacancies in ceramic materials under a reducing atmosphere.

[0007] In a preferred embodiment of the nickel electrode paste described in this application, the mass ratio of potassium sodium niobate to zirconium oxide is (7~8):(2~3). Preferably, the mass ratio of potassium sodium niobate to zirconium oxide is 7:3.

[0008] This application uses potassium sodium niobate and zirconium oxide in the above-mentioned mass ratio range to form a common material, which affects the firing temperature and can ensure the shrinkage rate. With the above ratio, the firing temperature will not be too high, and the continuity of the internal electrode and the bonding force between the internal electrode and the ceramic body are better. In particular, when the mass ratio of potassium sodium niobate and zirconium oxide is 7:3, the continuity of the internal electrode and the bonding force between the internal electrode and the ceramic body are optimal.

[0009] If the firing temperature is too high, this application uses oxide (zirconia) to improve the firing temperature and prevent nickel oxidation, thereby improving electrode reliability.

[0010] In the prior art, the shrinkage temperature of pure nickel metal slurry shrinks too early, which differs significantly from the shrinkage temperature of potassium sodium niobate-based piezoelectric ceramics, easily causing stress cracking. This application adds potassium sodium niobate as a core layer (co-material), which has a delaying effect on the firing temperature, but there is still a gap. In actual use, the potassium sodium niobate added to the inner electrode is corroded by the ceramic body, resulting in a decrease in the continuity of the inner electrode. Furthermore, the electrode layer and the ceramic body delaminate after firing, and the bonding force does not meet the molding requirements. To solve the above problems, this application attempted to change the co-material type to barium titanate, calcium zirconate, strontium zirconate, zirconium oxide, etc. It was found that, except for zirconium oxide, the other co-materials all have an adverse effect on the switching voltage of potassium sodium niobate-based piezoelectric ceramics.

[0011] In some specific embodiments, the zirconium oxide has a particle size of 30~80nm, preferably 30nm.

[0012] The average particle size of potassium sodium niobate is 200~400nm, preferably 400nm.

[0013] This application uses zirconium oxide with the above-mentioned particle size, which can guarantee the shrinkage rate.

[0014] This application also provides a method for preparing the above-mentioned nickel electrode paste, including the following steps: S1. Dissolve the resin in a solvent to form an adhesive; S2. Prepare a premixed solution by mixing MnO, CuO, potassium sodium niobate, zirconium oxide, dispersant I and solvent. S3. The premixed liquid from step S2 is pre-dispersed, and then the adhesive from step S1 is added to coat it to obtain the pre-treatment liquid. S4. Mix the nickel powder, binder, dispersant II and plasticizer, then add the pretreatment liquid obtained in step S3 and mix to obtain a mixture. Then add solvent to adjust the viscosity of the mixture to obtain nickel electrode slurry.

[0015] This application uses the above-described preparation method to prepare a nickel electrode slurry. This nickel electrode slurry has good dispersibility, can be matched with lead-free low-temperature piezoelectric ceramics to prepare piezoelectric elements, and has good co-firing properties with a low sintering temperature. The premixing method used in step S2 is a pre-coating process, which improves the coating uniformity. Further adding the binder in step S3 can improve the stability of the coating effect.

[0016] In a preferred embodiment of the method for preparing the nickel electrode slurry described in this application, in step S1, the resin includes at least one of ethyl cellulose, polyvinyl butyral, and rosin resin.

[0017] In a preferred embodiment of the method for preparing the nickel electrode paste described in this application, the solvent in steps S1, S2 and S4 includes D80 hydrocarbon solvent. And / or, in step S4, the plasticizer includes at least one of DBP, DOP, acetylated tributyl citrate, tributyl citrate, and poly(1,4-butanediol) adipate.

[0018] This application uses D80 hydrocarbon solvent as a solvent, which can reduce etching and increase the drying speed of printed graphics.

[0019] In a preferred embodiment of the method for preparing the nickel electrode slurry described in this application, dispersant I in step S2 includes BYK-102; and / or, dispersant II in step S4 includes OS221P.

[0020] In a preferred embodiment of the method for preparing the nickel electrode slurry described in this application, the mass ratio of CuO, MnO and dispersant I in step S2 is (0.2~0.4):0.5:0.5.

[0021] In some specific embodiments, the weight fraction of CuO is 0.2 parts; the weight fraction of MnO is 0.4 parts.

[0022] In some specific embodiments, the CuO particle size is 1~2μm, preferably 1μm.

[0023] This application uses CuO with the aforementioned particle size, which effectively adjusts the firing temperature range to be slightly lower than that of the ceramic body (facilitating early shrinkage), resulting in a final shrinkage rate close to that of the ceramic body. It also ensures good continuity of the internal electrodes, with no cracking or other problems observed, and no adverse effects on the piezoelectric properties of the product. If the CuO particle size is too small, it will preferentially migrate into the ceramic body, causing a decrease in the ceramic body temperature.

[0024] If the mass ratio of MnO and CuO is within the above range, the impact on firing temperature is small. If the weight of CuO is less than 0.2 parts, CuO will be consumed by the ceramic film. If the weight of CuO is more than 0.4 parts, CuO will cause an abnormal increase in firing temperature. If the weight of MnO is less than 0.5 parts or more than 0.5 parts, the impact on firing temperature is significant.

[0025] In a preferred embodiment of the method for preparing the nickel electrode slurry described in this application, the particle size of the nickel powder in step S4 is 200~600nm.

[0026] As a preferred embodiment of the preparation method of the nickel electrode slurry described in this application, in step S3, the pre-dispersion treatment conditions are: linear velocity of 9~12m / s, flow rate of 0.8~2kg / min, and circulation of 15~20 passes; preferably, the linear velocity is 10m / s, the flow rate is 1kg / min, and the circulation of 15~20 passes.

[0027] This application also provides the application of the above-mentioned nickel electrode paste in the preparation of lead-free low-temperature sintered piezoelectric ceramic elements.

[0028] This application provides a nickel electrode paste suitable for lead-free low-temperature sintering piezoelectric ceramic elements and its preparation method. The aforementioned nickel electrode paste enables the transformation of the electrode material within the piezoelectric ceramic element from a noble metal to a base metal, and allows for lowering the firing temperature in a reducing sintering atmosphere to achieve good co-firing with lead-free low-temperature sintering piezoelectric ceramic materials.

[0029] This application focuses on nickel metal and uses surface coating treatment with specific nickel metal, potassium sodium niobate, and zirconium oxide to effectively solve the problem of co-firing with KNN (potassium sodium niobate)-based low-temperature lead-free materials. The resulting KNN (potassium sodium niobate)-based devices have high internal electrode continuity and no delamination, realizing the transformation of internal electrode materials from noble metals to base metals.

[0030] Compared with the prior art, this application has the following beneficial effects: This application provides a nickel electrode paste, its preparation method, and its application. The paste uses nickel metal as the main body, potassium sodium niobate (KNN) mixed with zirconium oxide as the core layer, and is coated with MnO and CuO. This process adjusts the sintering shrinkage temperature and rate of the nickel paste, achieving good compatibility with lead-free low-temperature sintered piezoelectric ceramics. It avoids cracking and discontinuities caused by excessive potassium and sodium volatilization and shrinkage in the ceramic matrix due to excessively high temperatures. Specifically, the MnO and CuO coating of potassium sodium niobate, used as the co-fired phase in the nickel electrode paste, effectively lowers the sintering temperature of pure nickel paste, resulting in electrodes with good continuity. Simultaneously, it reduces the formation of oxygen vacancies in the ceramic material under a reducing atmosphere. The nickel electrode paste of this application enables the transformation of the electrode material within the piezoelectric ceramic element from a noble metal to a base metal, and allows for lower firing temperatures in a reducing sintering atmosphere, resulting in good co-firing with lead-free low-temperature sintered piezoelectric ceramic materials. Detailed Implementation

[0031] To better illustrate the purpose, technical solution, and advantages of this application, the following will provide further explanation of this application in conjunction with specific embodiments.

[0032] In the following examples and comparative examples, unless otherwise specified, the experimental methods used are conventional methods, and the materials and reagents used are commercially available unless otherwise specified. Furthermore, the raw materials used in each parallel experiment are the same.

[0033] This application uses KNN-based ceramic (without nickel electrode slurry). After air-bar pressing, the slices were tested for TMA under the same atmosphere. The initial shrinkage temperature of the KNN-based ceramic was 991℃, and the shrinkage rate was 21.47%, which is comparable to the shrinkage temperature and shrinkage rate of the internal electrode. Theoretically, the higher the consistency between the two, the better the co-firing performance.

[0034] In the following embodiments and comparative examples: D80 hydrocarbon solvent is sourced from Shell. BYK-102 and OS221P (Nippon Oil ESLEAM 221P) are sourced from BYK Chemical and NOF Nippon Oil Co., Ltd., respectively. Ultrafine nickel powder has an average particle size of 200~600nm and can be sourced from JFE, Dongbang Titanium Industry, Boqian New Materials, and Xinchuan.

