CN101786873A - Method for preparing electrolyte ceramic membrane of lithium ion battery - Google Patents
Method for preparing electrolyte ceramic membrane of lithium ion battery Download PDFInfo
- Publication number
- CN101786873A CN101786873A CN200910045906A CN200910045906A CN101786873A CN 101786873 A CN101786873 A CN 101786873A CN 200910045906 A CN200910045906 A CN 200910045906A CN 200910045906 A CN200910045906 A CN 200910045906A CN 101786873 A CN101786873 A CN 101786873A
- Authority
- CN
- China
- Prior art keywords
- ceramic membrane
- lithium ion
- powder
- ion battery
- electrolyte ceramic
- 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
Images
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
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 ionic conductivity ceramics material field.
Background technology
For inorganic solid electrolyte, the lithium ion conductor of NASICON structure has the 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 what research was maximum in crystalline state and the glass-ceramic lithium-ion electrolyte all is the lithium ion conductor of NASICON structure.
Electrolytical impedance is directly proportional with the thickness of pottery, therefore can reduce the impedance of electrolyte ceramics by the thickness that reduces electrolyte ceramics, is equivalent to improve electrolytical electric conductivity from another angle.
The preparation of film has a variety of methods.Methods such as physical vapor deposition are control thickness accurately, and the film that obtains is very fine and close, but the equipment complexity, the production cost height, 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 this method has equipment, process stabilizing, but operate continuously, and the production efficiency height can be realized advantages such as increasingly automated, is widely used in the preparation of film.
Summary of the invention
The objective of the invention is to use organic additives such as wedding agent, fluidizer, dispersion agent to prepare the slurry of good rheological, and obtain to have certain intensity and flexible lithium ion battery electrolyte green compact by flow casting molding.By follow-up sintering, can obtain electrolyte ceramic membrane to green compact.
The material powder of flow casting molding can be the whole bag of tricks synthetic ceramic powder, 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; The azeotropic solution of selecting ethanol, propyl alcohol, butanone, trieline or its any the two composition for use is as solvent; Polyvinyl butyral acetal (PVB) is as binding agent, and polyoxyethylene glycol, dibutyl phthalate are as plastic agent.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, promptly obtain the green compact band.The green compact band 700～1000 ℃ of following thermal treatments, is obtained electrolyte ceramics.
After some different solution mixed, their mixed solution had unified boiling point, in case occurred the common boiling point after two or more liquid mixing, just claims that this mixed solution is an 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 made the TEM photo of powder in 40 hours for high-energy ball milling.
Fig. 3 is to be that the precursor powder that citric acid complex method prepares is calcined the TEM photo that obtained the LATP powder in 2 hours for 800 ℃.
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
4The ball milling uniform mixing decomposed and synthesized 700 ℃ of thermal treatments then in 2 hours, and grind the cooling back, obtains powder.
With above-mentioned powder, join in butanone and the alcoholic acid azeotropic solution, add the trolamine of powder quality 2wt%, the PVB of 7wt% and the plastic agent of 10.5wt% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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
4The ball milling uniform mixing decomposed and synthesized 700 ℃ of thermal treatments then in 2 hours, and grind the cooling back, obtains powder.
With above-mentioned powder, join in the alcohol solvent, add the trolamine of powder quality 2wt.%, the PVB of 6wt.% and the plastic agent of 10wt.% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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
4The ball milling uniform mixing decomposed and synthesized 700 ℃ of thermal treatments then in 2 hours, and grind the cooling back, obtains powder.
With above-mentioned powder, join in the azeotropic solution of propyl alcohol and trieline, add the trolamine of powder quality 1wt%, the PVB of 9wt% and the plastic agent of 10.5wt% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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 divides the mixing back 700 ℃ of thermal treatments easy degradation production fully to be decomposed, and cooling is ground standby then.Forerunner's material with certain mass in the glove box of argon gas atmosphere places stainless jar, 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 butanone and the alcoholic acid azeotropic solution, add the phosphoric acid ester of powder quality 0.5wt.%, the PVB of 4wt.% and the plastic agent of 8wt.% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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 is fully divided and is mixed.The powder synthetic method is with embodiment 3.With the amorphous powder that obtains, join in the azeotropic solution of propyl alcohol and trieline, add the trolamine of powder quality 2wt.%, the PVB of 7wt.% and the polyoxyethylene glycol of 10.5wt.% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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 is fully divided and is mixed.The powder synthetic method is with embodiment 3.With the amorphous powder that obtains, join in the alcohol solvent, add the trolamine of powder quality 2wt.%, the PVB of 5wt.% and the plastic agent of 9wt.% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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 a 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 the 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 800 ℃ of thermal treatment preparation in 2 hours crystalline phase is the powder of LATP in the air then.
With above-mentioned powder, join in butanone and the alcoholic acid azeotropic solution, add the phosphoric acid ester of powder quality 2wt.%, the PVB of 8wt.% and the plastic agent of 8wt.% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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, the powder synthetic method is with embodiment 7.The powder that obtains is joined in the alcohol solvent, add the phosphoric acid ester of powder quality 2wt.%, the PVB of 7wt.% and the plastic agent of 10.5wt.% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.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, the powder synthetic method is with embodiment 7.The powder that obtains is joined in the azeotropic solution of propyl alcohol and trieline, add the trolamine of powder quality 1wt.%, the PVB of 8wt.% and the plastic agent of 12wt.% again, continued ball milling 4 hours, obtain the slurry that curtain coating is used; The film that obtains after the curtain coating has intensity and toughness preferably.1000 ℃ of sintering 6h obtain fine and close electrolyte ceramics.
Claims (6)
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 for use is Li
1.4Al
0.4(Ge
1-xTi
x)
1.6(PO
4)
3, ceramic powder is a material powder, wherein x=0～1.0;
Choose trolamine or phosphoric acid ester as dispersion agent;
The azeotropic solution of selecting ethanol, propyl alcohol, butanone, trieline or its any the two composition for use is as solvent;
Select for use polyvinyl butyral acetal (PVB) as binding agent;
Select for use polyoxyethylene glycol or dibutyl phthalate as plastic agent;
The control range of solid content of 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.
2. by the preparation method of the described electrolyte ceramic membrane of lithium ion battery of 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 the described electrolyte ceramic membrane of lithium ion battery of claim 1, it is characterized in that content of binder is that powder is 4wt.%～9wt.%.
4. by the preparation method of the described electrolyte ceramic membrane of lithium ion battery of claim 1, it is characterized in that binding agent: the weight ratio scope of plastic agent is 1: 1～1: 3.
5. by the preparation method of claim 1 or 2 or 3 or 4 described electrolyte ceramic membrane of lithium ion battery, it is characterized in that heat-treat condition is 700～1000 ℃.
6. by the preparation method of claim 1 or 2 or 3 or 4 described electrolyte ceramic membrane of lithium ion battery, it is characterized in that material powder can adopt the whole bag of tricks synthetic ceramic powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910045906 CN101786873B (en) | 2009-01-22 | 2009-01-22 | Method for preparing electrolyte ceramic membrane of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910045906 CN101786873B (en) | 2009-01-22 | 2009-01-22 | Method for preparing electrolyte ceramic membrane of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101786873A true CN101786873A (en) | 2010-07-28 |
| CN101786873B CN101786873B (en) | 2013-03-13 |
Family
ID=42530273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910045906 Expired - Fee Related CN101786873B (en) | 2009-01-22 | 2009-01-22 | Method for preparing electrolyte ceramic membrane of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101786873B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103843186A (en) * | 2011-09-30 | 2014-06-04 | 康宁股份有限公司 | Micromachined electrolyte sheet comprising lithium metal phosphates |
| CN105552380A (en) * | 2015-12-29 | 2016-05-04 | 香港科技大学 | Dual-layer composite structure glass ceramic, lithium-air battery and preparation method of dual-layer composite structure glass ceramic |
| US20170275770A1 (en) * | 2015-10-08 | 2017-09-28 | Low Emission Resources Corporation | Electrode-supported tubular solid-oxide electrochemical cell |
| CN108383517A (en) * | 2018-03-30 | 2018-08-10 | 华南理工大学 | A kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics and preparation method thereof |
| CN110127598A (en) * | 2011-11-29 | 2019-08-16 | 康宁股份有限公司 | The reactivity sintering of ceramic lithium ion solid electrolyte |
| CN110137564A (en) * | 2019-04-09 | 2019-08-16 | 中国科学院合肥物质科学研究院 | A kind of porous type solid electrolyte preparation method for lithium ion battery |
| CN111848151A (en) * | 2020-08-10 | 2020-10-30 | 西安航空学院 | Titanium magnesium aluminum lithium 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 |
| 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 |
| CN114605159A (en) * | 2015-07-21 | 2022-06-10 | 昆腾斯科普电池公司 | Method and material for casting and sintering green garnet films |
| WO2023282146A1 (en) * | 2021-07-05 | 2023-01-12 | Tdk株式会社 | All-solid-state battery |
| US11575153B2 (en) | 2013-10-07 | 2023-02-07 | Quantumscape Battery, Inc. | Garnet materials for Li secondary batteries and methods of making and using garnet materials |
| US11581576B2 (en) | 2016-01-27 | 2023-02-14 | Quantumscape Battery, Inc. | Annealed garnet electrolyte separators |
| US11592237B2 (en) | 2015-04-16 | 2023-02-28 | Quantumscape Battery, Inc. | Lithium stuffed garnet setter plates for solid electrolyte fabrication |
| 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 |
| US11876208B2 (en) | 2013-01-07 | 2024-01-16 | Quantumscape Battery, Inc. | Thin film lithium conducting powder material deposition from flux |
| US11901506B2 (en) | 2017-06-23 | 2024-02-13 | Quantumscape Battery, Inc. | Lithium-stuffed garnet electrolytes with secondary phase inclusions |
| 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 |
-
2009
- 2009-01-22 CN CN 200910045906 patent/CN101786873B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| JOYKUMAR S. THOKCHOM ET AL.: "Ionically Conducting Composite Membranes from the Li2O–Al2O3–TiO2–P2O5 Glass–Ceramic", 《J. AM. CERAM. SOC.》 * |
| 宋占永 等: "陶瓷薄片的流延成型工艺概述", 《材料导报：综述篇》 * |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103843186A (en) * | 2011-09-30 | 2014-06-04 | 康宁股份有限公司 | Micromachined electrolyte sheet comprising lithium metal phosphates |
| US11469446B2 (en) | 2011-09-30 | 2022-10-11 | Corning Incorporated | Micromachined electrolyte sheet |
| US10854918B2 (en) | 2011-09-30 | 2020-12-01 | Corning Incorporated | Micromachined electrolyte sheet |
| US10283811B2 (en) | 2011-09-30 | 2019-05-07 | Corning Incorporated | Micromachined electrolyte sheet |
| CN110127598A (en) * | 2011-11-29 | 2019-08-16 | 康宁股份有限公司 | The reactivity sintering of ceramic lithium ion solid electrolyte |
| US11502330B2 (en) | 2011-11-29 | 2022-11-15 | Corning Incorporated | Reactive sintering of ceramic lithium-ion solid electrolytes |
| US11876208B2 (en) | 2013-01-07 | 2024-01-16 | Quantumscape Battery, Inc. | Thin film lithium conducting powder material deposition from flux |
| US11600857B2 (en) | 2013-10-07 | 2023-03-07 | Quantumscape Battery, Inc. | Garnet materials for Li secondary batteries and methods of making and using garnet materials |
| US11658338B2 (en) | 2013-10-07 | 2023-05-23 | Quantumscape Battery, Inc. | Garnet materials for li secondary batteries and methods of making and using garnet materials |
| US11575153B2 (en) | 2013-10-07 | 2023-02-07 | Quantumscape Battery, Inc. | Garnet materials for Li secondary batteries and methods of making and using garnet materials |
| 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 |
| US11592237B2 (en) | 2015-04-16 | 2023-02-28 | Quantumscape Battery, Inc. | Lithium stuffed garnet setter plates for solid electrolyte fabrication |
| CN114605159A (en) * | 2015-07-21 | 2022-06-10 | 昆腾斯科普电池公司 | Method and material for casting and sintering green garnet films |
| US20170275770A1 (en) * | 2015-10-08 | 2017-09-28 | Low Emission Resources Corporation | Electrode-supported tubular solid-oxide electrochemical cell |
| CN105552380A (en) * | 2015-12-29 | 2016-05-04 | 香港科技大学 | Dual-layer composite structure glass ceramic, lithium-air battery and preparation method of dual-layer composite structure glass ceramic |
| CN105552380B (en) * | 2015-12-29 | 2018-10-16 | 香港科技大学 | Two-layer composite glass ceramics, lithium-air battery and preparation method thereof |
| US11581576B2 (en) | 2016-01-27 | 2023-02-14 | Quantumscape Battery, Inc. | 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 |
| US11901506B2 (en) | 2017-06-23 | 2024-02-13 | 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 |
| US11817551B2 (en) | 2017-11-06 | 2023-11-14 | 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 |
| CN108383517A (en) * | 2018-03-30 | 2018-08-10 | 华南理工大学 | A kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics and preparation method thereof |
| 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 |
| CN110137564A (en) * | 2019-04-09 | 2019-08-16 | 中国科学院合肥物质科学研究院 | A kind of porous type solid electrolyte preparation method for lithium ion battery |
| CN111848151A (en) * | 2020-08-10 | 2020-10-30 | 西安航空学院 | Titanium magnesium aluminum lithium 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 |
| WO2023282146A1 (en) * | 2021-07-05 | 2023-01-12 | Tdk株式会社 | All-solid-state battery |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101786873B (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101786873B (en) | Method for preparing electrolyte ceramic membrane of lithium ion battery | |
| CN102244257B (en) | High-temperature manganic acid lithium cathode material and preparation method thereof | |
| Li et al. | Optimizing Li+ conductivity in a garnet framework | |
| CN101462868B (en) | Method for preparing beta-alumina ceramic membrane | |
| Zhang et al. | Water-stable lithium ion conducting solid electrolyte of the Li1. 4Al0. 4Ti1. 6− xGex (PO4) 3 system (x= 0–1.0) with NASICON-type structure | |
| EP3719910A1 (en) | Solid electrolyte and all-solid-state battery | |
| CN102195042A (en) | High performance lithium ion battery anode material lithium manganate and preparation method thereof | |
| CN102820458A (en) | Synthetic method of nitrogen-enriched carbon coated lithium titanate composite material prepared by introduction of ionic liquid as carbon source | |
| Wei et al. | Challenges, fabrications and horizons of oxide solid electrolytes for solid‐state lithium batteries | |
| CN102403505B (en) | Method for preparing in-situ carbon coated lithium manganese borate composite material by lithium ion battery cathode material | |
| CN110885246A (en) | High-conductivity solid electrolyte prepared by sol-gel method | |
| CN102412390A (en) | Preparation method of Li4Ti5O12 wrapped natural graphite for lithium ion battery cathode | |
| CN109626996A (en) | A kind of ferro-aluminum codope carbuncle type Li7La3Zr2O12Lithium Ionic Conducting Materials and preparation method thereof | |
| CN102891303A (en) | Lithium ion secondary battery cathode material yttrium-doped lithium titanate and its preparation method and use | |
| CN104659412A (en) | Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery | |
| CN104009234B (en) | The method of microwave method synthesis of anode material of lithium-ion battery iron manganese phosphate for lithium | |
| EP3518251B1 (en) | Solid electrolyte and all-solid battery | |
| Xuefu et al. | High Lithium-Ion-Conducting NASICON-Type Li1+ x Al x Ge y Ti2− x− y (PO4) 3 Solid Electrolyte | |
| CN112382739A (en) | Preparation method of nickel cobalt lithium manganate ternary positive electrode material with surface coated and modified | |
| KR101614015B1 (en) | Cathode active material for lithium rechargeable batteries and manufacturing method of the same | |
| CN103435339B (en) | A kind of aluminium-doped zinc oxide target and preparation method thereof | |
| CN107623117A (en) | A kind of preparation method of high power capacity, high-tap-density lithium iron phosphate material | |
| CN112279643A (en) | Rapid synthesis Li7La3Zr2O12Base compound and method for producing solid electrolyte | |
| KR20230013089A (en) | Solid electrolyte materials, solid electrolytes, methods for producing them, and all-solid-state batteries | |
| CN102881892B (en) | Method for preparing lithium-rich solid solution cathode material through oxidation/sintering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130313 Termination date: 20190122 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |