CN109713361A - A kind of NASICON type solid electrolyte material and preparation method thereof - Google Patents
A kind of NASICON type solid electrolyte material and preparation method thereof Download PDFInfo
- Publication number
- CN109713361A CN109713361A CN201810477065.3A CN201810477065A CN109713361A CN 109713361 A CN109713361 A CN 109713361A CN 201810477065 A CN201810477065 A CN 201810477065A CN 109713361 A CN109713361 A CN 109713361A
- Authority
- CN
- China
- Prior art keywords
- transition
- solid electrolyte
- subgroup
- compound
- valence
- 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.)
- Pending
Links
Classifications
-
- 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
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of NASICON type solid electrolyte material, chemical formula is represented by Li1+x Al y (Ti1‑z M z )2‑y (PO4)3.The solid electrolyte material has good ionic conductance characteristic, and electrolyte can be fabricated separately.The electrolyte has good mechanical property simultaneously, can be used in mixed way with other series of electrolyte materials, to promote the macrostructure stability of other series of electrolyte.The present invention discloses the improvement sol-gel method for preparing the solid electrolyte material, process is simple, low raw-material cost, is easy to scale of mass production popularization.
Description
Invention field
The present invention relates to a kind of NASICON type solid electrolyte materials and preparation method thereof, are specifically related to a kind of chemistry
Formula is Li1+xAly(Ti1-zMz)2-y(PO4)3Solid electrolyte material and preparation method thereof.
Background technique
The electrolyte used of commercialization lithium battery is liquid electrolyte at present, has ionic conductivity height, charge/discharge speed
The advantages such as fast, but there is also following disadvantages: 1. liquid electrolytes are inflammable, and there are direct security risks；2. easily with electrolysis material
Interfacial reaction occurs for material, reduces specific capacity and cycle characteristics；3. otherwise cannot easily be formed with metal Li directly as negative electrode material
Li dendrite pierces through diaphragm, causes the danger of short circuit and explosion.
Solid lithium battery using solid material as electrolyte is widely recognized as next-generation lithium battery, in safety factor
Aspect is greatly improved.In all kinds of inorganic solid electrolyte materials, NASICON profile material has following advantage: 1. raw material
It is at low cost；2. high-temperature stability is good；3. not reacting with water, it is easy to save under atmospheric environment；4. allowing to use lithium metal as negative
Pole material will not promote the formation of Li dendrite.NASICON originally means super ion conductor Na1+mZr2SimP3-mO12(0 < m <
3).Broadly, when Na, Zr, Si are replaced by same valence element, material is referred to as NASICON type.
LiTi2(PO4)3It (LTP) is typical NASICON profile material, undoped LTP conductivity is 10-6S/cm, cannot
Directly meet lithium battery to the requirement of electrolyte.Therefore, it is necessary to be doped modification to LTP.Common doped chemical
For Al, there is certain effect to conductivity is promoted.But with the promotion of doping content, easily there is the second phase AlPO4, destroy electricity
Solve the original crystal structure of matter.
Based on there are many common preparation methods of LTP electrolyte, comprising: solid reaction process, hydro-thermal method, colloidal sol-are solidifying
Glue method, coprecipitation etc..Solid reaction process process is simple, but high-energy ball milling is needed early period to realize mechanical alloying, is not suitable for big
Scale volume production；Hydro-thermal method and the powder constituents of coprecipitation preparation are uniform but higher to reaction kettle equipment requirement；Traditional is molten
Glue-gel method is usually to mix raw material uniformly, and hydrolysis, condensation occurs etc. to react and formed transparent molten
Colloid forms three-dimensional netted gelinite finally by drying.The powder constituents of traditional sol-gel method preparation are uniform, and
It is of less demanding to consersion unit, but initial reaction stage severe reaction conditions, excessively rely on the control to pH value, it is not easy to obtain single-phase
Powder, and solvent used is usually organic solvent, at high cost.
Summary of the invention
The present invention proposes improvement to traditional sol-gel method, referred to as improvement sol-gel method.This method and tradition
Sol-gel method be compared to characteristic: do not need to be previously added a large amount of ammonium hydroxide in the solution and improve citric acids to each source metal
Complexation efficiency, it is only necessary to a small amount of citric acid is added, titanium source is prevented quickly to reunite generation white precipitate, therefore this method is to anti-
During answering pH variation and it is insensitive, process be simply easy to volume production popularization.This method is easier to obtain single-phase LTP base electrolysis
Material.The LTP original washing powder body sintering activity of this method preparation is more preferable, it is easier to obtain fine and close ceramic body and good ion is led
Electrical characteristics.
The present invention proposes a kind of complex element to Ti methods being doped of LTP electrolyte, and this method compares unit
Element doping can more effectively improve the conductivity of electrolyte.Complex element includes metal element A l and transition metal element
Collocation uses.
Wherein NASICON type electrolyte, element composition have Li, Al, Ti, M, P, O.Wherein M is transition element,
It may is that the first subgroup element, the second subgroup element, third subgroup element (including group of the lanthanides and actinium series), the 4th subgroup element,
Five subgroup elements, the 6th subgroup element, the 7th subgroup element, one of or several combination in the 8th subgroup element, knot
Structure basic material is titanium phosphate lithium (LTP), and chemical formula can be expressed as formula (1).
Li1+xAly(Ti1-zMz)2-y(PO4)3 (1)
In above-mentioned formula (1), 0≤x≤1,0 z≤1 the < < of y≤1, x-y≤0.1,0.
The atomic radius ratio of above-mentioned transition element M, atomic radius and Ti are RM/RTi.In order to maintain NASICON type
Crystal structure works as RM/RTi> 1.1 or RM/RTiWhen < 0.9, z value range is 0 z≤0.5 <.As 0.9≤RM/R-Ti≤1.1
When, z value range is 0 z≤1 <.
Preferably, transition element M, when its highest oxidation state is 4 valence of ﹢ and 0.9≤RM/RTiWhen≤1.1,0 z≤1 <,
Such as Li1+xAly(Ti0.5Zr0.5)2-y(PO4)3.Reach a small number of rare earth element (Ce, Pr, Nd, the Tb of 4 valence of ﹢ for highest oxidation state
And Dy), RM/RTi1.1,0 z≤0.5 < >, such as Li1+xAly(Ti0.5Ce0.5)2-y(PO4)3。
Preferably, the transition element M, when its highest oxidation state is higher than 4 valence of ﹢ and 0.9≤RM/RTiWhen≤1.1,
0 z≤0.5 <, such as Li1+xAly(Ti0.5V0.5)2-y(PO4)3.When its highest oxidation state is higher than 4 valence of ﹢ and RM/RTiWhen < 0.9,
0 z≤0.25 <, such as Li1+xAly(Ti0.75Mn0.25)2-y(PO4)3。
Preferably, the transition element M, when its highest oxidation state is lower than 4 valence of ﹢ and 0.9≤RM/RTiWhen≤1.1,
0 z≤0.5 <, such as Li1+xAly(Ti0.5Sc0.5)2-y(PO4)3.When its highest oxidation state is lower than 4 valence of ﹢ and RM/RTi> 1.1
When, 0 z≤0.25 <, such as Li1+xAly(Ti0.75Y0.25)2-y(PO4)3.When its highest oxidation state is lower than 4 valence of ﹢ and RM/RTi<
When 0.9,0 z≤0.25 <, such as Li1+xAly(Ti0.75Co0.25)2-y(PO4)3。
Preferably, in the case that the transition element M highest oxidation state is 4 valence of ﹢, element Li in formula (1) with
The relation with contents of element al are as follows: 0≤x-y≤0.05.
Preferably, in the case that the transition element M highest oxidation state is higher than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: x-y≤0.The relation with contents of element Li and element al in formula (1) are as follows: x-y≤0.
Preferably, in the case that the transition element M highest oxidation state is lower than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: 0 x-y≤0.1 <.
Li is prepared using sol-gel method is improved1+xAly(Ti1-zMz)2-y(PO4)3Powder step includes:
1) complexing agent and water are added into container, after completely dissolution to complexing agent, lithiumation conjunction is proportionally added into solution
Object, aluminium compound, phosphorus compound, transistion metal compound, titanium compound (raw material finally added is titanium compound).Addition
While not stopping stirring in the process, and add titanium compound, moisture content is supplemented into solution, and (supplement moisture content weight is complexing agent
1~2 times).Continue 2~4h of agitating solution, obtains milky white solution.
2) above-mentioned milky white solution is dry at 75~110 DEG C, obtain sticky gel；It is carried out again at 200~550 DEG C
2~4h of precalcining；Finally in 700~850 DEG C of 4~6h of calcining, porous white wadding body is obtained.
3) obtained porous white block is put into high-speed mixer, crushed, after sieving.Obtain even-grained white powder
End.
The Li obtained according to above-mentioned steps1+xAly(Ti1-zMz)2-y(PO4)3Powder granularity is in 300 mesh.
The present invention also utilizes above-mentioned Li1+xAly(Ti1-zMz)2-y(PO4)3Powder is prepared for solid electrolyte, by powder 30
Cold moudling under~300MPa obtains round green body having a size of 10~16mm of diameter, 1~2mm of thickness, then 700~1000
DEG C sinter ceramics into.Potsherd total conductivity obtained is up to 10-4S/cm。
Detailed description of the invention
Fig. 1 improves sol-gel method flow chart.
Fig. 2 X-ray diffractogram spectrum analysis white powder component, obtained map and titanium phosphate lithium standard card (PDF35-
0754) it compares without obvious dephasign peak.
Fig. 3 scanning electron microscope analysis white powder pattern.
Fig. 4 potsherd ac impedance spectroscopy.
Case study on implementation
Case study on implementation 1. is according to Li1.4Al0.4Ti1.6(PO4)3Stoichiometric ratio, take citric acid 55.38g be added 41.52g
It is sufficiently dissolved in water；Take 6.76g lithium nitrate, nine water aluminum nitrate of 10.5g, 24.15g ammonium dihydrogen phosphate addition aqueous solution sufficiently molten
Solution；Butyl titanate 38.08g is taken to be slowly added to above-mentioned mixed solution, while the moisturizing 60g into solution.It is stirred to react 4h, is obtained newborn
The solution of white.
Above-mentioned milky white solution is dried into 3h at 110 DEG C, obtains sticky gel；Again in 400 DEG C of precalcining 4h；Finally
In 800 DEG C of calcining 4h, white wadding body is obtained.It is crushed by high speed disintegrator, after sieving, obtains white powder.
It is 10mm, with a thickness of the disk of 1.5mm that white powder, which is depressed to diameter in the pressure of 46MPa,.Then at 880 DEG C
It is sintered 5h, obtains potsherd.Potsherd is connected on electrochemical operation and carries out ac impedance measurement.Electrochemical workstation test
Frequency range 100Hz~1MHz obtains the total conductivity of potsherd are as follows: 1 × 10-4S/cm。
Case study on implementation 2. is according to Li1.3Al0.3Ti1.7(PO4)3Stoichiometric ratio, take citric acid 221.52g be added
166.08g sufficiently being dissolved in water；27.04g lithium nitrate, nine water aluminum nitrate of 33.95g, 104.1g ammonium dihydrogen phosphate is taken to be added water-soluble
Liquid sufficiently dissolves；Butyl titanate 174.53g is taken to be slowly added to above-mentioned mixed solution, while the moisturizing 300g into solution.Stirring
4h is reacted, opalescent solution is obtained.
Above-mentioned milky white solution is dried into 3h at 110 DEG C, obtains sticky gel；Again in 450 DEG C of precalcining 4h；Finally
In 850 DEG C of calcining 5h, white wadding body is obtained.It is crushed by high speed disintegrator, after sieving, obtains white powder.
It is 10mm, with a thickness of the disk of 1.5mm that white powder, which is depressed to diameter in the pressure of 46MPa,.Then at 880 DEG C
It is sintered 5h, obtains potsherd.Potsherd is connected on electrochemical operation and carries out ac impedance measurement.Electrochemical workstation test
Frequency range 100Hz~1MHz obtains the total conductivity of potsherd are as follows: 1 × 10-4S/cm。
Case study on implementation 3~8, reference table 1
Table 1 improves sol-gel method and prepares solid electrolyte material case study on implementation
Applicant combines Figure of description to be described in detail and describe the embodiment of the present invention, but this field skill
Art personnel are it should be understood that above embodiments are only the preferred embodiments of the invention, and explanation is intended merely to help reader in detail
More fully understand spirit of that invention, and it is not intended to limit the protection scope of the present invention, on the contrary, any based on invention essence of the invention
Any improvement or modification made by mind should all be fallen within the scope and spirit of the invention.
Claims (13)
1. a kind of NASICON type solid electrolyte material, element composition has Li, Al, Ti, M, P, O；Wherein M is transition group member
Element, may is that the first subgroup element, the second subgroup element, third subgroup element, including group of the lanthanides and actinium series, the 4th subgroup element,
5th subgroup element, the 6th subgroup element, the 7th subgroup element, one of or several combination in the 8th subgroup element；Its
Structure basis material is titanium phosphate lithium (LTP), and chemical formula can be expressed as following structure fomula (1)
Li1+xAly(Ti1-zMz)2-y(PO4)3 (1)。
2. in formula described in claim 1 (1), 0≤x≤1,0 z≤1 the < < of y≤1, x-y≤0.1,0.
3. the atomic radius ratio of transition element M described in claim 1, atomic radius and Ti are RM/RTi.In order to maintain
NASICON type crystal structure, works as RM/RTi> 1.1 or RM/RTiWhen < 0.9, z value range is 0 z≤0.5 <, as 0.9≤RM/
RTiWhen≤1.1, z value range is 0 z≤1 <.
4. transition element M as claimed in claim 3, when its highest oxidation state is higher than 4 valence of ﹢ and RM/RTiWhen < 0.9,0 < z
≤0.25。
5. transition element M as claimed in claim 3, when its highest oxidation state is lower than 4 valence of ﹢ and RM/RTi> 1.1 or
RM/RTiWhen < 0.9,0 z≤0.25 <.
In the case that 6. transition element M highest oxidation state as claimed in claim 3 is 4 valence of ﹢, element Li in formula (1) with
The relation with contents of element al are as follows: 0≤x-y≤0.05.
In the case that 7. transition element M highest oxidation state as claimed in claim 3 is higher than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: x-y≤0.
In the case that 8. transition element M highest oxidation state as claimed in claim 3 is lower than 4 valence of ﹢, the element Li in formula (1)
With the relation with contents of element al are as follows: 0 x-y≤0.1 <.
9. a kind of method for preparing NASICON type solid electrolyte material improves sol-gel method, step includes: the first step,
Dissolution of raw material mixing, is added complexing agent into container and water after completely dissolution to complexing agent is proportionally added into lithiumation into solution
Object, aluminium compound, phosphorus compound, transistion metal compound, titanium compound are closed, is persistently stirred during addition；
The solution that the first step obtains is dried in second step, obtains sticky gel；
Third step is further dried and carries out multisection type calcining, obtains white fluffy solid；
4th step, it is Li that crushing, which obtains chemical formula,1+xAly(Ti1-zMz)2-y(PO4)3Powder.
5th step, Li1+xAly(Ti1-zMz)2-y(PO4)3Powder obtains solid electrolyte by cold pressing, sintering.It can also be by Li1+xAly
(Ti1-zMz)2-y(PO4)3Powder is mixed with the high molecular material with ionic conduction characteristic, then is cold-pressed and solid electrolyte is made.
10. improvement sol-gel the preparation method as claimed in claim 9 prepares Li1+xAly(Ti1-zMz)2-y(PO4)3Used in powder
Raw material include:
Complexing agent selects one of citric acid, glacial acetic acid；
Lithium compound, one of selective chlorination lithium, lithium nitrate, lithium sulfate, lithium hydroxide and its hydrate；
Aluminium compound, one of selective chlorination aluminium, aluminum nitrate, aluminum sulfate, aluminium hydroxide and its hydrate；
Phosphorus compound selects one of ammonium dihydrogen phosphate, phosphoric acid；
Transistion metal compound selects transition metal oxide, transition metal salt, transition metal hydroxide, transition metal
One of esters；
Titanium compound selects one of butyl titanate, metatitanic acid.
11. improvement sol-gel the preparation method as claimed in claim 9, the sequence of Xiang Shuizhong adding raw materials: is added into water first
Raw material be complexing agent, the raw material being finally added into solution is titanium compound.
12. the multisection type calcining: improvement sol-gel the preparation method as claimed in claim 9 must have before final calcining
The precalcining at least one stage, 200-550 DEG C of precalcining temperature range.
13. as claimed in claim 9 and with ionic conduction characteristic high molecular material includes polyethers, polyurethanes, poly- phenol
It is class, polyamide-based one such or a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810477065.3A CN109713361A (en) | 2018-05-18 | 2018-05-18 | A kind of NASICON type solid electrolyte material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810477065.3A CN109713361A (en) | 2018-05-18 | 2018-05-18 | A kind of NASICON type solid electrolyte material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109713361A true CN109713361A (en) | 2019-05-03 |
Family
ID=66253726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810477065.3A Pending CN109713361A (en) | 2018-05-18 | 2018-05-18 | A kind of NASICON type solid electrolyte material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109713361A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112768755A (en) * | 2021-01-04 | 2021-05-07 | 长沙矿冶研究院有限责任公司 | Preparation method of NASION type solid electrolyte aluminum-containing phosphate |
| CN113346127A (en) * | 2021-05-31 | 2021-09-03 | 东风汽车集团股份有限公司 | NASICON type lithium ion solid electrolyte, preparation method and battery |
| CN115849329A (en) * | 2022-12-29 | 2023-03-28 | 宜宾南木纳米科技有限公司 | Europium-doped lithium aluminum titanium phosphate solid electrolyte material and preparation method and application thereof |
| CN118281306A (en) * | 2024-05-29 | 2024-07-02 | 深圳博粤新材料科技有限公司 | LATP powder preparation process and solid electrolyte |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760860A (en) * | 2011-04-29 | 2012-10-31 | 三星电子株式会社 | Negative electrode for lithium secondary battery, method of manufacturing the same, and lithium secondary battery employing the same |
| CN104466238A (en) * | 2014-11-28 | 2015-03-25 | 深圳华中科技大学研究院 | Doped type solid ceramic electrolyte as well as preparation method and application thereof |
| CN107265430A (en) * | 2017-05-19 | 2017-10-20 | 中国电子科技集团公司第十八研究所 | Preparation method of titanium phosphate/germanium aluminum lithium type solid electrolyte |
-
2018
- 2018-05-18 CN CN201810477065.3A patent/CN109713361A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760860A (en) * | 2011-04-29 | 2012-10-31 | 三星电子株式会社 | Negative electrode for lithium secondary battery, method of manufacturing the same, and lithium secondary battery employing the same |
| CN104466238A (en) * | 2014-11-28 | 2015-03-25 | 深圳华中科技大学研究院 | Doped type solid ceramic electrolyte as well as preparation method and application thereof |
| CN107265430A (en) * | 2017-05-19 | 2017-10-20 | 中国电子科技集团公司第十八研究所 | Preparation method of titanium phosphate/germanium aluminum lithium type solid electrolyte |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112768755A (en) * | 2021-01-04 | 2021-05-07 | 长沙矿冶研究院有限责任公司 | Preparation method of NASION type solid electrolyte aluminum-containing phosphate |
| CN113346127A (en) * | 2021-05-31 | 2021-09-03 | 东风汽车集团股份有限公司 | NASICON type lithium ion solid electrolyte, preparation method and battery |
| CN113346127B (en) * | 2021-05-31 | 2022-08-30 | 东风汽车集团股份有限公司 | NASICON type lithium ion solid electrolyte, preparation method and battery |
| CN115849329A (en) * | 2022-12-29 | 2023-03-28 | 宜宾南木纳米科技有限公司 | Europium-doped lithium aluminum titanium phosphate solid electrolyte material and preparation method and application thereof |
| CN118281306A (en) * | 2024-05-29 | 2024-07-02 | 深圳博粤新材料科技有限公司 | LATP powder preparation process and solid electrolyte |
| CN118281306B (en) * | 2024-05-29 | 2024-08-06 | 深圳博粤新材料科技有限公司 | LATP powder preparation process and solid electrolyte |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109713361A (en) | A kind of NASICON type solid electrolyte material and preparation method thereof | |
| áP Wong | Synthesis and characterization of polypyrrole/vanadium pentoxide nanocomposite aerogels | |
| CN104124467B (en) | A kind of method utilizing lithium lanthanum zirconium oxygen presoma coated powder to prepare solid electrolyte | |
| CN100450933C (en) | Manufacture method of lithium lanthanum titanium oxide | |
| CN106232526A (en) | The manufacture method of garnet type compound and garnet type compound, and all solid lithium secondary battery containing this garnet type compound | |
| CN101787169B (en) | Polyvinylidene fluoride (PVDF)/Li1.3 Al0.3 Ti1.7 (PO4) 3 solid-state diphase electrolyte thin-film material and preparation method | |
| CN105977486B (en) | A kind of preparation method and application of the rich sodium transition metal silicate as sodium-ion battery positive material | |
| CN108878852A (en) | A kind of lithium ion battery mangaic acid lithium anode material and preparation method thereof | |
| CN108899524A (en) | A kind of lithium ion battery mangaic acid lithium anode material and preparation method thereof | |
| CN104103826B (en) | The manufacturing method of laminar structure lithium nickel metal oxide and lithium secondary battery comprising the oxide | |
| CN100546076C (en) | Method for synthesizing nano-scale lithium ion power battery cathode material by micro-reactor spontaneous combustion method | |
| CN102044700B (en) | Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof | |
| CN108232263A (en) | Composite solid electrolyte and preparation method thereof | |
| CN108221051A (en) | Nickelic nickel-cobalt-manganese ternary monocrystal material, preparation method and applications | |
| CN111477948A (en) | Preparation method of garnet type solid electrolyte and product | |
| CN109360984A (en) | A kind of preparation method on layered cathode material of lithium ion battery hydridization surface | |
| Cheng et al. | A novel electrolyte for intermediate solid oxide fuel cells | |
| CN114361575B (en) | Organic-inorganic composite electrolyte and preparation method thereof | |
| CN115947387A (en) | B-site five-element high-entropy double perovskite structure oxide electrode material and preparation method thereof | |
| Cheng et al. | Synthesis and electrical properties of scheelite Ca1− xSmxMoO4+ δ solid electrolyte ceramics | |
| CN110395980A (en) | Porous ceramic film material, solid electrolyte material and preparation method thereof and lithium ion battery | |
| JP6864323B2 (en) | Method for producing lithium-containing zirconium phosphate and its calcined powder and sintered body | |
| CN109888375A (en) | A kind of doping phosphoric acid titanium sodium porous nano crystalline substance electrolyte and its preparation method and application | |
| CN101572315B (en) | Method for preparing battery cathode material Re<2-x>A'<x>CuO<4 delta> with K<2>NiF<4> structure using electrostatic spinning method | |
| CN109742431B (en) | Cerium oxide matrix doped dysprosium oxide composite electrolyte material and preparation method thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190503 |