[0035] Zirconia particles have a diameter of 30 nm, originate from unrestricted sources, and have a purity of 99.9%. The CuO has a particle size of 1~2μm, comes from any source, and has a purity of 99.9%. The MnO has a particle size of 60~80 mesh, comes from any source, and has a purity of 99.9%.

[0036] The average particle size of the ultrafine nickel powder used in Examples 1-2 and Comparative Examples 1-17 was 400 nm.

[0037] Example 1: A nickel electrode paste and its preparation method This embodiment provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing MnO (0.5 parts by weight), CuO (0.2 parts by weight), potassium sodium niobate (8 parts by weight), zirconium oxide (2 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.02 parts by weight). S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0038] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 862℃; the final shrinkage rate was 15.03%.

[0039] Example 2: A nickel electrode paste and its preparation method This embodiment provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing MnO (0.5 parts by weight), CuO (0.4 parts by weight), potassium sodium niobate (7 parts by weight), zirconium oxide (3 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (8.82 parts by weight). S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0040] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 974℃; the final shrinkage rate was 16.13%.

[0041] Example 3: A nickel electrode paste and its preparation method Compared with Example 1, the difference in Example 3 is that the average particle size of the ultrafine nickel powder is 200 nm, while the rest of the preparation method is the same as in Example 1. The obtained nickel electrode slurry was heated to 1100 °C in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10 °C / min, and the shrinkage initiation temperature was 811 °C, with a final shrinkage rate of 15.11%.

[0042] Example 4: A nickel electrode paste and its preparation method This embodiment provides a method for preparing a nickel electrode paste, including the following steps: Compared with Example 2, the difference in Example 4 is that the average particle size of the ultrafine nickel powder is 600 nm, while the rest of the preparation method is the same as in Example 1. The obtained nickel electrode slurry is heated to 1100°C in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10°C / min, and the shrinkage initiation temperature is 975°C, with a final shrinkage rate of 15.96%.

[0043] Comparative Example 1 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (19.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (62.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (3.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0044] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 362℃; the final shrinkage rate was 22.20%.

[0045] Comparative Example 2 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (2.5 parts by weight), BYK-102 (0.5 parts by weight), and D80 hydrocarbon solvent (17.22 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (59.9 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (5.61 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0046] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 410℃; the final shrinkage rate was 18.31%.

[0047] Comparative Example 3 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (5 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (14.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (57.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (8.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0048] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 537℃; the final shrinkage rate was 16.52%.

[0049] Comparative Example 4 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (7.5 parts by weight), BYK-102 (0.5 parts by weight), and D80 hydrocarbon solvent (12.22 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (54.9 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (10.61 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0050] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 570℃; the final shrinkage rate was 15.32%.

[0051] Comparative Example 5 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing potassium sodium niobate (10 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0052] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 610℃; the final shrinkage rate was 15.11%.

[0053] Comparative Example 6 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing potassium sodium niobate (12.5 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (7.22 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (49.9 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (15.61 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0054] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 637℃; the final shrinkage rate was 14.90%.

[0055] Comparative Example 7 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (15 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (4.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (47.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (18.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0056] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 651℃; the final shrinkage rate was 14.82%.

[0057] Comparative Example 8 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (8 parts by weight), zirconium oxide (2 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0058] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1003℃; the final shrinkage rate was 15.03%.

[0059] Comparative Example 9 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (7 parts by weight), zirconium oxide (3 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0060] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1054℃; the final shrinkage rate was 16.01%.

[0061] Comparative Example 10 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (6 parts by weight), zirconium oxide (4 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0062] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1069℃; the final shrinkage rate was 16.54%.

[0063] Comparative Example 11 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (5 parts by weight), zirconium oxide (5 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0064] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1120℃; the final shrinkage rate was 17.01%.

[0065] Comparative Example 12 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (4 parts by weight), zirconium oxide (6 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0066] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1187℃; the final shrinkage rate was 17.63%.

[0067] Comparative Example 13 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing sodium potassium niobate (3 parts by weight), zirconium oxide (7 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.72 parts by weight); S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0068] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1199℃; the final shrinkage rate was 17.91%.

[0069] Comparative Example 14 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing MnO (0.5 parts by weight), CuO (0.6 parts by weight), potassium sodium niobate (6 parts by weight), zirconium oxide (4 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (8.62 parts by weight). S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0070] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1035℃; the final shrinkage rate was 16.15%.

[0071] Comparative Example 15 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing MnO (0.3 parts by weight), CuO (0.4 parts by weight), potassium sodium niobate (5 parts by weight), zirconium oxide (5 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (9.02 parts by weight). S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0072] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 1012℃; the final shrinkage rate was 16.07%.

[0073] Comparative Example 16 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing MnO (0.8 parts by weight), CuO (0.4 parts by weight), potassium sodium niobate (4 parts by weight), zirconium oxide (6 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (8.52 parts by weight). S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0074] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 752℃; the final shrinkage rate was 16.32%.

[0075] Comparative Example 17 This comparative example provides a method for preparing a nickel electrode paste, including the following steps: S1. Ethyl cellulose (10 parts by weight) and polyvinyl butyral (10 parts by weight) are dissolved in D80 hydrocarbon solvent (80 parts by weight) at a temperature of 85°C for 8 hours to form an adhesive. S2. Prepare a premixed solution by mixing MnO (1.1 parts by weight), CuO (0.4 parts by weight), potassium sodium niobate (3 parts by weight), zirconium oxide (4 parts by weight), BYK-102 (0.5 parts by weight) and D80 hydrocarbon solvent (8.52 parts by weight). S3. Use a suction-type powder disperser to pre-disperse the premixed liquid obtained in step S2, transfer it to an ultrafine nano-sand mill, use a linear speed of 10m / s and a flow rate of 1kg / min to complete 20 passes of circulation, then add the binder (0.85 parts by weight) from step S1, continue grinding for 5 passes, and coat to obtain the pre-treated liquid. S4. Mix ultrafine nickel powder (52.4 parts by weight), binder (12.64 parts by weight), OS221P (0.53 parts by weight), and plasticizer DOP (0.25 parts by weight). Disperse the mixture 7-8 times using a three-roll mill. Then add the pretreatment liquid (21.07 parts by weight) obtained in step S3 and mix to obtain a mixture. Disperse the mixture 3-4 times using a three-roll mill. Add D80 hydrocarbon solvent (13.11 parts by weight) to adjust the viscosity of the mixture to obtain a nickel electrode slurry with an inorganic solid content of 62.40%.

[0076] The nickel electrode slurry was heated to 1100℃ in a reducing atmosphere (N2:H2=90:10) at a heating rate of 10℃ / min, and the initial shrinkage temperature was 630℃; the final shrinkage rate was 16.27%.

[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit the scope of protection of this application. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the substance and scope of the technical solutions of this application.

Claims

1. A nickel electrode slurry characterized by, The nickel electrode paste comprises a core layer and a cladding layer cladding the core layer; The material of the core layer comprises nickel metal, potassium sodium niobate and zirconia; The material of the cladding layer comprises MnO and CuO.

2. The nickel electrode paste of claim 1, wherein The mass ratio of the potassium sodium niobate and the zirconia is (7-8):(2-3).

3. The method of preparing a nickel electrode paste according to claim 1 or 2, characterized in that, The method comprises the following steps: S1, dissolving resin in a solvent to form a binder; S2, configuring MnO, CuO, potassium sodium niobate, zirconia, dispersant I and the solvent into a premix; S3, pre-dispersing the premix of step S2, then adding the binder of step S1 to obtain a pretreatment liquid; S4, stirring and mixing nickel powder, the binder, dispersant II and plasticizer, then adding the pretreatment liquid obtained in step S3 to obtain a mixture, and then adding a solvent to adjust the viscosity of the mixture to obtain a nickel electrode paste.

4. The method of preparing a nickel electrode paste according to claim 3, wherein In step S1, the resin comprises at least one of ethyl cellulose, polyvinyl butyral and rosin resin.

5. The method of preparing a nickel electrode paste according to claim 3, wherein In steps S1, S2 and S4, the solvent comprises D80 carbon hydrogen solvent. In step S4, the plasticizer comprises at least one of DBP, DOP, acetyl tri-butyl citrate, tri-butyl citrate and polyadipic acid-1,4-butylene glycol ester.

6. The method of preparing a nickel electrode paste according to claim 3, wherein In step S2, the dispersant I comprises BYK-102; and / or in step S4, the dispersant II comprises OS221P.

7. The method of preparing a nickel electrode paste according to claim 3, wherein the nickel electrode paste is prepared by adding the dispersant to the nickel powder and the binder, and then adding the solvent. In step S2, the mass ratio of CuO, MnO and dispersant I is (0.2-0.4):0.5:0.

5.

8. The method of preparing a nickel electrode paste according to claim 3, wherein In step S4, the average particle size of the nickel powder is 200-600 nm.

9. The method of preparing a nickel electrode paste according to claim 3, wherein In step S3, the pre-dispersing treatment is performed at a linear speed of 9-12 m / s and a flow rate of 0.8-2 kg / min for 15-20 Passes.

10. Use of the nickel electrode paste according to claim 1 or 2 in the preparation of a lead-free low-temperature sintered piezoelectric ceramic element.