CN106785014A - A kind of lithium sulfide system solid electrolyte material for adding Li-Si alloy, silver bromide and silver chlorate and preparation method thereof - Google Patents

A kind of lithium sulfide system solid electrolyte material for adding Li-Si alloy, silver bromide and silver chlorate and preparation method thereof Download PDF

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CN106785014A
CN106785014A CN201710077198.7A CN201710077198A CN106785014A CN 106785014 A CN106785014 A CN 106785014A CN 201710077198 A CN201710077198 A CN 201710077198A CN 106785014 A CN106785014 A CN 106785014A
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lithium
silver
silver bromide
solid electrolyte
alloy
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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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    • 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
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    • 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

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Abstract

The invention provides a kind of lithium sulfide system solid electrolyte material for adding Li-Si alloy, silver bromide and silver chlorate and preparation method thereof.Described preparation method, comprises the following steps：1) under the conditions of atmosphere protection, by 2.5 3.5：0.5‑1.0：0.05‑0.20：0.01 0.1 mol ratio weighs lithium sulfide, phosphoric sulfide, Li-Si alloy powder and sulphur, is well mixed, and obtains lithium sulphur phosphorus silicon mixture；2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphorus silicon mixture, silver bromide and silver chlorate are taken, is placed in ball milling in ball grinder, obtain the amorphous li sulphur phosphorus silicon mixture containing silver bromide and silver chlorate；3) step 2) gained mixture seals under the conditions of atmosphere protection, be heat-treated after being warming up to 100 180 DEG C under vacuum condition, obtain final product.The present invention is by addition Li-Si alloy simultaneously, silver bromide and silver chlorate with the lithium ion conductivity of solid electrolyte material obtained by being lifted.

Description

A kind of lithium sulfide system solid electrolyte for adding Li-Si alloy, silver bromide and silver chlorate Material and preparation method thereof
Technical field
The present invention relates to lithium sulfide system solid electrolyte material, and in particular to one kind addition Li-Si alloy, silver bromide and chlorine Change lithium sulfide system solid electrolyte material of silver 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 S2S5) Mixture can form the result of lithium ion conduction body after being heat-treated through 200 degree, thus, amorphous state lithium sulfide system's solid electrolyte by Focus material of the step 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.
On the other hand, Li-Si Alloy Powder has been used for GND material as a kind of important materials of suitable Lithium-ion embeding The correlative study of material, such as patent of invention of Publication No. CN104766965A, there is provided a kind of nanoscale Li-Si alloy material and Preparation Method And The Use, the composition of the nanoscale Li-Si alloy material includes：Li, Si and doped chemical；Wherein, Li and Si Mol ratio be 1/100~5/1；Mole total content of Li and Si is more than or equal to 90% in the nanoscale Li-Si alloy material； The doped chemical is B, C, N, F, Na, Mg, Al, P, one or more in Cu；The nanoscale Li-Si alloy material is in office Size in one dimension of meaning is 1nm to 500nm；And explicitly point out the Li-Si Alloy Powder and can be used for thermal cell, lithium-ion electric The negative material of pond, lithium-ion capacitor, lithium sky battery, lithium-sulfur cell and all-solid-state battery.Even so, this kind of invention skill Art is used as the empty battery of thermal cell, lithium ion battery, lithium-ion capacitor, lithium-sulfur cell, lithium just with Li-Si alloy material Negative material receives the insertion of lithium ion in charging process, is not directed to by adding Li-Si Alloy Powder, silver bromide and chlorine simultaneously Change silver to improve the correlative study of solid electrolyte lithium ion conductivity.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of lithium sulfide system for adding Li-Si alloy, silver bromide and silver chlorate Solid electrolyte material and preparation method thereof, the method for the invention is on the one hand high by addition amount containing lithium and easily forms amorphous The Li-Si alloy powder of state lifts transportable lithium concentration in lithium sulfide system solid electrolyte, on the other hand by addition Silver bromide and silver chlorate simultaneously form a large amount of atom vacancies that can be used for lithium ion diffusion by subsequent treatment, so as to lift lithium sulfide It is the lithium ion conductivity of solid electrolyte material.
The preparation of the lithium sulfide system solid electrolyte material of addition Li-Si alloy of the present invention, silver bromide and silver chlorate Method, comprises the following steps：
1) under the conditions of atmosphere protection, by 2.5-3.5：0.5-1.0：0.05-0.20：The mol ratio of 0.01-0.1 weighs sulphur Change lithium, phosphoric sulfide, Li-Si alloy powder and sulphur, be well mixed, obtain lithium sulphur phosphorus silicon mixture；
2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphorus silicon mixture, the bromination equivalent to its quality 1-4% are taken Silver and equivalent to the silver chlorate of its quality 1-4%, is placed in ball milling in ball grinder, obtains the amorphous state containing silver bromide and silver chlorate Lithium sulphur phosphorus silicon mixture；Wherein, total addition of silver bromide and silver chlorate is less than or equal to lithium sulphur phosphorus silicon mixture quality 5%；
3) amorphous li sulphur phosphorus silicon mixture of the gained containing silver bromide and silver chlorate is sealed under the conditions of atmosphere protection, afterwards It is heat-treated in being warming up to 100-180 DEG C under vacuum condition, that is, is obtained adding the sulphur of Li-Si alloy, silver bromide and silver chlorate Change lithium system solid electrolyte material.
The step of above-mentioned preparation method 1) in, the mol ratio of the lithium sulfide, phosphoric sulfide, Li-Si alloy powder and sulphur is excellent Elect 2.5-3.0 as：0.5-0.75：0.05-0.10：0.01-0.05.Described Li-Si alloy powder preferably use principal phase structure for Li13Si4- 300 mesh Li-Si alloy powder, sulphur preferably using -200 mesh Cosan.
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, existing conventional techniques can be used by lithium sulfide, phosphoric sulfide, Li-Si Alloy Powder End and sulphur are well mixed, and are generally well mixed by the way of ball milling them, and dry type ball milling or Jie can be used during ball milling Matter ball milling, uses zirconium dioxide mill ball during ball milling, ratio of grinding media to material is preferably 2：0.5-1 (mass ratio).More preferably using planetary High-energy ball milling is well mixed lithium sulfide, phosphoric sulfide, Li-Si alloy powder and sulphur, now by Ball-milling Time control in 5-12h Realize being sufficiently mixed for they.
