Complex-phase proton conductor material as well as synthesis method and application thereof
By mixed sintering of high-entropy lithium-ion solid electrolyte and proton conductor solid electrolyte, the problem of high sintering temperature of proton conductor materials was solved, the proton conductivity was significantly improved, and the commercial application of proton conductor materials was promoted.
Patent Information
- Application Number
- CN202510907589.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-02
- Publication Date
- 2025-09-16
AI Technical Summary
The sintering temperature of existing proton conductor materials is high, which affects their commercialization process. In addition, high-temperature sintering can easily cause the volatilization of barium elements, reducing proton conductivity.
A high-entropy lithium-ion solid electrolyte and a proton conductor solid electrolyte are mixed in a certain proportion, and then sintered at a lower temperature through pressing or casting to form a multiphase proton conductor material.
The sintering temperature was lowered to 1000℃, which significantly improved the proton conductivity. The conductivity of the composite proton conductor material reached 0.1 S·cm-1 at 600℃, which is 3.6 times that of the non-high entropy lithium ion solid electrolyte composite proton conductor and 14 times that of the pure proton conductor solid electrolyte material.
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Figure CN120657186A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of solid oxide fuel cells, and in particular relates to a multiphase proton conductor material, a synthesis method and an application thereof. Background Art
[0002] Solid oxide fuel cells (SOFCs) are a key enabler for converting hydrogen into electricity. They can be categorized into oxygen ion conductor ceramic fuel cells (OICFCs) and proton conductor ceramic fuel cells (PCFCs). OICFCs require high temperatures (800-1000°C), a condition that presents a series of complex issues that limit their application. In contrast, PCFCs, with their proton-type electrolytes, have lower activation energy and superior ionic conductivity at medium to low temperatures (400-700°C), thus holding great potential for development.
[0003] The most intensively studied PCFCs are barium cerate and barium zirconate-based perovskite oxides, such as BaZr, which have high proton conductivity and chemical stability. 0.1 Ce 0.7 Y 0.2 O 3-δ (BZCY), but their sintering temperature is higher than 1400°C, which not only consumes a lot of energy, but also the long-term high-temperature sintering easily causes the volatilization of barium, affecting the proton conductivity, thus greatly restricting its commercialization process; currently, adding a trace amount of low-melting-point transition metal as a sintering aid is the mainstream strategy to improve the sintering activity, but this is likely to introduce impurities and affect the proton conductivity.
[0004] Another approach to improve sintering performance is to construct a multiphase proton conductor using an electrolyte with high sintering activity, such as by introducing 10 wt.% La 0.9 Sr 0.1 Ga 0.8 Mg 0.2O3-δ (LSGM) acts as a grain boundary pinning phase, which reduces the grain boundary mobility of BZCY, thereby improving the sintering density and conductivity of the 90 wt.% BZCY-10 wt.% LSGM (B9L1) composite electrolyte. The conductivity of the B9L1 composite electrolyte can reach 15.1 S·cm in a wet hydrogen atmosphere at 700°C. -1 However, the material still needs to be sintered at 1550℃ for 10 h to achieve the above properties. This harsh sintering condition may limit its practical application.
[0005] Therefore, for the synthesis of proton conductors, it is of great significance to find a strategy to reduce the sintering temperature and improve the proton conductivity. Summary of the Invention
[0006] The purpose of the embodiments of the present invention is to provide a method for synthesizing a multiphase proton conductor material, aiming to solve the problems raised in the above background technology.
[0007] The embodiment of the present invention is achieved by providing a method for synthesizing a multiphase proton conductor material, comprising the following steps:
[0008] According to the target chemical formula of the high-entropy lithium-ion solid electrolyte, the required lithium source and other metal oxides are calculated and weighed as raw materials, and mixed to obtain a precursor powder;
[0009] The precursor powder is calcined at a high temperature to obtain a high entropy lithium ion solid electrolyte powder;
[0010] mixing the prepared high entropy lithium ion solid electrolyte powder and proton conductor solid electrolyte powder according to a mass ratio to obtain a mixed powder;
[0011] forming the mixed powder;
[0012] The formed mixed powder is sintered to obtain a multiphase proton conductor material.
