CN1155520C - Process for preparing superfine lithium aluminate used for membrane of fused carbonate fuel battery - Google Patents

Process for preparing superfine lithium aluminate used for membrane of fused carbonate fuel battery Download PDF

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CN1155520C
CN1155520C CNB991130669A CN99113066A CN1155520C CN 1155520 C CN1155520 C CN 1155520C CN B991130669 A CNB991130669 A CN B991130669A CN 99113066 A CN99113066 A CN 99113066A CN 1155520 C CN1155520 C CN 1155520C
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lialo
gamma
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carbonate fuel
ball milling
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CN1279210A (en
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林化新
衣宝廉
孔莲英
张恩浚
王风霞
曲天锡
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to a preparation technique for superfine gamma-LiAlO2 used for a diaphragm of a fused carbonate fuel cell. The present invention is characterized in that the preparation technique has the steps that Li2CO3, gamma-AlOOH, KCl and NaCl are used as raw materials to be mixed, an anhydrous ball milling medium is added into the raw materials for ball milling; the mixture of the raw materials and the anhydrous ball milling medium reacts for 0.5 to 1 hour at a high temperature between 550 and 750 DEG C; materials after the reaction are repeatedly cleaned by deionized water; the aqua compound is calcined for 0.5 to 2 hours at the high temperature between 450 and 650 DEG C; and an anti-welding agent is added into generated fine alpha-LiAlO2 and is calcined for 1 to 2 hours at 850 to 950 DEG C to generate the superfine gamma-LiAlO2. The present invention has the advantages of simple technical process, high reliability and low energy consumption, and meets the requirement on powder mass production and high capacity cell diaphragm preparation.

Description

Preparation method of lithium aluminate superfine material for molten carbonate fuel cell diaphragm
The invention relates to a molten carbonate fuel cell, in particular to gamma-LiAlO for a molten carbonate fuel cell diaphragm2Preparation technology of superfine material.
The molten carbonate fuel cell runs at high temperature (650-700 ℃), and high-pressure reaction gas is respectively introduced to two sides of a membrane in the cell: hydrogen and oxygen. The diaphragm is one of the core components of the battery, and the material for forming the diaphragm is generally LiAlO2Powder, and LiAlO2The powder has α, β and gamma-LiAlO three different crystal forms2Is prepared from α -and β -LiAlO2Is obtained by long-term roasting at 900 ℃, so that the gamma-LiAlO2The crystal structure is relatively stable, and the gamma-LiAlO is generally used for preparing the diaphragm2Powder and is also gamma-LiAlO2Matching coarse and fine materials by using gamma-LiAlO2The existing technology for preparing lithium metaaluminate mainly includes 1.Arendt R.H. (J.Electrochem.Soc.1980, 127 (8): 1660-1667) and others, and the chloride method is used to prepare β -LiAlO2Fines (containing α -LiAlO)2) With LiOH. H2O and Al2O3·3H2Adding 50 wt% of chloride (NaCl + KCl) and ball-milling medium methanol and the like into O serving as a raw material, and performing ball milling → drying → reaction (662-672 ℃) → cleaning → β -LiAlO2Regeneration (500-600 ℃) due to β -LiAlO2And β -LiAlO2The X-ray diffraction peaks of the two-dimensional crystal are almost the same, and Arendt et al could not recognize β -LiAlO2→β-LiAlO2Hydrate → β -LiAlO2Finally β -LiAlO is generated2The BET specific surface area of the fine material is less than or equal to 80M2In terms of a particle size of 0.34. mu.m/g. Poeppeleier K.R (organic Chemistry1988, 27: 4523-4524) et al describe LiOH H2O and Al (OH)3α -LiAlO is prepared by wet reaction (salt absorption reaction mechanism) as raw material2The fine material is prepared by ball milling and mixing the raw materials uniformly, and introducing water vapor at 400 ℃ for 100 hours to obtain α -LiAlO2Particle size of about 1 μ M and BET specific surface area of 60M2And about/g. Mason David. M. (United States patent.1976, 3,998,939) et al in Li2CO3And α -LiAlO2Is prepared by ball milling and mixing raw materials uniformly to obtain β -LiAlO in carbonate (Li-K-Na or K-Na)2The first stage is at 480-550 ℃ for 4-15 hours, the second stage is at 600-650 ℃ for 20-100 hours, and β -LiAlO is prepared2(containing α -and a small amount of gamma-LiAlO)2) In the process, the requirement on the purity of the raw materials is high, and the content of total impurities cannot exceed 0.1 percent. Kadokura Hidekimi (United States patent.1987, 4,704,266) et al useLiOH H2Preparing gamma-LiAlO by using O and alkyl aluminium oxide as raw material2. Hydrolysis of aluminum alkyl oxides by water and ethanol to yield Al (OH)3。Al(OH)3With LiOH. H2O reaction to α -LiAlO2In the presence of water, α -LiAlO2Hydration takes place, produceα-LiAlO2A hydrate of (1). The hydrate is roasted for 3 hours at 650-1000 ℃ and finally becomes gamma-LiAlO2. The BET specific surface area is less than or equal to 20M2(ii) in terms of/g. Gamma-LiAlO is commonly used in the preparation of molten carbonate fuel cell membranes2And gamma-LiAlO2Prepared from α -or β -LiAlO2Is obtained by long-term roasting at 900 ℃. None of the first three methods has been developed to prepare gamma-LiAlO2In the technology of the superfine material, the energy consumption of some methods is high, such as introducing water vapor at 400 ℃ for 100 hours, such as introducing water vapor at 600-650 ℃ for 20-100 hours, and β -LiAlO is prepared by a third method2No granularity and specific surface area data of powder, using LiOH H2O is a raw material, the property of which is unstable and finally changed into Li2O (melting point>1700 ℃ C.) leads to difficulties in the preparation of fines. Gamma-LiAlO prepared by the above fourth method2Without particle sizeData similarly show that LiOH. H is used2O is used as a raw material and the preparation of fine materials is difficult, so the fourth method is called as the preparation of gamma-LiAlO at best2Fine material technology, more particularly to the asymmetric preparation of gamma-LiAlO2Technology of superfine material.
The invention aims to provide gamma-LiAlO for a molten carbonate fuel cell diaphragm2The preparation technology has simple and reliable process and low energy consumption, and is suitable for the requirements of batch production of powder and preparation of high-capacity battery diaphragms.
The invention provides gamma-LiAlO for a molten carbonate fuel cell membrane2The superfine material preparation technology is characterized by comprising the following steps:
(1) ingredients
With Li2CO3Mixing the raw materials of gamma-AlOOH, KCl and NaCl, adding an anhydrous ball milling medium, and performing ball milling until the granularity of reactants is less than 1 mu m; li2CO3The molar ratio of the KCl to the gamma-AlOOH is 1.02/2-1.05/2, and the molar ratio of the KCl to the NaCl is 0.9/1-1.1/1; the weight of the chloride accounts for 50-80% of the total material;
(2) high temperature reaction
Drying and crushing the materials, and reacting at the high temperature of 550-750 ℃ for 0.5-1 hour to generate α -LiAlO2；
(3) Cleaning and α -LiAlO2By hydration of
The reacted materials are repeatedly washed by deionized water to remove K+、Na+、Cl-Ions and reacting α -LiAlO2Generating white hydrate by hydration;
(4)α-LiAlO2regeneration of
Roasting the hydrate at the high temperature of 450-650 ℃ for 0.5-2 hours;
(5)α-LiAlO2production of ultra-fine materials
α -LiAlO generated above2Adding an anti-sintering agent into the fine materials, wherein the anti-sintering agent is selected from carbon substances of carbon black and acetylene black, and the addition amount is 2-5% by weight; ballmilling is carried out in an anhydrous ball milling medium for 5-20 hours, and the materials are dried(ii) a Finally, roasting for 1-2 hours at 850-950 ℃ to generate gamma-LiAlO2And (4) ultra-fine materials.
In addition, sodium citrate, potassium citrate, sodium oxalate, potassium oxalate, sodium tartrate and potassium tartrate can be added in the cleaning step of the invention as anionic flocculant to remove chloride ions in the powder material. The anhydrous ball milling medium used in the invention is anhydrous organic reagent such as anhydrous ethanol, anhydrous methanol and anhydrous acetone, and the adding weight is equivalent to that of the material.
The gamma-LiAlO provided by the invention2The preparation technology of the superfine material comprises the following steps:
(1) ingredients
The key point of the step is that LiCO is selected3As a Li source material, and the reaction mass was ball milled to<1 μm. Due to LiCO3In addition, the ball milling process of the reactants can reduce the particle size of the reactants to generate α -LiAlO2The reaction of (2) is mainly surface rapid reaction, can be completed in a short time, and simultaneously avoids high-temperature sintering.
(2) High temperature reaction
In this step Li2CO3And chloride, and existing in an ionic state, gamma-AlOOH dispersed in the melt as fine particles, Li+Is absorbed into crystal gaps near the crystal surface of the layered compound gamma-AlOOH to react with Al3+Reacting to generate LiAlO2I.e. salts (Li)+) The inhalation reaction mechanism generates α -LiAlO due to small reactant particle size (particle size<1 μm) and high surface atomic ratio2The reaction of (2) is mainly surface fast reaction, the reaction is completed within 1 hour, and the particle size of the reactant gamma-AlOOH determines the particle size of the product.
(3) Cleaning and hydrating
The key of the step is the removal of chloride ions which are α -LiAlO2The flocculant of the powder is also a high-temperature sintering agent, so that the chloride ions are thoroughly cleanedUntil chloride ions are not detected with the silver nitrate solution, the difficulty of cleaning is increased by suspending the powder in an aqueous solution as the concentration of chloride ions becomes lower during cleaning, and an anionic flocculant such as sodium (potassium) citrate, sodium (potassium) oxalate, sodium (potassium) tartrate, etc. is added to the powder suspension during cleaning, α -LiAlO2Simultaneously, hydration is generated:
(1) filtering to obtain white hydrate, and analyzing by X-ray and thermogravimetric analysis to obtain (LiAlO)2)2·5H2O(n＝5)。
(4)α-LiAlO2Regeneration of
The essence of this step is the loss of crystal water and the generation of α -LiAlO2The method comprises the following steps:
for quasi-reversible process, α -LiAlO is generated2The particle size of the powder is further reduced to 0.33 mu M, and the BET specific surface area is 130-140M2/g。
(5)γ-LiAlO2Production of ultra-fine materials
In the present step, α -LiAlO is generated2Small size of fine material, high surface atom ratio, and both surface atom and crystal latticeThe reactionis very active, the crystal form transformation can be completed by short-time high-temperature reaction, and α -LiAlO is used for the crystal form transformation reaction at 900 DEG C2Firstly, the amorphous carbon is transformed into amorphous carbon, and after the surface energy is absorbed, the amorphous carbon is transformed into gamma-LiAlO gradually2While releasing surface energy, α -LiAlO due to the small particle size of the powder2→ amorphous → gamma-LiAlO2The process is accompanied by an atomic rearrangement reaction, gamma-LiAlO2And finishing the high-temperature treatment when the crystal grains are not grown.
In summary, the present invention differs from the prior art in that:
(1) the reactant has small granularity and high surface atomic ratio, and α -LiAlO is generated2In the reaction, the surface rapid reaction is mainly used, the reaction can be completed within 1 hour at high temperature, and chloride ions (α -LiAlO) are thoroughly cleaned after the reaction2And sinteringAgent), α -LiAlO2Dehydrating the hydrate to obtain α -LiAlO2Fine material with particle size of 0.33 μ M and BET specific surface area of 130-140M2/g。
(2)α-LiAlO2Small grain size of fine material, high surface atomic ratio, fast crystal transformation reaction at 900 deg.c, short crystal transformation period, addition of sintering resisting agent and no high temperature sintering, α -LiAlO2Firstly converted into intermediate transition type-amorphous type, and then converted into gamma-LiAlO2The process is also accompanied by atom rearrangement reaction, and the anti-sintering agent is added to promote the process, and the final product gamma-LiAlO2Ultra-fine material ratio of its precursor α -LiAlO2The particle size of the fines is still small.
The two points are respectively used for preparing α -LiAlO2Fines and gamma-LiAlO2The technical characteristics (or technical key) in the process of superfine material, wherein the former is the basis of the latter, and the latter is the inevitable result of the former; on the basis of the former, technical measures such as adding anti-sintering agents and the like are further enhanced. The front and the back constitute the preparation of the gamma-LiAlO2The complete technology of superfine material can not be divided, which has never been seen in the past literature.
The invention uses Li2CO3And gamma-AlOOH as raw material, preparing gamma-LiAlO by chloride method2Ultrafine material with particle size less than 0.18 μ M and BET specific surface area>40M2The process is novel, simple and reliable, the energy consumption is about 10 percent of that of the prior literature method, and the method completely meets the requirements of batch production of powder and preparation of high-capacity battery diaphragms.
The present invention is described in detail below by way of examples.
FIG. 1 shows that gamma-LiAlO is obtained by treating at 900 ℃ for different times2X-ray diffraction pattern of the ultrafine material.
FIG. 2 is a view of γ -LiAlO2Particle size distribution curve of the superfine material.
FIG. 3 is an I-V characteristic curve of Molten Carbonate Fuel Cells (MCFC) (NiO-Ni), with fuel gas and oxidant utilization of 20% each.
Example 1
Li2CO3(analytical purity): 510 g (forreaction completion, Li)2CO3Excess 2%), γ -AlOOH: 810.8 g, 60 wt% chloride (KCl + NaCl, Mol) is added.KCl/Mol.NaCl≤ 1.0), and anhydrous ethanol. The preparation method comprises the following main steps: mixing Li2CO3gamma-AlOOH, chloride and absolute ethyl alcohol are ball milled together for 30 hours inKeeping the mixture at 100 ℃ for 10 hours for drying, roasting the mixture for 1 hour at 650 ℃, then cleaning the mixture by using deionized water and an anionic flocculant, filtering and drying the mixture, roasting the mixture for 1 hour at 550 ℃, adding an anti-sintering agent and absolute ethyl alcohol, ball-milling the mixture for 10 hours, roasting the mixture for 1 to 2 hours at 900 ℃, and analyzing the product by X-ray to obtain a crystal form of gamma-LiAlO2See figure 1, no other impurities; the yield is 90% (a small part is lost in cleaning), the particle size is less than 0.18 μ M, and the BET specific surface area is more than 40M2(g), see the attached figure 2.
Example 2
Li2CO3(analytical purity): 612 g, γ -AlOOH: 973 g, and the chloride and absolute ethyl alcohol are added, and the preparation is carried out according to the above process steps to obtain the reaction product of gamma-LiAlO2Ultrafine material with yield of 91%, particle size less than 0.17 μ M, BET specific surface area>43M2/g。
Example 3
γ-LiAlO2The granularity of the coarse material is 3.98 mu m, the granularity of the superfine material is less than 0.18 mu m, the battery diaphragm is prepared by the coarse and fine material (the weight percentage of the superfine material is 5-15 percent), and the battery is assembled by the diaphragm, the battery has high performance, and the I-V curve of the battery is shown infigure 3. As can be seen, the reaction gas pressure reaches 0.9MPa/cm2The reaction gas utilization rate was 20%, and the reaction gas utilization rates were 200 and 300mA/cm2When discharging, the output voltage of the battery is respectively above 0.85V and 0.75V, which shows that the diaphragm has very high gas barrier performance, the battery performance is basically not reduced after 10 times of restarting, and the thermal mechanical performance of the diaphragm is good.

Claims (3)

1. Gamma-LiAlO for molten carbonate fuel cell diaphragm2The preparation method of the superfine material is characterized by comprising the following steps:
(1) ingredients
With Li2CO3Mixing the raw materials of gamma-AlOOH, KCl and NaCl, adding an anhydrous ball milling medium, and performing ball milling until the granularity of reactants is less than 1 mu m; li2CO3The molar ratio of the KCl to the gamma-AlOOH is 1.02/2-1.05/2, and the molar ratio of the KCl to the NaCl is 0.9/1-1.1/1; the weight of the chloride accounts for 50-80% of the total material;
(2) high temperature reaction
Drying and crushing the materials, and reacting at the high temperature of 550-750 ℃ for 0.5-1 hour to generate α -LiAlO2；
(3) Cleaning and α -LiAlO2By hydration of
The reacted materials are repeatedly washed by deionized water to remove K+、Na+、Cl-Ions and reacting α -LiAlO2Generating white hydrate by hydration;
(4)α-LiAlO2regeneration of
Roasting the hydrate at the high temperature of 450-650 ℃for 0.5-2 hours:
(5)α-LiAlO2production of ultra-fine materials
α -LiAlO generated above2Adding an anti-sintering agent into the fine materials, wherein the anti-sintering agent is selected from carbon substances of carbon black and acetylene black, and the addition amount is 2-5% by weight; ball-milling the mixture in an anhydrous ball-milling medium for 5 to 20 hours, and drying the material; finally, roasting for 1-2 hours at 850-950 ℃ to generate gamma-LiAlO2And (4) ultra-fine materials.
2. The method of preparing the lithium metaaluminate ultrafine material for the molten carbonate fuel cell membrane according to claim 1, wherein the method comprises the steps of: and in the cleaning step, sodium citrate, potassium citrate, sodium oxalate, potassium oxalate, sodium tartrate and potassium are added as anion flocculating agents to remove chloride ions in the powder.
3. The method of preparing the lithium metaaluminate ultrafine material for the molten carbonate fuel cell membrane according to claim 1, wherein the method comprises the steps of: the anhydrous ball milling medium is an anhydrous organic reagent, and the adding weight is equivalent to that of the material.
CNB991130669A 1999-06-30 1999-06-30 Process for preparing superfine lithium aluminate used for membrane of fused carbonate fuel battery Expired - Fee Related CN1155520C (en)

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