CN107069080A - A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof - Google Patents
A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof Download PDFInfo
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- CN107069080A CN107069080A CN201710077404.4A CN201710077404A CN107069080A CN 107069080 A CN107069080 A CN 107069080A CN 201710077404 A CN201710077404 A CN 201710077404A CN 107069080 A CN107069080 A CN 107069080A
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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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof.Described preparation method comprises the following steps：1) under the conditions of atmosphere protection, by 2.5 4.0：0.5‑1.0：0.02‑0.1：0.01 0.05 mol ratio weighs lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and sulphur, is well mixed, obtains lithium sulphur phosphor tin mixture；2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphor tin mixture and the silver chlorate equivalent to its quality 1 5% is taken, ball milling in ball grinder is placed in, obtain the amorphous li sulphur phosphor tin mixture of chloride containing silver；3) the amorphous li sulphur phosphor tin mixture of gained chloride containing silver is sealed under the conditions of atmosphere protection, be heat-treated after being warming up to 80 150 DEG C under vacuum condition, produce.The present invention is as adding lithium-tin alloy and silver chlorate simultaneously with the lithium ion conductivity of solid electrolyte material obtained by being lifted.
Description
Technical field
The present invention relates to lithium sulfide system solid electrolyte material, and in particular to a kind of sulphur of addition lithium-tin alloy and silver chlorate
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 of lithium ion battery but the lithium ion containing organic electrolyte have been greatly improved in terms of material modification and battery structure
Battery safety problem in use is not solved fundamentally.
Flammable organic electrolyte solution is replaced to be to solve lithium ion battery to make using solid lithium-ion electrolyte material
The best approach of safety problem in.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 due to without
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, improves 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 after being heat-treated through 200 degree, thus, amorphous state sulphur
Changing lithium system solid electrolyte progressively turns into the focus material that all-solid lithium battery is researched and developed.
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 are smaller and easily migrate；2. the transportable lithium ion density of lithium ion solid electrolyte is as high as possible, i.e.,
Largely to exist to the contributive lithium ion of lithium ion conduction；3. diffusion of the lithium ion in solid electrolyte is empty by atom
Structural relaxation and fault of construction and its other party present in matrix in the quick diffusion in position, amorphous state or quasi- crystalline solid electrolyte
A large amount of atom vacancies that method is imported, will promote lithium ion quickly to be 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 ionic conduction can be improved by adding other compositions in lithium sulfide system solid electrolyte material
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, be respectively：(A)Li2A/I is AlI in S+A/I, formula3、ZnI2、ZrI4Or LaI3, 0.5≤x≤1.5；(B)
yLi2Y+z=9 in S-mA/I-zB/S, 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)yLi2Y+z=9 in S-mA/I-zB/S-nLiI, 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 made from technical scheme is amorphous state, although the invention can be improved Ion transfer ability,
The raising of resulting materials ionic conductance is unsatisfactory, with 6Li2S-0.5AlI3-3SiS2(y=6, m=exemplified 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 sulphur 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 is mixed, and 450 are warming up at a slow speed
DEG C insulation 24 hours, then grind into powder after quenching to room temperature is warming up to after 500-750 DEG C of reaction 10-14 hours.The invention institute
The raising for obtaining the ionic conductance of solid electrolyte is also undesirable, and its room temperature total conductivity is same 10-6S/cm.The applicant point
Analysis thinks that (1) additive (such as iodide or sulfide) is six sides or the rhomboidal crystal of stabilization in foregoing invention patent, is not had
Have and more atom vacancies are imported in system, it is impossible to provide more diffusion admittance for the diffusion of lithium ion；(2) additive contains
Amount it is too high, reduce the ratio in solid electrolyte dispensing as the lithium sulfide of lithium ion carrier, directly reduce to lithium from
The density of the contributive transportable lithium ion of son conduction；(3) additive of high content does not increase in solid electrolyte not only
Lithium ion diffusion admittance, hinders the diffusion of lithium ion on the contrary.Therefore, the composition added in foregoing invention patent does not play bright
It is aobvious to improve the effect of sulfide-based solid electrolyte ion conductive performance.
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 CN1930726A, CN101887965A patent of invention) in succession, 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
The negative material of the empty battery of sub- battery, lithium-ion capacitor, lithium-sulfur cell, lithium to receive the insertion of lithium ion in charging process,
It is not directed to by while adding lithium-tin alloy to silver chlorate to improve the related of transportable lithium ion density in solid electrolyte
Research.
The content of the invention
It can form what is largely spread available for lithium ion the technical problem to be solved in the present invention is to provide a kind of one side
Atom vacancy, on the other hand can lift transportable lithium concentration in lithium sulfide system solid electrolyte, and then effectively lifted again
The addition lithium-tin alloy and the lithium sulfide system solid electrolyte material of silver chlorate 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 and silver chlorate of the present invention, bag
Include following steps：
1) under the conditions of atmosphere protection, by 2.5-4.0：0.5-1.0：0.02-0.1：0.01-0.05 mol ratio weighs sulphur
Change lithium, phosphoric sulfide, lithium-tin alloy powder and sulphur, be well mixed, obtain lithium sulphur phosphor tin mixture；
2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphor tin mixture and the chlorine equivalent to its quality 1-5% are taken
Change silver, be placed in ball milling in ball grinder, obtain the amorphous li sulphur phosphor tin mixture of chloride containing silver；
3) gained chloride containing silver amorphous li sulphur phosphor tin mixture sealed under the conditions of atmosphere protection, after vacuum bar
80-150 DEG C is warming up under part to be heat-treated, that is, obtains adding the lithium sulfide system solid electrolytic material of lithium-tin alloy and silver chlorate
Material.
The step 1 of the above method) in, the lithium sulfide, phosphoric sulfide, the mol ratio of lithium-tin alloy and sulphur are preferably 2.5-
3.0：0.5-0.75：0.05-0.10：0.01-0.05.Lithium-tin alloy (the Li22Sn5) it is preferred to use -300 mesh powders, sulphur
Sulphur is preferred to use the simple substance sulphur powder of -200 mesh.
The step 1 of the above method) in, described atmosphere protection is typically such as argon gas, nitrogen under the protection of inert gas
Etc. conventional use of inert gas.It is typically to be carried out in the glove box protected with argon gas during concrete operations.
The step 1 of the above method) in, it is well mixed by the way of existing conventional ball mill each composition, during ball milling
Dry type ball milling or medium ball milling can be used, zirconium dioxide mill ball is used during ball milling, ball material mass ratio is preferably 2：0.5-1
(mass ratio).When using conventional rolling ball milling, make lithium sulfide and phosphoric sulfide is well mixed usually requires 6-10h, when using
During planetary milling, make lithium-tin alloy, sulphur, lithium sulfide and phosphoric sulfide are well mixed to usually require 2-5h.
The step 2 of the above method) in, described atmosphere protection is typically such as argon gas, nitrogen under the protection of inert gas
Etc. conventional use of inert gas.It is typically to be carried out in the glove box protected with argon gas during concrete operations.
The step 2 of above-mentioned preparation method) in, described silver chlorate is preferred to use 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 (mass ratio), more preferably 2：0.7 (mass ratio).This step
In, the Ball-milling Time usually 30-48h of the amorphous li sulphur phosphor tin mixture of chloride containing silver is obtained, is contained to be more quickly formed
The amorphous li sulphur phosphor tin mixture of silver chlorate, ball is placed in after preferably silver chlorate and lithium sulphur phosphor tin mixture stir again
Ball milling in grinding jar, now, Ball-milling Time control are completely amorphousization and chlorine that lithium sulphur phosphor tin mixture can be achieved in 30-40h
Change silver to be sufficiently mixed with lithium sulphur phosphor tin mixture.
The step 3 of the above method) in, described atmosphere protection is typically such as argon gas, nitrogen under the protection of inert gas
Etc. conventional use of inert gas.Specific seal operation, is typically to be carried out in the glove box protected with argon gas.
The step 3 of the above method) in, heat treatment operation is carried out to promote the part silver ion in silver chlorate and the sulphur of surrounding
Nanoscale silver sulfide (original position is separated out) is combined to form, promotes formation in the cubic structure based on chlorine largely to can be used as in lithium ion
The atom vacancy of diffusion admittance, while forming part lithium chloride (original position is separated out)；At the same time, amorphous li in heat treatment process
A part of lithium of tin and the reaction of Salmon-Saxl of surrounding are transformed into lithium sulfide and tinbase nanocrystal or nano-cluster containing lithium, are newly formed
Lithium sulfide improves the concentration of the transportable lithium ion in solid electrolytic plastidome, and the tinbase nanocrystal or nanometer newly formed
Cluster is imperfect crystal, and the lithium ion also possessed in its structure in substantial amounts of atom vacancy, solid electrolytic plastidome is being moved to
During the position of tinbase nanocrystal or nano-cluster and amorphous li tin containing lithium, there will be room to spread and lithium ion simultaneously
The advantage of diffusion is exchanged, so as to prepare the multicomponent mixture solid electrolyte with 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 80-120 DEG C as, under this temperature conditions, the time of heat treatment is preferably 1-3h.
Present invention additionally comprises the addition lithium-tin alloy prepared by the above method and the lithium sulfide system solid electricity of silver chlorate
Solve material.
Compared with prior art, the method have the characteristics that：
1st, the present invention adds lithium-tin alloy, sulphur and the chlorination galactic longitude of special ratios using lithium sulfide and phosphoric sulfide as matrix
After high-energy ball milling, while amorphous mixture of sulfides is formed, the third composition lithium-tin alloy, sulphur and silver chlorate is reached
It is uniformly distributed in the effect in matrix；On the one hand thermally treated technique promote part silver ion in chlorion stable cubic again afterwards
While structure, nanoscale silver sulfide is combined to form with the reaction of Salmon-Saxl of surrounding, the nanoscale silver sulfide formed can play stabilization
The effect of solid electrolyte matrix；On the other hand the atom of a large amount of suitable lithium ion diffusions is formed in the cubic structure based on chlorine
Room, so as to play the effect of effectively lifting lithium sulfide system solid electrolyte ion conductivity, shape is gone back while room is formed
Into partial oxidation lithium.At the same time, a part of lithium of amorphous li tin and the reaction of Salmon-Saxl of surrounding are transformed into sulphur in heat treatment process
Change lithium and tinbase nanocrystal or nano-cluster containing lithium, the lithium sulfide newly formed improves moving in solid electrolytic plastidome
The concentration of lithium ion is moved, and the tinbase nanocrystal or nano-cluster that are newly formed are imperfect crystals, also possess a large amount of in its structure
Atom vacancy, lithium ion in solid electrolytic plastidome moving to tinbase nanocrystal or nano-cluster containing lithium and non-
During the position of crystalline state lithium tin, will have the advantages that room diffusion and lithium ion exchanged spread simultaneously, so as to prepare high lithium
Ion concentration, the multicomponent mixture solid electrolyte powder of high atom vacancy.
The product nano silver sulfide and lithium chloride 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 sulfide-based solid electrolyte lithium-ion-conducting；What is formed receives
Rice vulcanization Argent grain, can obtain dispersion-strengthened effect, and silver sulfide nanometer particles particle 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.
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 sulphur etc., it is that chemistry is pure
Reagent, purity is 99.9%.
Embodiment 1
1) high-energy ball milling process is mixed：
In low moisture (≤1ppm), the glove box protected with argon gas atmosphere of low oxygen content (≤1ppm), it will vulcanize
Lithium, phosphoric sulfide, lithium-tin alloy powder and Cosan are 4 in molar ratio：1：0.1：0.05 ratio dispensing, stirring mixing, it is and straight
The zirconia balls and the ball material mass ratio of compound that footpath 3-10mm zirconia balls are enclosed in ball grinder, tank after coordinating are 2:
0.7；Ball grinder after sealing, which is mounted in planetary high-energy ball mill, uses dry type mixing ball milling, and Ball-milling Time is 5 hours, is obtained
Lithium sulphur phosphor tin mixture；
2) secondary high-energy ball milling process：
In the low moisture (≤1ppm), low oxygen content (≤1ppm) for having safety light (such as feux rouges) there is argon gas atmosphere to protect
In the glove box of shield, the chlorination silver powder (granularity is 300 mesh) and lithium of above-mentioned lithium sulphur phosphor tin mixture quality 2.5% will be equivalent to
Sulphur phosphor tin mixture stirring mixing by hand, gained mixed material presses 2 again:0.7 ball material mass ratio, the two of fit diameter 3-10mm
Ball grinder is enclosed after zirconia ball, is sealed, and the ball grinder after sealing is fitted into progress height in planetary milling ball mill
Energy dry type ball milling, Ball-milling Time is 36 hours, obtains the amorphous li sulphur phosphor tin mixture of chloride containing silver；
3) heat treatment step：
By gained chloride containing silver amorphous li sulphur phosphor tin mixture, low moisture (≤1ppm), low oxygen content (≤
1ppm) have argon gas atmosphere protect glove box in seal, after heated under vacuum to 150 DEG C be heat-treated 2 hours,
Obtain the lithium sulfide system solid electrolyte material of addition lithium-tin alloy of the present invention and silver chlorate.
Solid electrolyte powder made from the present embodiment is pressed into after standard sample of photo, CHI660 electrochemical operations are utilized
Stand, using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of the present embodiment is 2.2 × 10-4S/cm。
Comparative example
By lithium sulfide in low moisture (≤1ppm), the glove box protected with argon gas atmosphere of low oxygen content (≤1ppm)
It is 4 in molar ratio with phosphoric sulfide：1 ratio dispensing, stirring mixing, are enclosed in ball grinder, tank after coordinating with zirconia balls
The ball material mass ratio of zirconia balls and compound is 2:0.7；Ball grinder after sealing, which is mounted in planetary high-energy ball mill, to be adopted
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.
Solid electrolyte powder made from this comparative example is pressed into after standard sample of photo, CHI660 electrochemical operations are utilized
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
Embodiment 1 is repeated, unlike：
Step 1) in, lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and Cosan are 2.5 in molar ratio：0.5：0.02：
0.01 ratio dispensing mixing, Ball-milling Time is 3 hours；
Step 2) in, the granularity of chlorination silver powder is 250-300 mesh；
Step 3) in, heat treatment is carried out under the conditions of 80 DEG C, and heat treatment time is 5 hours.
Solid electrolyte powder made from the present embodiment is pressed into after standard sample of photo, CHI660 electrochemical operations are utilized
Stand, using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of the present embodiment is 3.7 × 10-4S/cm。
Embodiment 3
Embodiment 1 is repeated, unlike：
Step 1) in, lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and Cosan are 3.0 in molar ratio：0.7：0.05：
The ball material mass ratio of 0.02 ratio dispensing mixing, zirconia balls and compound is 2：0.5, Ball-milling Time is 2 hours；
Step 2) in, the granularity of chlorination silver powder is 200 mesh, and the addition of chlorination silver powder is mixed equivalent to lithium sulphur phosphor tin
The 5% of amount of substance；
Step 3) in, heat treatment is carried out under the conditions of 100 DEG C, and heat treatment time is 1 hour.
Solid electrolyte powder made from the present embodiment is pressed into after standard sample of photo, CHI660 electrochemical operations are utilized
Stand, using AC impedence method, at 25 DEG C of room temperature, the ionic conductance for measuring the print of the present embodiment is 4.4 × 10-4S/cm。
Embodiment 4
Embodiment 1 is repeated, unlike：
Step 1) in, lithium sulfide, phosphoric sulfide, lithium-tin alloy powder and Cosan are 3.1 in molar ratio：0.7：0.08：
0.03 ratio dispensing mixing；
Step 2) in, the granularity of chlorination silver powder is 200-260 mesh, and the addition of chlorination silver powder is equivalent to lithium sulphur phosphor tin
The 1% of mixture quality, Ball-milling Time is 40 hours；
Step 3) in, heat treatment is carried out under the conditions of 120 DEG C, and heat treatment time is 3 hours.
Solid electrolyte powder is pressed into after standard sample of photo made from 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 4.6 × 10-4S/cm。
Claims (7)
1. a kind of preparation method for the lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate, including following step
Suddenly：
1) under the conditions of atmosphere protection, by 2.5-4.0：0.5-1.0：0.02-0.1：0.01-0.05 mol ratio weighs vulcanization
Lithium, phosphoric sulfide, lithium-tin alloy powder and sulphur, are well mixed, obtain lithium sulphur phosphor tin mixture；
2) under the conditions of atmosphere protection and safe feux rouges, lithium sulphur phosphor tin mixture and the silver chlorate equivalent to its quality 1-5% are taken,
Ball milling in ball grinder is placed in, the amorphous li sulphur phosphor tin mixture of chloride containing silver is obtained；
3) gained chloride containing silver amorphous li sulphur phosphor tin mixture sealed under the conditions of atmosphere protection, after under vacuum condition
It is warming up to 80-150 DEG C to be heat-treated, that is, obtains adding the lithium sulfide system solid electrolyte material of lithium-tin alloy and silver chlorate.
2. preparation method according to claim 1, it is characterised in that：Step 3) in, the time of heat treatment is to 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 80-120 DEG C.
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. addition lithium-tin alloy and the lithium sulfide system solid electrolytic of silver chlorate that any one of claim 1-6 method is prepared
Material.
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| CN105140560A (en) * | 2015-09-15 | 2015-12-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery |
| CN105609870A (en) * | 2015-12-23 | 2016-05-25 | 山东玉皇新能源科技有限公司 | Preparation method of amorphous sulfide solid electrolyte |
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