[0013] Preferably, the high entropy lithium ion solid electrolyte is Li 6.5 LaPrNdZr 0.75 Ce 0.75 Ta 0.5 O 12 、Li 6.5 La 0.75 Pr 0.75 Nd 0.75 Sm 0.75 Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 、Li 6.5 La3Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 One of them.
[0014] Preferably, the proton conductor solid electrolyte is BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ , where δ is the non-stoichiometric amount of oxygen.
[0015] Preferably, in the step of mixing the prepared high entropy lithium ion solid electrolyte powder and the proton conductor solid electrolyte powder in a mass ratio, the mass ratio is 7-3:3-7.
[0016] Preferably, the step of molding the mixed powder is performed by compression molding or tape casting.
[0017] Preferably, the sintering temperature is 800-1200° C., and the sintering time is 1-1000 s.
[0018] Another object of an embodiment of the present invention is to provide a multiphase proton conductor material, which is synthesized using the above-mentioned synthesis method.
[0019] Another object of an embodiment of the present invention is to provide an application of a multiphase proton conductor material in constructing a solid oxide battery.
[0020] The present invention provides a method for synthesizing a multiphase proton conductor material, which is prepared from a high-entropy lithium-ion solid electrolyte material and a proton conductor solid electrolyte material. After the composite, the sintering temperature of the proton conductor solid electrolyte is reduced from 1400°C to 1000°C, while significantly improving the proton conductivity. The prepared multiphase proton conductor material has an electrical conductivity of nearly 0.1 S·cm at 600°C. -1 , which are 3.6 times that of non-high entropy lithium-ion solid electrolyte composite proton conductors and 14 times that of pure proton conductor solid electrolyte materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 XRD patterns of the high-entropy lithium-ion solid electrolyte and the multiphase proton conductor provided in the embodiments of the present invention;
[0022] Figure 2 Electron microscope images of the multiphase proton conductor material and the traditional proton conductor solid electrolyte provided by the embodiments of the present invention;
[0023] Figure 3 Nyquist plots of nickel symmetric batteries made using a multiphase proton conductor material and a traditional proton conductor solid electrolyte in a 600°C wet hydrogen atmosphere, provided in an embodiment of the present invention;
[0024] Figure 4 A comparison chart of the electrical conductivity and activation energy of the multiphase proton conductor material provided by an embodiment of the present invention and the traditional proton conductor solid electrolyte. DETAILED DESCRIPTION
[0025] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
[0026] A method for synthesizing a multiphase proton conductor material comprises the following steps:
[0027] Step 1. According to the target chemical formula of the high-entropy lithium-ion solid electrolyte, the required lithium source and other metal oxides are calculated and weighed as raw materials, and the mixture is mixed to obtain a precursor powder. The high-entropy lithium-ion solid electrolyte is selected from lithium lanthanum zirconium oxide and lithium lanthanum titanate, and 3-10 elements are doped at a single site (one of the lanthanum site, zirconium site or titanium site), or 2-10 elements are doped at two sites (lanthanum site and zirconium site or lanthanum site and titanium site).
[0028] Step 2: calcining the precursor powder at a high temperature to obtain a high entropy lithium ion solid electrolyte powder;
[0029] Step 3: mixing the prepared high entropy lithium ion solid electrolyte powder and proton conductor solid electrolyte powder in a mass ratio to obtain a mixed powder, wherein the proton conductor solid electrolyte material is selected from barium cerate and barium zirconate-based electrolytes;
[0030] Step 4: forming the mixed powder by pressing (cold pressing and hot pressing) or casting;
[0031] The pressing process includes sequentially grinding, drying, conventional pressing, and cold isostatic pressing (or hot pressing); the grinding process is selected from one or more of manual grinding, high-energy ball milling, drum ball milling, and planetary ball milling; the grinding time is 2 to 24 hours, and the grinding medium is selected from one of isopropyl alcohol and ethanol; the conventional pressing pressure is 3 to 10 tons and the time is 20 to 60 seconds, and the cold isostatic pressing pressure is 100 to 500 MPa and the time is 5 to 15 minutes;
[0032] The tape casting process includes sequentially performing slurry mixing, tape casting and drying. The slurry mixing process specifically comprises: mixing mixed powder, binder, dispersant and solvent to obtain a mixed slurry. Alternatively, lithium ion solid electrolyte powder and proton solid electrolyte powder may be directly mixed with other slurry components in proportion to obtain a mixed slurry.
