CN110165293A - A kind of preparation method of sulfide solid electrolyte - Google Patents
A kind of preparation method of sulfide solid electrolyte Download PDFInfo
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- CN110165293A CN110165293A CN201910454053.3A CN201910454053A CN110165293A CN 110165293 A CN110165293 A CN 110165293A CN 201910454053 A CN201910454053 A CN 201910454053A CN 110165293 A CN110165293 A CN 110165293A
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- 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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Abstract
The invention discloses a kind of preparation methods of sulfide solid electrolyte, comprising: sulfide solid mixed raw material, organic solvent, mill ball are carried out the processing of roller mill by step 1, and filtering obtains slurry；Slurry is stood, layering, removes supernatant by step 2, obtains sediment, sealing；Step 3 carries out vacuum distillation processing to sediment, dry, obtains presoma powder；Presoma powder is heat-treated by step 4, cooling, and grinding obtains sulfide solid electrolyte；In step 1, purity >=99% of sulfide solid mixed raw material；The water content of organic solvent is lower than 0.01wt%；The diameter of mill ball is less than 50mm；Step 1: Step 2: Step 3: the water content of environment locating for step 4 is less than 100ppm.The sulfide solid electrolyte that this method prepares not only have with the consistent crystal structure of standard spectrogram and lithium ion conductivity with higher, and this method also contributes to the production efficiency of sulfide solid electrolyte.
Description
Technical field
The present invention relates to technical field of lithium batteries, more specifically, it relates to a kind of preparation of sulfide solid electrolyte
Method.
Background technique
Electrochemical energy storage technology clean reproducible energy intermittent for wind energy, solar energy etc. using most important, together
When be also zero-emission pure electric automobile core.Lithium ion battery is considered as because of the features such as its energy density is high, long service life
One of most competitive electrochemical energy storage technology.However, existing lithium ion battery uses inflammable liquid organic electrolyte, deposit
In security risks such as leakage, burn into burning or even explosions.Currently, with the hair of the technologies such as power battery, smart grid energy storage
Exhibition, the security performance of lithium ion battery require to be further improved.Replace tradition with the inorganic solid electrolyte of good security
The solid lithium battery of liquid organic electrolyte is the effective way for solving lithium ion battery safety problem.
In addition to this, inorganic solid electrolyte can replace the liquid organic electrolyte and diaphragm in lithium battery completely, break through
The limitation of solid lithium battery shape is played the role of being further simplified its structure, improves the energy density of solid lithium battery,
Facilitate its production and uses；Meanwhile the price of inorganic solid electrolyte is lower than liquid organic electrolyte, it is all solid state so as to reduce
Lithium battery production cost makes have great application potential.And use solid electrolyte to replace traditional liquid organic electrolyte and
The all-solid lithium-ion battery prepared not only is expected to fundamentally solve the safety issue of battery, moreover it is possible to further be promoted
The energy density and cycle life of lithium battery meet the direction of the following high security lithium ion battery with high energy density development.
And it to realize the commercialization key of all-solid lithium-ion battery and seek to find a kind of while there is low cost, conductance
The inorganic solid electrolyte for the advantages that rate is high, chemical stability is good, voltage window mouth width.KANNO seminars in 2016 and Toyota and
High energy acceleration research institution R & D Cooperation goes out a kind of new sulfide compounds ceramic electrolyte Li9.54Si1.74P1.44S11.7Cl0.3, 27 DEG C
Lower ionic conductivity has reached surprising 2.5 × 10-2S/cm, higher than the conductivity of liquid organic electrolyte.Therefore, sulfide electricity
Solve material due to its higher conductivity and solid use state, in various electrolytes take off grain husk and
Out, extensive concern is caused.
However, being easy since the aerial stability of the raw material of sulfide electrolyte precursor and its preparation is poor
With water (H micro in air2O it) reacts, influences sulfide electrolyte electrochemical performance, and also release hydrogen sulfide (H2S)
Gas, it is therefore, most of that the operation of the raw material of sulfide electrolyte precursor and its preparation is carried out all in glove box, hold
It easily leads to inconvenient.
There are mainly three types of preparation methods for traditional sulfide solid electrolyte: ball-milling method, liquid phase method and melt pulling method.
Wherein, ball-milling method, i.e., it is raw material mixed powder is broken, sulfide solid electrolyte presoma is obtained, if high-energy ball milling is also
Glassy state sulfide solid electrolyte can be obtained by raw material is decrystallized.Ball-milling method is easy to operate, highly-safe, easy to control, but by
In raw material be all the lesser sulfide (Li of relative hardness2S、P2S5Deng), in mechanical milling process, it is easy to appear showing for viscous wall agglomeration
As, it needs to scrape off the agglomeration material adhered on inner wall and levigate either manually or by glove box after for a period of time in ball milling, from
Ball milling again is taken out in glove box, repeatedly, whole process is time-consuming and laborious.
Liquid phase method adds the raw material into organic solvent, mixture is stirred at a certain temperature, by being centrifuged or revolving
Steaming method therefrom isolates the solute after reaction, dries at a certain temperature, obtains sulfide solid electrolyte presoma.The method
Operating temperature is low, morphology controllable, and easy to operate, can not be by stirring but if there is the biggish raw material of hardness (such as LiCl) in raw material
It mixes and crushes raw material, influence the homogeneity of sulfide solid electrolyte presoma；In addition, this method is only applicable to a few sulphur
The preparation of compound electrolyte.
