CN102867985B - B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 - Google Patents
B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 Download PDFInfo
- Publication number
- CN102867985B CN102867985B CN201210349339.3A CN201210349339A CN102867985B CN 102867985 B CN102867985 B CN 102867985B CN 201210349339 A CN201210349339 A CN 201210349339A CN 102867985 B CN102867985 B CN 102867985B
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- solid electrolyte
- hours
- ramp
- thin slice
- 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.)
- Expired - Fee Related
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 discloses a B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 which is characterized in that a chemometry formula is Li7+y1+y2+2y3YxLa3-xBy1Aly2Mgy3Zr2-y1-y2-y3O12-mSm, wherein x=0.1-0.3; y1=0.1-0.2; y2=0.1-0.2; y3=0.1-0.3; m=0.1-0.3; and the B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 is prepared by the steps of uniformly mixing Li2CO3, Y2O3, La2O3, Al2O3, MgO, ZrO2 and thiourea according to a mole ratio of (3.7-4.0):(0.05-0.15):(1.35-1.45):(0.05-0.1):(0.05-0.1):(0.1-0.3):(1.3-1.7):(0.1-0.3), ball-grinding, pressing and sintering. A room-temperature lithium ion conductivity of more than 5*10<-4>S/cm can be obtained.
Description
Technical field
The present invention relates to a kind of solid lithium-ion electrolyte and manufacture 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 in global portable power source market and exceed 30,000,000,000 dollars of/year shares and the occupation rate of market far exceeding other batteries, the chemical power source [Wu Yuping most with market development prospect, Wan Chunrong, Jiang Changyin, lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.].Lithium rechargeable battery major part employing both at home and abroad is liquid electrolyte at present, liquid lithium ionic cell has some unfavorable factors, as: liquid organic electrolyte may be revealed, blast at too high a temperature thus cause security incident, the occasion that some are high to security requirement cannot be applied in; Liquid electrolyte lithium ion battery ubiquity Capacity fading problem, uses after a period of time due to electrode active material dissolving in the 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 fail safe is high, substantially do not have Capacity fading, solid electrolyte also serves the effect of barrier film, simplifies the structure of battery; In addition, due to without the need to isolated air, also simplify the requirement to equipment in production process, configuration design also more convenient and flexible [Wen Zhaoyin, Zhu Xiujian, the Xu Xiaoxiong etc. of battery, the research of solid state secondary battery, the 12 Chinese solid-state ionics academic meeting paper collection, 2004.]。
In all-solid lithium-ion battery, the rate determining step that the migration rate of charge carrier in solid electrolyte is often far smaller than the ion diffusion rates in the Charger transfer of electrode surface and positive electrode and becomes in whole electrode reaction dynamics, therefore development has the inorganic solid electrolyte of higher li ionic conductivity is the key place building high performance lithium ion battery.The solid lithium-ion electrolyte with Practical significance will be researched and developed in addition, require that it can have good stability (to carbon dioxide and moisture stabilization) in the environment simultaneously, in order to enable the all-solid-state battery of composition use lithium metal to have high energy density as negative pole, also wish that solid state electrolysis mass-energy is stablized lithium metal and has higher decomposition voltage.Lithium ion solid electrolyte from having report at present: 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 LLTO decomposition voltage is low, cannot form the above all-solid-state battery of discharge voltage 3.7V and unstable to lithium anode; There is the LiM of NASICON type polycrystalline
2(PO
4)
3(M=Ti, Ge, Zr) is by tetrahedron PO
4with octahedra MO
6the grid structure of common composition, the coordination creating structural hole and can fill, making it possible to a large amount of Li ions, is a kind of up-and-coming high-lithium ion conductivity solid electrolyte.By the replacement of aliovalent 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 the structure.As the Li that [woods ancestral Zuxiang, Li Shichun, silicate journal, 9 (3), 1981,253-257.] such as woods ancestral Zuxiang, Li Shichun find
1+xti
2-xga
xp
3o
12, Li
1+2xti
2-xmgxP
3o
12, Li
1+xge
2-xcrxP
30
12, Li
1+xge
2-xal
xp
3o
12, Li
1+xti
2-xin
xp
3o
12etc. system or other are 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
12etc. system, all there is higher lithium ion conductivity.But the normal temperature lithium ion conductivity of these systems is usually 10
-4s/cm-10
-6between S/cm, the requirement of non-film lithium ion battery to electrolytic conductivity can't be met very well.NASICON system is unstable to lithium anode equally in addition.Ramaswamy Murugan equals on German applied chemistry periodical, within 2007, reported a kind of novel lithium ion solid electrolyte Li
7la
3zr
2o
12its lithium ion conductivity is at normal temperatures more than 1 × 10
-4s.em
-1decomposition voltage is more than 5.5V, lithium metal can be used as negative pole, to air and moisture stabilization, a kind ofly have very much fast ion solid electrolyte (the Ramaswamy Murugan of the lithium of application potential, Venkataraman Thangadurai, Wemer Weppner, (2007). " Fast lithium ion conduction in garnet-type Li
7la
3zr
2o
12. " Angewandte Chemie-International Edition46 (41): 7778-7781.).But often to reach 5.0 × 10 in the occasion conductivity higher to current requirements
-4about S/cm just can meet the needs of normal battery operation, and this solid electrolyte synthesis temperature is at about 1350 DEG C in addition, and temperature is high, and energy consumption is large.
Ion doping improves a kind of very effective mode of solid lithium ion electrolytic conductivity, but the interaction of Doped ions and matrix is very complicated, the characteristic such as size, electronic structure, electronegativity of Doped ions all has a significant impact the ion conductivity of parent, and have interaction between different Doped ions, be promote lithium ion mobility or suppress the degree of lithium ion mobility and promotion and suppression all can have very large difference along with the ionic species mixed and concentration.The selection of Doped ions should meet transmission bottleneck and Li as far as possible in principle
+radius size is mated, Li
+, vacancy concentration weak with skeleton ionic bonding forces and Li
+moderate three conditions of ratio of concentration.The lithium ion mobility mechanism of this solid electrolyte also not yet complete studied personnel is understood.In addition, ion doping if form eutectic solid solution, then can reduce synthesis temperature to a certain extent.Therefore the solid electrolyte of contamination to exploitation high-lithium ion conductivity studying Doped ions further has very important meaning.
Summary of the invention
Technical problem to be solved by this invention is a kind of B provided for existing background technology
3+, A1
3+, Mg
2+, Y
3+, S
2-ion co-doped lithium ion solid electrolyte Li
7la
3zr
2o
12.Y
3+part replaces La
3+, both have similar electronic structure, but Y
3+radius is less, the Al that same radius is less
3+part replaces Zr
4+and the B that radius is less
3+part replaces Zr
4+make the contraction distortion that La-O is octahedra and the generation of Zr-O octahedron is certain, migrating channels size is more mated with lithium ion radius and improves lithium ion conductivity; But structural aberration is excessive easily causes the change of phase and have a negative impact to lithium ion conducting.And Mg
2+radius and Zr
4+closely (0.072nm), Mg
2+part replaces Zr
4+do not cause the remarkable distortion of lattice and bring a large amount of gap lithium ions, simultaneously low price B
3+and Al
3+part replaces Zr
4+produce extra calking lithium ion, they add to increase and move the quantity of lithium ion in lattice and improve lithium ion conductivity; S
2-part replaces O
2-, S
2-although compare O
2-greatly, lithium ion mobility aisle spare may be reduced, but S
2-electronegativity is little, weak to gap lithium ion active force, plays the effect promoting lithium ion mobility generally; The synergy of these factors makes the normal temperature ionic conductivity of this solid electrolyte more than 5.0 × 10
-4s/cm, more close to the ionic conductivity of liquid electrolyte.Meanwhile, boron oxide compound and other components form solid solution, can reduce this solid electrolyte synthesis temperature 100-150 DEG C.
The present invention reaches by the following technical solutions, and this technical scheme provides a kind of lithium ion conductivity more than 5.0 × 10
-4the lithium ion solid electrolyte of S/cm, its stoichiometric equation is Li
7+y1+y2+2y3y
xla
3-xb
y1al
y2mg
y3zr
2-y1-y2-y3o
12-ms
mwherein: x=0.1-0.3; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.3; M=0.1-0.3.
In this technical scheme, by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: MgO: ZrO
2: thiocarbamide is the ratio uniform mixing of 3.7-4.0: 0.05-0.15: 1.35-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.3: 1.3-1.7: 0.1-0.3 (mol ratio), add 95% ethanol of 2%-6%, with the rotating speed ball milling 10-20 hour of 200-400 rev/min in ball mill, after ball milling terminates in 60 DEG C of-80 DEG C of vacuum drying ovens (vacuum degree is at 10Pa-100Pa) dry 10-30 hour, grind in alms bowl at agate after taking-up and again grind 10-30 minute, powder after grinding is incubated 2-8 hour with the ramp of 5-10 DEG C/min to 200-250 DEG C, then be incubated 5-10 hour with the ramp of 5-10 DEG C/min to 750-850 DEG C, then within 10-30 hour, make solid electrolyte powder with the ramp of 2-10 DEG C/min to 1150-1250 DEG C of insulation.This powder mixing 1-5wt% be bonding agent (this bonding agent is PVC or PVA) under forcing press with keep under the pressure of 300-500MPa pressure 2-6 minute formed thin slice, this thin slice makes lithium ion solid electrolyte thin slice in 10-20 hour with the ramp of 10-20 DEG C/min to 1200-1300 DEG C of insulation in air atmosphere.As Fig. 1 consists of Li
7.4y
0.1la
2.9b
0.1al
0.1mg
0.1zr
1.7o
11.9s
0.1solid electrolyte sheet is AC impedance figure under electrochemical workstation, and from figure, calculate conductivity is 7.5 × 10
-4s/cm.
Compared with prior art, the invention has the advantages that: adopt B
3+, Al
3+, Mg
2+, Y
3+, S
2-ion co-doped lithium ion solid electrolyte Li
7la
3zr
2o
12.By the Y that radius is less
3+part replaces La
3+, the Al that same radius is less
3+part replaces Zr
4+and the B that radius is less
3+part replaces Zr
4+make the contraction distortion that La-O is octahedra and the generation of Zr-O octahedron is certain, migrating channels size is more mated with lithium ion radius and improves lithium ion conductivity; By radius and Zr
4+mg closely
2+part replaces Zr
4+make to roll up gap lithium ion when structure does not significantly distort, simultaneously by low price B
3+and Al
3+part replaces Zr
4+produce extra calking lithium ion, increase and move the quantity of lithium ion in lattice and improve lithium ion conductivity; S
2-part replaces O
2-, S
2-although compare O
2-greatly, lithium ion mobility aisle spare may be reduced, but S
2-electronegativity is little, weak to gap lithium ion active force, plays the effect promoting lithium ion mobility generally; The synergy of these factors makes the normal temperature ionic conductivity of this solid electrolyte more than 5.0 × 10
-4s/cm.Meanwhile, boron oxide compound and other components form solid solution, can reduce this solid electrolyte synthesis temperature 100-150 DEG C.
Accompanying drawing explanation
Fig. 1 is the AC impedance figure of lithium ion solid electrolyte thin slice under electrochemical workstation, frequency versus impedance and frequency-phase figure.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: MgO: ZrO
2: thiocarbamide is the ratio uniform mixing of 3.7: 0.05: 1.45: 0.05: 0.05: 0.1: 1.7: 0.1 (mol ratio), add 95% ethanol of 2%, with the rotating speed ball milling 10 hours of 250 revs/min in ball mill, the middle drying of 60 DEG C of vacuum drying ovens (vacuum degree 20Pa) 10 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 15 minutes, powder after grinding is incubated 3 hours with the ramp of 5 DEG C/min to 200 DEG C, then be incubated 6 hours with the ramp of 5 DEG C/min to 750 DEG C, then within 20 hours, make solid electrolyte powder with the ramp of 3 DEG C/min to 1150 DEG C of insulations.This powder mixing 2wt% bonding agent PVC is to keep pressure to form thin slice in 5 minutes under forcing press under the pressure of 300MPa, this thin slice makes lithium ion solid electrolyte thin slice in 10 hours with the ramp of 11 DEG C/min to 1220 DEG C of insulations in air atmosphere.
Embodiment 2: by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: MgO: ZrO
2: thiocarbamide is the ratio uniform mixing of 4.0: 0.15: 1.35: 0.1: 0.1: 0.3: 1.3: 0.3 (mol ratio), add 95% ethanol of 5.5%, with the rotating speed ball milling 15 hours of 380 revs/min in ball mill, the middle drying of 80 DEG C of vacuum drying ovens (vacuum degree 95Pa) 30 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 20 minutes, powder after grinding is incubated 5 hours with the ramp of 6 DEG C/min to 220 DEG C, then be incubated 10 hours with the ramp of 8 DEG C/min to 780 DEG C, then within 15 hours, make solid electrolyte powder with the ramp of 7 DEG C/min to 1200 DEG C of insulations.This powder mixing 5wt% bonding agent PVC to keep pressure to form thin slice in 2 minutes under the pressure of 450MPa, makes lithium ion solid electrolyte thin slice in 10 hours with the ramp of 15 DEG C/min to 1280 DEG C of insulations under this thin slice air atmosphere under forcing press.
Embodiment 3: by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: MgO: ZrO
2: thiocarbamide is the ratio uniform mixing of 3.85: 0.1: 1.4: 0.075: 0.075: 0.2: 1.5: 0.2 (mol ratio), add 95% ethanol of 3%, with the rotating speed ball milling 20 hours of 300 revs/min in ball mill, the middle drying of 70 DEG C of vacuum drying ovens (vacuum degree 50Pa) 20 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 10 minutes, powder after grinding is incubated 5 hours with the ramp of 9 DEG C/min to 250 DEG C, then be incubated 7 hours with the ramp of 10 DEG C/min to 800 DEG C, then within 12 hours, make solid electrolyte powder with the ramp of 2 DEG C/min to 1250 DEG C of insulations.This powder mixing 1wt% bonding agent PVA is to keep pressure to form thin slice in 6 minutes under forcing press under the pressure of 300MPa, this thin slice makes lithium ion solid electrolyte thin slice in 18 hours with the ramp of 15 DEG C/min to 1300 DEG C of insulations in air atmosphere.
Embodiment 4: by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: MgO: ZrO
2: thiocarbamide is the ratio uniform mixing of 3.8: 0.08: 1.42: 0.07: 0.08: 0.15: 1.55: 0.3 (mol ratio), add 95% ethanol of 6%, with the rotating speed ball milling 12 hours of 390 revs/min in ball mill, the middle drying of 80 DEG C of vacuum drying ovens (vacuum degree 100Pa) 15 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 20 minutes, powder after grinding is incubated 8 hours with the ramp of 5 DEG C/min to 230 DEG C, then be incubated 5 hours with the ramp of 8 DEG C/min to 750 DEG C, then within 20 hours, make solid electrolyte powder with the ramp of 9 DEG C/min to 1230 DEG C of insulations.This powder mixing 2.6wt% bonding agent PVA is to keep pressure to form thin slice in 4 minutes under forcing press under the pressure of 400MPa, this thin slice makes lithium ion solid electrolyte thin slice in 13 hours with the ramp of 20 DEG C/min to 1250 DEG C of insulations in air atmosphere.
Embodiment 5: by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: MgO: ZrO
2: thiocarbamide is the ratio uniform mixing of 3.76: 0.12: 1.38: 0.08: 0.08: 0.1: 1.58: 0.1 (mol ratio), add 95% ethanol of 4%, with the rotating speed ball milling 18 hours of 210 revs/min in ball mill, the middle drying of 60 DEG C of vacuum drying ovens (vacuum degree 10Pa) 25 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, powder after grinding is incubated 2 hours with the ramp of 10 DEG C/min to 210 DEG C, then be incubated 10 hours with the ramp of 5 DEG C/min to 850 DEG C, then within 28 hours, make solid electrolyte powder with the ramp of 7 DEG C/min to 1170 DEG C of insulations.This powder mixing 5wt% bonding agent PVC is to keep pressure to form thin slice in 2 minutes under forcing press under the pressure of 500MPa, this thin slice makes lithium ion solid electrolyte thin slice in 15 hours with the ramp of 10 DEG C/min to 1200 DEG C of insulations in air atmosphere.
Claims (3)
1. a B
3+, Al
3+, Mg
2+, y
3+, S
2-ion co-doped lithium ion solid electrolyte, is characterized in that stoichiometric equation is Li
7+ y1+y2+2y3y
xla
3-xb
y1al
y2mg
y3zr
2-y1-y2-y3o
12-ms
m, wherein: x=0.1-0.3; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.3; M=0.1-0.3.
2. lithium ion solid electrolyte according to claim 1, is characterized in that Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: MgO: ZrO
2: thiocarbamide mol ratio is the ratio uniform mixing of 3.7-4.0: 0.05-0.15: 1.35-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.3: 1.3-1.7: 0.1-0.3, add 95% ethanol of 2%-6%, with the rotating speed ball milling 10-20 hour of 200-400 rev/min in ball mill.
3. lithium ion solid electrolyte according to claim 1, is characterized in that the normal temperature lithium ion conductivity of the thin slice of the described solid electrolyte obtained is greater than 5 × 10
-4s/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210349339.3A CN102867985B (en) | 2012-09-04 | 2012-09-04 | B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210349339.3A CN102867985B (en) | 2012-09-04 | 2012-09-04 | B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102867985A CN102867985A (en) | 2013-01-09 |
| CN102867985B true CN102867985B (en) | 2015-06-17 |
Family
ID=47446686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210349339.3A Expired - Fee Related CN102867985B (en) | 2012-09-04 | 2012-09-04 | B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102867985B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070945A (en) * | 2015-07-30 | 2015-11-18 | 中国科学院西安光学精密机械研究所 | Nasicon fast ionic conductor (NASICON) lithium-ion solid electrolyte doped with B<3+> and Y<3+> ions collaboratively and preparation method of NASICON lithium-ion solid electrolyte |
| CN105295029B (en) * | 2015-12-04 | 2018-10-30 | 黄淮学院 | A kind of nano zine oxide-polyamide compoiste material and preparation method thereof |
| JP6669268B2 (en) | 2016-09-21 | 2020-03-18 | 株式会社村田製作所 | Solid electrolyte and all-solid battery |
| CN110098430A (en) * | 2018-01-30 | 2019-08-06 | 财团法人工业技术研究院 | Solid electrolyte and solid state battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2012005296A1 (en) * | 2010-07-07 | 2012-01-12 | 国立大学法人静岡大学 | Solid electrolyte material and lithium battery |
| US20120171562A1 (en) * | 2010-06-28 | 2012-07-05 | Ut-Battelle, Llc | Solid lithium ion conducting electrolytes and methods of preparation |
-
2012
- 2012-09-04 CN CN201210349339.3A patent/CN102867985B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20120171562A1 (en) * | 2010-06-28 | 2012-07-05 | Ut-Battelle, Llc | Solid lithium ion conducting electrolytes and methods of preparation |
| WO2012005296A1 (en) * | 2010-07-07 | 2012-01-12 | 国立大学法人静岡大学 | Solid electrolyte material and lithium battery |
Non-Patent Citations (2)
| Title |
|---|
| Mechanosynthesis of Solid Electrolytes: Preparation,Characterization, and Li Ion Transport Properties of Garnet-Type Al-Doped Li7La3Zr2O12 Crystallizing with Cubic Symmetry;Andre Düvel等;《The Journal of Physical Chemistry C》;20120625;第116卷;第15192-15202页 * |
| 无机固态锂离子电解质的研究进展;朱永明等;《化学通报》;20101218(第12期);第1073-1079页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102867985A (en) | 2013-01-09 |
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 | |
| Hou et al. | An aqueous rechargeable sodium ion battery based on a NaMnO 2–NaTi 2 (PO 4) 3 hybrid system for stationary energy storage | |
| CN102867987B (en) | A B3+, al3+, mg2+, Y3+, F- codoped solid electrolyte Li7La3Zr2O12 | |
| CN102780028B (en) | Four-component iron co-doped garnet type solid electrolyte | |
| CN102456918B (en) | F<->, Zn<2+>, and B<3+> co-doped NASICON type solid lithium-ion electrolyte | |
| CN107275606B (en) | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof | |
| CN102456919B (en) | Zn<2+> and B<3+> ion doped NASICON solid lithium ion electrolyte | |
| CN108155413A (en) | The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method | |
| CN102769147B (en) | Mg<2+>, Al<3+>, Zr<4+> and S<2-> ion co-doped garnet type solid electrolyte | |
| CN104953175A (en) | Solid electrolyte for lithium ion battery, preparation method for solid electrolyte, and lithium ion battery | |
| CN105140560A (en) | Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery | |
| CN102867985B (en) | B<3+>, Al<3+>, Mg<2+>, Y<3+> and S<2-> co-doped solid electrolyte Li7La3Zr2O12 | |
| Liu et al. | Strippable and flexible solid electrolyte membrane by coupling Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 and insulating polyvinylidene fluoride for solid state lithium ion battery | |
| CN102780029B (en) | A kind of three component cation codope carbuncle type solid lithium-ion electrolytes | |
| CN102856584B (en) | A B3+, al3+, ti4+, Y3+and S2- codoped solid electrolyte Li7La3Zr2O12 | |
| CN102867986B (en) | One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 | |
| Zhang et al. | Optimized preparation conditions of yttria doped zirconia coatings on potassium ferrate (VI) electrode for alkaline super-iron battery | |
| 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 | |
| CN110526697A (en) | A kind of liquid phase synthesis K6.25Be0.1Al0.1P0.05Ti0.05Si1.7O7Potassium 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 |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150617 Termination date: 20180904 |