[0033] Step 5: sintering the formed mixed powder material at a sintering temperature of 800-1200° C. for a time of 1-1000 s to obtain a multiphase proton conductor material.
[0034] BZCY=BaZr used in the embodiment of the present invention 0.1 Ce 0.7 Y 0.2 O 3–δ ; Purchased from Guangdong Ruier Chemical Technology Co., Ltd.
[0035] The specific implementation of the present invention is described in detail below with reference to specific embodiments.
[0036] Example 1: A method for synthesizing a multiphase proton conductor material, comprising the following steps:
[0037] The multiphase proton conductor solid electrolyte material X30Y70 (30 is the mass percentage of BZCY in the total electrolyte) was prepared according to the following steps; wherein: X is BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ (BZCY), δ is the non-stoichiometric amount of oxygen; Y is Li 6.5 LaPrNdZr 0.75 Ce 0.75 Ta 0.5 O 12 (LLPNZCTO), Li 6.5 La 0.75 Pr 0.75 Nd 0.75 Sm 0.75 Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 (LLPNSZCTNTO), Li 6.5 La3Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 One of (LLZCTNTO);
[0038] Step 1: Synthesize high entropy lithium-ion solid electrolyte materials;
[0039] When Y is LLPNZCTO, L2iCO3, La2O3, Pr6O 11 , Nd2O3, ZrO2, CeO2 and Ta2O5 were weighed, and all the reagents used were analytically pure; these powders were then added to a ball mill, and an appropriate amount of ethanol was added, and high-energy ball milling was performed for 1 hour. After the end, the mixture was placed in an 80°C oven to dry for 8 hours, and the dried powder was placed in a muffle furnace, heated to 950°C for 400 minutes, and then cooled to room temperature to obtain LLPNZCTO powder;
[0040] When Y is LLPNSZCTNTO, L2iCO3, La2O3, Pr6O 11 、Nd2O3、Sm2O3、ZrO2、CeO 2、TiO2, Nb2O5, and Ta2O5 were weighed, and all the reagents used were analytical grade. These powders were then added to a ball mill, and an appropriate amount of ethanol was added, and high-energy ball milling was performed for 1 hour. After the mixture was dried in an 80°C oven for 8 hours, the dried powder was placed in a muffle furnace, heated to 950°C for 400 minutes, and then cooled to room temperature to obtain LLPNSZCTNTO powder.
[0041] When Y is LLZCTNTO, L2iCO3, La2O3, ZrO2, CeO 2、 TiO2, Nb2O5, and Ta2O5 were weighed, and all the reagents used were analytically pure. These powders were then added to a ball mill, and an appropriate amount of ethanol was added, and high-energy ball milling was performed for 1 hour. After the mixture was dried in an 80°C oven for 8 hours, the dried powder was placed in a muffle furnace, heated to 950°C for 400 minutes, and then cooled to room temperature to obtain LLZCTNTO powder.
[0042] Step 2: Weigh the powders of BZCY and Y in a mass ratio of 3:7, add the powders to a ball mill, add an appropriate amount of ethanol, and perform high-energy ball milling for 1 hour. After completion, dry the mixture in an oven at 80°C for 8 hours.
[0043] Step 3: Next, the powder was sieved through a 40-mesh sieve and the resulting powder was removed. 0.3 g of the powder was weighed and poured into a mold with an inner diameter of 13 mm. A pressure of 5 tons was applied and held for 30 seconds to obtain a disc-shaped green body with a thickness of 0.5 to 0.7 mm. The green body was then cold isostatically pressed with a pressure of 300 MPa and a holding time of 8 minutes.
[0044] Step 4: The green body after pressure maintenance is subjected to ultrafast high-temperature sintering at a sintering temperature of 1000°C and a sintering time of 10 s to obtain a multiphase proton conductor solid electrolyte material X30Y70.
