CN110518281A - A kind of lithium battery lower bound resistance sulfide solid electrolyte material and preparation method - Google Patents

A kind of lithium battery lower bound resistance sulfide solid electrolyte material and preparation method Download PDF

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Publication number
CN110518281A
CN110518281A CN201910885578.2A CN201910885578A CN110518281A CN 110518281 A CN110518281 A CN 110518281A CN 201910885578 A CN201910885578 A CN 201910885578A CN 110518281 A CN110518281 A CN 110518281A
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solid electrolyte
lithium battery
preparation
sulfide
lower bound
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陈庆
李国松
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Chengdu New Keli Chemical Science Co Ltd
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Chengdu New Keli Chemical Science 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical fields of lithium battery preparation, and in particular to a kind of lithium battery lower bound resistance sulfide solid electrolyte material and preparation method.In preparation Li10SnP2S12When class solid electrolyte matrix, Al is introduced3+Replace part P5+, in order to compensate for charge, internal Li+ content increases, and improves conductivity；The Li of compound state10SnP2S12Contain crystalline state and amorphous state in solid electrolyte, Intergranular impedance is advantageously reduced, to further increase Li10SnP2S12The ionic conductivity of class solid electrolyte, using Li1.8N0.4Cl0.6In prepared Li10SnP2S12The surface coating decoration layer of solid electrolyte matrix, avoids Li10SnP2S12Class solid electrolyte directly contacts unstable caused chemical reaction with metal Li.

Description

A kind of lithium battery lower bound resistance sulfide solid electrolyte material and preparation method
Technical field
The invention belongs to the technical fields of lithium battery preparation, and in particular to a kind of lithium battery lower bound resistance sulfide solid state electrolysis Material and preparation method.
Background technique
In recent years, lithium ion battery is sufficient in occupation of lifting in fields such as electronics field, energy-storage battery, Vehicular dynamic batteries The position of weight.Lithium ion battery is high by its energy, and discharge capability is strong, memory-less effect, and energy storage efficiency height has extensive Application prospect also has been to be concerned by more and more people.It uses liquid electrolyte lithium battery mostly at present, contains liquid organic solvent Lithium ion battery, there are the security risks such as kindling, explosion.In order to thoroughly solve these problems of liquid electrolyte lithium ion, Liquid electrolyte is replaced using solid electrolyte.Solid electrolyte has high ionic conductivity, wide electrochemical window, stable boundary The advantages such as face.Solid electrolyte mainly includes oxide, sulfide, polymer and composite solid electrolyte etc..
For sulfide solid electrolyte compared with oxide electrolyte, the electronegativity of sulphur is small, smaller to the constraint of lithium ion, because The ionic conductivity of this sulfide solid electrolyte is bigger.Sulfide solid electrolyte is divided into binary sulfide and ternary vulcanization Object；Ternary sulfide solid electrolyte and GeS2、SiS2、P2S5The binary sulfides such as base electrolyte phase ratio, have its conductivity compared with High, the advantages that electrochemical stability is preferable.
The special application number 201810118912.7 of Chinese invention discloses a kind of solid-state lithium electricity of novel electrolytes complex method Pond and preparation method thereof belongs to lithium battery preparation technical field.The solid state lithium battery anode includes conductive agent, electrostrictive polymer Matter and positive electrode active materials are solved, cathode is lithium metal and its alloy, and electrolyte is inorganic solid electrolyte.The method is as follows: Polymeric matrix material is dissolved in organic solvent and lithium salts is added, then plus positive electrode active materials, conductive agent, stirs evenly, obtains Anode composite slurry；Anode composite slurry is coated on aluminium foil and in 80 DEG C of 12 h of vacuum drying, acquisition positive plate；With polymerization The homogeneous mixed solution of object electrolyte is poured and is dried repeatedly to positive plate, and the positive plate of high-compactness is obtained；It will be inorganic Solid electrolyte piece and high-compactness positive plate carry out lamination processing, and are heat-treated；Negative electrode material is placed in inorganic solid-state The other side of electrolyte sheet, is packaged battery, is assembled into solid state lithium battery.Anode composite compacted density prepared by the present invention Reach 2.3 ~ 3.5 g cm 3.
Chinese invention patent application number 201310027141.8 discloses a kind of production side of the anode of solid lithium battery Method, the production method include the following steps: step 1: providing one kind and mix the sheet of active pole piece of pressure, by the active pole Piece and sulfide are placed in vacuum sealing tube, are heat-treated 1 ~ 20 hour at 200 DEG C ~ 1000 DEG C, are then slowly cooled to room temperature, obtain Positive plate after the completion of to distillation；Step 2: the positive plate is placed on the collector for being coated with conducting resinl, is made after cold pressing is dry At anode.The invention further relates to a kind of anodes prepared by above method.The all solid lithium prepared using method of the invention Ion battery plays connecting bridge due to being filled in battery admittedly void among particles compared with traditional solid lithium battery The unbodied sulfide of beam effect increases lithium ion biography so that substantially improving battery consolidates intergranular contact area Defeated path improves the energy density and high rate performance of battery to improve conductivity and reduce the internal resistance of cell.
Chinese invention patent application number 201810286449.7 discloses a kind of preparation method of solid lithium battery, including Following steps: S1 forms clad on the surface of positive electrode powder using atomic layer deposition method；S2, by the anode of clad Material powder is sintered 2 10h at 300~1000 DEG C, forms LiXaYb solid-state electrolyte layer on positive electrode powder surface；S3, The positive electrode preparation anode of LiXaYb solid-state electrolyte layer is coated with using above-mentioned surface, and by cathode, solid electrolyte Solid lithium battery is assembled into the anode；The present invention also provides a kind of all solid lithium electricity prepared using above-mentioned preparation method Pond.Metal oxide, metal phosphate, metal fluoride or metal sulfide are coated on positive electrode using ALD by the present invention Surface, after heating and positive electrode remained on surface alkali substance reaction forms LiXaYb solid-state electrolyte layer, to reduce positive material The pH value of material and solid state battery internal resistance promote cycle performance of battery and high rate performance.
Chinese invention patent application number 201610555329.3 discloses a kind of sulfenyl electrolyte solution, wherein the sulphur Base electrolyte solution includes soluble polysulfide and organic solvent, wherein the chemical formula of the solubility polysulfide is Sy (Li2S) 100 x y z (LiX) z (P2S5) x, wherein one of X Cl, Br and I or a variety of, 15≤x≤90,0≤y≤ 80,0≤z≤60, and 10≤100 x y z≤x+10 of x；And wherein, the soluble polysulfide is in the sulfenyl electricity Mass concentration in electrolyte solution is 0.1% 40%.The present invention also provides using sulfenyl electrolyte solution preparation solid-state lithium electricity The method in pond and the solid state lithium battery of preparation.
Li10SnP2S12Belong to ternary sulfide solid electrolyte, room temperature lithium ion conductivity is higher, chemical stability compared with It is good, Li is used at present2S、P2S5And Li4SnS4For raw material, 3:1:1, quenches method by high temperature and synthesizes Li in molar ratio10SnP2S12, At 27 DEG C, Li10SnP2S12The ionic conductivity of crystal phase reaches 0.007S/cm, and total ionic conductivity is 0.004S/cm, this is Since it is with biggish Intergranular impedance.Li10SnP2S12Material is unstable for metal Li, and there are biggish Intergranular impedances, is It is limited in the main reason for field of lithium further develops.
Summary of the invention
Existing Li10SnP2S12Ternary sulfide solid electrolyte material has biggish Intergranular impedance, exists to metal Li not The defects of stablizing, the present invention propose that a kind of lithium battery lower bound hinders sulfide solid electrolyte material and preparation method.
A kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material, comprising the following steps:
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；
S2, the initial material that step S1 is obtained is heated in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide is with certain speed Rate sequentially enters two cooling ducts, and first channel outer wall slowly cools to 500~600 DEG C using recirculated cooling water, then into Enter another channel, first pass through a Surface heat-treatent device, sulfide grain passes through rapid thermal treatment, uses again after melt surface Liquid nitrogen is quenched to room temperature, finally obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained Li1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.
Further, the preparation method of above-mentioned a kind of lithium battery lower bound resistance sulfide solid electrolyte material, wherein S1 is walked Li described in rapid2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 10~30:5~10:5~10:2~5.
Further, the preparation method of above-mentioned a kind of lithium battery lower bound resistance sulfide solid electrolyte material, wherein S2 is walked The temperature range heated in high temperature furnace described in rapid is 950~1100 DEG C.
Further, the preparation method of above-mentioned a kind of lithium battery lower bound resistance sulfide solid electrolyte material, wherein S2 is walked Given pace described in rapid is 60~120m/s；It is still more preferably 80m/s.It is conveyed, is being conveyed by high pressure nitrogen Disperse in the process through high pressure draught, obtains subparticle.
Further, the preparation method of above-mentioned a kind of lithium battery lower bound resistance sulfide solid electrolyte material, wherein S2 is walked The heating temperature of Surface heat-treatent device described in rapid is 800~1000 DEG C；It is still more preferably 900 DEG C.
Li1.8N0.4Cl0.6The thickness of decorative layer is directly related to the performance of lithium-sulfur cell, in order to prepare a kind of low interface Impedance, the higher lithium battery sulfide solid electrolyte material of ionic conductivity, Li1.8N0.4Cl0.6Decorative layer thickness is preferably 10~100nm has found that the interface impedance of the lithium-sulfur cell solid electrolyte obtained at this time is low, ion by the research of inventor Conductivity is higher.
Plasma spraying is the modified technology of a kind of material surface strengthening and surface, can make matrix surface have it is wear-resisting, The performances such as anti-corrosion, high temperature oxidation resisting, electrical isolation, heat-insulated, radiation protection, anti-attrition and sealing.Plasma spraying technology is using by straight Electrically driven (operated) plasma-arc is flowed as heat source, and the materials such as ceramics, alloy, metal are heated to melting or semi-molten state, and Method to spray to the superficial layer for forming adhesion-tight by pretreated workpiece surface at a high speed.
Further, the preparation method of above-mentioned a kind of lithium battery lower bound resistance sulfide solid electrolyte material, wherein S3 is walked Plasma spraying method described in rapid sprays Li1.8N0.4Cl0.6Specifically:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 30~60r/ min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 50~70L/min, uses hydrogen as secondary gas, Secondary throughput follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 80~200mm, and spray gun speed is set as 3~ 6mm/s starts to spray to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer stirs complex phase sulphur in spraying Compound particle, so that Li1.8N0.4Cl0.6Decorative layer spraying is more uniform.
Further, the preparation method of above-mentioned a kind of lithium battery lower bound resistance sulfide solid electrolyte material, wherein described The revolving speed of powder feeder is adjusted to 50r/min;The primary air amount is 65L/min；The spray distance is selected as 110mm；It is described Spray gun speed is set as 3mm/s.Coating layer thickness is controlled by spray gun movement speed.
The present invention also provides a kind of lithium battery lower bounds that a kind of above-mentioned preparation method is prepared to hinder sulfide solid state electrolysis Material.With Li2S、P2S5And Li4SnS4For starting material, suitable aluminum phosphate is added, by ball milling, heat treatment, sulfide with Successively carry out Slow cooling, rapid thermal treatment, liquid nitrogen quenching；Obtain complex phase sulfide grain；Using plasma spraying method pair Li1.8N0.4Cl0.6It is sprayed, forms one layer of Li on complex phase sulfide grain surface1.8N0.4Cl0.6Decorative layer prepares one kind Low interface impedance, the higher lithium battery sulfide solid electrolyte material of ionic conductivity.
The present invention also provides a kind of lithium battery lower bounds that a kind of above-mentioned preparation method is prepared to hinder sulfide solid state electrolysis Material, in preparation Li10SnP2S12When class solid electrolyte matrix, Al is introduced3+Replace part P5+, internal in order to compensate for charge Li+Content increases, and improves conductivity；The Li of compound state10SnP2S12Contain crystalline state and amorphous state in solid electrolyte, is conducive to drop Low Intergranular impedance, to further increase Li10SnP2S12The ionic conductivity of class solid electrolyte.Li1.8N0.4Cl0.6It is anti-firefly One of stone-type structural behaviour preferred materials, conductivity at room temperature is higher, and decomposition voltage is high, and stablizes to lithium metal.It adopts Use Li1.8N0.4Cl0.6In prepared Li10SnP2S12The surface coating decoration layer of solid electrolyte matrix, avoids Li10SnP2S12Class solid electrolyte directly contacts unstable caused chemical reaction with metal Li.Present invention optimizes Li10SnP2S12The biggish Intergranular impedance of ternary sulfide solid electrolyte material, it is unstable to metal Li the defects of, prepare Have many advantages, such as that larger ionic conductivity, chemical stability are preferable, a kind of preferable lithium battery lower bound of performance is recycled and hinders sulphur Compound solid electrolyte material.
