CN117417187A - 一种固体电解质流延膜的制备方法 - Google Patents
一种固体电解质流延膜的制备方法 Download PDFInfo
- Publication number
- CN117417187A CN117417187A CN202311347983.1A CN202311347983A CN117417187A CN 117417187 A CN117417187 A CN 117417187A CN 202311347983 A CN202311347983 A CN 202311347983A CN 117417187 A CN117417187 A CN 117417187A
- Authority
- CN
- China
- Prior art keywords
- casting
- slurry
- temperature
- parts
- ball milling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005266 casting Methods 0.000 title claims abstract description 84
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000002002 slurry Substances 0.000 claims abstract description 65
- 238000005245 sintering Methods 0.000 claims abstract description 46
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 36
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 19
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 19
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 19
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- 235000015895 biscuits Nutrition 0.000 claims abstract description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920003023 plastic Polymers 0.000 claims description 17
- 239000004033 plastic Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 12
- 230000000630 rising effect Effects 0.000 claims description 10
- 239000004677 Nylon Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 229920001778 nylon Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 14
- 238000005452 bending Methods 0.000 abstract description 6
- 238000000227 grinding Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6025—Tape casting, e.g. with a doctor blade
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
一种固体电解质流延膜的制备方法,是将氧化锆粉体、水、聚丙烯酸铵、羧甲基纤维素、聚乙烯醇、聚乙二醇和对甲苯磺酸依次进行球磨和加热处理制成浆料,经过滤后脱泡制成流延浆料,将流延浆料经流延处理制成电解质素坯膜片,将电解质流延素坯膜片排塑后进行烧结得电解质流延膜。本发明制备的氧化锆流延浆料的固含量在83.4%以上,收缩率低至8~12%,浆料具有优异的稳定性,采用该浆料制备的流延电解质素坯膜片密度为3~5g/cm3,制备的电解质流延膜的烧结密度为98.7%以上,抗弯强度达到800MPa以上,断裂韧性达到10.51MPa·m1/2,具有优异的力学性能。
Description
技术领域
本发明涉及陶瓷材料制备技术领域,具体涉及一种固体电解质流延膜及其制备方法。
背景技术
由于现在汽车氧传感器的工作环境复杂,要求传感器具备信号稳定、机械强度高、抗热冲击性良好等性能。氧化锆陶瓷耐热、耐蚀、耐磨及其潜在的优良的电磁、光学机能,近年来随着制造技术的进步而得到充分利用,制成的传感器完全能够满足上述要求。
现在YSZ陶瓷基体大多是通过流延法生产,稳定料浆的制备是成型低缺陷、高质量陶瓷坯片的关键。特别是基体干燥成膜时流延膜收缩,产生内应力,导致膜出现畸形、开裂现象,流延膜的力学性能受损严重。浆料的稳定性主要与浆料中固含量、粘度等指标有很大的关系,本领域均知晓,高的固含量有利于提高材料的烧结密度;低的粘度会降低裂纹量、提高微观结构的均匀性,从而提高材料的力学性能。但是,固含量的增加,会导致浆料的粘度上升,降低粘度,又会导致浆料的固含量下降,氧化锆陶瓷浆料的高固含量和低粘度是相互矛盾的性质,想要保证较高固含量的同时具有较低粘度是非常困难的。在烧结过程中为了减少气孔等缺陷的产生,通常会选择高于1600℃的烧结温度,但是过高的烧结温度会导致晶粒异常长大,使得材料的致密度较低,烧结后的结构稳定性差。
发明内容
本发明目的在于提供一种固体电解质流延膜。
本发明另一目的在于提供固体电解质流延膜的制备方法,制备的流延浆料固含量高,粘度低,制备的流延膜基体收缩率低,致密度高,力学性能优异。
本发明目的通过如下技术方案实现:
一种固体电解质流延膜,其特征在于:是以氧化锆粉体、水、聚丙烯酸铵、羧甲基纤维素、聚乙烯醇和聚乙二醇经球磨、加热处理、过滤脱泡、流延处理、排塑和烧结制成。
进一步,按照重量份计,所述氧化锆粉体为100份、水为17~30份、聚丙烯酸铵为0.5~1.5份、羧甲基纤维素为0.5~4.2份、聚丙烯醇为2.5~6.3份、聚乙二醇为0.3~1.2份、对甲苯磺酸为0.02~0.15份。
进一步优选地,所述氧化锆粉体为100份、水为20~25份、聚丙烯酸铵为0.6~1.2份、羧甲基纤维素为1.2~3.6份、聚丙烯醇为3.0~4.8份、聚乙二醇为0.5~1.0份、对甲苯磺酸为0.04~0.1份。
进一步,所述加热处理的温度为70~80℃,保温时间为30~60min。
进一步,所述球磨是分为两步,第一步球磨是将氧化锆粉体、水和聚丙烯酸铵混合,在250~300rpm下球磨12~24h,第二步球磨是第一步球磨结束后,继续加入羧甲基纤维素、聚丙烯醇和聚乙二醇,以相同的球磨转速继续球磨8~30h。
进一步,所述过滤脱泡是采用100~400目尼龙网将球磨好的料浆过滤,然后加入消泡剂,真空抽滤1~5h,陈腐1~3h。
进一步,所述流延处理的流延刀高100~500μm,流延速度为0.5~3m/min,经三区温度,依次是一区温度为40~60℃,二区温度为70~90℃,三区温度为95~110℃。
进一步,所述排塑的温度为500~800℃,升温速率为0.5~1℃/min,保温时间为12~25h。
进一步,所述烧结是在常压下进行,烧剂的温度为1400~1700℃,升温速率为1~5℃/min,烧结时间为4~8h。
优选地,所述烧结温度为1600~1700℃,升温速率为2~4℃/min,烧结时间为5~6h。
一种固体电解质流延膜的制备方法,其特征在于:氧化锆粉体、水、聚丙烯酸铵、羧甲基纤维素、聚乙烯醇、聚乙二醇和对甲苯磺酸依次进行球磨和加热处理制成浆料,经过滤后脱泡制成流延浆料,将流延浆料经流延处理制成电解质素坯膜片,将电解质流延素坯膜片排塑后进行烧结得电解质流延膜。
进一步,所述球磨是分为两步,第一步球磨是将氧化锆粉体、水和聚丙烯酸铵混合,在250~300rpm下球磨12~24h,第二步球磨是第一步球磨结束后,继续加入羧甲基纤维素、聚丙烯醇和聚乙二醇,以相同的球磨转速继续球磨8~30h。
进一步,所述加热处理的温度为70~80℃,保温时间为30~60min。
本发明通过添加助剂,控制反应,改善陶瓷可以的分散性和均匀性,从而提高其固含量和胶含量,达到降低和稳定其基体烧结收缩率的目的,从而提高合格率。
本发明中通过羧甲基纤维的长链结构表面的羧基分散吸附YSZ颗粒,使得YSZ颗粒以羧甲基纤维素为载体形成桥链,从而达到稳定、分散均匀的浆料体系,其次,羧甲基纤维素和聚乙烯醇分别含有大量的羧基和羟基,在制备过程中通过加入对甲苯磺酸进行球磨,球磨后再进行热处理,有效调控羧甲基纤维素和聚乙烯醇表面的羧基和羟基反应形成凝胶,进一步对YSZ颗粒形成包裹,提高浆料的稳定性,有效减小后续材料在高温过程中的收缩率,但是若反应过程控制不好,容易造成浆料的粘度急剧上升,从而导致浆料的流延效果变差,在此过程中,通过调节剂对对甲苯磺酸的添加结合升温处理的作用,调控了体系的pH环境和温度,影响了反应进程,有效抑制了体系粘度不上升,从而减少高温烧结过程中裂纹的产生,提高结构的均匀性。
此外,体系中聚乙二醇除了作为增塑剂以外,在对甲苯磺酸的催化作用下,与羧甲基纤维形成酯,作为空隙填充物,提高后续材料的韧性,增强材料的力学性能,同时也作为抗连接组合物,有效降低了体系粘度。
进一步,按照重量份计,所述氧化锆粉体为100份、水为17~30份、聚丙烯酸铵为0.5~1.5份、羧甲基纤维素为0.5~4.2份、聚丙烯醇为2.5~6.3份、聚乙二醇为0.3~1.2份、对甲苯磺酸为0.02~0.15份。
进一步优选地,所述氧化锆粉体为100份、水为20~25份、聚丙烯酸铵为0.6~1.2份、羧甲基纤维素为1.2~3.6份、聚丙烯醇为3.0~4.8份、聚乙二醇为0.5~1.0份、对甲苯磺酸为0.04~0.1份。
进一步,所述过滤脱泡是采用100~400目尼龙网将球磨好的料浆过滤,然后加入消泡剂,真空抽滤1~5h,陈腐1~3h。
进一步,所述流延处理的流延刀高100~500μm,流延速度为0.5~3m/min,经三区温度,依次是一区温度为40~60℃,二区温度为70~90℃,三区温度为95~110℃。
进一步,所述排塑的温度为500~800℃,升温速率为0.5~1℃/min,保温时间为12~25h。
进一步,所述烧结是在常压下进行,烧结的温度为1400~1700℃,升温速率为1~5℃/min,烧结时间为4~8h。
优选地,所述烧结温度为1600~1700℃,升温速率为1~1.5℃/min,烧结时间为5~6h。
在较高的烧结温度下,容易导致晶粒异常长大,烧结后的产品结构稳定性差,本发明中通过前面形成凝胶对氧化锆形成包裹,并形成酯化物,通过常压下缓慢的升温过程,稳定对氧化锆的包裹结构,结合酯化物对空隙的填充,有效抑制高温烧结过程中的晶粒长大,从而增加流延膜的致密度。
进一步优选地,一种氧化锆陶瓷浆料的制备方法,是按照重量份称取YSZ粉体(氧化钇摩尔含量为1~8%)100份、水17~30份、聚丙烯酸铵0.5~1.5份,混合后在250~300rpm下球磨12~24h,再继续加入羧甲基纤维素0.5~4.2份、聚乙烯醇2.5~6.3份、聚乙二醇0.3~1.2份和对甲苯磺酸0.02~0.15份继续球磨8~30h,然后将球磨产物在70~80℃下保温30~60min。
最具体地,一种固体电解质流延膜的制备方法,其特征在于,按如下步骤进行:
(1)球磨制备浆料:按照重量份称取YSZ粉体(氧化钇摩尔含量为1~8%)100份、水17~30份、聚丙烯酸铵0.5~1.5份,混合后在250~300rpm下球磨12~24h,再继续加入羧甲基纤维素0.5~4.2份、聚乙烯醇2.5~6.3份、聚乙二醇0.3~1.2份和对甲苯磺酸0.02~0.15份继续球磨8~30h,然后将球磨产物在70~80℃下保温30~60min得浆料;
(2)制备流延素坯膜片
采用100~400目尼龙网将浆料过滤,然后加入消泡剂,真空脱泡1~5h,陈腐1~3h得流延浆料,采用流延机将流延浆料制成流延电解质素坯膜片,具体的刀高100~500μm,流延速度为0.5~3m/min,经三区温度,依次是一区温度为40~60℃,二区温度为70~90℃,三区温度为95~110℃;
(4)排塑
排塑的温度为500~800℃,升温速率为0.5~1℃/min,保温时间为12~25h;
(5)烧结
常压下烧结的温度为1400~1700℃,升温速率为1~5℃/min,烧结时间为4~8h。
本发明具有如下技术效果:
本发明制备的氧化锆流延浆料的固含量在83.4%以上,收缩率低至8~12%,浆料具有优异的稳定性,采用该浆料制备的流延电解质素坯膜片密度为3~5g/cm3,制备的电解质流延膜的烧结密度为98.7%以上,抗弯强度达到800MPa以上,断裂韧性达到10.51MPa·m1/2,具有优异的力学性能。
具体实施方式
下面通过实施例对本发明进行具体的描述,有必要在此指出的是,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。
实施例1
一种固体电解质流延膜的制备方法,按如下步骤进行:
(1)球磨制备浆料:按照重量份称取YSZ粉体(氧化钇摩尔含量为1~8%)100份、水20份、聚丙烯酸铵1份混合后在280rpm下球磨15h,再继续加入羧甲基纤维素2份、聚丙烯醇4份、聚乙二醇0.8份、对甲苯磺酸0.08份继续球磨8~30h,然后将球磨产物在75℃下保温50min制成浆料;
(2)制备流延素坯膜片
采用200目尼龙网将浆料过滤,然后加入消泡剂,真空脱泡4h,陈腐2h得流延浆料,采用流延机将流延浆料制成流延电解质素坯膜片,具体的刀高300μm,流延速度为2m/min,经三区温度,依次是一区温度为50℃,二区温度为80℃,三区温度为100℃;
(4)排塑
排塑的温度为600℃,升温速率为1℃/min,保温时间为20h;
(5)烧结
常压下的烧结的温度为1650℃,升温速率为4℃/min,烧结时间为6h。
本实施例制备的浆料的固含量为88.2wt%,在30S-1剪切速率下的粘度为0.84Pa·s,制备的素坯膜片的密度为4.92g/cm3,经烧结后制备的流延膜致密度为98.7%,收缩率为8.2%,稳定性优异,弯曲强度为846MPa、断裂韧性为10.51MPa·m1/2,具有优异的力学性能。
对比例1
与实施例1相比,在制备浆料时,球磨过程中添加对甲苯磺酸为0.2份,其余步骤保持不变。具体步骤如下:
(1)球磨制备浆料:按照重量份称取YSZ粉体(氧化钇摩尔含量为1~8%)100份、水20份、聚丙烯酸铵1份混合后在280rpm下球磨15h,再继续加入羧甲基纤维素2份、聚丙烯醇4份、聚乙二醇0.8份继续球磨8~30h,然后将球磨产物在75℃下保温50min制成浆料;
(2)制备流延素坯膜片
采用200目尼龙网将浆料过滤,然后加入消泡剂,真空脱泡4h,陈腐2h得流延浆料,采用流延机将流延浆料制成流延电解质素坯膜片,具体的刀高300μm,流延速度为2m/min,经三区温度,依次是一区温度为50℃,二区温度为80℃,三区温度为100℃;
(4)排塑
排塑的温度为600℃,升温速率为1℃/min,保温时间为20h;
(5)烧结
常压下的烧结的温度为1650℃,升温速率为1.5℃/min,烧结时间为6h。
该对比例制备的浆料的固含量为89.5wt%,在30S-1剪切速率下的粘度为2.94Pa·s,制备的素坯膜片的密度为1.82g/cm3,经烧结后制备的流延膜致密度为90.4%,收缩率为9.2%,弯曲强度为417MPa、断裂韧性为6.49MPa·m1/2,力学性能较差。
实施例2
一种固体电解质流延膜的制备方法,按如下步骤进行:
(1)球磨制备浆料:按照重量份称取YSZ粉体(氧化钇摩尔含量为1~8%)100份、水17份、聚丙烯酸铵1.5份,混合后在250rpm下球磨24h,再继续加入羧甲基纤维素0.5份、聚乙烯醇2.5份、聚乙二醇0.3份和对甲苯磺酸0.02份继续球磨8h,然后将球磨产物在70℃下保温60min得浆料;
(2)制备流延素坯膜片
采用400目尼龙网将浆料过滤,然后加入消泡剂,真空脱泡5h,陈腐1h得流延浆料,采用流延机将流延浆料制成流延电解质素坯膜片,具体的刀高500μm,流延速度为0.5m/min,经三区温度,依次是一区温度为40℃,二区温度为70℃,三区温度为95℃;
(4)排塑
排塑的温度为800℃,升温速率为0.5℃/min,保温时间为12h;
(5)烧结
常压下的烧结的温度为1400℃,升温速率为1℃/min,烧结时间为8h。
本实施例制备的浆料的固含量为83.4wt%,在30S-1剪切速率下的粘度为0.92Pa·s,制备的素坯膜片的密度为3.52g/cm3,经烧结后制备的流延膜致密度为97.4%,收缩率为11.1%,稳定性优异,弯曲强度为804MPa、断裂韧性为9.46MPa·m1/2,具有优异的力学性能。
实施例3
一种固体电解质流延膜的制备方法,按如下步骤进行:
(1)球磨制备浆料:按照重量份称取YSZ粉体(氧化钇摩尔含量为1~8%)100份、水30份、聚丙烯酸铵0.5份,混合后在300rpm下球磨12h,再继续加入羧甲基纤维素4.2份、聚乙烯醇6.3份、聚乙二醇1.2份和对甲苯磺酸0.15份继续球磨30h,然后将球磨产物在80℃下保温30min得浆料;
(2)制备流延素坯膜片
采用400目尼龙网将浆料过滤,然后加入消泡剂,真空脱泡1h,陈腐3h得流延浆料,采用流延机将流延浆料制成流延电解质素坯膜片,具体的刀高100μm,流延速度为3m/min,经三区温度,依次是一区温度为60℃,二区温度为90℃,三区温度为110℃;
(4)排塑
排塑的温度为500℃,升温速率为0.5℃/min,保温时间为25h;
(5)烧结
常压下烧结的温度为1700℃,升温速率为5℃/min,烧结时间为4~8h。
本实施例制备的浆料的固含量为84.9wt%,在30S-1剪切速率下的粘度为0.97Pa·s,制备的素坯膜片的密度为3.73g/cm3,经烧结后制备的流延膜致密度为97.8%,收缩率为11.9%,稳定性优异,弯曲强度为819MPa、断裂韧性为9.12MPa·m1/2,具有优异的力学性能。
Claims (9)
1.一种固体电解质流延膜的制备方法,其特征在于:是将氧化锆粉体、水、聚丙烯酸铵、羧甲基纤维素、聚乙烯醇、聚乙二醇和对甲苯磺酸依次进行球磨和加热处理制成浆料,经过滤后脱泡制成流延浆料,将流延浆料经流延处理制成电解质素坯膜片,将电解质流延素坯膜片排塑后进行烧结得电解质流延膜。
2.如权利要求1所述的一种固体电解质流延膜的制备方法,其特征在于:所述球磨是分为两步,第一步球磨是将氧化锆粉体、水和聚丙烯酸铵混合,在250~300rpm下球磨12~24h,第二步球磨是第一步球磨结束后,继续加入羧甲基纤维素、聚丙烯醇和聚乙二醇,以相同的球磨转速继续球磨8~30h。
3.如权利要求1或2所述的一种固体电解质流延膜的制备方法,其特征在于:所述加热处理的温度为70~80℃,保温时间为30~60min。
