CN109193026A - A kind of preparation method of argyrodite type sulfide solid electrolyte - Google Patents
A kind of preparation method of argyrodite type sulfide solid electrolyte Download PDFInfo
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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 present invention provides a kind of preparation methods of argyrodite type sulfide solid electrolyte, with more cheap LiH, P, S and LiX (X Cl, Br or I) for raw material, it is sintered through mixing and ball milling, sintering or in ball milling and argyrodite type sulfide solid electrolyte Li is made6PS5X；Raw material of the present invention is cheap, and reactivity is strong, and raw material availability is high, and preparation method is simple, solid electrolyte obtained ionic conductivity with higher, wider electrochemical window, are applied to and prepare all-solid-state battery, have high security, high-energy density, excellent cyclical stability.
Description
(1) technical field
The present invention relates to the preparation methods of lithium ion solid electrolyte, and in particular to a kind of high ionic conductivity argyrodite
The preparation method of type sulfide solid electrolyte.
(2) background technique
In recent years, using fossil fuel as the conventional vehicles of power to mixed power electric car even pure electric vehicle vapour
The conversion of vehicle is undoubtedly a kind of following trend.This trend can sufficiently alleviate the various challenges that the mankind are faced, including ring
Border deteriorates, the discharge of greenhouse gases and the exhaustion of fossil fuel.Since nineteen nineties first commercialized lithium ion
Since battery comes out, lithium ion battery is just received significant attention with its high-energy density.Traditional lithium ion secondary battery is general
It is made of solid state electrode and liquid electrolyte, therefore is usually present the disadvantages of electrolyte volatilizees, is inflammable, explosive.And solid-state is electric
Solution matter can solve safety problem brought by liquid electrolyte as the characteristics of its own.
Compared with liquid state batteries, solid electrolyte will not corroding electrode, it is nonflammable, will not leak, not will cause in battery
The characteristics of portion is short-circuit, and most of solid electrolytic confrontation lithium is stablized, solid-state makes it sufficiently inhibit the growth of Li dendrite, therefore
All-solid-state battery is a kind of modern high security lithium ion battery for replacing conventional liquid electrolyte with solid electrolyte.Solid-state electricity
Solution matter is broadly divided into solid polyelectrolyte and inorganic solid electrolyte this two major classes.Wherein, due to higher safety
Property and higher conductivity at room temperature, inorganic solid electrolyte obtained it is extensive concern and application.Inorganic solid electrolyte
Research concentrate in a series of materials with crystal structure, including lithium superionic conductors, sodium superionic conductors, argyrodite
The fast lithium ion conductor of structure, the fast lithium ion conductor of perovskite structure, the fast lithium ion conductor of carchedonia ore type structure etc..This hair
Sulfide solid electrolyte involved in bright is one kind of numerous inorganic solid electrolytes, ionic conductivity with higher,
The advantages that preferable mechanical property, preferable thermal stability, composition multiplicity.Sulfide solid electrolyte is by oxide solid
What electrolyte was derived, oxygen element is replaced by element sulphur in oxide body, forms sulfide solid electrolyte.Due to sulphur
The electronegativity of element is smaller than oxygen element, wants small to the constraint of lithium ion, is conducive to obtain more free-moving lithium ions.Together
When, the radius ratio oxygen element of element sulphur is big, when the position of element sulphur substitution oxygen element, can cause the expansion of electrolyte crystalline structure
Exhibition, is capable of forming biggish ion transmission channel, is conducive to the transmission of lithium ion.Originally, Li2S、P2S5、SiS2、GeS2Deng being sent out
The performance that now there is transmission to lead lithium, and Li2S-GeS2、Li2S-P2S5、Li2S-B2S3、Li2S-SiS2Equal lithium ion conductings sulfide
System, conductivity at room temperature are up to l0-4S/cm increases than unit sulfide solid electrolyte conductivity.With people
Deepen continuously to sulfide solid electrolyte research, sulfide is also continuously improved as the conductivity of solid electrolyte.
Toyota Motors in 2011 and Tokyo Institute of Technology's project have been combined into a kind of conductivity can be comparable with liquid electrolyte
Inorganic solid electrolyte: Li10GeP2S12, lithium ion is exceedingly fast in diffusion rate wherein, at room temperature up to 1.2 × 10-2S/
Cm, making sulfide solid electrolyte again becomes the focus of research.
Argyrodite type sulfide solid electrolyte Li mentioned by the present invention6PS5X (X Cl, Br or I) is latest find
A kind of fast-ionic conductor, conductivity can achieve 7 × 10 at room temperature-3S/cm.Its crystal structure is vertical based on anion
Square Mi Dui, space group areIn entire close pile structure, phosphorus atoms occupy part tetrahedron gap, form one and contain
Independent PS4Tetrahedral network, for lithium ion in occupation of remaining tetrahedron gap, the position that lithium ion occupies forms octahedron
Space is realized lithium ion in these spaces and is spread.In Li6PS5Cl and Li6PS5In Br, lithium ion passes through Cl-Or Br-
The clearance position diffusion of surrounding, in Li6PS5In I, lithium ion passes through S2-The clearance position diffusion of surrounding.This solid electrolyte
Activation energy it is relatively low, in 0.2-0.3eV, electrochemical window is wider, in 0-7V, can with common LiFePO 4 material,
The electrode materials such as cobalt acid lithium material, nickel-cobalt-manganese ternary material form High-safety all-solid-state lithium ion battery.
According to patent CN105229841A it is found that argyrodite type sulfide solid electrolyte Li6PS5X (X Cl, Br or
I synthesis material) is generally Li2S、P2S5, LiX (X Cl, Br or I), through ball milling, sintering obtain Li7-x-2yPS6-x-yXx(X is
Cl, Br, I), 0.8≤x≤1.7,0 < y≤- 0.25x+0.5.But wherein raw material Li2S is expensive, so that sulfide solid-state
Electrolyte is not easy to be mass produced.
(3) summary of the invention
A kind of method that the present invention devises new synthesis argyrodite type sulfide solid electrolyte, with more cheap
LiH, P, S and LiX (X Cl, Br or I) are raw material, and raw material reactivity is strong, and utilization rate is high.Through mixing and ball milling, sintering or side
Argyrodite type sulfide solid electrolyte Li can be made in the sintering of ball milling side6PS5X (X Cl, Br or I).
The present invention synthesizes Li by control material rate, Ball-milling Time, rotational speed of ball-mill, sintering temperature, sintering time6PS5X
(X Cl, Br, I).Application for all-solid-state battery, with anode material for lithium-ion batteries, Li6PS5X (X Cl, Br or I), it leads
Electrical carbon is black, binder ball milling mixing is as composite positive pole, forms all-solid-state battery using lithium metal or lithium indium alloy as cathode.
Technical scheme is as follows:
A kind of preparation method of argyrodite type sulfide solid electrolyte, the method are as follows:
(1) under inert atmosphere, LiH, P, S, LiX and ball milling pearl are added in ball grinder, (preferably with 300~600rpm
400~500rpm) 8~60h of revolving speed ball milling (preferably 12~for 24 hours), obtain pretreated solid electrolyte；
The ratio between amount of substance of described LiH, P, S, LiX be 1:0.1~0.3:0.8~1.1:0.1~0.3, preferably 1:
0.16~0.25:0.9~1.05:0.16~0.25；
In the LiX, X Cl, Br or I；
The ball milling pearl is the zirconium oxide ball milling pearl of diameter 12mm, it is recommended to use 12~15 ball milling pearls carry out ball milling, ball
Material mass ratio is 20~25:1；
(2) under inert atmosphere, pretreated solid electrolyte obtained by step (1) is warming up to the rate of 2~5 DEG C/min
It 200~600 DEG C (preferably 300~500 DEG C), is sintered 2~8h (preferably 2~4h), is down to room temperature (20~30 DEG C) later, is ground into
Powder is sieved (300~500 mesh), obtains the argyrodite type sulfide solid electrolyte.
Alternatively,
A kind of preparation method of argyrodite type sulfide solid electrolyte, the method are as follows:
Under inert atmosphere, LiH, P, S, LiX and ball milling pearl are added in ball grinder, heats in ball milling, is down to later
Room temperature (20~30 DEG C), grind into powder are sieved (300~500 mesh), obtain the argyrodite type sulfide solid state electrolysis
Matter；
Described heat in ball milling refers to: being heated up while ball milling with the rate of 2~5 DEG C/min (preferably 2~3 DEG C/min)
To 300~500 DEG C (preferably 400~500 DEG C), Ball-milling Time (including heating-up time) is 2~8h (preferably 4~6h), and ball milling turns
Speed is 300~600rpm (preferably 400~500rpm)；
The ratio between amount of substance of described LiH, P, S, LiX be 1:0.1~0.3:0.8~1.1:0.1~0.3, preferably 1:
0.16~0.25:0.9~1.05:0.16~0.25；
In the LiX, X Cl, Br or I；
The ball milling pearl is the zirconium oxide ball milling pearl of diameter 12mm, it is recommended to use 12~15 ball milling pearls carry out ball milling, ball
Material mass ratio is 20~25:1.
Argyrodite type sulfide solid electrolyte produced by the present invention can be applied in all-solid-state battery, specifically, institute
The method for stating application are as follows:
(1) under inert atmosphere, by 10~60 parts by weight positive electrodes, 5~15 parts by weight conductive carbon blacks, 25~85 parts by weight
Argyrodite type sulfide solid electrolyte and ball milling pearl are added in ball grinder, with 100~400rpm (preferably 200~300rpm)
1~12h of revolving speed ball milling (preferably 3~5h), obtain composite positive pole powder；
The positive electrode is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4 or Li (NiCoMn) O2(NCM)；
The ball milling pearl is zirconium oxide ball milling pearl, it is recommended to use ball milling pearl that 2 diameters are 20mm, 4~6 diameters are
The ball milling pearl that the ball milling pearl of 12mm or 20~25 diameters are 5mm carries out ball milling, and ball material mass ratio is 30~45:1；
(2) sheet metal is put into mold bottom, then composite positive pole powder obtained by step (1) is covered on sheet metal
On, it is pressed into positive plate under 200~600MPa (preferably 300~400MPa) pressure, later consolidates argyrodite type sulfide
State electrolyte is dispersed in its surface, tabletted with the pressure of 200~600MPa (preferably 300~400MPa)；
The sheet metal is selected from stainless steel substrates, aluminium flake or utter misery aluminium foil；
The mass ratio of the argyrodite type sulfide solid electrolyte and composite positive pole be 1:0.1~0.3 (preferably
0.125~0.2)；
(3) upper lithium piece is finally pressed with the pressure of 50~200MPa (preferably 100~150MPa) in the on piece of step (2) compacting
Or lithium indium alloy piece, form all-solid-state battery；
The composed structure of the all-solid-state battery is: sheet metal | anode | solid electrolyte | and lithium.
In the present invention, the preparation of the argyrodite type sulfide solid electrolyte and all-solid-state battery is in inert atmosphere
Lower progress, the gas of the atmosphere are argon gas or helium, and the water content of the atmosphere is less than 0.5ppm, and oxygen content is less than 0.5ppm.
The beneficial effects of the present invention are:
Compared with prior art, the raw material Li H used in the present invention is compared with Li2S is cheap, and LiH reactivity is strong, and raw material utilizes
Rate is high；Electrolyte is more stable, and distillation, burning, explosion will not occur in air for electrolyte exposure；Preparation is based on argyrodite type
Any solution is not used when the all-solid-state battery of sulfide solid electrolyte, effectively prevents electrolyte and solution reaction, shadow
The performance for ringing electrolyte, also avoids the processing of organic solvent.
The preparation method of argyrodite type sulfide solid electrolyte of the present invention is simple, it might even be possible to the one-step synthesis electrolysis
Matter, and raw material Li H price is low, reactivity is strong, realizes the high usage of raw material.The argyrodite type sulfide solid state electrolysis
Matter ionic conductivity with higher, wider electrochemical window, are applied to and prepare all-solid-state battery, have high safety
Property, high-energy density, excellent cyclical stability.
(4) Detailed description of the invention
Fig. 1 is the XRD diagram of obtained electrolyte in embodiment 1 and embodiment 2；
Fig. 2 is the scanning electron microscope diagram of obtained electrolyte in embodiment 1 and embodiment 2；
Fig. 3 is the curve graph that the ionic conductivity of obtained electrolyte in embodiment 1 varies with temperature；
Fig. 4 is the first charge-discharge curve of 12 all-solid-state battery of embodiment；
Fig. 5 is the cycle performance curve of 12 all-solid-state battery of embodiment.
(5) specific embodiment
The present invention is made below by embodiment and further being illustrated, but the invention is not limited to following realities
Example.
Embodiment 1
Solid electrolyte material is prepared according to the following steps:
(1) raw material Li H, P, S, LiCl are filled in the ball grinder that argon atmosphere is protected according to molar ratio 1:0.2:1:0.16
Bulb separation mill is 12, ratio of grinding media to material 20:1, rotational speed of ball-mill 400rpm, zirconium oxide ball milling pearl of 12mm using diameter, when ball milling
Between be 12 hours, obtain pretreated solid electrolyte；
(2) pre-treated solid electrolyte being put into tube furnace under an argon atmosphere and is sintered, heating rate is 2 DEG C/min,
Sintering temperature is 300 DEG C, and sintering time is 2 hours, and grind into powder selects 300 mesh powders to be sieved, obtains sulphur silver germanium
Mine type sulfide solid electrolyte, XRD is as shown in Fig. 1, and SEM figure is as shown in Figure 2.
The preparation of solid electrolyte carries out under an argon atmosphere in embodiment 1, and the water content of the atmosphere is less than 0.5ppm, contains
Oxygen amount is less than 0.5ppm.
Embodiment 2
Solid electrolyte material is prepared according to the following steps:
By LiH, P, S, LiCl according to molar ratio 1:0.2:1:0.16 on the ball grinder inner edge ball milling side that argon atmosphere is protected
Heating uses 12, ratio of grinding media to material 20:1, rotational speed of ball-mill 400rpm, zirconium oxide ball milling pearl that diameter is 12mm, heating rate
For 2 DEG C/min, heating temperature is 400 DEG C, and in ball milling, heating time is 4 hours, is then ground to powder, selects 300 purposes
Powder is sieved to obtain argyrodite type sulfide solid electrolyte, and XRD is as shown in Fig. 1, and SEM figure is as shown in Figure 2.
The preparation of solid electrolyte carries out under an argon atmosphere in embodiment 2, and the water content of the atmosphere is less than 0.5ppm, contains
Oxygen amount is less than 0.5ppm.
Embodiment 3
All-solid-state battery is prepared according to the following steps using electrolyte made from embodiment 2 in electrolyte layer:
(1) by 10 parts by weight NCM positive electrodes, 5 parts by weight conductive carbon blacks, 85 parts by weight argyrodite type sulfide solid-states
Electrolyte is added in the ball grinder full of argon gas, the 6 progress ball millings of zirconium oxide ball milling pearl for the use of diameter being 12mm, ball material weight
Amount is than being 30:1, and rotational speed of ball-mill 200rpm, Ball-milling Time is 3 hours, obtains composite positive pole；
(2) aluminium flake is placed on diameter is 15mm compression mold bottom, then covers 7.5mg composite positive pole powder,
Positive plate is made with the pressure pressurization of 300MPa, covering quality is the solid electrolyte powder of 60mg later, with the pressure of 300MPa
Power adds tabletted；
(3) the complete solid of upper lithium piece sandwich structure consisting is finally pressed with the pressure of 100MPa in the on piece of step (2) compacting
State battery.
The preparation of all-solid-state battery carries out under an argon atmosphere in embodiment 3, and the water content of the atmosphere is less than 0.5ppm, contains
Oxygen amount is less than 0.5ppm.
Embodiment 4
By LiH, P, S, LiCl according to molar ratio be 1:0.23:1:0.14, remaining is the same as embodiment 1.
Embodiment 5
By LiH, P, S, LiCl according to molar ratio be 1:0.25:1:0.2, remaining is the same as embodiment 1.
Embodiment 6
Rotational speed of ball-mill is changed to 500rpm, Ball-milling Time is 24 hours, remaining is the same as embodiment 1.
Embodiment 7
Rotational speed of ball-mill is changed to 500rpm, heating time is 6 hours in ball milling, remaining is the same as embodiment 2.
Embodiment 8
Sintering temperature is changed to 400 DEG C, sintering time is changed to 3 hours, remaining is the same as embodiment 1.
Embodiment 9
Heating temperature is changed to 400 DEG C, remaining is the same as embodiment 6.
Embodiment 10
Positive electrode NCM, conductive carbon black and argyrodite type sulfide solid electrolyte parts by weight are changed to 15 respectively, 5,
80, remaining is the same as embodiment 3.
Embodiment 11
Positive electrode NCM, conductive carbon black and argyrodite type sulfide solid electrolyte parts by weight are changed to 20 respectively, 5,
75, remaining is the same as embodiment 3.
Embodiment 12
Solid state electrolysis made from embodiment 1 and embodiment 2 is verified, and it carries out XRD test, and test results are shown in figure 1,
The peak of resulting solid electrolyte is almost the same, shows that the electrolyte of its synthesis is same substance.
It is tabletted to the resulting electrolyte of embodiment 1, it is clipped in two panels stainless steel substrates, carries out testing impedance, setting frequency
Rate 0.1Hz~106Hz, its conductivity varies with temperature curve as shown in figure 3, conductivity can reach 10 at room temperature after tested- 3The S/cm order of magnitude.
Solid state battery made of above-described embodiment 3, embodiment 10 and embodiment 11 is put into 2025 types in glove box
Number button cell, by the battery organized carry out different multiplying under constant current charge-discharge test, charging/discharging voltage section be 2.5
~4.0V, test temperature are 30 DEG C.First charge-discharge curve such as Fig. 4, cycle performance curve such as Fig. 5.
Although above having used general explanation, specific embodiment and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, some modifications or improvement can be made to it, this is aobvious and easy to those skilled in the art
See.Therefore, these modifications for being made without departing from theon the basis of the spirit of the present invention improve, and belong to that the present invention claims guarantors
The range of shield.
Claims (6)
1. a kind of preparation method of argyrodite type sulfide solid electrolyte, which is characterized in that the method are as follows:
(1) under inert atmosphere, LiH, P, S, LiX and ball milling pearl are added in ball grinder, with the revolving speed ball milling of 300~600rpm
8~60h obtains pretreated solid electrolyte；
The ratio between amount of substance of described LiH, P, S, LiX is 1:0.1~0.3:0.8~1.1:0.1~0.3；
In the LiX, X Cl, Br or I；
(2) under inert atmosphere, pretreated solid electrolyte obtained by step (1) is warming up to 200 with the rate of 2~5 DEG C/min
~600 DEG C, it is sintered 2~8h, is down to room temperature, grind into powder later, sieving obtains the argyrodite type sulfide solid-state electricity
Xie Zhi.
2. preparation method as described in claim 1, which is characterized in that in step (1), the substance of described LiH, P, S, LiX
The ratio between amount is 1:0.16~0.25:0.9~1.05:0.16~0.25.
3. preparation method as described in claim 1, which is characterized in that in step (1), the ball milling pearl is the oxygen of diameter 12mm
Change zirconium ball milling pearl, carries out ball milling using 12~15 ball milling pearls, ball material mass ratio is 20~25:1.
4. a kind of preparation method of argyrodite type sulfide solid electrolyte, which is characterized in that the method are as follows:
Under inert atmosphere, LiH, P, S, LiX and ball milling pearl are added in ball grinder, is heated in ball milling, is down to room temperature later,
Grind into powder, sieving, obtains the argyrodite type sulfide solid electrolyte；
Described heat in ball milling refers to: 300~500 DEG C is warming up to while ball milling with the rate of 2~5 DEG C/min, when ball milling
Between be 2~8h, rotational speed of ball-mill be 300~600rpm；
The ratio between amount of substance of described LiH, P, S, LiX is 1:0.1~0.3:0.8~1.1:0.1~0.3；
In the LiX, X Cl, Br or I.
5. preparation method as claimed in claim 4, which is characterized in that the ratio between amount of substance of described LiH, P, S, LiX is 1:
0.16~0.25:0.9~1.05:0.16~0.25.
6. preparation method as claimed in claim 4, which is characterized in that the ball milling pearl is the zirconium oxide ball milling of diameter 12mm
Pearl carries out ball milling using 12~15 ball milling pearls, and ball material mass ratio is 20~25:1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102714313A (en) * | 2010-01-08 | 2012-10-03 | 三菱化学株式会社 | Powder for positive electrode material for lithium secondary battery and process for production thereof, and positive electrode for lithium secondary battery and lithium secondary battery each utilizing the powder |
| CN103456932A (en) * | 2012-05-27 | 2013-12-18 | 湖南省正源储能材料与器件研究所 | Preparation method of energy storage material |
| CN106848391A (en) * | 2017-03-15 | 2017-06-13 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of lithium ion battery solid electrolyte and preparation method thereof |
| CN108134059A (en) * | 2017-12-20 | 2018-06-08 | 成都新柯力化工科技有限公司 | A kind of negative electrode active material and preparation method for low temperature lithium battery |
-
2018
- 2018-10-17 CN CN201811206762.1A patent/CN109193026A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102714313A (en) * | 2010-01-08 | 2012-10-03 | 三菱化学株式会社 | Powder for positive electrode material for lithium secondary battery and process for production thereof, and positive electrode for lithium secondary battery and lithium secondary battery each utilizing the powder |
| CN103456932A (en) * | 2012-05-27 | 2013-12-18 | 湖南省正源储能材料与器件研究所 | Preparation method of energy storage material |
| CN106848391A (en) * | 2017-03-15 | 2017-06-13 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of lithium ion battery solid electrolyte and preparation method thereof |
| CN108134059A (en) * | 2017-12-20 | 2018-06-08 | 成都新柯力化工科技有限公司 | A kind of negative electrode active material and preparation method for low temperature lithium battery |
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