CN105932327B - A kind of preparation method of cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano material - Google Patents
A kind of preparation method of cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano material Download PDFInfo
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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
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
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- 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 provides a kind of preparation methods of cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano material, using simple solution combustion synthetic technology, it is thermally treated to obtain solid electrolyte material, there is higher conductivity at room temperature, it can be as the solid electrolyte of all-solid-state battery.Solution combustion synthetic method prepares simple, prepared presoma one-step synthesis, and Elemental redistribution is uniform.The lamellar spacing of granular precursor is at 100 200 nanometers, large specific surface area, and when high temperature is conducive to elements diffusion, fully reacts.This method has great technical advantage relative to other sol-gal processes, solid phase method：It is at low cost, yield is big, easy to operate, industrialized production can be carried out.
Description
Technical field
The invention belongs to novel energy resource material technology fields, and in particular to the preparation of lithium lanthanum zirconium oxygen solid electrolyte nano material
Method.
Background technology
The energy and environmental protection are two big key factors of current sustainable economic development.Long-term a large amount of combustion of fossil fuel,
The non-renewable energy is not only increasingly consumed, but also has had resulted in quite serious air pollution.Use lithium ion battery etc.
Clean energy resource is extremely urgent to replace the fossil fuel of pollution, therefore occurs a large amount of lithium electric equipment in the market.Contain
There is the conventional lithium ion battery of liquid state organic electrolyte, it may occur however that electrolyte leakage, the burning even danger of explosion.With more
The all-solid-state battery of the solid electrolyte substitution conventional liquid organic electrolyte of safety is just attracting more and more concerns.Electric vehicle
(EV) it increases sharply with the application demand of the large-sized battery of Locating Type electric power storage purposes, it can be expected that the solid state battery of safety and long-life are
As a candidate products.In terms of the battery of new generation for pursuing high capacity, the importance of solid electrolyte figure
Increasingly improving.
Traditional commercial Li-ion batteries, using flammable organic electrolyte, there is electrolyte leakage, burning, explosions
Etc. hidden danger.Lithium sulphur, lithium sky battery, and often use lithium metal to improve the novel battery cathode of energy density, and lithium branch
Brilliant generation can cause battery short circuit, influence to use safely.Using the all-solid-state battery of solid electrolyte, by its solid electrolyte
It is non-combustible, corrosion-free, do not reveal, and the growth of Li dendrite can be prevented, fundamentally solve the short circuit problem of battery, carry
High security is also beneficial to the invention application of high energy density cells.In the solid lithium ion electrolyte reported, tool
There is the oxide lithium lanthanum zirconium oxygen (LLZO) of garnet structure that there are comprehensive excellent properties：High lithium ion conductivity；Lithium ion
Transport number is about 1；Electrochemical window mouth width (>7V vs.Li+/Li)；Lithium metal is stablized；To air stability height；It is easily operated,
It is very ideal solid electrolyte material.
However just at present, the production technology of lithium lanthanum zirconium oxygen solid electrolyte at home and abroad never obtains important prominent
It is broken, seriously constrain the application of all-solid-state battery.The method for making lithium lanthanum zirconium oxygen solid electrolyte in worldwide mainly has
Two kinds：Solid phase method and sol-gal process.Solid-phase process preparation is complicated, generally requires multiple ball milling and heat treatment process, cost
It is higher, better performances；Sol-gal process preparation process is relatively easy, but obtained electrolyte performance is insufficient, relatively
Solid phase method, the low 1-3 order of magnitude of conductivity at room temperature.Other preparation processes mostly use advanced instrument equipment, are unfavorable for dropping
Low cost and scale application.The present invention uses a kind of lithium lanthanum zirconium oxygen preparation process the simplest so far in the world, at
This is low, and less energy consumption, yield is big, and prepared electrolyte superior performance solves large-scale industrial production solid state electrolysis
The technical barrier of matter, and gained electrolyte particle can prepare thin electrolyte films to reduce cell body in nanosized
Product has high meaning to the marketization application of all-solid-state battery, promotes the arrival in all-solid-state battery epoch.
Invention content
The present invention mainly uses nitrate for raw material, and dopant is added, and solution combustion synthesizes the presoma of lithium lanthanum zirconium oxygen,
By tabletting, calcining, method that is simple and preparing lithium lanthanum zirconium oxygen solid electrolyte on a large scale, the lithium lanthanum zirconium oxygen being prepared are provided
Solid electrolyte has excellent chemical property, can be used as the electrolyte of all-solid-state battery.And this method have at
This is low, and yield is big, easy to operate, and purity is high, the advantages that being suitble to produce in enormous quantities, solves current lithium lanthanum zirconium oxygen industrialized production
Difficult problem.
To achieve the above object, technical scheme is as follows：
A kind of preparation method of cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano material, includes the following steps：
Include the following steps：
A precursor powder) is prepared using solution combustion synthetic method；
B) presoma obtains lithium lanthanum zirconium oxygen solid electrolyte through pyroreaction；
C) solid electrolyte that pyroreaction obtains obtains lithium lanthanum zirconium oxygen nano material after ball milling.
The step A) raw material includes：Commercial lithium nitrate, lanthanum nitrate, zirconium nitrate, glycine etc. are not necessarily to any pretreatment,
Lithium nitrate, lanthanum nitrate, zirconium nitrate, glycine and dopant are dissolved in deionized water in molar ratio, are placed in electric furnace heating, solution
Combustion reaction occurs after being evaporated, white precursor powder is obtained after several seconds.
The precursor powder bulk multi-hole, internal is two-dimensional slice structure, 100-300 nanometers of lamellar spacing, piece
There is the hole of 30-200nm in layer, ingredient is mostly zirconic acid lanthanum.
The wherein described step B) include：Precursor powder is ground in mortar first, then by precursor powder in 100-
300MPa depresses to diameter 10-15mm, the disk of thickness 1-3mm, then 700-1000 DEG C of roasting 2-8h under air atmosphere, finally
Obtain lithium lanthanum zirconium oxygen solid electrolyte；
Obtained lithium lanthanum zirconium oxygen solid electrolyte potsherd is white disk, and consistency is low, frangible, internal particle size 1-
3um。
The wherein described step C) include：By the cubic phase lithium lanthanum zirconium oxygen solid electrolyte potsherd obtained after roasting in mortar
Middle grinding, then in planetary ball mill ball milling 6-10h, rotational speed of ball-mill 300-400r/min, the powder obtained after ball milling is i.e. cube
Phase lithium lanthanum zirconium oxygen nano material.
Obtained lithium lanthanum zirconium oxygen nano-grain size 50-600nm.
The dopant include silicon source, tantalum source, niobium source, tungsten source it is one or more, wherein silicon source includes
Aluminum nitrate etc., tungsten source include ammonium metatungstate etc..
Beneficial effects of the present invention are：
1, the raw material sources employed in the present invention are abundant, and cheap, entire technique very simple can extensive flowing water
Line produces.Complete reference is provided for a series of processing of allied substances.
2, prepared lithium lanthanum zirconium oxygen solid electrolyte has high ionic conductivity, can be as the electricity of all-solid-state battery
Xie Zhi greatly improves safety and the capacity of battery.
3, the lithium lanthanum zirconium oxygen of cubic phase 2 orders of magnitude higher than the conductivity of tetragonal phase lithium lanthanum zirconium oxygen, and particle is due to tool
There is higher specific surface area, it is possible to reduce element segregation and raising agglutinating property improve boundary conductivity, to improve LLZO ceramics
Conductivity.
4, gained electrolyte can prepare thin electrolyte films to reduce battery volume and weight in nanosized.
5, the LLZO of nano particle can also be compound with the polymer such as PEO, prepares flexibility of the thickness within more than ten microns
Solid electrolyte is applied convenient for market.
Description of the drawings
Fig. 1 present invention prepares the stereoscan photograph of lithium lanthanum zirconium oxygen nano-powder；
The room temperature ac impedance spectroscopy of lithium lanthanum zirconium oxygen potsherd prepared by Fig. 2 present invention；
The Arrhenius curve of lithium lanthanum zirconium oxygen potsherd prepared by Fig. 3 present invention.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is only used for explaining the present invention, not
For limiting the present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiies
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to the thin of the present invention
It is detailed to describe some specific detail sections in section description.
The present invention provides a kind of preparation methods of lithium lanthanum zirconium oxygen solid electrolyte material, are synthetically prepared by solution combustion
Presoma, and doping element obtains cubic phase lithium lanthanum zirconium oxygen through high-temperature heat treatment；The lithium lanthanum zirconium oxygen electrolyte granular is several
Ten to hundreds of nanometers, particle shape is irregular, and the molar ratio containing element Li, Al, La, Zr, O is (5.5-7.7)：(0.1-
0.5)：3：2：(10-12).
The commercial nitrate of example 1 and glycine are raw material, are not necessarily to any pretreatment.15.4mmol nitric acid is weighed first
Lithium, 6mmol lanthanum nitrates, 4mmol zirconium nitrates, 0.48mmol aluminum nitrates and the dissolving of 12.94mmol glycine in deionized water, are set
In on electric furnace, combustion synthesis reaction occurs after being evaporated, obtains the powder body material of white puff for heating.By powder body material
The disk of diameter 15mm is cold-pressed at 300MPa, then 900 DEG C of 4h heat to obtain cubic phase lithium lanthanum zirconium oxygen in Muffle furnace.It will
Obtained cubic phase lithium lanthanum zirconium oxygen is through ball milling 10h, rotational speed of ball-mill 300r/min, and the powder after ball milling is cold-pressed into 300MPa again
The disk of diameter 15mm is fired into potsherd, 1 DEG C/min of heating rate through 1200 DEG C of 5h heat treatments.
Lithium lanthanum zirconium oxygen potsherd upper and lower surface metal spraying will be obtained, room temperature AC impedance is tested on electrochemical workstation, if
It is 0.1-1MHz to set parameter, and it is 3.54 × 10 to calculate its conductivity-4S/cm tests its conductivity at a temperature of 25-80 DEG C and obtains
Arrhenius curve simultaneously calculates its activation energy as 0.34eV.
The commercial nitrate of example 2 and urea are raw material, are not necessarily to any pretreatment.Weigh first 15.4mmol lithium nitrates,
6mmol lanthanum nitrates, 4mmol zirconium nitrates, 0.48mmol aluminum nitrates and the dissolving of 15mmol urea in deionized water, are placed in electric furnace
On, combustion synthesis reaction occurs after being evaporated, obtains the powder body material of white puff for heating.Powder body material is existed
The disk of diameter 15mm is cold-pressed under 200MPa, then 700 DEG C of 4h heat to obtain cubic phase lithium lanthanum zirconium oxygen in Muffle furnace.Will
The cubic phase lithium lanthanum zirconium oxygen arrived is through ball milling 15h, rotational speed of ball-mill 300r/min, and the powder after ball milling is cold-pressed into directly in 200MPa again
The disk of diameter 15mm is fired into potsherd, 1 DEG C/min of heating rate through 1200 DEG C of 4h heat treatments.
Lithium lanthanum zirconium oxygen potsherd upper and lower surface metal spraying will be obtained, room temperature AC impedance is tested on electrochemical workstation, if
It is 0.1-1MHz to set parameter, and it is 2.9 × 10 to calculate its conductivity-4S/cm, tested at a temperature of 25-80 DEG C its conductivity obtain Ah
Lun Niwusi curves simultaneously calculate its activation energy as 0.38eV.
The commercial nitrate of example 3 and glycine are raw material, are not necessarily to any pretreatment.15.4mmol nitric acid is weighed first
Lithium, 6mmol lanthanum nitrates, 4mmol zirconyl nitrates, 0.48mmol aluminum nitrates and the dissolving of 10mmol glycine in deionized water, are set
In on electric furnace, combustion synthesis reaction occurs after being evaporated, obtains the powder body material of white puff for heating.By powder body material
The disk of diameter 10mm is cold-pressed at 200MPa, then 800 DEG C of 4h heat to obtain cubic phase lithium lanthanum zirconium oxygen in Muffle furnace.It will
Obtained cubic phase lithium lanthanum zirconium oxygen is through ball milling 10h, rotational speed of ball-mill 300r/min, and the powder after ball milling is cold-pressed into 200MPa again
The disk of diameter 15mm is fired into potsherd, 1 DEG C/min of heating rate through 1200 DEG C of 5h heat treatments.
Lithium lanthanum zirconium oxygen potsherd upper and lower surface metal spraying will be obtained, room temperature AC impedance is tested on electrochemical workstation, if
It is 0.1-1MHz to set parameter, and it is 3.4 × 10 to calculate its conductivity-4S/cm, tested at a temperature of 25-80 DEG C its conductivity obtain Ah
Lun Niwusi curves simultaneously calculate its activation energy as 0.37eV.
The commercial nitrate of example 4 and urea are raw material, are not necessarily to any pretreatment.Weigh first 15.4mmol lithium nitrates,
6mmol lanthanum nitrates, 4mmol zirconyl nitrates, 0.48mmol aluminum nitrates and the dissolving of 15mmol urea in deionized water, are placed in electric furnace
On, it is heated while stirring, combustion synthesis reaction occurs after being evaporated, obtains the powder body material of white puff.By powder
Body material is cold-pressed into the disk of diameter 10mm at 200MPa, and then 700 DEG C of 4h heat to obtain cubic phase lithium lanthanum in Muffle furnace
Zirconium oxygen.By obtained cubic phase lithium lanthanum zirconium oxygen through ball milling 15h, rotational speed of ball-mill 300r/min, the powder after ball milling exists again
200MPa is cold-pressed into the disk of diameter 15mm, and potsherd, 1 DEG C/min of heating rate are fired into through 1200 DEG C of 5h heat treatments.
Lithium lanthanum zirconium oxygen potsherd upper and lower surface metal spraying will be obtained, room temperature AC impedance is tested on electrochemical workstation, if
It is 0.1-1MHz to set parameter, and it is 2.9 × 10 to calculate its conductivity-4S/cm, tested at a temperature of 25-80 DEG C its conductivity obtain Ah
Lun Niwusi curves simultaneously calculate its activation energy as 0.41eV.
Claims (3)
1. a kind of preparation method of cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano material, which is characterized in that include the following steps：
A precursor powder) is prepared using solution combustion synthetic method；
B) presoma obtains cubic phase lithium lanthanum zirconium oxygen solid electrolyte potsherd through pyroreaction；
C) the cubic phase lithium lanthanum zirconium oxygen solid electrolyte potsherd that pyroreaction obtains obtains cubic phase lithium lanthanum zirconium oxygen after ball milling
Solid electrolyte nano material；
The step A) raw material includes：Commercial lithium nitrate, lanthanum nitrate, zirconium nitrate, glycine, be not necessarily to any pretreatment, lithium nitrate,
Lanthanum nitrate, zirconium nitrate, glycine and dopant are dissolved in deionized water in molar ratio, electric furnace heating are placed in, after solution is evaporated
Combustion reaction occurs, white precursor powder is obtained after several seconds；
The precursor powder bulk multi-hole, internal is two-dimensional slice structure, 100-300 nanometers of lamellar spacing, in lamella
The also hole of 30-200nm, ingredient are mostly zirconic acid lanthanum；
The step B) include：Precursor powder is ground in mortar first, then by precursor powder at 100-300MPa
It is pressed into the disk of diameter 10-15mm, thickness 1-3mm, then 700-1000 DEG C of roasting 2-8h under air atmosphere, finally obtains cube
Phase lithium lanthanum zirconium oxygen solid electrolyte potsherd；
Obtained cubic phase lithium lanthanum zirconium oxygen solid electrolyte potsherd is white disk, and consistency is low, frangible, internal particle size
1-3um。
2. a kind of preparation method of cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano material according to claim 1, special
Sign is, the step C) include：The cubic phase lithium lanthanum zirconium oxygen solid electrolyte potsherd obtained after roasting is ground in mortar
It is broken, then in planetary ball mill ball milling 6-10h, rotational speed of ball-mill 300-400r/mi n, the powder i.e. cubic phase lithium obtained after ball milling
Lanthanum zirconium oxygen solid electrolyte nano material；Obtained cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano-grain size is in 50-
600nm。
3. a kind of preparation method of cubic phase lithium lanthanum zirconium oxygen solid electrolyte nano material according to claim 1, special
Sign is, the dopant include silicon source, tantalum source, niobium source, tungsten source it is one or more, wherein silicon source is aluminum nitrate, tungsten source
For ammonium metatungstate.
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| CN107162049A (en) * | 2017-06-05 | 2017-09-15 | 清华大学 | Lithium lanthanum zirconium epoxide oxide-based nanomaterial and preparation method thereof |
| CN109052473A (en) * | 2018-08-10 | 2018-12-21 | 淮安新能源材料技术研究院 | A kind of industrialized process for preparing of the zirconic acid lanthanum lithium solid electrolyte of tantalum aluminium codope |
| CN109378522B (en) * | 2018-10-22 | 2020-09-11 | 北京科技大学 | Preparation method of sodium zirconium silicon phosphorus composite solid electrolyte |
| CN109319837B (en) * | 2018-11-29 | 2020-12-01 | 江苏海基新能源股份有限公司 | Aluminum-containing cubic phase garnet Li7La3Zr2O12Preparation method of (1) |
| CN111732433A (en) * | 2020-07-02 | 2020-10-02 | 西安瑞智材料科技有限公司 | Preparation method of garnet type solid electrolyte with controllable particle size |
| CN112429770A (en) * | 2020-12-01 | 2021-03-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium lanthanum zirconium oxide particles, product and application thereof |
| CN113912120B (en) * | 2021-10-11 | 2023-05-12 | 福州大学 | Method for improving stability of lithium lanthanum zirconium oxygen cubic phase |
| CN115724463A (en) * | 2021-12-13 | 2023-03-03 | 湖州南木纳米科技有限公司 | Precursor material for preparing lithium lanthanum zirconium oxide |
| CN114349045B (en) * | 2021-12-28 | 2022-09-27 | 广东马车动力科技有限公司 | Preparation method of high-yield pure-phase lithium lanthanum zirconium oxide solid electrolyte material |
| CN114605152B (en) * | 2022-04-27 | 2022-11-29 | 佛山(华南)新材料研究院 | Cubic-phase lithium lanthanum zirconium oxide and preparation method thereof |
| CN115340378B (en) * | 2022-10-20 | 2023-02-03 | 江苏蓝固新能源科技有限公司 | Oxide solid electrolyte, preparation method thereof and lithium ion battery |
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| KR101568468B1 (en) * | 2013-07-04 | 2015-11-11 | 한국생산기술연구원 | SOLID ELECTROLYTE MATERIAL FOR All SOLID LITHIUM SECONDARY BATTERIES AND MANUFACTURING METHOD FOR THE SAME |
| CN103524128B (en) * | 2013-10-12 | 2016-04-20 | 南昌大学 | A kind of high-specific surface area yttria-stabilized zirconia cubic phase nano raw powder's production technology |
| CN104124467B (en) * | 2014-07-22 | 2016-06-01 | 武汉理工大学 | A kind of method utilizing lithium lanthanum zirconium oxygen presoma coated powder to prepare solid electrolyte |
| CN105406118A (en) * | 2015-12-30 | 2016-03-16 | 哈尔滨工业大学 | Ceramic solid electrolyte and preparation method thereof |
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