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 bromide is preferably using the bromination silver powder of -200 mesh, silver chlorate It is preferred that using the chlorination 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 (quality Than), more preferably 2：0.7 (mass ratio).In this step, the amorphous li sulphur phosphorus silicon mixture containing silver bromide and silver chlorate is obtained Ball-milling Time be usually 30-48h, it is excellent in order to the amorphous li sulphur phosphate mixture containing silver bromide and silver chlorate is more quickly formed Choosing is to be placed in ball milling in ball grinder again after silver bromide and silver chlorate stir with lithium sulphur phosphorus silicon mixture, now, during ball milling Between control to be capable of achieving completely amorphousization and silver bromide and silver chlorate and lithium sulphur phosphorus silicon of lithium sulphur phosphorus silicon mixture in 30-40h Mixture is sufficiently mixed.
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, carrying out heat treatment operation can promote a part of lithium and the week of amorphous li silicon The reaction of Salmon-Saxl for enclosing is transformed into lithium sulfide and silicon-based nano crystal or nano-cluster containing lithium, wherein the new lithium sulfide for being formed is improved The concentration of the transportable lithium ion in solid electrolytic plastidome；Another aspect heat treatment operation can promote part silver bromide and chlorination The reaction of Salmon-Saxl of silver ion in silver and surrounding, at the same is formed in by the body-centered cubic structure based on bromine/chlorion it is a large amount of suitably The atom vacancy of lithium ion diffusion；Two aspect collective effects are so that lithium sulfide system of the present invention solid electrolyte has simultaneously Have transportable lithium concentration high and atom vacancy more than advantage, effectively lift its ionic conductance.In this step, heat treatment Time is generally greater than or equal to 1h, preferably 1-5h；The temperature of heat treatment is more preferably 120-160 DEG C, in this temperature Under the conditions of, the time of heat treatment is preferably 1-3h.
Present invention additionally comprises the lithium sulfide system of addition Li-Si alloy, silver bromide and the silver chlorate prepared by the above method Solid electrolyte material.
Compared with prior art, the method have the characteristics that：
1st, using lithium sulfide and phosphoric sulfide as matrix, silver bromide, silver chlorate and the lithium silicon for adding certain content are closed the present invention Bronze end through high-energy ball milling after, formed amorphous mixtures while, reach adding ingredient Li-Si Alloy Powder and Cosan and Silver bromide is uniformly distributed in the effect in matrix with silver chlorate；Thermally treated technique promotes a part for amorphous li silicon again afterwards The reaction of Salmon-Saxl of lithium and surrounding is transformed into lithium sulfide and silicon-based nano crystal or nano-cluster containing lithium, the new lithium sulfide lifting for being formed The concentration of the transportable lithium ion in solid electrolytic plastidome；On the other hand, Technology for Heating Processing promotes part silver ion to depart from The cubic structure of silver bromide and silver chlorate, so as to form a large amount of suitable lithium ions in the cubic structure based on bromine and chlorion The interstitial void of diffusion, while forming nanoscale silver sulfide (original position separates out)；Additionally, silicon-based nano crystal or nanometer containing lithium Cluster is also imperfect crystal, and substantial amounts of atom vacancy is possessed in its structure, and the lithium ion in solid electrolytic plastidome is being moved to During the position of silicon-based nano crystal or nano-cluster and amorphous li silicon containing lithium, will simultaneously have room to spread and lithium ion The advantage of diffusion is exchanged, the solid electrolyte powder of high-lithium ion conductivity thus can be prepared.
The silver sulfide nanometer particles of evolution reaction in situ, lithium bromide and lithium chloride are produced when the 2, being heat-treated in the method for the invention Thing, all with ionic conductivity, can play the effect for further improving sulfide-based solid electrolyte lithium-ion-conducting；And Silver sulfide nanometer particles particle of the Dispersed precipitate in lithium sulphur phosphorus silicon mixture, can stablize the microcosmic of the lithium sulfide system solid electrolyte Tissue, suppresses the tissue change of the solid electrolyte powder in charge and discharge process.
3rd, three sections of process step combinations methods are employed in the method for the invention, wherein ready-mixed operation can ensure solid The principal component of electrolyte uniformly mixes；And second high-energy ball milling mixing is carried out after adding silver bromide and silver chlorate, can ensure While adding ingredient silver bromide and silver chlorate are uniformly distributed, realize that lithium sulphur phosphorus silicon mixture is decrystallized to ensure that lithium sulfide system consolidates The high-lithium ion transport properties of body electrolyte.
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) 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, Li-Si alloy powder and Cosan are in molar ratio 2.5：0.75：0.05：0.05 ratio dispensing, stirring are mixed Close, enclose ball grinder after coordinating with the zirconia balls of diameter 3-10mm, the ball material matter of the zirconia balls in tank and compound Amount is than being 2:0.75；Ball grinder after sealing uses dry type mixing ball milling in planetary high-energy ball mill, and Ball-milling Time is 5 Hour, obtain lithium sulphur phosphorus silicon mixture；
2) secondary high-energy ball milling operation：
Protected with argon gas atmosphere in the low moisture (≤1ppm), low oxygen content (≤1ppm) for having safety light (such as feux rouges) In the glove box of shield, will be equivalent to above-mentioned lithium sulphur phosphorus silicon mixture quality 2.5% bromination silver powder (granularity be 300 mesh) and Equivalent to the chlorination silver powder (granularity is 300 mesh) and lithium sulphur phosphorus silicon mixture hand of above-mentioned lithium sulphur phosphorus silicon mixture quality 1.5% Work stirring mixing, gained mixed material presses 2 again:0.7 ball material mass ratio, encloses after the zirconia balls of fit diameter 3-10mm Ball grinder, sealing, and the ball grinder after sealing is fitted into high energy dry type ball milling, Ball-milling Time are carried out in planetary high-energy ball mill It is 36 hours, obtains the amorphous li sulphur phosphorus silicon mixture containing silver bromide and silver chlorate；
3) heat treatment step：
By amorphous li sulphur phosphorus silicon mixture of the gained containing silver bromide and silver chlorate in low moisture (≤1ppm), low oxygen content Sealed in the glove box with argon gas atmosphere protection of (≤1ppm), it is 2 small to 140 DEG C of heat treatments after heated under vacuum When, that is, obtain the lithium sulfide system solid electrolyte material of addition Li-Si alloy of the present invention, silver bromide and silver chlorate.In heat In processing procedure, a part of lithium of amorphous li silicon and the reaction of Salmon-Saxl of surrounding are transformed into lithium sulfide and the crystalline substance of the silicon-based nano containing lithium Body or nano-cluster, the new lithium sulfide for being formed improve the concentration of the transportable lithium ion in solid electrolytic plastidome；On the other hand, Technology for Heating Processing promotes part silver ion to depart from the cubic structure of silver bromide and silver chlorate, so as to based on bromine and chlorion The interstitial void of a large amount of suitable lithium ion diffusions is formed in cubic structure, while forming nanoscale silver sulfide (original position separates out)；This The lithium ion of a large amount of atom vacancies and remaining in outer silicon-based nano crystal or nano-cluster, will cause that solid electrolyte has simultaneously The advantage that room is spread and lithium ion exchanged spreads, so that the ionic conduction for further improving gained solid electrolyte material is special Property.
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 2.4 × 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 3 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 grinder after sealing is adopted in planetary high-energy ball mill Ball milling is pre-mixed with dry type ball milling, Ball-milling Time is 36 hours, obtains lithium sulphur phosphorus ternary mixture solid electrolyte powder.
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 8.7 × 10-6S/cm。
Embodiment 2
Embodiment 1 is repeated, unlike：
Step 1) in, lithium sulfide and phosphoric sulfide and Li-Si alloy and Cosan are in molar ratio 3：1：0.1：0.05 ratio Dispensing mixes, and zirconia balls are 2 with the ball material mass ratio of compound：1, Ball-milling Time is 12 hours；
Step 2) in, the granularity of silver bromide and chlorination silver powder is 250 to 300 mesh, the addition phase of bromination silver powder When in the 2.5% of lithium sulphur phosphorus silicon mixture quality, the addition of chlorination silver powder is equivalent to lithium sulphur phosphorus silicon mixture quality 2.5%；
Step 3) in, heat treatment is carried out under the conditions of 150 DEG C, and heat treatment time is 2 hours.
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 4.1 × 10-4S/cm。
Embodiment 3
Embodiment 1 is repeated, unlike：
Step 1) in, lithium sulfide and phosphoric sulfide and Li-Si alloy and Cosan are in molar ratio 3：0.75：0.15：0.1 Ratio dispensing mixes, and zirconia balls are 2 with the ball material mass ratio of compound：0.5, Ball-milling Time is 8 hours；
Step 2) in, the granularity of bromination silver powder is 250 mesh, and the granularity of chlorination silver powder is 300 mesh；Bromination silver powder , equivalent to the 4% of lithium sulphur phosphorus silicon mixture quality, the addition of chlorination silver powder is equivalent to lithium sulphur phosphorus silicon compounding substances for addition The 1% of amount；
Step 3) in, sealing is heat-treated 1 hour after heated under vacuum to 160 DEG C；
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 5.2 × 10-4S/cm。
Embodiment 4
Embodiment 1 is repeated, unlike：
Step 1) in, lithium sulfide and phosphoric sulfide and Li-Si alloy and Cosan are in molar ratio 3.5：1.0：0.2：0.30 Ratio dispensing mixes；
Step 2) in, the granularity of bromination silver powder is 200 mesh, and the granularity of chlorination silver powder is 250 mesh；Bromination silver powder , equivalent to the 1% of lithium sulphur phosphorus silicon mixture quality, the addition of chlorination silver powder is equivalent to lithium sulphur phosphorus silicon compounding substances for addition The 4% of amount；
Step 3) in, sealing is heat-treated 3 hours after heated under vacuum to 100 DEG C；
After solid electrolyte powder is pressed into 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 4.2 × 10-4S/cm。

Claims (7)

1. it is a kind of to add Li-Si alloy, the preparation method of the lithium sulfide system solid electrolyte material of silver bromide and silver chlorate, including Following steps：
1) under the conditions of atmosphere protection, by 2.5-3.5：0.5-1.0：0.05-0.20：The mol ratio of 0.01-0.1 weighs vulcanization Lithium, phosphoric sulfide, Li-Si alloy powder and sulphur, are well mixed, and obtain lithium sulphur phosphorus silicon mixture；
2) under the conditions of atmosphere protection and safe feux rouges, take lithium sulphur phosphorus silicon mixture, the silver bromide equivalent to its quality 1-4% with And equivalent to the silver chlorate of its quality 1-4%, ball milling in ball grinder is placed in, obtain the amorphous li sulphur containing silver bromide and silver chlorate Phosphorus silicon mixture；Wherein, 5% of total addition of silver bromide and silver chlorate less than or equal to lithium sulphur phosphorus silicon mixture quality；
3) amorphous li sulphur phosphorus silicon mixture of the gained containing silver bromide and silver chlorate is sealed under the conditions of atmosphere protection, after true 100-180 DEG C is warming up under empty condition to be heat-treated, that is, obtain adding the lithium sulfide of Li-Si alloy, silver bromide and silver chlorate It is solid electrolyte material.
2. preparation method according to claim 1, it is characterised in that：Step 1) in, the lithium sulfide, phosphoric sulfide, lithium silicon The mol ratio of alloy powder and sulphur is 2.5-3.0：0.5-0.75：0.05-0.10：0.01-0.05.
3. 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.
4. preparation method according to claim 1, it is characterised in that：Step 3) in, the time of heat treatment is 1-5h.
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：Ratio of grinding media to material during ball milling is 2：0.5-1.
7. the lithium sulfide system of any one of claim 1-6 methods are prepared addition Li-Si alloy, silver bromide and silver chlorate Solid electrolyte material.
CN201710077198.7A 2017-02-13 2017-02-13 A kind of lithium sulfide system solid electrolyte material for adding Li-Si alloy, silver bromide and silver chlorate and preparation method thereof Pending CN106785014A (en)

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CN102823049A (en) * 2010-03-26 2012-12-12 国立大学法人东京工业大学 Sulfide solid electrolyte material, battery, and method for producing sulfide solid 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
CN105518906A (en) * 2013-05-15 2016-04-20 量子世界公司 SOLID STATE CATHOLYTE OR ELECTROLYTE FOR BATTERY USING LiAMPBSC (M=Si, Ge, AND/OR Sn)
CN105518923A (en) * 2014-07-16 2016-04-20 三井金属矿业株式会社 Sulfide-based solid electrolyte for lithium ion batteries

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0465070A (en) * 1990-07-02 1992-03-02 Matsushita Electric Ind Co Ltd All solid voltage memory element
CN102823049A (en) * 2010-03-26 2012-12-12 国立大学法人东京工业大学 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
CN105518906A (en) * 2013-05-15 2016-04-20 量子世界公司 SOLID STATE CATHOLYTE OR ELECTROLYTE FOR BATTERY USING LiAMPBSC (M=Si, Ge, AND/OR Sn)
CN105518923A (en) * 2014-07-16 2016-04-20 三井金属矿业株式会社 Sulfide-based solid electrolyte for lithium ion batteries
CN104393338A (en) * 2014-11-21 2015-03-04 东南大学 LiBH4-silver/silver halide compound fast-ion conductor and preparation method thereof

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