4.如权利要求1-3任一项所述的一种固体电解质流延膜的制备方法,其特征在于:按照重量份计,所述氧化锆粉体为100份、水为17~30份、聚丙烯酸铵为0.5~1.5份、羧甲基纤维素为0.5~4.2份、聚丙烯醇为2.5~6.3份、聚乙二醇为0.3~1.2份、对甲苯磺酸为0.02~0.15份。
5.如权利要求1-4任一项所述的一种固体电解质流延膜的制备方法,其特征在于:所述过滤脱泡是采用100~400目尼龙网将球磨好的料浆过滤,然后加入消泡剂,真空抽滤1~5h,陈腐1~3h。
6.如权利要求4或5所述的一种固体电解质流延膜的制备方法,其特征在于:所述流延处理的流延刀高100~500μm,流延速度为0.5~3m/min,经三区温度,依次是一区温度为40~60℃,二区温度为70~90℃,三区温度为95~110℃。
7.如权利要求6所述的一种固体电解质流延膜的制备方法,其特征在于:所述排塑的温度为500~800℃,升温速率为0.5~1℃/min,保温时间为12~25h。
8.如权利要求7所述的一种固体电解质流延膜的制备方法,其特征在于:所述烧结的温度为1400~1700℃,升温速率为1~5℃/min,烧结时间为4~8h。
9.一种固体电解质流延膜的制备方法,其特征在于,按如下步骤进行:
(1)球磨制备浆料:按照重量份称取YSZ粉体100份、水17~30份、聚丙烯酸铵0.5~1.5份,混合后在250~300rpm下球磨12~24h,再继续加入羧甲基纤维素0.5~4.2份、聚乙烯醇2.5~6.3份、聚乙二醇0.3~1.2份和对甲苯磺酸0.02~0.15份继续球磨8~30h,然后将球磨产物在70~80℃下保温30~60min得浆料;
(2)制备流延素坯膜片
采用100~400目尼龙网将浆料过滤,然后加入消泡剂,真空脱泡1~5h,陈腐1~3h得流延浆料,采用流延机将流延浆料制成流延电解质素坯膜片,具体的刀高100~500μm,流延速度为0.5~3m/min,经三区温度,依次是一区温度为40~60℃,二区温度为70~90℃,三区温度为95~110℃;
(4)排塑
排塑的温度为500~800℃,升温速率为0.5~1℃/min,保温时间为12~25h;
(5)烧结
烧结的温度为1400~1700℃,升温速率为1~5℃/min,烧结时间为4~8h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311347983.1A CN117417187B (zh) | 2023-10-18 | 2023-10-18 | 一种固体电解质流延膜的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311347983.1A CN117417187B (zh) | 2023-10-18 | 2023-10-18 | 一种固体电解质流延膜的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN117417187A true CN117417187A (zh) | 2024-01-19 |
CN117417187B CN117417187B (zh) | 2024-05-28 |
Family
ID=89525705
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311347983.1A Active CN117417187B (zh) | 2023-10-18 | 2023-10-18 | 一种固体电解质流延膜的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117417187B (zh) |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4957673A (en) * | 1988-02-01 | 1990-09-18 | California Institute Of Technology | Multilayer ceramic oxide solid electrolyte for fuel cells and electrolysis cells and method for fabrication thereof |
US20070298246A1 (en) * | 2006-06-26 | 2007-12-27 | Fabricas Monterrey, S.A. De C.V. | Corrosion-inhibiting coating for metal substrates and corrosion-resistant article |
