CN107425218A - A kind of lithium ion solid electrolyte and preparation method thereof, application - Google Patents
A kind of lithium ion solid electrolyte and preparation method thereof, application Download PDFInfo
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- CN107425218A CN107425218A CN201710661877.9A CN201710661877A CN107425218A CN 107425218 A CN107425218 A CN 107425218A CN 201710661877 A CN201710661877 A CN 201710661877A CN 107425218 A CN107425218 A CN 107425218A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of lithium ion solid electrolyte and preparation method thereof, application, belong to technical field of lithium ion.The lithium ion solid electrolyte of the present invention has chemical formula as follows：Li3+aMpAmBnY1‑b, wherein 0.25≤a≤0.25；0≤b≤0.5；0≤p≤0.5,0≤m≤1.25,0≤n≤1.25；M is any one in Ca, Ba, Mg, Al, Ti；A, B separately one kind in O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl, Br, I；Y is one kind in halogen or negative one valency ion cluster or room.The lithium ion solid electrolyte of the present invention has stable structure and good lithium ion transport performance, in the solid electrolyte as lithium ion battery with good chemical property and security performance.
Description
Technical field
The present invention relates to a kind of lithium ion solid electrolyte and preparation method thereof, application, belongs to lithium ion battery technology neck
Domain.
Background technology
Lithium ion battery is typically made up of the barrier film between positive pole, negative pole, setting and both positive and negative polarity, electrolyte, due to lithium from
The electrolyte that sub- battery uses uses organic solvent, and the organic solvent is very easy to burning, in order to improve lithium ion battery
Security, it usually needs on battery structure or battery material carries out particular design, to prevent electrolyte from revealing or avoiding
Electrolyte burns.The electrolyte that lithium ion battery uses is also very easy to form Li dendrite in negative terminal surface, causes inside battery
Short circuit simultaneously releases substantial amounts of heat in a short time.In order to avoid the appearance of Li dendrite to the full extent, typically by electricity
The safety device or structure for being used for suppressing battery short circuit are set in pond, to avoid internal temperature of battery from drastically raising.
Liquid organic electrolyte is substituted using all solid state electrolyte, is expected to fundamentally to solve the inflammable safety of lithium battery hidden
Suffer from, and overcome the problem of lithium Dendritic TiC is formed between electrolyte and metal lithium electrode interface.But with the ion-conductance of liquid electrolyte
Lead that (lithium ion conductance is more than 1mScm for standard-1), realize that the fast transport of Li ions is still great in solid electrolyte and choose
War.
The lithium ion conductivity of solid oxide electrolyte of the prior art is general all than relatively low, is typically each less than
1mScm-1Industry requirement, such as lithium titanium phosphate type Li1.3M0.3Ti1.7(PO4)3(M is Al or Sc) solid electrolyte, at 25 DEG C
At a temperature of lithium ion conductance be up to 0.7mScm-1, carbuncle type Li7La3Zr2O12Solid electrolyte, in the bar of 25 DEG C of temperature
Lithium ion conductance is 0.774mScm under part-1, Li2.88PO3.73N0.14Under conditions of 25 DEG C of temperature lithium ion conductance be 2.3 (±
0.7)×10-3mScm-1, diffusion activation energy is 0.55 (± 0.02) eV.
In recent years, with the progress that sulfide solid electrolyte correlative study works, some sulfenyl solid electrolyte performances
Go out higher lithium ion conductance.Wherein, tetragonal Li10GeP2S12Be recognized be solid electrolyte best at this stage it
One.At ambient temperature, its lithium ion conductance can exceed 10mScm-1, diffusion activation energy is between 0.22-0.285eV.So
And such material only has the one-dimensional lithium ion transport passage along c- direction of principal axis, the activation of horizontal proliferation can be too high, about
0.62eV so that this electrolytelike ion transport performance depends greatly on the distribution of orientations of crystal grain in electrolyte, only when
When the c- axial directions of most of crystal grain are close to ion transport direction, the ionic conductance of electrolyte can just give full play of.
Li10GeP2S12On the basis of, the Li with similar structures9.54Si1.74P1.44S11.7Cl0.3Five yuan of solid electrolytes were in quilt in 2016
Synthesis, due to the introducing of Cl ions, is modified to three-dimensional lithium ion tunnel by original one-dimensional passage, makes its lithium ion conductance significantly
Degree improves, it was reported that can reach 25mScm at ambient temperature-1, the lithium ion conductance that is far longer than in liquid electrolyte.But
When the material contacts with metal Li, electrochemical properties are unstable, thus hinder its practical application in all-solid-state battery technology.
Therefore, the ultrafast lithium-ion electrolyte for seeking and preparing new isotropic and stablizing, the technology for breaking through solid lithium battery
Barrier, there is highly important scientific meaning and application value.
The content of the invention
It is an object of the invention to provide the high lithium ion solid electrolyte of a kind of stabilization, lithium ion conductivity.
The present invention also aims to provide the preparation method and application of above-mentioned lithium ion solid electrolyte.
To achieve the above object, the technical scheme of lithium ion solid electrolyte of the invention is：
A kind of lithium ion solid electrolyte, the lithium ion solid electrolyte have chemical formula as follows：Li3+ aMpAmBnY1-b, wherein -0.25≤a≤0.25；0≤b≤0.5；0≤p≤0.5,0≤m≤1.25,0≤n≤1.25；M be Ca,
Any one in Ba, Mg, Al, Ti；A, B is separately in O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl, Br, I
One kind；Y is one kind in halogen or negative one valency ion cluster or room, and the halogen is any one in Cl, Br, I；It is described
Negative one valency ion cluster is OH-、BH4 -、NH2 -、CH3 -、CN-、MgX3 -、CaX3 -In one kind.
The lithium ion solid electrolyte of the present invention, has excellent lithium ion conductivity and thermodynamic stability.With one
Tie up the Li of lithium ion transport10GeP2S12Solid electrolyte is compared, and lithium ion solid electrolyte of the invention has three-dimensional equivalent
Ultrafast ion transport capability, diffusion activation energy is lower, and lithium ion conductivity is higher, and has good electrification with metal Li electrodes
Learn compatibility.Lithium ion solid electrolyte in the present invention is non-dosage than lithium ion solid electrolyte, now ensures a ≠ 0, or
B ≠ 0, or m+n ＞ 1.Lithium ion solid electrolyte with non-metering ratio is in terms of lithium ion transport with more protrusion
Ability.Preferably, as 0 ＜ b≤0.5, this anti-perovskite type compound has the structure more optimized.
In above-mentioned lithium ion solid electrolyte, metallic element M Li is not contained3+aMpAmBnY1-b(p=0) the AB elements in
Good passage, which can be provided, with the Li high ligand building blocks formed for the transmission of lithium ion makes it have extraordinary lithium
Ionic conductivity.Now, the p=0, it is 0 when m, n difference.Under the conditions of without rich lithium, i.e. during a=0, compound is still
With preferable lithium ion conductivity.Now, A, B are preferably separately in O, S, Se, Te, N, P, I, Cl, Br
It is a kind of.Or the one kind of n=0, A in O, S, Se, Te, N, P, I, Cl, Br.
Preferably, when m, n are not 0, above-mentioned lithium ion solid electrolyte has dimorphism anti-perovskite structure, space group
For(space group number is 225), has Li6A、Li6B octahedral structure units, on the angle of cube anti-perovskite；Y
It is filled in cube center.Now, p can be equal to 0, can also be not equal to 0.A can be equal to 0, can also be not equal to 0.
The solid electrolyte thermodynamic stability of the present invention, lattice dimensions are mainly by Li6A and Li6In B octahedrons between A-Li or B-Li
Ion bond distance is determined that the contribution of Y bits element is relatively weak.And the ion bond distance between A-Li or B-Li is decided by nonmetallic ion
The electronegativity of (A and B), electronegativity is stronger, and corresponding bond distance is shorter.It is brilliant when the sublattice position where A and B occupies by oxygen
Lattice yardstick is minimum, and the formation heat of compound is maximum, and Li ionic conductivities are minimum.(one in m, n in other words when A and B is identical
For 0 when), its structure is reduced to anti-perovskite structure, and space group number is 221, and symmetry class is
Preferably, in above-mentioned lithium ion solid electrolyte, the stoichiometric number of lithium can not be 3, i.e. a ≠ 0.Now, lithium
Ion solid electrolyte is divided into two kinds of situations of poor lithium and rich lithium, under both of these case, transmission of the lithium ion in solid electrolyte
Mode is different.
Lithium ion conductance is determined by its diffusion coefficient in solid electrolyte, and the long-range diffusion coefficient of lithium ion is then by lithium
Ion is in Li6Migration on A octahedrons is controlled.In such system, two major class Li ion transport modes are primarily present：(a)
Under conditions of lithium concentration is relatively low, Li+Migrated along the lithium room on octahedra drift angle, now diffusion activation energy is past
It is past bigger than normal；(b) under conditions of lithium concentration is higher, rich Li+With Li6Li on A octahedrons+Form Li+-Li+Dumbbell
Type match, and with the other end of Li on octahedron+Generation bulk migration, now diffusion activation energy is less than normal, often only defeated
/ 10th of fortune mode (a).Therefore, low temperature diffusion coefficient is mainly by lithium concentration, and overcomes it to be migrated on octahedron
Required diffusion activation energy is controlled.Due to diffusion activation energy and the Li number of ions in octahedron around nonmetallic ion (A or B)
Mesh is negatively correlated, such as works as Li6When A is surrounded by more Li ions in A octahedrons, diffusion barrier is smaller, and lithium ion conductance is got over
It is good.Therefore, when lithium concentration is higher than lithium content in standard stoichiometry in such solid electrolyte, rich lithium ion diffusion is more
Easily, diffusion activation energy is reduced by about 10 times.In order to improve lithium ion diffusion rate, -0.25≤a≤0.25 is limited；0≤b≤
0.5；0≤p≤0.5,0≤m≤1.25,0≤n≤1.25.Now, A, B preferably separately selected from O, S, Se, Te, N,
P, one kind in Si, C, Sb, Bi, F, Cl, Br, I.Or n=0, A be selected from O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl,
One kind in Br, I.Now, it is 0 when a ≠ 0, m, n difference.Preferably, p=0.Preferably, 0 ＜ a≤0.125.
Meanwhile in order to maintain the overall chemical key of electrolyte to balance as far as possible, while appropriate rich lithium, it shall be guaranteed that A
All exist with two kinds of elements of B, i.e., m, n are not 0.Now, larger octahedra Li is suitably increased6Nonmetallic B content in B, can
To realize ultrafast ground lithium ion transport.Meanwhile ensure, b ≠ 0, i.e., the appropriate content for reducing negative univalent anion can be further
Promote the speed of lithium ion transport.
Now, extra lithium (Li) ion is still adsorbed in Li6A or Li6Near A/B positions in B.A/B positions collect around
More lithium ions, so as to further reduce the average interaction between Li-A/B, enhance the diffusion activity of lithium ion.Separately
Outside, the interaction between Li-Li can effectively reduce the Li ion diffusion lengths between octahedron, hence it is evident that reduce diffusion barrier, table
It is now ultrafast lithium ion conductivity.
Preferably, dimorphism anti-perovskite Li3+aO0.5S0.5+aCl1-a(a=0.125), while rich lithium, realize S and Cl from
The mixing (with S for Cl) of son, lithium ion diffusion barrier is only 0.026-0.053eV, only tetragonal Li10GeP2S12It is (existing
One of stage best solid electrolyte) 1/1 to five/10ths, diffusion barrier is extremely low.
In the lithium ion solid electrolyte of the present invention, micro high-valence state metal ions M such as Ca is properly added2+、Ba2+、Mg2+、
Al3+、Ti4+In one kind, now, 0 ＜ p≤0.5, -0.05≤a≤0.125 and a ≠ 0,0≤m≤1.25,0≤n≤
1.25, and be 0 when m, n difference, help further to optimize lithium ion transport passage, and realize that various metals ion passes simultaneously
It is defeated, now 0≤b≤1.Preferably, the stoichiometry content of 0 ＜ p≤0.05, i.e. metallic element M is not higher than 5%.B value is excellent
Elect 0≤b≤0.5 as.
The compound for adding metallic element M can also be preferably Li3+aMpAmBnY1-a, 0≤a≤1,0≤p≤0.5；Or
Li3MpAmBnY1-2a, 0≤a≤0.5,0≤p≤0.5.
Above-mentioned lithium ion solid electrolyte can be preferably another structure, without Y, p=0；0<m<1,0<n<1, A and B
One kind respectively in Si, C, S, O.
MgX3 -、CaX3 -For Mg or Ca and the negative univalent perssad of halogen composition.
Above-mentioned lithium ion solid electrolyte is one kind in crystal, vitreum, amorphous.The lithium ion solid electrolysis of the present invention
Matter is typical ion combination objects system, therefore ion chemistry environment and crystal in its glassy state (especially relaxation glassy state)
State is similar, using glassy state electrolyte, is beneficial to the low temperature preparation (such as mechanical alloying method, Vacuum Coating method) of electrolyte,
Of a relatively high hole concentration in vitreum, lithium ion is spread it is favourable, ionic conductance may more 0, therefore, the solid electrolyte
Preferably vitreum.
The technical scheme of the preparation method of the lithium ion solid electrolyte of the present invention is as follows：
A kind of preparation method of above-mentioned lithium ion solid electrolyte, comprises the following steps：
1) ball milling 3-10h under being protected by raw material under vacuum either inert gas shielding or without protic solvent, before obtaining
Drive body；
2) presoma is incubated 5-16h in 150-500 DEG C under vacuum or inert gas shielding, produced.
The presoma that step 1) obtains is pressed into base substrate.Room temperature is cooled to after being incubated in step 2) or is carried out at quenching
Reason.The Quenching Treatment is quenched for frozen water.Insulation is carried out in Muffle furnace or vacuum tube furnace.Raw material is to prepare corresponding solid
The compound of corresponding element during electrolyte.Such as oxide either halide or sulfide.Specifically, as lithia, lithium chloride,
Lithium iodide, lithium sulfide.
Preferably, step 1) and inert gas described in step 2) are nitrogen or argon gas.
The no protic solvent is one kind in dinethylformamide, absolute ethyl alcohol, acetone, heptane, ethyl acetate.
The rotating speed of the ball milling is 250-350rpm.During ball milling, 5-10min is stood per ball milling 20-30min.Preferably, often
Ball milling 20min stands 5min.
The lithium ion solid electrolyte of the present invention can be prepared using method of the prior art, such as using melting
It is prepared by method, mechanical alloying method, powder metallurgic method, Vacuum Coating method or chemical vapour deposition technique.
Another preparation method of the lithium ion solid electrolyte of the present invention comprises the following steps：
A) ball milling 3-10h under being protected by raw material under vacuum either inert gas shielding or without protic solvent, before obtaining
Drive body；
B) presoma is suppressed into 2-30min under 20-320 DEG C, 1-50MPa pressure, produced.
Preferably, inert gas is nitrogen or argon gas described in step a) and step b).
The no protic solvent is one kind in dinethylformamide, absolute ethyl alcohol, acetone, heptane, ethyl acetate.
The rotating speed of the ball milling is 250-350rpm, and during ball milling, 5-10min is stood per ball milling 20-30min.Preferably, often
Ball milling 20min stands 5min.
The technical scheme of the application of the lithium ion solid electrolyte of the present invention is as follows：
A kind of application of above-mentioned lithium ion solid electrolyte in lithium ion battery, the lithium ion battery include electrode
Piece, the electrode slice includes collector and coating is arranged on the electrode material layer of collection liquid surface, and the electrode material layer includes
Electrode material and electrode material additive, the electrode material additive are above-mentioned lithium ion solid electrolyte
During concrete application, mass content of the lithium ion solid electrolyte in electrode material layer is 0-20%.The matter
It is preferably 2-20% to measure content.
The beneficial effects of the invention are as follows：
The lithium ion solid electrolyte of the present invention has stable structure and good lithium ion transport performance, as lithium
With good chemical property and security performance during the solid electrolyte of ion battery.Further, lithium ion of the invention
When solid electrolyte forms dimorphism anti-perovskite structure, there is very high ionic conductivity, highest can exceed 25mScm-1,
Have a good application prospect.
Brief description of the drawings
Fig. 1 is that the XRD of the lithium ion solid electrolyte in embodiment 7 tests collection of illustrative plates；
Fig. 2 is the structural representation of the lithium ion solid electrolyte in embodiment 7；
Fig. 3 is the structural representation of the lithium ion solid electrolyte of embodiment 1,4,7,29,30, wherein, (a) is embodiment
1 and embodiment 29 lithium ion solid electrolyte structural representation, (b) be embodiment 30 lithium ion solid electrolyte knot
Structure schematic diagram, (c) are the structural representation of the lithium ion solid electrolyte of embodiment 4, and (d) is the lithium ion solid of embodiment 7
The structural representation of electrolyte；
Fig. 4 is the diffusion activation energy schematic diagram of the lithium ion solid electrolyte in embodiment 7；
Fig. 5 is the ionic conductance variation with temperature curve of the lithium ion solid electrolyte in embodiment 1-12.
Embodiment
Technical scheme is described further with reference to specific embodiment.
Embodiment 1
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3Shown in OCl, structure such as Fig. 3 (a).
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1 lithia (Li2O) and lithium chloride (LiCl) powder dries 24h in vacuum drying chamber,
Then in glove box, under argon gas atmosphere protection, lithia and lithium chloride is uniformly mixed, are fitted into ball grinder, and is added
Several a diameter of 10mm zirconia ball abrading-ball, seal ball grinder.The ball grinder of good seal is taken out from glove box, loaded
Ball milling is carried out in comprehensive planetary ball mill, sets the rotating speed of ball mill as 280rpm, ball mill is stood cold per ball milling 20min
But 5min；Ball milling total time is 3h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body, a diameter of 16mm ceramic body is cold-pressed into, is heat-treated in vacuum tube furnace, heat treatment temperature is 230 DEG C, at heat
The reason time is 10h, and ceramic body, as LiOCl solid electrolyte are slowly cooled to room temperature to obtain after heat treatment.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 2%.
Embodiment 2
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3O1.25Cl0.5。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 2.5 by mol ratio:1 lithia (Li2O) dried with lithium chloride (LiCl) powder in vacuum drying chamber
24h, then in glove box, under argon gas atmosphere protection, lithia and lithium chloride are uniformly mixed, are fitted into ball grinder, and
Several a diameter of 10mm zirconia ball abrading-ball is added, seals ball grinder.The ball grinder of good seal is taken out from glove box,
It is fitted into comprehensive planetary ball mill and carries out ball milling, set the rotating speed of ball mill as 250rpm, ball mill is quiet per ball milling 20min
Put cooling 5min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body is fitted into quartz glass tube, sealing, under vacuum, is heat-treated in Muffle furnace, and heat treatment temperature is 330 DEG C,
Heat treatment time is 10h, and powder melts complete after heat treatment, then carries out Quenching Treatment using frozen water, obtains vitreum powder,
As Li3O1.25Cl0.5Non-crystal solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 10%.
Embodiment 3
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3.125O1.125Cl0.875。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1.125 by mol ratio:0.875 lithia (Li2O) and lithium chloride (LiCl) powder is in vacuum drying chamber
24h is dried, then in glove box, under argon gas atmosphere protection, lithia and lithium chloride is uniformly mixed, load ball grinder
In, and several a diameter of 10mm zirconia ball abrading-ball is added, seal ball grinder.By the ball grinder of good seal from glove box
Take out, be fitted into comprehensive planetary ball mill and carry out ball milling, set the rotating speed of ball mill as 350rpm, ball mill is per ball milling
20min, stand cooling 5min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body, a diameter of 16mm ceramic body is cold-pressed into, is heat-treated in vacuum tube furnace, heat treatment temperature is 250 DEG C, at heat
The reason time is 10h, and ceramic body, as Li are slowly cooled to room temperature to obtain after heat treatment3.125O1.125Cl0.875Solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 20%.
Embodiment 4
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3SI, as shown in Fig. 3 (c).
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1 lithium sulfide (Li2S) and lithium iodide (LiI) powder dries 24h in vacuum drying chamber,
Then in glove box, under argon gas atmosphere protection, by lithium sulfide (Li2S) uniformly mixed with lithium iodide (LiI), load ball milling
In tank, and several a diameter of 10mm zirconia ball abrading-ball is added, seal ball grinder.By the ball grinder of good seal from glove box
Middle taking-up, it is fitted into comprehensive planetary ball mill and carries out ball milling, set the rotating speed of ball mill as 280rpm, ball mill is per ball milling
20min, stand cooling 5min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body, it is heat-treated in vacuum tube furnace, heat treatment temperature is 220 DEG C, heat treatment time 10h, slowly cold after heat treatment
But it is Li to room temperature, gained powder3SI solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 10%.
Embodiment 5
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3S1.25I0.5。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 2.5 by mol ratio:1 lithium sulfide (Li2S) dried with lithium iodide (LiI) powder in vacuum drying chamber
24h, then in glove box, under argon gas atmosphere protection, by lithium sulfide (Li2S) uniformly mix, load with lithium iodide (LiI)
In ball grinder, and 15 a diameter of 10mm zirconia ball abrading-ball is added, seal ball grinder.By the ball grinder of good seal from gloves
Taken out in case, be fitted into comprehensive planetary ball mill and carry out ball milling, set the rotating speed of ball mill as 350rpm, ball mill is per ball milling
20min, stand cooling 5min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body is fitted into quartz glass tube, sealing, vacuumizes, is heat-treated in Muffle furnace, and heat treatment temperature is 500 DEG C, heat treatment
Time is 5h, and powder melts complete after heat treatment, then carries out Quenching Treatment using frozen water, obtains vitreum powder, is
Li3S1.25I0.5Solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 10%.
Embodiment 6
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3.125S1.125I0.875。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1.125 by mol ratio:0.875 lithium sulfide (Li2S) and lithium iodide (LiI) powder is in vacuum drying chamber
24h is dried, then in glove box, under argon gas atmosphere protection, by lithium sulfide (Li2S) uniformly mixed with lithium iodide (LiI),
It is fitted into ball grinder, and adds several a diameter of 10mm zirconia ball abrading-ball, seals ball grinder.By the ball grinder of good seal
Taken out from glove box, be fitted into comprehensive planetary ball mill and carry out ball milling, set the rotating speed of ball mill as 350rpm, ball mill
Per ball milling 20min, cooling 5min is stood；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, in vacuum tube furnace
It is heat-treated, heat treatment temperature is 430 DEG C, heat treatment time 10h, is slowly cooled to room temperature after heat treatment, gained powder
As Li3.125S1.125I0.875Solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 10%.
Embodiment 7
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3O0.5S0.5I, structure are as shown in Figure 2.
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1:2 lithia (Li2O), lithium sulfide (Li2S), lithium iodide (LiI) powder is being dried in vacuo
24h is dried in case, then in glove box, under argon gas atmosphere protection, by lithia (Li2O), lithium sulfide (Li2S), lithium iodide
(LiI) uniformly mixing, is fitted into ball grinder, and adds 15 a diameter of 10mm zirconia ball abrading-ball, seals ball grinder.Will be close
The ball grinder sealed takes out from glove box, is fitted into comprehensive planetary ball mill and carries out ball milling, set the rotating speed of ball mill as
350rpm, ball mill stand cooling 5min per ball milling 20min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, in vacuum tube furnace
It is heat-treated, heat treatment temperature is 150 DEG C, heat treatment time 16h, is slowly cooled to room temperature after heat treatment, gained powder
As Li3O0.5S0.5I solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 10%.
The XRD spectrum of solid electrolyte made from the present embodiment is as shown in Figure 1.
Embodiment 8
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3O0.5S0.5I。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1:2 lithia (Li2O), lithium sulfide (Li2S), lithium iodide (LiI) powder is being dried in vacuo
24h is dried in case, then in glove box, under argon gas atmosphere protection, by lithia (Li2O), lithium sulfide (Li2S), lithium iodide
(LiI) uniformly mixing, is fitted into ball grinder, and adds 15 a diameter of 10mm zirconia ball abrading-ball, seals ball grinder.Will be close
The ball grinder sealed takes out from glove box, is fitted into comprehensive planetary ball mill and carries out ball milling, set the rotating speed of ball mill as
350rpm, ball mill stand cooling 5min per ball milling 20min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body, slowly it is cold-pressed into a diameter of 16mm ceramic body, as Li3O0.5S0.5I solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, positive plate include plus plate current-collecting body and included just coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer
Pole material and positive electrode additive, positive electrode additive are above-mentioned lithium ion solid electrolyte, and positive electrode additive exists
Mass content in positive electrode material layer is 10%.
Embodiment 9
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3O0.5S0.75I0.5。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1.5:1 lithia (Li2O), lithium sulfide (Li2S), lithium iodide (LiI) powder is done in vacuum
24h is dried in dry case, then in glove box, under argon gas atmosphere protection, lithia, lithium sulfide, lithium iodide are uniformly mixed,
It is fitted into ball grinder, and adds several a diameter of 10mm zirconia ball abrading-ball, seals ball grinder.By the ball grinder of good seal
Taken out from glove box, be fitted into comprehensive planetary ball mill and carry out ball milling, set the rotating speed of ball mill as 350rpm, ball mill
Per ball milling 20min, cooling 5min is stood；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body is fitted into quartz glass tube, sealing, vacuumizes, is heat-treated in Muffle furnace, and heat treatment temperature is 250 DEG C, heat treatment
Time is 5h, and powder melts complete after heat treatment, then carries out Quenching Treatment using frozen water, obtains vitreum powder, is
Li3O0.5S0.75I0.5Solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, negative plate include negative current collector and include negative coated in the negative electrode material layer on negative current collector, negative electrode material layer
Pole material and negative material additive, negative material are graphite, and negative material additive is above-mentioned lithium ion solid electrolyte, are born
Mass content of the pole meterial additive in negative electrode material layer is 10%.
Embodiment 10
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3O0.5S0.75I0.5。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1.5:1 lithia (Li2O), lithium sulfide (Li2S), lithium iodide (LiI) powder is done in vacuum
24h is dried in dry case, then in glove box, under argon gas atmosphere protection, lithia, lithium sulfide, lithium iodide are uniformly mixed,
It is fitted into ball grinder, and adds several a diameter of 10mm zirconia ball abrading-ball, seals ball grinder.By the ball grinder of good seal
Taken out from glove box, be fitted into comprehensive planetary ball mill and carry out ball milling, set the rotating speed of ball mill as 350rpm, ball mill
Per ball milling 20min, cooling 5min is stood；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, is slowly cold-pressed into diameter
For 16mm ceramic body, as Li3O0.5S0.75I0.5Solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, negative plate include negative current collector and include negative coated in the negative electrode material layer on negative current collector, negative electrode material layer
Pole material and negative material additive, negative material are graphite, and negative material additive is above-mentioned lithium ion solid electrolyte, are born
Mass content of the pole meterial additive in negative electrode material layer is 10%.
Embodiment 11
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3.125O0.5S0.625I0.875。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1.25:1.75 lithia (Li2O), lithium sulfide (Li2S), lithium iodide (LiI) powder is true
24h is dried in empty drying box, it is under argon gas atmosphere protection, lithia, lithium sulfide, lithium iodide is uniform then in glove box
Mixing, is fitted into ball grinder, and adds several a diameter of 10mm zirconia ball abrading-ball, seals ball grinder.By good seal
Ball grinder takes out from glove box, is fitted into comprehensive planetary ball mill and carries out ball milling, sets the rotating speed of ball mill as 350rpm,
Ball mill stands cooling 5min per ball milling 20min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, in vacuum tube furnace
It is heat-treated, heat treatment temperature is 200 DEG C, heat treatment time 16h, is slowly cooled to room temperature after heat treatment, gained powder
As Li3.125O0.5S0.625I0.875Solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, negative plate include negative current collector and include negative coated in the negative electrode material layer on negative current collector, negative electrode material layer
Pole material and negative material additive, negative material are graphite, and negative material additive is above-mentioned lithium ion solid electrolyte, are born
Mass content of the pole meterial additive in negative electrode material layer is 20%.
Embodiment 12
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3.125O0.5S0.625I0.875。
The preparation method of the lithium ion solid electrolyte of the present embodiment comprises the following steps：
1) it is 1 by mol ratio:1.25:1.75 lithia (Li2O), lithium sulfide (Li2S), lithium iodide (LiI) powder is true
24h is dried in empty drying box, it is under argon gas atmosphere protection, lithia, lithium sulfide, lithium iodide is uniform then in glove box
Mixing, is fitted into ball grinder, and adds several a diameter of 10mm zirconia ball abrading-ball, seals ball grinder.By good seal
Ball grinder takes out from glove box, is fitted into comprehensive planetary ball mill and carries out ball milling, sets the rotating speed of ball mill as 350rpm,
Ball mill stands cooling 5min per ball milling 20min；Ball milling total time is 10h, and presoma is obtained after ball milling；
2) under argon gas atmosphere protection, the presoma that step 1) is obtained takes out from ball grinder, weighs a certain amount of powder
Body, slowly it is cold-pressed into a diameter of 16mm ceramic body, as Li3.125O0.5S0.625I0.875Solid electrolyte.
Application of the lithium ion solid electrolyte of the present embodiment in lithium ion battery：Lithium ion battery include positive plate and
Negative plate, negative plate include negative current collector and include negative coated in the negative electrode material layer on negative current collector, negative electrode material layer
Pole material and negative material additive, negative material are graphite, and negative material additive is above-mentioned lithium ion solid electrolyte, are born
Mass content of the pole meterial additive in negative electrode material layer is 20%.
The chemical composition of embodiment 13-30 lithium ion solid electrolyte is as shown in the table, and in addition to especially indicating, it is prepared
Method is the same as the method in embodiment 1.
The chemical composition of the embodiment 13-30 of table 1 lithium ion solid electrolyte
Note：Li in table3SCH3Preparation method reference implementation example 1-12 in method, utilize LiCH3Introduce CH3Negative one valency
Ion.Li3N0.5Cl0.5In I preparation method, N is by Li3N raw materials are introduced into material.Li3N0.5F0.5I、Li3P0.5Cl0.5I system
Preparation Method refers to preceding step, and negative monovalent ion is introduced into material by its lithium compound as raw material.
Test example
1) XRD is tested
The solid electrolyte that Example 7 obtains carries out XRD tests, and the XRD characteristic spectrums for testing to obtain are as shown in Figure 1.
The XRD spectrum for testing obtained solid electrolyte is found compared with the collection of illustrative plates that theoretical calculation obtains, implemented
The XRD of experiment gained crystal complies fully with result of calculation in example.
2) calculate and analyze
By material genome project method, in Density functional (DFT) method and first principle molecular dynamics
(AIMD) under theoretical frame, can or adjacent race element of the same clan with systematic research it is steady to the thermodynamics of the solid electrolyte of the present invention
Qualitative and ion transport performance.
Li in embodiment 73O0.5S0.5Li in I and embodiment 243N0.5Cl0.5I belongs to the anti-calcium state ore deposit structure of dimorphism.
With Li3O0.5S0.5Exemplified by I, its structure is as shown in Fig. 2 the structure has Li6O and Li6S octahedral structure units, two kinds of structure lists
The structural framing of first constituent material that is staggeredly connected, while large scale I-Ion is filled out in interstitial void, plays raising Stability Analysis of Structures
The effect of property.
Dimorphism anti-perovskite possessesSymmetry, hence it is evident that be different from traditional anti-perovskite symmetry(such as Li3OCl), dimorphism anti-perovskite is a kind of solid electrolyte of brand-new system.
According to XRD measurement data, corresponding lattice constant magnitude relationship：Li3OCl<Li3OI<Li3OI<Li3O0.5S0.5I<
Li3N0.5Cl0.5I, show as the shifting of XRD feature peak positions integral left.
For standard chemical formula Li3AB, according to Goldschmidt calculation formula, calculate structure tolerance factor：As shown in table 2, Li3The key whether AB types can form anti-calcium state ore deposit structure is that structure tolerance factor t is
It is no within the scope of 0.8-1.As shown in table 2, Li3OCl and Li3OI tolerance factor is respectively 0.85 and 0.98, therefore their energy
The anti-perovskite structure of formation standard, as shown in Fig. 3 (a)；For Li3SCl, tolerance factor 0.7, less than 0.8, therefore show
For layer structure, as shown in Fig. 3 (b)；For Li3SI, tolerance factor 0.81, slightly larger than 0.8, although deformation, whole
Body remains in that anti-perovskite architectural feature, as shown in Fig. 3 (c)；For Li3O0.5S0.5I(Li3OI+Li3SI average appearance)
It is 0.895 to bear the factor, therefore shows as the anti-calcium state ore deposit structure of dimorphism, as shown in Fig. 3 (d).
The structure tolerance factor of 2 each material of table
Li is primarily present two kinds of diffusion ways in the anti-calcium state ore deposit solid electrolyte of dimorphism.With Li3O0.5S0.5Exemplified by I, such as
Shown in Fig. 4：(a) under the conditions of poor Li, spread along Li rooms；Corresponding diffusion activation energy is 0.026-0.17eV, such as Fig. 4 (b)
Shown in (e)；(d) under the conditions of rich Li, Li-Li pairing dumbbell shaped transmission.Under the conditions of rich Li, diffusion activation activation can continue
Reduce, only 0.053-0.055eV, as shown in Fig. 4 (c) and (f).Diffusion activation energy significantly reduces, the Li with O/S arest neighbors
Ion populations increase has direct contact.With the Li ion populations increase around O/S, pacts of the O/S to Li ions is weakened
Beam force, therefore Li ion activities are remarkably reinforced.
For adding for the solid electrolyte of micro high volence metal ion, in embodiment 13
Li2.99Ba0.01O1.25Cl0.5With the Li in embodiment 163.125Ca0.01O1.125Cl0.875, its structure can further optimize Li from
Sub- diffusion admittance, and more metal ion conduction can be realized simultaneously, be advantageous to the performance of further lifting solid state battery.
3) lithium ion conductivity is tested
The lithium ion conductivity of testing example 1-30 lithium ion solid electrolyte at different temperatures respectively, and will survey
Test result is normalized, as a result as shown in table 3.By Li3OCl、Li3SI、Li3O0.5S0.5I、Li3S1.25I0.5、
Li3.125S1.125I0.875、Li3.125O1.125Cl0.875、Li3O1.25Cl0.5、Li3O0.5S0.75I0.5、Li3.125O0.5S0.625I0.875Lithium
The data of ionic conductivity and temperature make conductance profile, as shown in Figure 5.
The lithium ion conductivity and diffusion activation energy Ea of the lithium ion solid electrolyte of the embodiment 1~30 of table 3
Similar chemical composition deviates it can be seen from the data in table 3, and adds the knot of micro high volence metal ion
Structure is modified, and can increase substantially the lithium ion conductance of perovskite or the lithium ion solid electrolyte of dimorphism anti-perovskite structure
The order of magnitude of rate.
As shown in Figure 5, composition is standard analysis Li in embodiment3OCl, Li3During SI, the lithium of lithium ion solid electrolyte from
Sub- conductance is below 1mScm-1, form as Li3O0.5S0.5During I, lithium ion conductance is relatively low；When composition deviates standard stoichiometry
Than when, lithium ion conductivity increases substantially during room temperature, can be higher than 10mScm-1.Now, lithium ion conductance significantly breaks through
The technical indicator of existing business liquid organic electrolyte, has great importance.When dimorphism anti-perovskite structure adds composition
Deviate collective effect, can further significantly improve electrical conductivity.Further, Li3.125O0.5S0.625I0.875、
Li3Ca0.01O1.25Cl0.5Deng the lithium ion conductance of the solid electrolyte of composition, 25mScm is had been above-1, better than with
Li10GeP2S12For the LGPS systems of representative.
Claims (10)
1. a kind of lithium ion solid electrolyte, it is characterised in that the lithium ion solid electrolyte has chemistry as follows
Formula：Li3+aMpAmBnY1-b, wherein -0.25≤a≤0.25；0≤b≤0.5；0≤p≤0.5,0≤m≤1.25,0≤n≤1.25；
M is any one in Ca, Ba, Mg, Al, Ti；A, B separately selected from O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl,
One kind in Br, I；Y is one kind in halogen or negative one valency ion cluster or room, and the halogen is any one in Cl, Br, I
Kind；The negative one valency ion cluster is OH-、BH4 -、NH2 -、CH3 -、CN-、MgX3 -、CaX3 -In one kind.
2. lithium ion solid electrolyte as claimed in claim 1, it is characterised in that 0 ＜ b≤0.5.
3. lithium ion solid electrolyte as claimed in claim 2, it is characterised in that the p=0, a=0, be when m, n difference
0；A, B separately one kind in O, S, Se, Te, N, P, I, Cl, Br.
4. lithium ion solid electrolyte as claimed in claim 2, it is characterised in that the p=0, a ≠ 0, be when m, n difference
0；A, B separately one kind in O, S, Se, Te, N, P, I, Cl, Br.
5. lithium ion solid electrolyte as claimed in claim 2, it is characterised in that 0 the ＜ p≤0.1, a ≠ 0, m, n are different
When be 0；A, B separately one kind in O, S, Se, Te, N, P, I, Cl, Br.
6. the lithium ion solid electrolyte as described in claim any one of 1-5, it is characterised in that the lithium ion solid electrolysis
Matter is one kind in crystal, vitreum, amorphous.
7. a kind of preparation method of lithium ion solid electrolyte as claimed in claim 1, it is characterised in that including following step
Suddenly：
A) ball milling 3-10h under being protected by raw material under vacuum either inert gas shielding or without protic solvent, obtains presoma；
B) presoma is incubated 5-16h in 150-500 DEG C under vacuum or inert gas shielding, produced.
8. the preparation method of lithium ion solid electrolyte as claimed in claim 7, it is characterised in that the no protic solvent
For one kind in dinethylformamide, absolute ethyl alcohol, acetone, heptane, ethyl acetate.
9. a kind of preparation method of lithium ion solid electrolyte as claimed in claim 1, it is characterised in that including following step
Suddenly：
A) ball milling 3-10h under being protected by raw material under vacuum either inert gas shielding or without protic solvent, obtains presoma；
B) presoma is suppressed into 2-30min under 20-320 DEG C, 1-50MPa pressure, produced.
A kind of 10. application of the lithium ion solid electrolyte in lithium ion battery as claimed in claim 1, it is characterised in that
The lithium ion battery includes electrode slice, and the electrode slice includes collector and coating is arranged on the electrode material of collection liquid surface
Layer, the electrode material layer include electrode material and electrode material additive, and the electrode material additive is such as claim 1
Described lithium ion solid electrolyte.
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