[0045] Example 2: A method for synthesizing a multiphase proton conductor material, comprising the following steps:
[0046] The multiphase proton conductor solid electrolyte material X50Y50 (50 is the mass percentage of BZCY in the total electrolyte) was prepared according to the following steps:
[0047] Where: X is BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ (BZCY) (δ is the non-stoichiometric amount of oxygen); Y is Li 6.5 LaPrNdZr 0.75 Ce0.75 Ta 0.5 O 12 (LLPNZCTO), Li 6.5 La 0.75 Pr 0.75 Nd 0.75 Sm 0.75 Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 (LLPNSZCTNTO), Li 6.5 La3Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 One of (LLZCTNTO);
[0048] Step 1: According to step 1 in Example 1, synthesize a high entropy lithium ion solid electrolyte Y;
[0049] Step 2: Weigh the powders of BZCY and Y in a mass ratio of 5:5, add the powders to a ball mill, add an appropriate amount of ethanol, and perform high-energy ball milling for 1 hour. After completion, dry the mixture in an oven at 80°C for 8 hours.
[0050] Step 3: Next, the powder was sieved through a 40-mesh sieve and the resulting powder was removed. 0.3 g of the powder was weighed and poured into a mold with an inner diameter of 13 mm. A pressure of 5 tons was applied and held for 30 seconds to obtain a disc-shaped green body with a thickness of 0.5 to 0.7 mm. The green body was then cold isostatically pressed with a pressure of 300 MPa and a holding time of 8 minutes.
[0051] Step 4: Finally, the green body after pressure maintenance is subjected to ultrafast high-temperature sintering at a sintering temperature of 1000°C and a sintering time of 10 s to obtain the multiphase proton conductor solid electrolyte material X50Y50.
[0052] Example 3: A method for synthesizing a multiphase proton conductor material, comprising the following steps:
[0053] The multiphase proton conductor solid electrolyte material X70Y30 (70 is the mass percentage of BZCY in the total electrolyte) was prepared according to the following steps; 0.1 Ce 0.7 Y 0.2 O 3–δ (BZCY) (δ is the non-stoichiometric amount of oxygen); Y is Li 6.5 LaPrNdZr 0.75 Ce0.75 Ta 0.5 O 12 (LLPNZCTO), Li 6.5 La 0.75 Pr 0.75 Nd 0.75 Sm 0.75 Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 (LLPNSZCTNTO), Li 6.5 La3Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 One of (LLZCTNTO);
[0054] Step 1: According to step 1 in Example 1, synthesize a high entropy lithium ion solid electrolyte Y;
[0055] Step 2: Weigh the powders of BZCY and synthetic high-entropy lithium-ion solid electrolyte Y in a mass ratio of 7:3, add the powders to a ball mill, add an appropriate amount of ethanol, and high-energy ball mill for 1 hour; after completion, place the mixture in an 80°C oven to dry for 8 hours;
[0056] Step 3: Next, the powder was sieved through a 40-mesh sieve and the resulting powder was removed. 0.3 g of the powder was weighed and poured into a mold with an inner diameter of 13 mm. A pressure of 5 tons was applied and held for 30 seconds to obtain a disc-shaped green body with a thickness of 0.5 to 0.7 mm. The green body was then cold isostatically pressed with a pressure of 300 MPa and a holding time of 8 minutes.
[0057] Step 4: Finally, the green body after pressure maintenance is subjected to ultrafast high-temperature sintering at a sintering temperature of 1000°C and a sintering time of 10 s to obtain the multiphase proton conductor solid electrolyte material X70Y30.
[0058] Comparative Example 1: Prepare the conventional proton conductor electrolyte material BaZr according to the following steps: 0.1 Ce 0.7 Y 0.2 O 3–δ (BZCY):
[0059] A certain amount of BZCY powder was weighed, and the reagents used were analytical grade. The powder was added to a ball mill, and an appropriate amount of ethanol was added. High-energy ball milling was performed for 1 hour. After the end, the mixture was placed in an 80°C oven to dry for 8 hours.
[0060] Next, the powder was sieved through a 40-mesh sieve and the resulting powder was removed. 0.3 g of the powder was then weighed and poured into a mold with an inner diameter of 13 mm. A pressure of 5 tons was applied and held for 30 seconds to obtain a disc-shaped green body with a thickness of 0.5 to 0.7 mm. The green body was then cold isostatically pressed with a pressure of 300 MPa and a holding time of 8 minutes.
[0061] Finally, the green compact after pressure maintenance was subjected to ultrafast high-temperature sintering at a sintering temperature of 1400°C and a sintering time of 15 s to obtain the proton conductor electrolyte material BZCY.
