CN109888373A - A kind of organic/inorganic composite solid electrolyte and preparation method thereof - Google Patents
A kind of organic/inorganic composite solid electrolyte and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of organic/inorganic composite solid electrolytes and preparation method thereof, sulfide is pre-processed, the sulfide that pretreatment obtains is subjected to high-temperature heat treatment and obtains sulfenyl solid electrolyte, then is added in organic solvent and is mixed with organic polymer, lithium salts；Organic solvent is removed, is dried to obtain organic/inorganic composite solid electrolyte.The internal layer of the organic/inorganic composite solid electrolyte material is sulfenyl solid electrolyte, organic polymer is coated on the outside of sulfenyl solid electrolyte, the sulfenyl solid electrolyte is the structure of three-phase and three-phase or more, or the organic/inorganic composite electrolyte of two-phase sulfide solid electrolyte and low decomposition temperature polymer organic object composition, the activity of obtained organic/inorganic composite solid electrolyte improves, conductivity improves, and is conducive to the cycle performance for improving lithium-sulfur cell.
Description
Technical field
The invention belongs to energy new material technology fields, and in particular to lithium ion battery solid electrolyte is prepared and answered
With.
Background technique
Lithium ion battery has the characteristics that energy density is high, has extended cycle life, memory-less effect, is widely used in daily
Consumer electronics product and electric car, power grid energy storage etc..Commercial li-ion battery generally uses organic liquid at present
Electrolyte and gel state electrolyte, liquid and gel-like electrolyte ionic conductivity with higher, but easily waved due to containing
Hair, inflammable, explosive organic solvent have serious security hidden trouble.Solid electrolyte can effectively solve lithium-ion electric
The security hidden trouble that pond is caused due to liquid electrolyte, while solid electrolyte can inhibit Li dendrite during circulating battery
Generation, such that lithium metal as battery cathode, further increases the energy density of lithium ion battery.All solid state electricity
Pond development and the key of application are solid electrolytes, and solid electrolyte mainly has organic and two kinds of inorganic at present, wherein having
Machine class solid electrolyte has the characteristics that good flexibility, good film forming, viscoelasticity, light weight, but there are its power
It is poor to learn performance, at room temperature the low problem of ionic conductivity, and inorganic solid electrolyte has conductivity height, electrification at room temperature
The wide advantage of window is learned, but its film forming is bad, therefore combines answering for preparation with inorganic solid electrolyte for organic
Class solid electrolyte is closed, can be effectively combined respective advantage, being formed has consolidating for good ionic conductivity and mechanical property
State electrolyte.
Sulfenyl solid electrolyte has high ionic conductivity, wide electrochemical window, it is considered to be most have application prospect
One of solid electrolyte.But sulfide solid electrolyte can react with lithium anode interface, cause sulfenyl solid-state
Electrolyte decomposes, so that the interface resistance of electrolyte and lithium metal increases, influences the electrochemistry cycle performance of solid state battery.It is organic
Class solid electrolyte have good film forming and flexibility, but its ionic conductivity is low at room temperature.Such as patent No. CN
What 105680092 A were proposed reduces organic polymer crystallinity using the certain silica of addition, to improve organic solid-state electricity
Matter ionic conductivity is solved, 60 DEG C of tests obtain ionic conductivity~10-4S/cm, relative to current business application at room temperature~
10-2The ionic conductivity of S/cm is much lower.Liquid phase method, which prepares sulfide, to be had the characteristics that easy to operate, controllable, but liquid phase is former
The organic/inorganic composite solid electrolyte that position is formed has certain restrictions.
Summary of the invention
For above-mentioned problems of the prior art, it is an object of the present invention to provide a kind of composite solid electrolytes
The preparation method of material.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
A kind of preparation method of composite solid electrolyte material, specific steps are as follows:
(1) sulfide is pre-processed；
(2) it is heat-treated the pretreated sulfide that step (1) obtains to obtain sulfenyl solid-state under certain high temperature
Electrolyte；
(3) the sulfenyl solid electrolyte that step (2) obtains is added in organic solvent with organic polymer, lithium salts and is carried out
Mixing；
(4) organic solvent is removed, is dried.
To the preparation of organic/inorganic composite solid electrolyte material in the present invention, can effectively solve some sulfide without
Method synthesizes the problem of sulfenyl solid electrolyte of three-phase and three-phase or more in liquid phase organic solvent, while avoiding heat treatment temperature
The excessively high decomposition for causing organic polymer.This method is suitable for the sulfenyl solid electrolyte of three-phase or more, while being suitable for dividing
Solve the low organic polyelectrolyte of temperature.Organic solid state electrolysis confrontation sulfenyl solid electrolyte carries out surface cladding, isolation
Direct contact between lithium metal and sulfenyl solid electrolyte, it is suppressed that between sulfenyl solid electrolyte and lithium anode
Interfacial reaction, so that solid electrolyte and lithium metal have good interface compatibility.Meanwhile composite electrolyte uses organic
Solid state electrolysis confrontation sulfenyl solid electrolyte carries out in-stiu coating, since organic electrolyte can be filled in inorganic electrolyte
Between particle, the intergranular interface resistance of sulfenyl solid electrolyte is effectively reduced, therefore the ion-conductance of solid electrolyte at room temperature
Conductance is further enhanced.
The effect for forming the sulfenyl solid electrolyte of this three-phase and the above structure of three-phase is to improve sulfenyl solid electrolyte
Ionic conductivity, expand electrolyte electrochemical window, while can reduce its chemistry and electro-chemical activity, improve its stabilization
Property.
Preferably, the sulfide in the step (1) is the mixture of lithium sulfide, phosphorus pentasulfide.
Lithium sulfide, phosphorus pentasulfide mixture through Overheating Treatment form be two phase structure sulfenyl solid electrolyte.
Preferably, the sulfide in the step (1) is lithium sulfide, the mixture of phosphorus pentasulfide and aluminium sulfide, vulcanization
One of germanium, silicon sulfide, artificial gold, selenium sulfide, molybdenum sulfide or a variety of combinations.
Since aluminium sulfide, germanium sulfide, silicon sulfide, artificial gold, selenium sulfide, molybdenum sulfide sulfide active are lower, can not have
The sulfenyl solid electrolyte of three-phase and the above structure of three-phase is prepared in liquid phase reactor in machine solution, can using solid reacting method
Effectively to solve this problem.
Preferably, the pretreated method in the step (1) is grinding or ball milling.
Preferably, the heat-treatment temperature range in the step (2) is 200 DEG C -900 DEG C；It is preferred that 250 DEG C -800 DEG C.
The microstructure for the sulfenyl solid electrolyte that heat treatment process influences, in above-mentioned heat-treatment temperature range,
The structure of obtained sulfenyl solid electrolyte is that the crystal structure of three-phase and three-phase or more can be made if temperature is lower or excessively high
Specific crystal phase can not be crystallized or can not formed at electrolyte, directly affect the ionic conductivity of electrolyte.
Preferably, heat treatment time range is 2h-20h in the step (2)；Preferably 2h-12h.
Preferably, in the step (3) organic polymer be PPC, PEC, PEG, PVCA, PSI, PEO, PMMA, PVA,
One of PVDF.
The organic polymer of the application includes that pyrolysis temperature is lower and the higher different material of pyrolysis temperature, organic polymer
Different pyrolysis temperatures organic/inorganic composite solid electrolyte material is not influenced in this application, because of the system of the application
The heat treatment of sulfenyl solid electrolyte is arranged before the formation of organic/inorganic composite solid electrolyte material in Preparation Method, so having
The pyrolysis temperature of machine polymer can reduce, and ensure that the realizability of preparation method, applied widely, while be suitable for two-phase
Sulfide Li2S-P2S5Compound, the organic/inorganic solid electrolyte of formation is carried out with the organic polymer of low decomposition temperature.
Preferably, the lithium salts in the step (3) is LiClO4、LiBF4、LiBOB、LiDFOB、LiDTI、LiTFSI、
One of LiFSI.
Preferably, the molar ratio of the organic polymer in the step (3) and lithium salts is in 1:1-50:1, preferably 3:1-
30:1。
Preferably, the matter for the mixture that the sulfenyl solid electrolyte in the step (3), organic polymer-lithium salts are formed
Amount is than being 1:1-250:1, preferably 10:1-150:1.
Preferably, the organic solvent in the step (3) be acetonitrile, tetrahydrofuran, dimethyl ether, N-METHYLFORMAMIDE, 1,
2- dimethoxy-ethane, one of normal heptane.
Preferably, in the step (3) sulfenyl solid electrolyte and organic polymer, lithium salts, organic solvent mixing side
Formula is magnetic agitation.
Inorganic solid electrolyte and organic polymer and lithium salts can be sufficiently mixed uniformly in the solution.
Preferably, the magnetic agitation time is preferably for 24 hours -40h between 20h-60h in the step (3).
Preferably, the method for organic solvent is removed in the step (4) to be evaporated, be evaporated in vacuo to filter, rotating.
Preferably, the temperature dried in the step (4) is 50 DEG C -200 DEG C, preferably 50 DEG C -120 DEG C.
Preferably, the solution drying time range in the step (4) is preferably for 24 hours -40h between 12-48h.
The organic/inorganic composite solid electrolyte material that above-mentioned preparation method is prepared, the organic/inorganic composite solid
The internal layer of state electrolyte is sulfenyl solid electrolyte, and the organic polymer solid electrolyte formed with lithium salts is coated on sulfenyl
The outside of solid electrolyte, the sulfenyl solid electrolyte are the structure of three-phase and three-phase or more.
Application of the above-mentioned organic/inorganic composite solid electrolyte material in lithium ion battery, supercapacitor etc..
A kind of all-solid lithium-ion battery is anode with sulphur simple substance, with above-mentioned organic/inorganic composite solid electrolyte material
Material is electrolyte, and lithium metal is that cathode is assembled to obtain.
Beneficial effects of the present invention:
(1) organic/inorganic composite solid electrolyte material prepared by the present invention, due to organic solid state electrolysis confrontation sulfenyl
Solid electrolyte carries out in-stiu coating, since organic electrolyte can be filled between inorganic electrolyte granular, effectively drops
The intergranular interface resistance of low-sulfur base solid electrolyte, therefore the ionic conductivity of solid electrolyte is further mentioned at room temperature
It is high.
(2) organic/inorganic composite solid electrolyte material prepared by the present invention, due to organic solid state electrolysis confrontation sulfenyl
Solid electrolyte carries out surface cladding, has completely cut off the direct contact between lithium metal and sulfenyl solid electrolyte, it is suppressed that sulfenyl
Interfacial reaction between solid electrolyte and lithium anode, so that solid electrolyte has good interface compatible with lithium metal
Property.
(3) preparation of the present invention to organic/inorganic composite solid electrolyte material, can effectively solve some specific sulphur
Compound can not synthesize the problem of sulfenyl solid electrolyte of three-phase and three-phase or more in liquid phase organic solution.Hot place is avoided simultaneously
Manage the excessively high decomposition for causing organic polymer of temperature.This method is suitable for the sulfenyl solid electrolyte of three-phase or more, fits simultaneously
For two-phase sulfide Li2S-P2S5The organic/inorganic combined electrolysis that the electrolyte organic polymer low with decomposition temperature is formed
Matter.
(4) present invention uses the assembled battery of organic/inorganic composite solid electrolyte, can use to avoid organic electrolyte
Security hidden trouble.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the organic/inorganic composite solid electrolyte scanning electron microscope (SEM) photograph that embodiment 1 obtains；
Fig. 2 is the organic/inorganic composite solid electrolyte XRD diagram that embodiment 1 obtains；
Fig. 3 is the organic/inorganic composite solid electrolyte scanning electron microscope (SEM) photograph that embodiment 2 obtains；
Fig. 4 is the organic/inorganic composite solid electrolyte XRD diagram that embodiment 2 obtains；
Fig. 5 is all solid lithium sulphur battery electrochemical cycle performance figure assembled with composite electrolyte.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Below with reference to embodiment, the present invention is further described
Embodiment 1
Lithium sulfide, phosphorus pentasulfide are subjected to ground and mixed with 1:1 (molar ratio) in mortar, carry out ball in the ball mill
6h is ground, 4h is heat-treated at 280 DEG C, obtains sulfenyl solid electrolyte, by PMMA polymer and LiClO4It is mixed with 10:1 molar ratio
It closes, sulfide powder and polymer/lithium salts is added in normal heptane by 9:1 mass ratio, 50 DEG C of magnetic agitation 12h utilize rotation
Method of evaporating removes organic solvent, and 80 DEG C of the temperature of drying obtains organic/inorganic composite solid electrolyte.Organic polymer
Clad with a thickness of 20-30nm, ionic conductivity is 10 at room temperature-4S/cm。
On the one hand, which is suitable for preparing the sulfenyl solid electrolyte of three-phase or more, while being suitable for decomposing
The low organic polyelectrolyte of temperature.In addition, the composite electrolyte uses organic solid state electrolysis confrontation sulfenyl solid state electrolysis
Matter carries out in-stiu coating, and since organic electrolyte can be filled between inorganic electrolyte granular, it is solid that sulfenyl is effectively reduced
Interface resistance between state electrolyte granular, therefore the ionic conductivity of solid electrolyte is further enhanced at room temperature.Simultaneously
Since organic solid state electrolysis confrontation sulfenyl solid electrolyte carries out surface cladding, lithium metal and sulfenyl solid electrolyte are completely cut off
Between direct contact, it is suppressed that the interfacial reaction between sulfenyl solid electrolyte and lithium anode so that solid electrolyte
There is good interface compatibility with lithium metal.It can effectively be solved with the all-solid-state battery of composite solid electrolyte assembling simultaneously
The interface problem of lithium metal and sulfenyl solid electrolyte avoids lithium metal bring security risk.
Fig. 1 is organic/inorganic composite solid electrolyte scanning of materials electron microscope prepared by example 1, and Fig. 2 is the preparation of example 1
Organic/inorganic composite solid electrolyte material XRD diagram.As seen from Figure 1, Figure 2, inorganic solid electrolyte is micron order
Grain, organic polymer solid electrolyte are coated on particle surface organic/inorganic composite solid electrolyte.
Embodiment 2
Lithium sulfide, phosphorus pentasulfide, germanium sulfide are subjected to ball milling 12h with 5:2:1 (molar ratio) in the ball mill, 600
It is heat-treated 6h at DEG C and obtains sulfenyl solid electrolyte, PVDF polymer and LiTFSI are mixed with 30:1 molar ratio, by sulfide
Powder and polymer/lithium salts are added in acetonitrile by 1:1 mass ratio, at room temperature magnetic agitation 48h, are removed using the method for suction filtration organic
Solvent, the temperature 50 C of drying obtain organic/inorganic composite solid electrolyte.The clad of organic polymer with a thickness of
100-120nm, ionic conductivity is~10 at room temperature-3S/cm。
Organic/inorganic composite solid electrolyte scanning of materials electron microscope prepared by embodiment 2, Fig. 4 are prepared by example 2
The XRD diagram of organic/inorganic composite solid electrolyte material.By Fig. 3, Fig. 4 it is found that inorganic solid electrolyte is micron particles,
Organic polymer solid electrolyte is coated on particle surface organic/inorganic composite solid electrolyte.
Embodiment 3
Lithium sulfide, phosphorus pentasulfide, aluminium sulfide are subjected to ball milling 16h with 6:2:1 (molar ratio) in the ball mill, 400
It is heat-treated 10h at DEG C and obtains sulfenyl solid electrolyte, PEO polymer and LiTFSI are mixed with 5:1 molar ratio, by sulfide powder
End is added in tetrahydrofuran with polymer/lithium salts by 150:1 mass ratio, at room temperature magnetic agitation 36h, is removed using the method for suction filtration
Organic solvent, 120 DEG C of the temperature of drying, obtains organic/inorganic composite solid electrolyte.The thickness of the clad of organic polymer
For 5-10nm, ionic conductivity is~10 at room temperature-5S/cm。
It is assembled into all-solid lithium-ion battery using organic/inorganic composite solid electrolyte prepared by embodiment 1, with simple substance
Sulphur is anode, is assembled into all solid state lithium-sulfur cell with metal lithium sheet.
Fig. 5 is the lithium-sulfur cell electrochemistry cycle performance test result assembled with organic/inorganic composite solid electrolyte, from
In figure as can be seen that since organic/inorganic solid electrolyte has good ionic conductivity, while can be improved and lithium metal
The interface stability of cathode, therefore all-solid-state battery has good electrochemistry cycle performance.
Comparative example 1
Lithium sulfide, phosphorus pentasulfide are subjected to ground and mixed with 1:1 (molar ratio) in mortar, carry out ball in the ball mill
6h is ground, by PMMA polymer and LiClO4With the mixing of 10:1 molar ratio, sulfide powder and polymer/lithium salts are pressed into 9:1 mass
Than be added normal heptane in, 50 DEG C of magnetic agitation 12h, using rotary evaporation method remove organic solvent, 80 DEG C of the temperature of drying,
It is heat-treated 4h at 280 DEG C, obtains organic/inorganic composite solid electrolyte.
The organic solid state electrolysis confrontation sulfenyl solid electrolyte that example 1 obtains carries out in-stiu coating, while can fill
Organic/inorganic composite electrolyte is formed between inorganic electrolyte granular.And comparative example 1 is higher than organic polymer due to temperature
The decomposition temperature of PMMA, PMMA segment decomposes, therefore obtained sulfenyl solid electrolyte does not have good polymer overmold structure,
At room temperature ionic conductivity it is very low~10-7S/cm。
Comparative example 2
Lithium sulfide, phosphorus pentasulfide, germanium sulfide are subjected to ball milling 12h with 5:2:1 (molar ratio) in the ball mill, 300
It is heat-treated 6h at DEG C and obtains sulfenyl solid electrolyte, PVDF polymer and LiTFSI are mixed with 30:1 molar ratio, by sulfide
Powder and polymer/lithium salts are added in acetonitrile by 1:1 mass ratio, at room temperature magnetic agitation 48h, are removed using the method for suction filtration organic
Solvent, the temperature 50 C of drying obtain organic/inorganic composite solid electrolyte.
The organic/inorganic composite solid electrolyte that embodiment 2 and comparative example 2 obtain compares, available embodiment 2
By the Li of the available three-phase of high-temperature heat treatment10GeP2S12The sulfenyl solid electrolyte of phase, conductivity is~10 at room temperature- 3S/cm, and 300 DEG C of heat treatments, sulfide material can not crystallize, and form the Li of three-phase10GeP2S12Phase, ion-conductance at room temperature
Conductance is very low~and 10-7S/cm。
Comparative example 3
Lithium sulfide, phosphorus pentasulfide, germanium sulfide are subjected to ball milling 12h with 5:2:1 (molar ratio) in the ball mill, by PVDF
With the mixing of 30:1 molar ratio acetonitrile is added by 1:1 mass ratio in sulfide powder and polymer/lithium salts by polymer and LiTFSI
In, magnetic agitation 48h, removes organic solvent using the method for suction filtration, the temperature 50 C of drying is heat-treated at 200 DEG C at room temperature
6h obtains organic/inorganic composite solid electrolyte.
Comparative example 3 and embodiment 2 are distinguished as heat treatment step after drying, due in organic polymer pyrolysis temperature
Relatively low, in order to avoid the decomposition of organic polymer solid electrolyte, therefore the temperature being heat-treated cannot be too high.In comparison example 3
After 200 DEG C of middle low temperature heat treatments, the uncrystallizable formation three-phase of lithium sulfide-phosphorus pentasulfide-germanium sulfide mixed sulfides
Li10GeP2S12Phase, at room temperature substantially to lithium ion substantially without ionic conductivity.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of composite solid electrolyte material, it is characterised in that: specific steps are as follows:
(1) sulfide is pre-processed；
(2) it is heat-treated the pretreated sulfide that step (1) obtains to obtain sulfenyl solid state electrolysis under certain high temperature
Matter；
(3) the sulfenyl solid electrolyte that step (2) obtains is added in organic solvent and is mixed with organic polymer, lithium salts
It closes；
(4) organic solvent is removed, is dried；
Preferably, the sulfide in the step (1) includes lithium sulfide, phosphorus pentasulfide, aluminium sulfide, germanium sulfide, silicon sulfide, sulphur
Change one of tin, selenium sulfide, molybdenum sulfide etc. or a variety of；
Preferably, the pretreated method in the step (1) is grinding or ball milling etc.；
Preferably, the lithium salts in the step (3) is LiClO4, LiBF4, LiBOB, LiDFOB, LiDTI, LiTFSI, LiFSI etc.
One of；
Preferably, the organic solvent in the step (3) is acetonitrile, tetrahydrofuran, dimethyl ether, N-METHYLFORMAMIDE, 1,2- bis-
Ethyl Methyl Ether, one of normal heptane；
Preferably, sulfenyl solid electrolyte and the hybrid mode of organic polymer, lithium salts, organic solvent are in the step (3)
Magnetic agitation.
2. preparation method according to claim 1, it is characterised in that: the heat-treatment temperature range in the step (2) is
200℃-900℃；It is preferred that 280 DEG C -800 DEG C；Heat treatment time range is 2h-20h in the step (2)；Preferably 2h-12h.
3. preparation method according to claim 1, it is characterised in that: in the step (3) organic polymer be PPC,
One of PEC, PEG, PVCA, PSI, PEO, PMMA, PVA, PVDF.
4. preparation method according to claim 1, it is characterised in that: organic polymer and lithium salts in the step (3)
Molar ratio in 1:1-50:1, preferably 3:1-30:1.
5. preparation method according to claim 1, it is characterised in that: sulfenyl solid electrolyte in the step (3) with
The mass ratio of organic polymer is in 1:1-250:1, preferably 10:1-150:1.
6. preparation method according to claim 1, it is characterised in that: in the step (3) sulfenyl solid electrolyte with have
Machine polymer, lithium salts, organic solvent hybrid mode be magnetic agitation；The magnetic agitation time is 20h-60h in the step (3)
Between, preferably for 24 hours -40h.
7. preparation method according to claim 1, it is characterised in that: remove the method for organic solvent in the step (4)
For suction filtration or rotary evaporation；The temperature dried in the step (4) is 50 DEG C -200 DEG C, preferably 50 DEG C -120 DEG C.
8. the organic/inorganic composite solid electrolyte material that the described in any item preparation methods of claim 1-7 are prepared,
Be characterized in that: the internal layer of the organic/inorganic composite solid electrolyte material is sulfenyl solid electrolyte, organic polymer cladding
In the outside of sulfenyl solid electrolyte, the sulfenyl solid electrolyte is the structure or two-phase vulcanization of three-phase and three-phase or more
Object Li2S-P2S5The organic/inorganic composite electrolyte of solid electrolyte and low decomposition temperature polymer organic object composition.
9. organic/inorganic composite solid electrolyte material answering in lithium ion battery, supercapacitor according to any one of claims 8
With.
10. a kind of all-solid lithium-ion battery, using above-mentioned organic/inorganic composite solid electrolyte material as electrolyte, with sulphur
Simple substance is anode, and lithium metal is that cathode is assembled to obtain.
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| CN110247109A (en) * | 2019-07-16 | 2019-09-17 | 广州天赐高新材料股份有限公司 | A kind of sulfide solid electrolyte and its preparation method and application |
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