Detailed description of the invention
Fig. 1: the pictorial diagram after electrolyte sheet 500 times circulations of embodiment 1.
Fig. 2: the pictorial diagram after electrolyte sheet 500 times circulations of comparative example 1.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material, comprising the following steps:
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；The Li2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 30:10:10:3；
S2, the initial material that step S1 is obtained is heated to 1000 DEG C in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide with Rate is that 80m/s sequentially enters two cooling ducts, and first channel outer wall slowly cools to 550 DEG C using recirculated cooling water, Another channel is entered back into, a Surface heat-treatent device is first passed through, sulfide grain passes through rapid thermal treatment, and temperature is 900 DEG C, It is quenched using liquid nitrogen to room temperature after melt surface, obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained With a thickness of the Li of 20nm1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.It is described Plasma spraying method sprays Li1.8N0.4Cl0.6The step of are as follows:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 40r/min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 60L/min, uses hydrogen as time gas, secondary gas Flow follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 160mm, and spray gun speed is set as 4mm/s, Start to spray to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer.
Embodiment 2
A kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material, comprising the following steps:
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；The Li2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 12:5:5:3；
S2, the initial material that step S1 is obtained is heated to 950 DEG C in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide with Rate is that 70m/s sequentially enters two cooling ducts, and first channel outer wall slowly cools to 500 DEG C using recirculated cooling water, Another channel is entered back into, a Surface heat-treatent device is first passed through, sulfide grain passes through rapid thermal treatment, and temperature is 900 DEG C, It is quenched again using liquid nitrogen to room temperature after melt surface, obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained With a thickness of the Li of 40nm1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.It is described Plasma spraying method sprays Li1.8N0.4Cl0.6The step of are as follows:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 30r/min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 60L/min, uses hydrogen as time gas, secondary gas Flow follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 90mm, and spray gun speed is set as 5mm/s, opens Beginning sprays to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer.
Embodiment 3
A kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material, comprising the following steps:
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；The Li2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 30:10:10:5；
S2, the initial material that step S1 is obtained is heated to 1000 DEG C in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide with Rate is that 100m/s sequentially enters two cooling ducts, and first channel outer wall slowly cools to 600 DEG C using recirculated cooling water, Another channel is entered back into, a Surface heat-treatent device is first passed through, sulfide grain passes through rapid thermal treatment, and temperature is 900 DEG C, It is quenched again using liquid nitrogen to room temperature after melt surface, obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained With a thickness of the Li of 60nm1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.It is described Plasma spraying method sprays Li1.8N0.4Cl0.6The step of are as follows:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 40r/min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 70L/min, uses hydrogen as time gas, secondary gas Flow follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 200mm, and spray gun speed is set as 6mm/s, Start to spray to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer.
Embodiment 4
A kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material, comprising the following steps:
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；The Li2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 15:5:5:3；
S2, the initial material that step S1 is obtained is heated to 1100 DEG C in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide with Rate is that 90m/s sequentially enters two cooling ducts, and first channel outer wall slowly cools to 520 DEG C using recirculated cooling water, Another channel is entered back into, a Surface heat-treatent device is first passed through, sulfide grain passes through rapid thermal treatment, and temperature is 900 DEG C, It is quenched again using liquid nitrogen to room temperature after melt surface, obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained With a thickness of the Li of 80nm1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.It is described Plasma spraying method sprays Li1.8N0.4Cl0.6The step of are as follows:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 50r/min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 75L/min, uses hydrogen as time gas, secondary gas Flow follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 160mm, and spray gun speed is set as 6mm/s, Start to spray to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer.
Embodiment 5
A kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material, comprising the following steps:
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；The Li2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 24:8:8:4；
S2, the initial material that step S1 is obtained is heated to 950 DEG C in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide with Rate is that 80m/s sequentially enters two cooling ducts, and first channel outer wall slowly cools to 580 DEG C using recirculated cooling water, Another channel is entered back into, a Surface heat-treatent device is first passed through, sulfide grain passes through rapid thermal treatment, and temperature is 900 DEG C, It is quenched again using liquid nitrogen to room temperature after melt surface, obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained With a thickness of the Li of 100nm1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.Institute State plasma spraying method injection Li1.8N0.4Cl0.6The step of are as follows:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 45r/min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 65L/min, uses hydrogen as time gas, secondary gas Flow follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 180mm, and spray gun speed is set as 6mm/s, Start to spray to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer.
Comparative example 1
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；The Li2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 30:10:10:3；
S2, the initial material that step S1 is obtained is heated to 1000 DEG C in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide with Rate is that 80m/s sequentially enters two cooling ducts, and first channel outer wall slowly cools to 550 DEG C using recirculated cooling water, Another channel is entered back into, a Surface heat-treatent device is first passed through, sulfide grain passes through rapid thermal treatment, and temperature is 900 DEG C, It is quenched using liquid nitrogen to room temperature after melt surface, obtains complex phase sulfide grain.
Comparative example 1 is not in complex phase sulfide grain surface modification Li1.8N0.4Cl0.6Decorative layer, the ion of solid electrolyte Conductivity is promoted unobvious；And it is unstable to lithium metal, there is biggish Intergranular impedance.
Comparative example 2
S1, with Li2S、P2S5And Li4SnS4For raw material, it is uniformly mixed in applying argon gas ball mill, obtains initial material；The Li2S、 P2S5、Li4SnS4Molar ratio be 30:10:10；
S2, the initial material that step S1 is obtained is heated to 1000 DEG C in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide with Rate is that 80m/s sequentially enters two cooling ducts, and first channel outer wall slowly cools to 550 DEG C using recirculated cooling water, Another channel is entered back into, a Surface heat-treatent device is first passed through, sulfide grain passes through rapid thermal treatment, and temperature is 900 DEG C, It is quenched using liquid nitrogen to room temperature after melt surface, obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained With a thickness of the Li of 20nm1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.It is described Plasma spraying method sprays Li1.8N0.4Cl0.6The step of are as follows:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 40r/min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 60L/min, uses hydrogen as time gas, secondary gas Flow follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 160mm, and spray gun speed is set as 4mm/s, Start to spray to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer.
Comparative example 2 is not in preparation Li10SnP2S12Al is introduced when class solid electrolyte matrix3+, improve finite conductivity.
Performance test:
Ionic conductivity: by the obtained solid electrolyte of embodiment 1-5, comparative example 1-2 and polyethylene glycol oxide with mass ratio 100:5 It is uniformly mixed, is compressed to the thin flake electrolyte of 0.5mm thickness, apply silver paste on the two sides of solid electrolyte sheet, tested after drying AC impedance, measures ionic conductivity, and test result is shown in Table 1.
Table 1:
Test item Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
Ionic conductivity (S/cm) 5.2×10-3 6.1×10-3 6.8×10-3 5.2×10-3 4.6×10-3 8.5×10-4 1.6×10-4
Stability test of the electrolyte to lithium: the solid electrolyte and polyethylene glycol oxide that embodiment 1, comparative example 1 are obtained are with matter Amount than 100:5 be uniformly mixed, be compressed to the superthin section electrolyte of 0.2mm thickness, then with cobalt acid lithium base positive plate, lithium cathode sheet Composition test battery, after under equal conditions 0.1C is recycled 500 times, there is serious Li dendrite in the electrolyte sheet of comparative example 1, and (breakdown is similar to penetrate) electrolyte lamella.Attached drawing 1 is the electrolyte sheet of embodiment 1, without obvious punch-through；Attached drawing 2 is There is apparent breakdown in the electrolyte sheet of comparative example 1.By comparative analysis, Li is utilized1.8N0.4Cl0.6The electrolyte of moditied processing Its decomposition voltage is high, and stablizes to lithium metal, avoids Li10SnP2S12Class solid electrolyte directly contacts instead with metal Li It answers, decorative layer inhibits the interfacial reaction between lithium metal and sulfide electrolyte.

Claims (10)

1. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material, which comprises the following steps:
S1, with Li2S、P2S5And Li4SnS4For raw material, suitable aluminum phosphate is added, is uniformly mixed, obtains in applying argon gas ball mill To initial material；
S2, the initial material that step S1 is obtained is heated in the closed high temperature furnace of applying argon gas, obtains sulfide, sulfide is with certain speed Rate sequentially enters two cooling ducts, and first channel outer wall slowly cools to 500~600 DEG C using recirculated cooling water, then into Enter another channel, first pass through a Surface heat-treatent device, sulfide grain passes through rapid thermal treatment, uses again after melt surface Liquid nitrogen is quenched to room temperature, finally obtains complex phase sulfide grain；
S3, Li is sprayed using plasma spraying method1.8N0.4Cl0.6, formed in the surface for the complex phase sulfide grain that step S2 is obtained Li1.8N0.4Cl0.6A kind of lithium battery dedicated vulcanization object solid electrolyte material is prepared in decorative layer.
2. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 1, feature It is, Li described in S1 step2S、P2S5、Li4SnS4, aluminum phosphate molar ratio be 10~30:5~10:5~10:2~5.
3. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 1, feature It is, the temperature range heated in high temperature furnace described in S2 step is 950~1100 DEG C.
4. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 1, feature It is, the pressure of high pressure gas described in S2 step is 30~40MPa.
5. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 1, feature It is, given pace described in S2 step is 60~120m/s.
6. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 1, feature It is, the heating temperature of Surface heat-treatent device described in S2 step is 800~1000 DEG C.
7. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 1, feature It is, Li described in S3 step1.8N0.4Cl0.6Decorative layer with a thickness of 10~100nm.
8. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 1, feature It is, plasma spraying method described in S3 step sprays Li1.8N0.4Cl0.6Specifically:
I, by Li1.8N0.4Cl0.6It is fitted into the powder feeder of plasma spraying equipment, the revolving speed of powder feeder is adjusted to 30~60r/ min；
II, Plasma Spraying Process Using uses argon gas as main gas, and primary air amount is 50~70L/min, uses hydrogen as secondary gas, Secondary throughput follows voltage, and carrier gas uses compressed air, carrier gas flux 4L/min；
III, electric current is set as 650A, and voltage is set as 65V, and spray distance is selected as 80~200mm, and spray gun speed is set as 3~ 6mm/s starts to spray to form Li on the surface of complex phase sulfide grain1.8N0.4Cl0.6Decorative layer.
9. a kind of preparation method of lithium battery lower bound resistance sulfide solid electrolyte material according to claim 8, feature It is, the revolving speed of the powder feeder is adjusted to 50r/min；The primary air amount is 65L/min；The spray distance is selected as 110mm；The spray gun speed is set as 3mm/s.
10. a kind of lithium battery lower bound resistance sulfide solid-state that any one preparation method is prepared according to claim 1~9 Electrolyte.
CN201910885578.2A 2019-09-19 2019-09-19 A kind of lithium battery lower bound resistance sulfide solid electrolyte material and preparation method Withdrawn CN110518281A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111463479A (en) * 2020-04-10 2020-07-28 上海电气集团股份有限公司 Solid electrolyte, composite solid electrolyte, lithium ion battery and preparation method and application thereof
CN112768761A (en) * 2021-02-25 2021-05-07 江汉大学 Sulfide solid electrolyte and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111463479A (en) * 2020-04-10 2020-07-28 上海电气集团股份有限公司 Solid electrolyte, composite solid electrolyte, lithium ion battery and preparation method and application thereof
CN111463479B (en) * 2020-04-10 2022-11-22 上海电气集团股份有限公司 Solid electrolyte, composite solid electrolyte, lithium ion battery, and preparation method and application thereof
CN112768761A (en) * 2021-02-25 2021-05-07 江汉大学 Sulfide solid electrolyte and preparation method and application thereof
CN112768761B (en) * 2021-02-25 2022-06-07 江汉大学 Sulfide solid electrolyte and preparation method and application thereof

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Application publication date: 20191129