CN106887639B - One kind opening fluorine-based solid electrolyte material of frame and preparation method thereof - Google Patents
One kind opening fluorine-based solid electrolyte material of frame and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to one kind to open fluorine-based solid electrolyte material of frame and preparation method thereof, the chemical composition of the electrolyte are as follows: AxMyFx+3y, wherein 0 < x≤6,0 < y≤3, A is Na and/or Li, and M is Al and/or Ga.Of the invention opens the fluorine-based solid electrolyte material A of framexMyFx+3yIt is rich lithium or rich sodium phase aluminium base or gallium base fluoride, present invention firstly provides the novel applications 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 promote its intrinsic ionic conductivity, by means such as nanosizing, disordering, surface modifications, the conductivity of body phase and granule boundary can be improved.
Description
Technical field
The invention belongs to field of new energy technologies, in particular to a kind of solid lithium battery or sode cell open frame fluorine
Base solid electrolyte material especially opens frame richness lithium or the fluorine-based solid electrolyte material of rich sodium and preparation method thereof.
Background technique
In recent years, with the raising of fossil fuel price and its increasingly sharpening for environmental pollution, for clean energy resource
Demand is particularly strong, especially using and pushing away in fields, the secondary cell such as electric car and energy storage system based on green network
Extensively industrial circle and academia is made to put into more energy in the research of its novel framework and critical material.Currently based on having
The lithium ion battery of machine electrolyte system has two large problems that can not overcome, i.e. the high volatile and corrosivity of (1) electrolyte are easily made
At pollution dangerous and to environment, (2) lithium metal is formed in the dendrite of electrode electrolyte interface easily causes battery short circuit.Cause
This needs to develop all-solid-state battery framework and its solid electrolyte material to solve the above problems.
The wherein exploitation of solid electrolyte is always the difficult point of solid state battery research, the work of forefathers focus mostly in crystal phase and
The glass ceramics solid electrolyte of amorphous phase, such as the Li of NASICON type1+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 type and glass-ceramic type based on Li2S-P2S5Sulfide etc..Although oxide electrolyte is in air
Middle stability is preferable, but big granule boundary resistance makes their overall conductivity have a greatly reduced quality, and the rare earth gold contained
Belong to expensive；And the electronegativity of S is less than oxygen, makes the ionic conductivity of sulfide electrolyte commonly greater than oxide, and vulcanizes
Object is easier to densify, their interfacial conductive rate can even be ignored, the disadvantage is that air-sensitive (H easily generated2S), phasor compared with
For complexity, component deviation is affected to conductivity.Many unorganic glass ceramic electrolytes contain the element of oxidation-reduction quality
Potentially unstable when (such as Ti, Ge), interface and lithium contact, this will limit its electrochemical stability windows.
Although lithium salts LiPF6It is widely used in lithium battery, but fluoride is as solid electrolyte or seldom
It is reported.The beginning of the eighties, Hitachi, Ltd reported unbodied LiF-AlF3And NaF-AlF3Thin film system, discovery conductivity is with multiple
It closes the difference of object metering ratio and changes, but optimal conductivity at room temperature rate still only has 10-7-10-6S/cm；Northeastern Japan in 2012
University proposes Li3AlF6Be conducive to the height at being obviously improved for lithium ion conducting rate, especially granule boundary with LiCl mixing and ball milling
Lithium ion conducting 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 for falling into chemistry and space charge effect, realizes 3 magnitudes of the gradually disordering and its ionic conductivity to LiF film
Increase, realize transformation of the LiF from insulator to fast-ionic conductor, conductivity values are close to thin-film electrolyte best at present
The level of LiPON；Lu and Archer etc. adds LiF nano particle in organic electrolyte, effectively improves the electro-deposition of lithium, suppression
The growth of dendrite is made.Electrolysis of fluorides matter has potential advantage compared with oxide ceramic electrolyte: (1) pattern can be achieved
Controllable nanosizing, (2) reduce granule boundary resistance, and (3) eliminate the use of expensive rare earth metal；With testing sulphide ratio, fluorination
Object is more stable in air.Rich lithium (sodium) mutually and open frame strategy be exploitation fluoride solid electrolyte new structure prototype
Provide completely new thinking.
In conclusion this field be badly in need of developing a kind of high ion conductivity, low electronic conductivity, wide electrochemical window 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 suitble to big rule
Mould application.
Summary of the invention
The fluorine-based solid electrolyte of frame is opened the purpose of the present invention is to provide a kind of solid lithium battery or sode cell
Material mutually opens frame structure prototype to provide new rich lithium phase or rich sodium.
Here, the present invention, which provides one kind, opens the fluorine-based solid electrolyte material of frame, chemical composition are as follows:
AxMyFx+3y, wherein 0 < x≤6,0 < y≤3, A is Na and/or Li, and M is Al and/or Ga.
Of the invention opens the fluorine-based solid electrolyte material A of framexMyFx+3yIt is rich lithium or rich sodium phase aluminium base or the fluorination of gallium base
Object, present invention firstly provides the novel applications for opening frame structure prototype in fluoride solid electrolyte, and realize it simultaneously
Rich lithiumation or rich sodium are conducive to promote its intrinsic ionic conductivity, pass through by increasing the concentration of transportable alkali metal ion
The conductivity of body phase and granule boundary can be improved in the means such as nanosizing, disordering, surface modification.This fluorine-based electrolyte without
Expensive thulium need to be used, the transition metal element for using redox active is not needed yet.Solid-state of the invention
Electrolyte can be used for the construction of perfluoro-compound solid state battery, to inhibit anode-electrolyte solid solid interface migration of element (especially high
Electronegative element) caused by cell performance decay.And material of the present invention does not generate in production preparation process and toxic has
Evil substance, it is environmentally protective, and synthetic method is easily operated, process flow is simple, Yi Shixian scale volume production.
Preferably, 3≤x≤6,1≤y≤3.
Preferably, the electrolyte is Li3AlF6、Na3Li3Al2F12、LiNa2AlF6、Na3AlF6、Na5Al3F14、
Li3GaF6、Na3Li3Ga2F12、Na3GaF6、Na5Ga3F14One of.
The present invention also provides preparing this method for opening the fluorine-based solid electrolyte material of frame, with expand its in doping and
The improvement potentiality of surface modification etc. overcome technology present in current all-solid-state battery framework and its crucial electrolyte
Problem.
The present invention provides a kind of preparation method for opening the fluorine-based solid electrolyte material of frame, the electrolyte is used
High temperature process heat, comprising the following steps: by AxMyFx+3yIn each metallic element fluoride as raw material according to stoichiometry
Than mixing；By mixture tabletting, sealing keeps the temperature 5~15 hours in 500~700 DEG C, obtains out the fluorine-based solid state electrolysis material of frame
Material.
Preferably, high temperature process heat carries out under an inert atmosphere.
The present invention also provides a kind of preparation method for opening the fluorine-based solid electrolyte material of frame, the electrolyte is adopted
It is synthesized with high-energy ball milling, comprising 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 subjected to ball milling, raw mixture, solvent, abrading-ball amount ratio be 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 is small
When, it is washing after ball milling, dry, obtain out the fluorine-based solid electrolyte material of frame.
This solid electrolyte is synthesized from precursor material direct in-situ using high-energy ball milling method for the first time in the present invention, this
Automatic reaction process is conducive to the nanosizing and structural disorder of electrolyte simultaneously, to realize the defect knot of fast ion transmission
The formation of structure and multi phase interface improves ionic conductivity, reduces activated energy barrier.
Preferably, the solvent is N-Methyl pyrrolidone, at least one in anhydrous propanone, dehydrated alcohol, anhydrous isopropyl alcohol
Kind.
The present invention also provides a kind of preparation method for opening the fluorine-based solid electrolyte material of frame, the electrolyte base
It is synthesized in the deposition of ionic liquid, comprising the following steps: by AxMyFx+3yIn the salt of each metallic element be stoichiometrically added
Contain anion BF4 -Ion liquid solvent in, stirred 6~12 hours at 25~100 DEG C, obtain sediment；By sediment
Washing, drying, obtain out the fluorine-based solid electrolyte material of frame.
It is used for the first time in the present invention based on the synthesis of the deposition of ionic liquid and prepares this solid electrolyte, be conducive to it and receive
The rice control of pattern sum and the surface modification of ionic liquid ingredient, to realize intergranular come into full contact with and granule boundary conduction region
The formation in domain reduces granule boundary resistance.
Preferably, the salt of M element and the amount ratio of ionic liquid are (1~2) g:10mL in deposition synthesis.
The object of the invention is also to provide a kind of all-solid-state battery, especially solid lithium battery or all solid state sodium electricity
The fluorine-based solid electrolyte material of frame is opened including described in pond.
Detailed description of the invention
Fig. 1 is the Li based on ionic liquid synthesis obtained by embodiment 13AlF6SEM figure；
Fig. 2 is the Li based on ionic liquid synthesis obtained by embodiment 13AlF6XRD diagram；
Fig. 3 is the Na based on ionic liquid synthesis obtained by embodiment 23AlF6XRD diagram；
Fig. 4 is the Na based on ionic liquid synthesis obtained by embodiment 23AlF6In the Allan of different lifting thermophases
Ni Wusitu；
Fig. 5 is the Na based on high temperature solid state reaction synthesis obtained by embodiment 33Li3Al2F12XRD diagram；
Fig. 6 is the Na based on high temperature solid state reaction synthesis obtained by embodiment 33Li3Al2F12In different lifting thermophases
Arrhenius figure；
Fig. 7 is the Na based on high-energy ball milling reaction synthesis obtained by embodiment 43Li3Ga2F12In different lifting thermophases
AC impedance figure；
Fig. 8 is the Na based on high-energy ball milling reaction synthesis obtained by embodiment 43Li3Ga2F12As solid electrolyte
Na4Fe(CN)6As anode, sodium piece as cathode, the electrochemical profiles figure of obtained all solid state sode cell.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, is not intended to limit the present invention.
The fluorine-based solid electrolyte material of frame is opened for solid lithium battery or sode cell the present invention provides a kind of, is mentioned
The novel application for opening frame structure prototype in fluoride solid electrolyte out, and its rich lithiumation or rich sodium are realized simultaneously,
Without using expensive thulium, the transition metal element for using redox active is not needed yet.The present invention simultaneously
It additionally provides and prepares that this to open frame fluorine-based solid by high temperature solid state reaction, high-energy ball milling, the deposition method based on ionic liquid
The method of state electrolyte, with expand its doping and in terms of improvement potentiality, overcome current all solid state electricity
Technical problem present in pond framework and its crucial electrolyte.In addition, the present invention also provides open frame fluorine including described
The all-solid-state battery of base solid electrolyte material.
The chemical formula for opening the fluorine-based solid electrolyte material of frame of the invention is AxMyFx+3y, wherein 0 < x≤6,0 < y≤3,
Preferably, 3≤x≤6,1≤y≤3, A are Na and/or Li, and M is Al and/or Ga.The electrolyte is by rich lithium phase or rich sodium
The aluminium base or gallium base fluoride of 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 all solid state
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.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)、
Na5Al3F14One of (chiolite), rich lithium phase gallium base fluoride can be Li3GaF6, rich sodium phase gallium base fluoride can be with
It is Na3Li3Ga2F12、Na3GaF6、Na5Ga3F14One of.
The method that the fluorine-based solid electrolyte material of frame is opened described in high temperature solid state reaction synthesis is conducive to improve product purity,
Potentiality with subsequent doping regulation.As an example, for example including following steps.
By a certain amount of LiF and/or NaF and AlF3And/or GaF3A is pressed under an inert atmospherexMyFx+3yStoichiometry
It is more uniform than ground and mixed, wherein A is Na and/or Li, and M is Al and/or Ga, such as: synthesis Li3AlF6Or Li3GaF6Required
LiF:AlF3Or LiF:GaF3Molar ratio is 3:1, synthesizes Na3Li3Al2F12Or Na3Li3Ga2F12Required LiF:NaF:AlF3Or
LiF:NaF:GaF3Molar ratio is 1.5:1.5:1, synthesizes LiNa2AlF6Required LiF:NaF:AlF3Molar ratio is 1:2:1, is closed
At Na3AlF6Or Na3GaF6Required NaF:AlF3Or NaF:GaF3Molar ratio is 3:1, synthesizes Na5Al3F14Or Na5Ga3F14It is required
NaF:AlF3Or NaF:GaF3Molar ratio is 5:3.
Then, by mixture tabletting, as an example, such as disc diameter is 10mm, wafer thickness 1-5mm, pressure
Piece pressure is 15-20MPa；Disk is sealed in the stainless steel cauldron filled with inert atmosphere, solid phase reaction is carried out, solid phase is anti-
It should be carried out 5-15 hours at 500-700 DEG C, required product can be obtained.After high temperature solid state reaction, product is smashed to pieces, is ground
Characterized to fine homogeneous, or for physical property, or again pressure target (with a thickness of 1mm) for conductivity test (two-sided plating Au electrode, directly
Diameter is 8mm) 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 automatic reaction process has
Conducive to the nanosizing and structural disorder of electrolyte, to realize the defect sturcture of fast ion transmission and the shape of multi phase interface
At raising ionic conductivity reduces activated energy barrier.As an example, for example including following steps.
By a certain amount of LiF and/or NaF and AlF3And/or GaF3It is more mixed than grinding by product molar under an inert atmosphere
The step of conjunction is uniform, and mixed molar ratio ingredient 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.The solvent includes but not
It is limited to N-Methyl pyrrolidone (NMP), anhydrous propanone, dehydrated alcohol, anhydrous isopropyl alcohol.In one example, mixture 2.0-
2.5g and NMP 10mL is added in the zirconia ball grinding jar (zirconia ball for including 75g, diameter 3mm) of 45mL.In glove box
Sealing, carries out 5-10 hours at revolving speed 500-800r/min；Drying is taken out in washing after ball milling, and required product can be obtained.
For example, the condition of ball milling can be set are as follows: ball material mass ratio is 30:1, each circular flow 5min of ball-milling reaction, is stopped
15min, totally 60 recycle, and are cooled to can opening after room temperature after ball-milling reaction, and sample is equally taken out using NMP as solvent, from
Then heart washing is dried powder, or is characterized for physical property, or pressure target (with a thickness of 1mm, diameter 10mm) is used for conductivity test
It (two-sided plating Au electrode, diameter 8mm) or is tested for all-solid-state battery.
Solid electrolyte of the invention is prepared based on the synthesis of the deposition of ionic liquid, makes full use of the soft mode of ionic liquid
Plate agent or structure directing agent function have using surface defect sturcture to the physical/chemical adsorption of ionic liquid charged group
Conducive to the control of its nanotopography and the surface modification of ionic liquid ingredient, to realize intergranular come into full contact with and granule boundary
The formation of conductive region reduces granule boundary resistance.As an example, for example including following steps.
By a certain amount of AxMyFx+3yIn each metallic element salt by product molar than be added contain anion BF4 -From
It is stirred 6-12 hours at 25-100 DEG C in sub- liquid solvent.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 not limited to nitric acid
Salt and/or its hydrate (such as Al (NO3)3·9H2O、Ga(NO3)3·xH2O), chloride and/or its hydrate (such as
AlCl3·xH2O、GaCl3·xH2O).In one example, raw material Li2CO3And/or Na2CO3And Al (NO3)3·9H2O
And/or Ga (NO3)3·xH2O.Such as: synthesis Li3AlF6Or Li3GaF6Required Li2CO3: Al (NO3)3·9H2O or Li2CO3:
Ga(NO3)3·xH2O molar ratio is 1.5:1, synthesizes Na3Li3Al2F12Or Na3Li3Ga2F12Required Li2CO3: Na2CO3: Al
(NO3)3·9H2O or Li2CO3: Na2CO3: Ga (NO3)3·xH2O molar ratio is 0.75:0.75:1, synthesizes LiNa2AlF6Required
Li2CO3: Na2CO3: Al (NO3)3·9H2O molar ratio is 0.5:1:1, synthesizes Na3AlF6Or Na3GaF6Required Na2CO3: Al
(NO3)3·9H2O or Na2CO3: Ga (NO3)3·xH2O molar ratio is 1.5:1, synthesizes Na5Al3F14Or Na5Ga3F14Required
Na2CO3: Al (NO3)3·9H2O or Na2CO3: Ga (NO3)3·xH2O molar ratio is 2.5:3.The ionic liquid can serve as reasons
Low temperature molten salt composed by tetrafluoroborate anion and cation group, cation are organic cation, are selected from 1,3- bis-
The alkyl-substituted pyridinium ion of alkyl-substituted imidazol ion, N-, alkyl quaternary ammonium ion, alkyl quaternary are seen ion.With the Al of 1-2g
(NO3)3·9H2O or Ga (NO3)3·xH2Precursor mixture on the basis of O is added in the ionic liquid of 10mL, in differential responses
In temperature and different ionic liquid environment, product is adjusted according to the hydrolysis rate of ionic liquid and positive and negative group phase distribution character
Nucleation and growth, formed different nanostructures or different surfaces modification sediment.
Then, sediment centrifuge washing is dry, required product can be obtained, for example, by sediment anhydrous propanone
Then centrifuge washing 3-5 times is dried powder, or is characterized for physical property, or pressure target (with a thickness of 1mm, diameter 10mm) is for leading
Electric rate test (two-sided plating Au electrode, diameter 8mm) is tested for all-solid-state battery.
The all-solid-state battery provided by the invention that the fluorine-based solid electrolyte material of frame is opened including described in can be all solid state
Lithium battery is also possible to all solid state sode cell.
As an example, based in the solid lithium battery for opening the fluorine-based solid electrolyte of frame, the solid electrolyte
For the aluminium base or gallium base fluoride of above-mentioned rich lithium phase, positive electrode is conversion reaction fluoride (BiF3、BiOF、FeF3、FeF2、
FeOF、CuF2、Fe0.5Cu0.5F2、CoF2), polysulfide (FeS, FeS2、CoS2、CuS、TiS2、TiS3、MoS2、MoS3), sulphur/carbon
One of compound (CMK-S, PAN-S, microporous carbon-S), cathode is metal lithium sheet.
As an example, based in all solid state sode cell for opening the fluorine-based solid electrolyte of frame, the solid electrolyte
For the aluminium base or gallium base fluoride of above-mentioned rich sodium phase, positive electrode is to open frame fluoride (HTB-FeF3、TTB-FeF3, pyrochlore
FeF3·0.5H2O), Prussian blue derivative (Na4Fe(CN)6、Fe[Fe(CN)6]3), polyanion frame compound (Na3V2
(PO4)3), stratiform transition metal oxide (Na [Fe1/2Mn1/2]O2One of), cathode is metallic sodium piece.
The beneficial effects of the present invention are:
(1) present invention firstly provides several novel applications for opening frame structure prototype in fluoride solid electrolyte, and
Realize its rich lithiumation or rich sodium simultaneously, by increasing the concentration of transportable alkali metal ion, be conducive to be promoted its it is intrinsic from
Subconductivity rate.This kind of fluorine-based electrolyte does not need to use redox active without using expensive thulium yet
Transition metal element；
(2) it is used for the first time in the present invention based on the synthesis of the deposition of ionic liquid and prepares this kind of solid electrolyte, be conducive to
The control of its nanotopography sum and the surface modification of ionic liquid ingredient, to realize that intergranular come into full contact with is led with granule boundary
The formation in electric region reduces granule boundary resistance；
(3) this kind of solid electrolyte is synthesized from precursor material direct in-situ using high-energy ball milling method for the first time in the present invention,
This automatic reaction process is conducive to the nanosizing and structural disorder of electrolyte simultaneously, to realize lacking for fast ion transmission
The formation of structure and multi phase interface is fallen into, ionic conductivity is improved, 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 inhibit anode-electrolysis
Cell performance decay caused by matter solid solid interface migration of element (especially high electronegative element)；
(5) present invention in be put forward for the first time from rich sodium and open the thinking of frame explore novel sodium base solid electrolyte and its
The framework of all solid state sode cell；
(6) material of the present invention does not generate poisonous and harmful substance in production preparation process, environmentally protective, and synthesizes
Method is easily operated, and process flow is simple, Yi Shixian scale volume production.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
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 tetrafluoroborate (BmimBF of 10mL4) from
It in sub- liquid, is stirred at room temperature 6 hours, obtains uniform turbid solution.It is stirred with back, while being slowly added to 1g's into solution
Al(NO3)3·9H2O is continuously stirred 12 hours, obtains the turbid solution that sediment can be precipitated.Cleaning is centrifuged repeatedly with anhydrous propanone
Reaction precipitate, up to the solid electrolyte material after 80 DEG C of vacuum drying.Li3AlF6Solid electrolyte nano particle
SEM is as shown in Fig. 1, illustrates that the nanoscale solid state electrolysis material of 20-50nm scale can be successfully prepared in embodiment (1)
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, is conducive to
Even dispersion is without serious agglomeration.XRD is as shown in Fig. 2, wide in range Li3AlF6Diffraction maximum illustrates prepared material
Material is the pure phase of nanostructure.
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 tetrafluoroborate (BmimBF of 10mL4)
It in ionic liquid, is stirred at room temperature 6 hours, obtains uniform turbid solution.It is stirred with back, while being slowly added to 1g into solution
Al (NO3)3·9H2O is continuously stirred 12 hours, obtains the turbid solution that sediment can be precipitated.It is centrifuged repeatedly clearly with anhydrous propanone
Reaction precipitate is washed, up to Na after 80 DEG C of vacuum drying3AlF6For the solid electrolyte material of main phase.XRD is as shown in Fig. 3, can
To find more sharp main phase Na3AlF6Diffraction maximum map in doped with broad miscellaneous phase Na5Al3F14Diffraction maximum.
2) conductivity test of solid electrolyte piece:
By Na prepared by embodiment 23AlF6Solid electrolyte powder is pressed into a thickness of 1mm, the disk that diameter is 10mm,
Tableting pressure is 15MPa.The Au electrode that upper diameter is 8mm is deposited on the two sides of tabletting with magnetically controlled sputter method, under a nitrogen into
Row ac impedance measurement.As shown in 4 Arrhenius point of attached drawing, the first round since 40 DEG C, heats up every 15 degree, until 100
DEG C, after 100 DEG C stop 12 hours, cool down every 15 degree, each temperature is tested after stopping 2 hours；Second wheel is opened from 115 DEG C
Begin, heats up every 20 degree, until 195 DEG C, after 195 DEG C stop 12 hours, cool down every 20 degree, until room temperature, each temperature
It is tested after stopping 2 hours.Stable room-temperature ion conductivity 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 existed
15MPa pressure depresses to the disk that diameter is 10mm, is then sealed in the stainless steel cauldron filled with Ar atmosphere, at 700 DEG C
Lower solid phase reaction 10 hours, tabletting is smashed to pieces, and uniformly grinding, can be obtained required product again.Its XRD is as shown in Fig. 5,
Sharp Na3Li3Al2F12Diffraction maximum confirms the pure phase of material.
2) conductivity test of solid electrolyte piece:
By Na prepared by embodiment 33Li3Al2F12Solid electrolyte powder is pressed into a thickness of 1mm, the circle that diameter is 10mm
Piece, tableting pressure 15MPa.The Au electrode that upper diameter is 8mm is deposited on the two sides of tabletting with magnetically controlled sputter method, under a nitrogen
Carry out ac impedance measurement.As shown in 6 Arrhenius point of attached drawing, the first round since 40 DEG C, heats up every 15 degree, until
100 DEG C, after 100 DEG C stop 12 hours, cool down every 15 degree, each temperature is tested after stopping 2 hours；Second wheel is from 115 DEG C
Start, heats up every 20 degree, until 195 DEG C, after 195 DEG C stop 12 hours, cool down every 20 degree, until room temperature, Mei Gewen
Degree is tested after stopping 2 hours.Stable room-temperature ion conductivity is 10-6-10-7Between S/cm.
Embodiment 4
1)Na3Li3Ga2F12The high-energy ball milling of solid electrolyte reacts preparation:
Weigh the GaF of the LiF and 1g of NaF, 0.31g of 0.5g3, uniformly ground in agate mortar, by mixture and
The nmp solvent of 10mL is fitted into the zirconia ball grinding jar (zirconia ball for including 54.3g, diameter 3mm) of 45mL in glove box,
Ball material mass ratio is 30:1, and ball-milling reaction carries out (each circular flow 5min, stopping in 5 hours in the case where revolving speed is 800r/min
15min, totally 60 circulations), can opening after room temperature is cooled to after ball-milling reaction, then uses NMP washing sample, takes out drying,
Required powder product can be obtained.
2) conductivity test of solid electrolyte piece:
By Na prepared by embodiment 43Li3Ga2F12Solid electrolyte powder is pressed into a thickness of 1mm, the circle that diameter is 10mm
Piece, tableting pressure 15MPa.The Au electrode that upper diameter is 8mm is deposited on the two sides of tabletting with magnetically controlled sputter method, under a nitrogen
Carry out ac impedance measurement.As shown in 7 ac impedance spectroscopy of attached drawing, test temperature is increased to 105 DEG C from 30 DEG C, then cools to again
25 DEG C, every 15 or 20 degree of heating and cooling, each temperature is tested after stopping 2 hours.Ac impedance spectroscopy shows small semicircle even
Insignificant semicircle implies preferable ionic conductivity, and stable room-temperature ion conductivity is 10-3-10-4It is living between S/cm
Change can be in 0.3eV or so.
3) it is based on Na3Li3Ga2F12The construction of all solid state sode cell of solid electrolyte and test:
By Na prepared by embodiment 43Li3Ga2F12Solid electrolyte powder is pressed into a thickness of 1mm, the circle that diameter is 10mm
Piece, tableting pressure 15MPa.By the Na of synthesis4Fe(CN)6Powder and conductive carbon Super P, binder PVDF are according to 8:1:1's
The uniform mixed grinding of mass ratio is added dropwise suitable NMP and uniform sizing material is made, and 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)6Anode and sodium metal negative electrode, are filling
Swagelok type battery is assembled into the glove box of full argon gas.As shown in Fig. 8, this all solid state sode cell is in room temperature, 22mA/g
Current density condition under can successfully carry out charge and discharge, preliminary reversible capacity is in 40mAh/g, and reaction potential is in 3V or so.
Industrial applicability: material of the present invention does not generate poisonous and harmful substance, green ring in production preparation process
It protects, and synthetic method is easily operated, process flow is simple, Yi Shixian scale volume production.
Claims (7)
1. a kind of electrolyte opens the application in the fluorine-based solid electrolyte of frame in preparation, which is characterized in that the electrolyte
The chemical composition of material are as follows:
AxMyFx+3y, wherein 0 < x≤6,0 < y≤3, A is Na and/or Li, M Ga.
2. application according to claim 1, which is characterized in that 3≤x≤6,1≤y≤3.
3. application according to claim 2, which is characterized in that the electrolyte is Li3GaF6、Na3Li3Ga2F12、
Na3GaF6、Na5Ga3F14One of.
4. a kind of all-solid-state battery, which is characterized in that described to open the fluorine-based solid-state electricity of frame including opening the fluorine-based solid electrolyte of frame
It is A that matter, which is solved, by chemical compositionxMyFx+3yElectrolyte preparation, wherein 0 < x≤6,0 < y≤3, A is Na and/or Li, and M is
Ga。
5. all-solid-state battery according to claim 4, which is characterized in that 3≤x≤6,1≤y≤3.
6. all-solid-state battery according to claim 5, which is characterized in that the electrolyte is Li3GaF6、
Na3Li3Ga2F12、Na3GaF6、Na5Ga3F14One of.
7. all-solid-state battery according to claim 4, which is characterized in that the all-solid-state battery be solid lithium battery or
All solid state sode cell.
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| JPWO2020175171A1 (en) * | 2019-02-28 | 2021-12-23 | パナソニックＩｐマネジメント株式会社 | Electrolyte material and batteries using it |
| 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 |
| EP3920280B1 (en) * | 2020-06-02 | 2024-09-25 | Samsung Electronics Co., Ltd. | Solid electrolyte, method of preparing the same, protected cathode, electrochemical battery, and electrochemical device including the same |
| 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 |
| 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 |
| 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 |
| 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 |
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