CN110444806A - A kind of sulfide solid electrolyte precursor solution and its preparation method and application - Google Patents
A kind of sulfide solid electrolyte precursor solution and its preparation method and application Download PDFInfo
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- CN110444806A CN110444806A CN201910720245.4A CN201910720245A CN110444806A CN 110444806 A CN110444806 A CN 110444806A CN 201910720245 A CN201910720245 A CN 201910720245A CN 110444806 A CN110444806 A CN 110444806A
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Abstract
The present invention provides sulfide solid electrolyte precursor solution of a kind of solid-state lithium-sulfur cell and preparation method thereof and using the sulfide solid electrolyte of precursor solution preparation and the preparation method of composite positive pole and the sulfide solid electrolyte and the composite positive pole, wherein the solid electrolyte precursor solution includes the Li that overall nominal molar ratios are in the ratio section of 70:30~80:202S and P2S5, and as the acetonitrile and other at least one aprotic polar solvents of solvent, wherein the sulfide solid electrolyte precursor solution is the Li using acetonitrile as solvent, with 1:1~1:2 nominal molar ratios2S and P2S5Solution, the uniform blended liquid phase with more lithium sulfide solution using other described aprotic polar solvents as solvent.
Description
Technical field
The present invention relates to solid-state lithium-sulfur cell field more particularly to a kind of sulfide solid electrolytes of solid-state lithium-sulfur cell
Precursor solution and preparation method thereof and the sulfide solid electrolyte and anode composite material prepared using the precursor solution
The preparation method of material and the sulfide solid electrolyte and the composite positive pole.
Background technique
Solid-state lithium-sulfur cell has the advantages such as specific capacity height, low raw-material cost, safety be good, while solid battery knot
Structure can effectively eliminate the shuttle effect that its positive reaction intermediate is shifted to cathode, have splendid anti-self discharge ability.Cause
This, develops high performance solid-state lithium-sulfur cell to the secondary cell of new generation of exploitation high-energy density, high security with important
Meaning.
Core material of the solid electrolyte as solid-state lithium-sulfur cell plays a part of ion transmission between positive and negative electrode,
Selecting suitable solid electrolyte is to improve battery high rate performance, cycle life and the key point for guaranteeing safety, this field
It will be appreciated by the skilled person that the ionic conductivity of solid electrolyte directly determines the high rate performance of solid-state lithium-sulfur cell, many
In solid electrolytic plastidome, sulfide solid electrolyte has highest ionic conductivity, and conductivity at room temperature is up to 10- 2S/cm, it is suitable with electrolyte, therefore sulfide solid electrolyte has a good application prospect.However, it is some have it is higher from
The contact stabilization of the electrode material of the sulfide solid electrolyte and lithium-sulfur cell of electron conductivity is not good enough, so that sulfide is solid
Body electrolyte is difficult to give full play to the high ionic conductivity of sulfide solid electrolyte in the practical application of solid-state lithium-sulfur cell
Characteristic, wherein by reduction solid electrolyte particle size and particle size uniformity is improved, for obtaining fine and close, stable and having one
The artificial solid electrolyte interface layer for determining ionic conductivity has great importance.But the routine of sulfide solid electrolyte
Preparation method, sulfide solid electrolyte particle made from Mechanical Alloying and high-temperature melting method including high-energy ball milling compared with
To be coarse, partial size arrives some tens of pm at a few micrometers, and coarse particle limits many applications of sulfide solid electrolyte, is based on
The drawbacks described above of the characteristic advantage of the high ionic conductivity of sulfide solid electrolyte and preparation method thereof, sulfide solid electrolysis
Matter is widely studied as the research focus in solid-state lithium-sulfur cell field, is ground including the doping vario-property to sulfide solid electrolyte
Study carefully, the composite modified improvement studied and prepare synthetic method.Wherein, using liquid phase process synthesizing sulfide solid electrolyte,
And anode constituents are carried out in liquid phase environment it is compound, to reduce sulfide solid electrolyte particle size and to improve partial size equal
Even property, and interfacial contact even closer between sulfide solid electrolyte and corresponding positive electrode is obtained, become right at present
One of main direction of studying of modification of sulfide solid electrolyte, however, being limited to prepare the original of sulfide solid electrolyte
Material and/or the dissolubility and hydrolysis properties for preparing the intermediate product during sulfide solid electrolyte, it is existing to use liquid
It is difficult to obtain the sulfide solid of dissolved state by convenient and fast technology during phase method synthesizing sulfide solid electrolyte
Electrolyte precursor liquid solution, so be difficult to further decrease sulfide solid electrolyte particle size and improve particle size uniformity,
And sulfide can not be obtained by the way that anode constituents are carried out compound mode in sulfide solid electrolyte precursor solution and consolidated
Even closer interfacial contact between body electrolyte and corresponding positive electrode.
That is, sulfide solid electrolyte has a good application prospect and grinding as solid-state lithium-sulfur cell field
Study carefully focus to be widely studied, how to obtain fine and close, stable and solid electricity with certain ionic conductivity by convenient and fast technology
Matter boundary layer is solved, is suitable for the solid electrolyte diaphragm of high-performance solid-liquid mixing lithium-sulfur cell and solid-state lithium-sulfur cell for developing
It is of great significance.
Summary of the invention
The purpose of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and its preparation method and application,
Wherein hold the sulfide solid electrolyte forerunner of liquid and preparation method thereof preparation by the sulfide solid electrolyte presoma
Liquid solution is the liquid phase of stable homogeneous.
Another object of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and preparation method thereof and
Using, wherein each component stable homogeneous of the sulfide solid electrolyte precursor solution be dissolved in the sulfide solid
Electrolyte precursor liquid solution is conducive to reduce the sulfide solid obtained by the sulfide solid electrolyte precursor solution
The particle size of electrolyte and the particle uniformity for improving the sulfide solid electrolyte.
Another object of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and preparation method thereof and
Using wherein the particle ruler of the sulfide solid electrolyte obtained by the sulfide solid electrolyte precursor solution
It is very little to be reduced and particle size uniformity, be conducive to the premise for maintaining the high ionic conductivity of the sulfide solid electrolyte
The lower interface stability for improving the sulfide solid electrolyte as solid electrolyte diaphragm when.
Another object of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and preparation method thereof and
Using, wherein the sulfide solid electrolyte precursor solution be stable homogeneous solution, convenient for by common wet process at
Membrane technology obtains form compact and stable sulfide solid electrolyte coating, is conducive in the sulfide solid electrolyte coating in solid
The voltage stability and appearance of the solid-liquid mixing lithium-sulfur cell are improved when in liquid mixing lithium-sulfur cell as solid electrolyte diaphragm
Measure conservation rate.
Another object of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and preparation method thereof and
Using, wherein the sulfide solid electrolyte precursor solution be stable homogeneous solution, convenient for by common wet process at
Membrane technology obtains the form compact and stable sulfide solid electrolyte coating, i.e., by the sulfide solid electrolyte presoma
The method that solution obtains the sulfide solid electrolyte coating has synthesis technology simple, strong and at low cost excellent of controllability
Gesture and be conducive to industrialized production.
Another object of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and preparation method thereof and
Using, wherein the sulfide solid electrolyte precursor solution be stable homogeneous solution, be conducive to by the vulcanization
Electrode active material, lithium ion transport material and electron transport material or above-mentioned material is added in object solid electrolyte precursor
The mode of persursor material forms the sulfide solid electrolyte, the electrode active material, the lithium ion transport material
And the mixed uniformly composite positive pole of electron transport material nanoscale, have described in high ionic conductivity to obtain
Composite positive pole.
Another object of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and preparation method thereof and
Using wherein by the way that the electrode active material, the lithium ion transport is added in the sulfide solid electrolyte presoma
The mode of the persursor material of material and the electron transport material or above-mentioned material formed the sulfide solid electrolyte,
The electrode active material, the lithium ion transport material and the electron transport material nanoscale are mixed uniformly described multiple
Positive electrode is closed, then each group interface has excellent contact performance, while the anode composite in the composite positive pole
Material and the sulfide solid electrolyte have excellent contact performance, are conducive to the sulfide solid electrolyte and described
Composite positive pole is in the assembling of solid-state lithium-sulfur cell.
Another object of the present invention is to provide a kind of sulfide solid electrolyte precursor solution and preparation method thereof and
Using wherein the sulfide solid electrolyte precursor solution is liquid phase, convenient for based on before the sulfide solid electrolyte
Drive that liquid solution is simple, accurately realizes to the doping vario-property of the sulfide solid electrolyte and composite modified.
Another object of the present invention is to provide a kind of sulfide solid electrolyte presoma hold liquid and preparation method thereof and
Using wherein the sulfide solid electrolyte precursor solution is liquid phase, i.e., by the sulfide solid electrolyte forerunner
Liquid solution obtain the sulfide solid electrolyte use liquid-phase synthesis process, have synthesis technology it is simple, controllability by force with
And advantage at low cost and be conducive to industrialized production.
Another object of the present invention is to provide a kind of sulfide solid electrolyte presoma hold liquid and preparation method thereof and
Using, wherein the preparation method of the sulfide solid electrolyte precursor solution and by the sulfide solid electrolyte before
Drive liquid solution obtains the sulfide solid electrolyte and the composite modified method for obtaining the composite positive pole avoids
Using the conventional mechanical hybrid mode of ball-milling technology, simplifies synthesis technology and be conducive to improve the sulfide solid electrolyte
With the production efficiency of the composite positive pole, and then be conducive to industrialized batch production.
To realize that the above at least purpose, the present invention provide a kind of sulfide solid electrolyte precursor solution, the sulphur
Compound solid electrolyte precursor solution includes the Li that overall nominal molar ratios are in the ratio section of 70:30~80:202S and
P2S5, and as the acetonitrile and other at least one aprotic polar solvents of solvent, wherein before the sulfide solid electrolyte
Driving liquid solution is the Li using acetonitrile as solvent, with 1:1~1:2 nominal molar ratios2S and P2S5Solution, with it is described other
Uniform blended liquid phase of the aprotic polar solvent as more lithium sulfide solution of solvent.
In one embodiment, wherein using acetonitrile as solvent, the Li with 1:1~1:2 nominal molar ratios2S and P2S5It is molten
In liquid, Li2S and P2S5Mass concentration be 0.2~30g/L.
In one embodiment, wherein in more lithium sulfide solution using other described aprotic polar solvents as solvent, tool
Having nominal molar concentration is the Li of 0.01~1mol/L2S。
In one embodiment, wherein other described aprotic polar solvents are tetrahydrofuran.
In one embodiment, wherein other described aprotic polar solvents are glycol dimethyl ether.
In one embodiment, wherein more lithium sulfide solution are to utilize Li in other described aprotic polar solvents2S
With the more lithium sulfide solution for reacting acquisition of S.
In one embodiment, wherein being in other described aprotic polar solvents using rubbing in more lithium sulfide solution
You are the Li than the ratio section in 1:4~1:102S reacts the more lithium sulfide solution obtained with S's.
In one embodiment, wherein in the sulfide solid electrolyte precursor solution, Li2S and P2S5Overall name
Molar ratio is preferably 75:25.
Other side under this invention, the present invention further provides a kind of sulfide solid electrolyte precursor solutions
Preparation method, comprising the following steps:
S1, it prepares using other aprotic polar solvents described at least one as solvent, there is 0.01~1mol/L name
The Li of molar concentration2The solution A of S；
S2, using acetonitrile as the Li of solvent and 1:1~1:2 nominal molar ratios2S and P2S5Prepare B solution；And
S3, Li is prepared in a manner of mixing the solution A and the B solution2S and P2S5Overall nominal molar ratios be in
The sulfide solid electrolyte precursor solution in the ratio section of 70:30~80:20.
In one embodiment, wherein in the step S1, being in 1:4~1 by solvent and molar ratio of tetrahydrofuran:
The Li in 10 ratio section2S and S prepares the Li with 0.01~1mol/L name molar concentration2More lithium sulfide solution As of S.
In one embodiment, wherein in the step S1, being in 1:4 by solvent and molar ratio of glycol dimethyl ether
The Li in the ratio section of~1:102S and S prepares the Li with 0.01~1mol/L name molar concentration2More lithium sulfide A of S are molten
Liquid.
In one embodiment, wherein according to the step S2, in the B solution, Li2S and P2S5Mass concentration be
The concentration ranges of 0.2~30g/L.
In one embodiment, wherein the step S1, the step S2 and the step S3 are in anhydrous and oxygen-free atmosphere
It carries out.
In one embodiment, wherein in the step S3, in such a way that the solution A is added dropwise in the B solution
Mix the solution A and the B solution.
Another aspect under this invention, the present invention further provides a kind of preparation method of sulfide solid electrolyte,
Described in sulfide solid electrolyte preparation method based on the preparation side of the sulfide solid electrolyte precursor solution
Method further comprises step:
After S4, the drying sulfide solid electrolyte precursor solution, 180~250 under anhydrous and oxygen-free atmosphere protection
DEG C heat treatment 0.5~5 hour.
In one embodiment, the preparation method of sulfide solid electrolyte according to claim 18, wherein in institute
Further comprise step before stating step S4:
S34, the coating sulfide solid electrolyte precursor solution are in solid electrolyte diaphragm surface, in described solid
Body electrolyte membrance surface forms the sulfide solid electrolyte solvation precursor thin-film.
In one embodiment, wherein in the step S34, the sulfide solid electricity is coated by water-laid film technique
Matter precursor solution is solved in solid electrolyte diaphragm surface, is consolidated with forming the sulfide in the solid electrolyte diaphragm surface
Body electrolyte solvent precursor thin-film.
Another aspect under this invention, the present invention further provides a kind of preparation method of composite positive pole, wherein institute
The preparation method for stating composite positive pole is further based on the preparation method of the sulfide solid electrolyte precursor solution
Comprising steps of
Electrode active material is added in S5, Yu Suoshu sulfide solid electrolyte precursor solution to obtain uniform sizing material
Afterwards, the slurry is dried, and in subsequent 180~250 DEG C heat treatment 0.5~3 hour under anhydrous and oxygen-free atmosphere protection.
In one embodiment, wherein in the step S5, the electrode active material is corresponding positive electrode or phase
The persursor material for the positive electrode answered.
In one embodiment, further molten in the sulfide solid electrolyte presoma wherein in the step S5
The persursor material of conductive agent or the conductive agent is added in liquid.
In one embodiment, wherein in the step S5, the conductive agent is ion transmission material or electron-transport material
Material.
By the understanding to subsequent description and attached drawing, further aim of the present invention and advantage will be fully demonstrated.
These and other objects of the invention, feature and advantage, by following detailed descriptions, drawings and claims are obtained
To fully demonstrate.
Detailed description of the invention
Fig. 1 is described prepared by the preparation method of the sulfide solid electrolyte of first embodiment under this invention
The XRD spectrum of sulfide solid electrolyte.
Fig. 2A is prepared by the preparation method of the sulfide solid electrolyte with second embodiment under this invention
Sulfide solid electrolyte coating solid electrolyte diaphragm prepared by solid-liquid mixing lithium-sulfur cell voltage-specific capacity it is bent
Line.
Fig. 2 B is prepared by the preparation method of the sulfide solid electrolyte of no second embodiment under this invention
Sulfide solid electrolyte coating solid electrolyte diaphragm prepared by solid-liquid mixing lithium-sulfur cell voltage-specific capacity it is bent
Line.
Fig. 3 is the anode composite as prepared by the preparation method of the composite positive pole of an embodiment under this invention
The solid-state lithium-sulfur cell of material assembling stablizes specific capacity-voltage curve under charge and discharge in 100mA/g constant current.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.It defines in the following description
Basic principle of the invention can be applied to other embodiments, deformation scheme, improvement project, equivalent program and do not carry on the back
Other technologies scheme from the spirit and scope of the present invention.
It will be understood by those skilled in the art that in exposure of the invention, term " longitudinal direction ", " transverse direction ", "upper",
The orientation or position of the instructions such as "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside"
Relationship is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of description of the present invention and simplification of the description, rather than
The device or element of indication or suggestion meaning must have a particular orientation, be constructed and operated in a specific orientation, therefore above-mentioned
Term is not considered as limiting the invention.
It is understood that term " one " is interpreted as " at least one " or " one or more ", i.e., in one embodiment,
The quantity of one element can be one, and in a further embodiment, the quantity of the element can be it is multiple, term " one " is no
It can be interpreted as the limitation to quantity.
The present invention relates to sulfide solid electrolyte precursor solution of a kind of solid-state lithium-sulfur cell and preparation method thereof and
Sulfide solid electrolyte and composite positive pole and sulfide solid electrolysis using precursor solution preparation
The preparation method of matter and the composite positive pole, can be mentioned that, the sulfide solid electrolyte presoma is molten
Liquid is uniform liquid phase, that is to say, that in the present invention, to " solution " in the sulfide solid electrolyte precursor solution
Understand the clarification part that should be believed to comprise but be not limited in clear solution, sol solutions and liquid with sediment,
The traditional chemical of ie in solution defines the restriction not constituted to the sulfide solid electrolyte precursor solution of the invention, In
Under the component ratio of the sulfide solid electrolyte precursor solution of the invention, sulfide solid electrolysis of the invention
Matter precursor solution active principle is rendered as uniform liquid phase.
Specifically, the sulfide solid electrolyte precursor solution includes that overall nominal molar ratios are in 70:30~80:
The Li in 20 ratio section2S and P2S5, and as the acetonitrile and other at least one aprotic polar solvents of solvent, wherein institute
Stating other aprotic polar solvents is the aprotic polar solvent in addition to acetonitrile to more lithium sulfides with certain solubility, wherein
Utilize the Li of 1:1~1:2 nominal molar ratios2S and P2S5It is capable of forming the feature of solable matter in acetonitrile solvent, realizes one
Part Li2S and whole P2S5Being completely dissolved in the sulfide solid electrolyte precursor solution, and by it is described its
His aprotic polar solvent is to another part Li2The dissolution of S realizes that overall nominal molar ratios are in the ratio of 70:30~80:20
The Li in section2S and P2S5Being sufficiently mixed in liquid phase environment and make the sulfide solid electrolyte precursor solution in equal
One liquid phase.
That is, the sulfide solid electrolyte precursor solution is to have 1:1~1:2 using acetonitrile as solvent
The Li of nominal molar ratios2S and P2S5Solution have certain name dense and using other described aprotic polar solvents as solvent
The Li of degree2The uniform blended liquid phase of more lithium sulfide solution of S.
Preferably, using acetonitrile as solvent, the Li with 1:1~1:2 nominal molar ratios2S and P2S5Solution in, Li2S
And P2S5Mass concentration be 0.2~30g/L, using other described aprotic polar solvents as solvent, with certain nominal concentration
Li2Li in more lithium sulfide solution of S2The nominal molar concentration of S is 0.01~1mol/L.
It is noted that Li2S and P2S5It is enough formed in the sulfide solid electrolyte precursor solution soluble
Substance and not exclusively with Li2S and P2S5Molecular state form exist, therefore, the sulfide solid electrolyte forerunner of the invention
Li in liquid solution2S and P2S5Overall nominal molar ratios be in the ratio section of 70:30~80:20 and should be understood as to the sulphur
Li is corresponded in compound solid electrolyte precursor solution2Lithium (Li) sulphur (S) element of S number and corresponding P2S5Phosphorus (P) sulphur of number
(S) the molar ratio limitation between element, rather than to the Li of molecular state2S and P2S5Between molar ratio limitation.
Similarly, using acetonitrile as solvent, the Li with 1:1~1:2 nominal molar ratios2S and P2S5Solution in name
Molar ratio should be understood as corresponding Li2Lithium (Li) sulphur (S) element of S number and corresponding P2S5Phosphorus (P) sulphur (S) element of number it
Between molar ratio limitation, using other described aprotic polar solvents as solvent, have certain nominal concentration Li2S's is molten
Li in liquid2The nominal concentration of S should be understood as corresponding Li2The concentration of lithium (Li) sulphur (S) element of S number limits.
It is understood that using other described aprotic polar solvents as solvent, the Li with certain nominal concentration2S
Solution be meet Li2The nominal molar concentration of S is more lithium sulfide solution of 0.01~1mol/L, such as by simple substance Li and simple substance S
Heating reaction obtains more lithium sulfide solution in other described aprotic polar solvents, or utilizes Li2S is reacted with S's, and synthesis exists
The aprotic polar solvent more lithium sulfides for having larger solubility, or it is molten by more lithium sulfides that electrochemical reaction method obtains
Liquid, the invention is not limited in this regard.
Further to disclose the present invention, the present invention provides the preparation side of the sulfide solid electrolyte precursor solution
Method, wherein the preparation method of the sulfide solid electrolyte precursor solution the following steps are included:
S1, it prepares using other aprotic polar solvents described at least one as solvent, there is 0.01~1mol/L name
The Li of molar concentration2The solution A of S；
S2, using acetonitrile as the Li of solvent and 1:1~1:2 nominal molar ratios2S and P2S5Prepare B solution；And
S3, Li is prepared in a manner of mixing the solution A and the B solution2S and P2S5Overall nominal molar ratios be in
The sulfide solid electrolyte precursor solution in the ratio section of 70:30~80:20.
Further, in the step S1, other described aprotic polar solvents include but is not limited to tetrahydrofuran and
Glycol dimethyl ether.Particularly, in some embodiments of the invention, wherein in the step S1, the solution A is with four
Hydrogen furans or glycol dimethyl ether are in the Li in the ratio section of 1:4~1:10 as solvent in molar ratio2S and S is prepared more
Lithium sulfide solution.
It is noted that being limited to Li in the step S22S and P2S5And Li2S and P2S5In acetonitrile solvent
Intermediate product in the solubility of acetonitrile, be to obtain the uniform B solution without precipitating, the B solution meets Li2S and
P2S5Mass concentration be 0.2~30g/L, that is to say, that in the step S2, the B solution may be derived from using acetonitrile as
The Li of solvent and 1:1~1:2 nominal molar ratios2S and P2S5The clarification part in the liquid with sediment prepared.
Similarly, in the step S3, the sulfide solid electrolyte precursor solution may be derived from by a certain percentage
The clarification part in the liquid with sediment that the solution A and the B solution are prepared is mixed, wherein the solution A and institute
The ratio for stating B solution should meet Li in the sulfide solid electrolyte precursor solution2S and P2S5Overall nominal molar ratios
Ratio section in 70:30~80:20.
It is understood that the sequence of the step S1 and the step S2 are not intended to limit, it is preferable that the step S1,
The step S2 and the step S3 are carried out in anhydrous and oxygen-free atmosphere, are such as carried out in an inert atmosphere, those skilled in the art
Member is it should be appreciated that anhydrous and oxygen-free atmosphere should be understood as that the water having in atmosphere and oxygen content are electrolysed the sulfide solid
The concentration ranges of the influence of the preparation process of matter precursor solution within an acceptable range, and it is anhydrous to be not limited to absolute anaerobic
Atmosphere.
It is noted that the present invention is by way of mixing the solution A and the B solution by Li2S-P2S5The institute of base
The preparation process substep for stating sulfide solid electrolyte precursor solution is completed, to obtain the sulfide solid of uniform liquid phase
Electrolyte precursor liquid solution, wherein there is larger dissolution in aprotic polar solvent using more lithium sulfides in the solution A
The characteristic of degree realizes the corresponding Li of a part2Homogeneous distribution of lithium (Li) sulphur (S) element of S number in the solution A, and in institute
It states in B solution, utilizes the Li of 1:1~1:2 nominal molar ratios2S and P2S5The spy of solable matter is capable of forming in acetonitrile solvent
Sign realizes corresponding P2S5Phosphorus (P) sulphur (S) element and another part of number correspond to Li2Lithium (Li) sulphur (S) element of S number is in institute
The homogeneous distribution in B solution is stated, to prepare Li in a manner of being mixed in a certain ratio the solution A and the B solution2S and
P2S5Overall nominal molar ratios be in 70:30~80:20 ratio section the uniform sulfide solid electrolyte forerunner
Liquid solution.
It will be appreciated by those skilled in the art that when the sulfide solid electrolyte precursor solution is uniform liquid phase, institute
It is distributed in the sulfide solid electrolyte forerunner with stating each component stable homogeneous of sulfide solid electrolyte precursor solution
Liquid solution is conducive to for reducing the sulfide solid electrolyte obtained by the sulfide solid electrolyte precursor solution
Particle size and the particle uniformity for improving the sulfide solid electrolyte, and then be conducive to that the sulfide solid is maintained to be electrolysed
It is steady that interface of the sulfide solid electrolyte as solid electrolyte diaphragm when is improved under the premise of the high ionic conductivity of matter
It is qualitative.
It is the beneficial effect of uniform liquid phase in view of the sulfide solid electrolyte precursor solution, the present invention is based on described
The preparation method of sulfide solid electrolyte precursor solution further provides for the sulfide using precursor solution preparation
The preparation method of solid electrolyte and the sulfide solid electrolyte, wherein the preparation method of the sulfide solid electrolyte
Preparation method based on the sulfide solid electrolyte precursor solution further comprises step:
After S4, the drying sulfide solid electrolyte precursor solution, 180~250 under anhydrous and oxygen-free atmosphere protection
DEG C heat treatment 0.5~5 hour.
It is noted that in the step S4, it is excellent to the drying of the sulfide solid electrolyte precursor solution
It is selected under the anhydrous and oxygen-free atmosphere protection of low temperature and carries out, such as the inert atmosphere under 100 DEG C.
Particularly, the sulfide solid electrolyte as electrolyte in actual use and test often with coating
Form is present in solid electrolyte diaphragm surface and is assembled in solid-state lithium-sulfur cell or solid-liquid mixing lithium-sulfur cell, will be described
Sulfide solid electrolyte improves the corresponding solid electrolyte as the accordingly boundary layer of the solid electrolyte diaphragm
The interface stability of diaphragm.Therefore, in some embodiments of the invention, wherein in the step S4, the sulfide is solid
Body electrolyte precursor liquid solution is present in the corresponding solid electrolyte diaphragm in the form of solvation presoma before being oven-dried
Surface, it is solid to form fine and close, the stable sulfide in the corresponding solid electrolyte diaphragm surface through the step S4
The coating of body electrolyte, and then improve the interfacial contact and stability of the corresponding solid electrolyte diaphragm, specifically, In
Further comprise step between the step S3 and the step S4:
S34, the coating sulfide solid electrolyte precursor solution are in solid electrolyte diaphragm surface, in described solid
Body electrolyte membrance surface forms sulfide solid electrolyte solvation precursor thin-film.
It is understood that since the sulfide solid electrolyte precursor solution is uniform liquid phase, in the step
It, can be in the corresponding solid electrolyte diaphragm table by the water-laid film technique that dipping, lifting, spin coating etc. are common in S34
Face forms the uniform sulfide solid electrolyte solvation precursor thin-film, and can be in corresponding after the step S4
The solid electrolyte diaphragm surface forms the coating of the sulfide solid electrolyte of even compact.
Particularly, when the corresponding solid electrolyte diaphragm is sulfide solid electrolyte diaphragm, such as by sulfide
The sulfide solid electrolyte diaphragm that the powder of solid electrolyte obtains after cold moudling and heat treatment, due to the sulfide
Solid electrolyte and corresponding sulfide solid electrolyte diaphragm have good contact, and the sulfide solid electrolyte is molten
The coating for the sulfide solid electrolyte that agent precursor thin-film is further formed through the step S4 and corresponding described
There is good contact between solid electrolyte diaphragm and can be formed in the solid electrolyte diaphragm surface fine and close, stable
The sulfide solid electrolyte coating, be conducive to maintaining the same of the high ionic conductivity of the solid electrolyte diaphragm
When, improve interface stability of the solid electrolyte diaphragm in corresponding solid-state lithium-sulfur cell or solid-liquid mixing lithium-sulfur cell
Property, and then be conducive to improve the voltage stability and capacity retention ratio of corresponding solid-state lithium-sulfur cell or solid-liquid mixing lithium-sulfur cell.
It will be appreciated by those skilled in the art that positive electrode ionic conductivity and positive electrode with it is corresponding described solid
Interfacial contact between body electrolyte membrance is equally that the voltage stability for restricting corresponding solid-state lithium-sulfur cell and capacity are kept
An important factor for rate, high ionic conductivity and the anode between corresponding solid electrolyte diaphragm with good interfacial contact
Material can be improved the voltage stability and capacity retention ratio and high rate performance of corresponding solid-state lithium-sulfur cell.Current positive material
The modification of material is based primarily upon doping and cladding to positive electrode, wherein based on uniform liquid phase environment to the doping of positive electrode and
Cladding can realize the uniform and stable doping and cladding to positive electrode in microstructure, that is to say, that due to the present invention
The sulfide solid electrolyte precursor solution be uniform liquid phase, be based on the sulfide solid electrolyte precursor solution
Coating modification of the liquid phase environment to positive electrode, can improve just while improving the ionic conductivity of corresponding positive electrode
Interfacial contact between pole material and sulfide solid electrolyte diaphragm.
In consideration of it, the present invention further provides based on the sulfide solid electrolyte precursor solution prepare it is compound just
The preparation method of pole material and the composite positive pole, wherein the preparation method of the composite positive pole is based on the vulcanization
The preparation method of object solid electrolyte precursor solution further comprises step:
Electrode active material is added in S5, Yu Suoshu sulfide solid electrolyte precursor solution to obtain uniform sizing material
Afterwards, the slurry is dried, and in subsequent 180~250 DEG C heat treatment 0.5~3 hour under anhydrous and oxygen-free atmosphere protection.
It is noted that the electrode active material is corresponding positive electrode or corresponding institute in the step S5
State the persursor material of positive electrode.It particularly, is the conductivity for further increasing the composite positive pole, of the invention
In some embodiments, wherein further adding in Yu Suoshu sulfide solid electrolyte precursor solution and leading in the step S5
The persursor material of electric agent or the conductive agent, such as Ketjen black, acetylene black, carbon nanotube carbon material for electrode, wherein described
Conductive agent includes but is not limited to ion transmission material and electron transport material.
In this way, in the step S5, by the way that electrode activity material is added in the sulfide solid electrolyte presoma
It is solid that the mode of the persursor material of material, lithium ion transport material and electron transport material or above-mentioned material forms the sulfide
Body electrolyte, the electrode active material, the lithium ion transport material and the electron transport material nanoscale uniformly mix
The composite positive pole of conjunction obtains the composite positive pole with high ionic conductivity, wherein the composite positive pole
Middle each group interface has excellent contact performance, while the composite positive pole has with the sulfide solid electrolyte
Excellent contact performance is conducive to improve the solid-state lithium sulphur for using sulfide solid electrolyte diaphragm and the composite positive pole
The voltage stability and capacity retention ratio of battery or solid-liquid mixing lithium-sulfur cell.
It is noted that the preparation method of the sulfide solid electrolyte precursor solution, the sulfide solid
The preparation method of electrolyte preparation method and the composite positive pole is all made of liquid-phase synthesis process, avoids using ball
The conventional mechanical hybrid mode of grinding process, have synthesis technology it is simple, the strong and at low cost advantage of controllability and be conducive to industry
Metaplasia produces.
Further to disclose the present invention, the preparation method of the sulfide solid electrolyte precursor solution under this invention
First embodiment be described in detail, wherein under an argon atmosphere, weighing Li according to molar ratio 1:5 according to the step S12S
With S, after being mixed into uniform powder with mortar, appropriate tetrahydrofuran is added to Li2The nominal concentration of S is 0.1mol/L, is persistently stirred
It mixes 20 hours, obtains the solution A for containing more lithium sulfides.
According to the step S2, under an argon atmosphere, P is weighed respectively according to molar ratio 1:12S5With Li2S, it is mixed with mortar
After synthesizing uniform powder, appropriate acetonitrile is added to Li2S and P2S5Mass concentration be 15g/L, persistently stir 0.5 hour, obtain
Obtain the B solution.
According to the step S3, the lasting stirring to the solution A is kept, the B solution is added dropwise in solution A,
The additional amount of B solution is controlled, so that Li after mixing2S and P2S5Overall nominal molar ratios example is 75:25, continues stirring 3 hours
Afterwards, 10 hours are stood, obtains the sulfide solid electrolyte precursor solution.
The preparation method of the sulfide solid electrolyte precursor solution based on above-mentioned first embodiment, the vulcanization
The first embodiment of object method for preparing solid electrolyte is disclosed for, wherein according to the step S4, by the sulfide solid
Electrolyte precursor liquid solution is dried under protection of argon gas, and gained powder is in the argon atmosphere of 0.04MPa, 180 DEG C of heat treatments 1 are small
When, then it is heat-treated 1 hour for 230 DEG C.
As shown in Figure 1, prepared by the preparation method of the sulfide solid electrolyte of first embodiment under this invention
The XRD spectrum of the sulfide solid electrolyte be demonstrated, wherein the XRD spectrum based on the sulfide solid electrolyte with
β-Li3PS4And the XRD spectrum comparison of α-S (standard card 83-2283) is it is found that the sulfide solid electrolyte is Li2S-
P2S5Sulfide solid electrolyte β-the Li of base3PS4With the mixed-powder of positive active material α-S, and use AC impedence method
The ionic conductivity that the sulfide solid electrolyte is obtained when surveying the ionic conductivity of the sulfide solid electrolyte is 3.0
×10-6S/cm。
The preparation method of the sulfide solid electrolyte precursor solution based on above-mentioned first embodiment, the vulcanization
The second embodiment of object method for preparing solid electrolyte is further disclosed, wherein according to the step S34 and the step
S4, by solid electrolyte (Li7P3S11) diaphragm spontaneously dries after lifting in the sulfide solid electrolyte precursor solution,
It is repeated 5 times, to be attained at solid electrolyte (Li7P3S11) the sulfide solid electrolyte presoma that uniformly adheres to of diaphragm is thin
Film, and in the argon atmosphere of 0.04MPa, 230 DEG C be heat-treated 1 hour.
The preparation method of the sulfide solid electrolyte based on above-mentioned second embodiment, solid electrolyte
(Li7P3S11) membrane surface is formed with the coating of the fine and close sulfide solid electrolyte, comparison is solid without the sulfide
Solid electrolyte (the Li of body electrolyte coating treatment7P3S11) diaphragm, respectively using lithium metal as anode, infiltration organic electrolyte
The S-C composite material of (1M LiTFSI, DME/DOL=1:1) is cathode, prepares solid-liquid mixing lithium-sulfur cell sample, preparation is consolidated
Voltage-specific capacity curve of liquid mixing lithium-sulfur cell sample charge and discharge under 0.2C multiplying power is shown by Fig. 2A and Fig. 2 B respectively.
As shown in Figure 2 A and 2 B, wherein Fig. 2A corresponds to the sulfide solid electrolyte painting that surface is formed with densification
Solid electrolyte (the Li of layer7P3S11) diaphragm preparation solid-liquid mixing lithium-sulfur cell sample (sample A) charge and discharge under 0.2C multiplying power
Voltage-specific capacity curve of electricity, Fig. 2 B correspond to the solid electrolyte without the sulfide solid electrolyte coating treatment
(Li7P3S11) diaphragm preparation solid-liquid mixing lithium-sulfur cell sample (sample B) charge and discharge under 0.2C multiplying power voltage-specific capacity
Curve, wherein sample A still keeps the specific capacity of 1437mAh/g, conservation rate 96.6% after charge and discharge 15 are enclosed under 0.2C multiplying power,
And discharge voltage plateau is without significant changes；The specific capacity of sample B is reduced to 1295mAh/g, conservation rate 89.1%, and discharge voltage
It significantly reduces, and occurs voltage pit between first and second discharge platform.
The preparation method of the sulfide solid electrolyte precursor solution based on above-mentioned first embodiment, it is described compound
One embodiment of the preparation method of positive electrode is disclosed for, wherein according to the step S5, under an argon atmosphere in the vulcanization
Ketjen black is added in object solid electrolyte precursor solution, is calculated by all positive electrode mass ratios, wherein the matter of Ketjen black
For amount than being 30w%, lasting stirring dries the slurry, gained powder is 0.04MPa's to obtain uniform sizing material under protection of argon gas
In argon atmosphere, 180 DEG C be heat-treated 1 hour, then 230 DEG C be heat-treated 1 hour, obtain contain sulfide solid electrolyte β-
Li3PS4, positive active material α-S and Ketjen black the composite positive pole.
By the conventional batteries packaging technology assembled battery of following solid-state lithium-sulfur cells, the property of the composite positive pole is tested
Can: in argon atmosphere, solid electrolyte Li prepared by conventional mechanical synthetic method7P3S11Thickness is pressed under 50MPa pressure
The diaphragm disk for spending 0.7mm, diameter 15mm, then uniformly dispenses the positive electrode to be measured of 3.0mg in diaphragm side, uses
Diaphragm and positive electrode are pressed into one by 300MPa pressure；Diameter 13mm lithium piece is taken, 10 μ l lithium-sulfur cells are added dropwise in one side
Electrolyte (1M LiTFSI, DME/DOL=1:1)；Then solid electrolyte diaphragm piece is covered on it, and diaphragm is without anode
The side of material is contacted with lithium piece, and the addition of above-mentioned microelectrolysis liquid can increase the contact of lithium piece with solid electrolyte diaphragm piece
Property；Above-mentioned lithium piece/solid electrolyte diaphragm/anode composite three-decker is finally packed into battery case, with 300kg/cm2Pressure pressure
Button cell is made for testing.
With reference to Fig. 3 of Figure of description of the invention, the composite positive pole is according to the normal of above-mentioned solid-state lithium-sulfur cell
Specific capacity-voltage curve after 100mA/g constant current charge and discharge is stablized of the battery sample of rule battery assembly technique assembling is demonstrated,
The composite positive pole can provide after the battery sample assembled according to the conventional batteries packaging technology of above-mentioned solid-state lithium-sulfur cell
More stable charging/discharging voltage platform, and overvoltage is lower than 0.2V.
Further to disclose the present invention, the preparation method of the sulfide solid electrolyte precursor solution under this invention
Second embodiment be described in detail, wherein under an argon atmosphere, weighing Li according to molar ratio 1:1 according to the step S12S
With S, after being mixed into uniform powder with mortar, appropriate tetrahydrofuran is added to Li2The nominal concentration of S is 0.1mol/L, is persistently stirred
It mixes 20 hours, obtains the solution A for containing more lithium sulfides.
According to the step S2, under an argon atmosphere, P is weighed respectively according to molar ratio 1:12S5With Li2S, it is mixed with mortar
After synthesizing uniform powder, appropriate acetonitrile is added to Li2S and P2S5Mass concentration be 15g/L, persistently stir 0.5 hour, obtain
Obtain the B solution.
According to the step S3, the lasting stirring to the solution A is kept, the B solution is added dropwise in solution A,
The additional amount of B solution is controlled, so that Li after mixing2S and P2S5Overall nominal molar ratios example is 70:30, continues stirring 3 hours
Afterwards, 10 hours are stood, obtains the sulfide solid electrolyte precursor solution.
The preparation method of the sulfide solid electrolyte precursor solution based on above-mentioned second embodiment, the vulcanization
One embodiment of object method for preparing solid electrolyte is disclosed for, wherein according to the step S4, by the sulfide solid electricity
Solution matter precursor solution is dried under protection of argon gas, and gained powder is in the argon atmosphere of 0.04MPa, 180 DEG C of heat treatments 1 are small
When, then it is heat-treated 1 hour for 230 DEG C.It is obtained when surveying the ionic conductivity of the sulfide solid electrolyte using AC impedence method
The ionic conductivity for obtaining the sulfide solid electrolyte is 1.1 × 10-6S/cm。
Further, the third of the preparation method of the sulfide solid electrolyte precursor solution under this invention is implemented
Example is described in detail, wherein under an argon atmosphere, weighing Li according to molar ratio 1:5 according to the step S12S and S, uses mortar
After being mixed into uniform powder, appropriate tetrahydrofuran is added to Li2The nominal concentration of S is 0.1mol/L, persistently stirs 20 hours, obtains
Obtain the solution A containing more lithium sulfides.
According to the step S2, under an argon atmosphere, P is weighed respectively according to molar ratio 1:12S5With Li2S, it is mixed with mortar
After synthesizing uniform powder, appropriate acetonitrile is added to Li2S and P2S5Mass concentration be 15g/L, persistently stir 0.5 hour, obtain
Obtain the B solution.
According to the step S3, the lasting stirring to the solution A is kept, the B solution is added dropwise in solution A,
The additional amount of B solution is controlled, so that Li after mixing2S and P2S5Overall nominal molar ratios example is 73:27, continues stirring 3 hours
Afterwards, 10 hours are stood, obtains the sulfide solid electrolyte precursor solution.
The preparation method of the sulfide solid electrolyte precursor solution based on above-mentioned 3rd embodiment, the vulcanization
One embodiment of object method for preparing solid electrolyte is disclosed for, wherein according to the step S4, by the sulfide solid electricity
Solution matter precursor solution is dried under protection of argon gas, and gained powder is in the argon atmosphere of 0.04MPa, 180 DEG C of heat treatments 1 are small
When, then it is heat-treated 1 hour for 230 DEG C.It is obtained when surveying the ionic conductivity of the sulfide solid electrolyte using AC impedence method
The ionic conductivity for obtaining the sulfide solid electrolyte is 2.8 × 10-6S/cm。
Further, the 4th of the preparation method of the sulfide solid electrolyte precursor solution under this invention implements
Example is described in detail, wherein under an argon atmosphere, weighing Li according to molar ratio 1:5 according to the step S12S and S, uses mortar
After being mixed into uniform powder, appropriate tetrahydrofuran is added to Li2The nominal concentration of S is 0.1mol/L, persistently stirs 20 hours, obtains
Obtain the solution A containing more lithium sulfides.
According to the step S2, under an argon atmosphere, P is weighed respectively according to molar ratio 1:12S5With Li2S, it is mixed with mortar
After synthesizing uniform powder, appropriate acetonitrile is added to Li2S and P2S5Mass concentration be 15g/L, persistently stir 0.5 hour, obtain
Obtain the B solution.
According to the step S3, the lasting stirring to the solution A is kept, the B solution is added dropwise in solution A,
The additional amount of B solution is controlled, so that Li after mixing2S and P2S5Overall nominal molar ratios example is 80:20, continues stirring 3 hours
Afterwards, 10 hours are stood, obtains the sulfide solid electrolyte precursor solution.
The preparation method of the sulfide solid electrolyte precursor solution based on above-mentioned fourth embodiment, the vulcanization
One embodiment of object method for preparing solid electrolyte is disclosed for, wherein according to the step S4, by the sulfide solid electricity
Solution matter precursor solution is dried under protection of argon gas, and gained powder is in the argon atmosphere of 0.04MPa, 180 DEG C of heat treatments 1 are small
When, then it is heat-treated 1 hour for 230 DEG C.It is obtained when surveying the ionic conductivity of the sulfide solid electrolyte using AC impedence method
The ionic conductivity for obtaining the sulfide solid electrolyte is 2.0 × 10-9S/cm。
Further, the 5th of the preparation method of the sulfide solid electrolyte precursor solution under this invention implements
Example is described in detail, wherein under an argon atmosphere, weighing Li according to molar ratio 1:5 according to the step S12S and S, uses mortar
After being mixed into uniform powder, proper amount of glycol dimethyl ether is added to Li2The nominal concentration of S is 0.05mol/L, and it is small persistently to stir 20
When, obtain the solution A for containing more lithium sulfides.
According to the step S2, under an argon atmosphere, P is weighed respectively according to molar ratio 1:12S5With Li2S, it is mixed with mortar
After synthesizing uniform powder, appropriate acetonitrile is added to Li2S and P2S5Mass concentration be 15g/L, persistently stir 0.5 hour, obtain
Obtain the B solution.
According to the step S3, the lasting stirring to the solution A is kept, the B solution is added dropwise in solution A,
The additional amount of B solution is controlled, so that Li after mixing2S and P2S5Overall nominal molar ratios example is 75:25, continues stirring 3 hours
Afterwards, 10 hours are stood, the sulfide solid electrolyte precursor solution is obtained, wherein the sulfide solid electrolyte forerunner
Liquid solution is the clarification part mixed in the liquid with sediment that the solution A and the B solution are prepared.
The preparation method of the sulfide solid electrolyte precursor solution based on above-mentioned 5th embodiment, the vulcanization
One embodiment of object method for preparing solid electrolyte is disclosed for, wherein according to the step S4, by the sulfide solid electricity
Solution matter precursor solution is dried under protection of argon gas, and gained powder is in the argon atmosphere of 0.04MPa, 180 DEG C of heat treatments 1 are small
When, then it is heat-treated 1 hour for 230 DEG C.It is obtained when surveying the ionic conductivity of the sulfide solid electrolyte using AC impedence method
The ionic conductivity for obtaining the sulfide solid electrolyte is 5.7 × 10-7S/cm。
It should be understood by those skilled in the art that foregoing description and the embodiment of the present invention shown in the drawings are only used as illustrating
And it is not intended to limit the present invention.The purpose of the present invention has been fully and effectively achieved.Function and structural principle of the invention exists
It shows and illustrates in embodiment, under without departing from the principle, embodiments of the present invention can have any deformation or modification.
Claims (24)
1. a kind of sulfide solid electrolyte precursor solution, which is characterized in that including overall nominal molar ratios be in 70:30~
The Li in the ratio section of 80:202S and P2S5, and acetonitrile and other at least one aprotic polar solvents as solvent,
Described in sulfide solid electrolyte precursor solution be using acetonitrile as solvent, have 1:1~1:2 nominal molar ratios Li2S
And P2S5Solution, the uniform blended liquid phase with more lithium sulfide solution using other described aprotic polar solvents as solvent.
2. sulfide solid electrolyte precursor solution according to claim 1, wherein having 1 using acetonitrile as solvent:
The Li of 1~1:2 nominal molar ratios2S and P2S5Solution in, Li2S and P2S5Mass concentration be 0.2~30g/L.
3. sulfide solid electrolyte precursor solution according to claim 2, wherein with other described aprotonic polars
Solvent has the Li that nominal molar concentration is 0.01~1mol/L as in more lithium sulfide solution of solvent2S。
4. sulfide solid electrolyte precursor solution according to claim 3, wherein other described aprotonic polars are molten
Agent is tetrahydrofuran.
5. sulfide solid electrolyte precursor solution according to claim 3, wherein other described aprotonic polars are molten
Agent is glycol dimethyl ether.
6. according to the sulfide solid electrolyte precursor solution any in claim 3-5, wherein more lithium sulfides
Solution is that Li is utilized in other described aprotic polar solvents2S reacts the more lithium sulfide solution obtained with S's.
7. sulfide solid electrolyte precursor solution according to claim 6, wherein being in more lithium sulfide solution
The Li in the ratio section of 1:4~1:10 is in using molar ratio in other described aprotic polar solvents2S is obtained with reacting for S
The more lithium sulfide solution obtained.
8. sulfide solid electrolyte precursor solution according to claim 7, wherein the sulfide solid electrolyte
In precursor solution, Li2S and P2S5Overall nominal molar ratios be preferably 75:25.
9. a kind of preparation method of sulfide solid electrolyte precursor solution, which is characterized in that the sulfide solid electrolysis
The preparation method of matter precursor solution the following steps are included:
S1, it prepares using other aprotic polar solvents described at least one as solvent, there is 0.01~1mol/L name mole
The Li of concentration2More lithium sulfide solution As of S；
S2, using acetonitrile as the Li of solvent and 1:1~1:2 nominal molar ratios2S and P2S5Prepare B solution；And
S3, Li is prepared in a manner of mixing the solution A and the B solution2S and P2S5Overall nominal molar ratios be in 70:30
The sulfide solid electrolyte precursor solution in the ratio section of~80:20.
10. the preparation method of sulfide solid electrolyte precursor solution according to claim 9, wherein in the step
In S1, the Li in the ratio section of 1:4~1:10 is in using tetrahydrofuran as solvent and molar ratio2S and S, which are prepared, has 0.01~
The Li of 1mol/L name molar concentration2More lithium sulfide solution As of S.
11. the preparation method of sulfide solid electrolyte precursor solution according to claim 9, wherein in the step
In S1, the Li in the ratio section of 1:4~1:10 is in using glycol dimethyl ether as solvent and molar ratio2S and S preparation has
The Li of 0.01~1mol/L name molar concentration2More lithium sulfide solution As of S.
12. according to the preparation method of the sulfide solid electrolyte precursor solution any in claim 9-11, wherein
According to the step S2, in the B solution, Li2S and P2S5Mass concentration be 0.2~30g/L concentration ranges.
13. the preparation method of sulfide solid electrolyte precursor solution according to claim 12, wherein the step
S1, the step S2 and the step S3 are carried out in anhydrous and oxygen-free atmosphere.
14. the preparation method of sulfide solid electrolyte precursor solution according to claim 12, wherein step S1, institute
It states step S2 and the step S3 is carried out in argon atmosphere.
15. the preparation method of sulfide solid electrolyte precursor solution according to claim 13, wherein in the step
In rapid S3, the solution A and the B solution are mixed in such a way that the solution A is added dropwise in the B solution.
16. the preparation method of sulfide solid electrolyte precursor solution according to claim 15, wherein in the step
Further comprise step in rapid S3:
Persistently stir the solution A.
17. the preparation method of sulfide solid electrolyte precursor solution according to claim 12, wherein according to
Step S3, Li2S and P2S5Overall nominal molar ratios be preferably 75:25.
18. a kind of preparation method of sulfide solid electrolyte, which is characterized in that the preparation side of the sulfide solid electrolyte
Preparation method of the method based on the sulfide solid electrolyte precursor solution any in claim 9-17 further comprise
Step:
After S4, the drying sulfide solid electrolyte precursor solution, 180~250 DEG C of heat under anhydrous and oxygen-free atmosphere protection
Processing 0.5~5 hour.
19. the preparation method of sulfide solid electrolyte according to claim 18, wherein before the step S4, into
One step comprising steps of
S34, the coating sulfide solid electrolyte precursor solution are in solid electrolyte diaphragm surface, in the solid electricity
Solution matter membrane surface forms the sulfide solid electrolyte solvation precursor thin-film.
20. the preparation method of sulfide solid electrolyte according to claim 19, wherein in the step S34, by
The sulfide solid electrolyte precursor solution is coated in solid electrolyte diaphragm surface, in described by water-laid film technique
Solid electrolyte diaphragm surface forms the sulfide solid electrolyte solvation precursor thin-film.
21. a kind of preparation method of composite positive pole, which is characterized in that the preparation method of the composite positive pole is based on power
It further comprises step that benefit, which requires the preparation method of any sulfide solid electrolyte precursor solution in 9-17:
After electrode active material is added in S5, Yu Suoshu sulfide solid electrolyte precursor solution to obtain uniform sizing material, dry
The slurry is done, and in subsequent 180~250 DEG C heat treatment 0.5~3 hour under anhydrous and oxygen-free atmosphere protection.
22. the preparation method of composite positive pole according to claim 21, wherein in the step S5, the electrode
Active material is the persursor material of corresponding positive electrode or the corresponding positive electrode.
23. the preparation method of composite positive pole according to claim 22, wherein in the step S5, further in
The persursor material of conductive agent or the conductive agent is added in the sulfide solid electrolyte precursor solution.
24. the preparation method of composite positive pole according to claim 23, wherein in the step S5, the conduction
Agent is ion transmission material or electron transport material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112820858A (en) * | 2021-01-07 | 2021-05-18 | 北京理工大学 | Lithium metal negative electrode protected by phosphorus-sulfur-based interfacial film and preparation method thereof |
| CN113363566A (en) * | 2021-06-17 | 2021-09-07 | 高能时代(佛山)新能源科技有限公司 | Method for preparing sulfide solid electrolyte in low cost and large scale |
| CN113471519A (en) * | 2021-06-29 | 2021-10-01 | 深圳大学 | Sulfide solid electrolyte diaphragm, precursor sol thereof and preparation method |
| CN114267833A (en) * | 2021-12-23 | 2022-04-01 | 中南大学 | Method for coating ternary cathode material with sulfide solid electrolyte |
| CN114335705A (en) * | 2020-09-28 | 2022-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Integrated all-solid-state battery and preparation method thereof |
| CN114709471A (en) * | 2022-03-29 | 2022-07-05 | 上海屹锂新能源科技有限公司 | Preparation method of sulfide solid electrolyte |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500853A (en) * | 2013-10-08 | 2014-01-08 | 中国科学院宁波材料技术与工程研究所 | Sulfide electrolyte material and preparation method thereof |
| JP2014049361A (en) * | 2012-09-03 | 2014-03-17 | Furukawa Co Ltd | Solid electrolyte material for lithium ion battery, solid electrolyte for lithium ion battery, lithium ion battery, and method for producing solid electrolyte material for lithium ion battery |
| JP2015232965A (en) * | 2014-06-10 | 2015-12-24 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Sulfide solid electrolyte, and method of producing sulfide solid electrolyte |
| JP2016213006A (en) * | 2015-05-01 | 2016-12-15 | 出光興産株式会社 | Polysulfide complex and method for producing lithium sulfide composite, positive electrode mixture and all solid battery |
| CN107180992A (en) * | 2017-06-09 | 2017-09-19 | 中国科学院宁波材料技术与工程研究所 | A kind of solid lithium battery combination electrode material and preparation method thereof and a kind of solid lithium battery |
| CN107591563A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院物理研究所 | A kind of sulfenyl electrolyte solution and its application in solid state lithium battery |
| CN107768714A (en) * | 2016-08-18 | 2018-03-06 | 现代自动车株式会社 | The negative electrode of the cathode slurry composition of all solid state ion battery and all solid state ion battery including the composition |
| US20190074544A1 (en) * | 2017-09-06 | 2019-03-07 | Idemitsu Kosan Co., Ltd. | Method for producing solid electrolyte |
| CN109888373A (en) * | 2018-12-27 | 2019-06-14 | 山东大学 | A kind of organic/inorganic composite solid electrolyte and preparation method thereof |
-
2019
- 2019-08-06 CN CN201910720245.4A patent/CN110444806B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014049361A (en) * | 2012-09-03 | 2014-03-17 | Furukawa Co Ltd | Solid electrolyte material for lithium ion battery, solid electrolyte for lithium ion battery, lithium ion battery, and method for producing solid electrolyte material for lithium ion battery |
| CN103500853A (en) * | 2013-10-08 | 2014-01-08 | 中国科学院宁波材料技术与工程研究所 | Sulfide electrolyte material and preparation method thereof |
| JP2015232965A (en) * | 2014-06-10 | 2015-12-24 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Sulfide solid electrolyte, and method of producing sulfide solid electrolyte |
| JP2016213006A (en) * | 2015-05-01 | 2016-12-15 | 出光興産株式会社 | Polysulfide complex and method for producing lithium sulfide composite, positive electrode mixture and all solid battery |
| CN107591563A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院物理研究所 | A kind of sulfenyl electrolyte solution and its application in solid state lithium battery |
| CN107768714A (en) * | 2016-08-18 | 2018-03-06 | 现代自动车株式会社 | The negative electrode of the cathode slurry composition of all solid state ion battery and all solid state ion battery including the composition |
| CN107180992A (en) * | 2017-06-09 | 2017-09-19 | 中国科学院宁波材料技术与工程研究所 | A kind of solid lithium battery combination electrode material and preparation method thereof and a kind of solid lithium battery |
| US20190074544A1 (en) * | 2017-09-06 | 2019-03-07 | Idemitsu Kosan Co., Ltd. | Method for producing solid electrolyte |
| CN109888373A (en) * | 2018-12-27 | 2019-06-14 | 山东大学 | A kind of organic/inorganic composite solid electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QI LI等: "Progress in electrolytes for rechargeable Li-based batteries and beyond", 《GREEN ENERGY & ENVIRONMENT》 * |
| 张锦等: "墨水涂覆法制备硫化物全固态锂离子电池", 《中南大学学报(自然科学版)》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335705A (en) * | 2020-09-28 | 2022-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Integrated all-solid-state battery and preparation method thereof |
| CN114335705B (en) * | 2020-09-28 | 2024-05-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Integrated all-solid-state battery and preparation method thereof |
| CN112820858A (en) * | 2021-01-07 | 2021-05-18 | 北京理工大学 | Lithium metal negative electrode protected by phosphorus-sulfur-based interfacial film and preparation method thereof |
| CN113363566A (en) * | 2021-06-17 | 2021-09-07 | 高能时代(佛山)新能源科技有限公司 | Method for preparing sulfide solid electrolyte in low cost and large scale |
| CN113363566B (en) * | 2021-06-17 | 2022-03-01 | 深圳高能时代科技有限公司 | Method for preparing sulfide solid electrolyte in low cost and large scale |
| CN113471519A (en) * | 2021-06-29 | 2021-10-01 | 深圳大学 | Sulfide solid electrolyte diaphragm, precursor sol thereof and preparation method |
| CN114267833A (en) * | 2021-12-23 | 2022-04-01 | 中南大学 | Method for coating ternary cathode material with sulfide solid electrolyte |
| CN114267833B (en) * | 2021-12-23 | 2024-05-17 | 湖南恩捷前沿新材料科技有限公司 | Method for coating ternary positive electrode material by sulfide solid electrolyte |
| CN114709471A (en) * | 2022-03-29 | 2022-07-05 | 上海屹锂新能源科技有限公司 | Preparation method of sulfide solid electrolyte |
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