CN106887639A - One kind opens fluorine-based solid electrolyte material of framework and preparation method thereof - Google Patents
One kind opens fluorine-based solid electrolyte material of framework and preparation method thereof Download PDFInfo
- Publication number
- CN106887639A CN106887639A CN201510943654.2A CN201510943654A CN106887639A CN 106887639 A CN106887639 A CN 106887639A CN 201510943654 A CN201510943654 A CN 201510943654A CN 106887639 A CN106887639 A CN 106887639A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- framework
- fluorine
- based solid
- electrolyte material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
Fluorine-based solid electrolyte material of framework and preparation method thereof is opened the present invention relates to one kind, the chemical composition of the electrolyte is：AxMyFx+3y, wherein 0<X≤6,0<Y≤3, A is Na and/or Li, M are Al and/or Ga.It is of the invention to open the fluorine-based solid electrolyte material A of frameworkxMyFx+3yIt is rich lithium or rich sodium phase aluminium base or gallium base fluoride, present invention firstly provides the new application for opening frame structure prototype in fluoride solid electrolyte, and its rich lithiumation or rich sodium are realized simultaneously, by the concentration for increasing transportable alkali metal ion, be conducive to lifting its intrinsic ionic conductivity, by means such as nanosizing, disordering, surface modifications, the electrical conductivity of body phase and granule boundary can be improved.
Description
Technical field
The invention belongs to technical field of new energies, more particularly to a kind of solid lithium battery or sode cell to open framework fluorine-based
Solid electrolyte material, especially open framework richness lithium or rich fluorine-based solid electrolyte material of sodium and preparation method thereof.
Background technology
In recent years, with the raising of fossil fuel price and its increasingly sharpening for environmental pollution, for the need of clean energy resource
Ask particularly strong, especially the field such as energy storage system in electric automobile and based on green network, secondary cell using and promoting just
More energy are put into industrial circle and academia is made in the research of its new framework and critical material.It is currently based on organic electrolysis
The lithium ion battery of liquid system has the two large problems cannot to overcome, i.e. the high volatile and corrosivity of (1) electrolyte easily cause uneasiness
The complete and pollution to environment, (2) lithium metal is formed in the dendrite of electrode electrolyte interface and easily causes battery short circuit.Therefore need
All-solid-state battery framework and its solid electrolyte material is developed to solve the above problems.
The exploitation of wherein solid electrolyte is always the difficult point of solid state battery research, and the work of forefathers focuses mostly in crystalline phase and non-
The glass ceramics solid electrolyte of crystalline phase, such as Li of NASICON types1+xAlyGe2-y(PO4)3(LAGP), Ca-Ti ore type
La0.5Li0.5TiO3(LLTO), the Li of carbuncle type (garnet)7La3Zr2O12(LLZO), unformed LiPON
(LIPON), LISICON types and glass-ceramic type based on Li2S-P2S5Sulfide etc..Although oxide electrolyte exists
Stability is preferable in air, but big granule boundary resistance makes their overall conductivity have a greatly reduced quality, and the rare earth for containing
Metal price is expensive；And the electronegativity of S is less than oxygen, make the ionic conductivity of sulfide electrolyte commonly greater than oxide, and sulphur
Compound is easier densification, and their interfacial conductive rate can even be ignored, and have the disadvantage that air-sensitive (easily generates H2S), phase
Figure is complex, and influence of the component deviation to conductance is larger.Many unorganic glass ceramic electrolytes contain the unit of oxidation-reduction quality
Plain (such as Ti, Ge), potentially unstable when its interface contacts with lithium, this can limit its electrochemical stability windows.
Although lithium salts LiPF6It is widely used in lithium battery, but fluoride is still seldom reported as solid electrolyte
Road.The beginning of the eighties, Hitachi, Ltd reported unbodied LiF-AlF3And NaF-AlF3Thin film system, finds conductance with compound
Thing measures the difference of ratio and changes, but optimal conductivity at room temperature rate still only 10-7-10-6S/cm；Northeastern Japan is big within 2012
Learn and propose Li3AlF6Be conducive to the lithium high at being obviously improved for lithium ion conducting rate, particularly granule boundary with LiCl mixing and ball millings
Ionic conduction characteristic, but its conductivity at room temperature rate also only has 2 × 10-6S/cm.Recently, Li and Maier etc. is lacked by heterogeneous interface
The regulation and control of chemistry and space charge effect are fallen into, 3 magnitudes of the progressively disordering and its ionic conductivity to LiF films are realized
Increase, realize transformations of the LiF from insulator to fast-ionic conductor, its conductivity values is close to thin-film electrolyte best at present
The level of LiPON；Lu and Archer etc. adds LiF nano particles in organic electrolyte, and the electricity for effectively improving lithium sinks
Product, it is suppressed that the growth of dendrite.Electrolysis of fluorides matter has potential advantage compared with oxide ceramic electrolyte：(1) can be real
The nanosizing of existing morphology controllable, (2) reduce granule boundary resistance, and (3) eliminate the use of expensive rare earth metal；With testing sulphide
Than fluoride is more stablized in atmosphere.Rich lithium (sodium) mutually and open framework strategy be develop fluoride solid electrolyte it is new
Architecture prototyping provides brand-new thinking.
In sum, this area be badly in need of a kind of high ion conductivity of exploitation, low electronic conductivity, electrochemical window wide it is complete
The fluorine-based solid electrolyte material system of solid state lithium battery or sode cell, and the production technology of material is easy, is adapted to extensive
Using.
The content of the invention
The fluorine-based solid state electrolysis material of framework is opened it is an object of the invention to provide a kind of solid lithium battery or sode cell
Material, frame structure prototype is mutually opened to provide new rich lithium phase or rich sodium.
Here, the present invention provides one kind opens the fluorine-based solid electrolyte material of framework, its chemical composition is：
AxMyFx+3y, wherein 0<X≤6,0<Y≤3, A is Na and/or Li, M are Al and/or Ga.
It is of the invention to open the fluorine-based solid electrolyte material A of frameworkxMyFx+3yIt is rich lithium or rich sodium phase aluminium base or gallium base fluoride,
Present invention firstly provides the new application for opening frame structure prototype in fluoride solid electrolyte, and its rich lithiumation is realized simultaneously
Or rich sodium, by increasing the concentration of transportable alkali metal ion, be conducive to lifting its intrinsic ionic conductivity, by nanometer
The means such as change, disordering, surface modification, can improve the electrical conductivity of body phase and granule boundary.This fluorine-based electrolyte need not make
With expensive thulium, it is not required that use the transition metal of redox active.Solid electrolyte of the invention
Can be used for the construction of perfluoro-compound solid state battery, to suppress positive pole-electrolyte solid solid interface migration of element (electronegativity particularly high
Element) cell performance decay that causes.And material of the present invention does not produce poisonous and harmful substance in preparation process is produced,
Environmental protection, and synthetic method is easily operated, technological process is simple, easily realizes scale volume production.
It is preferred that 3≤x≤6,1≤y≤3.
It is preferred that the electrolyte is Li3AlF6、Na3Li3Al2F12、LiNa2AlF6、Na3AlF6、
Na5Al3F14、Li3GaF6、Na3Li3Ga2F12、Na3GaF6、Na5Ga3F14In one kind.
Present invention also offers this method for opening the fluorine-based solid electrolyte material of framework is prepared, to expand it on doping and surface
The improvement potentiality of the aspects such as modification, overcome technical problem present in current all-solid-state battery framework and its crucial electrolyte.
The invention provides a kind of preparation method for opening the fluorine-based solid electrolyte material of framework, the electrolyte is using high
Warm synthesis in solid state, comprises the following steps：By AxMyFx+3yIn each metallic element fluoride as raw material according to stoichiometry
Than mixing；Mixture compressing tablet, sealing are incubated 5~15 hours, obtain out the fluorine-based solid state electrolysis of framework in 500~700 DEG C
Material.
It is preferred that high temperature process heat is carried out under an inert atmosphere.
Present invention also offers a kind of preparation method for opening the fluorine-based solid electrolyte material of framework, the electrolyte is used
High-energy ball milling synthesizes, and comprises the following steps：By AxMyFx+3yIn each metallic element fluoride as raw material according to chemistry count
Amount is than mixing；Raw mixture and solvent are carried out into ball milling, raw mixture, solvent, the amount ratio of abrading-ball are 1g：(0~
60)mL：(10~60) g, preferably 1g：(4~6) mL：(25~45) g, 500~800 revs/min of rotational speed of ball-mill
Clock, ball milling 5~10 hours is washed after ball milling, dried, and obtains out the fluorine-based solid electrolyte material of framework.
Synthesize this solid electrolyte, this machine from precursor material direct in-situ using high-energy ball milling method first in the present invention
Tool course of reaction is conducive to the nanosizing and structural disorder of electrolyte simultaneously, with realize defect sturcture that fast ion transmits and
The formation of multi phase interface, improves ionic conductivity, reduces activated energy barrier.
It is preferred that the solvent is at least one in 1-METHYLPYRROLIDONE, anhydrous propanone, absolute ethyl alcohol, anhydrous isopropyl alcohol
Kind.
Present invention also offers a kind of preparation method for opening the fluorine-based solid electrolyte material of framework, the electrolyte is based on
The deposition synthesis of ionic liquid, comprises the following steps：By AxMyFx+3yIn the salt of each metallic element stoichiometrically add
Contain anion BF4 -Ion liquid solvent in, at 25~100 DEG C stir 6~12 hours, be precipitated thing；Will precipitation
Thing is washed, dried, and obtains out the fluorine-based solid electrolyte material of framework.
This solid electrolyte is prepared using the deposition synthesis based on ionic liquid first in the present invention, is conducive to its nanometer
The control of pattern sum and the surface modification of ionic liquid composition, to realize intergranular being fully contacted and granule boundary conductive region
Formed, reduce granule boundary resistance.
It is preferred that in deposition synthesis, the salt of M element is (1~2) g with the amount ratio of ionic liquid：10mL.
The present invention also aims to provide a kind of all-solid-state battery, especially solid lithium battery or all solid state sode cell,
The fluorine-based solid electrolyte material of framework is opened including described.
Brief description of the drawings
Fig. 1 is the Li synthesized based on ionic liquid obtained by embodiment 13AlF6SEM figure；
Fig. 2 is the Li synthesized based on ionic liquid obtained by embodiment 13AlF6XRD；
Fig. 3 is the Na synthesized based on ionic liquid obtained by embodiment 23AlF6XRD；
Fig. 4 is the Na synthesized based on ionic liquid obtained by embodiment 23AlF6In the Arrhenius of different lifting thermophases
Figure；
Fig. 5 is the Na synthesized based on high temperature solid state reaction obtained by embodiment 33Li3Al2F12XRD；
Fig. 6 is the Na synthesized based on high temperature solid state reaction obtained by embodiment 33Li3Al2F12In the Allan Buddhist nun of different lifting thermophases
Wu Situ；
Fig. 7 is the Na being synthesized based on high-energy ball milling obtained by embodiment 43Li3Ga2F12In the exchange resistance of different lifting thermophases
Anti- figure；
Fig. 8 is the Na being synthesized based on high-energy ball milling obtained by embodiment 43Li3Ga2F12As solid electrolyte Na4Fe(CN)6
As positive pole, sodium piece as negative pole, the electrochemical profiles figure of all solid state sode cell for obtaining.
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following implementation methods, it should be appreciated that following implementation methods are only used for
The bright present invention, is not intended to limit the present invention.
The fluorine-based solid electrolyte material of framework is opened for solid lithium battery or sode cell the invention provides a kind of, is proposed
The new application for opening frame structure prototype in fluoride solid electrolyte, and its rich lithiumation or rich sodium are realized simultaneously, without
Use expensive thulium, it is not required that use the transition metal of redox active.The present invention is also provided simultaneously
Prepared by high temperature solid state reaction, high-energy ball milling, the deposition process based on ionic liquid and this open the fluorine-based solid electrolyte of framework
The method of material, to expand its improvement potentiality at the aspect such as doping and surface modification, overcome current all-solid-state battery framework and its
Technical problem present in crucial electrolyte.In addition, opening the fluorine-based solid electrolyte of framework present invention also offers including described
The all-solid-state battery of material.
The chemical formula for opening the fluorine-based solid electrolyte material of framework of the invention is AxMyFx+3y, wherein 0<X≤6,0<Y≤3, it is excellent
Selection of land, 3≤x≤6,1≤y≤3, A is Na and/or Li, M are Al and/or Ga.The electrolyte is by rich lithium phase or richness
The aluminium base or gallium base fluoride of sodium phase are constituted.In one example, the chemical formula of the electrolyte is NaaLix- aMyFx+3y, 0≤a≤x.As a ＜ x-a, the electrolyte is rich lithium phase.The electrolyte of rich lithium phase is preferably suitable
For solid lithium battery.As a >=x-a, the electrolyte is rich sodium phase.The electrolyte of rich sodium phase is preferably
Suitable for all solid state sode cell.Used as an example, in the electrolyte, rich lithium phase aluminium base fluoride can be
Li3AlF6, rich sodium phase aluminium base fluoride can be Na3Li3Al2F12(garnet)、LiNa2AlF6(simmonsite)、Na3AlF6
(cryolite)、Na5Al3F14(chiolite) one kind in, rich lithium phase gallium base fluoride can be Li3GaF6, rich sodium phase gallium base fluorination
Thing can be Na3Li3Ga2F12、Na3GaF6、Na5Ga3F14In one kind.
The method that the fluorine-based solid electrolyte material of framework is opened described in high temperature solid state reaction synthesis is conducive to improving product purity, tool
There are the potentiality of follow-up doping regulation and control.As an example, for example, comprise the following steps.
By a certain amount of LiF and/or NaF and AlF3And/or GaF3A is pressed under an inert atmospherexMyFx+3yChemistry meter
Amount is more uniform than ground and mixed, wherein, A is Na and/or Li, M are Al and/or Ga, for example：Synthesis Li3AlF6Or
Li3GaF6Required LiF：AlF3Or LiF：GaF3Mol ratio is 3:1, synthesize Na3Li3Al2F12Or Na3Li3Ga2F12Institute
The LiF for needing：NaF：AlF3Or LiF：NaF：GaF3Mol ratio is 1.5：1.5：1, synthesize LiNa2AlF6Required
LiF：NaF：AlF3Mol ratio is 1：2：1, synthesize Na3AlF6Or Na3GaF6Required NaF：AlF3Or NaF：
GaF3Mol ratio is 3:1, synthesize Na5Al3F14Or Na5Ga3F14Required NaF：AlF3Or NaF：GaF3Mol ratio is
5:3。
Then, by mixture compressing tablet, used as an example, such as a diameter of 10mm of disk, wafer thickness is 1-5mm,
Tableting pressure is 15-20MPa；Disk is sealed in the stainless steel cauldron filled with inert atmosphere, solid phase reaction is carried out, Gu
Phase reaction is carried out 5-15 hours at 500-700 DEG C, you can obtain required product.After high temperature solid state reaction, product is smash
It is broken, fine homogeneous are ground to, or characterized for physical property, or pressure target (thickness is 1mm) is (double for conductivity test again
Plate Au electrodes, a diameter of 8mm in face) or for all-solid-state battery test.
High-energy ball milling method synthesizes solid electrolyte of the invention from precursor material direct in-situ, and its automatic reaction process is favourable
In the nanosizing and structural disorder of electrolyte, to realize the formation of defect sturcture and multi phase interface that fast ion is transmitted, carry
High ion conductivity, reduces activated energy barrier.As an example, for example, comprise the following steps.
By a certain amount of LiF and/or NaF and AlF3And/or GaF3It is more mixed than grinding that product molar is pressed under an inert atmosphere
The step of closing uniform, the molar ratio ingredient of mixing is with above-mentioned high temperature process heat is identical.
Then, mixture and solvent are fitted into ball grinder in glove box.Wherein, raw mixture, solvent, abrading-ball
Amount ratio can be 1g：(0~60) mL：(10~60) g, preferably 1g：(4~6) mL：(25~45) g.It is described
Solvent includes but is not limited to 1-METHYLPYRROLIDONE (NMP), anhydrous propanone, absolute ethyl alcohol, anhydrous isopropyl alcohol.Show at one
In example, mixture 2.0-2.5g and NMP 10mL adds the zirconia ball grinding jar of 45mL (to include 75g, diameter 3mm
Zirconia ball) in.In glove box interior sealing, carried out under rotating speed 500-800r/min 5-10 hours；Washed after ball milling and taken out
Dry, you can obtain required product.For example, the condition of ball milling could be arranged to：Ball material mass ratio is 30:1, ball-milling reaction
Each circular flow 5min, stops 15min, totally 60 circulations, and ball-milling reaction is cooled to can opening after room temperature after terminating, equally
Sample is taken out as solvent using NMP, then centrifuge washing dries powder, or is characterized for physical property, or pressure target (thickness is
1mm, a diameter of 10mm) for conductivity test (two-sided plating Au electrodes, a diameter of 8mm) or for all-solid-state battery
Test.
Deposition based on ionic liquid synthesizes to prepare solid electrolyte of the invention, makes full use of the soft template of ionic liquid
Agent or structure directing agent function, using its surface defect sturcture to the physical/chemical adsorption of ionic liquid charged group, favorably
Control and the surface modification of ionic liquid composition in its nanotopography, to realize intergranular being fully contacted and granule boundary conduction
The formation in region, reduces granule boundary resistance.As an example, for example, comprise the following steps.
By a certain amount of AxMyFx+3yIn the salt of each metallic element press product molar than adding containing anion BF4 -Ion
Stirred 6-12 hours at 25-100 DEG C in liquid flux.As the salt of element A, including but not limited to carbonate (Li2CO3、
Na2CO3), nitrate (LiNO3、NaNO3), sulfate (Li2SO4、Na2SO4).As the salt of M element, including
But it is not limited to nitrate and/or its hydrate (such as Al (NO3)3·9H2O、Ga(NO3)3·xH2O), chloride and/or its water
Compound (such as AlCl3·xH2O、GaCl3·xH2O).In one example, raw material is Li2CO3And/or Na2CO3And
Al(NO3)3·9H2O and/or Ga (NO3)3·xH2O.For example：Synthesis Li3AlF6Or Li3GaF6Required Li2CO3：
Al(NO3)3·9H2O or Li2CO3：Ga(NO3)3·xH2O mol ratios are 1.5:1, synthesize Na3Li3Al2F12Or
Na3Li3Ga2F12Required Li2CO3：Na2CO3：Al(NO3)3·9H2O or Li2CO3：Na2CO3：Ga(NO3)3·xH2O
Mol ratio is 0.75：0.75：1, synthesize LiNa2AlF6Required Li2CO3：Na2CO3：Al(NO3)3·9H2O mol ratios are
0.5：1：1, synthesize Na3AlF6Or Na3GaF6Required Na2CO3：Al(NO3)3·9H2O or Na2CO3：
Ga(NO3)3·xH2O mol ratios are 1.5:1, synthesize Na5Al3F14Or Na5Ga3F14Required Na2CO3：
Al(NO3)3·9H2O or Na2CO3：Ga(NO3)3·xH2O mol ratios are 2.5:3.Described ionic liquid can be by tetrafluoro
The low temperature molten salt that borate anion and cation group are constituted, cation is organic cation, selected from 1,3- dialkyl group
Substituted imidazol ion, the alkyl-substituted pyridinium ions of N-, alkyl quaternary ammonium ion, alkyl quaternary are seen ion.With 1-2g's
Al(NO3)3·9H2O or Ga (NO3)3·xH2Precursor mixture on the basis of O is added in the ionic liquid of 10mL, in difference
In reaction temperature and different ionic liquid environment, hydrolysis rate and positive and negative group distributed mutually characteristic according to ionic liquid adjust product
The nucleation of thing and growth, form the sediment of different nanostructureds or different surfaces modification.
Then, sediment centrifuge washing is dried, you can obtain required product, for example, by sediment anhydrous propanone
Centrifuge washing 3-5 times, then dries powder, or is characterized for physical property, or pressure target (thickness is 1mm, a diameter of 10mm)
For conductivity test (two-sided plating Au electrodes, a diameter of 8mm) or for all-solid-state battery test.
What the present invention was provided can be all solid lithium electricity including the all-solid-state battery for opening the fluorine-based solid electrolyte material of framework
Pond, or all solid state sode cell.
Used as an example, based in the solid lithium battery for opening the fluorine-based solid electrolyte of framework, the solid electrolyte is
The aluminium base or gallium base fluoride of above-mentioned rich lithium phase, positive electrode are conversion reaction fluoride (BiF3、BiOF、FeF3、FeF2、
FeOF、CuF2、Fe0.5Cu0.5F2、CoF2), polysulfide (FeS, FeS2、CoS2、CuS、TiS2、TiS3、
MoS2、MoS3), the one kind in sulphur/carbon complex (CMK-S, PAN-S, microporous carbon-S), negative pole is metal lithium sheet.
Used as an example, based in all solid state sode cell for opening the fluorine-based solid electrolyte of framework, the solid electrolyte is
The aluminium base or gallium base fluoride of above-mentioned rich sodium phase, positive electrode are to open framework fluoride (HTB-FeF3、TTB-FeF3, burn it is green
Stone FeF3·0.5H2O), Prussian blue derivative (Na4Fe(CN)6、Fe[Fe(CN)6]3), polyanion framework compound
(Na3V2(PO4)3), stratiform transition metal oxide (Na [Fe1/2Mn1/2]O2) in one kind, negative pole be metallic sodium piece.
The beneficial effects of the invention are as follows：
(1) present invention firstly provides some new applications for opening frame structure prototype in fluoride solid electrolyte, and realize simultaneously
Its rich lithiumation or rich sodium, by increasing the concentration of transportable alkali metal ion, are conducive to lifting its intrinsic ionic conductivity.
This kind of fluorine-based electrolyte is without using expensive thulium, it is not required that use the transition metal unit of redox active
Element；
(2) this kind of solid electrolyte is prepared using the deposition synthesis based on ionic liquid first in the present invention, is conducive to its nanometer of shape
The control of looks sum and the surface modification of ionic liquid composition, to realize the intergranular shape being fully contacted with granule boundary conductive region
Into reduction granule boundary resistance；
(3) this kind of solid electrolyte is synthesized from precursor material direct in-situ using high-energy ball milling method first in the present invention, this machinery
Course of reaction is conducive to the nanosizing and structural disorder of electrolyte simultaneously, to realize defect sturcture that fast ion transmits and many
The formation of boundary, improves ionic conductivity, reduces activated energy barrier；
(4) this kind of solid electrolyte can be used for the construction of perfluoro-compound solid state battery in the present invention, to suppress positive pole-electrolyte Gu Gu circle
The cell performance decay that surface element migration (electronegative element particularly high) is caused；
(5) propose to explore new sodium base solid electrolyte and its all solid state sodium with the thinking for opening framework from rich sodium first in the present invention
The framework of battery；
(6) material of the present invention does not produce poisonous and harmful substance, environmental protection in preparation process is produced, and synthetic method is easy
In operation, technological process is simple, easily realizes scale volume production.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
Bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is of the invention
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by the explanation of this paper
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
1)Li3AlF6The preparation based on ionic liquid of solid electrolyte nano particle：
Weigh the Li of 0.3g2CO3It is added to the 1- butyl -3- methyl imidazolium tetrafluoroborates (BmimBF of 10mL4) ionic liquid
In body, it is stirred at room temperature 6 hours, obtains uniform turbid solution.Stirred with back, while to being slowly added to 1g's in solution
Al(NO3)3·9H2O, continuously stirs 12 hours, obtains separating out the turbid solution of sediment.Cleaning is centrifuged repeatedly with anhydrous propanone
Reaction precipitate, described solid electrolyte material is obtained final product after 80 DEG C of vacuum drying.Li3AlF6Solid electrolyte nano particle
SEM as shown in Figure 1, illustrates that embodiment (1) can successfully prepare the nanoscale solid state electrolyte of 20-50nm yardsticks
Material, and due to potential surface modification (i.e. the conformal cladding of the positive group of ionic liquid), particle surface energy can be reduced, favorably
In dispersed without there is serious agglomeration.XRD as shown in Figure 2, wide in range Li3AlF6Diffraction maximum explanation is made
Standby material is the pure phase of nanostructured.
Embodiment 2
1)Na3AlF6The preparation based on ionic liquid of solid electrolyte：
Weigh the Na of 0.424g2CO3It is added to the 1- butyl -3- methyl imidazolium tetrafluoroborates (BmimBF of 10mL4) ion
In liquid, it is stirred at room temperature 6 hours, obtains uniform turbid solution.Stirred with back, while to being slowly added to 1g in solution
Al (NO3)3·9H2O, continuously stirs 12 hours, obtains separating out the turbid solution of sediment.It is centrifuged repeatedly with anhydrous propanone
Cleaning reaction precipitate, Na is obtained final product after 80 DEG C of vacuum drying3AlF6It is the solid electrolyte material of principal phase.XRD such as accompanying drawings 3
It is shown, it can be found that more sharp principal phase Na3AlF6Diffraction maximum collection of illustrative plates in doped with broad dephasign Na5Al3F14Spread out
Penetrate peak.
2) conductivity test of solid electrolyte piece：
By the Na prepared by embodiment 23AlF6Solid electrolyte powder is pressed into thickness for 1mm, the disk of a diameter of 10mm, pressure
Piece pressure is 15MPa.With magnetically controlled sputter method compressing tablet two sides be deposited with a diameter of 8mm Au electrodes, under a nitrogen
Carry out ac impedance measurement.As shown in the Arrhenius point of accompanying drawing 4, the first round since 40 DEG C, heats up, directly every 15 degree
To 100 DEG C, after being stopped 12 hours at 100 DEG C, every 15 degree of coolings, each temperature is tested after stopping 2 hours；Second wheel
Since 115 DEG C, heated up every 20 degree, until 195 DEG C, after being stopped 12 hours at 195 DEG C, lower the temperature every 20 degree,
Up to room temperature, each temperature is tested after stopping 2 hours.The room-temperature ion conductance of stabilization is 10-4-10-5Between S/cm.
Embodiment 3
1)Na3Li3Al2F12It is prepared by the high temperature solid state reaction of solid electrolyte：
Weigh the AlF of the LiF and 0.67g of NaF, 0.31g of 0.5g3, uniformly ground in agate mortar, mixture is existed
15MPa pressure depresses to the disk of a diameter of 10mm, is then sealed in the stainless steel cauldron filled with Ar atmosphere,
Solid phase reaction 10 hours, compressing tablet is smashed to pieces at 700 DEG C, again uniform grinding, you can obtain required product.Its XRD is such as
Shown in accompanying drawing 5, sharp Na3Li3Al2F12Diffraction maximum confirms the pure phase of material.
2) conductivity test of solid electrolyte piece：
By the Na prepared by embodiment 33Li3Al2F12Solid electrolyte powder is pressed into thickness for 1mm, the disk of a diameter of 10mm,
Tableting pressure is 15MPa.With the Au electrodes of magnetically controlled sputter method a diameter of 8mm on the two sides of compressing tablet is deposited with, in nitrogen
Under carry out ac impedance measurement.As shown in the Arrhenius point of accompanying drawing 6, the first round since 40 DEG C, heats up every 15 degree,
Until 100 DEG C, after being stopped 12 hours at 100 DEG C, every 15 degree of coolings, each temperature is tested after stopping 2 hours；Second
Wheel heats up since 115 DEG C every 20 degree, until 195 DEG C, after being stopped 12 hours at 195 DEG C, every 20 degree of drops
Temperature, until room temperature, each temperature is tested after stopping 2 hours.The room-temperature ion conductance of stabilization is 10-6-10-7S/cm it
Between.
Embodiment 4
1)Na3Li3Ga2F12It is prepared by the high-energy ball milling reaction of solid electrolyte：
Weigh the GaF of the LiF and 1g of NaF, 0.31g of 0.5g3, uniformly ground in agate mortar, by mixture and 10mL
Nmp solvent load the zirconia ball grinding jar (including 54.3g, the zirconia ball of diameter 3mm) of 45mL in glove box
In, ball material mass ratio is 30:1, ball-milling reaction rotating speed be 800r/min under carry out 5 hours (each circular flow 5min,
Stop 15min, totally 60 circulations), ball-milling reaction is cooled to can opening after room temperature after terminating, then use NMP washing samples,
Take out drying, you can obtain required powder product.
2) conductivity test of solid electrolyte piece：
By the Na prepared by embodiment 43Li3Ga2F12Solid electrolyte powder is pressed into thickness for 1mm, the circle of a diameter of 10mm
Piece, tableting pressure is 15MPa.With magnetically controlled sputter method compressing tablet two sides be deposited with a diameter of 8mm Au electrodes,
Ac impedance measurement is carried out under nitrogen.As shown in the ac impedance spectroscopy of accompanying drawing 7, test temperature is increased to 105 DEG C from 30 DEG C, so
Cool to 25 DEG C again afterwards, every 15 or 20 degree of heating and cooling, each temperature is tested after stopping 2 hours.Ac impedance spectroscopy is showed
Go out small semicircle even insignificant semicircle, imply that preferable ionic conductivity, the room-temperature ion conductance of stabilization is 10-3-
10-4Between S/cm, activation energy is in 0.3eV or so.
3) based on Na3Li3Ga2F12The construction of all solid state sode cell of solid electrolyte and test：
By the Na prepared by embodiment 43Li3Ga2F12Solid electrolyte powder is pressed into thickness for 1mm, the circle of a diameter of 10mm
Piece, tableting pressure is 15MPa.The Na that will synthesize4Fe(CN)6Powder and conductive carbon Super P, binding agent PVDF according to
8：1：The 1 uniform mixed grinding of mass ratio, is added dropwise appropriate NMP and is made uniform sizing material, is coated in aluminum foil current collector,
80 DEG C of vacuum dryings at least 6 hours.By Na3Li3Ga2F12Na is sticked respectively in solid electrolyte piece two sides4Fe(CN)6Positive pole and
Sodium metal negative electrode, is assembled into Swagelok type batteries in the glove box full of argon gas.As shown in Figure 8, this all solid state sodium
Battery can successfully carry out discharge and recharge under room temperature, the current density condition of 22mA/g, preliminary reversible capacity in 40mAh/g,
Reaction potential is in 3V or so.
Industrial applicability：Material of the present invention does not produce poisonous and harmful substance, green ring in preparation process is produced
Protect, and synthetic method is easily operated, technological process is simple, easily realizes scale volume production.
Claims (10)
1. one kind opens the fluorine-based solid electrolyte material of framework, it is characterised in that the chemical composition of the electrolyte is：
AxMyFx+3y, wherein 0<X≤6,0<Y≤3, A is Na and/or Li, M are Al and/or Ga.
2. electrolyte according to claim 1, it is characterised in that 3≤x≤6,1≤y≤3.
3. electrolyte according to claim 1 and 2, it is characterised in that the electrolyte is Li3AlF6、Na3Li3Al2F12、LiNa2AlF6、Na3AlF6、Na5Al3F14、Li3GaF6、Na3Li3Ga2F12、Na3GaF6、Na5Ga3F14In one kind.
4. the preparation method for opening the fluorine-based solid electrolyte material of framework any one of a kind of claims 1 to 3, it is characterised in that the electrolyte uses high temperature process heat, comprises the following steps：By AxMyFx+3yIn each metallic element fluoride as raw material according to stoichiometric proportion mix；Mixture compressing tablet, sealing are incubated 5~15 hours, obtain out the fluorine-based solid electrolyte material of framework in 500~700 DEG C.
5. preparation method according to claim 4, it is characterised in that preparation is carried out under an inert atmosphere.
6. the preparation method for opening the fluorine-based solid electrolyte material of framework any one of a kind of claims 1 to 3, it is characterised in that the electrolyte is synthesized using high-energy ball milling, is comprised the following steps：By AxMyFx+3yIn each metallic element fluoride as raw material according to stoichiometric proportion mix；Raw mixture and solvent are carried out into ball milling, raw mixture, solvent, the amount ratio of abrading-ball are 1g：（0~60）mL：（10~60）G, preferably 1g：（4~6）mL：（25~45）G, 500~800 revs/min of rotational speed of ball-mill, ball milling 5~10 hours is washed after ball milling, dried, and obtains out the fluorine-based solid electrolyte material of framework.
7. the preparation method for opening the fluorine-based solid electrolyte material of framework according to claim 6, it is characterised in that the solvent is at least one of 1-METHYLPYRROLIDONE, anhydrous propanone, absolute ethyl alcohol, anhydrous isopropyl alcohol.
8. the preparation method for opening the fluorine-based solid electrolyte material of framework any one of a kind of claims 1 to 3, it is characterised in that the deposition that the electrolyte is based on ionic liquid synthesizes, and comprises the following steps：By AxMyFx+3yIn the salt of each metallic element stoichiometrically add and contain anion BF4 -Ion liquid solvent in, at 25~100 DEG C stir 6~12 hours, be precipitated thing；By sediment washing, dry, obtain out the fluorine-based solid electrolyte material of framework.
9. preparation method according to claim 8, it is characterised in that the salt of M element is with the amount ratio of ionic liquid（1~2）g：10mL.
10. a kind of all-solid-state battery, especially solid lithium battery or all solid state sode cell, it is characterised in that including opening the fluorine-based solid electrolyte material of framework any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943654.2A CN106887639B (en) | 2015-12-15 | 2015-12-15 | One kind opening fluorine-based solid electrolyte material of frame and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943654.2A CN106887639B (en) | 2015-12-15 | 2015-12-15 | One kind opening fluorine-based solid electrolyte material of frame and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106887639A true CN106887639A (en) | 2017-06-23 |
| CN106887639B CN106887639B (en) | 2019-06-11 |
Family
ID=59175031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510943654.2A Active CN106887639B (en) | 2015-12-15 | 2015-12-15 | One kind opening fluorine-based solid electrolyte material of frame and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106887639B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534367A (en) * | 2017-12-29 | 2019-03-29 | 蜂巢能源科技有限公司 | Anti-perovskite type solid electrolyte and synthetic method, battery, vehicle |
| CN110534802A (en) * | 2019-09-11 | 2019-12-03 | 蜂巢能源科技有限公司 | Solid electrolyte and its preparation method and application |
| CN111900461A (en) * | 2020-07-17 | 2020-11-06 | 国联汽车动力电池研究院有限责任公司 | Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof |
| CN112670563A (en) * | 2020-12-30 | 2021-04-16 | 广东微电新能源有限公司 | Solid electrolyte material, preparation method thereof and solid battery |
| CN113454735A (en) * | 2019-02-28 | 2021-09-28 | 松下知识产权经营株式会社 | Electrolyte material and battery using the same |
| CN113735145A (en) * | 2020-05-28 | 2021-12-03 | 中国科学院上海硅酸盐研究所 | Negative and positive ion co-doped sodium-rich opposite perovskite type solid electrolyte material, preparation method thereof and all-solid-state sodium battery |
| EP3920280A1 (en) * | 2020-06-02 | 2021-12-08 | Samsung Electronics Co., Ltd. | Solid electrolyte, method of preparing the same, protected cathode, electrochemical battery, and electrochemical device including the same |
| CN115332623A (en) * | 2022-08-19 | 2022-11-11 | 华中科技大学 | Coordination polymer solid electrolyte, preparation method thereof and solid battery |
| US11677097B2 (en) | 2020-06-02 | 2023-06-13 | Samsung Electronics Co., Ltd. | Solid electrolyte, method of preparing the same, and electrochemical device including the same |
| CN116396052A (en) * | 2023-06-05 | 2023-07-07 | 蓝固(常州)新能源有限公司 | Core-shell-glassy solid electrolyte and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367267A (en) * | 1980-04-25 | 1983-01-04 | Hitachi, Ltd. | Amorphous lithium fluoaluminate |
| CN1162021A (en) * | 1997-01-29 | 1997-10-15 | 河南省地质矿产厅第二地质队 | Aluminium-sodium composite lithium salt and application thereof |
| JP2005093376A (en) * | 2003-09-19 | 2005-04-07 | Nitto Denko Corp | Solid polyelectrolyte film and battery made by using this |
| US20100143769A1 (en) * | 2007-06-11 | 2010-06-10 | Midwest Research Institute | Anodic Dendritic Growth Suppression System for Secondary Lithium Batteries |
| CN102414901A (en) * | 2009-05-01 | 2012-04-11 | 丰田自动车株式会社 | Solid electrolyte material, electrode element that includes solid electrolyte material, all-solid battery that includes solid electrolyte material, and manufacturing method for solid electrolyte material |
-
2015
- 2015-12-15 CN CN201510943654.2A patent/CN106887639B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367267A (en) * | 1980-04-25 | 1983-01-04 | Hitachi, Ltd. | Amorphous lithium fluoaluminate |
| CN1162021A (en) * | 1997-01-29 | 1997-10-15 | 河南省地质矿产厅第二地质队 | Aluminium-sodium composite lithium salt and application thereof |
| JP2005093376A (en) * | 2003-09-19 | 2005-04-07 | Nitto Denko Corp | Solid polyelectrolyte film and battery made by using this |
| US20100143769A1 (en) * | 2007-06-11 | 2010-06-10 | Midwest Research Institute | Anodic Dendritic Growth Suppression System for Secondary Lithium Batteries |
| CN102414901A (en) * | 2009-05-01 | 2012-04-11 | 丰田自动车株式会社 | Solid electrolyte material, electrode element that includes solid electrolyte material, all-solid battery that includes solid electrolyte material, and manufacturing method for solid electrolyte material |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534367A (en) * | 2017-12-29 | 2019-03-29 | 蜂巢能源科技有限公司 | Anti-perovskite type solid electrolyte and synthetic method, battery, vehicle |
| CN113454735A (en) * | 2019-02-28 | 2021-09-28 | 松下知识产权经营株式会社 | Electrolyte material and battery using the same |
| CN113454735B (en) * | 2019-02-28 | 2023-12-08 | 松下知识产权经营株式会社 | Electrolyte material and battery using the same |
| CN110534802A (en) * | 2019-09-11 | 2019-12-03 | 蜂巢能源科技有限公司 | Solid electrolyte and its preparation method and application |
| CN113735145A (en) * | 2020-05-28 | 2021-12-03 | 中国科学院上海硅酸盐研究所 | Negative and positive ion co-doped sodium-rich opposite perovskite type solid electrolyte material, preparation method thereof and all-solid-state sodium battery |
| US11677097B2 (en) | 2020-06-02 | 2023-06-13 | Samsung Electronics Co., Ltd. | Solid electrolyte, method of preparing the same, and electrochemical device including the same |
| EP3920280A1 (en) * | 2020-06-02 | 2021-12-08 | Samsung Electronics Co., Ltd. | Solid electrolyte, method of preparing the same, protected cathode, electrochemical battery, and electrochemical device including the same |
| CN111900461A (en) * | 2020-07-17 | 2020-11-06 | 国联汽车动力电池研究院有限责任公司 | Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof |
| CN111900461B (en) * | 2020-07-17 | 2022-06-28 | 国联汽车动力电池研究院有限责任公司 | Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof |
| CN112670563A (en) * | 2020-12-30 | 2021-04-16 | 广东微电新能源有限公司 | Solid electrolyte material, preparation method thereof and solid battery |
| CN112670563B (en) * | 2020-12-30 | 2022-05-17 | 广东微电新能源有限公司 | Solid electrolyte material, preparation method thereof and solid battery |
| CN115332623A (en) * | 2022-08-19 | 2022-11-11 | 华中科技大学 | Coordination polymer solid electrolyte, preparation method thereof and solid battery |
| CN116396052A (en) * | 2023-06-05 | 2023-07-07 | 蓝固(常州)新能源有限公司 | Core-shell-glassy solid electrolyte and preparation method and application thereof |
| CN116396052B (en) * | 2023-06-05 | 2023-09-22 | 蓝固(常州)新能源有限公司 | Core-shell-glassy solid electrolyte and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106887639B (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106887639B (en) | One kind opening fluorine-based solid electrolyte material of frame and preparation method thereof | |
| Liu et al. | Nanosphere-rod-like Co3O4 as high performance cathode material for aluminium ion batteries | |
| Wang et al. | Molecular design of a metal–organic framework material rich in fluorine as an interface layer for high-performance solid-state Li metal batteries | |
| CN104953175A (en) | Solid electrolyte for lithium ion battery, preparation method for solid electrolyte, and lithium ion battery | |
| CN103151508B (en) | Mix composite cathode material for lithium ion cell of lanthanum lithium titanate and preparation method thereof | |
| CN102820458A (en) | Synthetic method for preparing nitrogen-carbon-containing coated lithium titanate composite material by introducing ionic liquid as carbon source | |
| CN1907844A (en) | High density ultrafine composite ferric lithium phosphate anode material and preparation method | |
| CN102324511A (en) | Preparation method for lithium ion battery composite cathode material | |
| CN102097616A (en) | Preparation method of high-energy and high-power density nano-scale lithium iron phosphate powder | |
| CN104659412A (en) | Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery | |
| CN114335681B (en) | Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application | |
| CN106450306A (en) | Preparation method and application of negative electrode material of tin phosphide sodium ion battery | |
| Kou et al. | Enhanced ionic conductivity of novel composite polymer electrolytes with Li1. 3Al0. 3Ti1. 7 (PO4) 3 NASICON-type fast ion conductor powders | |
| Zhang et al. | Research status of spinel LiMn2O4 cathode materials for lithium ion batteries | |
| CN101764227A (en) | Lithium ferrosilicon silicate/carbon composite cathode material and preparation method thereof | |
| CN105514375A (en) | Carbon-coated Na0.55 Mn2O4.1.5H2O nanocomposite and preparation method thereof | |
| CN102227022A (en) | Li2FeSiO4 anode material for lithium ion battery and preparation method thereof | |
| 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 | |
| Gan et al. | Zr doped NASICON-type LATP glass-ceramic as a super-thin coating onto deoxidized carbon wrapped CNT-S cathode for lithium-sulphur battery | |
| CN104577111A (en) | Composite material containing fluorine-containing titanium phosphate compound as well as preparation method and application of composite material | |
| Wang et al. | Microwave-assisted sol-gel modification of Al-or C-doped Li4Ti5O12 samples as anode materials for Li-ion batteries | |
| Shang et al. | The preparation of NASICON-type solid electrolyte lithium-ion Li1+ xAlxGe0. 2Ti1. 8-x (PO4) 3 by conventional solid-state method | |
| CN114361577A (en) | Pure cubic phase nano lithium gallium lanthanum zirconium oxygen powder and preparation method and application thereof | |
| CN114447423A (en) | Sulfide solid electrolyte with lithium supplement and moisture absorption functions | |
| CN114188521A (en) | Light coating layer on surface of graphite positive electrode material of double-ion battery and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |