CN106785002A - A kind of lithium sulfide system solid electrolyte material containing silver iodide and preparation method thereof - Google Patents

A kind of lithium sulfide system solid electrolyte material containing silver iodide and preparation method thereof Download PDF

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CN106785002A
CN106785002A CN201710077206.8A CN201710077206A CN106785002A CN 106785002 A CN106785002 A CN 106785002A CN 201710077206 A CN201710077206 A CN 201710077206A CN 106785002 A CN106785002 A CN 106785002A
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lithium
solid electrolyte
silver iodide
preparation
sulfide
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朱凌云
王振宇
张天锦
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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
    • H01M10/052—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
    • 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
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a kind of lithium sulfide system solid electrolyte material containing silver iodide and preparation method thereof.Described preparation method is comprised the following steps：1) under the conditions of atmosphere protection, by mass percentage, 35 50% lithium sulfide and the phosphoric sulfide of surplus are weighed, is well mixed, obtain lithium sulphur phosphorus ternary mixture；2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphorus ternary mixture and the silver iodide equivalent to its quality 2 10% are taken, is placed in ball milling in ball grinder, obtain the amorphous li sulphur phosphate mixture containing silver iodide；3) after the amorphous li sulphur phosphate mixture of gained silver iodide is sealed under the conditions of atmosphere protection and feux rouges, 120 200 DEG C are warming up under the conditions of vacuum or atmosphere protection and are heat-treated, obtained final product.A large amount of atom vacancies that can be used for lithium ion diffusion, and then the effectively ionic conduction performance of lifting lithium sulfide system solid electrolyte can be formed when preparing lithium sulfide system solid electrolyte material using the method for the invention.

Description

A kind of lithium sulfide system solid electrolyte material containing silver iodide and preparation method thereof
Technical field
The present invention relates to lithium sulfide system solid electrolyte material, and in particular to a kind of lithium sulfide system solid electricity containing silver iodide Solution material and preparation method thereof.
Background technology
Lithium ion battery with high voltage and high-energy-density, has been widely used in notebook computer and mobile phone etc. and has disappeared Take electronic product.In recent years, the lithium battery of high-energy-density has shown that as the electrokinetic cell of electric automobile and increasingly weigh The market prospects wanted, have been considered as the ideal capacity conversion equipment of 21 century development.General lithium ion battery is by positive pole, negative Pole, barrier film and organic electrolyte and the housing of sealing are constituted, and are caught fire caused by flammable organic electrolyte therein etc. great Security incident happens occasionally.Although numerous research greatly improves traditional lithium in terms of material modification and battery structure improvement The performance of ion battery, but the safety problem in use of the lithium ion battery containing organic electrolyte do not solve at all.
Flammable organic electrolyte solution is replaced to be to solve lithium ion battery in use using solid electrolyte material The best approach of safety problem.All-solid-state lithium-ion battery is generally by cathode film, negative electrode film and the solid between both positive and negative polarity layer Dielectric film is combined.Due to possessing high security without flammable organic electrolyte solution, simple layer structure energy Manufacturing cost, improve production efficiency are further reduced, while the lamination that can connect realizes Towards Higher Voltage and improves all-solid-state lithium-ion The energy density of battery, therefore all-solid-state lithium-ion battery is of increased attention in recent years.
The critical material of all-solid-state lithium-ion battery is the total solids electrolyte of high-lithium ion electrical conductivity.2000 11 Month, (p174) reports lithium sulfide (Li in the 26th solid-state ionics seminar summary of Japan2) and phosphoric sulfide P S2S5It is mixed Compound can form the result of lithium ion conduction body after being heat-treated through 200 degree, thus, amorphous state lithium sulfide system solid electrolyte is progressively Focus material as 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. the smaller easy migration of binding force；2. the transportable lithium ion density of lithium ion solid electrolyte is as high as possible, i.e., right The contributive lithium ion of lithium ion conduction will largely be present；3. diffusion of the lithium ion in solid electrolyte is by atom vacancy Quick to spread, structural relaxation present in amorphous state or quasi- crystalline solid electrolyte matrix and fault of construction and other manner are led The a large amount of atom vacancies for entering, will promote lithium ion quickly to be spread by atom vacancy, so as to possess lithium ion conductivity high.Tool The lithium sulfide based material for having lithium ion conductivity high 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 Rate, such as patent of invention of Publication No. CN101013761A, disclose three classes 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 from 5.0 to 7.0, m from 0.5 to 3, B/S be SiS2、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 from 0.5 to 3.0, A/I be AlI3、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, grind into powder after quenching to room temperature after being reacted 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 can be improved cation transport ability, But 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 lithium for solid lithium battery Sulfur 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/S is the sulfide of Ag, Zn, Al or Zr；Its preparation technology rises at a slow speed after dispensing, to be placed in Vacuum Package in quartz glass tube Temperature is incubated 24 hours to 450 DEG C, then is warming up to after 500-750 DEG C of reaction 10-14 hours grind into powder after quenching to room temperature.Should The raising of the ionic conductance of invention gained solid electrolyte is also undesirable, and its room temperature total conductivity is same 10-6S/cm.This Shen Ask someone to think, foregoing invention patent gained solid electrolyte ionic conductance raising it is undesirable the reason for be mainly： (1) material (such as iodide or sulfide) of addition is the hexagonal or rhomboidal crystal of stabilization, it is impossible to sent out with ambient substance Raw reaction, and more atom vacancies cannot be imported in system, it is impossible to for the diffusion of lithium ion provides more diffusion admittance； (2) content of material of addition is too high, on the one hand reduces the content as the lithium sulfide component of lithium ion carrier, on the other hand, High content, stable in properties additive does not increase the lithium ion diffusion admittance in solid electrolyte not only, hinders on the contrary The diffusion of lithium ion.Therefore, the composition for being added in foregoing invention patent is not played and is obviously improved sulfide-based solid electrolyte The effect of ionic conduction performance.
The patent of invention of Publication No. CN104752756A, discloses a kind of silver iodide system with high ionic conductivity and consolidates The preparation method of body electrolyte, it is in molar ratio Ag that the material is2S:P2S5:AgI=3:1:14 ratio, in silver iodide In be mixed into after a small amount of phosphoric sulfide and silver sulfide the solid electrolyte that the utilization silver ion being made through high-energy ball milling conducts.By the hair Although solid electrolyte obtained in bright methods described is with conductivity at room temperature higher (up to 10-3S/cm), but, the hair Bright obtained solid electrolyte is the fast conductor of silver ion, and what is utilized is the ionic conduction characteristic of silver iodide, a small amount of by adding Phosphoric sulfide simultaneously combines preamorphization process in order to Ag+Migration, so as to improve the silver ion electrical conductivity of material.Even so, Applicants contemplate that, the invention is that one kind relies on Ag without lithium ion+Conductive solid electrolyte is big not by producing The new atom vacancy of amount lifts sulfide-based solid electrolyte lithium ion conduction to increase the diffusion admittance of lithium ion and then reach The effect of rate；The silver ion conducting solid electrolyte as obtained in the invention methods described is not suitable for being used as all-solid lithium battery just Solid electrolyte between pole and negative pole, because：Ag under electric field action in discharge and recharge+Migration is not accompanied by electrochemistry The generation of reaction can not thus turn into battery, and on the other hand, Ag during discharge and recharge+The interface for moving to low potential can form obstruction The barrier that lithium ion passes through, and cause a large amount of lithium ions to be stranded in silver iodide system solid electrolyte, the consumption of a large amount of lithium ions To cause that the coulombic efficiency of the first cycle of battery is very low, it is difficult to maintain charge and discharge cycles.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of can formation and largely can be used for the atoms sky of lithium ion diffusion Position, and then the effectively lithium sulfide system solid electrolytic material containing silver iodide of lifting lithium sulfide system solid electrolyte ion conductive performance Material and preparation method thereof.
The preparation method of the lithium sulfide system solid electrolyte material containing silver iodide of the present invention, comprises the following steps：
1) under the conditions of atmosphere protection, by mass percentage, the lithium sulfide of 35-50% and the phosphoric sulfide of surplus are weighed, It is well mixed, obtain lithium sulphur phosphorus ternary mixture；
2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphorus ternary mixture is taken and equivalent to its quality 2-10%'s Silver iodide, are placed in ball milling in ball grinder, obtain the amorphous li sulphur phosphate mixture containing silver iodide；
3) after the amorphous li sulphur phosphate mixture of gained silver iodide is sealed under the conditions of the atmosphere protection and feux rouges, in vacuum or 120-200 DEG C is warming up under the conditions of atmosphere protection to be heat-treated, that is, obtain the lithium sulfide system solid electrolytic material containing silver iodide Material.
The present invention using lithium sulfide and phosphoric sulfide as matrix, after adding the iodate galactic longitude high-energy ball milling of special ratios, in shape While into amorphous mixture of sulfides, the effect that the third composition silver iodide is uniformly distributed in matrix is reached；Afterwards Again thermally treated technique promote iodate silver powder be transformed at relatively high temperatures stabilize exist " rigid bone is constituted by iodide ion The body centred cubic crystal silver iodide of frame ", while iodide ion stable cubic skeleton, in part silver ion and surrounding lithium sulfide Sulphur combines to form nanoscale silver sulfide, and the nanoscale silver sulfide for being formed can play a part of stabilization of solid electrolyte matrix；Together When body-centered cubic structure based on iodine in form the atom vacancies of a large amount of suitable lithium ions diffusions, so as to play effectively lifting sulphur Change the effect of lithium system solid electrolyte ion conductivity, forming part lithium iodide is gone back while atom vacancy is formed；The opposing party Face, the formed silver sulfide nanometer particles of reaction and lithium iodide also have the effect for improving ionic conduction characteristic.
The step of above-mentioned preparation method 1) in, described atmosphere protection is typically under the protection of inert gas, such as argon gas, The conventional use of inert gas such as nitrogen.During concrete operations, typically carried out in the glove box protected with argon gas.
The step of above-mentioned preparation method 1) in, using existing conventional techniques lithium sulfide and phosphoric sulfide can be made well mixed, Generally it is well mixed by the way of ball milling them, dry type ball milling or medium ball milling can be used during ball milling, is used during ball milling Zirconium dioxide mill ball, ratio of grinding media to material is preferably 2：0.5-1 (mass ratio).When using conventional rolling ball milling, make lithium sulfide and Phosphoric sulfide is well mixed generally to need 6-10h, when using planetary milling, makes lithium sulfide and phosphoric sulfide well mixed logical Often need 25h.
The step of above-mentioned preparation method 2) in, described atmosphere protection is typically under the protection of inert gas, such as argon gas, The conventional use of inert gas such as nitrogen.During concrete operations, typically carried out in the glove box protected with argon gas.
The step of above-mentioned preparation method 2) in, described silver iodide are preferably iodate silver powder of the granularity less than 200 mesh.Ball During mill, 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 In step, the time usually 30-48h of the amorphous li sulphur phosphate mixture ball milling containing silver iodide is obtained, in order to be more quickly formed Amorphous li sulphur phosphate mixture containing silver iodide, is placed in again after preferably silver iodide are stirred with lithium sulphur phosphorus ternary mixture Ball milling in ball grinder, now, Ball-milling Time control is completely amorphousization and iodine for being capable of achieving lithium sulphur phosphate mixture in 30-40h Change silver to be sufficiently mixed with amorphous li sulphur phosphate mixture.
The step of above-mentioned preparation method 3) in, described atmosphere protection is typically under the protection of inert gas, such as argon gas, The conventional use of inert gas such as nitrogen.Specific seal operation, is typically carried out in the glove box protected with argon gas.
The step of above-mentioned preparation method 3) in, carry out heat treatment operation and pacified at relatively high temperatures with promoting silver iodide to be transformed into The fixed body centred cubic crystal silver iodide that " rigid backbone " is made up of iodide ion for existing, at the same time part silver ion and surrounding sulphur Change the sulphur in lithium and combine to form nanoscale silver sulfide (original position separates out), promote to form a large amount of in the body-centered cubic structure based on iodine Can be used as the atom vacancy of the diffusion admittance in lithium ion, while forming part lithium iodide (original position separates out), so as to prepare The granuloplastic lithium sulphur phosphorus iodine multicomponent mixture solid electrolyte powder of silver sulfide nanometer particles.In this step, the time of heat treatment leads to Often it is more than or equal to 1h, preferably 1-5h；The temperature of heat treatment is more preferably 150-180 DEG C, under this temperature conditions, The time of heat treatment is preferably 1-3h.
Present invention additionally comprises the lithium sulfide system solid electrolyte material containing silver iodide that the above method is prepared.
Compared with prior art, the method have the characteristics that：
1st, it is of the invention using lithium sulfide and phosphoric sulfide as matrix, after adding the iodate galactic longitude high-energy ball milling of special ratios, While forming amorphous mixture of sulfides, the effect that the third composition silver iodide is uniformly distributed in matrix is reached；It Afterwards again thermally treated technique promote iodate silver powder be transformed at relatively high temperatures stabilize exist " rigid bone is constituted by iodide ion The body centred cubic crystal silver iodide of frame ", while iodide ion stable cubic structure, part silver ion therein vulcanizes with surrounding Sulphur in lithium combines to form nanoscale silver sulfide；Formed in body-centered cubic structure based on iodine simultaneously a large amount of new suitable lithiums from The atom vacancy of son diffusion, it is former being formed so as to play the effect of effectively lifting lithium sulfide system solid electrolyte ion conductivity Forming part lithium iodide is gone back while sub- room.
The product nano silver sulfide and lithium iodide of evolution reaction in situ, all have when the 2, being heat-treated in the method for the invention Ionic conductivity, can play the effect for further improving lithium sulfide system solid electrolyte lithium-ion-conducting；What is formed receives Rice vulcanization Argent grain, can obtain dispersion-strengthened effect, and silver sulfide nanometer particles of the Dispersed precipitate in lithium sulphur phosphorus ternary mixture Grain, can stablize the microstructure of the lithium sulfide system solid electrolyte, suppress the lithium sulphur phosphorus iodine Diversity in charge and discharge process The tissue change of thing solid electrolyte powder.
3rd, three sections of process step combinations methods are employed in the method for the invention, wherein lithium sulfide and phosphoric sulfide makees ready-mixed Operation can ensure that the principal component lithium sulfide of solid electrolyte forms lithium sulphur phosphorus ternary mixture in being uniformly mixed in phosphoric sulfide；And Second high-energy ball milling mixing is carried out after adding the third composition silver iodide, can ensure that adding ingredient silver iodide are equally distributed Meanwhile, realize the decrystallized high-lithium ion transport properties to ensure lithium sulfide system solid electrolyte of lithium sulphur phosphorus ternary mixture.
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 (Li2) and phosphoric sulfide (P S2S5) etc., chemically pure reagent is, Purity is 99.9%.
Embodiment 1
1) sulfide ready-mixed operation：
By mass percentage, 40% lithium sulfide and 60% phosphoric sulfide is weighed to contain in low moisture (≤1ppm), hypoxemia Dispensing mixing, ball grinder is enclosed after coordinating with zirconia balls in the glove box with argon gas atmosphere protection of amount (≤1ppm), Zirconia balls and the ball material mass ratio of compound in tank are 2:0.7；Ball grinder after sealing is mounted in planetary milling Ball milling is pre-mixed using dry type ball milling in machine, Ball-milling Time is 5 hours, (abbreviation LiPS mixes to obtain lithium sulphur phosphorus ternary mixture Thing)；
2) secondary high-energy ball milling operation：
In the low moisture (≤1ppm), low oxygen content (≤1ppm) for having safety light (such as feux rouges) with argon gas atmosphere In the glove box of protection, the iodate silver powder (granularity is 300 mesh) and LiPS of above-mentioned LiPS mixture qualities 2.5% are will be equivalent to Mixture stirring mixing by hand, gained mixed material presses 2 again:0.7 ball material mass ratio, the zirconium dioxide of fit diameter 3-10mm Ball grinder is enclosed after ball, is sealed, and the ball grinder after sealing is fitted into planetary milling ball mill carries out high energy dry type Ball milling, Ball-milling Time is 36 hours, obtains the amorphous li sulphur phosphate mixture containing silver iodide；
3) evolution reaction operation in situ：
By the amorphous li sulphur phosphate mixture containing silver iodide of gained, have safety light (such as feux rouges) low moisture (≤ 1ppm), low oxygen content (≤1ppm) with argon gas atmosphere protection glove box in, sealing, after heated under vacuum It is heat-treated 2 hours to 150 DEG C, that is, obtains the lithium sulfide system solid electrolyte material containing silver iodide.In heat treatment process, iodate Silver is transformed into the body centred cubic crystal silver iodide that " rigid backbone " is made up of iodide ion stabilized exist at relatively high temperatures, its knot Part silver ion in structure combines to form nanoscale silver sulfide with the sulphur in surrounding lithium sulfide, while being stood in the body-centered based on iodine Formed in square structure and largely can be used for the atom vacancy of lithium ion diffusion admittance；On the other hand, also being formed has ionic conductivity Product silver sulfide and lithium iodide so that the ionic conduction characteristic of gained solid electrolyte material is further carried It is high.
After solid electrolyte powder is pressed into standard sample of photo obtained in the present embodiment, 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 4.5 × 10-4S/cm。
Comparative example
By mass percentage, 40% lithium sulfide and 60% phosphoric sulfide is weighed to contain in low moisture (≤1ppm), hypoxemia Dispensing mixing, ball grinder is enclosed after coordinating with zirconia balls in the glove box with argon gas atmosphere protection of amount (≤1ppm), Zirconia balls and the ball material mass ratio of compound in tank are 2:0.7；Ball grinder after sealing is mounted in planetary milling Ball milling is pre-mixed using dry type ball milling in machine, Ball-milling Time is 36 hours, obtains lithium sulphur phosphorus ternary mixture solid electrolyte powder End.
After solid electrolyte powder is pressed into standard sample of photo obtained in this comparative example, 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 8.6 × 10-6S/cm。
Embodiment 2
Embodiment 1 is repeated, unlike：
Step 1) in, the mass percent of lithium sulfide and phosphoric sulfide is respectively 50% and 50%, and the time of ball milling is 10 small When.
After solid electrolyte powder is pressed into standard sample of photo obtained in the present embodiment, 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 8.1 × 10-4S/cm。
Embodiment 3
Embodiment 1 is repeated, unlike：
Step 1) in, the mass percent of lithium sulfide and phosphoric sulfide is respectively 50% and 50%, and the time of ball milling is 2 small When；
Step 2) in, the granularity of iodate silver powder is 400 mesh, and the addition of iodate silver powder is equivalent to LiPS compounding substances The 5% of amount；
After solid electrolyte powder is pressed into standard sample of photo obtained in the present embodiment, 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 8.7 × 10-4S/cm。
Embodiment 4
Embodiment 1 is repeated, unlike：
Step 1) in, the mass percent of lithium sulfide and phosphoric sulfide is respectively 50% and 50%, and the time of ball milling is 4 small When；
Step 2) in, the granularity of iodate silver powder is 220-260 mesh, and the addition of iodate silver powder mixes equivalent to LiPS The 10% of amount of substance, the time of ball milling is 40 hours；
Step 3) in, heat treatment is carried out in argon gas atmosphere, and the temperature of heat treatment is 200 DEG C, and the time of heat treatment is 1 small When.
After solid electrolyte powder is pressed into standard sample of photo obtained in the present embodiment, 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 7.2 × 10-4S/cm。
Embodiment 5
Embodiment 1 is repeated, unlike：
Step 1) in, the mass percent of lithium sulfide and phosphoric sulfide is respectively 35% and 65%, and the time of ball milling is 6 small When；
Step 2) in, the granularity of iodate silver powder is 100-200 mesh, and the addition of iodate silver powder mixes equivalent to LiPS The 2% of amount of substance, the time of ball milling is 30 hours；
Step 3) in, heat treatment is carried out in argon gas atmosphere, and the temperature of heat treatment is 120 DEG C, and the time of heat treatment is 5 small When.
After solid electrolyte powder is pressed into standard sample of photo obtained in the present embodiment, 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 2.7 × 10-4S/cm。

Claims (7)

1. a kind of preparation method of the lithium sulfide system solid electrolyte material containing silver iodide, comprises the following steps：
1) under the conditions of atmosphere protection, by mass percentage, the lithium sulfide of 35-50% and the phosphoric sulfide of surplus are weighed, is mixed Uniformly, lithium sulphur phosphorus ternary mixture is obtained；
2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphorus ternary mixture and the iodate equivalent to its quality 2-10% are taken Silver, is placed in ball milling in ball grinder, obtains the amorphous li sulphur phosphate mixture containing silver iodide；
3) after the amorphous li sulphur phosphate mixture of gained silver iodide is sealed under the conditions of atmosphere protection and feux rouges, in vacuum or atmosphere 120-200 DEG C is warming up under protective condition to be heat-treated, that is, obtain the lithium sulfide system solid electrolyte material containing silver iodide.
2. preparation method according to claim 1, it is characterised in that：Step 2) in, the time of ball milling is 30-48h.
3. preparation method according to claim 1, it is characterised in that：Step 2) in, ratio of grinding media to material during ball milling is 2：0.5- 1。
4. 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.
5. preparation method according to claim 1, it is characterised in that：Step 3) in, the time of heat treatment is 1-5h.
6. preparation method according to claim 1, it is characterised in that：Step 3) in, the temperature of heat treatment is 150-180 ℃。
7. the lithium sulfide system solid electrolyte material containing silver iodide that any one of claim 1-6 methods are prepared.
CN201710077206.8A 2017-02-13 2017-02-13 A kind of lithium sulfide system solid electrolyte material containing silver iodide and preparation method thereof Pending CN106785002A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101136496A (en) * 2006-08-31 2008-03-05 精工爱普生株式会社 Secondary battery and a method for manufacturing the secondary battery
CN102334225A (en) * 2009-02-27 2012-01-25 丰田自动车株式会社 Solid sulfide electrolyte material
CN104393338A (en) * 2014-11-21 2015-03-04 东南大学 LiBH4-silver/silver halide compound fast-ion conductor and preparation method thereof
CN104752756A (en) * 2015-04-23 2015-07-01 武汉理工大学 Preparation method of high-ion electrical conduction solid electrolyte material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101136496A (en) * 2006-08-31 2008-03-05 精工爱普生株式会社 Secondary battery and a method for manufacturing the secondary battery
CN102334225A (en) * 2009-02-27 2012-01-25 丰田自动车株式会社 Solid sulfide electrolyte material
CN104393338A (en) * 2014-11-21 2015-03-04 东南大学 LiBH4-silver/silver halide compound fast-ion conductor and preparation method thereof
CN104752756A (en) * 2015-04-23 2015-07-01 武汉理工大学 Preparation method of high-ion electrical conduction solid electrolyte material

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