CN101786873B - Method for preparing electrolyte ceramic membrane of lithium ion battery - Google Patents

Method for preparing electrolyte ceramic membrane of lithium ion battery Download PDF

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Publication number
CN101786873B
CN101786873B CN 200910045906 CN200910045906A CN101786873B CN 101786873 B CN101786873 B CN 101786873B CN 200910045906 CN200910045906 CN 200910045906 CN 200910045906 A CN200910045906 A CN 200910045906A CN 101786873 B CN101786873 B CN 101786873B
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powder
ceramic membrane
lithium ion
ion battery
electrolyte ceramic
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CN101786873A (en
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温兆银
许晓雄
刘宇
王秀艳
李宁
张群喜
黄颖
宋树丰
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a method for preparing an electrolyte ceramic membrane of a lithium ion battery, in particular to a tape casting method for preparing the electrolyte ceramic membrane of the lithium ion battery, and belongs to the field of ion conductive ceramic materials. The invention adopts the tape casting method; ceramic powder with a chemical formula of Li1.4Al0.4(Gel-xTix)1.6(PO4)3 (wherein x is equal to 0-1.0) is selected as raw material powder; triethanolamine or phosphate are selected as a dispersing agent; ethanol, propyl alcohol, butanone, triclene, or azeotropic solution prepared from any two of the ethanol, propyl alcohol, butanone and triclene is selected as a solvent; polyvinyl butyral (PVB) is selected as an adhesive; polyethylene glycol or dibutyl phthalate is selected as a plasticizer; the range of solid content of slurry is controlled between 18 and 30vol percent; the uniform slurry is prepared through ball milling, and then is prepared into a green belt by the tape casting method, and the green belt is subjected to heat treatment to form the electrolyte ceramic membrane; and the electrolyte ceramic membrane has good strength and toughness, and can be applied to actual production.

Description

The preparation method of electrolyte ceramic membrane of lithium ion battery
Technical field
The present invention relates to a kind of preparation method of electrolyte ceramic membrane of lithium ion battery, be specifically related to casting method and prepare electrolyte ceramic membrane of lithium ion battery, belong to the ionic conductivity ceramics Material Field.
Background technology
For inorganic solid electrolyte, the lithium ion conductor of NASICON structure has tunnel size and the skeleton of the most suitable lithium ion migration.The lithium ion solid electrolyte of NASICON structure is the material system that is hopeful to be applied to solid lithium battery most, so most study all is the lithium ion conductor of NASICON structure in crystalline state and the glass-ceramic lithium-ion electrolyte.
Electrolytical impedance is directly proportional with the thickness of pottery, therefore can reduce by the thickness that reduces electrolyte ceramics the impedance of electrolyte ceramics, is equivalent to improve electrolytical electric conductivity from another angle.
Film be prepared with a variety of methods.The methods such as physical vapor deposition can accurately be controlled thickness, and the film that obtains is very fine and close, but equipment is complicated, and production cost is high, and the production cycle is long, can not satisfy the requirement of large-scale production and application.Flow casting molding is the forming method of a kind of typical banded green compact, two-dirnentional structure thin slice or plate, and it is simple that the method has equipment, process stabilizing, but operate continuously, and production efficiency is high, can realize the advantages such as increasingly automated, is widely used in the preparation of film.
Summary of the invention
The object of the invention is to use the organic additives such as wedding agent, fluidizer, dispersion agent to prepare the slurry of good rheological property, and obtain to have certain intensity and flexible lithium ion battery electrolyte green compact by flow casting molding.By the follow-up sintering to green compact, can obtain electrolyte ceramic membrane.
The material powder of flow casting molding can be the synthetic ceramic powder of the whole bag of tricks, and its chemical formula is Li 1.4Al 0.4(Ge 1-xTi x) 1.6(PO 4) 3(x=0-1.0).Choose trolamine or phosphoric acid ester as dispersion agent; Select the azeotropic solution of ethanol, propyl alcohol, butanone, trieline or its any the two composition as solvent; Polyvinyl butyral acetal (PVB) is as binding agent, and polyoxyethylene glycol, dibutyl phthalate are as plastic agent.The range of solid content of slurry is controlled between 18～30vol%; The addition of dispersion agent is the 0.5wt.%～2wt.% of powder; Content of binder is that powder is 4wt.%～9wt.%; Binding agent: the weight ratio scope of plastic agent is 1: 1～1: 3.
In the above-mentioned raw materials powder, add solvent, dispersion agent, binding agent and plastic agent, prepare uniform slurry by ball milling.Adopt casting method, the slurry curtain coating on stainless steel plate or plastic substrate, is peeled off after the seasoning in air, namely obtain the green compact band.The green compact band 700～1000 ℃ of lower thermal treatments, is obtained electrolyte ceramics.
After some different solution mixed, their mixed solution had unified boiling point, in case occurred common boiling point after two or more liquid mixing, just claims that this mixed solution is azeotropic solution." practical solvent handbook (Shanghai science tech publishing house, Mu Guangzhao chief editor) is seen in its solution composition.
Description of drawings
Fig. 1 is the biscuit film photo after the curtain coating.
Fig. 2 is the TEM photo that high-energy ball milling made powder in 40 hours.
Fig. 3 is to be the TEM photo that 800 ℃ of calcinings of precursor powder of citric acid complex method preparation obtained the LATP powder in 2 hours.
Embodiment
Below by concrete comparative example technique effect of the present invention is described, but be not only to be confined to following example.
Comparative example 1
At first will be according to Li 1.4Al 0.4Ge 1.6(PO 4) 3The Li of stoichiometric ratio (LAG-TP) 2CO 3, Al (OH) 3, GeO 2With NH 4H 2PO 4Ball milling evenly mixes, and then decomposes and synthesizes in 2 hours 700 ℃ of thermal treatments, grinds after the cooling, obtains powder.
With above-mentioned powder, join in the azeotropic solution of butanone and ethanol, add again the trolamine of powder quality 2wt%, the PVB of 7wt% and the plastic agent of 10.5wt%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Biscuit film is shown in figure one.Obtain fine and close electrolyte ceramics behind 900 ℃ of sintering 12h.
Embodiment 1
Method is with comparative example 1, according to Li 1.4Al 0.4Ge 0.8Ti 0.8(PO 4) 3The Li of stoichiometric ratio (LAG-TP) 2CO 3, TiO 2, Al (OH) 3, GeO 2With NH 4H 2PO 4Ball milling evenly mixes, and then decomposes and synthesizes in 2 hours 700 ℃ of thermal treatments, grinds after the cooling, obtains powder.
