CN104103859A - Preparation method for solid electrolyte beta''-Al2O3 powder - Google Patents

Preparation method for solid electrolyte beta''-Al2O3 powder Download PDF

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Publication number
CN104103859A
CN104103859A CN201310128273.XA CN201310128273A CN104103859A CN 104103859 A CN104103859 A CN 104103859A CN 201310128273 A CN201310128273 A CN 201310128273A CN 104103859 A CN104103859 A CN 104103859A
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Prior art keywords
powder
preparation
agar
solid electrolyte
al2o3
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CN201310128273.XA
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惠志锋
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CHENGDU HUICHENG TECHNOLOGY Co Ltd
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CHENGDU HUICHENG TECHNOLOGY Co Ltd
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Priority to CN201310128273.XA priority Critical patent/CN104103859A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H01M10/3918—Sodium-sulfur cells characterised by the electrolyte
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to the field of chemical engineering, and especially relates to a preparation method for a solid electrolyte beta''-Al2O3 powder. According to the preparation method, firstly, alpha-Al2O3 is subjected to surface modification before raw materials are mixed, a proper amount of acrylic acid is grafted to the surface of the alpha-Al2O3 powder, so that once-more agglomeration of separated alpha-Al2O3 powder particles is avoided, the hydrophilicity of the particles is improved, the dispersity and the stability of aluminium oxide are enhanced, and thus the uniformity of the mixed materials is increased. Secondly, a soluble sodium salt and a soluble magnesium salt are dissolved in a suspension liquid of modified alpha-Al2O3, and agar is added as a gelata, so that a three-dimensional network skeleton is formed and the uniformly-mixed raw materials are fixedly disposed in the skeleton, thus the problem of composition nonuniformity caused by settlement can be avoided to a certain degree, and composition density gradient does not appear, and thus uniform dispersion of multiple compositions, especially trace elements is greatly facilitated. Also, a porous structure obtained by performing sintering on foams formed by stirring agar is capable of preventing sintering coarsening of raw-material power particles, and a power block obtained through calcining is loosened and easy to crush.

Description

A kind of solid electrolyte β 〞-Al 2o 3the preparation method of powder
Technical field
The present invention relates to chemical field, particularly a kind of solid electrolyte β 〞-Al 2o 3the preparation method of powder.
Background technology
Sodium-sulphur battery has that capacity is large, volume is little, energy storage and conversion efficiency is high, the life-span long, be not subject to the advantages such as regional limits, is therefore widely used in the fields such as peak load shifting, emergency power supply, regenerative resource (wind energy, solar energy) energy storage.Solid electrolyte is the critical component of sodium-sulphur battery, and the quality of its quality will affect performance and the life-span of sodium-sulphur battery to a great extent.Mainly β 〞-Al for the solid electrolyte material of sodium-sulphur battery at present 2o 3.Preparation β 〞-Al 2o 3the prior synthesizing method of powder is solid reaction process: by high-purity α-Al 2o 3, Na 2cO 3or Na 2c 2o 4, and a small amount of Li 2o or MgO stabilizer mix, and sintering forms under higher than 1580 DEG C of environment.The advantage of solid reaction process is that cost is low, output is high and preparation is simple, but in solid-phase synthesis, raw mixture directly reacts with solid-state form, each constituent element composition is difficult to mix, and this can cause ceramic crystalline phase not single, and ionic conductivity declines, and the powder being generated by solid reaction process has sintering in various degree conventionally, or have coarsening phenomenon to occur, be not easy further dispersion and fining, particle size and the more difficult control that distributes thereof.
Summary of the invention
The present invention is for overcoming above deficiency, and a kind of solid electrolyte β 〞-Al is provided 2o 3the preparation method of powder, raw material mixes and product is loose easily pulverizes, loose easy pulverizing of powder agglomates that calcination is obtained.
A kind of solid electrolyte powder β 〞-Al 2o 3preparation method, comprise the following steps:
Step 1: take a certain amount of α-Al 2o 3powder, adds a certain amount of acryloyl chloride, reacts at normal temperatures after certain hour, by deionized water eccentric cleaning repeatedly, until filtrate is aobvious neutral, then in 80 DEG C of vacuum drying chambers, dries, thereby obtains the α-Al of modification 2o 3powder.
Step 2: appropriate sodium salt and magnesium salts are dissolved in a certain amount of deionized water, and vigorous stirring is until dissolve wiring solution-forming completely.Then add the α-Al of the appropriate modification that step 1 obtains 2o 3powder, in maintenance system, the stoichiometric proportion of metallic element is Al according to target product 11-ymg yo 16(Na 1+yo) stoichiometric proportion in, wherein 0.45<y<1.0, ball milling 3 ~ 10h obtains slurry.
Step 3: slurry is heated to more than 85 DEG C, then adds appropriate agar, stirs and makes agar dissolve to obtain agar colloidal sol slurry.
Step 4: add surfactant in agar colloidal sol slurry, stir and bubble, then the foam colloidal sol after bubbling is put into-5 DEG C of refrigerators and made it gelation, through the dry porous ceramic green compact that obtain of the demoulding.
Step 5: porous ceramic green compact are carried out to Quenching Treatment again through heating schedule, obtain β 〞-Al after ball milling 2o 3powder.
Further, the sodium salt described in step 2 is NaNO 3, NaCOOCH 3, Na 2c2O 4or Na 2sO 4deng, magnesium salts is Mg (NO 3) 2, MgSO 4deng.
Further, the solution temperature of agar described in step 3 is 85 ~ 90 DEG C.
Further, the surfactant described in step 4 is dodecyl triethanolamine, neopelex, lauryl sulfosuccinate monoesters disodium etc.
Further, the heating schedule in step 5 is that the programming rate of 2 ~ 5 DEG C/min is heated to 800 ~ 1100 DEG C of insulation 2h, is then warming up to 1450 ~ 1550 DEG C with the speed of 10 DEG C/min, calcining 15 ~ 45min.
Principle of the present invention is, before raw material mixes first to α-Al 2o 3carry out surface modification, make appropriate acrylic acid-grafted at α-Al 2o 3powder surface, stops the α-Al having separated 2o 3reunion once again between powder particles, has improved particle hydrophily, has strengthened dispersiveness and the stability of alumina slurry, thereby increases the uniformity of mixing of materials.Next is that soluble sodium salt and magnesium salts are dissolved in to modified alpha-Al 2o 3in suspension, add agar as gel, form three-dimensional network skeleton, the raw slurry mixing is fixed to wherein, can avoid to a great extent the inhomogeneous problem of component of bringing because of sedimentation, there will not be composition density gradient, this for multicomponent particularly trace element dispersed highly beneficial, and the foam that under agitation forms of agar forms loose structure and can also hinder the sintering alligatoring of raw material powder after sintering, powder agglomates that calcination obtains is loose easily to be pulverized.
Embodiment
Embodiment 1
Take 89.3g α-Al 2o 3powder, adds the acryloyl chloride of its mass fraction 1%, reacts at normal temperatures after certain hour, by deionized water eccentric cleaning repeatedly, until filtrate is aobvious neutral, then in 80 DEG C of vacuum drying chambers, dries, and obtains acrylic graft-modified α-Al 2o 3powder; By 22.68gNaNO 3with 14.81gMg (NO 3) 2be dissolved in the deionized water of 300ml, vigorous stirring is until dissolve wiring solution-forming completely; In above-mentioned solution, add modified alpha-Al 2o 3powder, ball milling 5h.Slurry is heated to more than 90 DEG C, adds 4.27g agar, stir agar is dissolved; In agar colloidal sol slurry, add 34.1g dodecyl triethanolamine, stir 3min by electric mixer, then the foam colloidal sol after bubbling is put into-5 DEG C of refrigerators make it gelation, through the dry porous ceramic green compact that obtain of the demoulding; Be heated to 900 DEG C of insulation 2h with the programming rate of 5 DEG C/min again, continue to be warming up to 1500 DEG C with the speed of 10 DEG C/min, calcine 30min, and then obtain the pottery of loose and porous structure through Quenching Treatment, after ball milling, obtain β 〞-Al 2o 3powder.
Embodiment 2
Take 89.30g α-Al 2o 3powder, adds its mass fraction 1% acryloyl chloride, reacts at normal temperatures after certain hour, by deionized water eccentric cleaning repeatedly, until filtrate is aobvious neutral, then in 80 DEG C of vacuum drying chambers, dries, and obtains acrylic graft-modified α-Al 2o 3powder; By 26.27g NaNO 3with 20.28g Mg (NO 3) 2be dissolved in the deionized water of 450ml, vigorous stirring is until dissolve wiring solution-forming completely; In above-mentioned solution, add modified alpha-Al 2o 3powder, ball milling 10h.Slurry is heated to more than 90 DEG C, adds appropriate 11.72 agar, stir agar is dissolved; In agar colloidal sol slurry, add 58.60g dodecyl triethanolamine, stir 3min by electric mixer, then the foam colloidal sol after bubbling is put into-5 DEG C of refrigerators make it gelation, through the dry porous ceramic green compact that obtain of the demoulding; Be heated to 900 DEG C of insulation 2h with the programming rate of 3 DEG C/min again, continue to be warming up to 1500 DEG C with the speed of 10 DEG C/min, calcine 30min, and then obtain the pottery of loose and porous structure through Quenching Treatment, after ball milling, obtain β 〞-Al 2o 3powder.

Claims (5)

1. a solid electrolyte powder β 〞-Al 2o 3preparation method, it is characterized in that comprising the following steps:
Step 1: take a certain amount of α-Al 2o 3powder, adds a certain amount of acryloyl chloride, reacts at normal temperatures after certain hour, by deionized water eccentric cleaning repeatedly, until filtrate is aobvious neutral, then in 80 DEG C of vacuum drying chambers, dries, thereby obtains the α-Al of modification 2o 3powder;
Step 2: appropriate sodium salt and magnesium salts are dissolved in a certain amount of deionized water, and vigorous stirring is until dissolve wiring solution-forming completely; .then add the α-Al of the appropriate modification that step 1 obtains 2o 3powder, in maintenance system, the stoichiometric proportion of metallic element is Al according to target product 11-ymg yo 16(Na 1+yo) stoichiometric proportion in, wherein 0.45<y<1.0, ball milling 3 ~ 10h obtains slurry;
Step 3: slurry is heated to more than 85 DEG C, then adds appropriate agar, stirs and makes agar dissolve to obtain agar colloidal sol slurry;
Step 5: add surfactant in agar colloidal sol slurry, stir and bubble, then the foam colloidal sol after bubbling is put into-5 DEG C of refrigerators and made it gelation, through the dry porous ceramic green compact that obtain of the demoulding;
Step 6: porous ceramic green compact are carried out to Quenching Treatment again through heating schedule, obtain β 〞-Al after ball milling 2o 3powder.
2. a kind of solid electrolyte powder β 〞-Al according to claim 1 2o 3preparation method, it is characterized in that described sodium salt is NaNO 3, NaCOOCH 3, Na 2c 2o 4or Na 2sO 4deng, magnesium salts is Mg (NO 3) 2, MgSO 4deng.
3. a kind of solid electrolyte powder β 〞-Al according to claim 1 2o 3preparation method, it is characterized in that the solution temperature of described agar is 85 ~ 90 DEG C.
4. a kind of solid electrolyte powder β 〞-Al according to claim 1 2o 3preparation method, it is characterized in that described surfactant is dodecyl triethanolamine, neopelex, lauryl sulfosuccinate monoesters disodium etc.
5. a kind of solid electrolyte powder β 〞-Al according to claim 1 2o 3preparation method, it is characterized in that described heating schedule is that the programming rate of 2 ~ 5 DEG C/min is heated to 800 ~ 1100 DEG C of insulation 2h, be then warming up to 1450 ~ 1550 DEG C with the speed of 10 DEG C/min, calcine 15 ~ 45min.
CN201310128273.XA 2013-04-15 2013-04-15 Preparation method for solid electrolyte beta''-Al2O3 powder Pending CN104103859A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86100599A (en) * 1986-06-18 1987-12-30 中国科学院上海硅酸盐研究所 Solid electrolyte that protecting cathode of overhead metal pipe is used and preparation method thereof
CN101734911A (en) * 2009-12-22 2010-06-16 南京工业大学 Na-beta' -Al2O3Method for preparing solid electrolyte
CN102838379A (en) * 2012-09-18 2012-12-26 武汉理工大学 Lightweight foamed ceramics and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86100599A (en) * 1986-06-18 1987-12-30 中国科学院上海硅酸盐研究所 Solid electrolyte that protecting cathode of overhead metal pipe is used and preparation method thereof
CN101734911A (en) * 2009-12-22 2010-06-16 南京工业大学 Na-beta' -Al2O3Method for preparing solid electrolyte
CN102838379A (en) * 2012-09-18 2012-12-26 武汉理工大学 Lightweight foamed ceramics and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
尹良果: "纳米α-氧化铝的制备及其改性", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 200706, 15 December 2007 (2007-12-15), pages 014 - 35 *

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Application publication date: 20141015