CN108899486A - Sulfur electrolyte-coated positive electrode active material and preparation method thereof, and all-solid-state lithium sulfur battery and preparation method thereof - Google Patents
Sulfur electrolyte-coated positive electrode active material and preparation method thereof, and all-solid-state lithium sulfur battery and preparation method thereof Download PDFInfo
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- CN108899486A CN108899486A CN201810614217.XA CN201810614217A CN108899486A CN 108899486 A CN108899486 A CN 108899486A CN 201810614217 A CN201810614217 A CN 201810614217A CN 108899486 A CN108899486 A CN 108899486A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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 sulfur electrolyte-coated positive active material and a preparation method thereof, and an all-solid-state lithium sulfur battery and a preparation method thereof, wherein the positive active material comprises L i2S and coating L i2L i of S surface3PS4or L i10GeP2S12. The preparation method comprises the preparation of P2S5Powder, GeS2mixing the above powders with L i2Mixing and ball-milling S powder; and (6) heat treatment. An all-solid-state lithium-sulfur battery includes a positive electrode layer made of a positive electrode active material coating a sulfur-based electrolyte and a conductive carbon material. The all-solid-state lithium-sulfur battery is manufactured by a cold isostatic pressing method. The positive active material coated with the chalcogenide electrolyte has the advantages of good electrochemical stability, high ionic conductivity, good interface contact property and the like, and is a promising positive active material. The all-solid-state lithium-sulfur battery has the advantages of high utilization rate of active substances, good cycling stability, high safety performance and the like, and is a novel all-solid-state lithium battery with extremely high use value.
Description
Technical field
The invention belongs to all solid lithium sulphur field of batteries, be related to a kind of positive electrode active materials for coating sulphur system electrolyte and its
Preparation method, all solid state lithium-sulfur cell and preparation method thereof.
Background technique
With the development of human society, the demand to the energy also becomes more and more urgent.Biography used in people's production and living
The energy of uniting mostly is non-renewable energy resources, and can cause adverse effect to environment in use.Therefore, environmental problem and the energy are asked
Facing mankind and urgently to be resolved two big hot issues since topic is 21st century.
Lithium ion battery is as a kind of low-carbon green new energy, big, memory-less effect and circulation longevity by its energy density
Ordering the features such as long is widely used to the portable devices such as mobile phone, laptop and camera, in electric car power supply and storage
The fields such as energy power grid also possess huge application prospect.Currently, the dominant contribution in lithium ion battery market is based on organic liquid
Occupied by the lithium ion battery of electrolyte, but potential safety problem constrains it and widely applies.With solid electrolyte generation
For organic liquid electrolytes solid lithium battery, the security performance of lithium battery can be increased substantially, to be applied to wider
General field.In existing all solid state lithium-sulfur cell, solid-state lithium-sulfur cell anode composite usually with active material, solid electrolyte and
Carbon is formed through mechanical mixture, and active material utilization is lower, and the volume change of active material easily causes boundary in cyclic process
Face separation, directly affects the cycle performance of battery.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of electrochemical stability it is good, from
The positive electrode active materials of cladding sulphur system electrolyte and preparation method thereof that electron conductivity is high, interfacial contact is good, additionally provide one
Kind active material utilization height, all solid state lithium-sulfur cell that stable circulation performance is good, security performance is high and preparation method thereof.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of positive electrode active materials coating sulphur system electrolyte, including positive electrode active materials, the surface of positive electrode active material packet
It is covered with sulphur system solid electrolyte；The positive electrode active materials are Li2S；Sulphur system solid electrolyte is Li3PS4Or
Li10GeP2S12。
The positive electrode active materials of above-mentioned cladding sulphur system electrolyte, further improved, the positive electrode active materials and sulphur
The mass ratio for being solid electrolyte is 0.55~4: 1.
As a general technical idea, the present invention also provides a kind of positive-actives of above-mentioned cladding sulphur system electrolyte
The preparation method of material, includes the following steps：
S1, by P2S5、GeS2Ball milling is carried out respectively, obtains P2S5Powder, GeS2Powder；
S2, by P obtained in step S12S5Powder or P2S5And GeS2Mixed-powder, with Li2The mixing of S powder carries out ball milling；
S3, the product after ball milling in step S2 is heat-treated, obtains the positive electrode active materials of cladding sulphur system electrolyte.
The preparation method of the positive electrode active materials of above-mentioned cladding sulphur system electrolyte, further improved, the step S1
In, the ball milling carries out under argon atmosphere protection；The revolving speed of the ball milling is 380rpm~510rpm；The time of the ball milling
For 3h~5h；Every ball milling 40min in the mechanical milling process stands cooling 20min.
The preparation method of the positive electrode active materials of above-mentioned cladding sulphur system electrolyte, further improved, the step S2
In, the ball milling carries out under argon atmosphere protection；The revolving speed of the ball milling is 380rpm~510rpm；The time of the ball milling
For 5h~20h；Every ball milling 40min in the mechanical milling process stands cooling 20min.
The preparation method of the positive electrode active materials of above-mentioned cladding sulphur system electrolyte, further improved, the step S3
In, the heating rate in the heat treatment process is 5 DEG C/min~10 DEG C/min；The temperature of the heat treatment is 240 DEG C~280
℃；The time of the heat treatment is 0.5h~3h.
As a general technical idea, the present invention also provides a kind of all solid state lithium-sulfur cells, including anode layer, solid-state
Electrolyte layer and negative electrode layer, the solid-state electrolyte layer are set between anode layer and negative electrode layer, and the anode layer includes by upper
All solid state lithium-sulfur battery composite cathode material made of the positive electrode active materials and conductive carbon material of the cladding sulphur system electrolyte stated.
Above-mentioned all solid state lithium-sulfur cell, it is further improved, according to mass percent meter each component in the anode layer
For：
Conductive carbon material 20%~30%,
Coat the positive electrode active materials 70%~80% of sulphur system electrolyte.
Above-mentioned all solid state lithium-sulfur cell, further improved, the conductive carbon material is acetylene black, superconduction carbon, graphite
At least one of alkene, carbon nanotube, carbon nano-fiber and active carbon；The negative electrode layer includes negative electrode active material；It is described negative
Pole active material is at least one of metal lithium sheet, indium lithium alloy piece；The solid-state electrolyte layer is all solid state sulfide electricity
Solve material；The all solid state sulfide electrolyte material is Li3PS4Or Li10GeP2S12。
Above-mentioned all solid state lithium-sulfur cell, it is further improved, the anode layer with a thickness of 0.1 μm~50 μm；It is described
Solid-state electrolyte layer with a thickness of 100 μm~1000 μm.
As a general technical idea, the present invention also provides a kind of preparation sides of above-mentioned all solid state lithium-sulfur cell
Method includes the following steps：
（1）Solid-state electrolyte layer is made in the progress cold moudling of all solid state sulfide electrolyte material；
（2）All solid state lithium-sulfur battery composite cathode material is placed in step（1）Obtained in solid-state electrolyte layer side into
Row cold moudling obtains anode layer/solid electrolyte layer material；
（3）Using solid-state electrolyte layer as middle layer, negative electrode active material is placed in step（2）Obtained anode layer/solid-state electricity
The other side for solving solid-state electrolyte layer in matter layer material carries out cold moudling, obtains all solid state lithium-sulfur cell.
The preparation method of above-mentioned all solid state lithium-sulfur cell, further improved, the step（1）In, it is described all solid state
Sulfide electrolyte material is prepared by following methods：Under argon atmosphere protection, by P2S5Powder or P2S5And GeS2It is mixed
Close powder and Li2The mixing of S powder is ball milling 5h~20h under 380rpm~510rpm, every ball milling in mechanical milling process in revolving speed
40min stands cooling 20min；The product obtained after ball milling is heat-treated 0.5h~3h at 240 DEG C~280 DEG C, is obtained entirely solid
State sulfide electrolyte material；Pressure during the cold moudling is 191 MPa~637MPa.
The preparation method of above-mentioned all solid state lithium-sulfur cell, further improved, the step（2）In, it is described all solid state
Lithium-sulfur battery composite cathode material is prepared by following methods：The positive electrode active materials and conductive carbon of sulphur system electrolyte will be coated
Material mixing, ball milling 1h~5h in the case where revolving speed is 380rpm~510rpm, obtains all solid state lithium-sulfur battery composite cathode material；Institute
Stating the pressure during cold moudling is 191MPa~637MPa.
The preparation method of above-mentioned all solid state lithium-sulfur cell, further improved, the step（3）In, it is described to be cold-pressed into
Pressure during type is 128MPa~255MPa.
The present invention coats in the preparation method of the positive electrode active materials of sulphur system electrolyte, when raw material is P2S5And GeS2It is mixed
When closing powder, GeS2And P2S5Molar ratio≤1.
Compared with the prior art, the advantages of the present invention are as follows：
（1）The present invention provides a kind of positive electrode active materials for coating sulphur system electrolyte, including positive electrode active materials and are coated on
The sulphur system solid electrolyte of surface of positive electrode active material, wherein positive electrode active materials are Li2S, sulphur system solid electrolyte are Li3PS4
Or Li10GeP2S12.In the present invention, by the way that sulphur system solid electrolyte is coated on surface of positive electrode active material, so that positive-active
Interface between material and sulphur system solid electrolyte is changed into chemical interface by physical interface admittedly, to improve interfacial contact
Performance solves the problems, such as active material in cyclic process because of interfacial separation caused by volume change；Meanwhile sulphur will be coated
When being that the positive electrode active materials of electrolyte are used to prepare all solid state lithium-sulfur cell, it is also able to ascend the activity of all solid state lithium-sulfur cell
Material utilization and cycle performance.As it can be seen that the positive electrode active materials that the present invention coats sulphur system electrolyte have electrochemical stability
Good, ionic conductivity height, interface（The interface refers to the interface of the sulphur system electrolyte of positive active material and cladding）Contact is good
The advantages that, it is a kind of positive electrode active materials of great future.
（2）The present invention coats in the positive electrode active materials of sulphur system electrolyte, positive electrode active materials and sulphur system solid electrolyte
Mass ratio 0.55~4: 1 be conducive to improve utilization of the active material in charge and discharge process by the mass ratio of both optimization
Rate is also beneficial to promote total energy density, this is because the content for improving sulphur system solid electrolyte can be improved active material
Utilization rate in charge and discharge process, and the content for improving positive electrode active materials is able to ascend total energy density.
（3）It is solid with sulphur system the present invention also provides a kind of preparation method of positive electrode active materials for coating sulphur system electrolyte
State electrolyte, positive electrode active materials are raw material, and sulphur system solid electrolyte is coated on positive work by the methods of ball milling, heat treatment
Property material surface, i.e., by in-situ chemical reaction surface of positive electrode active material generate sulphur system solid electrolyte, to be prepared into
To the positive electrode active materials for the cladding sulphur system electrolyte that electrochemical stability is good, ionic conductivity is high, interfacial contact is good, have
The advantages that process conditions are simple, easy to operate, at low cost, is suitable for large scale preparation, is conducive to industrialized production.
（4）The present invention also provides a kind of all solid state lithium-sulfur cell, including anode layer, solid-state electrolyte layer and negative electrode layer,
Solid-state electrolyte layer is set between anode layer and negative electrode layer, and wherein anode layer includes the positive-active by cladding sulphur system electrolyte
All solid state lithium-sulfur battery composite cathode material made of material and conductive carbon material.In the present invention, all solid state lithium-sulfur cell is based on
The positive electrode active materials of cladding sulphur system electrolyte are made, sulphur system solid state electrolysis in the positive electrode active materials of the cladding sulphur system electrolyte
Matter is coated on surface of positive electrode active material, so that the interface between positive electrode active materials and sulphur system solid electrolyte is by physics admittedly
Interface is changed into chemical interface, and the utilization rate of cathode active material, Yi Jiti can be effectively improved in charge and discharge process
The energy density of high battery, while active material can be improved in cyclic process because volume change is led in cyclic process
The interfacial separation problem of cause, to promote the cycle performance of all solid state lithium-sulfur cell.As it can be seen that the present invention is based on the electrolysis of cladding sulphur system
The all solid state lithium-sulfur cell of the positive electrode active materials of matter is not only able to satisfy the conductive, diversion to positive electrode of all solid lithium sulphur battery
The requirement of son, while active material utilization can be improved and improve the boundary of active material and solid electrolyte in composite positive pole
The advantages that face problem, active material utilization is high, stable circulation performance is good and security performance is high, be a kind of use value pole
High novel solid lithium battery.
（5）The present invention also provides a kind of preparation methods of all solid state lithium-sulfur cell, prepare by using cold isostatic pressing process
The all solid state lithium-sulfur cell that active material utilization is high, stable circulation performance is good, security performance is high is obtained, there is process conditions letter
The advantages that single, easy to operate, at low cost, it is suitable for large scale preparation, is conducive to industrialized production.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is the positive electrode active materials of cladding sulphur system electrolyte prepared by the embodiment of the present invention 1（A3）SEM figure.
Fig. 2 is the positive electrode active materials of cladding sulphur system electrolyte prepared by the embodiment of the present invention 1（A3）XRD spectra.
Fig. 3 is the positive-active material of the cladding sulphur system electrolyte prepared at a temperature of different heat treatment in the embodiment of the present invention 1
The XRD spectra of material.
Fig. 4 is the positive electrode active materials obtained for coating sulphur system electrolyte in the embodiment of the present invention 1（A2）It varies with temperature
Conductivity spectrogram.
Fig. 5 is the positive-active material of the cladding sulphur system electrolyte prepared at a temperature of different heat treatment in the embodiment of the present invention 1
The ionic conductivity spectrogram of material.
Fig. 6 is all solid state lithium-sulfur cell obtained in the embodiment of the present invention 2（a）With all solid lithium obtained in comparative example 2
Sulphur battery（b）Voltage-specific capacity curve graph.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument are commercially available.The experiment side of actual conditions is not specified in embodiment
Method according to conventional methods and conditions, or is selected according to product manual.Unless otherwise noted, the data obtained in following embodiment
It is the average value for repeating experiment more than three times.
Embodiment 1
A kind of positive electrode active materials coating sulphur system electrolyte, including positive electrode active materials and it is coated on surface of positive electrode active material
Sulphur system solid electrolyte, wherein positive electrode active materials Li2S, sulphur system solid electrolyte are Li3PS4。
In the present embodiment, the mass ratio of positive electrode active materials and sulphur system solid electrolyte is 0.82: 1.
A kind of preparation method of the positive electrode active materials of cladding sulphur system electrolyte in above-mentioned example, including following step
Suddenly：
（1）Under argon atmosphere protection, P is taken2S5It is added into high energy ball grinder, the ball milling 3h in the case where revolving speed is 450rpm, wherein
Every ball milling 40min in mechanical milling process stands cooling 20min, obtains P2S5Powder.
（2）Under argon atmosphere protection, by Li2S、P2S5Molar ratio be 90.5: 9.5, weigh Li respectively2S powder and step
Suddenly（1）In P obtained2S5Powder；It places them in high-energy ball milling tank and mixes, the ball milling 8h in the case where revolving speed is 510rpm, wherein
Every ball milling 40min in mechanical milling process stands cooling 20min, obtains mixed-powder.
（3）By step（2）The product obtained after middle ball milling（Mixed-powder）It is transferred to tube furnace, under argon atmosphere protection
It is that 5 DEG C/min is warming up to 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C and 280 DEG C respectively with heating rate, at different temperatures at heat
Manage 1h, obtain under different temperatures it is obtained cladding sulphur system electrolyte positive electrode active materials, wherein heat treatment temperature be 240 DEG C,
To number respectively is A1, A2 to the positive electrode active materials of 250 DEG C, 260 DEG C, 270 DEG C and 280 DEG C corresponding cladding sulphur system electrolyte, A3,
A4、A5。
Embodiment 2
A kind of all solid state lithium-sulfur cell, all solid state lithium-sulfur cell are made of anode layer, solid-state electrolyte layer and negative electrode layer.Wherein
Anode layer is all solid state lithium-sulfur battery composite cathode material, by the positive-active of cladding sulphur system electrolyte obtained in embodiment 1
Material（A3）It is prepared with acetylene black, wherein the mass ratio of the positive electrode active materials of cladding sulphur system electrolyte, acetylene black is 75:
25, i.e., the mass content of acetylene black is 25% in all solid state lithium-sulfur battery composite cathode material, and the anode of cladding sulphur system electrolyte is living
Property material mass content be 75%.
In the present embodiment, solid-state electrolyte layer is all solid state sulfide electrolyte material, specially Li3PS4。
In the present embodiment, negative electrode layer is negative electrode active material, specially metal lithium sheet.
In the present embodiment, anode layer with a thickness of 20 μm；Solid-state electrolyte layer with a thickness of 680 μm.
A kind of preparation method of all solid state lithium-sulfur cell of the embodiments of the present invention, includes the following steps：
（1）Prepare all solid state lithium-sulfur battery composite cathode material and all solid state sulfide solid electrolyte：
Mass ratio according to the positive electrode active materials of cladding sulphur system electrolyte, acetylene black is 75: 25, is weighed in embodiment 1 respectively
The positive electrode active materials of cladding sulphur system electrolyte obtained（A3）It is placed in ball grinder with acetylene black, with 380rpm revolving speed ball milling
3h obtains all solid state lithium-sulfur battery composite cathode material.
Under argon atmosphere protection, by Li2S、P2S5Molar ratio be 75: 25, weigh P respectively2S5Powder and Li2S powder,
It is placed in high-energy ball milling tank and mixes, with 510rpm revolving speed ball milling 8h, wherein every ball milling 40min in mechanical milling process, stands cooling
20min.Then the product obtained after ball milling is transferred into tube furnace, at being warming up to 250 DEG C under argon atmosphere protection at heat
1h is managed, grinding obtains all solid state sulfide electrolyte powder.
（2）Take 100mg step（1）In all solid state sulfide electrolyte powder obtained be placed in mold（PEEK, 10mm）In,
Cold moudling under conditions of pressure is 446MPa, is made solid-state electrolyte layer.
（3）Take 4mg step（1）In all solid state lithium-sulfur battery composite cathode material obtained be placed in step（2）It is obtained
The side of solid-state electrolyte layer, cold moudling under conditions of pressure is 446MPa, is made anode layer/solid-state electrolyte layer material
Material.
（4）Using solid-state electrolyte layer as middle layer, metal lithium sheet is placed in step（3）Anode layer obtained/solid-state electricity
Solve matter layer material in solid-state electrolyte layer the other side, pressure be 191MPa under conditions of cold moudling, Gu be made anode layer/
State electrolyte layer/cathode layer material, all solid state lithium-sulfur cell as of the invention.
Comparative example 1
A kind of all solid state lithium-sulfur cell, essentially identical with all solid state lithium-sulfur cell of embodiment 2, difference is only that：In comparative example 1
All solid state lithium-sulfur battery composite cathode material used is different.
The preparation method of all solid state lithium-sulfur battery composite cathode material used, includes the following steps in comparative example 1：
（1）Under argon atmosphere protection, by Li2S、P2S5Molar ratio be 75: 25, weigh Li respectively2S powder and P2S5Powder,
It is placed in high-energy ball milling tank, with 510rpm revolving speed ball milling 8h, wherein every ball milling 40min, stands cooling 20min.Then again will
Ball milling product is transferred to tube furnace, is warming up at 250 DEG C under argon atmosphere protection and is heat-treated 1h, and all solid state sulfide electrolysis is obtained
Matter.
（2）Under argon atmosphere protection, by Li2S, all solid state sulfide electrolyte and the mass ratio of acetylene black are 34: 41:
25, step is weighed respectively（1）All solid state sulfide electrolyte, Li2S and acetylene black, are placed in ball grinder, are turned with 380rpm
Fast ball milling 3h, obtains all solid state lithium-sulfur battery composite cathode material.
It will be all solid state in the positive electrode active materials of the cladding sulphur system electrolyte in embodiment 1, embodiment 2 and comparative example 1
Lithium-sulfur cell is tested as follows：
（1）Scanning electron microscope（SEM）Test：After sample to be tested is carried out metal spraying processing, with field emission scanning electron microscope to packet
The surface of positive electrode active material pattern for covering sulphur system solid electrolyte is characterized.
（2）Ionic conductivity：It is assembled into simulated battery using stainless steel as blocking electrode, in 25~60 DEG C of different temperature points
Lower carry out electrochemical alternate impedance spectrum（EIS）Test, passes through σ=d/ (RbS ionic conductivity) is calculated.
（3）Cyclic voltammetric：Be assembled into non-obstruction symmetry electrode battery, scanning speed 0.1mV/s, voltage range be 1V~
4.5V carries out cyclic voltammetric CV test.
（4）Constant current charge-discharge performance：The all solid state lithium-sulfur cell assembled in embodiment 2 and comparative example 2 is subjected to cyclicity
It can test.Test voltage range is 1.5V~4.5V, and test temperature is 60 DEG C.
Above test method belongs to the standard method of test of this field, according to this when being related to undocumented parameter
Field routine operation is chosen.
Fig. 1 is the positive electrode active materials of cladding sulphur system electrolyte prepared by the embodiment of the present invention 1（A3）SEM figure.In Fig. 1
（a）To be heat-treated preceding sample, as step（2）In mixed-powder obtained；（b）For sample after heat treatment, as cladding sulphur system
The positive electrode active materials of electrolyte（A3）；（a）With（b）Amplification factor be 5000 times.As shown in Figure 1, heat treatment front and back sample
Product pattern is without too big variation.Though sample after heat treatment has Li3PS4Crystal occurs, but is formed by sulphur system electrolyte as glass pottery
Porcelain electrolyte, surface still show amorphous state pattern.
Fig. 2 is the positive electrode active materials of cladding sulphur system electrolyte prepared by the embodiment of the present invention 1（A3）XRD spectra.Fig. 1
In（a）To be heat-treated preceding sample, as step（2）In mixed-powder obtained；（b）For sample after heat treatment, as cladding sulphur
It is the positive electrode active materials of electrolyte（A3）.From fig. 2 it can be seen that sample XRD spectra after heat treatment（b）In not there is only
Li2The characteristic peak of S, there is also corresponding sulphur system solid electrolytes（SE）Characteristic peak.
Fig. 3 is the positive-active material of the cladding sulphur system electrolyte prepared at a temperature of different heat treatment in the embodiment of the present invention 1
The XRD spectra of material.As seen from Figure 3, when heat treatment temperature is 250 DEG C, sulphur system solid electrolyte is begun in XRD spectra
Characteristic peak occurs, and with the further promotion of heat treatment temperature, the feature peak intensity of sulphur system solid electrolyte enhances therewith.This
In invention, the main purpose of heat treatment allow the sulphur system solid electrolyte of clad from glassy transition be glass ceramics state, be one
A crystallization process, wherein different temperatures is heat-treated, and the highly conductor phase content of generation is different, and heat treatment temperature is 240 DEG C~280
DEG C, resulting materials have preferable ionic conductivity.
Fig. 4 is the positive electrode active materials obtained for coating sulphur system electrolyte in the embodiment of the present invention 1（A2）It varies with temperature
Conductivity spectrogram.As shown in Figure 4, the positive electrode active materials of sulphur system electrolyte are coated prepared by the embodiment of the present invention 1（A2）'s
Ionic conductivity is excellent in, and can reach 1.24 × 10 at room temperature-4 S·cm-1。
Fig. 5 is the positive-active material of the cladding sulphur system electrolyte prepared at a temperature of different heat treatment in the embodiment of the present invention 1
The ionic conductivity spectrogram of material.As shown in Figure 5, when heat treatment temperature is between 240 DEG C~270 DEG C, cladding sulphur system electrolyte
The ionic conductivity of positive electrode active materials is increased with the promotion of heat treatment temperature, through coating sulphur system obtained by 270 DEG C of heat treatment 1h
The ionic conductivity of the positive electrode active materials of electrolyte is up to 1.29 × 10-4 S·cm-1.When heat treatment temperature rises to 280 DEG C,
The ionic conductivity for coating the positive electrode active materials of sulphur system electrolyte occurs being decreased obviously trend.
Fig. 6 is all solid state lithium-sulfur cell obtained in the embodiment of the present invention 2（a）With all solid lithium obtained in comparative example 1
Sulphur battery（b）Voltage-specific capacity curve graph.It will be appreciated from fig. 6 that all solid state lithium-sulfur cell prepared in the embodiment of the present invention 2 exists
60 DEG C with 0.05mA cm-2Electric current carries out charge-discharge cycle, and discharge capacity is 512mAh g to battery for the first time-1, discharge platform is about
1.98V.Battery the 5th time, ten times and 15 cyclic discharge capacities are respectively 598.7 mAh g-1、533.0 mAh g-1With
500.0 mAh g-1.And all solid state lithium-sulfur cell prepared in comparative example 1 at 60 DEG C with 0.05mA cm-2Electric current carries out charge and discharge and follows
Ring, discharge capacity is 321.8 mAh g to battery for the first time-1, discharge platform is about 1.96V.It follows for battery the 5th time, ten times and 15 times
Ring discharge capacity is respectively 295.7 mAh g-1、282.6 mAh g-1With 279.8 mAh g-1.It can be seen that in embodiment 2
All solid state lithium-sulfur cell has higher discharge capacity and better cycle performance, and basic reason is of the invention all solid state
In lithium-sulfur cell just using the cladding sulphur system electrolyte that electrochemical stability is good, ionic conductivity is high, interfacial contact is good
Pole active material.
It can be seen that it is provided by the invention cladding sulphur system electrolyte positive electrode active materials have electrochemical stability it is good,
The advantages that ionic conductivity is high, good with sulphur system solid electrolyte interface contact, all solid lithium sulphur lithium-sulfur cell assembled with this
Charge/discharge capacity is obviously improved, and active material utilization is higher, possesses preferable cycle performance.
In the present invention, gained coats sulphur when the mass ratio of positive electrode active materials and sulphur system solid electrolyte is 0.55~4: 1
It is the positive electrode active materials of electrolyte, can obtains same as Example 1 or similar technical effect.It is prepared with this all solid state
Lithium-sulfur cell can obtain and implement 2 the same or similar technical effects.
Above embodiments are only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that being led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of positive electrode active materials for coating sulphur system electrolyte, which is characterized in that including positive electrode active materials, the anode is living
Property material surface is coated with sulphur system solid electrolyte；The positive electrode active materials are Li2S；Sulphur system solid electrolyte is
Li3PS4Or Li10GeP2S12。
2. the positive electrode active materials of cladding sulphur system electrolyte according to claim 1, which is characterized in that the positive-active
The mass ratio of material and sulphur system solid electrolyte is 0.55~4: 1.
3. a kind of preparation method of the positive electrode active materials of cladding sulphur system electrolyte as claimed in claim 1 or 2, feature exist
In including the following steps：
S1, by P2S5、GeS2Ball milling is carried out respectively, obtains P2S5Powder, GeS2Powder；
S2, by P obtained in step S12S5Powder or P2S5And GeS2Mixed-powder, with Li2The mixing of S powder carries out ball milling；
S3, the product after ball milling in step S2 is heat-treated, obtains the positive electrode active materials of cladding sulphur system electrolyte.
4. the preparation method of the positive electrode active materials of cladding sulphur system electrolyte according to claim 3, which is characterized in that institute
It states in step S1, the ball milling carries out under argon atmosphere protection；The revolving speed of the ball milling is 380rpm~510rpm；The ball
The time of mill is 3h~5h；Every ball milling 40min in the mechanical milling process stands cooling 20min；
In the step S2, the ball milling carries out under argon atmosphere protection；The revolving speed of the ball milling is 380rpm~510rpm；
The time of the ball milling is 5h~20h；Every ball milling 40min in the mechanical milling process stands cooling 20min；
In the step S3, the heating rate in the heat treatment process is 5 DEG C/min~10 DEG C/min；The temperature of the heat treatment
Degree is 240 DEG C~280 DEG C；The time of the heat treatment is 0.5h~3h.
5. a kind of all solid state lithium-sulfur cell, including anode layer, solid-state electrolyte layer and negative electrode layer, the solid-state electrolyte layer setting
Between anode layer and negative electrode layer, which is characterized in that the anode layer includes the cladding sulphur system as described in claims 1 or 2
All solid state lithium-sulfur battery composite cathode material made of the positive electrode active materials and conductive carbon material of electrolyte.
6. all solid state lithium-sulfur cell according to claim 5, which is characterized in that according to mass percent in the anode layer
Meter each group is divided into：
Conductive carbon material 20%~30%,
Coat the positive electrode active materials 70%~80% of sulphur system electrolyte.
7. all solid state lithium-sulfur cell according to claim 5 or 6, which is characterized in that the conductive carbon material be acetylene black,
At least one of superconduction carbon, graphene, carbon nanotube, carbon nano-fiber and active carbon；The negative electrode layer includes negative electrode active
Material；The negative electrode active material is at least one of metal lithium sheet, indium lithium alloy piece；The solid-state electrolyte layer is complete solid
State sulfide electrolyte material；The all solid state sulfide electrolyte material is Li3PS4Or Li10GeP2S12。
8. all solid state lithium-sulfur cell according to claim 5 or 6, which is characterized in that the anode layer with a thickness of 0.1 μm
~50 μm；The solid-state electrolyte layer with a thickness of 100 μm~1000 μm.
9. a kind of preparation method of all solid state lithium-sulfur cell as described in any one of claim 5~8, which is characterized in that packet
Include following steps：
（1）Solid-state electrolyte layer is made in the progress cold moudling of all solid state sulfide electrolyte material；
（2）All solid state lithium-sulfur battery composite cathode material is placed in step（1）Obtained in solid-state electrolyte layer side into
Row cold moudling obtains anode layer/solid electrolyte layer material；
（3）Using solid-state electrolyte layer as middle layer, negative electrode active material is placed in step（2）Obtained anode layer/solid-state electricity
The other side for solving solid-state electrolyte layer in matter layer material carries out cold moudling, obtains all solid state lithium-sulfur cell.
10. the preparation method of all solid state lithium-sulfur cell according to claim 9, which is characterized in that the step（1）In,
The all solid state sulfide electrolyte material is prepared by following methods：Under argon atmosphere protection, by P2S5Powder or P2S5
And GeS2Mixed-powder and Li2S powder mixes, ball milling 5h~20h in the case where revolving speed is 380rpm~510rpm, in mechanical milling process
Every ball milling 40min stands cooling 20min；The product obtained after ball milling is heat-treated 0.5h~3h at 240 DEG C~280 DEG C, is obtained
To all solid state sulfide electrolyte material；Pressure during the cold moudling is 191 MPa~637MPa；
The step（2）In, all solid state lithium-sulfur battery composite cathode material is prepared by following methods：Sulphur system will be coated
The positive electrode active materials and conductive carbon material of electrolyte mix, and ball milling 1h~5h in the case where revolving speed is 380rpm~510rpm is obtained
All solid state lithium-sulfur battery composite cathode material；Pressure during the cold moudling is 191MPa~637MPa；
The step（3）In, the pressure during the cold moudling is 128MPa~255MPa.
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