CN103224394A - Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof - Google Patents

Abstract

The invention discloses a lithium carbonate modified cerium barium zirconate proton conductor material. Raw material components and molar ratio percentage content thereof are BaCe0.7Zr0.1Y0.2O3-delta, and on the basis, 0%-7.5% by mass of lithium carbonate and 0%-4% by mole of zinc oxide are added. BaCe0.7Zr0.1Y0.2O3-delta powder is synthesized by a nitrate-citric acid gel auto-combustion method; then an inorganic salt sintering aid lithium carbonate zinc oxide are added in the power; the powder is shaped by dry pressing and sintered at a temperature of 1,150-1,300 DEG C. The raw materials of the lithium carbonate modified cerium barium zirconate proton conductor material are low in cost; the preparation process is simple and time-saving; relatively high conductivity can be obtained under the premise of increasing sintering performance of the materials; and the lithium carbonate modified cerium barium zirconate proton conductor material provides a foundation for low temperature development of solid oxide fuel cells.

Description

Lithium carbonate modified barium cerium zirconate proton conductor material and preparation method thereof

technical field

The invention belongs to a ceramic composition characterized by components, in particular to a lithium carbonate modified cerium barium zirconate proton conductor material and a preparation method thereof.

Background technique

Due to the advantages of high energy conversion efficiency, no pollution, strong fuel adaptability, light weight and solid-state structure, fuel cells have great development potential and application prospects, and are known as the most promising new generation of green chemical power generation in the 21st century. device. One of the development trends of solid oxide fuel cells (SOFCs) is to reduce the operating temperature of the cells. The perovskite structure proton conductor has high conductivity and proton migration number and low conduction activation energy (Iwallara H, OnoK.Proton conductinsintered oxides based on BaCeO ₃ [J].J.Electrochem.Soc., 1988, 135 (2):529~533), which is one of the best choices of electrolyte materials for intermediate temperature solid oxide fuel cells (IT-SOFC). The simple perovskite-structured proton conductors can be divided into low-valent ion-doped decoration salts and zirconates. Salt-decorated proton conductors mainly include BaCeO ₃ , SrCeO ₃ doped with various low-valent ions, etc. These materials have high conductivity, and the conductivity of single crystal materials can reach the order of S/cln at high temperatures. Multiphase ceramics One is between 10 ^-2 and lS/cln, but its chemical stability is poor, and it is easy to react in the CO ₂ and H ₂ S atmosphere to form CeO ₂ and the corresponding carbonates, which will lead to a decrease in electrical conductivity and reduce the efficiency of the fuel cell. service life, or have higher requirements on the gas purity and the atmosphere in the reaction process, resulting in higher use cost and maintenance cost. Zirconate proton conductors include BaZrO ₃ and SrZrO ₃ , etc. This type of material is almost purely proton-conductive, with stable chemical properties and superior mechanical properties, but it is difficult to prepare, requires a high sintering temperature, and has low grain boundary conductivity. As a fuel cell, the internal resistance of the electrolyte is large, which affects the efficiency of the battery (Lguchi F, Tsurui T, SataN, et al. Therelationship between chemical composition distributions and specific grain boundary conductivity in Y-doped BaZrO ₃ pfotonconductors[J].Solid State Ionics, 2009 , 180(6-8):563-568). For a single zirconium-based and cerium-based oxide, it is difficult to satisfy high proton conductivity and high stability at the same time, and it is not ideal as a fuel cell electrolyte alone. It is reported that BaCeO ₃ and BaZrO ₃ can form an infinite solid solution BaZr _x Ce _1-x O ₃ , and by replacing some of the Zr in BaZrO ₃ with Ce, the electrical conductivity of the material can be improved under the premise of ensuring high chemical stability of the material. . In the past ten years, researchers have conducted extensive research on zirconium-cerium-based solid solution materials. The properties of solid solution materials change with the ratio of zirconium to cerium. The increase of zirconium content is beneficial to the stability of the material, and the increase of cerium content is beneficial to the electrical conductivity of the material. Liu et al. synthesized BaZf _0.1 Ce _0.7 Y _0.2 O _3-δ powder by citric acid self-combustion method, and prepared BaZf _0.1 Ce _0.7 Y _0.2 O _3-δ zirconium cerium solid solution with a thickness of 20 μm using Ni base as the anode. Thin film electrolyte, using Sln _0.5 Sr _0.5 CoO _3-δ -BaZr _0.1 Ce _0.7 Y _0.2 O _3-δ as composite cathode, the output power of the assembled fuel cell can reach 650mW/cm ² at 700°C, and at 600° C. The test at a constant voltage of 0.5V has good chemical stability and does not affect the normal operation of the battery, which is a major breakthrough compared with previous research results (Mhgfei L, Jianfeng G. High performance of anode supported BaZr _0.1 Ce _0.7 Y _0.2 O _3-δ (BZCY)electrolyte cell for IT-SOFC[J].International Journal of Hydrogen Energy, 2011, 36(21)13741~13745). However, due to the existence of BaZrO ₃ , it is still difficult to sinter and densify the material, and high-temperature sintering may easily cause Ba to be missing from the A site, thereby degrading the performance of the material. Therefore, it is very important to study an easier sintering method.