JP2009045911A (ja) * | 2007-08-23 | 2009-03-05 | Toyota Motor Corp | 多孔質材料の製造方法、多孔質膜の製造方法、高分子電解質の製造方法、多孔質材料、多孔質膜、高分子電解質膜、及び固体高分子型燃料電池 |
WO2010051345A2 (en) * | 2008-10-31 | 2010-05-06 | Corning Incorporated | Methods and apparatus for casting ceramic sheets |
JP2014141394A (ja) * | 2012-12-26 | 2014-08-07 | Murata Mfg Co Ltd | セラミックグリーンシートおよびその製造方法 |
CN104446518A (zh) * | 2013-09-23 | 2015-03-25 | 比亚迪股份有限公司 | 一种nfc磁芯用水基流延浆料及制备方法、nfc磁芯及其制备方法 |
CN105637685A (zh) * | 2013-10-07 | 2016-06-01 | 日产自动车株式会社 | 非水电解质二次电池用电极材料、以及使用了其的非水电解质二次电池用电极和非水电解质二次电池 |
US20170137326A1 (en) * | 2014-09-04 | 2017-05-18 | Ngk Insulators, Ltd. | Zinc oxide sintered body and method for producing same |
CN107399969A (zh) * | 2016-05-19 | 2017-11-28 | 张尚权 | 一种原位流延制备氧化锆陶瓷片的方法 |
CN108493389A (zh) * | 2018-05-03 | 2018-09-04 | 厦门大学 | 一种酚醛树脂改性陶瓷隔膜及其应用 |
CN112919904A (zh) * | 2021-04-21 | 2021-06-08 | 上海大学 | 氧化锆陶瓷基板及其制备方法 |
CN114085057A (zh) * | 2021-11-18 | 2022-02-25 | 湖南志洲新型干混建材有限公司 | 一种抹灰抗裂砂浆及其制备方法 |
WO2022252504A1 (zh) * | 2021-05-31 | 2022-12-08 | 广东工业大学 | 一种氧化锆增韧氧化铝陶瓷板及其制备方法 |
CN116111183A (zh) * | 2023-03-08 | 2023-05-12 | 昆明理工大学 | 一种应用于全固态锂电池的固态陶瓷电解质膜的制备方法 |
-
2023
- 2023-10-18 CN CN202311347983.1A patent/CN117417187B/zh active Active
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4957673A (en) * | 1988-02-01 | 1990-09-18 | California Institute Of Technology | Multilayer ceramic oxide solid electrolyte for fuel cells and electrolysis cells and method for fabrication thereof |
US20070298246A1 (en) * | 2006-06-26 | 2007-12-27 | Fabricas Monterrey, S.A. De C.V. | Corrosion-inhibiting coating for metal substrates and corrosion-resistant article |
JP2009045911A (ja) * | 2007-08-23 | 2009-03-05 | Toyota Motor Corp | 多孔質材料の製造方法、多孔質膜の製造方法、高分子電解質の製造方法、多孔質材料、多孔質膜、高分子電解質膜、及び固体高分子型燃料電池 |
WO2010051345A2 (en) * | 2008-10-31 | 2010-05-06 | Corning Incorporated | Methods and apparatus for casting ceramic sheets |
JP2014141394A (ja) * | 2012-12-26 | 2014-08-07 | Murata Mfg Co Ltd | セラミックグリーンシートおよびその製造方法 |
CN104446518A (zh) * | 2013-09-23 | 2015-03-25 | 比亚迪股份有限公司 | 一种nfc磁芯用水基流延浆料及制备方法、nfc磁芯及其制备方法 |
CN105637685A (zh) * | 2013-10-07 | 2016-06-01 | 日产自动车株式会社 | 非水电解质二次电池用电极材料、以及使用了其的非水电解质二次电池用电极和非水电解质二次电池 |
US20170137326A1 (en) * | 2014-09-04 | 2017-05-18 | Ngk Insulators, Ltd. | Zinc oxide sintered body and method for producing same |
CN107399969A (zh) * | 2016-05-19 | 2017-11-28 | 张尚权 | 一种原位流延制备氧化锆陶瓷片的方法 |
CN108493389A (zh) * | 2018-05-03 | 2018-09-04 | 厦门大学 | 一种酚醛树脂改性陶瓷隔膜及其应用 |
CN112919904A (zh) * | 2021-04-21 | 2021-06-08 | 上海大学 | 氧化锆陶瓷基板及其制备方法 |
WO2022252504A1 (zh) * | 2021-05-31 | 2022-12-08 | 广东工业大学 | 一种氧化锆增韧氧化铝陶瓷板及其制备方法 |
CN114085057A (zh) * | 2021-11-18 | 2022-02-25 | 湖南志洲新型干混建材有限公司 | 一种抹灰抗裂砂浆及其制备方法 |
CN116111183A (zh) * | 2023-03-08 | 2023-05-12 | 昆明理工大学 | 一种应用于全固态锂电池的固态陶瓷电解质膜的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN117417187B (zh) | 2024-05-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108516820B (zh) | 一种氧化铟锡靶材的短流程烧结工艺 | |
CN113563103B (zh) | 一种采用流延成型法制备梯度氧化铝多孔陶瓷的方法 | |
CN107986777B (zh) | 一种氧化锆陶瓷基复合材料及其制备方法 | |
CN112174668B (zh) | 一种多层复合结构透明陶瓷的制备方法及其应用 | |
CN115124339B (zh) | 多元素高熵掺杂氧化锆基陶瓷材料及其制备方法和应用 | |
CN112939582A (zh) | 一种掺杂氧化锆的氧化铝陶瓷及其制备方法 | |
CN112279650A (zh) | 一种高致密度的碳化硅陶瓷复合材料的制备方法 | |
CN114890797A (zh) | 一种氮化硅陶瓷基片的制备方法 | |
CN112094109B (zh) | 变压器骨架用氧化铝陶瓷浆料及其制备方法和应用方法 | |
CN117417187B (zh) | 一种固体电解质流延膜的制备方法 | |
CN114685149A (zh) | 一种功能化氧化铝陶瓷纤维及制备方法 | |
CN109336562B (zh) | 一种氧化铝基陶瓷复合材料的制备方法 | |
CN112645714B (zh) | 一种氮化硅陶瓷脱水元件及其制备方法和应用 | |
CN113999032A (zh) | 一种硅硼氮纤维增强石英陶瓷材料及其制备方法 | |
CN110563477B (zh) | 一种原位生长氧化铝晶须增强补韧锆铝复合陶瓷材料的制备方法 | |
CN114835473B (zh) | 一种氧化铝陶瓷及其制备方法 | |
CN111574224B (zh) | 一种易脱除陶瓷型芯及其制备方法和应用 | |
JP2006248858A (ja) | イットリア安定化ジルコニア質焼結体及びその製造方法 | |
CN109796197A (zh) | 一种类单晶结构氧化铝透明陶瓷的制备方法 | |
CN113173586B (zh) | 一种堇青石微晶粉及其制备方法、氧化铝陶瓷基片及其制备方法 | |
CN115849884B (zh) | 一种高强度氧化铝陶瓷材料及其制备方法 | |
CN115611639B (zh) | 一种硅片流延浆料及硅片成型方法 | |
KR101884976B1 (ko) | 수계 바인더를 이용한 세라믹 후막 제조방법 및 이를 이용한 고체산화물연료전지 | |
CN115028436B (zh) | 一种低收缩率耐高温氧化铝材料及其制备方法和应用 | |
CN115784742B (zh) | 高红外透过率透明陶瓷的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant |