CN106159320A - A kind of modified LAGP solid electrolyte material and preparation method thereof - Google Patents
A kind of modified LAGP solid electrolyte material and preparation method thereof Download PDFInfo
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- CN106159320A CN106159320A CN201610710455.1A CN201610710455A CN106159320A CN 106159320 A CN106159320 A CN 106159320A CN 201610710455 A CN201610710455 A CN 201610710455A CN 106159320 A CN106159320 A CN 106159320A
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- solid electrolyte
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- lagp
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- 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 present invention relates to a kind of modified LAGP solid electrolyte material and preparation method thereof.Described modified LAGP solid electrolyte material is the New Solid electrolyte that inorganic electrolyte material LAGP and material modified Y is composited, and its general structure is Li1.5Al0.5Ge1.5P3O12XY, wherein Y is a kind of material modified, x=0.5 3.The preparation method of described modified LAGP solid electrolyte material, comprises the following steps: (1) ball milling mixing raw material；(2) be dried prepare solid electrolyte precursor powder；(3) high temperature sintering solid electrolyte precursor powder.Products therefrom is described modified LAGP solid electrolyte material.
Description
Technical field
The invention belongs to new energy field, particularly to a kind of modified LAGP solid electrolyte material and preparation method thereof.
Background technology
All-solid lithium-ion battery is as the accumulation power supply of a new generation, because it possesses higher energy density, excellent electricity
Chemical stability and the advantage such as nonflammable and receive much concern.Last century, the seventies rose, and solid electrolyte material enters at a high speed
Developing period.Polymer dielectric, perofskite type oxide material, sulfuration crystallization lithium superionic conductors material, glass ceramics material
The solid electrolyte materials such as material have all obtained certain applications in all-solid lithium-ion battery system, but the ion-conductance of this kind of material
Conductance is still less than conventional liquid organic bath, and therefore its development receives and significantly limits.The solid phase of Recent study
Crystalline material such as LGPS, LAGP etc. the most also possess higher ionic conductivity and wider potential window, thus cause
The biggest concern of academia.
But this type of solid electrolyte exists the problems such as mechanical strength is the highest because material is more crisp, this leverages complete solid
The life-span of state lithium ion battery and security performance.For solving the problems referred to above, the most relatively conventional method is at solid electrolyte
Surface meet one layer of ceramic material.Although taking this method to improve the machinery of solid electrolyte material to a certain extent
Intensity, but the low conductivity of ceramic material will have a strong impact on the ionic conductivity of solid electrolyte material.Therefore ionic conductivity
With the contradiction between mechanical strength becomes the big factor limiting all-solid lithium-ion battery development at present.
Summary of the invention
Present invention is primarily targeted at improvement above-mentioned technology when present in problem, it is provided that one has both macroion conductance
New Solid electrolyte of rate and high mechanical properties and preparation method thereof.For improving above-mentioned technical problem, the present invention provides
Scheme be:
A kind of modified LAGP solid electrolyte material is provided.Described modified LAGP solid electrolyte material is inorganic electrolyte
The New Solid electrolyte that material LAGP and material modified titanium dioxide are composited, its general structure is
Li1.5Al0.5Ge1.5P3O12·xY。
As further improving, described material modified Y is silicon dioxide or titanium dioxide.
As further improving, the x=0.5-3 in described general structure.
The preparation method of a kind of modified LAGP solid electrolyte material is provided, comprises the steps of
Step A: LAGP and material modified Y is mixed according to the molar ratio in general structure, and is milled to powder
Shape, is dissolved in pressed powder in the middle of organic solvent, and agitating solution is to mix homogeneously.
Step B: the mixed solution in drying steps A obtains solid electrolyte precursor powder.
Step C: the solid electrolyte precursor powder prepared in step B is placed in closed quartz tube, in argon gas atmosphere
Middle heated quarty tube is to 600-900 DEG C and is incubated 24-48 hour, i.e. prepares described modified LAGP solid electrolyte material.
As further improving, the Ball-milling Time in described step A is 4-6 hour.
As further improving, the drum's speed of rotation in described step A is 200-600rpm.
As further improving, the organic solvent in described step A be glycol dimethyl ether, diethylene glycol dimethyl ether,
TRIGLYME, tetraethyleneglycol dimethyl ether, NHD, N-N dimethylformamide, oxolane, 1-3-bis-
At least one in oxygen pentane, thioether, carbonate-based solvent or multiple mixture.
As further improving, the drying means in described step B is vacuum drying, lyophilization, pneumatic conveying drying, micro-
Ripple be dried at least one.
As further improving, the argon gas atmosphere purity in described step C is 99.99%.
As further improving, the rate of heat addition in described step C is 0.2-5 DEG C/min.
Accompanying drawing explanation
Fig. 1 illustrates the charging and discharging curve using modified LAGP solid electrolyte material lithium-sulfur cell.
Detailed description of the invention
The present invention proposes a kind of new modified LAGP solid electrolyte material and preparation method thereof.Described modified LAGP is solid
State electrolyte achieves material by the way of composite inorganic electrolyte LAGP and material modified earth silicon/titanic oxide
Have both the excellent properties of high ionic conductivity and high mechanical properties.With detailed description of the invention the present invention done below in conjunction with the accompanying drawings into
One step describes in detail.
Embodiment one
Solid electrolyte material LAGP and material modified TiO2 is placed in ball mill with the molar ratio of 2:1 and with
The rotating speed ball milling of 400rpm 5 hours is to powder.Gained pressed powder is dissolved in glycol dimethyl ether and N-N dimethyl formyl
In the middle of the 1:1 mixed solution of amine, electromagnetic agitation solution is to mix homogeneously.This mixed solution of vacuum lyophilization prepares solid state electrolysis
Matter precursor powder.Solid electrolyte precursor powder is placed in closed quartz tube, in the argon gas atmosphere of 99.99% purity
To 750 DEG C and it is incubated 36 hours with the speed heated quarty tube of 2 DEG C/min, i.e. prepares described modified LAGP after room temperature cooling solid
State electrolyte.
Embodiment two
Solid electrolyte material LAGP and material modified TiO2 is placed in ball mill with the molar ratio of 1:1 and with
The rotating speed ball milling of 400rpm 5 hours is to powder.Gained pressed powder is dissolved in glycol dimethyl ether and N-N dimethyl formyl
In the middle of the 1:1 mixed solution of amine, electromagnetic agitation solution is to mix homogeneously.This mixed solution of vacuum lyophilization prepares solid state electrolysis
Matter precursor powder.Solid electrolyte precursor powder is placed in closed quartz tube, in the argon gas atmosphere of 99.99% purity
To 800 DEG C and it is incubated 12 hours with the speed heated quarty tube of 2 DEG C/min, i.e. prepares described modified LAGP after room temperature cooling solid
State electrolyte.
Embodiment three
Solid electrolyte material LAGP and material modified TiO2 is placed in ball mill with the molar ratio of 1:2 and with
The rotating speed ball milling of 400rpm 5 hours is to powder.Gained pressed powder is dissolved in glycol dimethyl ether and N-N dimethyl formyl
In the middle of the 1:1 mixed solution of amine, electromagnetic agitation solution is to mix homogeneously.This mixed solution of vacuum lyophilization prepares solid state electrolysis
Matter precursor powder.Solid electrolyte precursor powder is placed in closed quartz tube, in the argon gas atmosphere of 99.99% purity
To 850 DEG C and it is incubated 36 hours with the speed heated quarty tube of 2 DEG C/min, i.e. prepares described modified LAGP after room temperature cooling solid
State electrolyte.
Embodiment four
Solid electrolyte material LAGP and material modified SiO2 is placed in ball mill with the molar ratio of 1:3 and with
The rotating speed ball milling of 400rpm 5 hours is to powder.Gained pressed powder is dissolved in glycol dimethyl ether and N-N dimethyl formyl
In the middle of the 1:1 mixed solution of amine, electromagnetic agitation solution is to mix homogeneously.This mixed solution of vacuum lyophilization prepares solid state electrolysis
Matter precursor powder.Solid electrolyte precursor powder is placed in closed quartz tube, in the argon gas atmosphere of 99.99% purity
To 750 DEG C and it is incubated 36 hours with the speed heated quarty tube of 2 DEG C/min, i.e. prepares described modified LAGP after room temperature cooling solid
State electrolyte.
Fig. 1 shows the charging and discharging curve of one group of experiment lithium sulfur solid state battery.This lithium sulfur solid state battery have employed by upper
Modified LAGP material prepared by method described in embodiment four of stating is as cell electrolyte materials.It will be seen that battery charging and discharging
Stable performance.In 31 charge and discharge cycles, battery Average specific capacities is 360mAh/g, and coulombic efficiency is about 88%.Use this
In invention, modified LAGP electrolyte is as the lithium-sulfur cell of cell electrolyte materials, and its charge-discharge performance is common with employing
The lithium-sulfur cell of LAGP electrolyte is essentially identical.But the modification in the present invention, LAGP material carried out so that LAGP class is solid
The mechanical performance of state electrolyte significantly improves, reduce because of solid electrolyte mechanical damage cause battery failure probability, from
And improve cycle-index and the service life of battery.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto.
Any those familiar with the art is within the technical scope that disclosed herein, according to technical scheme
And inventive concept carries out equivalent or change, all should contain within protection scope of the present invention.
Claims (10)
1. a modified LAGP solid electrolyte material, it is characterised in that described solid electrolyte material is LAGP and modified material
The combination product of material Y, its general structure is Li1.5Al0.5Ge1.5P3O12·xY。
Modified LAGP solid electrolyte material the most according to claim 1, it is characterised in that material modified Y is titanium dioxide
Silicon or titanium dioxide.
Modified LAGP solid electrolyte material the most according to claim 1, it is characterised in that x=0.5-3.
4., according to a preparation method for the modified LAGP solid electrolyte material described in claim 1-3 any one, it is special
Levy and be, comprise the steps of
Step A: carry out mixing and being milled to powder according to the molar ratio in general structure by LAGP and material modified Y, will
Pressed powder is dissolved in the middle of organic solvent, and agitating solution is to mix homogeneously；
Step B: the mixed solution in drying steps A, obtains solid electrolyte precursor powder；
Step C: the solid electrolyte precursor powder prepared in step B is placed in closed quartz tube, adds in argon gas atmosphere
Hot quartz ampoule is to 600-900 DEG C, and is incubated 24-48 hour, i.e. prepares described modified LAGP solid electrolyte material.
The preparation method of modified LAGP solid electrolyte material the most according to claim 4, it is characterised in that described step
Ball-milling Time in A is 4-6 hour.
The preparation method of modified LAGP solid electrolyte material the most according to claim 4, it is characterised in that described step
Drum's speed of rotation in A is 200-600rpm.
The preparation method of modified LAGP solid electrolyte material the most according to claim 4, it is characterised in that described step
Organic solvent in A is glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, poly-second
In glycol dimethyl ether, N-N dimethylformamide, oxolane, 1-3-dioxolane, thioether, carbonate-based solvent at least one
Kind or multiple mixture.
The preparation method of modified LAGP solid electrolyte material the most according to claim 4, it is characterised in that described step
Drying means in B is at least one in vacuum drying, lyophilization, pneumatic conveying drying, microwave drying.
The preparation method of modified LAGP solid electrolyte material the most according to claim 4, it is characterised in that described step
Argon gas atmosphere purity in C is 99.99%.
The preparation method of modified LAGP solid electrolyte material the most according to claim 4, it is characterised in that described step
The rate of heat addition in rapid C is 0.2-5 DEG C/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110554078A (en) * | 2019-09-27 | 2019-12-10 | 溧阳天目先导电池材料科技有限公司 | Method for detecting LATP (LATP) of solid electrolyte lithium titanium aluminum phosphate |
| KR102059494B1 (en) * | 2018-03-09 | 2019-12-26 | 한국화학연구원 | Composite electrolyte for secondary battery and method of preparing thereof |
| CN115732751A (en) * | 2022-11-28 | 2023-03-03 | 蜂巢能源科技(无锡)有限公司 | Halide solid electrolyte material, preparation method thereof and lithium ion battery |
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| CN101325094A (en) * | 2008-07-25 | 2008-12-17 | 清华大学 | Lithium lanthanum titanium oxygen LLTO composite solid-state electrolyte material and synthesizing method thereof |
| CN104659412A (en) * | 2015-01-29 | 2015-05-27 | 中国科学院物理研究所 | Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery |
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| CN1512518A (en) * | 2002-12-27 | 2004-07-14 | 中国科学院物理研究所 | Composite electrolyte and its use |
| CN101325094A (en) * | 2008-07-25 | 2008-12-17 | 清华大学 | Lithium lanthanum titanium oxygen LLTO composite solid-state electrolyte material and synthesizing method thereof |
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| KR102059494B1 (en) * | 2018-03-09 | 2019-12-26 | 한국화학연구원 | Composite electrolyte for secondary battery and method of preparing thereof |
| CN110554078A (en) * | 2019-09-27 | 2019-12-10 | 溧阳天目先导电池材料科技有限公司 | Method for detecting LATP (LATP) of solid electrolyte lithium titanium aluminum phosphate |
| CN110554078B (en) * | 2019-09-27 | 2022-02-22 | 溧阳天目先导电池材料科技有限公司 | Method for detecting LATP (LATP) of solid electrolyte lithium titanium aluminum phosphate |
| CN115732751A (en) * | 2022-11-28 | 2023-03-03 | 蜂巢能源科技(无锡)有限公司 | Halide solid electrolyte material, preparation method thereof and lithium ion battery |
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