CN107611476A - A kind of surface is inorganic solid electrolyte of amorphous substance and preparation method thereof - Google Patents
A kind of surface is inorganic solid electrolyte of amorphous substance and preparation method thereof Download PDFInfo
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Abstract
A kind of preparation method the invention provides surface for the inorganic solid electrolyte of amorphous substance, comprises the following steps：A) prepared and solid electrolyte matrix material chemical composition identical amorphous substance using melt quenching method or high-energy ball milling method；B) amorphous substance, binding agent and solvent are mixed, obtain composite material sizing agent；C) composite material sizing agent is coated on to the surface of the solid electrolyte matrix material, remove solvent and binding agent and soften the amorphous substance, obtains the inorganic solid electrolyte that surface is amorphous substance.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of surface is electric for the inoganic solids of amorphous substance
Solve matter and preparation method thereof.
Background technology
Lithium secondary battery is with output power, energy density is high, cyclicity is superior, memory-less effect and non-environmental-pollution etc.
Many advantages extensive use in daily life, turn into the first choice of the rechargable power supplies of portable type electronic product, also recognized
To be the Vehicular dynamic battery of most competitiveness.
Current commercial li-ion battery widely uses liquid electrolyte, is characterized in possessing higher electrical conductivity and excellent
Chemical property.But the flash point of liquid electrolyte is relatively low, heavy-current discharge, overcharge, internal short-circuit etc. it is abnormal
Electrolyte may be caused to generate heat spontaneous combustion, or even the safety problem such as set off an explosion during situation.Meanwhile from safety considerations, it is all kinds of
Electronic product is often used as negative pole using graphite.But the theoretical specific capacity of graphite only has 372mAh/g, and during first charge-discharge
Larger irreversible capacity loss be present, so it is difficult to negative material as high-energy-density secondary cell.With science and technology it is continuous
Development and the active demand to high-energy-density negative material, lithium metal obtain again as the research of the negative material of secondary cell
To concern.But its charge density causes it to be easy to polarize other molecules or ion very much greatly, causes wholly liquid state electrolyte
The power supply apparatus being full of produces unstability factor and potential safety hazard.Therefore, develop to lithium metal chemically stable and with good
The new material of good lithium ion conducting characteristic, to developing all kinds of high-energy-densities, macrocyclic secondary electricity based on lithium anode
Pool technology plays an important roll.
There is the incomparable security of liquid lithium secondary battery using all solid lithium secondary battery of solid electrolyte, and
It is expected to thoroughly eliminate the potential safety hazard during use, more meets the demand of electric automobile and scale energy storage field future development.
Solid electrolyte widely studied at present is broadly divided into two classes：Inorganic electrolyte and polymer dielectric.Inorganic electrolyte can
It is further separated into as crystalline state and amorphous state, and crystalline state can be subdivided into sulfide and the class of oxide two.
Sulfide has higher ionic conductivity, but in electrode/solid electrolyte interface because oxygen-lithium key is than sulphur-lithium
Ionic bond is eager to excel a lot, and it is often oxide to be commercialized positive electrode, the Schottky type space charge layer of high impedance will electrode/
Produced at electrolyte interface, cause battery that there is higher DC internal resistance and poor cycle performance.Meanwhile partly Ge containing high price
The sulfide electrolyte of element is unstable to lithium metal (such as LGPS), and interface can produce mixed conductor layer after being contacted with lithium metal
With high impedance material.
Oxide electrolyte such as NASICON structures LAGP, LATP, perovskite structure LLTO, garnet structure LLZO,
LISICON structures LGZO etc., not only cost is relatively low, good mechanical property, easy processing and chemical stability are preferable, electrical conductivity and sulphur
Compound electrolyte is close, has larger application space and practical value.Although however, in the battery because lithium it is uneven heavy
Lithium dendrite growth phenomenon caused by product and dissolving can be suppressed by the solid electrolyte of high shear modulus, but still have some problems
Applied for lithium metal in the solid lithium battery based on oxide electrolyte and cause challenge：First, lithium metal and electrolyte it
Between solid point contact cause interface impedance big, cell dynamics poor performance；2nd, in charge and discharge process, especially under big multiplying power,
The volumetric expansion and contraction of lithium metal can produce the stress gradually accumulated to interface, and electrolyte slug, which produces, causes deformation so that broken
It is broken, contact is further deteriorated；3rd, lithium metal and (such as Ti of metallic element containing high-valence state4+、Ge4+) solid electrolyte between deposit
In interfacial reaction that is lasting, being permeated to electrolyte body, ion-electron hybrid conductive region and low conductance accessory substance are generated,
Interracial contact and electrolyte body construction intensity are destroyed while lithium ion conductivity is reduced.4th, lithium metal and part are fine and close
Not high electrolyte (such as LLZO) the crystal boundary material of degree produces spontaneous chemical reaction, generates electronic conduction phase, causes battery short circuit.
Amorphous state electrolyte mainly passes through thing phase sedimentation with amorphous Li-P-O-N, Li-B-Si-O, Li-B-P-O-N etc.
The film of preparation.Their ionic conductivity is generally 10-6Below S/cm, ultra-thin battery can only be come across in a thin-layered way
In, such battery plus-negative plate load capacity is extremely low, not yet realizes requirement of each field to solid state lithium battery high-energy.
Copolymer solid electrolyte, the film such as formed by lithium salts and linear polyether complexing, has easier
Preparation technology, good film forming, high viscoplasticity and lighter quality.It is difficult but its room-temperature conductivity is relatively low, and mechanical performance is poor
To suppress the puncture of Li dendrite.
In order to solve the stability of lithium metal in all-solid-state battery as negative pole with contacting sex chromosome mosaicism, and realize all solid state electricity
The high-energy-density in pond, it is necessary to reference to all kinds of electrolyte each the advantages of.How composition, the knot of each component structure-activity relationship is found
The equalization point of structure, form, while prevention lithium metal is directly contacted with electrolyte and chemically reacted, suppress the life of Li dendrite
It is long, improve electrolyte/electrode solids contact interface, the long circulating for reaching solid state battery negative side is stable, it has also become be badly in need of solving
Technical problem.
In terms of inorganic matter modification solid electrolyte, MasashiKotobuki and Xiaogang Han are selected in LLZO
The aluminum oxide of one layer of nanometer grade thickness of surface magnetic control sputtering, they think what is formed in bath surface by elements diffusion
Li-Al-O compounds can not only increase exposure level of the lithium metal on its surface, and not influence original electrolytic conductance
Rate.Mitsuyasu Ogawa have sputtered thin layer Si, Sn, Al in metallic lithium surface, and thus negative pole, sulfide are electrolysis respectively
Matter, cobalt acid lithium are positive pole assembled battery, and cycle performance characterizes the reduction for showing that thin layer Si can more effectively suppress electrolyte, increases
Strong interface stability.The A of patent CN 104183871 are mentioned Li:BPO4As one layer of new electrolyte, thermal jet is coated onto original
Electrolyte Li7La3Zr2O12On matrix.These ways have harvested good modified effect to a certain extent, but due to modification
Layer is still amorphous material, and Li dendrite is possible to grow in its electrolyte crystal boundary, while the interface of Li/ electrolyte is still firm
Property contact, contact area is limited, it is impossible to further improves interface compatibility.
In terms of polymer-modified modified solid electrolyte, Kaoru Dokko use LATP as solid electrolyte, in positive pole
After spin coating prepares lithium manganate material, negative pole face is coated with one layer of PMMA-LiClO4- EC-DEC semi liquid state electrolyte is as lithium metal
Interface-modifying layer, battery can obtain 60mAh g at ambient temperature-1Specific capacity, but do not show this boundary layer improve battery
Help in terms of cyclical stability.Y Kobayashi use the side that the co- 2- of oxirane (2- methoxy ethoxies) ether sprays
Formula improves contacts of the LLTO with lithium an- ode, but cycle performance does not effectively improve yet, and 50 cycle battery capacity attenuations are to first
The nearly half to begin.What is more important, the modulus of shearing of polymer dielectric is usually very low, (60 DEG C especially at the working temperature
More than) it is much smaller than the modulus of shearing of inorganic solid electrolyte.This make it that, when it is applied, it is smaller to obtain straticulation can not be prepared
Impedance, otherwise Li dendrite will grow wherein rapidly, wear out polymer-modified layer, make lithium and contacted with internal layer electrolyte, produce
Raw possible side reaction, causes interface conductance to deteriorate.
Above technical characteristic is summarized, it can be found that following two problems：
First, amorphous material modification interfacial effect is not notable, the big property of its intrinsic more crystal boundary, rigidity, determines it not
, contact well both, i.e. poor compatibility stable to lithium can be taken into account.
2nd, in existing polymer modification, although the short time is effective, Li dendrite hidden danger is usually present, it is inreal
Realize excellent compatibility of the electrolyte to lithium metal.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide the inoganic solids that a kind of surface is amorphous substance
Electrolyte and preparation method thereof, surface provided by the invention are a kind of amorphous state of inorganic solid electrolyte of amorphous substance, crystalline substance
State coexists, and the purely inorganic solid electrolyte of multiple integral, solves solid electrolyte in all-solid-state battery/lithium metal interface
Unstable and contact difference consistency problem.
A kind of preparation method the invention provides surface for the inorganic solid electrolyte of amorphous substance, including following step
Suddenly：
A) prepared using melting-quenching method or high-energy ball milling method non-with solid electrolyte matrix material chemical composition identical
Amorphous material；
B) amorphous substance, binding agent and solvent are mixed, obtain composite material sizing agent；
C) composite material sizing agent is coated on to the surface of the solid electrolyte matrix material, remove solvent and bonding
Agent simultaneously softens the amorphous substance, obtains the inorganic solid electrolyte that surface is amorphous substance.
Preferably, the melting-quenching method is：
The mixture of raw material is incubated 1~24 hour under conditions of 700~900 DEG C；
Above-mentioned product is crushed, then quenched after being incubated 1~24 hour under conditions of 1200~1500 DEG C using liquid nitrogen
It is cold, obtain solid electrolyte matrix material amorphous block；
The solid electrolyte matrix material amorphous block is crushed, obtained and solid electrolyte matrix material chemical composition
Identical amorphous substance.
Preferably, the high-energy ball milling method is：
It is (5~30) by mass ratio:1 ball milling ball and solid electrolyte matrix material be placed in ball grinder with 400~
600rpm rotating speed 1~50h of ball milling, obtain and solid electrolyte matrix material chemical composition identical amorphous substance.
Preferably, the mass ratio of the amorphous substance, binding agent and solvent is 1:(2~5):8.
Preferably, the binding agent is selected from cellulose nitrate, polyvinyl alcohol, Kynoar, polyoxyethylene and hydroxyl
One or more in cellulose.
The solvent is a kind of or more in water, ethanol, acetonitrile, tetrahydrofuran, acetone, dimethyl sulfoxide (DMSO) and terpinol
Kind.
Preferably, the temperature of the softening is 500~700 DEG C, and the time of the softening is 1~24h.
Preferably, the solid electrolyte matrix is selected from NASICON structures or perovskite structure, the amorphous substance choosing
From amorphous state titanium phosphate (germanium) aluminium lithium or amorphous state lanthanium titanate lithium.
The surface being prepared present invention also offers a kind of above-mentioned preparation method is electric for the inoganic solids of amorphous substance
Xie Zhi, including solid electrolyte matrix and the amorphous substance layer for being compound in the solid electrolyte matrix surface are described non-
Amorphous material be and solid electrolyte matrix material chemical composition identical amorphous substance.
Preferably, the thickness of the amorphous substance layer is 0.1 μm~50 μm.
Compared with prior art, the preparation the invention provides a kind of surface for the inorganic solid electrolyte of amorphous substance
Method, comprise the following steps：A) using melting-quenching method or high-energy ball milling method prepare with solid electrolyte matrix material chemistry into
Divide identical amorphous substance；B) amorphous substance, binding agent and solvent are mixed, obtain composite material sizing agent；C) will
The composite material sizing agent is coated on the surface of the solid electrolyte matrix material, removes described in solvent and binding agent and softening
Amorphous substance, obtain the inorganic solid electrolyte that surface is amorphous substance.The present invention answers in solid electrolyte matrix surface
The amorphous substance of conjunction can strangle growth of the Li dendrite in crystal boundary without grain boundary features from source, and its softer quality
Plastic deformation can be produced to a certain extent, so there will be bigger advantage in terms of the contact with lithium and the release of stress.Meanwhile
Although identical with inorganic crystalline state electrolyte matrix chemical element composition, using the randomness of non crystalline structure, atom randomness it is big,
Elemental redistribution is uneven to suppress the reaction of element-specific in lithium metal and electrolyte, destroys original orderly electron channel, makes
Obtain and keep apart inside amorphous with top layer, prevent lithium metal from directly being contacted with more element-specifics and chemically reacts, greatly
Ground protects body portion solid electrolyte, reduces the high impedance of electrolyte/electrode solids contact interface, so as to obtain pair
Have concurrently stable to lithium and contact good Composite Pure inorganic solid electrolyte.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the inorganic solid electrolyte that surface prepared by embodiment 1 is amorphous substance；
Fig. 2 is that the surface in embodiment 1 is that the inorganic solid electrolyte top layer of amorphous substance and the XRD of internal layer are contrasted
Figure；
Fig. 3 is that the inorganic solid electrolyte that surface in embodiment 1 is amorphous substance is assembled into Li/Li Symmetrical cells and existed
60 DEG C, 0.1mA cm-2M- voltage pattern during lower charge and discharge cycles；
Fig. 4 is that the inorganic solid electrolyte that surface in embodiment 1 is amorphous substance is assembled into Li/Li Symmetrical cells and existed
AC impedance monitoring figure at 60 DEG C；
Fig. 5 is amorphous state and the XRD comparison diagrams of crystalline state electrolyte prepared by embodiment 2；
Fig. 6 is the surface of inorganic solid electrolyte and the SEM in section that surface prepared by embodiment 2 is amorphous substance
Figure；
Fig. 7 is that the inorganic solid electrolyte that surface in embodiment 2 is amorphous substance is assembled into Li/Li Symmetrical cells and existed
60 DEG C, 0.3mA cm-2M- voltage pattern during lower charge and discharge cycles；
Fig. 8 is amorphous state and the XRD of crystalline state electrolyte prepared by embodiment 3；
Fig. 9 is the section SEM figures for the inorganic solid electrolyte that surface prepared by embodiment 3 is amorphous substance；
Figure 10 is that the inorganic solid electrolyte that surface in embodiment 3 is amorphous substance is assembled into Li/Li Symmetrical cells
At 60 DEG C, 0.3mA cm-2M- voltage pattern during lower charge and discharge cycles；
Figure 11 is amorphous state and the XRD of crystalline state electrolyte prepared by embodiment 4；
Figure 12 is the superficial layer microscopic appearance for the inorganic solid electrolyte that surface prepared by embodiment 4 is amorphous substance
Figure；
Figure 13 is that the inorganic solid electrolyte that surface prepared by the embodiment of the present invention 4 is amorphous substance is assembled into Li/Li
Symmetrical cells AC impedance at 60 DEG C monitors；
Figure 14 is that the inorganic solid electrolyte that surface prepared by the embodiment of the present invention 4 is amorphous substance is assembled into Li/Li
Symmetrical cells are at 60 DEG C, 0.1mA cm-2M- voltage pattern during lower charge and discharge cycles；
Figure 15 is amorphous state and the XRD of crystalline state electrolyte prepared by embodiment 5；
Figure 16 is the scanning electron microscope (SEM) photograph for the inorganic solid electrolyte that surface prepared by embodiment 5 is amorphous substance；
Figure 17 is that to be assembled into Li/Li symmetrically electric for inorganic solid electrolyte that surface prepared by embodiment 5 is amorphous substance
Pond AC impedance at 60 DEG C monitors；
Figure 18 is the Li in comparative example 1 of the present invention1.5Al0.5Ge1.5(PO4)372 are contacted at 60 DEG C of electrolyte sheet and lithium metal
The cross-sectional scans electron microscope of (a) (b) afterwards before hour；
Figure 19 is the Li in comparative example 1 of the present invention1.5Al0.5Ge1.5(PO4)3Electrolyte sheet assembles Li/Li Symmetrical cells 60
DEG C AC impedance monitoring figure；
Li in Figure 20 comparative examples 1 of the present invention1.5Al0.5Ge1.5(PO4)3Electrolyte sheet is assembled into Li/Li Symmetrical cells 60
DEG C, 0.1mA cm-2M- voltage pattern during lower charge and discharge cycles；
Figure 21 is the Li in comparative example 2 of the present invention1.5Al0.5Ti1.5(PO4)372 are contacted at 60 DEG C of electrolyte sheet and lithium metal
The cross-sectional scans electron microscope of (a) (b) afterwards before hour；
Figure 22 is the Li in comparative example 2 of the present invention1.5Al0.5Ti1.5(PO4)3Electrolyte sheet is assembled into Li/Li Symmetrical cells and existed
60 DEG C, 0.1mAcm-2M- voltage pattern during lower charge and discharge cycles；
Figure 23 is the Li in comparative example 2 of the present invention1.5Al0.5Ti1.5(PO4)3Electrolyte sheet is assembled into Li/Li Symmetrical cells and existed
60 DEG C of AC impedance monitoring figure；
Figure 24 is the Li in comparative example 3 of the present invention0.35La0.55TiO3Contacted 72 hours at 60 DEG C of electrolyte sheet and lithium metal
Before (a) (b) afterwards table scan electron microscope；
Figure 25 is the Li in comparative example 3 of the present invention0.35La0.55TiO3Electrolyte sheet is assembled into Li/Li Symmetrical cells 60
DEG C, 0.3mA cm-2M- voltage pattern during lower charge and discharge cycles.
Embodiment
A kind of preparation method the invention provides surface for the inorganic solid electrolyte of amorphous substance, including following step
Suddenly：
A) prepared using melting-quenching method or high-energy ball milling method non-with solid electrolyte matrix material chemical composition identical
Amorphous material；
B) amorphous substance, binding agent and solvent are mixed, obtain composite material sizing agent；
C) composite material sizing agent is coated on to the surface of the solid electrolyte matrix material, remove solvent and bonding
Agent simultaneously softens the amorphous substance, obtains the inorganic solid electrolyte that surface is amorphous substance.
The present invention is prepared identical with solid electrolyte matrix material chemical composition using melting-quenching method or high-energy ball milling method
Amorphous substance.
Wherein, the melting-quenching method is：
Solid electrolyte matrix material is crushed, then used after being incubated 1~24 hour under conditions of 1200~1500 DEG C
Liquid nitrogen carries out quenching, obtains solid electrolyte matrix material amorphous block；
The solid electrolyte matrix material amorphous block is crushed, obtained and solid electrolyte matrix material chemical composition
Identical amorphous substance.
Wherein, the present invention is not particularly limited to the source of the solid electrolyte matrix material and preparation method, this
Preparation method known to art personnel.
In the present invention, the solid electrolyte matrix material is preferably prepared as follows：
Raw material is well mixed according to the stoichiometric proportion of the solid electrolyte matrix material chemical formula, obtains original
The mixture of material matter, the container of the mixing is preferably ball grinder.
Then the mixture is incubated 1~24 hour under conditions of 700~900 DEG C；Preferably 750~850 DEG C
Under the conditions of be incubated 5~20 hours.By aforesaid operations, discharge the escaping gas in mixture, and obtain crystalline state electrolyte
Matrix.
Above-mentioned product is crushed, then 1~24 hour is incubated under conditions of 1200~1500 DEG C, preferably 1300~1400
2~20 hours are incubated under conditions of DEG C, aforesaid operations are carried out preferably in platinum crucible, after insulation terminates, pour into liquid nitrogen
Row quenching, obtain solid electrolyte matrix material amorphous block.
The solid electrolyte matrix material amorphous block is crushed, obtained and solid electrolyte matrix material chemical composition
Identical amorphous substance.
The present invention can also use high-energy ball milling method to prepare and solid electrolyte matrix material chemical composition identical amorphous
State material.
The high-energy ball milling method is specially：
It is (5~30) by mass ratio:1 ball milling ball and solid electrolyte matrix material be placed in ball grinder with 400~
600rpm rotating speed 1~50h of ball milling, obtain and solid electrolyte matrix material chemical composition identical amorphous substance.
The rotating speed preferably 450~550rpm, the time of the ball milling is preferably 10~35 hours.
One or more of the quality of the ball grinder in agate, zirconium oxide and stainless steel.The matter of the ball milling ball
One or more of the ground in agate, zirconium oxide and stainless steel.
In the mechanical milling process, water and organic solvent are not added, only enters ball milling ball and solid electrolyte matrix material
Row ball milling.
The device that the ball milling uses is preferably planetary high-energy ball mill.
After obtaining amorphous substance, the amorphous substance, binding agent and solvent are mixed, obtain composite material sizing agent.
The mass ratio of the amorphous substance, binding agent and solvent is 1:(2~5):8, preferably 1:(3~4):8.
The binding agent is selected from cellulose nitrate, polyvinyl alcohol, Kynoar, in polyoxyethylene and hydroxylated cellulose
One or more.
The solvent is a kind of or more in water, ethanol, acetonitrile, tetrahydrofuran, acetone, dimethyl sulfoxide (DMSO) and terpinol
Kind.
After obtaining composite material sizing agent, the composite material sizing agent is coated on to the table of the solid electrolyte matrix material
Face, the method for the coating are selected from spraying, spin coating, blade coating or silk-screen printing.
The amorphous substance is coated on to the surface of the solid electrolyte matrix material, removes solvent and binding agent simultaneously
Soften the amorphous substance.
In the present invention, the bating step is realized by being heat-treated, and the temperature of the softening is 500~700 DEG C, preferably
For 550~650 DEG C, the time of the softening is 1~24 hour, preferably 2~10 hours.
Softened, by temperature it is elevated during, when temperature rises to 100~200 DEG C by room temperature condition, solvent quilt
Remove, the solvent removal that can volatilize at ambient temperature can also heat removal；When temperature rises to 300~400 DEG C, glue
Knot agent is removed；When temperature rises to 500~700 DEG C, bating step is carried out.
Finally give the inorganic solid electrolyte that surface is amorphous substance.
In the present invention, the solid electrolyte matrix is selected from NASICON structures or perovskite structure, the amorphous state thing
Matter is selected from amorphous state titanium phosphate (germanium) aluminium lithium or amorphous state lanthanium titanate lithium.
Wherein, the solid electrolyte matrix material of the NASICON structures is preferably Li1+xAlxM2-x(PO4)3, wherein, x
=0~0.50, M are selected from Ti, Ge；The solid electrolyte matrix material of the perovskite structure is preferably LixLa2/3-x/3TiO3, its
In, x=0~0.50
The surface being prepared present invention also offers a kind of above-mentioned preparation method is electric for the inoganic solids of amorphous substance
Xie Zhi, including solid electrolyte matrix and the amorphous substance layer for being compound in the solid electrolyte matrix surface are described non-
Amorphous material be and solid electrolyte matrix material chemical composition identical amorphous substance.
In the present invention, the thickness of the amorphous substance layer be 0.1 μm~50 μm, preferably 0.5~40 μm, more preferably
For 1~10 μm.
The present invention using inorganic amorphous material characteristic, such as can hot mastication deformation, modulus it is higher, without crystal boundary, have one
Structure in nanometer that the atom packing of fixed lithium ion conductivity and longrange disorder shortrange order is brought, micro-meter scale is uneven
Even property, inorganic amorphous material is compound on inorganic solid electrolyte surface, forms a kind of matrix as the inorganic of high conductivity
The fast lithium ion conductor of solid-state, top layer are the integrated, multi-level electrolyte of amorphous substance to lithium stabilization, that contact is good.
Amorphous substance can strangle growth of the Li dendrite in crystal boundary without grain boundary features from source, and its softer matter
Ground can produce plastic deformation to a certain extent, so will have bigger advantage in terms of the contact with lithium and the release of stress.Together
When, although identical with inorganic crystalline state electrolyte matrix chemical element composition, utilize the randomness of non crystalline structure, atom randomness
Greatly, Elemental redistribution is uneven suppresses the reaction of element-specific in lithium metal and electrolyte, destroys original orderly electron channel,
So that keeping apart inside amorphous with top layer, prevent lithium metal from directly being contacted with more element-specifics and chemically react, pole
The earth protects body portion solid electrolyte, the high impedance of electrolyte/electrode solids contact interface is reduced, so as to obtain
To having concurrently stable to lithium and contacting good Composite Pure inorganic solid electrolyte.
For a further understanding of the present invention, the nothing with reference to embodiment to surface provided by the invention for amorphous substance
Machine solid electrolyte and preparation method thereof is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Stoichiometrically weigh Li1.5Al0.5Ge1.5(PO4)3Raw material Li needed for solid electrolyte2CO3、Al2O3、P2O5、
GeO2And batch mixing is dried, and amorphous block is prepared using melting-quenching method after 700 DEG C of pre-burning 2h.1400 DEG C of melting temperature, protect
Warm time 2h.Amorphous block wet ball grinding is crushed, ceramic solid state is made in 300MPa lower sheetings and in 900 DEG C of insulation 5h sintering
Electrolyte sheet.
The cellulose nitrate of 2 times of precise amorphous powder quality, the ethanol of 8 times of its quality, is collectively disposed at beaker and exists
24h is stirred under argon atmosphere, obtains composite mortar；Composite mortar is coated in Li successively with blade coating mode1.5Al0.5Ti1.5(PO4)3
Solid electrolyte sheet two sides, is placed in Muffle furnace after the solvent is volatilized, and 500 DEG C of heat treatment 2h, gained surface is amorphous substance
Inorganic solid electrolyte, wherein, the thickness of the amorphous substance layer on surface is about 3 microns.
Electron-microscope scanning is carried out for the inorganic solid electrolyte of amorphous substance to the surface, it is real as a result to see Fig. 1, Fig. 1
The surface for applying the preparation of example 1 is the scanning electron microscope (SEM) photograph of the inorganic solid electrolyte of amorphous substance.
XRD detections are carried out for the top layer of the inorganic solid electrolyte of amorphous substance and internal layer to the surface, as a result seen
Fig. 2, Fig. 2 are the XRD comparison diagrams of the inorganic solid electrolyte top layer that surface is amorphous substance and internal layer.As shown in Figure 2, top layer
Material be amorphous state, without obvious diffraction maximum, the material of internal layer is the Li of pure phase1.5Al0.5Ti1.5(PO4)3, this illustrates logical
Cross the method can obtain surface be amorphous state and inside be crystalline state composite integrated electrolyte.
Using lithium metal as electrode, Symmetrical cells are assembled into, in 60 DEG C, 0.1mA cm-2Charge and discharge electrical measurement is carried out under current density
Examination, as a result as shown in figure 3, it is that the inorganic solid electrolyte of amorphous substance is assembled into that Fig. 3, which is surface in the embodiment of the present invention 1,
Li/Li Symmetrical cells are at 60 DEG C, 0.1mA cm-2M- voltage pattern during lower charge and discharge cycles.After 200h is tested, test curve according to
Old stabilization, battery are not also significantly increased without short circuit or open circuit, voltage, illustrate that combined electrolysis confrontation lithium metal is stable.
Using lithium as electrode assembling Symmetrical cells, EIS tests are carried out under the conditions of 60 DEG C, test it to lithium interface impedance at any time
Between change, as a result as shown in figure 4, Fig. 4 is surface in the embodiment of the present invention 1 be amorphous substance inorganic solid electrolyte
It is assembled into Li/Li Symmetrical cells AC impedance monitoring figure at 60 DEG C.In the interface impedance 14 days of composite electrolyte and lithium metal
Keep stable, meanwhile, compared with Figure 19 in comparative example 1, interface impedance is lower.
Embodiment 2
By Li0.35La0.55TiO3Electrolyte raw material La2O3、Li2CO3And TiO2With agate ball according to mass ratio 1:30 weigh,
The 50h that dry grinds is placed in agate pot.Period, often cross 2h and open ball grinder, continue ball after the powder for being bonded at ball milling top tank structure is scraped
Mill, it is final to obtain amorphous state Li0.35La0.55TiO3Electrolyte powder.
Gained powder is subjected to tabletting, 1000 DEG C of high annealing 3h obtain Li0.35La0.55TiO3Ceramic electrolyte sheet.Gained
Amorphous state Li0.35La0.55TiO3Powder and crystalline state Li0.35La0.55TiO3Fig. 5 is shown in potsherd XRD contrasts.Fig. 5 is prepared by embodiment 2
Amorphous state and crystalline state Li0.35La0.55TiO3XRD comparison diagrams.
By amorphous powder and polyvinyl alcohol, dimethyl sulfoxide (DMSO) according to mass ratio 1:3:After 50h being stirred after 8 weighings, rotation
It is coated in Li0.35La0.55TiO3Electrolyte sheet both side surface, anneal 3h in 600 DEG C, and it is amorphous layer to obtain surface thickness to be 0.5 micron
Li0.35La0.55TiO3Electrolyte sheet.Surface and section SEM are shown in that Fig. 6, Fig. 6 are that surface prepared by embodiment 2 is amorphous substance
Inorganic solid electrolyte surface and section SEM figure.
Assemble Li/ electrolyte/Li Symmetrical cells 0.3mA/cm at 60 DEG C2The charge-discharge test of current density, during circulation
M- voltage pattern is shown in Fig. 7.Fig. 7 is that the inorganic solid electrolyte that surface in embodiment 2 is amorphous substance is assembled into Li/Li pairs
Claim battery at 60 DEG C, 0.3mA cm-2M- voltage pattern during lower charge and discharge cycles.And its stability to lithium is also very good, in 250h
Under interior high current charge-discharge, battery does not polarize.Figure 23 in reference examples 3 is contrasted, this explanation surface is amorphous
Li0.35La0.55TiO3It is stable to lithium, and the decorative layer prepared plays a very good protection.
Embodiment 3
According to stoichiometric proportion precise and measure Li0.5La0.5TiO3Raw material Li NO3、La(NO3)3.6H2O、
C16H36O4Ti, and be dissolved in proper amount of glycol, it is spin-coated on after stirring 24h on aluminum oxide film sheet matrix, carries out 1000 DEG C
After high temperature sintering 3h, by aluminum oxide film from Li0.5La0.5TiO3Electrolyte is peeled off by way of grinding and polishing, obtains crystalline state solid-state
Li0.5La0.5TiO3Electrolytic thin-membrane.
By above-mentioned Li0.5La0.5TiO3Electrolyte ball mill grinding is incubated 2h into after powder at 1400 DEG C, after being quenched in liquid nitrogen
It is cold, obtain Li0.5La0.5TiO3Amorphous block, ball mill grinding obtain Li0.5La0.5TiO3Non- crystalline flour, non-crystalline flour, the XRD of potsherd
It is the Li of amorphous state prepared by embodiment 3 and crystalline state to see Fig. 8, Fig. 80.5La0.5TiO3XRD.
By non-crystalline flour, hydroxylated cellulose, terpinol according to mass ratio 1:2:8 weigh, after ball milling mixing is uniform, by slurry silk
Wire mark brush is to electrolytic thin-membrane both side surface and dries.Afterwards, above-mentioned composite electrolyte is incubated 5h for 700 DEG C in Muffle furnace,
After surface non-crystalline flour melting and firmly with substrate adhesive it is integral after, take out and obtain surface be amorphous substance it is inorganic solid
Body electrolyte, the thickness of wherein amorphous substance layer is about 2 μm.The section SEM of composite electrolyte piece is shown in that Fig. 9, Fig. 9 are embodiment
Scheme for the section SEM of the inorganic solid electrolyte of amorphous substance on 3 surfaces prepared.
Assemble Li/ electrolyte/Li Symmetrical cells and carry out electrochemical Characterization, the charging and discharging currents density 0.3mA at 60 DEG C
cm-2.Test result is shown in that Figure 10, Figure 10 are the inorganic solid electrolyte group that surface in the embodiment of the present invention 3 is amorphous substance
Li/Li Symmetrical cells are dressed up at 60 DEG C, 0.3mA cm-2M- voltage pattern during lower charge and discharge cycles.Symmetrical cells are in high current density
Under, stable charge/discharge is more than 360h, without the increased phenomenon of polarizing voltage.It is right to illustrate that amorphous surface layer can significantly improve its
Lithium stability.
Embodiment 4
According to Li1.5Al0.5Ti1.5(PO4)3Stoichiometric proportion weigh Li2CO3,TiO2,Al2O3,(NH4)2H2PO4And mix
Close, heated 30 minutes at 300 DEG C by the abundant wet-milling of mixture and in Muffle furnace.After cooling, mixture is ground into thin white
Color powder, and it is heated to 800 DEG C about 30 minutes, and the Slow cooling in stove again.Fine powder is regrind 30 minutes, and
It is cold-pressed under 70MPa pressure, forms a diameter of 50mm, thickness is 3mm thin slice.Then the thin slice is sintered at 1100 DEG C
5 hours, and slowly cooled down in stove, obtain Li1.5Al0.5Ge1.5(PO4)3Ceramic electrolyte sheet.
1500 DEG C are warming up to after another part material powder is well mixed and is incubated 2h, and liquation is directly poured into liquid nitrogen basin
Middle quenching obtains amorphous state electrolyte, and XRD is shown in that Figure 11, Figure 11 are amorphous state Li prepared by embodiment 41.5Al0.5Ti1.5(PO4)3Electricity
Solve the XRD of matter.
By amorphous state electrolyte powder and polyoxyethylene, acetonitrile according to mass ratio 1:3:8 mix 24h, obtain uniformly
Glue.Glue is spin-coated on ceramic electrolyte sheet two sides, 300 DEG C of insulation 5h are risen to 1 DEG C/min programming rate after drying
Fully to decompose the organic matter in glue, then being warming up to 600 DEG C of insulation 5h melts amorphous powder, and it is amorphous state thing to obtain surface
The inorganic solid electrolyte of matter, wherein, the thickness of amorphous substance layer is about 2 μm.
Morphology analysis is carried out for the superficial layer of the inorganic solid electrolyte of amorphous substance to the surface, as a result seen
Figure 12, Figure 12 are that the superficial layer for the inorganic solid electrolyte that surface prepared by embodiment 4 is amorphous substance carries out microscopic appearance
Figure.
Electrolyte and electrode lithium lithium Symmetrical cells are assembled into composite electrolyte, lithium piece, at 60 DEG C carry out EIS monitoring with
0.1mA cm-2The charge-discharge test of current density, specific data are shown in Figure 13 and Figure 14.Figure 13 is prepared by the embodiment of the present invention 4
Surface is assembled into Li/Li Symmetrical cells AC impedance at 60 DEG C for the inorganic solid electrolyte of amorphous substance and monitored；Figure 14
The surface prepared for the embodiment of the present invention 4 is that the inorganic solid electrolyte of amorphous substance is assembled into Li/Li Symmetrical cells 60
DEG C, 0.1mA cm-2M- voltage pattern during lower charge and discharge cycles.
From Figure 12, it is apparent that the bath surface of big crystal grain has one layer of melt substance, its table is equably covered in
Face.Meanwhile after Figure 13 testing impedance has shown amorphous layer, electrolyte can keep interface stability to lithium in 60 days,
And due to being applied with pressure, the contact of electrolyte/lithium improves, and impedance does not increase counter subtract.Figure 14 be shown in have passed through it is 1000 small
When low current discharge and recharge after, lithium lithium Symmetrical cells can still keep stable polarizing voltage.
Embodiment 5
According to Li1.3Al0.3Ti1.7(PO4)3Stoichiometric proportion weigh TiO2,Al(OH)3,(NH4)2HPO4And LiOH
H2O.Raw material ball milling is carried out to 750 DEG C of heat treatment 12h after well mixed, is pressed into thin slice afterwards, carries out 900 DEG C of heat treatment
24h obtains ceramic electrolyte sheet.
Then this electrolyte sheet is warming up to 1400 DEG C of holding 1h, quenching obtains amorphous state electrolyte, XRD into liquid nitrogen
See the XRD that Figure 15, Figure 15 are amorphous state electrolyte and crystalline state electrolyte sheet prepared by embodiment 5.
By amorphous state electrolyte powder, Kynoar, acetone according to 1:3:8 mass ratio mixes plastic, with scraping
Knife is scratched on ceramic electrolyte sheet surface.After to be dried, above-mentioned sample is carried out to 550 DEG C of annealing in atmosphere as Muffle furnace
5h, the inorganic solid electrolyte that surface is amorphous substance is obtained, wherein, the thickness of amorphous substance layer is about 10 μm.Scanning
Electron microscope is shown in the electron-microscope scanning figure that Figure 16, Figure 16 are the inorganic solid electrolyte that surface prepared by embodiment 5 is amorphous substance.
Lithium/composite electrolyte/lithium Symmetrical cells are assembled, by the impedance variations that it is monitored at 60 DEG C, data are shown in that Figure 17, Figure 17 are real
The surface for applying the preparation of example 5 is assembled into Li/Li Symmetrical cells resistance is exchanged at 60 DEG C for the inorganic solid electrolyte of amorphous substance
Anti- monitoring.
From Figure 15, it is apparent that having prepared amorphous Li by melting-quenching1.3Al0.3Ti1.7(PO4)3.Together
When Figure 16 show crystalline state Li1.3Al0.3Ti1.7(PO4)3Electrolyte sheet is provided with amorphous layer.Figure 17 then shows that combined electrolysis is verified
Lithium can keep stable interface impedance, Figure 23 of vs comparative examples 2 in 20 days, it can be deduced that surface is amorphous
Li1.3Al0.3Ti1.7(PO4)3With than simple Li1.3Al0.3Ti1.7(PO4)3More preferably to lithium stability.
Comparative example 1
By lithium metal and Li1.5Al0.5Ge1.5(PO4)3Electrolyte sheet at 60 DEG C directly place 3 days by contact, before and after contact
Li1.5Al0.5Ge1.5(PO4)3The SEM photograph of electrolyte sheet is as shown in figure 18, and Figure 18 is in comparative example 1 of the present invention
Li1.5Al0.5Ge1.5(PO4)3The cross-sectional scans electron microscope of (a) (b) afterwards before being contacted 72 hours at 60 DEG C of electrolyte sheet and lithium metal.
As shown in Figure 18, the conversion zone of a layer depth color occurs；Using lithium metal as electrode, Li/Li is assembled into1.5Al0.5Ge1.5(PO4)3/Li
Symmetrical cells, battery being subjected to ac impedance measurement at 60 DEG C, test electrolyte changes over time to lithium metal interface impedance,
Test result is as shown in figure 19, and Figure 19 is the Li in comparative example 1 of the present invention1.5Al0.5Ge1.5(PO4)3Electrolyte sheet assembles Li/Li
Symmetrical cells monitor figure in 60 DEG C of AC impedance.It can be seen that after 4 days, interface impedance increases to initial about 100
Times.Symmetrical cells are subjected to 0.1mA cm at 60 DEG C-2The discharge and recharge of current density, polarizing voltage is observed, as a result sees Figure 20, schemed
20 be the Li in comparative example 1 of the present invention1.5Al0.5Ge1.5(PO4)3Electrolyte sheet is assembled into Li/Li Symmetrical cells at 60 DEG C,
0.1mAcm-2M- voltage pattern during lower charge and discharge cycles.As shown in Figure 20, the polarizing voltage of battery has reached 5V about after 95h, is
About 50 times of initial value.These, which are characterized, proves, pure Li1.5Al0.5Ge1.5(PO4)3Its is unstable to lithium electrode for electrolyte sheet.
Comparative example 2
By lithium metal and Li1.5Al0.5Ti1.5(PO4)3Electrolyte sheet at 60 DEG C directly place 3 days by contact, before and after contact
Li1.5Al0.5Ti1.5(PO4)3The SEM photograph of electrolyte sheet is as shown in figure 21, and Figure 21 is in comparative example 2 of the present invention
Li1.5Al0.5Ti1.5(PO4)3The cross-sectional scans electron microscope of (a) (b) afterwards before being contacted 72 hours at 60 DEG C of electrolyte sheet and lithium metal,
As shown in Figure 21, the reaction interface layer of a layer depth color occurs；Using lithium metal as electrode, Li/Li is assembled into1.5Al0.5Ti1.5
(PO4)3/ Li Symmetrical cells, by battery in 60oC, 0.1mAcm-2Ac impedance measurement is carried out under electric current, test result such as Figure 22
Shown, Figure 22 is the Li in comparative example 2 of the present invention1.5Al0.5Ti1.5(PO4)3Electrolyte sheet is assembled into Li/Li Symmetrical cells 60
DEG C, 0.1mA cm-2M- voltage pattern during lower charge and discharge cycles.As shown in Figure 22, as battery charge and discharge about 300h, polarizing voltage is
Through for initial about 500 times, polarizing voltage has arrived at 5V (initially about 0.01V).Electrolyte/lithium interface impedance is monitored simultaneously
Change over time, as shown in figure 23, Figure 23 is the Li in comparative example 2 of the present invention1.5Al0.5Ti1.5(PO4)3Electrolyte sheet is assembled into
Li/Li Symmetrical cells monitor figure in 60 DEG C of AC impedance.As shown in Figure 23, after 3 days, interface impedance is about the 150 of first day
Times.This illustrates the Li of no decorative layer1.5Al0.5Ti1.5(PO4)3To lithium electrode, its is unstable.
Comparative example 3
By lithium metal and Li0.35La0.55TiO3Electrolyte sheet at 60 DEG C directly place 3 days by contact, before and after contact
Li0.35La0.55TiO3The surface SEM photograph of electrolyte sheet is as shown in figure 24, and Figure 24 is in comparative example 3 of the present invention
Li0.35La0.55TiO3The table scan electron microscope of (a) (b) afterwards before being contacted 72 hours at 60 DEG C of electrolyte sheet and lithium metal.It can send out
Existing surface is dimmed and heterosphere occurs；Using lithium metal as electrode, Li/Li is assembled into0.35La0.55TiO3/ Li Symmetrical cells,
By battery in 60oC, 0.3mAcm-2Ac impedance measurement is carried out under electric current, test electrolyte is to lithium metal interface impedance with the time
Change, test result is as shown in figure 25, and Figure 25 is the Li in comparative example 3 of the present invention0.35La0.55TiO3Electrolyte sheet is assembled into Li/
Li Symmetrical cells are at 60 DEG C, 0.3mA cm-2M- voltage pattern during lower charge and discharge cycles.It can be found that after 80h battery polarization
Voltage rises to 0.5V (being initially 0.02V), illustrates exposed Li0.35La0.55TiO3It is highly unstable to lithium.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of surface is the preparation method of the inorganic solid electrolyte of amorphous substance, it is characterised in that is comprised the following steps：
A) prepared and solid electrolyte matrix material chemical composition identical amorphous state using melting-quenching method or high-energy ball milling method
Material；
B) amorphous substance, binding agent and solvent are mixed, obtain composite material sizing agent；
C) composite material sizing agent is coated on to the surface of the solid electrolyte matrix material, remove solvent and binding agent simultaneously
Soften the amorphous substance, obtain the inorganic solid electrolyte that surface is amorphous substance.
2. preparation method according to claim 1, it is characterised in that the melting-quenching method is：
Solid electrolyte matrix material is crushed, then liquid nitrogen is used after being incubated 1~24 hour under conditions of 1200~1500 DEG C
Quenching is carried out, obtains solid electrolyte matrix material amorphous block；
The solid electrolyte matrix material amorphous block is crushed, obtained identical with solid electrolyte matrix material chemical composition
Amorphous substance.
3. preparation method according to claim 1, it is characterised in that the high-energy ball milling method is：
It is (5~30) by mass ratio:1 ball milling ball is placed in ball grinder with 400~600rpm with solid electrolyte matrix material
Rotating speed 1~50h of ball milling, obtain and solid electrolyte matrix material chemical composition identical amorphous substance.
4. preparation method according to claim 1, it is characterised in that the matter of the amorphous substance, binding agent and solvent
Amount is than being 1:(2~5):8.
5. preparation method according to claim 1, it is characterised in that the binding agent is selected from cellulose nitrate, poly- second
Enol, Kynoar, the one or more in polyoxyethylene and hydroxylated cellulose；
The solvent is one or more in water, ethanol, acetonitrile, tetrahydrofuran, acetone, dimethyl sulfoxide (DMSO) and terpinol.
6. preparation method according to claim 1, it is characterised in that the temperature of the softening is 500~700 DEG C, described
The time of softening is 1~24h.
7. preparation method according to claim 1, it is characterised in that the solid electrolyte matrix is tied selected from NASICON
Structure or perovskite structure, the amorphous substance are selected from amorphous state titanium phosphate (germanium) aluminium lithium or amorphous state lanthanium titanate lithium.
8. the surface that a kind of preparation method as described in claim 1~7 any one is prepared is the nothing of amorphous substance
Machine solid electrolyte, it is characterised in that including solid electrolyte matrix and be compound in the solid electrolyte matrix surface
Amorphous substance layer, the amorphous substance are and solid electrolyte matrix material chemical composition identical amorphous substance.
9. inorganic solid electrolyte according to claim 8, it is characterised in that the thickness of the amorphous substance layer is
0.1 μm~50 μm.
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