Contents of the invention

The purpose of the present invention is to provide a new type of proton conductor material for solid oxide fuel cells which has a simple preparation method, saves cost, can be sintered densely at a relatively low temperature and can obtain excellent electrical conductivity.

The invention adopts citric acid gel self-combustion method to prepare cerium barium zirconate proton conductor powder wood, and adds lithium carbonate sintering auxiliary agent to reduce sintering temperature and improve density. Change the addition amount of lithium carbonate, study the properties of lithium carbonate-barium zirconate cerate material, determine its optimal addition amount, and prepare an anode-supported solid oxide fuel cell with excellent performance.

The present invention is achieved through the following technical solutions:

Carbonic acid passivation modified barium cerium zirconate proton conductor material, its raw material components and molar content are: BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , on this basis, add 0% to 7.5% of carbonic acid Lithium and zinc oxide with a molar percentage of 0% to 4%;

The preparation method of this lithium carbonate modified cerium barium zirconate proton conductor material, the steps are as follows:

(1) Weigh the raw materials according to BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ stoichiometric ratio: Ba(NO ₃ ) ₂ , ZrWO ₃ ) ₄ 5H ₂ O, Ce(NO ₃ ) ₃ 6H ₂ O, Y (NO ₃ ) ₃ 6H ₂ O; mix according to the molar ratio of total metal salt ions: ethylenediaminetetraacetic acid (EDTA: citric acid) 1:1.5:1～1:2:1, add to 500mL deionized water, use Adjust the pH value of concentrated ammonia water to 6-8, heat and stir to evaporate water, obtain a viscous colloid, and react in a stainless steel reaction vessel; then pre-fire at 240°C and keep it warm for 5 hours; finally, at 1000-1100°C Calcined at lower temperature and kept for 5 hours to obtain light yellow pure phase BaCe _0.7 Zf _0.1 Y _0.2 O _3-δ powder;

(2) Taking the powder prepared in step (1) as the base material, adding 0% to 7.5% by mass percentage of lithium carbonate and 0% to 4% by mole percentage of zinc oxide, and using absolute ethanol as the medium for ball milling; drying, After grinding and sieving, put the powder into the mold, and dry press it at 100-200MPa to form a green body; then sinter the obtained green body in an air atmosphere at 1150-1300°C, keep it warm for 4-6 hours, and cool naturally to At room temperature, a lithium carbonate-modified cerium barium zirconate proton conductor material is prepared.

The sintering method of the step (2) is buried firing, and the heating rate is 5°C/min.

The relative density of the barium cerium zirconate proton conductor material is above 90%.

Beneficial effects of the present invention: BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ is used as the electrolyte material, and Li ₂ CO ₃ is added as the liquid phase sintering aid, so that the electrolyte material can be dense at a lower sintering temperature. Due to the addition of inorganic salt lithium carbonate, the number of proton conduction is increased and the grain boundary condition of the material is improved. The conductivity at 600°C is expected to reach 10 ^-2 Siemens/cm. The invention improves its sintering performance and simultaneously improves its electrical performance and stability, and lays a theoretical foundation for continuously promoting the application of cerium barium zirconate proton conductor materials and developing solid oxide fuel cells.

Description of drawings

Fig. 1 is the XRD collection of illustrative plates of BZCY2.5L and BZCY sample in the embodiment of the present invention 1;

Fig. 2 is the relative density curve of adding lithium carbonate sample in the embodiment of the invention 1;

Fig. 3 is the scanning electron microscope (SEM) photograph of the electrolyte section after sintering in the embodiment 1 of the present invention;

Fig. 4 is the scanning electron micrograph of BZCY-5L sample in the embodiment of the present invention 2;

Fig. 5 is the conductivity curves of materials with different Li ₂ CO ₃ doping contents in Examples 1, 2 and 5 of the present invention.

Detailed ways

The raw materials used in the present invention are analytical reagents, and the BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ powder is prepared by the self-combustion method of nitrate-citric acid gel; the present invention will be further described in conjunction with specific examples below.

Example 1

According to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , 1 mole of Ba(NO ₃ ) ₂ , _0.7 mole of CeWO ₃ ) ₃ ·6H ₂ O, 0.1 mole of Zr(NO ₃ ) ₄ · 5H ₂ O, 0.2 moles of Y(NO ₃ ) ₃ 6H ₂ O, mixed according to the total metal ion: EDTA: citric acid (molar ratio) = 1:1.5:1, dissolved in 50OlnL deionized water, and adjusted the pH of the solution with ammonia water The value is 8, heat and stir to make the water evaporate continuously so as to obtain a viscous light yellow gel, burn the organic matter in the stainless steel reaction vessel to obtain off-white powder, then pre-fire at 240 ° C, keep the temperature for 5 hours, and finally in Calcined at 1000°C and kept for 5 hours, the pure-phase BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ (BZCY) light yellow powder was prepared. Add 2.5% lithium carbonate by mass to the base powder, and use absolute ethanol as the medium for ball milling and mixing for 6 hours. After drying, grinding, and sieving, weigh 0.7 grams of the mixed electrolyte powder and pour it into a 12mm mold. Carry out dry pressing molding, the pressure is 100MPa, embed lithium carbonate doped cerium barium zirconate powder, bury and burn in 1250 ℃ in air atmosphere, heating rate 5 ℃/min, keep warm for 5 hours, then naturally cool to At room temperature, BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -2.5%Li ₂ CO ₃ (BZCY2.5L) composite electrolyte was prepared. Figure 1 shows the XIRD patterns of BZCY and BZCY2.5L. It can be seen from the figure that both materials present a single perovskite structure. For the sample BZCY-2.5L, although lithium carbonate was added as an independent phase, the sintering test Lithium carbonate peak does not appear in the sample, indicating that lithium carbonate is in solid solution with the main crystal phase, thereby promoting sintering and making the material more compact.

The density was measured by the Archimedes drainage method. It can be seen from Figure 2 that the relative density of BZCY2.5L after sintering at 1250°C reaches 93%. It can be seen from the scanning electron microscope photo of the material in Figure 3 that the grains are closely arranged. There is no porosity, and the material exhibits good sintering performance, indicating that the addition of lithium carbonate improves the sintering performance of the material.

Example 2

According to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , 1 mole of Ba(NO ₃ ) ₂ , 0.7 mole of CeWO ₃ ) ₃ ·6H ₂ O, 0.1 mole of Zf(NO ₃ ) ₄ ·5H ₂ O, 0.2 moles of Y(NO ₃ ) ₃ 6H ₂ O were mixed according to total metal ions: EDTA: citric acid (molar ratio) = 1:2:1, dissolved in 500mL deionized water, and the pH value of the solution was adjusted to 6 with ammonia water. Heat and stir to continuously evaporate the water to obtain a viscous light yellow gel, burn the organic matter in a stainless steel reaction vessel to obtain off-white powder, then pre-calcine at 240°C for 5 hours, and finally calcined at 1050°C for 5 hours Hours, a pure-phase BZCY light yellow powder was prepared. Add lithium carbonate with a mass percentage of 5% to the matrix powder, mix and ball mill with absolute ethanol for 6 hours, then dry, grind, and sieve, weigh 0.7 grams of the mixed electrolyte powder and pour it into a 12mm mold Carry out dry pressing molding in the middle, the pressure is 150MPa, embed lithium carbonate doped with cerium barium zirconate powder, bury and burn in air atmosphere at 1250°C, heating rate 5°C/min, keep warm for 5 hours, and then cool naturally to room temperature to prepare BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -5%Li ₂ CO ₃ (BZCY-5L) composite electrolyte.

The density is measured by the Archimedes drainage method, and the relative density reaches more than 95%. Figure 4 is a scanning photo of the sintered sample, the grains of the sample are closely arranged, and the material shows good sintering performance.

Example 3

According to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , 1 mole of Ba(NO ₃ ) ₂ , 0.7 mole of CeWO ₃ ) ₃ ·6H ₂ O, 0.1 mole of Zr(NO ₃ ) ₄ ·5H ₂ O, 0.2 moles of YWO ₃ ) ₃ 6H ₂ O, mixed according to total metal ions: EDTA: citric acid (molar ratio) = 1:1.5:1, dissolved in 500mL deionized water, using ammonia water to adjust the pH of the solution to 7, heating and stirring The water is continuously evaporated to obtain a viscous light yellow gel, and the organic matter is burned in a stainless steel reaction vessel to obtain off-white powder wood, then pre-calcined at 240°C for 5 hours, and finally calcined at 1100°C for 5 hours , the pure phase BZCY light yellow powder was prepared. Add 7% lithium carbonate by mass to the matrix powder, mix and ball mill for 6 hours with absolute ethanol as the medium, then dry, grind and sieve, weigh 0.7 g of the mixed electrolyte powder and pour it into a 15mm mold Carry out dry pressing molding, the pressure is 200MPa, embed lithium carbonate doped cerium barium zirconate powder, bury and burn in 1150 ℃ in air atmosphere, heating rate 5 ℃/min, keep warm for 6 hours, then naturally cool to At room temperature, BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -7%Li ₂ CO ₃ (BZCY7L) composite electrolyte was prepared.

The density was measured by the Archimedes drainage method, and the relative density reached 90%, and the material showed good sintering performance.

Example 4

According to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , 1 mole of Ba(NO ₃ ) ₂ , 0.7 mole of CeWO ₃ ) ₃ ·6H ₂ O, 0.1 mole of Zr(NO ₃ ) ₄ ·5H ₂ O, 0.2 moles of Y(NO ₃ ) ₃ 6H ₂ O were mixed according to total metal ions:EDTA:citric acid (molar ratio)=1:2:1, dissolved in 500mL deionized water, and the pH value of the solution was adjusted to 8 with ammonia water. Heat and stir to evaporate the water continuously to obtain a viscous light yellow gel, burn the organic matter in a stainless steel reaction vessel to obtain off-white powder wood, then pre-calcine at 240°C for 5 hours, and finally calcined at 1100°C After 5 hours, a pure-phase BZCY light yellow powder was prepared. Add a mass percentage of 7.5% lithium carbonate to the matrix powder, mix and ball mill it with absolute ethanol for 6 hours, then dry, grind, and sieve, weigh 0.7 grams of the mixed electrolyte powder and pour it into a 12mm mold Carry out dry pressing molding, the pressure is 100MPa, embed lithium carbonate doped cerium barium zirconate powder, bury and burn in 1150 ℃ in air atmosphere, heating rate 5 ℃/min, keep warm for 5 hours, then naturally cool to At room temperature, BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -7.5%Li ₂ CO ₃ (BZCY7.5L) composite electrolyte was prepared.

Its density was measured by the Archimedes drainage method, and the relative density reached 89%. Compared with the BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ matrix, the material showed better sintering performance.

Example 5

According to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , take 1 mole of Ba(NO ₃ ) ₂ , 0.7 mole of Ce(NO ₃ ) ₃ ·6H ₂ O, and 0.1 mole of Zr(NO ₃ ) ₄ ·5H ₂ O, 0.2 moles of Y(NO ₃ ) ₃ 6H ₂ O, mixed according to total metal ions: EDTA: citric acid (molar ratio) = 1:1.5:1, dissolved in 500mL deionized water, and adjusted the pH value of the solution with ammonia water 7, heat and stir to make the water evaporate continuously to obtain a viscous light yellow gel, burn the organic matter in a stainless steel reaction vessel to obtain off-white powder, then pre-fire at 240°C for 5 hours, and finally heat it at 1100°C Calcined at lower temperature for 5 hours, the pure-phase BZCY light yellow powder was prepared. Add 2.5% lithium carbonate by mass percentage and 2.5% zinc oxide by mole percentage to the base powder, mix ball milling with absolute ethanol as the medium for 6 hours, and then dry, grind and sieve the mixed electrolyte powder. Amount of 0.7 grams is poured into a 12mm mold for dry pressing molding, the pressure is 100MPa, embedded lithium carbonate doped with cerium barium zirconate powder, buried and fired at 1250°C in an air atmosphere, the heating rate is 5°C/min, Keeping it warm for 4 hours, and then naturally cooling to room temperature, the BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -2.5%ZnO-2.5%Li ₂ CO ₃ (BZCY-2.5L-2.5Z) composite electrolyte was prepared.

The density was measured by the Archimedes drainage method, and the relative density reached 90%, and the material showed good sintering performance.

Example 6

According to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , take 1 mole of Ba(NO ₃ ) ₂ , 0.7 mole of Ce(NO ₃ ) ₃ ·6H ₂ O, and 0.1 mole of Zr(NO ₃ ) ₄ ·5H ₂ O, 0.2 moles of Y(NO ₃ ) ₃ 6H ₂ O, mixed according to total metal ions: EDTA: citric acid (molar ratio) = 1:1.5:1, dissolved in 500mL deionized water, using ammonia water to adjust the pH value of the solution 7. Heat and stir to continuously evaporate the water to obtain a viscous light yellow gel, burn the organic matter in a stainless steel reaction vessel to obtain off-white powder wood, then pre-burn at 240°C for 5 hours, and finally heat it at 1100°C Calcined at lower temperature for 5 hours, the pure-phase BZCY light yellow powder was prepared. Add zinc oxide with a molar percentage of 2.5% to the base powder, mix and ball mill with absolute ethanol for 6 hours, then dry, grind, and sieve, weigh 0.7 grams of the mixed electrolyte powder and pour it into a 15mm mold Carry out dry pressing molding, the pressure is 150MPa, embed lithium carbonate doping barium oxide powder, bury and burn in 1200 ℃ in air atmosphere, heating rate 5 ℃/min, keep warm for 5 hours, then naturally cool to At room temperature, BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -2.5ZnO (BZCY-2.5Z) composite electrolyte was prepared.

The density was measured by the Archimedes drainage method, and the relative density reached 90%, and the material showed good sintering performance.

Example 7

According to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , 1 mole of Ba(NO ₃ ) ₂ , 0.7 mole of Ce(NO ₃ ) ₃ 6H ₂ O, 0.1 mole of ZfWO ₃ ) ₄ 5H ₂ O, 0.2 moles of Y(NO ₃ ) ₃ 6H ₂ O were mixed according to total metal ions:EDTA:citric acid (molar ratio)=1:1.5:1, dissolved in 500mL deionized water, and the pH value of the solution was adjusted to 8 with ammonia water. Heat and stir to continuously evaporate the water to obtain a viscous light yellow gel, burn the organic matter in a stainless steel reaction vessel to obtain off-white powder, then pre-calcine at 240°C for 5 hours, and finally calcined at 1100°C for 5 hours Hours, a pure-phase BZCY light yellow powder was prepared. Add 2.5% lithium carbonate by mass percentage and 4% zinc oxide by mole percentage to the base powder, mix and ball mill with absolute ethanol for 6 hours, and then dry, grind and sieve the mixed electrolyte powder. Amount of 0.7 grams is poured into a 12mm mold for dry pressing molding, the pressure is 100MPa, embedded lithium carbonate doped with cerium barium zirconate powder, buried and fired at 1300°C in an air atmosphere, the heating rate is 5°C/min, Keeping it warm for 5 hours, and then naturally cooling to room temperature, the BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -4%ZnO-2.5%Li ₂ CO ₃ (BZCY-2.5L-4Z) composite electrolyte was prepared.

The density was measured by the Archimedes drainage method, and the relative density reached 96%. The material showed good sintering performance.

Application Example 1

Using BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ -Li ₂ CO ₃ (2.5% by mass) powder as the electrolyte material, put it into a 12mm diameter mold for dry pressing at a pressure of 150MPa; The passivated doped cerium barium zirconate electrolyte powder was sintered in air at 1250°C, the heating rate was 5°C/min, kept for 5 hours, and then naturally cooled to room temperature. Place the obtained sample piece on a self-made conductivity test tube, introduce silver wires at both ends as electrodes, and conduct the test under a wet hydrogen atmosphere. The electrochemical workstation uses linear sweep voltammetry to test, and uses the formula O=L/RA to calculate the conductivity. It can be seen from Figure 5 that at 600°C, 650°C, and 700°C, the electrical conductivity is 7.27X10 ^-3 S/cm, 9.81×10 ^-3 S/cm, 1.11×10 ^-2 S/cm .

Application Example 2

BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ Li ₂ CO ₃ (5% by mass) powder was used as the electrolyte material, and the same batching method, pressing method, heat treatment technology and conductivity testing method as in Application Example 1 were used. It can be seen from Figure 5 that at 600°C, 650°C, and 700°C, the electrical conductivity of the electrolyte material is ^8.58X10-3 S/cm, 1.39× ^10-3 S/cm, and 1.6× ^10-2 S/cm.

Application Example 3

Using BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ ZnO (2.5% by mass)-Li ₂ CO ₃ (2.5% by mass) powder as the electrolyte material, using the same batching method, pressing method, and heat treatment technology as in Application Example 1 and conductivity testing methods. It can be seen from Figure 5 that at 600°C, 650°C, and 700°C, the electrical conductivity is 2.89×10 ^-3 S/cm, 3.51×10 ^-3 S/cm, 4.32X10 ^-3 S/cm .

The lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof proposed by the present invention have been described through the examples, and those skilled in the art can obviously understand the content, spirit and scope of the present invention. The content is modified or appropriately modified and combined to realize the present invention. In particular, it should be pointed out that all similar substitutions and modifications would be obvious to those skilled in the art, and they are all considered to be included in the spirit, scope and content of the present invention.

Claims (3)

1. A lithium carbonate modified barium cerium zirconate proton conductor material, its raw material components and molar content are: BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ , on this basis, an additional mass percentage of 0% to 7.5% lithium carbonate and 0% to 4% zinc oxide by molar percentage; The preparation method of this lithium carbonate modified cerium barium zirconate proton conductor material, the steps are as follows: (1) Weigh the raw materials according to the stoichiometric ratio of BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ : Ba(NO ₃ ) ₂ , Zr(NO ₃ ) ₄ 5H ₂ O, Ce(NO ₃ ) ₃ 6H ₂ O, Y(NO ₃ ) ₃ 6H ₂ O; according to the total metal salt ion: ethylenediaminetetraacetic acid (EDTA: citric acid) mixed in a molar ratio of l:1.5:1～1:2:1, add to 500mL Deionize in water, shake concentrated ammonia water to adjust the pH value to 6-8, heat and stir to evaporate water, obtain a viscous colloid, and react in a stainless steel reaction vessel; then pre-burn at 240 ° C, keep it warm for 5 hours; finally Calcined at 1000-1100°C and kept for 5 hours to obtain light yellow pure phase BaCe _0.7 Zr _0.1 Y _0.2 O _3-δ powder; (2) Taking the powder prepared in step (1) as the base material, adding 0% to 7.5% by mass percentage of lithium carbonate and 0% to 4% by mole percentage of zinc oxide, and using absolute ethanol as the medium for ball milling; drying, After grinding and sieving, put the powder into the mold, and dry press it at 100-200MPa to form a green body; then sinter the obtained green body in an air atmosphere at 1150-1300°C, keep it warm for 4-6 hours, and cool naturally to At room temperature, a lithium carbonate-modified cerium barium zirconate proton conductor material is prepared. 2. lithium carbonate modified cerium barium zirconate proton conductor material according to claim 1, is characterized in that, the sintering mode of described step (2) is buried firing, and heating rate 5 ℃/min. 3. The lithium carbonate modified barium cerium zirconate proton conductor material according to claim 1, characterized in that the relative density of the barium cerium zirconate proton conductor material is more than 90%.

Images