CN102867986A - One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 - Google Patents
One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 Download PDFInfo
- Publication number
- CN102867986A CN102867986A CN2012103495242A CN201210349524A CN102867986A CN 102867986 A CN102867986 A CN 102867986A CN 2012103495242 A CN2012103495242 A CN 2012103495242A CN 201210349524 A CN201210349524 A CN 201210349524A CN 102867986 A CN102867986 A CN 102867986A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- lithium ion
- hours
- solid
- lithium
- 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
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
Abstract
The invention relates to solid electrolyte Li7La3Zr2O12 co-doped with four groups of positive ions B<3+>, Al<3+>, Ti<4+> and Y<3+>, which is characterized by having a chemical stoichiometric equation as follows: Li7+y1+y2YxLa3-xBy1Aly2Tiy3Zr2-y1-y2-y3O12, wherein, x=0.1-0.5; y1=0.1-0.2; y2=0.1-0.2; y3=0.1-0.2. The electrolyte is obtained by mixing LiCO2, Y2O3, La2O3, B2O3, Al2O3, TiO2 and ZrO according to the molar ratio of 3.6-3.7:0.05-0.25:1.25-1.45:0.05-0.1:0.05-0.1:0.1-0.2:1.4-1.7, carrying out ball-milling, pressing and firing; and Li-ion conductivity is higher than 5*10<-4>s/cm under room temperature.
Description
Technical field
The present invention relates to a kind of solid lithium-ion electrolyte and make the field.
Background technology
Lithium ion battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density, have the occupation rate of market that exceedes 30,000,000,000 dollars of/year shares and far surpass other batteries in global portable power source market, the chemical power source [Wu Yuping that has future develop most, Wan Chunrong, Jiang Changyin, lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.].The most of employing of lithium rechargeable battery both at home and abroad is liquid electrolyte at present, liquid lithium ionic cell has some unfavorable factors, as: liquid organic bath may be revealed, thereby under too high temperature, blast and cause security incident, can't be applied in some occasions high to security requirement; Liquid electrolyte lithium ion battery ubiquity Capacity fading problem is used after a period of time because the dissolving of electrode active material in electrolyte, reaction and degradation failure [Z.R.Zhang, Z.L.Gong, and Y.Yang, J.Phys.Chem.B, 108,2004,17546.].And all-solid-state battery is safe, substantially do not have Capacity fading, and solid electrolyte has also played the effect of barrier film, has simplified the structure of battery; In addition, owing to need not secluding air, also simplified in the production process requirement to equipment, the configuration design of battery is more convenient and flexible [Wen Zhaoyin, Zhu Xiujian, Xu Xiaoxiong etc. also, the research of solid state secondary battery, the 12 Chinese solid-state ionics academic meeting paper collection, 2004.]。
In all solid state lithium ion battery, the electric charge that the migration rate of charge carrier in solid electrolyte often is far smaller than electrode surface shift and positive electrode in the ion diffusion rate and become rate determining step in the whole electrode reaction dynamics, therefore to have the inorganic solid electrolyte of higher li ionic conductivity be the core key point that makes up high performance lithium ion battery in development.To research and develop the solid lithium-ion electrolyte with Practical significance in addition, require simultaneously it can in environment, have good stability (to carbon dioxide and moisture stabilization), have high energy density for the all-solid-state battery that makes composition can use lithium metal as negative pole, wish that also solid state electrolysis mass-energy is stable and have a higher decomposition voltage to lithium metal.From having at present the lithium ion solid electrolyte of report: LLTO (Li, La) TiO
3Solid electrolyte has very high intracrystalline conductivity (10
-3About S/cm) and higher normal temperature total conductivity (10
-4S/cm-10
-5S/cm), but the LLTO decomposition voltage is low, can't consist of the above all-solid-state battery of discharge voltage 3.7V and unstable to lithium anode; LiM with NASICON type polycrystalline
2(PO
4)
3(M=Ti, Ge, Zr) is by tetrahedron PO
4With octahedra MO
6The common grid structure that forms, the coordination that has produced structural hole and can fill so that can regulate and control a large amount of Li ions, is a kind of up-and-coming high-lithium ion conductivity solid electrolyte.By the replacement of different valency ion, introducing hole or calking lithium ion can further improve ionic conductivity [Xiaoxiong Xu, Zhaoyin Wen, ZhonghuaGu, et al., Solid State Ionics, 171,2004,207-212.] in structure.Li such as the discovery such as woods ancestral Zuxiang, Li Shichun [woods ancestral Zuxiang, Li Shichun, silicate journal, 9 (3), 1981,253-257.]
1+xTi
2-xGa
xP
3O
12, Li
1+2xTi
2-xMgxP
3O
12, Li
1+xGe
2-xCrxP
3O
12, Li
1+xGe
2-xAl
xP
3O
12, Li
1+xTi
2-xIn
xP
3O
12Etc. system or other are such as Li
1+2x+2yAl
xMg
yTi
2-x-ySi
xP
3-xO
12, Li
1+x+yAl
xTi
2-xSi
yP
3-yO
12, Li
1+xAl
xTi
2-xP
3O
12All has higher lithium ion conductivity etc. system.But the normal temperature lithium ion conductivity of these systems is usually 10
-4S/cm-10
-6Between the S/cm, can't finely satisfy non-film lithium ion battery to the requirement of electrolytic conductivity.The NASICON system is unstable to lithium anode equally in addition.Ramaswamy Murugan equals to report a kind of novel lithium ion solid electrolyte Li at German applied chemistry periodical in 2007
7La
3Zr
2O
12Its lithium ion conductivity at normal temperatures surpasses 1 * 10
-4S.cm
-1Decomposition voltage surpasses 5.5V, can use lithium metal as negative pole, to air and moisture stabilization, a kind of fast ion solid electrolyte (Ramaswamy Murugan of lithium that application potential is arranged very much, Venkataraman Thangadurai, Werner Weppner, (2007). " Fast lithium ion conduction in garnet-type Li
7La
3Zr
2O
12. " Angewandte Chemie-International Edition46 (41): 7778-7781.).Yet often to reach 5.0 * 10 to the higher occasion conductivity of current requirements
-4Just can satisfy the needs of battery normal operation about S/cm, this solid electrolyte synthesis temperature is about 1350 ℃ in addition, and temperature is high, and energy consumption is large.
Ion doping is to improve a kind of very effective mode of solid lithium ion electrolytic conductivity, but the interaction of doping ion and matrix is very complicated, the characteristics such as the size of doping ion, electronic structure, electronegativity all have a significant impact the ionic conduction ability of parent, and have interaction between the different doping ions, be that the degree of the migration of promotion lithium ion or the migration of inhibition lithium ion and promotion and inhibition all can be along with the ionic species that mixes and concentration have very large difference.The selection of ion of mixing in principle should be satisfied transmission bottleneck and Li as far as possible
+The radius size coupling, Li
+With skeleton ionic bond make a concerted effort weak, vacancy concentration and Li
+Moderate three conditions of the ratio of concentration.The lithium ion migration mechanism of this solid electrolyte also not yet complete studied personnel is understood.In addition, ion doping is if formation eutectic solid solution then can reduce synthesis temperature to a certain extent.Therefore further the contamination of research doping ion has very important meaning to the solid electrolyte of developing the high-lithium ion conductivity.
Summary of the invention
Technical problem to be solved by this invention is a kind of B that provides for existing background technology
3+, Al
3+, Ti
4+, Y
3+The lithium ion solid electrolyte Li of four component cation codopes
7La
3Zr
2O
12Y
3+Part replaces La
3+, both have similar electronic structure, but Y
3+Radius is less, the Ti that same radius is less
4+Part replaces Zr
4+, the Al that radius is less
3+Part replaces Zr
4+And the less B of radius
3+Part replaces Zr
4+Produce certain contraction distortion so that La-O is octahedra and Zr-O is octahedra, migrating channels size and lithium ion radius more mate and improve lithium ion conductivity; And low price B
3+And Al
3+Part replaces Zr
4+Produce extra calking lithium ion, increase the quantity of migration lithium ion in the lattice and improve lithium ion conductivity; The synergy of these factors is so that the normal temperature ionic conductivity of this solid electrolyte surpasses 5.0 * 10
-4S/cm is more near the ionic conductivity of liquid electrolyte.Simultaneously, boron oxide compound and other components form solid solution, can reduce 100-150 ℃ of this solid electrolyte synthesis temperature.
The present invention reaches by the following technical solutions, and this technical scheme provides a kind of lithium ion conductivity to surpass 5.0 * 10
-4The lithium ion solid electrolyte of S/cm, its stoichiometric equation are Li
7+y1+y2Y
xLa
3-xB
Y1Al
Y2Ti
Y3Zr
2-y1-y2-y3O
12Wherein: x=0.1-0.5; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.2.
In this technical scheme, with Li
2CO
3: Y
2O
3: La
2O
3: B
2O
3: Al
2O
3: TiO
2: ZrO
2The ratio that is 3.6-3.7: 0.05-0.25: 1.25-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.2: 1.4-1.7 (mol ratio) is evenly mixed, 95% ethanol that adds 2%-6%, in ball mill with 200-400 rev/min rotating speed ball milling 10-20 hour, after ball milling finishes in 60 ℃ of-80 ℃ of vacuum drying ovens (vacuum degree is at 10Pa-100Pa) dry 10-30 hour, in agate stone roller alms bowl, again ground 10-30 minute after taking out, powder after the grinding is warmed up to 700-900 ℃ of insulation 5-10 hour with 5-10 ℃/minute speed, then is warmed up to 1150-1250 ℃ of insulation with 2-10 ℃/minute speed and makes the solid electrolyte powder in 10-30 hour.This powder mixing 1-5wt% be bond (this bond is PVC or PVA) under forcing press keeping pressure to form thin slice in 2-6 minute under the pressure of 300-500MPa, this thin slice is warmed up to 1200-1300 ℃ of insulation with 10-20 ℃/minute speed and made the lithium ion solid electrolyte thin slice in 10-20 hour under air atmosphere.To consist of Li such as Fig. 1
7.2Y
0.1La
2.9B
0.1Al
0.1Ti
0.1Zr
1.7O
12Solid electrolyte sheet is AC impedance figure under electrochemical workstation, and calculating conductivity from figure is 5.7 * 10
-4S/cm.
Compared with prior art, the invention has the advantages that: adopt B
3+, Al
3+, Ti
4+, Y
3+The lithium ion solid electrolyte Li of four component cation codopes
7La
3Zr
2O
12By the less Y of radius
3+Part replaces La
3+, the Ti that radius is less
4+Part replaces Zr
4+, the Al that radius is less
3+Part replaces Zr
4+And the less B of radius
3+Part replaces Zr
4+Produce certain contraction distortion so that La-O is octahedra and Zr-O is octahedra, migrating channels size and lithium ion radius more mate and improve lithium ion conductivity; Low price B
3+And Al
3+Part replaces Zr
4+Produce extra calking lithium ion, increase the quantity of migration lithium ion in the lattice and improve lithium ion conductivity; The synergy of these factors is so that the normal temperature ionic conductivity of this solid electrolyte surpasses 5.0 * 10
-4S/cm.Simultaneously, boron oxide compound and other components form solid solution, can reduce 100-150 ℃ of this solid electrolyte synthesis temperature.
Description of drawings
Fig. 1 is AC impedance figure, frequency-impedance and the frequency-phase diagram of lithium ion solid electrolyte thin slice under electrochemical workstation.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1: with Li
2CO
3: Y
2O
3: La
2O
3: B
2O
3: Al
2O
3: TiO
2: ZrO
2Be 3.6: 0.05: 1.45: 0.05: 0.05: 0.1: the ratio of 1.7 (mol ratios) is evenly mixed, 95% ethanol of adding 6%, in ball mill with 250 rev/mins rotating speed ball milling 10 hours, after ball milling finishes in 60 ℃ of vacuum drying ovens (vacuum degree 10Pa) drying 10 hours, in agate stone roller alms bowl, again ground 30 minutes after taking out, powder after the grinding is warmed up to 900 ℃ of insulations 6 hours with 5 ℃/minute speed, then is warmed up to 1150 ℃ of insulations with 3 ℃/minute speed and makes the solid electrolyte powder in 20 hours.Keeping pressure to form thin slice in 5 minutes under the pressure of 300MPa, this thin slice is warmed up to 1220 ℃ of insulations with 11 ℃/minute speed and made the lithium ion solid electrolyte thin slice in 20 hours this powder mixing 2wt% bond PVC under air atmosphere under forcing press.
Embodiment 2: with Li
2CO
3: Y
2O
3: La
2O
3: B
2O
3: Al
2O
3: TiO
2: ZrO
2Be 3.7: 0.25: 1.25: 0.1: 0.1: 0.2: the ratio of 1.4 (mol ratios) is evenly mixed, 95% ethanol of adding 2%, in ball mill with 380 rev/mins rotating speed ball milling 15 hours, after ball milling finishes in 80 ℃ of vacuum drying ovens (vacuum degree 95Pa) drying 30 hours, in agate stone roller alms bowl, again ground 20 minutes after taking out, powder after the grinding is warmed up to 780 ℃ of insulations 10 hours with 6 ℃/minute speed, then is warmed up to 1200 ℃ of insulations with 7 ℃/minute speed and makes the solid electrolyte powder in 15 hours.This powder mixing 5wt% bond PVC keeping pressure to form thin slice in 2 minutes under the pressure of 450MPa, is warmed up to 1280 ℃ of insulations with 15 ℃/minute speed under this thin slice air atmosphere and made the lithium ion solid electrolyte thin slice in 10 hours under forcing press.
Embodiment 3: with Li
2CO
3: Y
2O
3: La
2O
3: B
2O
3: Al
2O
3: TiO
2: ZrO
2Be 3.64: 0.15: 1.35: 0.07: 0.07: 0.15: the ratio of 1.57 (mol ratios) is evenly mixed, 95% ethanol of adding 3%, in ball mill with 300 rev/mins rotating speed ball milling 15 hours, after ball milling finishes in 70 ℃ of vacuum drying ovens (vacuum degree 50Pa) drying 20 hours, in agate stone roller alms bowl, again ground 10 minutes after taking out, powder after the grinding is warmed up to 800 ℃ of insulations 7 hours with 9 ℃/minute speed, then is warmed up to 1250 ℃ of insulations with 2 ℃/minute speed and makes the solid electrolyte powder in 12 hours.Keeping pressure to form thin slice in 6 minutes under the pressure of 300MPa, this thin slice is warmed up to 1300 ℃ of insulations with 15 ℃/minute speed and made the lithium ion solid electrolyte thin slice in 18 hours this powder mixing 1wt% bond PVA under air atmosphere under forcing press.
Embodiment 4: with Li
2CO
3: Y
2O
3: La
2O
3: B
2O
3: Al
2O
3: TiO
2: ZrO
2Be 3.64: 0.1: 1.4: 0.06: 0.08: 0.15: the ratio of 1.57 (mol ratios) is evenly mixed, 95% ethanol of adding 5.5%, in ball mill with 390 rev/mins rotating speed ball milling 20 hours, after ball milling finishes in 65 ℃ of vacuum drying ovens (vacuum degree 100Pa) drying 10 hours, in agate stone roller alms bowl, again ground 20 minutes after taking out, powder after the grinding is warmed up to 750 ℃ of insulations 5 hours with 5 ℃/minute speed, then is warmed up to 1230 ℃ of insulations with 9 ℃/minute speed and makes the solid electrolyte powder in 20 hours.Keeping pressure to form thin slice in 4 minutes under the pressure of 400MPa, this thin slice is warmed up to 1250 ℃ of insulations with 20 ℃/minute speed and made the lithium ion solid electrolyte thin slice in 13 hours this powder mixing 2.6wt% bond PVA under air atmosphere under forcing press.
Embodiment 5: with Li
2CO
3: Y
2O
3: La
2O
3: B
2O
3: Al
2O
3: TiO
2: ZrO
2Be 3.66: 0.2: 1.3: 0.08: 0.08: 0.1: the ratio of 1.58 (mol ratios) is evenly mixed, 95% ethanol of adding 4%, in ball mill with 200 rev/mins rotating speed ball milling 10 hours, after ball milling finishes in 75 ℃ of vacuum drying ovens (vacuum degree 20Pa) drying 15 hours, in agate stone roller alms bowl, again ground 30 minutes after taking out, powder after the grinding is warmed up to 710 ℃ of insulations 10 hours with 10 ℃/minute speed, then is warmed up to 1170 ℃ of insulations with 7 ℃/minute speed and makes the solid electrolyte powder in 28 hours.Keeping pressure to form thin slice in 2 minutes under the pressure of 500MPa, this thin slice is warmed up to 1200 ℃ of insulations with 10 ℃/minute speed and made the lithium ion solid electrolyte thin slice in 15 hours this powder mixing 5wt% bond PVC under air atmosphere under forcing press.
Claims (3)
1. B
3+, Al
3+, Ti
4+, Y
3+The lithium ion solid electrolyte Li of four component cation codopes
7La
3Zr
2O
12, it is characterized in that stoichiometric equation is Li
7+y1+y2Y
xLa
3-xB
Y1Al
Y2Ti
Y3Zr
2-y1-y2-y3O
12Wherein: x=0.1-0.5; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.2.
2. solid lithium-ion electrolyte according to claim 1 is characterized in that Li
2CO
3: Y
2O
3: La
2O
3: B
2O
3: Al
2O
3: TiO
2: ZrO
2The ratio that is 3.6-3.7: 0.05-0.25: 1.25-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.2: 1.4-1.7 (mol ratio) is evenly mixed, 95% ethanol that adds 2%-6%, in ball mill with 200-400 rev/min rotating speed ball milling 10-20 hour.
3. solid lithium-ion electrolyte according to claim 1 is characterized in that the normal temperature lithium ion conductivity of the solid electrolyte flake that makes is greater than 5 * 10
-4S/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210349524.2A CN102867986B (en) | 2012-09-04 | 2012-09-04 | One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210349524.2A CN102867986B (en) | 2012-09-04 | 2012-09-04 | One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102867986A true CN102867986A (en) | 2013-01-09 |
| CN102867986B CN102867986B (en) | 2015-07-15 |
Family
ID=47446687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210349524.2A Expired - Fee Related CN102867986B (en) | 2012-09-04 | 2012-09-04 | One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102867986B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830742A (en) * | 2019-03-27 | 2019-05-31 | 中南大学 | A kind of new type lithium ion conducting electrolyte material |
| CN113562762A (en) * | 2020-04-29 | 2021-10-29 | 肖特股份有限公司 | Aluminum-doped lithium ion conductors based on garnet structures |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110053001A1 (en) * | 2008-06-27 | 2011-03-03 | Excellatron Solid State Llc | Ionically-conductive amorphous lithium lanthanum zirconium oxide |
| CN102308425A (en) * | 2009-02-04 | 2012-01-04 | 株式会社丰田中央研究所 | Garnet-type lithium ion-conducting oxide and all-solid-state lithium ion secondary battery containing the same |
-
2012
- 2012-09-04 CN CN201210349524.2A patent/CN102867986B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110053001A1 (en) * | 2008-06-27 | 2011-03-03 | Excellatron Solid State Llc | Ionically-conductive amorphous lithium lanthanum zirconium oxide |
| CN102308425A (en) * | 2009-02-04 | 2012-01-04 | 株式会社丰田中央研究所 | Garnet-type lithium ion-conducting oxide and all-solid-state lithium ion secondary battery containing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830742A (en) * | 2019-03-27 | 2019-05-31 | 中南大学 | A kind of new type lithium ion conducting electrolyte material |
| CN113562762A (en) * | 2020-04-29 | 2021-10-29 | 肖特股份有限公司 | Aluminum-doped lithium ion conductors based on garnet structures |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102867986B (en) | 2015-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102867988B (en) | B3+, Al3 +, Ti4 +, Y3+ F-codoped solid electrolyte Li7La3Zr2Ol2 | |
| CN102780031B (en) | A kind of Mg 2+, Al 3+, Zr 4+, F -ion co-doped garnet-type solid electrolyte | |
| CN102780028B (en) | Four-component iron co-doped garnet type solid electrolyte | |
| CN102867987B (en) | A B3+, al3+, mg2+, Y3+, F- codoped solid electrolyte Li7La3Zr2O12 | |
| CN102456918B (en) | F<->, Zn<2+>, and B<3+> co-doped NASICON type solid lithium-ion electrolyte | |
| CN101894972B (en) | NASICON type solid lithium-ion electrolyte and preparation method thereof | |
| CN102456919B (en) | Zn<2+> and B<3+> ion doped NASICON solid lithium ion electrolyte | |
| CN102769147B (en) | Mg<2+>, Al<3+>, Zr<4+> and S<2-> ion co-doped garnet type solid electrolyte | |
| CN102867985B (en) | B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 | |
| CN102780029B (en) | A kind of three component cation codope carbuncle type solid lithium-ion electrolytes | |
| CN102867986B (en) | One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 | |
| CN102856584B (en) | A B3+, al3+, ti4+, Y3+and S2- codoped solid electrolyte Li7La3Zr2O12 | |
| CN102780030B (en) | Four-component cation and anion co-doped garnet-type solid electrolyte | |
| CN110372350A (en) | A kind of B3+、Al3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method | |
| CN102456917B (en) | F<-> and Zn<2+> co-doped NASICON type solid lithium ion electrolyte | |
| CN110372357A (en) | A kind of P5+、Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof | |
| CN110265706A (en) | A kind of electric field induction crystallization P5+、Al3+、B3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof | |
| CN110372348A (en) | A kind of electric field induction crystallization K6.15Zn0.05B0.2Al0.1P0.05Zr0.05Si1.6O7Potassium fast-ionic conductor and preparation method | |
| CN101958429B (en) | Solid lithium oil electrolyte using kaolin as raw material and preparation method thereof | |
| CN110371996A (en) | A kind of Al3+、B3+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof | |
| CN110372349A (en) | A kind of P5+、Al3+、Be2+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof | |
| CN110372351A (en) | A kind of P5+、Al3+The K of ion collaboration doping6Si2O7Potassium fast-ionic conductor and preparation method thereof | |
| CN110304912A (en) | A kind of electric field induction crystallization P5+、Be2+Cooperate with the K of doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof | |
| CN110357599A (en) | A kind of P5+、Al3+、Be2+、Zn2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof | |
| CN110357598A (en) | A kind of P5+、Be2+The K of ion collaboration doping2MgSi5O12Potassium fast-ionic conductor and preparation method thereof |
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: 20150715 Termination date: 20180904 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |