CN106684442A - Lithium sulfide solid electrolyte material with added lithium tin alloy and silver iodide and preparation method of lithium sulfide solid electrolyte material - Google Patents

Lithium sulfide solid electrolyte material with added lithium tin alloy and silver iodide and preparation method of lithium sulfide solid electrolyte material Download PDF

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Publication number
CN106684442A
CN106684442A CN201710077196.8A CN201710077196A CN106684442A CN 106684442 A CN106684442 A CN 106684442A CN 201710077196 A CN201710077196 A CN 201710077196A CN 106684442 A CN106684442 A CN 106684442A
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lithium
sulfur
silver iodide
solid electrolyte
preparation
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王振宇
朱凌云
张天锦
赵霞妍
王奐然
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Guilin Electrical Equipment Scientific Research Institute Co Ltd
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Guilin Electrical Equipment Scientific Research Institute Co Ltd
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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
    • 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
    • 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
    • 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 lithium sulfide solid electrolyte material with added lithium tin alloy and silver iodide and a preparation method of the lithium sulfide solid electrolyte material. The preparation method comprises the following steps of (1) weighing lithium sulfide, phosphorus sulfide, lithium tin alloy powder and sulfur at the molar ratio of (2.5-4.0):(0.5-1.0):(0.02-0.1):(0.01-0.05) under the condition of atmosphere protection and mixing evenly to obtain a lithium-sulfur-phosphorus-tin mixture; (2) putting taken lithium-sulfur-phosphorus-tin mixture and silver iodide which is equivalent to 1%-5% of the mass of the lithium-sulfur-phosphorus-tin mixture into a ball mill tank for ball-milling under conditions of atmosphere protection and safe red light to obtain an amorphous lithium-sulfur-phosphorus-tin mixture containing the silver iodide; and (3) sealing the amorphous lithium-sulfur-phosphorus-tin mixture containing the silver iodide under the condition of atmosphere protection and then heating the amorphous lithium-sulfur-phosphorus-tin mixture to 120-200 DEG C under a vacuum condition for thermal treatment. Through addition of the lithium tin alloy and the silver iodide, the lithium ion conductivity of the obtained solid electrolyte material is improved.

Description

It is a kind of addition lithium-tin alloy and silver iodide lithium sulfide system solid electrolyte material and its Preparation method
Technical field
The present invention relates to lithium sulfide system solid electrolyte material, and in particular to the sulfur of a kind of addition lithium-tin alloy and silver iodide Change lithium system solid electrolyte material and preparation method thereof.
Background technology
The lithium ion battery of high-energy-density has shown that more and more important market as the electrokinetic cell of electric automobile Prospect and widely paid attention to.General lithium ion battery is by positive pole, negative pole, barrier film and organic electrolyte and the shell of sealing Body is constituted, and the serious accident such as catch fire caused by flammable organic electrolyte therein happens occasionally.Although numerous research The performance but the lithium ion containing organic electrolyte of lithium ion battery are greatly improved in terms of material modification and battery structure Battery safety problem in use is not fundamentally solved.
It is to solve lithium ion battery to make to replace flammable organic electrolyte solution using solid lithium-ion electrolyte material The best approach of the safety problem with.All-solid-state lithium-ion battery is generally by anode thin film, negative film and in both positive and negative polarity layer Between all-solid-state lithium-ion dielectric film combine.This simple layer structure all-solid-state lithium-ion battery is not due to containing There is flammable organic electrolyte solution and there is high security, it is of increased attention in recent years.All-solid lithium Ion battery is the series connection lamination structure of powder film, therefore can further reduce manufacturing cost, and improve production efficiency can also be real Existing Towards Higher Voltage is so that the energy density of battery is improved significantly.
The critical material of all-solid-state lithium-ion battery is the total solids that suitable lithium ion conduction has high-lithium ion electrical conductivity Electrolyte.In November, 2000, (p174) reports lithium sulfide in the 26th solid-state ionics seminar summary of Japan (Li2) and phosphoric sulfide P S2S5Mixture can form the result of lithium ion conduction body, thus, amorphous state sulfur Jing after 200 degree of heat treatments Changing lithium system solid electrolyte progressively becomes the focus material of all-solid lithium battery research and development.
Lithium ion solid electrolyte should have following features：1. the lithium ion in lithium ion carrier compound wants easy pole Change, i.e. binding force is smaller and easily migrate；2. the transportable lithium ion density of lithium ion solid electrolyte is as high as possible, i.e., The contributive lithium ion of lithium ion conduction will be present in a large number；3. diffusion of the lithium ion in solid electrolyte is empty by atom The quick diffusion in position, structural relaxation and fault of construction and its other party present in matrix in amorphous state or quasi- crystalline solid electrolyte A large amount of atom vacancies that method is imported, will promote lithium ion quickly to spread by atom vacancy and show high lithium ion conductance Rate.Lithium sulfide based material with high lithium ion conductivity is suitable for use as the solid electrolyte of all-solid-state lithium-ion battery.
Existing research shows that adding other compositions in lithium sulfide system solid electrolyte material can improve ionic conduction The patent of invention of rate, such as Publication No. CN101013761A, disclosing three classes is used for the solid electrolytic of all-solid lithium-ion battery Material system, respectively：(A)Li2S+A/I, A/I is AlI in formula3、ZnI2、ZrI4Or LaI3, 0.5≤x≤1.5；(B) yLi2S-mA/I-zB/S, y+z=9 in formula, y are SiS from 5.0 to 7.0, m from 0.5 to 3, B/S2、0.5P2S5, CeS2Or 0.5B2S3；A/I is AlI3、ZnI2、ZrI4Or LaI3；(C)yLi2S-mA/I-zB/S-nLiI, y+z=9 in formula, y from 5.0 to 7.0, m from 0.5 to 3.0, n are AlI from 0.5 to 3.0, A/I3、ZnI2、ZrI4Or LaI3；B/S is SiS2、0.5P2S5, CeS2Or 0.5B2S3.The preparation method of this three based solid electrolytes material is：After dispensing is completed, vacuum seal in quartz glass tube is placed in Dress, quenching is to grind into powder after room temperature after reacting 10-14 hours at a high temperature of 500-750 DEG C afterwards.As described in the invention Solid electrolyte structure obtained in technical scheme is amorphous state, although the invention is improved can ion migration ability, The raising of resulting materials ionic conductance is unsatisfactory, with 6Li2S-0.5AlI3-3SiS2(y=6, m=as a example by-LiI systems 0.5, z=3, n=1), the system (≤200 DEG C) under room temperature and higher temperature is mainly shown as lithium ion conductor, and its room temperature is total Electrical conductivity is only up to 3.80 × 10-6S/cm.And for example, CN101013753A also discloses that a kind of sulfur for solid lithium battery Compound system solid electrolyte material, the material presses Li2S：A/S：P2S5=6：0.1-4.0：1.5 mol ratio is composited, in formula A is Ag, Zn, Al or Zr；Its preparation technology is to be placed in Vacuum Package in quartz glass tube after dispensing mixing, and 450 are warming up at a slow speed DEG C insulation 24 hours, then be warming up to 500-750 DEG C reaction 10-14 hours after quenching to grind into powder after room temperature.The invention institute The raising for obtaining the ionic conductance of solid electrolyte is also undesirable, and its room temperature total conductivity is equally 10-6S/cm.The applicant point Analysis thinks, (1) additive (such as iodide or sulfide) is stable six sides or rhomboidal crystal in foregoing invention patent, is not had Have and more atom vacancies are imported in system, it is impossible to which the diffusion for lithium ion provides more diffusion admittance；(2) additive contains Amount is too high, reduces ratio of the lithium sulfide as lithium ion carrier in solid electrolyte dispensing, directly reduce to lithium from The density of the contributive transportable lithium ion of son conduction；(3) additive of high-load does not only increase in solid electrolyte Lithium ion diffusion admittance, hinders on the contrary the diffusion of lithium ion.Therefore, the composition for adding in foregoing invention patent does not play bright The aobvious effect for improving sulfide-based solid electrolyte ion conductive performance.
The patent of invention of Publication No. CN104752756A, discloses a kind of system of macroion conductance solid electrolyte material Preparation Method, it, with silver iodide as main constituent, is in molar ratio Ag that the material is2S:P2S5:AgI=3:1:Jing is high after 14 mixes Can Ag made by ball-milling reaction+The solid electrolyte of ionic conduction.Although the solid electrolyte as obtained in the invention methods described With higher conductivity at room temperature (up to 10-3S/cm), but, what the invention was utilized be silver iodide ionic conductivity it is special Property, lead to too small amount of phosphoric sulfide and silver iodide composite amorphousization, to form Ag+Conductive express passway, is easy to Ag+Migration, from And improve the ionic conductivity of material.It can be seen that, the invention be not by produce can be used for lithium ion diffusion atom vacancy with Increase the diffusion admittance of lithium ion, and then reach the effect for lifting sulfide-based solid electrolyte lithium ion conductivity；The application People Jing thinks that the invention is that one kind relies on Ag without lithium ion+Conductive solid electrolyte, is not suitable for being used as total solids Solid electrolyte between lithium battery anode and negative pole, this is because：Ag under electric field action in discharge and recharge+Migration is without electrification Learning reaction can not become battery, and Ag during discharge and recharge+Moving to the interface of low potential can form the barrier for hindering lithium ion to pass through, The consumption of a large amount of lithium ions, the cycle characteristics of battery will be caused to be difficult to maintain.
On the other hand, the research of tin-based material stems primarily from NSK Electronics Industry Company, subsequent Sanyo Electric, pine The companies such as lower electrical equipment, Fuji Photo film are studied (such as the patent of invention of CN1930726A, CN101887965A), but this A little researchs be only by the use of lithium-tin alloy powder as a kind of cell negative electrode material of suitable Lithium-ion embeding, as thermal cell, lithium from Sub- battery, lithium-ion capacitor, lithium-sulfur cell, the negative material of lithium sky battery to receive charging process in lithium ion it is embedded, Transportable lithium ion density is related in being not directed to by adding lithium-tin alloy and silver iodide simultaneously to improve solid electrolyte Research.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of one side and can be formed and can be used for lithium ion diffusion in a large number Atom vacancy, on the other hand can lift transportable lithium concentration in lithium sulfide system solid electrolyte again, and then effectively be lifted The addition lithium-tin alloy and the lithium sulfide system solid electrolyte material of silver iodide of sulfide-based solid electrolyte ion conductive performance And preparation method thereof.
The preparation method of the lithium sulfide system solid electrolyte material of addition lithium-tin alloy of the present invention and silver iodide, bag Include following steps：
1) under the conditions of atmosphere protection, by 2.5-4.0：0.5-1.0：0.02-0.1：The mol ratio of 0.01-0.05 weighs sulfur Change lithium, phosphoric sulfide, lithium-tin alloy powder and sulfur, mix homogeneously, obtain lithium sulfur phosphor tin mixture；
2) under the conditions of atmosphere protection and safe HONGGUANG, lithium sulfur phosphor tin mixture and the iodine equivalent to its quality 1-5% are taken Change silver, be placed in ball milling in ball grinder, obtain the amorphous li sulfur phosphor tin mixture containing silver iodide；
3) gained is sealed containing the amorphous li sulfur phosphor tin mixture of silver iodide under the conditions of atmosphere protection, after vacuum bar 120-200 DEG C is warming up under part carries out heat treatment, that is, obtain adding the lithium sulfide system solid electrolyte of lithium-tin alloy and silver iodide Material.
The step of said method 1) in, the mol ratio of the lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and sulfur is preferably 2.5-3.0：0.5-0.75：0.05-0.10：0.01-0.05.Lithium-tin alloy powder (the Li22Sn5) preferably adopt -300 purposes Powder, sulfur is preferably using the simple substance sulphur powder of -200 mesh.
The step of said method 1) in, described atmosphere protection is typically under the protection of noble gases, such as argon, nitrogen Etc. conventional use of noble gases.During concrete operations, typically carry out in the glove box protected with argon.
The step of said method 1) in, can be to make each composition mix homogeneously by the way of existing conventional ball mill, during ball milling Using dry type ball milling or medium ball milling zirconium dioxide mill ball, ball material mass ratio can be used during ball milling to be preferably 2：0.5-1 (mass ratio).When using conventional rolling ball milling, lithium sulfide and phosphoric sulfide mix homogeneously is set generally to need 6-10h, when using During planetary milling, lithium-tin alloy, sulfur, lithium sulfide and phosphoric sulfide mix homogeneously is set generally to need 2-5h.
The step of said method 2) in, described atmosphere protection is typically under the protection of noble gases, such as argon, nitrogen Etc. conventional use of noble gases.During concrete operations, typically carry out in the glove box protected with argon.
The step of above-mentioned preparation method 2) in, described silver iodide are preferably using the iodate silver powder of -200 mesh.During ball milling, Using zirconium dioxide mill ball, ratio of grinding media to material is preferably 2：0.5-1 (mass ratio), more preferably 2：0.7 (mass ratio).This step In, the Ball-milling Time for obtaining the amorphous li sulfur phosphor tin mixture containing silver iodide is usually 30-48h, contains to be more quickly formed The amorphous li sulfur phosphor tin mixture of silver iodide, after preferably silver iodide and lithium sulfur phosphor tin mixture stir ball is placed in again Ball milling in grinding jar, now, Ball-milling Time controls completely amorphousization and iodine that lithium sulfur phosphor tin mixture is capable of achieving in 30-40h Change silver to be sufficiently mixed with lithium sulfur phosphor tin mixture.
The step of said method 3) in, described atmosphere protection is typically under the protection of noble gases, such as argon, nitrogen Etc. conventional use of noble gases.Specific seal operation, is typically carried out in the glove box protected with argon.
The step of said method 3) in, carry out heat treatment operation to promote silver iodide to be transformed into stable at relatively high temperatures depositing The body centred cubic crystal silver iodide that " rigid backbone " is made up of iodide ion, at the same time the sulfur of part silver ion and surrounding tie Conjunction forms nanoscale Argentous sulfide. (original position separate out), promote to be formed in the body-centered cubic structure based on iodine can be used as in a large number in lithium from The atom vacancy of the diffusion admittance of son, while forming part lithium iodide (original position separates out)；At the same time, amorphous in heat treatment process A part of lithium of state lithium stannum and the reaction of Salmon-Saxl of surrounding are transformed into lithium sulfide and tinbase nanocrystal or nano-cluster containing lithium, new shape Into lithium sulfide improve the concentration of the transportable lithium ion in solid electrolytic plastidome, and the tinbase nanocrystal that newly formed or Nano-cluster is imperfect crystal, and substantial amounts of atom vacancy is also possessed in its structure, and the lithium ion in solid electrolytic plastidome is being moved When moving on to the position of the tinbase nanocrystal containing lithium or nano-cluster and amorphous li stannum, will simultaneously have room diffusion and lithium The advantage of ion exchange diffusion, so as to prepare the multicomponent mixture solid electrolyte of high-lithium ion concentration, high atom vacancy Powder.In this step, the time of heat treatment is generally greater than or equal to 1h, preferably 1-5h；The temperature of heat treatment is further excellent Elect 150-180 DEG C as, under this temperature conditions, the time of heat treatment is preferably 1-3h.
Present invention additionally comprises the lithium sulfide system solid electricity of the addition lithium-tin alloy prepared by said method and silver iodide Solution material.
Compared with prior art, the method have the characteristics that：
1st, the present invention is using lithium sulfide and phosphoric sulfide as matrix, add the lithium-tin alloy of special ratios, sulfur (i.e. sulfur) and After iodate galactic longitude high-energy ball milling, while amorphous mixture of sulfides is formed, the third composition lithium-tin alloy, sulfur is reached The effect being uniformly distributed in silver iodide in matrix；Afterwards again thermally treated technique promotes iodate silver powder to be transformed in higher temperatures The lower stable body centred cubic crystal silver iodide that " rigid backbone " is made up of iodide ion for existing of degree, in iodide ion stable cubic structure While, part silver ion therein combines to form nanoscale Argentous sulfide. with surrounding sulfur；Simultaneously the body-centered cubic based on iodine is tied The atom vacancy of a large amount of suitable lithium ion diffusions is formed in structure, effectively lifted sulfide-based solid electrolyte ion biography so as to play The effect of conductance, goes back forming part lithium iodide while atom vacancy is formed.At the same time, amorphous li in heat treatment process A part of lithium of stannum and the reaction of Salmon-Saxl of surrounding are transformed into lithium sulfide and tinbase nanocrystal or nano-cluster containing lithium, new formation Lithium sulfide improves the concentration of the transportable lithium ion in solid electrolytic plastidome, and the tinbase nanocrystal that newly formed or nanometer Cluster is imperfect crystal, and substantial amounts of atom vacancy is also possessed in its structure, and the lithium ion in solid electrolytic plastidome is being moved to During the position of the tinbase nanocrystal containing lithium or nano-cluster and amorphous li stannum, will simultaneously have room diffusion and lithium ion The advantage of diffusion is exchanged, so as to prepare the multicomponent mixture solid electrolyte with high-lithium ion concentration, high atom vacancy Powder.
2nd, in the method for the invention during heat treatment evolution reaction in situ product nano Argentous sulfide. and lithium iodide, all have Ionic conductivity, can play the effect for further improving sulfide-based solid electrolyte lithium-ion-conducting；What is formed receives Rice sulfuration Argent grain, can obtain dispersion-strengthened effect, and silver sulfide nanometer particles granule of the Dispersed precipitate in electrolyte mixture, can To stablize the microstructure of the lithium sulfide system solid electrolyte, suppress the multicomponent mixture solid electrolyte powder in charge and discharge process The tissue change at end.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, to more fully understand present disclosure, but The present invention is not limited to following examples.
The reagent used in following embodiment such as lithium sulfide (Li2S), phosphoric sulfide (P2S5) and sulfur etc., it is chemistry pure Reagent, purity is 99.9%.
Embodiment 1
1) high-energy ball milling operation is mixed：
In low moisture (≤1ppm), the glove box with argon gas atmosphere protection of low oxygen content (≤1ppm), will vulcanize Lithium, phosphoric sulfide, lithium-tin alloy powder and Cosan are in molar ratio 4：1：0.1：0.05 ratio dispensing, stirring mixing, it is and straight The zirconia balls of footpath 3-10mm enclose ball grinder after coordinating, and the zirconia balls in tank are 2 with the ball material mass ratio of compound: 0.7；Ball milling after sealing is potted in planetary high-energy ball mill using dry type mixing ball milling, and Ball-milling Time is 5 hours, is obtained Lithium sulfur phosphor tin mixture；
2) secondary high-energy ball milling operation：
Protect with argon gas atmosphere in the low moisture (≤1ppm), low oxygen content (≤1ppm) for having safety light (such as HONGGUANG) In the glove box of shield, the iodate silver powder (granularity is 300 mesh) and lithium sulfur of above-mentioned lithium sulfur phosphor tin mixture quality 1% is will be equivalent to Phosphor tin mixture stirring mixing by hand, gained mixed material presses again 2:0.7 ball material mass ratio, the dioxy of fit diameter 3-10mm Change and enclose ball grinder after zirconium ball, seal, and the ball grinder after sealing is fitted in planetary milling ball mill carries out high energy Dry type ball milling, Ball-milling Time is 34 hours, obtains the amorphous li sulfur phosphor tin mixture containing silver iodide；
3) heat treatment step：
By gained containing silver iodide amorphous li sulfur phosphor tin mixture, low moisture (≤1ppm), low oxygen content (≤ Seal in the glove box with argon gas atmosphere protection 1ppm), after heated under vacuum to 150 DEG C of heat treatments 2 hours, Obtain the lithium sulfide system solid electrolyte material of addition lithium-tin alloy of the present invention and silver iodide.In heat treatment process In, silver iodide are transformed into stabilizes at relatively high temperatures the body centred cubic crystal iodate that " rigid backbone " is made up of iodide ion for existing Silver, the part silver ion in its structure combines to form nanoscale Argentous sulfide. with the sulfur in surrounding lithium sulfide, while based on iodine Body-centered cubic structure in form the atom vacancy that can be used for lithium ion diffusion admittance in a large number；On the other hand, also formed have from The conductive product Argentous sulfide. of son and lithium iodide, so that the ionic conduction characteristic of gained solid electrolyte material is entered One step is improved.Additionally, in heat treatment process, a part of lithium of amorphous li stannum can also be transformed into sulfuration with the reaction of Salmon-Saxl of surrounding Lithium and tinbase nanocrystal or nano-cluster containing lithium, the new lithium sulfide for being formed improves transportable in solid electrolytic plastidome The concentration of lithium ion；The lithium ion of a large amount of atom vacancies and remaining in another aspect tinbase nanocrystal or nano-cluster, will be same When have the advantages that room diffusion and lithium ion exchanged diffusion so that the ionic conduction characteristic of gained solid electrolyte material is obtained To further raising.
Solid electrolyte powder obtained in the present embodiment is pressed into after standard sample of photo, using CHI660 electrochemical operations Stand, using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of the present embodiment is 3.2 × 10-4S/cm。
Comparative example
By lithium sulfide in low moisture (≤1ppm), the glove box with argon gas atmosphere protection of low oxygen content (≤1ppm) It is in molar ratio 4 with phosphoric sulfide：1 ratio dispensing, stirring mixing, encloses ball grinder, in tank after coordinating with zirconia balls Zirconia balls are 2 with the ball material mass ratio of compound:0.7；Ball milling after sealing is potted in planetary high-energy ball mill to be adopted With dry type ball milling premixing ball milling, Ball-milling Time is 34 hours, obtains lithium sulfur phosphorus ternary mixture solid electrolyte powder.
Solid electrolyte powder obtained in this comparative example is pressed into after standard sample of photo, using CHI660 electrochemical operations Stand, using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of this comparative example is 8.9 × 10-6S/cm。
Embodiment 2
Repeat embodiment 1, except for the difference that：
Step 1) in, lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and Cosan are in molar ratio 2.5：0.5：0.02： 0.01 ratio dispensing mixing, Ball-milling Time is 3 hours；
Step 2) in, the granularity of iodate silver powder is 250-300 mesh；
Step 3) in, heat treatment is carried out under the conditions of 120 DEG C, and heat treatment time is 5 hours.
Solid electrolyte powder obtained in the present embodiment is pressed into after standard sample of photo, using CHI660 electrochemical operations Stand, using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of the present embodiment is 5.3 × 10-4S/cm。
Embodiment 3
Repeat embodiment 1, except for the difference that：
Step 1) in, lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and Cosan are in molar ratio 3.3：0.9：0.06： 0.02 ratio dispensing mixing, zirconia balls are 2 with the ball material mass ratio of compound：0.5, Ball-milling Time is 4 hours；
Step 2) in, the granularity of iodate silver powder is 200 mesh, and the addition of iodate silver powder mixes equivalent to lithium sulfur phosphor tin The 5% of amount of substance；
Step 3) in, heat treatment is carried out under the conditions of 200 DEG C, and heat treatment time is 1 hour.
Solid electrolyte powder obtained in the present embodiment is pressed into after standard sample of photo, using CHI660 electrochemical operations Stand, using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of the present embodiment is 6.2 × 10-4S/cm。
Embodiment 4
Repeat embodiment 1, except for the difference that：
Step 1) in, lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and Cosan are in molar ratio 2.8：0.8：0.07： 0.03 ratio dispensing mixing；
Step 2) in, the granularity of iodate silver powder is 200-260 mesh, and the addition of iodate silver powder is equivalent to lithium sulfur phosphor tin The 3% of mixture quality, Ball-milling Time is 40 hours；
Step 3) in, heat treatment is carried out under the conditions of 280 DEG C, and heat treatment time is 1 hour.
Solid electrolyte powder is pressed into after standard sample of photo obtained in the present embodiment, using CHI660 electrochemical workstations, Using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of the present embodiment is 5.4 × 10-4S/cm。

Claims (7)

1. a kind of preparation method of the lithium sulfide system solid electrolyte material of addition lithium-tin alloy and silver iodide, including following step Suddenly：
1) under the conditions of atmosphere protection, by 2.5-4.0：0.5-1.0：0.02-0.1：The mol ratio of 0.01-0.05 weighs sulfuration Lithium, phosphoric sulfide, lithium-tin alloy powder and sulfur, mix homogeneously, obtain lithium sulfur phosphor tin mixture；
2) under the conditions of atmosphere protection and safe HONGGUANG, lithium sulfur phosphor tin mixture and the silver iodide equivalent to its quality 1-5% are taken, Ball milling in ball grinder is placed in, the amorphous li sulfur phosphor tin mixture containing silver iodide is obtained；
3) gained is sealed containing the amorphous li sulfur phosphor tin mixture of silver iodide under the conditions of atmosphere protection, under vacuum condition Being warming up to 120-200 DEG C carries out heat treatment, that is, obtain adding the lithium sulfide system solid electrolyte material of lithium-tin alloy and silver iodide.
2. preparation method according to claim 1, it is characterised in that：Step 3) in, time of heat treatment be more than or wait In 1h.
3. preparation method according to claim 1, it is characterised in that：Step 3) in, the time of heat treatment is 1-5h.
4. preparation method according to claim 1, it is characterised in that：Step 3) in, the temperature of heat treatment is 150-180 ℃。
5. the preparation method according to any one of claim 1-4, it is characterised in that：Step 2) in, the time of ball milling is 30-48h。
6. preparation method according to claim 5, it is characterised in that：Step 2) in, ratio of grinding media to material during ball milling is 2：0.5- 1。
7. any one of claim 1-6 method is prepared addition lithium-tin alloy and the lithium sulfide system solid electrolytic of silver iodide Material.
CN201710077196.8A 2017-02-13 2017-02-13 Lithium sulfide solid electrolyte material with added lithium tin alloy and silver iodide and preparation method of lithium sulfide solid electrolyte material Pending CN106684442A (en)

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