[0062] Comparative Example 2: Prepare high entropy lithium ion solid electrolyte Li according to the following steps: 6.5 La3Zr 1.4 Ta 0.6 O 12 (LLZTO);
[0063] According to the molar ratio of 7.15:1.5:1.4:0.3, L2iCO3, La2O3, ZrO2 and Ta2O5 were weighed, and the reagents used were all analytically pure. Then these powders were added to a ball mill, and an appropriate amount of ethanol was added. High-energy ball milling was performed for 1 hour. After the end, the mixture was placed in an 80℃ oven to dry for 8 hours. The dried powder was then placed in a muffle furnace, heated to 1170℃ for 400 min, and then cooled to room temperature to obtain Li 6.5 La3Zr 1.4 Ta 0.6 O 12 powder.
[0064] Performance Analysis:
[0065] The multiphase proton conductor solid electrolyte material 30 wt.% BZCY - 70 wt.% LLPNZCTO (recorded as Example 1), LLPNZCTO (recorded as Example 2), LLPNSZCTNTO (recorded as Example 3), LLZCTNTO (recorded as Example 4) prepared in Example 1, the traditional proton conductor electrolyte material BZCY prepared in Comparative Example 1 (recorded as Control 1), and the Li prepared in Comparative Example 2 were mixed. 6.5 La3Zr 1.4 Ta 0.6 O 12 (denoted as control 2) was analyzed and the XRD pattern was obtained as shown Figure 1 As shown;
[0066] The multiphase proton conductor solid electrolyte material 30 wt.% BZCY - 70 wt.% LLPNZCTO prepared in Example 1 (referred to as Example 1) and the traditional proton conductor electrolyte material BZCY prepared in Comparative Example 1 (referred to as Control 1) were analyzed, and the electron microscope images were obtained as shown in FIG. Figure 2 As shown;
[0067] Nickel symmetrical batteries were prepared from Example 1 and Control 1, and their performance was analyzed in a 600°C wet hydrogen atmosphere. The Nyquist plots were obtained as shown in Figure 2. Figure 3 As shown;
[0068] The conductivity and activation energy of Example 1 and Control 1 were analyzed and the comparative results were obtained as follows: Figure 4 shown.
[0069] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A method for synthesizing a multiphase proton conductor material, characterized in that: The following steps are involved: According to the target chemical formula of the high-entropy lithium-ion solid electrolyte, the required lithium source and other metal oxides are calculated and weighed as raw materials, and mixed to obtain a precursor powder; The precursor powder is calcined at a high temperature to obtain a high entropy lithium ion solid electrolyte powder; mixing the prepared high entropy lithium ion solid electrolyte powder and proton conductor solid electrolyte powder according to a mass ratio to obtain a mixed powder; forming the mixed powder; The formed mixed powder is sintered to obtain a multiphase proton conductor material.
2. The method for synthesizing a multiphase proton conductor material according to claim 1, wherein: The high entropy lithium ion solid electrolyte is Li 6.5 LaPrNdZr 0.75 Ce 0.75 Ta 0.5 O 12 、Li 6.5 La 0.75 Pr 0.75 Nd 0.75 Sm 0.75 Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 、Li 6.5 La3Zr 0.5 Ce 0.5 Ti 0.5 Nb 0.25 Ta 0.25 O 12 One of them.
3. The method for synthesizing a multiphase proton conductor material according to claim 2, wherein: The proton conductor solid electrolyte is BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ , where δ is the non-stoichiometric amount of oxygen.
4. The method for synthesizing a multiphase proton conductor material according to claim 3, wherein: In the step of mixing the prepared high entropy lithium ion solid electrolyte powder and the proton conductor solid electrolyte powder according to a mass ratio, the mass ratio is 7-3:3-7.
5. The method for synthesizing a multiphase proton conductor material according to claim 1, wherein: In the step of molding the mixed powder, compression molding or tape casting is adopted.
6. The method for synthesizing a multiphase proton conductor material according to claim 1, wherein: In the step of sintering the formed mixed powder, the sintering temperature is 800-1200° C. and the sintering time is 1-1000 s.
7. A multiphase proton conductor material, characterized in that: The compound is synthesized by the synthesis method according to any one of claims 1 to 6.
8. Use of the multiphase proton conductor material according to claim 7 in constructing a solid oxide battery.