Melt quenching method, i.e., by raw material, high-temperature process is melted after evenly mixing, obtains glassy state sulphur after melted material quenching
Compound solid electrolyte precursor.The method equipment investment is low and requires simply, but operating temperature is high, risk is big, energy consumption is high,
Yield is lower.
Since above-mentioned three kinds of existing preparation methods have time-consuming, laborious, power-consuming, risk is big, reacts uneven etc. to lack
Point, high expensive needed for leading to sulfide solid electrolyte preparation, significantly limits the production of sulfide solid electrolyte,
To also limit application of the sulfide solid electrolyte in solid lithium battery.Therefore, a kind of to have raising sulfide solid
The preparation method of body electrolyte production efficiency has wide commercial promise.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of preparation of sulfide solid electrolyte
Method, the sulfide solid electrolyte prepared not only have with the consistent crystal structure of standard spectrogram and with excellent
Electric conductivity also contributes to the production efficiency of sulfide solid electrolyte.
To achieve the above object, the present invention provides the following technical scheme that
A kind of preparation method of sulfide solid electrolyte, includes the following steps:
Sulfide solid mixed raw material, organic solvent, mill ball are carried out the processing of roller mill, mistake in a sealed meter environment by step 1
Filter obtains slurry；
The slurry obtained in step 1 is stood, layering, removes supernatant by step 2, obtains sediment, sealing；
Step 3 carries out vacuum distillation processing to the sediment obtained in step 2, dry, obtains presoma powder；
Step 4 will be heat-treated the presoma powder obtained in step 3 in dry environment, be cooled to room temperature, grind
Mill obtains sulfide solid electrolyte；
In the step 1, purity >=99% of sulfide solid mixed raw material；The water content of the organic solvent is lower than
0.01wt%；The diameter of the mill ball is less than 50mm；
The mill ball and the mass ratio of sulfide solid mixed raw material be less than 100:1, the sulfide solid mixed raw material,
The solid content in system that organic solvent, mill ball are formed is less than 100%；
It is described Step 1: Step 2: Step 3: the water content of environment locating for step 4 be less than 100ppm.
By using above-mentioned technical proposal, using the sulfide solid mixed raw material of very high purity and organic molten in the present invention
Agent reduces influence of the introduced contaminants to preparation process from the root, helps to improve the sulfide solid electrolyte finally obtained
Purity and quality.
Sulfide solid mixed raw material is mainly made of following several situations: the raw material in binary sulfide carries out phase interworking
It closes；It can be doped in binary sulfide and form mutually matched raw material with binary sulfide；Raw material in ternary sulfide into
Row cooperates；It can be doped in ternary sulfide and form mutually matched raw material with ternary sulfide.Sulfide solid is mixed
Conjunction raw material, which is described in detail and illustrates in embodiment part, finally can get the ideal sulfide solid of conductivity
Electrolyte.Such as: Li2S and P2S5It cooperates, finally can get Li3PS4、Li7P3S11Sulfides solid electrolyte；
Li2S、P2S5, LiCl be used cooperatively together, final available 95 (75Li of sulfide solid electrolyte2S·25P2S5)·5LiCl；
Li2S、P2S5、GeS2It is used cooperatively together, finally available sulfide solid electrolyte Li10GeP2S12；Li2S、P2S5、GeS2、
Li3PO4It is used cooperatively together, finally available sulfide solid electrolyte 98Li10GeP2S12·2Li3PO4Situations such as.
Step 1: Step 2: Step 3: the water content of environment locating for step 4 is less than 100ppm, wherein described " institute
Place's environment " includes external environment and organic solvent, only keeps the degree of drying of high requirement, could reduce vulcanization as far as possible
Object solid mixed raw material is by being influenced；And either sulfide solid mixed raw material, organic solvent, mill ball place mistake
Journey or other need to touch the process of outside air, be required to adequately protect using inert gas (such as argon gas), reduce
The case where sulfide solid mixed raw material is reacted appearance, to improve the yield and its matter of the sulfide solid electrolyte of acquisition
Amount.
It during the roller of step 1 mill, generallys use roller mill and is operated, and sulfide solid mixed raw material, have
In solvent, the system of mill ball composition, the molar ratio and solid content of mill ball and sulfide solid mixed raw material are above-mentioned
Range facilitates during roller is ground, and organic solvent is fully dispersed by sulfide solid mixed raw material, mill ball, is not easy out
The phenomenon that now gluing wall；And diameter range more appropriate mill ball sulfide solid mixed raw material can be played preferable extruding,
The effect of grinding, to improve the effect of roller mill.Compared to compared with the prior art, can disposably grinding more raw materials and obtain
More sulfide solid electrolytes are obtained, to reduce repeated workload, and increase substantially sulfide solid electrolyte
Production efficiency reduces its production cost, to also reduce the production cost of solid lithium battery to a certain extent.If grinding
The diameter of abrading-ball is greater than 50mm, and grinding effect is easy to cause to be deteriorated.
After the processing of roller mill, mill ball is filtered, obtains the slurry of texture uniformly, fine and smooth, which needs in inertia
It is carried out under the protection of gas.There is apparent lamination after the standing of 0.5-1h in slurry, removes supernatant, that is, eliminates
A large amount of organic solvents remain sediment, which is also required to carry out under the protection of inert gas.In step 3, to sediment
Vacuum distillation processing is carried out, remaining organic solvent is removed, more easy to remove due to the very high purity of organic solvent, sediment
After vacuum distillation is handled, also it is easier to be dried.The presoma powder of acquisition will form sulfide solid electricity by heat treatment
Xie Zhi can be used after supercooling, grinding.
Further preferably are as follows: in the step 1, organic solvent includes that nitrile solvents, alkane solvents, arene are molten
One or more of agent, ether solvent.
By using above-mentioned technical proposal, nitrile solvents, alkane solvents, aromatic hydrocarbon solvent, ether solvent can make
Sulfide solid mixed raw material disperses and is not susceptible to bonding phenomenon, in the organic solvent in above-mentioned major class, there is acetonitrile, positive heptan
It is representative that alkane, toluene and tetrahydrofuran etc., which have the organic solvent of preferable dispersion effect, is made to sulfide solid mixed raw material
Grinding efficiency improves.
Further preferably are as follows: in the step 3, the temperature for being evaporated under reduced pressure processing is the vacuum distillation processing lower than 150 DEG C
Time be less than 10h.
By using above-mentioned technical proposal, under above-mentioned temperature and time, remaining organic solvent quilt in sediment can be made
Sufficiently removal.
Further preferably are as follows: in the step 3, dry temperature is 20-200 DEG C, and the dry time is less than 72h.
By using above-mentioned technical proposal, under above-mentioned temperature and time, sediment can be made sufficiently to be dried.
Further preferably are as follows: in the step 4, the heating rate of heat treatment is less than 10 DEG C/min, the temperature of heat treatment
It is 100-700 DEG C, the time of heat treatment is less than 20h.
By using above-mentioned technical proposal, the temperature after the heating rate of heat treatment and later period stabilization is to keep stablizing
It is more appropriate, and it is moderate to handle the time, to help to promote presoma powder that sufficiently reaction occurs and forms sulfide solid
Electrolyte.
Further preferably are as follows: in the step 1, when roller mill processing, the revolving speed of roller mill be less than 500rpm, roller mill when
Between for less than 200h.
By using above-mentioned technical proposal, the revolving speed cooperation high-purity of organic solvent of roller mill, the suitable diameter of mill ball,
The time of roller mill, sulfide solid mixed raw material is fully ground, the uniform and fine and smooth slurry of texture is obtained.
Further preferably are as follows: in the step 1, roller grind handle when, with sulfide solid mixed raw material, organic solvent,
Mill ball formed contact equipment material be stainless steel, polyurethane, zirconium oxide, hard alloy, polytetrafluoro, corundum, nylon with
One kind of agate；The mill ball includes zirconia ball, alumina balls, stainless steel ball, sintered carbide ball, polyurethane ball and agate
At least one of ball.
By using above-mentioned technical proposal, the roller grinding jar in roller mill that roller mill uses when handling is mixed with sulfide solid
Raw material, organic solvent, mill ball form contact, the quality of the material used intensity with higher, and good toughness, hardness and fit
In.And the quality of the mill ball used is also more hard, and is less prone to the high problem of brittleness, intensity is also high.In the honed journey of roller
In, it is formed between roller grinding jar and sulfide solid mixed raw material, mill ball and squeezes, grinds, sulfide solid mixing can be kept former
In the case that material is not damaged with mill ball, sulfide solid mixed raw material is ground to required degree.It is suitable for quality mistake simultaneously
In hard sulfide solid mixed raw material, therefore, the range of raw material is widened, has helped to increase the sulfide solid electricity obtained
Solve the type of matter.
In conclusion the invention has the following advantages:
The first, using the preparation method of wet process roller mill in the present invention, by sulfide solid mixed raw material, organic solvent, mill ball
It cooperates according to certain, respective requirement, handles, filtering, stands through roller mill, removal supernatant, sediment depressurize
Distillation processing and dry, presoma powder carry out after the operation such as being heat-treated, the crystal structure of the sulfide solid electrolyte of acquisition
Excellent electric conductivity consistent with the crystal structure of standard spectrogram, and obtaining.
The second, it in the present invention, is matched using reasonable compound solid mixed raw material, organic solvent, mill ball, makes three's shape
Architectonical has preferable dispersibility, to improve the amount of disposable triturable raw material and obtain more sulfide solids
Electrolyte to reduce repeated workload, and increases substantially the production efficiency of sulfide solid electrolyte, reduces its life
Cost is produced, to also reduce the production cost of solid lithium battery to a certain extent.
The sulfide solid mixed raw material and organic solvent that very high purity is used in third, the present invention, are reduced from the root
Influence of the introduced contaminants to preparation process helps to improve the purity and quality of the sulfide solid electrolyte finally obtained.
4th, the present invention drying, seal, have inert gas shielding under conditions of carry out, can reduce during the preparation process
The possibility for causing sulfide solid electrolyte to occur reacting, to keep sulfide solid electrolyte performance constant.
Detailed description of the invention
Fig. 1 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 1；
Fig. 3 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 2；
Fig. 4 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 2；
Fig. 5 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 3；
Fig. 6 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 3；
Fig. 7 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 4；
Fig. 8 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 4；
Fig. 9 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 5；
Figure 10 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 5；
Figure 11 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 6；
Figure 12 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 6；
Figure 13 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 7；
Figure 14 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 7；
Figure 15 is the AC impedance spectroscopy of sulfide solid electrolyte prepared by the embodiment of the present invention 8；
Figure 16 is the XRD spectra of sulfide solid electrolyte prepared by the embodiment of the present invention 8；
Figure 17 is the AC impedance spectroscopy of the sulfide solid electrolyte of comparative example 1 of the present invention preparation；
Figure 18 is the XRD spectra of the sulfide solid electrolyte of comparative example 1 of the present invention preparation；
Figure 19 is the AC impedance spectroscopy of the sulfide solid electrolyte of comparative example 2 of the present invention preparation；
Figure 20 is the XRD spectra of the sulfide solid electrolyte of comparative example 2 of the present invention preparation；
Figure 21 is the AC impedance spectroscopy of the sulfide solid electrolyte of comparative example 3 of the present invention preparation；
Figure 22 is the XRD spectra of the sulfide solid electrolyte of comparative example 3 of the present invention preparation；
Figure 23 is the AC impedance spectroscopy of the sulfide solid electrolyte of comparative example 4 of the present invention preparation；
Figure 24 is the XRD spectra of the sulfide solid electrolyte of comparative example 4 of the present invention preparation.
Specific embodiment
Below in conjunction with drawings and examples, invention is further described in detail.
Embodiment 1: a kind of preparation method of sulfide solid electrolyte, the equipment used is zirconium oxide roller grinding jar, preparation
Method includes the following steps:
Under argon atmosphere protection, the clean zirconia ball of 500g Φ 5mm is put into 500mL zirconium oxide roller grinding jar, and will be pure
Degree is respectively 99% or more Li2S、P2S5According to molar ratio Li2S∶P2S5Form sulfide solid mixed raw material at=3: 1, weighs
100mL acetonitrile (water content 0.005wt%) is added in roller grinding jar, sealed roller grinding jar in 100g sulfide solid mixed raw material.
It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, and revolving speed 200rpm, the time of roller mill is for 24 hours.Roller mill knot
Shu Hou dismantles roller grinding jar under an argon atmosphere, and by zirconia ball and pulp separation, the slurry after separation is placed in quiet in cucurbit
1h is set, supernatant liquor is poured out, slurry is taken out in sealing.The vacuum distillation processing 0.5h at 60 DEG C of constant temperature.It is put into argon atmosphere protection
Under baking oven in, at 100 DEG C dry 12h after, grind 0.5h.Powder after grinding is placed in crucible, is put into argon atmosphere protection
Under batch-type furnace in, 250 DEG C of heat preservation 2h are warming up to 2 DEG C/min rate, after cooling to room temperature with the furnace, sintered product are ground equal
It is even, obtain sulfide solid electrolyte Li3PS4。
Embodiment 2: a kind of preparation method of sulfide solid electrolyte, the equipment used is corundum roller grinding jar, preparation side
Method includes the following steps:
Under argon atmosphere protection, it is put into 200g Φ 15mm and 200g Φ 10mm and 200g Φ 5mm's in 500mL corundum roller grinding jar
Purity is respectively 99% or more Li by clean alumina balls2S、P2S5, LiCl is according to molar ratio Li2S∶P2S5: LiCl=5: 1:
2 form sulfide solid mixed raw material, weigh 100g sulfide solid mixed raw material, and 200mL normal heptane is added in roller grinding jar
(water content 0.005wt%), sealed roller grinding jar.It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, turns
Speed is 150rpm, the time 48h of roller mill.After roller is ground, under an argon atmosphere, roller grinding jar is dismantled, by zirconia ball and slurry
Separation, the slurry after separation, which is placed in cucurbit, stands 0.5h, pours out supernatant liquor, and slurry is taken out in sealing.At 70 DEG C of constant temperature
Vacuum distillation processing 1h.120 DEG C of baking 12h in the baking oven under argon atmosphere protection are put into, 0.5h is ground.Powder after grinding is placed in
In crucible, it is put into the batch-type furnace under argon atmosphere protection, is warming up to 520 DEG C with 5 DEG C/min rate and keeps the temperature 4h, furnace cooling
To room temperature, sintered product is ground uniformly, sulfide solid electrolyte Li is obtained6PS5Cl。
Embodiment 3: a kind of preparation method of sulfide solid electrolyte, the equipment used is nylon roller grinding jar, preparation side
Method includes the following steps:
Under argon atmosphere protection, the clean stainless steel with 300g Φ 10mm and 100g Φ 5mm is put into 500mL nylon roller grinding jar
Purity is respectively 99% or more Li by ball2S、P2S5、GeS2According to molar ratio Li2S∶P2S5∶GeS2Form sulfide at=5: 1: 1
Solid mixed raw material weighs 100g sulfide solid mixed raw material, and toward addition 250mL toluene in roller grinding jar, (water content is
0.008wt%), sealed roller grinding jar.It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, and revolving speed is
200rpm, the time 72h of roller mill.After roller is ground, under an argon atmosphere, roller grinding jar is dismantled, by zirconia ball and pulp separation,
Slurry after separation, which is placed in cucurbit, stands 0.5h, pours out supernatant liquor, and slurry is taken out in sealing.It depressurizes and steams at 75 DEG C of constant temperature
Evaporate processing 1h.120 DEG C of baking 6h in the baking oven under argon atmosphere protection are put into, 0.5h is ground.Powder after grinding is placed in crucible,
It is put into the batch-type furnace under argon atmosphere protection, is warming up at 600 DEG C with 2.5 DEG C/min rate and keeps the temperature 8h, cool to room with the furnace
Sintered product is ground uniformly, obtains sulfide solid electrolyte Li by Wen Hou10GeP2S12。
Embodiment 4: a kind of preparation method of sulfide solid electrolyte, the equipment used is polytetrafluoro roller grinding jar, preparation
Method includes the following steps:
Under argon atmosphere protection, the clean agate ball with 800g Φ 10mm is put into 500mL polytetrafluoro roller grinding jar, by purity
Respectively 99% or more Li2S、P2S5According to molar ratio Li2S∶P2S5Form sulfide solid mixed raw material at=7: 3, weighs
200mL tetrahydrofuran (water content 0.003wt%) is added in roller grinding jar, sealed roller in 100g sulfide solid mixed raw material
Grinding jar.It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, revolving speed 100rpm, the time 12h of roller mill.Roller
After mill, under an argon atmosphere, roller grinding jar is dismantled, by zirconia ball and pulp separation, the slurry after separation is placed in cucurbit
Middle standing 1h, pours out supernatant liquor, and slurry is taken out in sealing.The vacuum distillation processing 1h at 50 DEG C of constant temperature.It is put into argon atmosphere guarantor
It is dried for 24 hours for 100 DEG C in baking oven under shield, grinds 0.5h.Powder after grinding is placed in crucible, the case being put under argon atmosphere protection
It in formula furnace, is warming up at 300 DEG C with 1 DEG C/min rate and keeps the temperature 2h, after cooling to room temperature with the furnace, sintered product is ground uniformly,
Obtain sulfide solid electrolyte Li7P3S11。
Embodiment 5: a kind of preparation method of sulfide solid electrolyte, the equipment used is zirconium oxide roller grinding jar, preparation
Method includes the following steps:
Under argon atmosphere protection, the clean zirconia ball of 500g Φ 5mm is put into 500mL zirconium oxide roller grinding jar, and will be pure
Degree is respectively 99% or more Li2S、P2S5, LiCl is according to molar ratio Li2S∶P2S5: form vulcanization at LiCl=71.25: 23.75: 5
Object solid mixed raw material weighs 100g sulfide solid mixed raw material, and toward addition 100mL acetonitrile in roller grinding jar, (water content is
0.005wt%), sealed roller grinding jar.It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, and revolving speed is
200rpm, the time of roller mill is for 24 hours.After roller is ground, under an argon atmosphere, roller grinding jar is dismantled, by zirconia ball and pulp separation,
Slurry after separation, which is placed in cucurbit, stands 1h, pours out supernatant liquor, and slurry is taken out in sealing.It is evaporated under reduced pressure at 60 DEG C of constant temperature
Handle 0.5h.It is put into the baking oven under argon atmosphere protection, after drying 12h at 100 DEG C, grinds 0.5h.Powder after grinding is set
In crucible, it is put into the batch-type furnace under argon atmosphere protection, 260 DEG C of heat preservation 2h, furnace cooling is warming up to 2 DEG C/min rate
To room temperature, sintered product is ground uniformly, 95 (75Li of sulfide solid electrolyte is obtained2S·25P2S5)·5LiCl。
Embodiment 6: a kind of preparation method of sulfide solid electrolyte, the equipment used is polytetrafluoro roller grinding jar, preparation
Method includes the following steps:
Under argon atmosphere protection, the clean agate ball with 800g Φ 10mm is put into 500mL polytetrafluoro roller grinding jar, by purity
Respectively 99% or more Li2S、P2S5、P2O5According to molar ratio Li2S∶P2S5∶P2O5Form sulfide solid at=70: 27: 3 mixes
Raw material is closed, 100g sulfide solid mixed raw material is weighed, (water content is toward addition 200mL tetrahydrofuran in roller grinding jar
0.003wt%), sealed roller grinding jar.It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, and revolving speed is
100rpm, the time 12h of roller mill.After roller is ground, under an argon atmosphere, roller grinding jar is dismantled, by zirconia ball and pulp separation,
Slurry after separation, which is placed in cucurbit, stands 1h, pours out supernatant liquor, and slurry is taken out in sealing.It is evaporated under reduced pressure at 50 DEG C of constant temperature
Handle 1h.It is dried for 24 hours for 100 DEG C in the baking oven being put under argon atmosphere protection, grinds 0.5h.Powder after grinding is placed in crucible,
It is put into the batch-type furnace under argon atmosphere protection, is warming up at 280 DEG C with 2 DEG C/min rate and keeps the temperature 3h, cool to room temperature with the furnace
Afterwards, sintered product is ground uniformly, obtains sulfide solid electrolyte 70Li2S·27P2S5·3P2O5。
Embodiment 7: a kind of preparation method of sulfide solid electrolyte, the equipment used is corundum roller grinding jar, preparation side
Method includes the following steps:
Under argon atmosphere protection, it is put into 200g Φ 15mm and 200g Φ 10mm and 200g Φ 5mm's in 500mL corundum roller grinding jar
Purity is respectively 99% or more Li by clean alumina balls2S、P2S5, LiCl, LiBr be according to molar ratio Li2S∶P2S5∶LiCl∶
Form sulfide solid mixed raw material at LiBr=25: 5: 6: 4, weighs 100g sulfide solid mixed raw material, adds in roller grinding jar
Enter 200mL normal heptane (water content 0.005wt%), sealed roller grinding jar.It takes out, is placed on roller mill from argon atmosphere, if
Fixed roll grinds parameter, revolving speed 150rpm, the time 48h of roller mill.After roller is ground, under an argon atmosphere, roller grinding jar is dismantled, by oxygen
Change zirconium ball and pulp separation, the slurry after separation, which is placed in cucurbit, stands 0.5h, pours out supernatant liquor, and slurry is taken out in sealing.
