CN106684432A - High ionic conductivity sulfide solid electrolyte material, and preparation method and application thereof - Google Patents
High ionic conductivity sulfide solid electrolyte material, and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high ionic conductivity sulfide solid electrolyte material, and a preparation method and application of the high ionic conductivity sulfide solid electrolyte material in a full-solid lithium-sulfur battery. A chemical composition of the material is Li7P3-xMnxS11-(3x+y)/2Iy, wherein x is greater than 0 and less than 0.5, and y is greater than 0 and less than 1. The preparation method of the material comprises the following steps: mixing and ball-milling Li2S, P2S5, MnS and LiI to obtain an initial solid electrolyte material; and performing heat treatment for the initial solid electrolyte material under the inert gas, and then grinding into powder to obtain the high ionic conductivity sulfide solid electrolyte material. The lithium-sulfur solid battery is prepared by preparing a composite positive electrode formed by ball milling and uniformly mixing sulfur, conductive carbon black and solid electrolyte, and the positive electrode is used for solving the disadvantages of low electron conductivity rate of the sulfur and low ion conductivity. The prepared lithium-sulfur battery has the advantages of high safety, high energy density and high cycling stability.
Description
Technical field
The present invention relates to lithium ion battery solid electrolyte material technical field, and in particular to a kind of high ionic conductivity sulfur
Compound solid electrolyte material and its preparation method and application.
Background technology
The popularization of portable set such as mobile phone, computer, people for the demand sustainable growth of high power capacity energy storage device,
And lithium battery is at present in the electrochmical power source can in charge-discharge battery with high-energy-density and preferable cyclical stability, lithium battery
Just applied on a large scale.However, organic liquid electrolytes lithium ion battery is same what is developed to energy storage, mobile electron field
When, the safety problem for being showed can not be ignored.On the one hand, organic electrolyte has volatility and combustibility, when battery exists
Overcharge, cross put and the state such as high temperature under can expand, the problems such as electrolyte is revealed, the safety problem such as pole fire hazardous.Separately
On the one hand, battery is in discharge and recharge is overcharged, and lithium ion is easily produced in negative terminal surface growth in shuttle conductive process in the electrolytic solution
Li dendrite, Li dendrite can penetrate barrier film and cause battery plus-negative plate directly contact so as to be short-circuited, and produce potential safety hazard.Therefore,
The reliable new type lithium ion battery of research safety becomes task very urgent at present.
All-solid-state battery is with the battery of new generation of solid electrolyte replacement conventional liquid organic bath, its high security
Increasingly cause the concern of people with high-energy-density.Composition according to electrolyte be segmented into inorganic solid electrolyte and
Solid polyelectrolyte.
For inorganic solid electrolyte, its advantage mainly has the following aspects：
(1) inorganic solid electrolyte does not contain organic liquid electrolyte, there is no the safety that organic electrolyte is revealed and caused
Hidden danger；
(2) inorganic solid electrolyte can replace liquid electrolyte and barrier film, play obstruct both positive and negative polarity and pass to lithium ion
Effect, reduces battery volume, improves the energy density of battery；
(3) the operating temperature range width of inorganic solid electrolyte, is applicable to the severe working condition such as low temperature and high temperature；
(4) inorganic solid electrolyte has a comparatively wide electrochemical window, most of inorganic solid electrolytes there is 5V with
On electrochemical window, the strong adaptability to Different electrodes material；
(5) inorganic solid electrolyte electrochemical stability is high, and electrolyte is slow with interelectrode side reaction, it is ensured that solid-state electricity
Pond has very excellent cycle performance；
(6) machining property of inorganic solid electrolyte is excellent, and processing technology is easy, needed for being prepared into arbitrarily
Shape；
(7) inorganic solid electrolyte has higher ionic conductivity and high-lithium ion coefficient of migration, is future development
Direction.
But solid electrolyte still suffers from some problems and disadvantages, the electrical conductivity of solid electrolyte is still low.
It is the effective ways for improving its ionic conductivity at present by other associated materials doping sulfide solid electrolytes.
The material of general doping is that different valence state, atomic radius differ larger element, can so widen lithium ion transport passage, have
Effect improves the ionic conductivity of solid electrolyte material.
Additionally, the intermediate reaction product Li of traditional liquid lithium-sulfur cell2SnElectrolyte is highly soluble in, and is had very strong
Mobility, to cell active materials utilization rate, high rate performance and cycle life affect very big to these characteristics.Electric discharge when
Wait, elemental sulfur is reduced to the S of long chainn 2-, it is dissolved in electrolyte and is accumulated in sulfur electrode surface, it is dense in inside battery formation one
Spend poor, the S of so long chainn 2-(n >=4) will be spontaneous move to negative terminal surface and Li react the S for generating short chain shapen 2-(n<
4).If on the one hand forming insoluble Li2S2Or Li2S, can affect the performance of negative pole Li；On the other hand accordingly in negative terminal surface
The S of short chain shapen 2-(n<4) concentration is higher than positive electrode surface so that the S of short chain shapen 2-(4 >=n >=2) migrate back positive pole, again quilt after allowing
It is reduced to the S of long chainn 2-(n≥4)；So phenomenon is referred to as so-called " shuttle effect " repeatedly.On the one hand shuttle effect is made
Into inside battery self discharge, the positive active material for being on the other hand is reduced, and this is to cause capacity attenuation, what cycle life was shortened
Key factor.
And solid state battery then completely solves the problem of liquid lithium-sulfur cell shuttle effect, solid electrolyte in solid state battery
Equivalent to the effect of liquid state batteries septation and electrolyte.High ionic conductivity sulfide solid electrolyte system used in the present invention
Standby lithium sulfur solid state battery, had both improve the security performance of battery, and had solved the problems, such as lithium-sulfur cell shuttle effect again, greatly improve
Battery cycle performance.Therefore, to high security, height ratio capacity is high for the lithium sulfur solid state battery of design synthesis high ionic conductivity
The energy storage device exploitation of energy density is significant.
The content of the invention
Object of the present invention is to provide a kind of high ionic conductivity sulfide solid electrolyte material and its preparation side
Method and the application in all solid state lithium-sulfur cell, the solid electrolyte material are used to prepare lithium sulfur solid state battery, with high safety
Property, high charge-discharge specific capacity, excellent cyclical stability.
A kind of high ionic conductivity sulfide solid electrolyte material, its chemical composition are Li7P3-xMnxS11-(3x+y)/2Iy,
Wherein, 0 ＜ x ＜, 0.5,0 ＜ y ＜ 1.
Further preferably, 0.1≤x≤0.3,0.3≤y≤0.8.
Still more preferably, x=0.1, y=0.3, i.e. high ionic conductivity sulfide solid electrolyte material are worked as, its change
Study and be divided into Li7P2.9Mn0.1S10.7I0.3, with very high charging and discharging capacity, very excellent cyclical stability.
The present invention forms a kind of new solid electrolyte Li by sulfide solid electrolyte doping MnS and LiI7P3- xMnxS11-(3x+y)/2Iy。
The preparation method of high ionic conductivity sulfide solid electrolyte material of the present invention, comprises the following steps：
(1) by Li2S、P2S5, MnS, LiI mixing and ball milling, obtain Initial solid electrolyte；
(2) the Initial solid electrolyte for obtaining step (1), heat treatment, is pulverized afterwards under an inert gas
End, obtains high ionic conductivity sulfide solid electrolyte material.
It is following as the preferred technical solution of the present invention：
In step (1), Li2S、P2S5Mol ratio with alloy MnS and LiI is (3~3.5)：(1.25~1.5)：(0.1
~0.5)：(0.1~1), i.e., described Li2S、P2S5, MnS, LiI mol ratio be (3~3.5)：(1.25~1.5)：(0.1~
0.5)：(0.1~1).Further preferably, described Li2S、P2S5, MnS, LiI mol ratio be (3.1~3.35)：(1.35~
1.45)：(0.1~0.3)：(0.3~0.8).
Described ball milling is high-energy mechanical ball milling, and the rotating speed of described ball milling is 370~510rpm, described ball milling when
Between be 40~60 hours.
In step (2), described noble gases are argon.The argon flow amount of described heat treatment, is 80~120sccm,
More preferably 100sccm, the temperature of described heat treatment is 240~260 DEG C, and the time of described heat treatment is 1~3 little
When.
Described grinding is carried out under an inert atmosphere, and the gas of the atmosphere is argon, and the water content of the atmosphere is less than 1ppm,
Oxygen content is less than 1ppm.Selected screen size is 200~450 mesh.
Grind into powder, filters out the powder of 200~450 mesh, used as high ionic conductivity sulfide solid state electrolysis material
Material.
Application of the described high ionic conductivity sulfide solid electrolyte material in lithium sulfur all-solid-state battery is prepared, tool
Body includes：
Sulphur powder, conductive carbon black and high ionic conductivity sulfide solid electrolyte material are mixed, is mixed after being ground
Close uniform, be positioned over ball grinder 4~10h of mechanical ball milling under an argon atmosphere afterwards, rotating speed arranges 370~510rpm, consolidate
The electrolyte powder of state；
The electrolyte powder of the solid-state of preparation is positioned in compression mold, solid electrolyte piece is pressed into, afterwards will just
Pole powder is dispersed in the side of solid electrolyte, and plus-pressure compacting, and finally the opposite side in solid electrolyte encloses lithium paper tinsel, pressure
Make lithium sulfur all-solid-state battery.
The all-solid-state battery preparation method that the present invention is provided prepares positive electrode first, by sulphur powder, conductive carbon black and system
The standby Li for obtaining7P3-xMnxS11-(3x+y)/2IySolid electrolyte mixes by a certain percentage.Mix homogeneously after being ground, Zhi Houfang
Ball grinder 4~10h of mechanical ball milling under an argon atmosphere is placed in, rotating speed arranges 370~510rpm.By ball milling, battery sulfur positive pole
Add conductive carbon black and solid electrolyte.It is to improve the electronic conductivity of sulfur, composite solid that positive pole is compounded with conductive carbon black purpose
State electrolyte purpose is to improve the ionic conductivity of sulfur, overcomes the inferior position of the low electronic conductivity of the intrinsic low ion of sulfur materials, realizes
The high usage and high circulation stability of active material.
Secondly the electrolyte powder (60~100mg) for preparing the solid-state of gained is positioned over the compression mold of 10mm diameters
In, (240~400MPa) is pressed into solid electrolyte piece under a certain pressure, is dispersed in positive pole powder (2~5mg) afterwards solid
The side of state electrolyte, and plus-pressure (240~400MPa) compacting, finally the opposite side in solid electrolyte encloses lithium paper tinsel, and
Lithium sulfur solid state battery of the compacting (80~150MPa) into sandwich structure.It is in the present invention, solid by high ionic conductivity sulfide
Prepared by state electrolyte, improve the ionic conductivity and electrochemical stability of solid electrolyte.By the system of lithium sulfur solid state battery
It is standby, the shuttle effect for thoroughly solving lithium-sulfur cell is realized, and is obtained with high circulation stability, high-energy-density, high safety
The all solid state lithium-sulfur cell of property.
Compared with prior art, the invention has the advantages that：
(1) by doping, impurity is introduced in sulfide solid state electrolysis plastidome, it is more so as to produce in electrolyte system
Room, widens the transmission channel of lithium ion, improves the ionic conductivity of sulfide solid electrolyte.
(2) the sulfide solid electrolyte material prepared by has preferable electrochemical stability after doping, and test can
There must be the electrochemical window higher than 5V, meet battery assembling application.
(3) solid electrolyte is applied to into lithium-sulfur cell, solves the shortcoming of conventional liquid lithium-sulfur cell shuttle effect, carry
The cyclical stability of high battery.
(4) conductive carbon black and macroion sulfide solid electrolyte are introduced when preparing sulfur positive pole, sulfur positive electrode electronic is overcome
The low inferior position of electrical conductivity and ionic conductivity, improves battery entirety chemical property.
Description of the drawings
Fig. 1 is that the preparation process of the high ionic conductivity sulfide solid electrolyte of the doping prepared by embodiment 1 is illustrated
Figure；
Assembling schematic diagrams of the Fig. 2 for all solid state lithium-sulfur cell prepared in embodiment 1；
Sulfide solid electrolyte Lis of the Fig. 3 (a) for obtained doping in embodiment 17P2.9Mn0.1S10.7I0.3With undoped p
Sulfide solid electrolyte Li7P3S11XRD figure；Fig. 3 (b) is obtained S-Li in embodiment 17P2.9Mn0.1S10.7I0.3-C
Anode composite and S-Li7P3S11The Raman figure of-C；
The curve chart that Fig. 4 (a) ionic conductivities of the solid electrolyte of doping obtained in embodiment 1 are varied with temperature
And corresponding AC impedance spectroscopy；Fig. 4 (b) is the worth lithium of the solid electrolyte of obtained doping in embodiment 1/solid-state electricity
The cyclic voltammetry curve of solution matter/rustless steel asymmetrical cell.
Specific embodiment
The present invention is made below by embodiment and further being illustrated, but the invention is not limited in following realities
Example.
Embodiment 1
(1) by Li2S、P2S5With alloy MnS and LiI according to mol ratio be 3.35：1.45：0.1：0.3 mixing high energy
Mechanical ball milling, the rotating speed and time 370rpm of high-energy mechanical ball milling and 40 hours, so as to obtain Initial solid electrolyte.
(2) expect to be positioned in tube furnace at the beginning of the solid electrolyte for obtaining step (1), under an argon atmosphere heat treatment.Instead
The argon flow amount answered is 100sccm, and the temperature and time of reaction is 240 DEG C and 1 hour respectively.
(3) and then by grinding, the solid electrolyte grind into powder that step (2) is obtained, grinding is under an inert atmosphere
Carry out, the water content of the atmosphere is less than 1ppm, and oxygen content is less than 1ppm.Appropriate particle size is filtered out with 200-450 mesh sieve afterwards
Solid electrolyte powder obtain MnS and LiI doping high ionic conductivity sulfide solid electrolyte material
Li7P2.9Mn0.1S10.7I0.3。
(4) by sulphur powder, conductive carbon black and the Li for preparing7P2.9Mn0.1S10.7I0.3Solid electrolyte is mixed in proportion.
Mix homogeneously after being ground, is positioned over ball grinder mechanical ball milling 2h under an argon atmosphere afterwards, and rotating speed arranges 370rpm, obtains
The electrolyte powder of solid-state.
(5) the electrolyte powder 60mg for preparing the solid-state of gained is positioned in the compression mold of 10mm diameters,
380MPa is pressed into solid electrolyte piece, and positive pole powder 2mg is dispersed in the side of solid electrolyte, and plus-pressure afterwards
380MPa is suppressed, and finally the opposite side in solid electrolyte encloses lithium paper tinsel, and it is solid into the lithium sulfur of sandwich structure to suppress 120MPa
State battery.
Fig. 1 is that the preparation process of the high ionic conductivity sulfide solid electrolyte of the doping prepared by embodiment 1 is illustrated
Figure；Assembling schematic diagrams of the Fig. 2 for all solid state lithium-sulfur cell prepared in embodiment 1.
Embodiment 2
(1) by Li2S、P2S5With alloy MnS and LiI according to mol ratio be 3.25：1.4：0.2：0.5 mixing high energy machine
Tool ball milling, the rotating speed and time 510rpm of high-energy mechanical ball milling and 40 hours, so as to obtain Initial solid electrolyte.
(2) expect to be positioned in tube furnace at the beginning of the solid electrolyte for obtaining step (1), under an argon atmosphere heat treatment.Instead
The argon flow amount answered is 100sccm, and the temperature and time of reaction is 250 DEG C and 2 hours respectively.
(3) and then by grinding, the solid electrolyte grind into powder that step (2) is obtained, grinding is under an inert atmosphere
Carry out, the water content of the atmosphere is less than 1ppm, and oxygen content is less than 1ppm.Appropriate particle size is filtered out with 200-450 mesh sieve afterwards
Solid electrolyte powder obtain MnS and LiI doping high ionic conductivity sulfide solid electrolyte material
Li7P2.8Mn0.2S10.45I0.5。
(4) by sulphur powder, conductive carbon black and the Li for preparing7P2.8Mn0.2S10.45I0.5Solid electrolyte is mixed in proportion
Close.Mix homogeneously after being ground, is positioned over ball grinder mechanical ball milling 4h under an argon atmosphere afterwards, and rotating speed arranges 510rpm,
Obtain the electrolyte powder of solid-state.
(5) the electrolyte powder 60mg for preparing the solid-state of gained is positioned in the compression mold of 10mm diameters,
380MPa is pressed into solid electrolyte piece, and positive pole powder 3mg is dispersed in the side of solid electrolyte, and plus-pressure afterwards
380MPa is suppressed, and finally the opposite side in solid electrolyte encloses lithium paper tinsel, and it is solid into the lithium sulfur of sandwich structure to suppress 120MPa
State battery.
Embodiment 3
(1) by Li2S、P2S5With alloy MnS and LiI according to mol ratio be 3.1：1.35：0.3：0.8 mixing high energy machine
Tool ball milling, the rotating speed and time 510rpm of high-energy mechanical ball milling and 60 hours, so as to obtain Initial solid electrolyte.
(2) expect to be positioned in tube furnace at the beginning of the solid electrolyte for obtaining step (1), under an argon atmosphere heat treatment.Instead
The argon flow amount answered is 100sccm, and the temperature and time of reaction is 260 DEG C and 3 hours respectively.
(3) and then by grinding, the solid electrolyte grind into powder that step (2) is obtained, grinding is under an inert atmosphere
Carry out, the water content of the atmosphere is less than 1ppm, and oxygen content is less than 1ppm.Appropriate particle size is filtered out with 200-450 mesh sieve afterwards
Solid electrolyte powder obtain MnS and LiI doping high ionic conductivity sulfide solid electrolyte material
Li7P2.7Mn0.3S10.15I0.8。
(4) by sulphur powder, conductive carbon black and the Li for preparing7P2.7Mn0.3S10.15I0.8Solid electrolyte is mixed in proportion
Close.Mix homogeneously after being ground, is positioned over ball grinder mechanical ball milling 8h under an argon atmosphere afterwards, and rotating speed arranges 510rpm.
(5) the electrolyte powder 60mg for preparing the solid-state of gained is positioned in the compression mold of 10mm diameters,
380MPa is pressed into solid electrolyte piece, and positive pole powder 5mg is dispersed in the side of solid electrolyte, and plus-pressure afterwards
380MPa is suppressed, and finally the opposite side in solid electrolyte encloses lithium paper tinsel, and it is solid into the lithium sulfur of sandwich structure to suppress 120MPa
State battery.
Comparative example 1
Without alloy MnS and LiI, remaining is with embodiment 1.
Comparative example 2
Without alloy LiI, remaining is with embodiment 1.
Comparative example 3
Without alloy MnS, remaining is with embodiment 1.
Performance test
All solid state lithium-sulfur cell made by above-described embodiment 1~3 and comparative example 1~3 is installed in glove box specially
In the test device of door, battery performance is tested in two electrode systems, while the liquid lithium-sulfur cell for assembling is carried out permanent electricity
Stream charge-discharge test, it is 1.5~3.0V that charging/discharging voltage is interval.During test temperature is the room temperature of 25 DEG C of environment.
The doped and undoped solid state electrolysis prepared in embodiment 1 is verified, and which carries out XRD tests, test result
As shown in Fig. 3 (a).As can be seen that the solid electrolyte and Li of obtained doping from Fig. 3 (a)7P3S11Solid electrolyte
Peak is basically identical, and showing to adulterate does not change the body construction of solid electrolyte, only increases room, widens the biography of lithium ion
Defeated passage.Raman analysis test is carried out to the positive electrode of described solid-state lithium-sulfur cell, as a result as shown in Fig. 3 (b), from Fig. 3
In (b) it can clearly be seen that S Raman peaks and carbon G peaks and D peaks, due to electrolyte Raman active for sulfur compared with
It is weak, therefore not it is observed that the Raman peaks of solid electrolyte in combination electrode.Additionally, the sulfur to preparation-obtained doping
Compound solid electrolyte carries out the test of ac impedance spectroscopy and the analysis of ionic conductivity.Fig. 4 (a) is prepared by embodiment 1 mixing
Ac impedance spectroscopy under curve that the ionic conductivity of miscellaneous solid electrolyte is varied with temperature and different temperatures, it can be seen that
At room temperature, the sulfide solid electrolyte ionic conductivity at room temperature can reach 5.6mS cm-1, this result show system
The standby solid electrolyte for obtaining has very good ionic conductivity, meets all-solid-state battery for solid electrolyte ion-conductance
The requirement of conductance.By solid electrolyte using rustless steel as to electrode, lithium metal is assembled in glove box as reference electrode
Asymmetrical cell, tests its cyclic voltammetry curve between -0.2~5.0V, as a result as shown in Fig. 4 (b), prepared doping
Sulfide solid electrolyte is stable within 5.0V, with good electrochemical stability.For the sulfide prepared in embodiment 1
The sem test of solid electrolyte can be seen that prepared solid electrolyte piece even compact, and hole and space are less,
Quick transmission for lithium ion provides safeguard.Composite sulfur positive pole sulfur, conductive carbon black and the solid electrolyte prepared in embodiment 1
It is evenly distributed in anode composite, it is ensured that the just high electronic conductivity of sulfur and ionic conductivity, improves the profit of sulfur positive pole
With rate, it is ensured that the cyclical stability of solid state battery.The solid-state lithium-sulfur cell being assembled in embodiment 1 obvious charge and discharge is not shown into
Level platform, corresponding electrochemical reaction isProduce without polysulfide intermediate, that is, do not have
The generation of the problems such as having shuttle effect, therefore solid-state lithium-sulfur cell will be greatly improved to the utilization rate of active substance.And show
Excellent cyclical stability, still keeps 95% capacity under 0.05C through 200 circulations.
Solid-state lithium-sulfur cell prepared by embodiment 1~3 and comparative example 1~3 is at room temperature under the discharge-rate of 0.05C
Capability retention after 200 circulations is as shown in Table 1 and Table 2：
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Capability retention | 95% | 88% | 84% |
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Capability retention | 70% | 56% | 57% |
Claims (10)
1. a kind of high ionic conductivity sulfide solid electrolyte material, it is characterised in that its chemical composition is Li7P3- xMnxS11-(3x+y)/2Iy, wherein, 0 ＜ x ＜, 0.5,0 ＜ y ＜ 1.
2. high ionic conductivity sulfide solid electrolyte material according to claim 1, it is characterised in that 0.1≤x≤
0.3,0.3≤y≤0.8.
3. the preparation method of high ionic conductivity sulfide solid electrolyte material according to claim 1, its feature exist
In comprising the following steps：
(1) by Li2S、P2S5, MnS, LiI mixing and ball milling, obtain Initial solid electrolyte；
(2) the Initial solid electrolyte that step (1) is obtained, heat treatment under an inert gas, grind into powder, obtains afterwards
To high ionic conductivity sulfide solid electrolyte material.
4. preparation method according to claim 3, it is characterised in that in step (1), described Li2S、P2S5、MnS、LiI
Mol ratio be (3~3.5)：(1.25~1.5)：(0.1~0.5)：(0.1~1).
5. preparation method according to claim 3, it is characterised in that in step (1), the rotating speed of described ball milling is 370
~510rpm, the time of described ball milling is 40~60 hours.
6. preparation method according to claim 3, it is characterised in that in step (2), described noble gases are argon,
Argon flow amount is 80~120sccm.
7. preparation method according to claim 3, it is characterised in that in step (2), the temperature of described heat treatment is
240~260 DEG C, the time of described heat treatment is 1~3 hour.
8. preparation method according to claim 3, it is characterised in that in step (2), filter out the powder of 200~450 mesh
End, as high ionic conductivity sulfide solid electrolyte material.
9. high ionic conductivity sulfide solid electrolyte material according to claim 1 and 2 is to prepare lithium sulfur all solid state
Application in battery.
10. application according to claim 9, it is characterised in that specifically include：
Sulphur powder, conductive carbon black and high ionic conductivity sulfide solid electrolyte material are mixed, after being ground, mixes equal
It is even, ball grinder 4~10h of mechanical ball milling under an argon atmosphere is positioned over afterwards, rotating speed arranges 370~510rpm, obtains solid-state
Electrolyte powder；
The electrolyte powder of the solid-state of preparation is positioned in compression mold, solid electrolyte piece is pressed into, afterwards by positive powder
End is dispersed in the side of solid electrolyte, and plus-pressure compacting, and finally the opposite side in solid electrolyte encloses lithium paper tinsel, is pressed into
Lithium sulfur all-solid-state battery.
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| US11108080B2 (en) | 2017-06-01 | 2021-08-31 | Samsung Electronics Co., Ltd | Lithium and sodium solid-state electrolyte materials |
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| CN114899479A (en) * | 2022-05-11 | 2022-08-12 | 南开大学 | Double-doped sulfide solid electrolyte and preparation method and application thereof |
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