With above-mentioned powder, join in the alcohol solvent, add again the trolamine of powder quality 2wt.%, the PVB of 6wt.% and the plastic agent of 10wt.%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Obtain fine and close electrolyte ceramics behind 900 ℃ of sintering 12h.
Embodiment 2
Method is with comparative example 1, according to Li 1.4Al 0.4Ti 1.6(PO 4) 3The Li of stoichiometric ratio (LAG-TP) 2CO 3, TiO 2, Al (OH) 3, GeO 2With NH 4H 2PO 4Ball milling evenly mixes, and then decomposes and synthesizes in 2 hours 700 ℃ of thermal treatments, grinds after the cooling, obtains powder.
With above-mentioned powder, join in the azeotropic solution of propyl alcohol and trieline, add again the trolamine of powder quality 1wt%, the PVB of 9wt% and the plastic agent of 10.5wt%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Behind 1000 ℃ of sintering 12h, obtain fine and close electrolyte ceramics.
Embodiment 3
With analytically pure Li 2CO 3,, Al (OH) 3,, TiO 2With NH 4H 2PO 4Be raw material, according to Li 1.4Al 0.4Ge 0.96Ti 0.64(PO 4) 3Stoichiometric ratio fully made easy degradation production fully decompose in 4 hours 700 ℃ of thermal treatments after minute mixing, and then cooling is ground for subsequent use.Forerunner's material with certain mass in the glove box of argon gas atmosphere places stainless tank, adds the ball-milling medium Stainless Steel Ball, and the ratio of grinding media to material of selection is 15: 1, and the rotating speed of ball milling is 500rpm, and ball milling under the room temperature obtains amorphous powder.Powder TEM as shown in Figure 2.
With above-mentioned amorphous powder, join in the azeotropic solution of butanone and ethanol, add again the phosphoric acid ester of powder quality 0.5wt.%, the PVB of 4wt.% and the plastic agent of 8wt.%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Obtain fine and close electrolyte ceramics behind 900 ℃ of sintering 6h.
Embodiment 4
With analytically pure Li 2CO 3,, Al (OH) 3,, TiO 2With NH 4H 2PO 4Be raw material, according to Li 1.4Al 0.4Ge 0.64Ti 0.96(PO 4) 3Stoichiometric ratio, fully minute mixing.Synthesis method is with embodiment 3.With the amorphous powder that obtains, join in the azeotropic solution of propyl alcohol and trieline, add again the trolamine of powder quality 2wt.%, the PVB of 7wt.% and the polyoxyethylene glycol of 10.5wt.%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Obtain fine and close electrolyte ceramics behind the sintering behind 1000 ℃ of sintering 6h.
Embodiment 5
With analytically pure Li 2CO 3,, Al (OH) 3,, TiO 2With NH 4H 2PO 4Be raw material, according to Li 1.4Al 0.4Ge 0.32Ti 1.28(PO 4) 3Stoichiometric ratio, fully minute mixing.Synthesis method is with embodiment 3.With the amorphous powder that obtains, join in the alcohol solvent, add again the trolamine of powder quality 2wt.%, the PVB of 5wt.% and the plastic agent of 9wt.%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Obtain fine and close electrolyte ceramics behind 900 ℃ of sintering 6h.
Embodiment 6
Raw material is chemical pure tetrabutyl titanate (Ti (C 4H 9) 4), analytical pure lithium nitrate (LiNO 3H 2O), analytical pure aluminum nitrate (Al (NO 3) 39H 2O), analytical pure ammonium di-hydrogen phosphate (NH 4H 2PO 4) and the analytical pure citric acid, deionized water is solvent.By chemical constitution Li 1.4Al 0.4Ti 1.6(PO 4) 3Mol ratio accurately take by weighing each raw material.Behind the homogeneous solution to be formed, add certain volume ethylene glycol to improve polymerization and the polycondensation ability of solution.Total concentration of metal ions is defined as 0.2mol/L.The thermal treatment of the xerogel of preparation is divided into two steps and carries out: at first xerogel obtained amorphous powder in 4 hours 500 ℃ of thermal treatments, and then 800 ℃ of thermal treatment preparation in 2 hours crystalline phase is the powder of LATP in the air.
With above-mentioned powder, join in the azeotropic solution of butanone and ethanol, add again the phosphoric acid ester of powder quality 2wt.%, the PVB of 8wt.% and the plastic agent of 8wt.%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Obtain fine and close electrolyte ceramics behind 950 ℃ of sintering 6h.
Embodiment 7
Chemical constitution is Li 1.4Al 0.4Ge 0.8Ti 0.8(PO 4) 3, synthesis method is with embodiment 7.The powder that obtains is joined in the alcohol solvent, add again the phosphoric acid ester of powder quality 2wt.%, the PVB of 7wt.% and the plastic agent of 10.5wt.%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.Obtain fine and close electrolyte ceramics behind 950 ℃ of sintering 6h.
Embodiment 8
Chemical constitution is Li 1.4Al 0.4Ge 0.16Ti 1.44(PO 4) 3, synthesis method is with embodiment 7.The powder that obtains is joined in the azeotropic solution of propyl alcohol and trieline, add again the trolamine of powder quality 1wt.%, the PVB of 8wt.% and the plastic agent of 12wt.%, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has preferably intensity and toughness.1000 ℃ of sintering 6h obtain fine and close electrolyte ceramics.

Claims (4)

1. the preparation method of electrolyte ceramic membrane of lithium ion battery adopts the casting method preparation, it is characterized in that,
Selecting chemical formula is Li 1.4Al 0.4(Ge 1-xTi x) 1.6(PO 4) 3, ceramic powder is material powder, wherein x=0～1.0;
Choose trolamine or phosphoric acid ester as dispersion agent;
Select the azeotropic solution of ethanol, propyl alcohol, butanone, trieline or its any the two composition as solvent;
Select polyvinyl butyral acetal (PVB) as binding agent;
Select polyoxyethylene glycol or dibutyl phthalate as plastic agent, binding agent: the weight ratio scope of plastic agent is 1: 1～1: 3;
The range of solid content of control slurry is controlled between 18～30vol%;
Obtain uniform sizing material by ball milling, slurry adopts casting method to obtain to heat-treat behind the green compact band, and heat-treat condition is 700～1000 ℃.
2. by the preparation method of electrolyte ceramic membrane of lithium ion battery claimed in claim 1, it is characterized in that the addition of dispersion agent is the 0.5wt.%～2wt.% of powder.
3. by the preparation method of electrolyte ceramic membrane of lithium ion battery claimed in claim 1, it is characterized in that content of binder is that powder is 4wt.%～9wt.%;
4. by the preparation method of claim 1 or 2 or 3 described electrolyte ceramic membrane of lithium ion battery, it is characterized in that material powder can adopt the synthetic ceramic powder of the whole bag of tricks,
CN 200910045906 2009-01-22 2009-01-22 Method for preparing electrolyte ceramic membrane of lithium ion battery Expired - Fee Related CN101786873B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US10411288B2 (en) * 2011-11-29 2019-09-10 Corning Incorporated Reactive sintering of ceramic lithium-ion solid electrolytes
US9362546B1 (en) 2013-01-07 2016-06-07 Quantumscape Corporation Thin film lithium conducting powder material deposition from flux
CN105636921A (en) 2013-10-07 2016-06-01 昆腾斯科普公司 Garnet materials for Li secondary batteries
CN103613366A (en) * 2013-11-25 2014-03-05 山东神工海特电子科技有限公司 Ceramic membrane slurry for lithium battery and method for preparing pole pieces coated with same
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CN107851774A (en) * 2015-07-21 2018-03-27 昆腾斯科普公司 Casting and the method and material of sintering green compact garnet
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US9966630B2 (en) 2016-01-27 2018-05-08 Quantumscape Corporation Annealed garnet electrolyte separators
US11916200B2 (en) 2016-10-21 2024-02-27 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same
US11489193B2 (en) 2017-06-23 2022-11-01 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with secondary phase inclusions
US11600850B2 (en) 2017-11-06 2023-03-07 Quantumscape Battery, Inc. Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets
CN108383517B (en) * 2018-03-30 2020-12-22 华南理工大学 Low-temperature sintered Li-Mg-P-O solid electrolyte ceramic and preparation method thereof
CN110137564B (en) * 2019-04-09 2021-08-10 中国科学院合肥物质科学研究院 Preparation method of porous solid electrolyte for lithium ion battery
CN111848151B (en) * 2020-08-10 2022-10-14 西安航空学院 Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof
CN112919898A (en) * 2021-01-28 2021-06-08 中汽创智科技有限公司 Precursor for preparing ceramic material, ceramic material and preparation method
JPWO2023282146A1 (en) * 2021-07-05 2023-01-12
CN113698199A (en) * 2021-08-26 2021-11-26 佛山(华南)新材料研究院 Oxide ceramic electrolyte membrane and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
贺连星 等.流延法制备陶瓷燃料电池电解质膜的研究进展.《材料科学与工程》.1997,第15卷(第3期),第二部分及第三部分第2节. *

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