The vacuum distillation processing 1h at 70 DEG C of constant temperature.120 DEG C of baking 12h in the baking oven under argon atmosphere protection are put into, 0.5h is ground.Grinding
Powder afterwards is placed in crucible, is put into the batch-type furnace under argon atmosphere protection, is warming up to 530 DEG C with 5 DEG C/min rate and protects
Warm 3h after cooling to room temperature with the furnace, sintered product is ground uniformly, sulfide solid electrolyte Li is obtained6PSsCl0.6Br0.4。
Embodiment 8: a kind of preparation method of sulfide solid electrolyte, the equipment used is nylon roller grinding jar, preparation side
Method includes the following steps:
Under argon atmosphere protection, the clean stainless steel with 300g Φ 10mm and 100g Φ 5mm is put into 500mL nylon roller grinding jar
Purity is respectively 99% or more Li by ball2S、P2S5、GeS2、Li3PO4According to molar ratio Li2S∶P2S5∶GeS2∶Li3PO4=35
: form sulfide solid mixed raw material at 7: 7: 1, weighs 100g sulfide solid mixed raw material, and 250mL first is added in roller grinding jar
Benzene (water content 0.008wt%), sealed roller grinding jar.It taking out, is placed on roller mill from argon atmosphere, setting roller grinds parameter,
Revolving speed is 200rpm, the time 72h of roller mill.After roller is ground, under an argon atmosphere, roller grinding jar is dismantled, by zirconia ball and slurry
Material separation, the slurry after separation, which is placed in cucurbit, stands 0.5h, pours out supernatant liquor, and slurry is taken out in sealing.At 75 DEG C of constant temperature
Lower vacuum distillation handles 1h.120 DEG C of baking 6h in the baking oven under argon atmosphere protection are put into, 0.5h is ground.Powder after grinding is set
In crucible, it is put into the batch-type furnace under argon atmosphere protection, is warming up at 580 DEG C with 2.5 DEG C/min rate and keeps the temperature 6h, with furnace
After being cooled to room temperature, sintered product is ground uniformly, sulfide solid electrolyte 98Li is obtained10GeP2S12·2Li3PO4。
Comparative example 1: a kind of preparation method of sulfide solid electrolyte, the difference from embodiment 1 is that, the equipment of use
For ball grinder, preparation method includes the following steps:
Under argon atmosphere protection, the clean alumina balls of 200g Φ 10mm and 200g Φ 5mm are put into 500mL ball grinder, it will
Purity is respectively 99% or more Li2S、P2S5According to molar ratio Li2S∶P2S5Weigh 20g sulfide solid mixed raw material at=3: 1,
It is placed in 500mL ball milling, sealing is taken out.It is put into high energy ball mill, with high-energy ball milling under 500rpm revolving speed, is during which needed every 2h
It will be sticked under the material chisel of inner wall, and finely ground under argon atmosphere protection.Powder initial material is obtained after 50h, is taken out powder initial material and is ground
It is carefully uniformly placed in crucible, is put into the batch-type furnace under argon atmosphere protection, 250 DEG C of heat preservations are warming up to 2 DEG C/min rate
2h after cooling to room temperature with the furnace, sintered product is ground uniformly, powder, i.e. Li are obtained3PS4Sulfide solid electrolyte.
Comparative example 2: a kind of preparation method of sulfide solid electrolyte, the equipment used is zirconium oxide roller grinding jar, preparation
Method includes the following steps:
Under argon atmosphere protection, the clean zirconia ball of 500g Φ 5mm is put into 500mL zirconium oxide roller grinding jar, and will be pure
Degree is respectively 99% or more Li2S、P2S5According to molar ratio Li2S∶P2S5Form sulfide solid mixed raw material at=3: 1, weighs
100mL acetonitrile (water content 0.005wt%) is added in roller grinding jar, sealed roller grinding jar in 100g sulfide solid mixed raw material.
It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, and revolving speed 200rpm, the time of roller mill is for 24 hours.Roller mill knot
Shu Hou dismantles roller grinding jar under an argon atmosphere, and by zirconia ball and pulp separation, the slurry after separation is placed in quiet in cucurbit
1h is set, supernatant liquor is poured out, slurry is taken out in sealing.The vacuum distillation processing 0.5h at 160 DEG C of constant temperature.It is put into argon atmosphere protection
Under baking oven in, at 100 DEG C dry 12h after, grind 0.5h.Powder after grinding is placed in crucible, is put into argon atmosphere protection
Under batch-type furnace in, 250 DEG C of heat preservation 2h are warming up to 2 DEG C/min rate, after cooling to room temperature with the furnace, sintered product are ground equal
It is even, obtain sulfide solid electrolyte Li3PS4.Comparative example 3: a kind of preparation method of sulfide solid electrolyte, use are set
Standby is zirconium oxide roller grinding jar, and preparation method includes the following steps:
Under argon atmosphere protection, the clean zirconia ball of 500g Φ 5mm is put into 500mL zirconium oxide roller grinding jar, and will be pure
Degree is respectively 99% or more Li2S、P2S5According to molar ratio Li2S∶P2S5Form sulfide solid mixed raw material at=3: 1, weighs
100mL acetonitrile (water content 0.5wt%) is added in roller grinding jar, sealed roller grinding jar in 100g sulfide solid mixed raw material.From
It takes out, is placed on roller mill in argon atmosphere, setting roller grinds parameter, and revolving speed 200rpm, the time of roller mill is for 24 hours.Roller mill terminates
Afterwards, under an argon atmosphere, roller grinding jar is dismantled, by zirconia ball and pulp separation, the slurry after separation, which is placed in cucurbit, to be stood
1h, pours out supernatant liquor, and slurry is taken out in sealing.The vacuum distillation processing 12h at 60 DEG C of constant temperature.It is put under argon atmosphere protection
In baking oven, after drying 12h at 100 DEG C, 0.5h is ground.Powder after grinding is placed in crucible, is put under argon atmosphere protection
In batch-type furnace, 250 DEG C of heat preservation 2h are warming up to 2 DEG C/min rate, after cooling to room temperature with the furnace, sintered product is ground uniformly,
Obtain sulfide solid electrolyte Li3PS4。
Comparative example 4: a kind of preparation method of sulfide solid electrolyte, the equipment used is zirconium oxide roller grinding jar, preparation
Method includes the following steps:
Under argon atmosphere protection, the clean zirconia ball of 500g Φ 5mm is put into 500mL zirconium oxide roller grinding jar, and will be pure
Degree is respectively 99% or more Li2S、P2S5According to molar ratio Li2S∶P2S5Form sulfide solid mixed raw material at=3: 1, weighs
100mL acetonitrile (water content 0.005wt%) is added in roller grinding jar, sealed roller grinding jar in 100g sulfide solid mixed raw material.
It takes out, is placed on roller mill from argon atmosphere, setting roller grinds parameter, revolving speed 400rpm, the time 200h of roller mill.Roller mill knot
Shu Hou dismantles roller grinding jar under an argon atmosphere, and by zirconia ball and pulp separation, the slurry after separation is placed in quiet in cucurbit
1h is set, supernatant liquor is poured out, slurry is taken out in sealing.The vacuum distillation processing 0.5h at 60 DEG C of constant temperature.It is put into argon atmosphere protection
Under baking oven in, at 100 DEG C dry 12h after, grind 0.5h.Powder after grinding is placed in crucible, is put into argon atmosphere protection
Under batch-type furnace in, 250 DEG C of heat preservation 2h are warming up to 2 DEG C/min rate, after cooling to room temperature with the furnace, sintered product are ground equal
It is even, obtain sulfide solid electrolyte Li3PS4。
Test one: electrochemical property test
Test specimen: the sulfide solid electrolyte obtained in embodiment 1-8 is chosen as test sample 1-8, chooses comparative example 1-4
The sulfide solid electrolyte of middle acquisition is as control sample 1-4.
Test method: test sample 1-8, control sample are less than under 10ppm, 10MPa pressure condition, in water content 25 respectively
At a temperature of DEG C, being pressed into diameter is 10mm, the corresponding sheet lithium ion solid conductor with a thickness of 1mm.It then is obstruction with carbon
Electrode carries out EIS test under the conditions of 25 DEG C, tests its electric conductivity.
Test result: test sample 1-8, control sample 1-4 electric conductivity respectively such as Fig. 1, Fig. 3, Fig. 5, Fig. 7, Fig. 9, Figure 11,
Figure 13, Figure 15, Figure 17, Figure 19, Figure 21 and Figure 23 are that is, shown in AC impedance spectroscopy.
As shown in Figure 1,1 conductivity of test sample is 5.10 × 10-4S·cm-1；
From the figure 3, it may be seen that the conductivity of test sample 2 is 3.35 × 10-3S·cm-1；
As shown in Figure 5, the conductivity of test sample 3 is 5.10 × 10-3S·cm-1；
As shown in Figure 7, the conductivity of test sample 4 is 1.50 × 10-3S·cm-1；
As shown in Figure 9, the conductivity of test sample 5 is 5.69 × 10-4S·cm-1；
As shown in Figure 11, the conductivity of test sample 6 is 1.87 × 10-3S·cm-1；
As shown in Figure 13, the conductivity of test sample 7 is 4.16 × 10-3S·cm-1；
As shown in Figure 15, the conductivity of test sample 8 is 8.77 × 10-3S·cm-1；
As shown in Figure 17, the conductivity of control sample 1 is 4.11 × 10-4S·cm-1；
It appears from figure 19 that the conductivity of control sample 2 is 2.66 × 10-4S·cm-1；
As shown in Figure 21, the conductivity of control sample 3 is 4.06 × 10-4S·cm-1；
As shown in Figure 23, the conductivity of control sample 4 is 2.00 × 10-45·cm-1。
By Fig. 1, Fig. 3, Fig. 5, Fig. 7, Fig. 9, Figure 11, Figure 13 and Figure 15 it is found that being prepared using the method in the present invention
Sulfide solid electrolyte there is better conductivity at room temperature.
Test two: crystal structure test
Test specimen: the sulfide solid electrolyte obtained in embodiment 1-8 is chosen as test sample 1-8, chooses comparative example 1-4
The sulfide solid electrolyte of middle acquisition is as control sample 1-4.
Test method: it is less than in 10ppm glove box in water content, test sample 1-8, control sample are prepared into required sample
Product, and X-ray diffraction test is carried out, obtain Sample crystals structural information such as Fig. 2, Fig. 4, Fig. 6, Fig. 8, Figure 10, Figure 12, Tu14He
Shown in Figure 16.
Test result: by Fig. 2 and Figure 10 it is found that test sample 1 and test sample 5 are Li3PS4With 95 (75Li2S·25P2S5)·
5LiCl is consistent with the crystal structure of standard spectrogram respectively；By Fig. 4 and Figure 14 it is found that test sample 2 and test sample 7 are Li6PS5Cl and
Li6PS5Cl0.6Br0.4It is consistent with the crystal structure of standard spectrogram respectively；By Fig. 6 and Figure 16 it is found that test sample 3 and test sample 8 are
Li10GeP2S12And 98Li10GeP2S12·22Li3PO4It is consistent with the crystal structure of standard spectrogram respectively；By Fig. 8 and Figure 12 it is found that
Test sample 4 and test sample 6 are Li7P3S11And 70Li2S·27P2S5·3P2O5It is consistent with the crystal structure of standard spectrogram respectively.By
Figure 18, Figure 20, Figure 22 and Figure 24 are it is found that control sample 1, control sample 2, control sample 3 and control sample 4 are Li3PS4With standard spectrogram
Crystal structure is consistent.
In conjunction with the test result of test one and test two, although the crystal of control sample 1-4 its crystal structure and standard spectrogram
Structure is consistent, but its conductivity is more slightly worse than the electric conductivity of test sample 1, illustrates the sulphur prepared using the method in the present invention
Compound solid electrolyte has higher conductivity.
Test three: single batch production efficiency test
Test method: by single batch mixing time, single batch yield, the number of operations during mixing in embodiment 1 and comparative example
It is recorded and is analyzed, the results are shown in Table 1.
1 embodiment 1 of table compares situation with comparative example single batch production efficiency
As shown in Table 1, for embodiment 1 compares comparative example, single batch mixing time is shorter, and single batch yield is more
Height improves production efficiency up to 5 outputs of comparative example；And without carrying out manual operation during mixing, save manpower and
Material resources further decrease production cost.Therefore, using the preparation method in the present invention, single batch in the prior art can be overcome
The disadvantages of low output, repeated workload is big, and the production efficiency of sulfide solid electrolyte is greatly improved, reduce it
Production cost, to also reduce the production cost of solid lithium battery.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (7)
1. a kind of preparation method of sulfide solid electrolyte, which comprises the steps of:
Sulfide solid mixed raw material, organic solvent, mill ball are carried out the processing of roller mill, mistake in a sealed meter environment by step 1
Filter obtains slurry；
The slurry obtained in step 1 is stood, layering, removes supernatant by step 2, obtains sediment, sealing；
Step 3 carries out vacuum distillation processing to the sediment obtained in step 2, dry, obtains presoma powder；
Step 4 will be heat-treated the presoma powder obtained in step 3, be cooled to room temperature, grind in dry environment
Mill obtains sulfide solid electrolyte；
In the step 1, purity >=99% of sulfide solid mixed raw material；The water content of the organic solvent is lower than
0.01wt%；The diameter of the mill ball is less than 50mm；
The mill ball and the mass ratio of sulfide solid mixed raw material be less than 100:1, the sulfide solid mixed raw material,
The solid content in system that organic solvent, mill ball are formed is less than 100%；
It is described Step 1: Step 2: Step 3: the water content of environment locating for step 4 be less than 100ppm.
2. a kind of preparation method of sulfide solid electrolyte according to claim 1, which is characterized in that the step 1
In, organic solvent includes one or more of nitrile solvents, alkane solvents, aromatic hydrocarbon solvent, ether solvent.
3. a kind of preparation method of sulfide solid electrolyte according to claim 1, which is characterized in that the step 3
In, the temperature for being evaporated under reduced pressure processing is to be evaporated under reduced pressure the time of processing lower than 150 DEG C as less than 10h.
4. a kind of preparation method of sulfide solid electrolyte according to claim 1, which is characterized in that the step 3
In, dry temperature is 20-200 DEG C, and the dry time is less than 72h.
5. a kind of preparation method of sulfide solid electrolyte according to claim 1, which is characterized in that the step 4
In, the heating rate of heat treatment is less than 10 DEG C/min, and the temperature of heat treatment is 100-700 DEG C, the time of heat treatment be less than
20h。
6. a kind of preparation method of sulfide solid electrolyte according to claim 1, which is characterized in that the step 1
In, when roller mill is handled, the revolving speed of roller mill is less than 500rpm, and the time of roller mill is less than 200h.
7. a kind of preparation method of sulfide solid electrolyte according to claim 1, which is characterized in that the step 1
In, when roller grinds and handles, the material for forming the equipment contacted with sulfide solid mixed raw material, organic solvent, mill ball is not
Become rusty steel, polyurethane, zirconium oxide, hard alloy, polytetrafluoro, one kind of corundum, nylon and agate；The mill ball includes zirconium oxide
At least one of ball, alumina balls, stainless steel ball, sintered carbide ball, polyurethane ball and agate ball.
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| CN113363566A (en) * | 2021-06-17 | 2021-09-07 | 高能时代(佛山)新能源科技有限公司 | Method for preparing sulfide solid electrolyte in low cost and large scale |
| CN113410513A (en) * | 2021-06-16 | 2021-09-17 | 多氟多新能源科技有限公司 | Preparation method of sulfide solid electrolyte |
| CN114709471A (en) * | 2022-03-29 | 2022-07-05 | 上海屹锂新能源科技有限公司 | Preparation method of sulfide solid electrolyte |
| CN114933320A (en) * | 2022-04-29 | 2022-08-23 | 广东马车动力科技有限公司 | Method for refining lithium chloride |
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