CN101013761A - Solid electrolyte material system for all solid state lithium battery and preparation method - Google Patents
Solid electrolyte material system for all solid state lithium battery and preparation method Download PDFInfo
- Publication number
- CN101013761A CN101013761A CNA2007100374796A CN200710037479A CN101013761A CN 101013761 A CN101013761 A CN 101013761A CN A2007100374796 A CNA2007100374796 A CN A2007100374796A CN 200710037479 A CN200710037479 A CN 200710037479A CN 101013761 A CN101013761 A CN 101013761A
- Authority
- CN
- China
- Prior art keywords
- electrolyte material
- solid electrolyte
- lithium ion
- solid
- preparation
- 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
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 one solid electrolyte materials and its process method for fix lithium battery, which is characterized by the following: Li2S and other sulfur compound B/S and A/I according to certain mole proportion for compounds to form non-crystal system to provide space for lithium ion transmission to get higher ion conductive rate, wherein, the materials have wider heat stable range to provide one ideal electrolyte prepare materials for solid lithium ion battery.
Description
Technical field
The present invention relates to be used for the solid electrolyte material system and the preparation method of solid lithium battery.This material (≤160 ℃) under room temperature and higher temperature mainly shows as lithium ion conductor, belongs to the energy and uses the solid electrolyte material field.
Background technology
Be accompanied by extensive uses such as portable electronics such as mobile phone, video camera and notebook computer, lithium ion two battery eliminators are well received.These batteries have high output voltage, high energy storage density and carry light advantage.The most employed electrolyte of lithium battery comprises volatile and incendive organic solvent at present.In order to make more high output voltage, the more high-energy-density and the battery of large scale more, just need to use the electrolyte that contains a large amount of organic solvents.And the organic bath in the battery causes serious fire and electrolyte leakage to happen occasionally.Overcome these safety problems and produce reliable battery, effective method is exactly to replace inflammable liquid electrolyte with the solid electrolyte that does not fire.In order to guarantee the high-performance of solid lithium battery, solid electrolyte must have the high-lithium ion conductance similar with liquid electrolyte.The research of current solid electrolyte is concentrated with organic substance and is taken as the leading factor or the novel porous material of construction unit.Pure inorganic system does not cause concern widely, and some important researchs are arranged recently.
At present main research and the inorganic solid electrolyte of using (fast-ionic conductor) material relevant that focus mostly on greatly with oxide.This class material has bigger ion activation energy usually, and just its ionic conductivity is higher when high temperature (＞100 ℃), but very low during the room temperature left and right sides.Discover that in a large number the oxide with open architecture can improve normal temperature Xiayang ionic conductivity, because open passage provides possibility for the ion migration.In order to improve the cationic mobility of conduction, the oxide fast-ionic conductor generally adopts amorphous batch mixing or glass physics attitude, this decrystallized structure makes material internal have more defectives, bigger sponginess and high-energy more, promptly improve the openness of its structure, reduce oxonium ion to cationic binding force, thereby improve cationic transfer ability.However, the oxonium ion (O on oxide holes frame surface
2-) to the conductive ion (Li in the through hole
+And Na
+) still have very strong charge effect, cause these mobility of charge carrier to be subjected to very big constraint.
Compare with oxide, the chalcogenide of open architecture then is more suitable for as fast-ionic conductor.The sulfur family atomic electronegativity does not have oxygen strong, sulfur family ion (Q
2-) on CHARGE DISTRIBUTION compare O
2-Delocalizationization more, the just easier polarization of the sulfur family ion on frame surface, hole, so chalcogenide is more suitable for cationic migration.Such as, at normal temperatures, sulfide 0.6Li
2S: 0.4SiS
2The conductance of (mol ratio) reaches 10
-3The S/cm order of magnitude, and corresponding oxide 0.6Li
2O: 0.4SiO
2Conductance have only 10
-6The S/cm order of magnitude [1-3] [(1) Yamamoto H, Machida N, et.al.Solid State Ionics 175 (1-4): 707-711,2004. (2) Hayashi A, Araki R, et.al.Solid State Ionics 113-115,733,1998. (3) Zheng N, Bu X, Feng P, Nature 426,428, and 2003.], this shows that chalcogenide has very big advantage as fast-ionic conductor.
Sulfide amorphous batch mixing or glass are focuses as fast-ionic conductor research at present.Their method is mainly Li
2S and sulfide M S
2(M=Si, Ge), P
2S
5Deng in one or more mixing, by ball milling, high-energy ball milling or fuse and obtain.The sulfide crystallization shape material of open architecture also is one of optimal candidate of fast-ionic conductor.Delivered the synthetic loose structure that contains of the inorganic sulfur compounds of group fast-ionic conductor of crystallization in November, 2003 in Britain's " nature ", wherein contain Li
+Or Na
+CuINS-Na in the literary composition (ICF-5) and InSe-Na (ICF-21) conductance at normal temperatures are respectively 1.2 * 10
-2With 3.4 * 10
-2S/cm.Show that thus the crystalline state material can have the conductance that is higher than or is similar to glassy state.
From the practical application angle, all-solid lithium battery is compared with traditional liquid electrolyte battery, except higher energy is arranged, also avoided the corrosion of liquid electrolytic confrontation containers such as soda acid, and have do not have to reveal, storage life is long, be easy to advantage such as miniaturization, and the serviceability temperature scope is extensive especially, makes the range of application of lithium battery expand to space flight, the operational environment of multiple specific (special) requirements such as biology and human body, it will more and more influence and change people's life.
In sum, the search research and development utilization that is used for the solid electrolyte material of solid lithium battery is of great immediate significance.
Summary of the invention
The object of the present invention is to provide a kind of solid lithium battery solid electrolyte material and preparation method thereof, being contemplated that of invention: theory analysis and literature research show, the sulfide of open architecture can have good ionic conductivity and chemical stability, is expected to become the most promising fast-ionic conductor after oxide.In order to guarantee that sulfide can have the skeleton of negative electrical charge, M
N+The ratio of/S is the smaller the better, and just the valence state of M is high more good more, as the valence state n of M can be+3 ,+4 ,+5 ,+6.M is early transition metal (the 3rd, 4,5 family) or back metallic element (the 13rd, 14,15 family) and rare earth element.These materials have the structure type of enriching, from three-dimensional to the two dimension, a peacekeeping zero-dimension structural.Lithium ion is positioned between duct, interlayer, interchain or point, and its coordination mode is various.Coordination mode as lithium ion and sulfur family ion can be coordinated to 5,4 coordinations from 6.Represent material as, LiLnS
2(Ln is a rare earth element), Na
5Li
3Ti
2S
8, NaLiMS
2(M=Zn, Cd) etc., described sulfide system is compared with the oxide solid electrolyte of present main flow, and sulphion is compared easier polarization because radius is bigger with oxonium ion, is more suitable for the lithium ion diffusion, thereby obtains higher lithium ion conductivity.
Solid lithium battery solid electrolyte material provided by the invention has following 3 classes:
(A) Li
2S+A/I, A/I is AlI in the formula
3, ZnI
2, ZrI
4Or LaI
3, 0.5≤x≤1.5;
(B) yLi
2S-mA/I-zB/S, y+z=9 in the formula, y from 5.0 to 7.0, and m from 0.5 to 3, and B/S is SiS
2, 0.5P
2S
5, CeS
2Or 0.5B
2S
3A/I is AlI
3, ZnI
2, ZrI
4Or LaI
3
(C) yLi
2S-mA/I-zB/S-nLiI, y+z=9 in the formula, y from 5.0 to 7.0, and m from 0.5 to 3.0, and n from 0.5 to 3.0, and A/I is AlI
3, ZnI
2, ZrI
4Or LaI
3B/S is SiS
2, 0.5P
2S
5, CeS
2Or 0.5B
2S
3
Compare with the oxide solid electrolyte of present main flow,, compare easier polarization, be more suitable for ions diffusion, thereby obtain higher lithium ion conductivity with oxonium ion because of the ionic radius of sulphion and iodide ion is bigger;
Above-mentioned three its structures of based solid electrolyte material system are amorphous state, material internal has more defectives, bigger sponginess and high-energy more, promptly improve enterprise's structure openness, reduced anion to cationic binding force, thereby cationic transfer ability is improved.With 6Li
2S-0.5AlI
3-3SiS
2-LiI system be example (y=6, m=0.5, z=3, n=1), this system (≤200 ℃) under room temperature and higher temperature mainly shows as lithium ion conductor, room temperature total conductivity is the highest can reach 3.80 * 10 for it
-6S/cm, 150 ℃ is to reach 2.40 * 10
-3S/cm, activation energy are 0.50eV.
Adopt vacuum condition reaction down, the back ball grinding method that quenches then prepares powder body material, and concrete steps are:
Select above-described A, B, C three based solid electrolyte material mixture ratios for use, mix in accordance with the appropriate ratio and prepare burden, the quartz glass tube of packing into then is through vacuumizing (＜10
-2Behind the Pa=, adopt the sealing-in of oxyhydrogen flame sealing by fusing, carry out solid phase reaction at 500 ℃～750 ℃, the reaction time is 10～14 hours.High temperature takes out, and quenching is to room temperature.Powder grinds under the argon atmospher protection again behind the open pipe.
The performance evaluation of described electric property is with the powder compressing tablet of above preparation (diameter 10mm, about thickness 1mm, pressure is 10MPa), finally makes lithium ion fast-ionic conductor test material.Then at two sides evaporation one deck gold film as conductive electrode, on electrochemical workstation (Shanghai occasion China 660B), carry out the electric conductivity evaluation.
Description of drawings
Figure 16 Li
2S-0.5AlI
3-3SiS
2-LiI alternating temperature impedance spectrum (Nyquist curve)
Figure 26 Li
2S-0.5AlI
3-3SiS
2The product of-LiI conductivity and temperature varies with temperature curve
Figure 36 Li
2S-0.5AlI
3-3SiS
2The product of conductivity and temperature varies with temperature curve
Figure 41 .5Li
2S-AlI
3The product of conductivity and temperature varies with temperature curve
Embodiment
Embodiment 1
Select Li for use
2S, SiS
2, AlI
3With the LiI powder (Li of perhaps an amount of mol ratio
2S, silica flour, S powder, aluminium powder and iodine particle and LiI powder) (z=3 n=1) mixes and prepares burden for y=6, m=0.5, and the quartz glass tube of packing into then encapsulates (10 through vacuumizing after in selected ratio
-2Pa, the hydrogen-oxygen sealing by fusing), carry out solid phase reaction at 500 ℃～750 ℃, the reaction time is 10～14 hours.High temperature takes out, and quenching is to room temperature.Powder grinds behind the open pipe, and compressing tablet (diameter 10mm, about thickness 1mm, pressure is 10MPa) is finally made lithium ion fast-ionic conductor test material.
The conducting performance test (see figure 1) shows that it has the ionic conductance performance, and the low frequency end of the ac impedance spectroscopy under different temperatures can clearly observe the peculiar straightway of ionic conductivity.By calculating, can obtain its room temperature total conductivity is 3.80 * 10
-6S/cm can reach 2.40 * 10 in the time of 150 ℃
-3S/cm, simultaneously, to 1000/T mapping (Fig. 2, fabulous linearisation shows the ionic conductivity of body series), the ion transfer activation energy that calculates this material is (0.50eV) by 1g σ T.
Embodiment 2
Select Li for use
2S, SiS
2, AlI
3(z=3) prepare burden for y=6, m=0.5, and the quartz glass tube of packing into then encapsulates after vacuumizing, and carries out solid phase reaction at 500 ℃～750 ℃, and the reaction time is 10～14 hours by mixing in selected ratio for powder.High temperature takes out, and quenching is to room temperature.Powder grinds behind the open pipe, and compressing tablet (diameter 10mm, about thickness 1mm, pressure is 10MPa) is finally made lithium ion fast-ionic conductor test material.
Embodiment 3
Select Li for use
2S, AlI
3Powder mixes in selected ratio (x=1.5) prepares burden, the quartz glass tube of packing into then, and encapsulation is carried out solid phase reaction at 500 ℃～750 ℃ after vacuumizing, and the reaction time is 10～14 hours.High temperature takes out, and quenching is to room temperature.Powder grinds behind the open pipe, and compressing tablet (diameter 10mm, about thickness 1mm, pressure is 10MPa) is finally made lithium ion fast-ionic conductor test material.
To this system conducting performance test, Fig. 4 maps to 1000/T with 1g σ T, and fabulous linearisation shows the ionic conductivity of body series; The ion transfer activation energy that calculates this material is (0.53eV).The room temperature total conductivity is 3.60 * 10
-7S/cm can reach 2.36 * 10 in the time of 150 ℃
-3S/cm.
Claims (10)
1, the solid electrolyte material system that is used for all solid state lithium ion battery is characterized in that described solid electrolyte material has three classes:
(A) Li
2S+A/I, A/I is AlI in the formula
3, ZnI
2, ZrI
4Or LaI
3, 0.5≤x≤1.5;
(B) yLi
2S-mA/I-zB/S, y+z=9 in the formula, y from 5.0 to 7.0, and m from 0.5 to 3, and B/S is SiS
2, 0.5P
2S
5, CeS
2Or 0.5B
2S
3A/I is AlI
3, ZnI
2, ZrI
4Or LaI
3
(C) yLi
2S-mA/I-zB/S-nLiI, y+z=9 in the formula, y from 5.0 to 7.0, and m from 0.5 to 3.0, and n from 0.5 to 3.0, and A/I is AlI
3, ZnI
2, ZrI
4Or LaI
3B/S is SiS
2, 0.5P
2S
5, CeS
2Or 0.5B
2S
3
2,, it is characterized in that described solid electrolyte material is an amorphous state by the described solid electrolyte material that is used for all solid state lithium ion battery of claim 1.
3, the preparation method that is used for the solid electrolyte material of all solid state lithium ion battery as claimed in claim 1 is characterized in that described category-A solid electrolyte material is by solid phase reaction under the vacuum condition, the back ball milling preparation of quenching then, concrete steps are:
(a) press Li
2The S+A/I mixed is prepared burden, and A/I is AlI in the formula
3, ZnI
2, ZrI
4Or LaI
3, 0.5≤x≤1.5;
(b) quartz glass tube of packing into then vacuumizes back oxyhydrogen flame sealing by fusing; Slowly rise to 450 ℃, insulation 24h;
(c) then carry out solid phase reaction being warming up to 500-750 ℃, the reaction time is 10-14h, grinds under the argon atmospher protection behind the open pipe behind the water-cooled cold quenching.
4,, it is characterized in that vacuum degree that step (b) vacuumizes is less than 10 by the described preparation method who is used for the solid electrolyte material of all solid state lithium ion battery of claim 3
-2Pa.
5, the preparation solid electrolyte material that is used for all solid state lithium ion battery as claimed in claim 1 is characterized in that described category-B solid electrolyte material is by solid phase reaction under the vacuum condition, the back ball milling preparation of quenching then, concrete steps are:
(a) press yLi
2The S-mA/I-zB/S mixed is prepared burden, y+z=9 in the formula, and y from 5.0 to 7.0, and m from 0.5 to 3, and B/S is SiS
2, 0.5P
2S
5, CeS
2Or 0.5B
2S
3
(b) quartz glass tube of packing into then vacuumizes back oxyhydrogen flame sealing by fusing; Slowly rise to 450 ℃, insulation 24h;
(c) then carry out solid phase reaction being warming up to 500-750 ℃, the reaction time is 10-14h, grinds under the argon atmospher protection behind the open pipe behind the water-cooled cold quenching.
6,, it is characterized in that B/S sulfide in the step (a) is is that 99% sublimed sulfur reacts and generates by Si, P, Ce or B and purity by the described solid electrolyte material preparation method who is used for all solid state lithium ion battery of claim 5.
7, by the described solid electrolyte material preparation method who is used for all solid state lithium ion battery of claim 5, the vacuum degree that it is characterized in that vacuumizing in the step (b) is less than 10
-2Pa.
8, the preparation solid electrolyte material method that is used for all solid state lithium ion battery as claimed in claim 1 is characterized in that described C based solid electrolyte material is by solid phase reaction under the vacuum condition, the back ball milling preparation of quenching then, concrete steps are:
(a) yLi
2S-mA/I-zB/S-nLiI, y+z=9 in the formula, y from 5.0 to 7.0, and m from 0.5 to 3.0, and n from 0.5 to 3.0, and A/I is AlI
3, ZnI
2, ZrI
4Or LaI
3B/S is SiS
2, 0.5P
2S
5, CeS
2Or 0.5B
2S
3
(b) quartz glass tube of packing into then vacuumizes back oxyhydrogen flame sealing by fusing; Slowly rise to 450 ℃, insulation 24h;
(c) then carry out solid phase reaction being warming up to 500-750 ℃, the reaction time is 10-14h, grinds under the argon atmospher protection behind the open pipe behind the water-cooled cold quenching.
9, the solid electrolyte material preparation method who is used for all solid state lithium ion battery as claimed in claim 8 is characterized in that B/S sulfide in the step (a) is is that 99% sublimed sulfur reacts and generates by Si, P, Ce or B and purity.
10, the solid electrolyte material preparation method who is used for all solid state lithium ion battery as claimed in claim 8, the vacuum degree that it is characterized in that vacuumizing in the step (b) is less than 10
-2Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100374796A CN100524927C (en) | 2007-02-13 | 2007-02-13 | Solid electrolyte material system for all solid state lithium battery and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100374796A CN100524927C (en) | 2007-02-13 | 2007-02-13 | Solid electrolyte material system for all solid state lithium battery and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101013761A true CN101013761A (en) | 2007-08-08 |
| CN100524927C CN100524927C (en) | 2009-08-05 |
Family
ID=38701131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100374796A Active CN100524927C (en) | 2007-02-13 | 2007-02-13 | Solid electrolyte material system for all solid state lithium battery and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100524927C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106785017A (en) * | 2017-02-13 | 2017-05-31 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy, silver iodide and silver chlorate and preparation method thereof |
| CN106785015A (en) * | 2017-02-13 | 2017-05-31 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding Li-Si alloy and silver bromide and preparation method thereof |
| CN106785004A (en) * | 2017-02-13 | 2017-05-31 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy powder and preparation method thereof |
| CN107069080A (en) * | 2017-02-13 | 2017-08-18 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof |
| CN107710455A (en) * | 2015-06-24 | 2018-02-16 | 昆腾斯科普公司 | Composite electrolyte |
| CN108780683A (en) * | 2016-03-14 | 2018-11-09 | 出光兴产株式会社 | Solid electrolyte and method for producing solid electrolyte |
| CN111344812A (en) * | 2017-11-14 | 2020-06-26 | 出光兴产株式会社 | Sulfide-based solid electrolyte containing metal element and method for producing same |
| US11139479B2 (en) | 2013-05-15 | 2021-10-05 | Quantumscape Battery, Inc. | Solid state catholyte or electrolyte for battery using LiaMPbSc (M=Si, Ge, and/or Sn) |
| CN114122503A (en) * | 2020-08-27 | 2022-03-01 | 比亚迪股份有限公司 | Solid electrolyte, preparation method thereof and battery |
| US11342630B2 (en) | 2016-08-29 | 2022-05-24 | Quantumscape Battery, Inc. | Catholytes for solid state rechargeable batteries, battery architectures suitable for use with these catholytes, and methods of making and using the same |
| US11476496B2 (en) | 2015-12-04 | 2022-10-18 | Quantumscape Battery, Inc. | Lithium, phosphorus, sulfur, and iodine including electrolyte and catholyte compositions, electrolyte membranes for electrochemical devices, and annealing methods of making these electrolytes and catholytes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4550066A (en) * | 1984-11-01 | 1985-10-29 | Combustion Engineering, Inc. | Solid electrolyte |
| US5217826A (en) * | 1990-07-31 | 1993-06-08 | Matsushita Electric Industrial Co., Ltd. | Lithium-ion conducting solid electrolyte |
| JP3744665B2 (en) * | 1997-12-09 | 2006-02-15 | トヨタ自動車株式会社 | Lithium ion conductive solid electrolyte and battery |
| CN100362683C (en) * | 2006-01-23 | 2008-01-16 | 浙江大学 | Full-solid-state minisize lithium cell electrolyte preparing method |
-
2007
- 2007-02-13 CN CNB2007100374796A patent/CN100524927C/en active Active
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11139479B2 (en) | 2013-05-15 | 2021-10-05 | Quantumscape Battery, Inc. | Solid state catholyte or electrolyte for battery using LiaMPbSc (M=Si, Ge, and/or Sn) |
| US11211611B2 (en) | 2013-05-15 | 2021-12-28 | Quantumscape Battery, Inc. | Solid state catholyte or electrolyte for battery using LiaMPbSc (M=Si, Ge, and/or Sn) |
| CN107710455A (en) * | 2015-06-24 | 2018-02-16 | 昆腾斯科普公司 | Composite electrolyte |
| US11145898B2 (en) | 2015-06-24 | 2021-10-12 | Quantumscape Battery, Inc. | Composite electrolytes |
| CN107710455B (en) * | 2015-06-24 | 2021-12-17 | 昆腾斯科普电池公司 | Composite electrolyte |
| US11955603B2 (en) | 2015-06-24 | 2024-04-09 | Quantumscape Battery, Inc. | Composite electrolytes |
| US11476496B2 (en) | 2015-12-04 | 2022-10-18 | Quantumscape Battery, Inc. | Lithium, phosphorus, sulfur, and iodine including electrolyte and catholyte compositions, electrolyte membranes for electrochemical devices, and annealing methods of making these electrolytes and catholytes |
| CN108780683A (en) * | 2016-03-14 | 2018-11-09 | 出光兴产株式会社 | Solid electrolyte and method for producing solid electrolyte |
| US11038198B2 (en) | 2016-03-14 | 2021-06-15 | Idemitsu Kosan Co., Ltd. | Solid electrolyte and method for producing solid electrolyte |
| US11342630B2 (en) | 2016-08-29 | 2022-05-24 | Quantumscape Battery, Inc. | Catholytes for solid state rechargeable batteries, battery architectures suitable for use with these catholytes, and methods of making and using the same |
| CN106785017A (en) * | 2017-02-13 | 2017-05-31 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy, silver iodide and silver chlorate and preparation method thereof |
| CN107069080A (en) * | 2017-02-13 | 2017-08-18 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof |
| CN106785004A (en) * | 2017-02-13 | 2017-05-31 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy powder and preparation method thereof |
| CN106785015A (en) * | 2017-02-13 | 2017-05-31 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding Li-Si alloy and silver bromide and preparation method thereof |
| CN111344812A (en) * | 2017-11-14 | 2020-06-26 | 出光兴产株式会社 | Sulfide-based solid electrolyte containing metal element and method for producing same |
| CN114122503A (en) * | 2020-08-27 | 2022-03-01 | 比亚迪股份有限公司 | Solid electrolyte, preparation method thereof and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100524927C (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100524927C (en) | Solid electrolyte material system for all solid state lithium battery and preparation method | |
| CN100502111C (en) | Lithium-sulfur system solid electrolyte material for all solid state lithium battery and preparation method | |
| Yao et al. | All-solid-state lithium batteries with inorganic solid electrolytes: Review of fundamental science | |
| Zhang et al. | Enhancing ionic conductivity of solid electrolyte by lithium substitution in halogenated Li-Argyrodite | |
| Kanno et al. | Lithium ionic conductor thio-LISICON: the Li2 S GeS2 P 2 S 5 system | |
| Kanno et al. | Synthesis of a new lithium ionic conductor, thio-LISICON–lithium germanium sulfide system | |
| Minami et al. | Recent progress of glass and glass-ceramics as solid electrolytes for lithium secondary batteries | |
| Seino et al. | Synthesis of phosphorous sulfide solid electrolyte and all-solid-state lithium batteries with graphite electrode | |
| Noi et al. | Structure and properties of the Na2S–P2S5 glasses and glass–ceramics prepared by mechanical milling | |
| Ujiie et al. | Structure, ionic conductivity and electrochemical stability of Li2S–P2S5–LiI glass and glass–ceramic electrolytes | |
| Trevey et al. | High lithium ion conducting Li2S–GeS2–P2S5 glass–ceramic solid electrolyte with sulfur additive for all solid-state lithium secondary batteries | |
| Xu et al. | Recent developments of all‐solid‐state lithium secondary batteries with sulfide inorganic electrolytes | |
| Wang et al. | Improved performance all-solid-state electrolytes with high compacted density of monodispersed spherical Li1. 3Al0. 3Ti1. 7 (PO4) 3 particles | |
| CN108832172B (en) | All-solid-state electrolyte material, preparation method thereof and all-solid-state lithium secondary battery | |
| CN112018458B (en) | Sulfide-polymer composite solid electrolyte and preparation method and application thereof | |
| Wan et al. | A first principle study of the phase stability, ion transport and substitution strategy for highly ionic conductive sodium antipervoskite as solid electrolyte for sodium ion batteries | |
| Trevey et al. | Preparation of Li2S–GeSe2–P2S5 electrolytes by a single step ball milling for all-solid-state lithium secondary batteries | |
| Okumura et al. | All-solid-state batteries with LiCoO2-type electrodes: realization of an impurity-free interface by utilizing a cosinterable Li3. 5Ge0. 5V0. 5O4 electrolyte | |
| Ooura et al. | A new lithium-ion conducting glass ceramic in the composition of 75Li2S· 5P2S3· 20P2S5 (mol%) | |
| CN111403805A (en) | Composite solid electrolyte, preparation method thereof and lithium ion battery | |
| CN100486024C (en) | Lithium-lanthanum-silicon-sulfur solid electrolyte material for secondary lithium cell and its preparing method | |
| CN100486025C (en) | Li2S-Al2S3 solid electrolyte material for secondary lithium cell and its preparing method | |
| Huan et al. | Factors influencing Li+ migration in garnet-type ceramic electrolytes | |
| Gao et al. | Sb‐and O‐Cosubstituted Li10SnP2S12 with High Electrochemical and Air Stability for All‐Solid‐State Lithium Batteries | |
| Zhang et al. | Mechanistic insight into La2O3 dopants with high chemical stability on Li3PS4 sulfide electrolyte for lithium metal batteries |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20070808 Assignee: FSPG Hi-Tech Co., Ltd. Assignor: Shanghai Silicates Institute, the Chinese Academy of Sciences Contract record no.: 2017310000043 Denomination of invention: Solid electrolyte material system for all solid state lithium battery and preparation method Granted publication date: 20090805 License type: Common License Record date: 20170724 |
|
| EE01 | Entry into force of recordation of patent licensing contract |