CN107403955A - A kind of dimorphism anti-perovskite lithium ion solid electrolyte and preparation method thereof, application - Google Patents
A kind of dimorphism anti-perovskite lithium ion solid electrolyte and preparation method thereof, application Download PDFInfo
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Abstract
The present invention relates to a kind of dimorphism anti-perovskite 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+aMpAmBn(XxYy)1‑b, wherein 0.25≤a≤0.25；0≤b≤0.5；0≤p≤0.5,0 ＜ m≤1.25,0 ＜ n≤1.25；0≤x≤1,0≤y≤1；M is any one in Ca, Ba, Mg, Al, Ti；A, B is any two kinds in O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl, Br, I；X, Y separately one kind in halogen or negative one valency ion cluster or room.The structure of the lithium ion solid electrolyte of the present invention is dimorphism anti-perovskite structure, has stable structure and good lithium ion transport performance.
Description
Technical field
The present invention relates to a kind of dimorphism anti-perovskite lithium ion solid electrolyte and preparation method thereof, application, belong to lithium from
Sub- cell art.
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.
Material with perovskite structure or anti-perovskite structure typically with ideal performance, as activation energy compared with
It is low, electrical conductivity is higher etc., and electronic conductivity is very low, it is often more important that, such material is good with stability, and it is very steady to meet lithium
It is fixed, also with certain heat endurance, there is preferable application space.But current Ca-Ti ore type or anti-perovskite type
The ionic conductivity of solid electrolyte still has much room for improvement.
The content of the invention
It is an object of the invention to provide a kind of high dimorphism anti-perovskite lithium ion solid electrolyte of lithium ion conductivity.
The present invention also aims to provide the preparation method of above-mentioned dimorphism anti-perovskite lithium ion solid electrolyte and answer
With.
To achieve the above object, the technical scheme of lithium ion solid electrolyte of the invention is：
A kind of dimorphism anti-perovskite lithium ion solid electrolyte, the lithium ion solid electrolyte have change as follows
Formula：Li3+aMpAmBn(XxYy)1-b, wherein -0.25≤a≤0.25；0≤b≤0.5；0≤p≤0.5,0 ＜ m≤1.25,0 ＜ n
≤1.25；0≤x≤1,0≤y≤1；M is any one in Ca, Ba, Mg, Al, Ti；A, B be O, S, Se, Te, N, P, Si, C,
Any two kinds in Sb, Bi, F, Cl, Br, I；X, Y separately in halogen or negative one valency ion cluster or room one
Kind, the halogen is any one in Cl, Br, I；The 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 is dimorphism anti-perovskite type compound, A, B location in compound structure
Contain two kinds of elements in O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl, Br, I.The space group of the structure is Fm(space
Group number is 225), to have Li6A、Li6B octahedral structure units, on the angle of cube anti-perovskite；X, Y 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 of the present invention
Electrolyte thermodynamic stability, lattice dimensions are mainly by Li6A and Li6Ion bond distance in B octahedrons between A-Li or B-Li is determined
Fixed, the contribution of X bits element is relatively weak.And the ion bond distance between A-Li or B-Li is decided by that the electricity of nonmetallic ion (A and B) is born
Property, electronegativity is stronger, and corresponding bond distance is shorter.When the sublattice position where A and B occupies by oxygen, lattice yardstick is minimum, changes
The formation heat of compound is maximum, and Li ionic conductivities are minimum.
Preferably, x=0, y=1, a kind of element or group in X and Y are only retained.
In the dimorphism anti-perovskite type solid electrolyte of the present invention, there is the material of non-stoichiometric, can be in dimorphism
On the basis of anti-perovskite structure, ionic conductivity is further improved.
The element of X positions or the content of group are reduced, can further promote the speed of lithium ion transport.When the member of X positions
When the stoichiometry of element deviates 1, a=0,0 ＜ b≤0.5, any two kinds in A, B O, S, Se, Te, N, P, I, Cl, Br.This
If when m+n=1, A, B bit element still measures for normal chemical, only X bits element nonstoichiometry.If m+n ＞ 1, A, B position
The stoichiometry of element is measured higher than normal chemical.Preferably, p=0, metallic element is free of in compound structure.Appropriate increase
Larger octahedra Li6Nonmetallic B content in B, it is possible to achieve ultrafast ground lithium ion transport.
In above-mentioned lithium ion solid electrolyte, the stoichiometric number of lithium can deviate normal chemical metering, i.e. a ≠ 0.This
When, lithium ion solid electrolyte is divided into two kinds of situations of poor lithium and rich lithium, and under both of these case, lithium ion is in solid electrolyte
Transmission means 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.
When X positions element stoichiometry deviate 1 when, a ≠ 0,0 ＜ b≤0.5, A, B O, S, Se, Te, N, P, I, Cl,
Any two kinds in Br.Now the stoichiometric number of lithium deviates normal chemical metering, particularly under the conditions of rich lithium, lithium ion
Diffusion is more prone to, and diffusion activation energy is also very small.If now m+n=1, A, B bit element still measure for normal chemical, only X
Bit element nonstoichiometry.If m+n ＞ 1, the stoichiometry of A, B bit element is measured higher than normal chemical.Preferably, p=
0, metallic element is free of in compound structure.Suitably increase larger octahedra Li6Nonmetallic B content in B, it is possible to achieve ultrafast
Ground lithium ion transport.
During rich lithium, extra lithium (Li) ion is still adsorbed in Li6A or Li6Near A/B positions in B.A/B positions are poly- nearby
Collect more lithium ions, so as to further reduce the average interaction between Li-A/B, enhance the diffusion activity of lithium ion.
In addition, the interaction between Li-Li can effectively reduce the Li ion diffusion lengths between octahedron, hence it is evident that reduce diffusion barrier,
Show as ultrafast lithium ion conductivity.
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, help further to optimize lithium ion transport passage, and realize simultaneously various metals ion transmit.On
Metal ion can be added in right amount by stating in various schemes, that is, ensure 0 ＜ p≤0.5.Preferably, 0 ＜ p≤0.05, i.e. metal member
Plain M stoichiometry content is not higher than 5%.
When being not required to add metal ion, p=0, now only rely on the cooperations of other elements to optimize structure, ensure lithium from
The transmission rate of son.Metallic element M Li is not contained3+aMpAmBnY1-b(p=0) the octahedra knot that the AB elements in are formed with Li
Structure unit can provide good passage for the transmission of lithium ion and make it have extraordinary lithium ion conductivity.Now, not
Under the conditions of rich lithium, compound still has preferable lithium ion conductivity.
For not adding metal ion, while the stoichiometric number of each element is also without departing from the compound of standard stoichiometry
For, a=0, b=0, p=0, m+n=1, any two kinds in A, B O, S, Se, Te, N, P, I, Cl, Br.Such as
Li3O0.5S0.5I、Li3N0.5Cl0.5I、Li3N0.5F0.5I、Li3P0.5Cl0.5I, there is the dimorphism anti-perovskite structure of standard.
Compound for not adding metal ion, the element of X positions can also lack, now, x=0, y=0；-0.125
≤ a≤0.125, p=0；0<m<1.25 0<n<1.25, A and B is respectively one kind in Si, C, S, O.Preferably, 0<m<1,0<n
<1。
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.
MgX3 -、CaX3 -The negative univalent perssad formed for Mg or Ca and halogen.
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 being spread favorably, ionic conductance may be more preferable, therefore, the solid electrolytic
It is of fine quality to elect vitreum as.
The technical scheme of the preparation method of the dimorphism anti-perovskite lithium ion solid electrolyte of the present invention is as follows：
A kind of preparation method of above-mentioned dimorphism anti-perovskite 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 dimorphism anti-perovskite 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,
Obtain presoma；
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 dimorphism anti-perovskite lithium ion solid electrolyte of the present invention is as follows：
A kind of application of above-mentioned dimorphism anti-perovskite lithium ion solid electrolyte in lithium ion battery, the lithium ion
Battery includes electrode slice, and the electrode slice includes collector and coating is arranged on the electrode material layer of collection liquid surface, the electricity
Pole material layer includes electrode material and electrode material additive, and the electrode material additive is above-mentioned dimorphism anti-perovskite lithium
Ion solid electrolyte
During concrete application, mass content of the lithium ion solid electrolyte in electrode material layer is 0-20%.
The beneficial effects of the invention are as follows：
The structure of the lithium ion solid electrolyte of the present invention is dimorphism anti-perovskite structure, with stable structure and well
Lithium ion transport performance, in the solid electrolyte as lithium ion battery with good chemical property and security
Energy.The lithium ion solid electrolyte of the present invention has very high ionic conductivity, and highest can exceed 25mScm-1, have good
Good application prospect.
Brief description of the drawings
Fig. 1 is that the XRD of the lithium ion solid electrolyte in embodiment 1 tests collection of illustrative plates；
Fig. 2 is the structural representation of the lithium ion solid electrolyte in embodiment 1；
Fig. 3 is the structural representation of embodiment 1 and the lithium ion solid electrolyte of comparative example 1,2,3,4, wherein, (a) is
The structural representation of the lithium ion solid electrolyte of comparative example 1 and comparative example 3, (b) are the lithium ion solid electrolyte of comparative example 4
Structural representation, (c) be comparative example 2 lithium ion solid electrolyte structural representation, (d) be embodiment 1 lithium ion
The structural representation of solid electrolyte；
Fig. 4 is the diffusion activation energy schematic diagram of the lithium ion solid electrolyte in embodiment 1.
Embodiment
Technical scheme is described further with reference to specific embodiment.
Embodiment 1
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 2%.
The XRD spectrum of solid electrolyte made from the present embodiment is as shown in Figure 1.
Embodiment 2
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 5%.
Embodiment 3
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 4
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 5
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 6
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 7-14 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 7-14 of table 1 lithium ion solid electrolyte
| Embodiment | The chemical composition of solid electrolyte |
| 7 | Li2.99Ba0.01O0.5S0.75I0.5 |
| 8 | Li2.99Ca0.01O0.5S0.75I0.5 |
| 9 | Li3.125Ba0.01O0.5S0.625I0.875 |
| 10 | Li3.125Ca0.01O0.5S0.625I0.875 |
| 11 | Li3N0.5Cl0.5I |
| 12 | Li3N0.5F0.5I |
| 13 | Li3P0.5Cl0.5I |
| 14 | Li3C0.5S0.5 |
Note：Method in reference implementation example 1-6, Li in table3N0.5Cl0.5In I preparation method, N is by Li3N raw materials introduce material
In material.Li3N0.5F0.5I、Li3P0.5Cl0.5I preparation method refers to preceding step, bears monovalent ion and makees by its lithium compound
It is introduced into for raw material in material.
Comparative example 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 10%.
Comparative example 2
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%.
Comparative example 3
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3OI。
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 iodide (LiI) powder dries 24h in vacuum drying chamber,
Then in glove box, under argon gas atmosphere protection, by lithia (Li2O) 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 260 DEG C, heat treatment time 8h, Slow cooling after heat treatment
To room temperature, gained powder is Li3OI 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%.
Comparative example 4
The lithium ion solid electrolyte of the present embodiment, chemical composition Li3SCl。
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 chloride (LiCl) powder dries 24h in vacuum drying chamber,
Then in glove box, under argon gas atmosphere protection, by lithium sulfide (Li2S) uniformly mixed with lithium chloride (LiCl), 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 260rpm, ball mill is per ball milling
20min, stand cooling 5min；Ball milling total time is 6h, 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 300 DEG C, heat treatment time 10h, slowly cold after heat treatment
But it is Li to room temperature, gained powder3SCl 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%.
Comparative example 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%.
Comparative example 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%.
Test example
1) XRD is tested
The solid electrolyte that Example 1 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 13O0.5S0.5Li in I and embodiment 103N0.5Cl0.5I 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 possesses Fm(225) symmetry, hence it is evident that be different from traditional anti-perovskite symmetry Pm
(221) (such as Li3), OCl 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 7
Li2.99Ba0.01O0.5S0.75I0.5With the Li in embodiment 93.125Ba0.01O0.5S0.625I0.875, its structure can further optimize Li
Ion 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 electric of testing example 1-13 and comparative example 1-6 lithium ion solid electrolyte at different temperatures respectively
Conductance, and test result is normalized, as a result as shown in table 3.
The lithium ion conductivity and diffusion activation energy of the embodiment 1-13 of table 3 and comparative example 1-6 lithium ion solid electrolyte
Ea
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 quantity of the lithium ion conductivity of the lithium ion solid electrolyte of dimorphism anti-perovskite structure
Level.
Claims (10)
1. a kind of dimorphism anti-perovskite lithium ion solid electrolyte, it is characterised in that the lithium ion solid electrolyte has such as
Lower shown chemical formula：Li3+aMpAmBn(XxYy)1-b, wherein -0.25≤a≤0.25；0≤b≤0.5；0≤p≤0.5,0 ＜ m≤
1.25,0 ＜ n≤1.25；0≤x≤1,0≤y≤1；M is any one in Ca, Ba, Mg, Al, Ti；A, B be O, S, Se, Te,
N, any two kinds in P, Si, C, Sb, Bi, F, Cl, Br, I；X, Y is separately selected from halogen or negative one valency ion cluster or sky
One kind in position, the halogen are any one in Cl, Br, I；The negative one valency ion cluster is OH-、BH4 -、NH2 -、CH3 -、
CN-、MgX3 -、CaX3 -In one kind.
2. dimorphism anti-perovskite lithium ion solid electrolyte according to claim 1, it is characterised in that a ≠ 0,0 ＜ b≤
Any two kinds in 0.5, m+n ＞ 1, A, B O, S, Se, Te, N, P, I, Cl, Br.
3. dimorphism anti-perovskite lithium ion solid electrolyte according to claim 1, it is characterised in that a=0,0 ＜ b≤
Any two kinds in 0.5, m+n ＞ 1, A, B O, S, Se, Te, N, P, I, Cl, Br.
4. the dimorphism anti-perovskite lithium ion solid electrolyte according to Claims 2 or 3, it is characterised in that p=0.
5. dimorphism anti-perovskite lithium ion solid electrolyte according to claim 1, it is characterised in that a=0, b=0, p
Any two kinds in=0, m+n=1, A, B O, S, Se, Te, N, P, I, Cl, Br.
6. dimorphism anti-perovskite lithium ion solid electrolyte according to claim 1, it is characterised in that x=0, y=0；-
0.125≤a≤0.125, p=0；0<m<1,0<n<1, A and B is respectively one kind in Si, C, S, O.
7. dimorphism anti-perovskite lithium ion solid electrolyte according to claim 1, it is characterised in that the lithium ion is consolidated
Body electrolyte is one kind in crystal, vitreum, amorphous.
A kind of 8. preparation method of dimorphism anti-perovskite lithium ion solid electrolyte as claimed in claim 1, it is characterised in that
Comprise the following steps：
1) ball milling 3-10h under being protected by raw material under vacuum either inert gas shielding or without protic solvent, obtains presoma；
2) presoma is incubated 5-16h in 150-500 DEG C under vacuum or inert gas shielding, produced.
A kind of 9. preparation method of dimorphism anti-perovskite lithium ion solid electrolyte as claimed in claim 1, it is characterised in that
Comprise the following steps：
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.
10. a kind of application of the dimorphism anti-perovskite lithium ion solid electrolyte in lithium ion battery as claimed in claim 1,
Characterized in that, the lithium ion battery includes electrode slice, the electrode slice includes collector and coating is arranged on afflux body surface
The electrode material layer in face, the electrode material layer include electrode material and electrode material additive, the electrode material additive
For lithium ion solid electrolyte as claimed in claim 1.
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