CN115579511A - Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium ion battery - Google Patents

Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium ion battery Download PDF

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CN115579511A
CN115579511A CN202211182287.5A CN202211182287A CN115579511A CN 115579511 A CN115579511 A CN 115579511A CN 202211182287 A CN202211182287 A CN 202211182287A CN 115579511 A CN115579511 A CN 115579511A
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sulfide solid
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田冰冰
陈寒楠
黄晓
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Shenzhen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention provides a sulfide solid electrolyte, a preparation method thereof and an all-solid-state lithium ion battery. The preparation method replaces the traditional ball milling mode, adopts a high-efficiency and large-batch high-speed stirring mode to prepare the precursor, and has wide applicable sulfide material system; the sulfide solid electrolyte material can furthest retain the valence state of S, and avoids valence change of an S element caused by improper energy in ball milling preparation, so that the generation of a sintered heterogeneous phase is reduced, the crystallinity of the sulfide solid electrolyte is improved, a pure phase is obtained as far as possible, the ionic conductivity and stability of the sulfide solid electrolyte at room temperature are improved, and the coulombic efficiency, the cycling stability, the cycle life and the stable cycling capability under high voltage of a first circle of an all-solid lithium battery can be further improved. Meanwhile, the time cost is greatly reduced by the efficient preparation time and large batch treatment capacity, and the commercialization process of the sulfide solid electrolyte material is improved.

Description

Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion solid electrolyte batteries, in particular to a sulfide solid electrolyte, a preparation method thereof and an all-solid-state lithium ion battery.
Background
The lithium ion battery has higher energy density and longer service lifeAnd the environment-friendly effect, and the like, and can be widely applied to the fields of mobile phones, computers, automobiles, energy storage and the like. At present, the traditional lithium ion battery has revolutionized the energy industry, but the more and more extensive energy storage requirements put higher demands on the safety, energy density and lifetime of lithium ions. Therefore, all-solid-state batteries using solid electrolytes instead of flammable liquid electrolytes are not the second choice for next-generation lithium ion batteries. Not only because of the higher safety of the solid electrolyte, but also because of the high voltage cathode material (such as Li (NiCoMn) O) 2 ) And a large capacity electrode (such as a lithium metal negative electrode) to achieve a high energy density battery.
The current solid-state electrolytes are in a wide variety, and sulfide electrolytes, which are widely studied due to their conductivity comparable to that of conventional electrolytes and electrochemical stability, are the fastest-going commercialization of all solid-state batteries, and are considered as a new breakthrough point for the development of all solid-state lithium ion batteries. The electrolyte material is one of the core materials of the lithium ion battery, and the conductivity and stability of the electrolyte material have great influence on the electrochemical performance of the lithium ion battery. The traditional sulfide material is prepared by ball milling through a zirconia pot, but is easy to agglomerate in the ball milling process, so that the ball milling efficiency is reduced. Therefore, how to prepare the electrolyte material with high ionic conductivity with high efficiency is a key process to be solved in the commercial process of the sulfide-based lithium ion battery. Meanwhile, based on the requirement of large-scale production, how to reduce the production cost is also a practical problem.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a sulfide solid electrolyte, a preparation method thereof and an all-solid-state lithium ion battery, aiming at solving the problems of poor stability, low conductivity and high preparation material cost of the conventional sulfide electrolyte.
The technical scheme of the invention is as follows:
a sulfide solid state electrolyte, wherein the sulfide isThe solid electrolyte comprises Li 7-N PS 6-N X N 、Li 7-M- A PS 6-M-A Cl A I M 、Li 7-A-V PS 6-A-V Cl A Br V 、Li 7-M-V PS 6-M-V Br V I M 、Li 7-N+B P 1-B Y B S 6-N X N 、Li 7-N P 1-C Z C S 6-N X N 、Li 7-A-V+B P 1-B Y B S 6-A-V Cl A Br V 、Li 7-M-A+B P 1-B Y B S 6-M-A Cl A I M 、Li 7-M-V+B P 1-B Y B S 6-M-V Br V I M 、Li 7-A-V P 1- C Y C S 6-A-V Cl A Br V 、Li 7-M-A P 1-C Y C S 6-M-A Cl A I M 、Li 7-M-V P 1-C Y C S 6-M-V Br V I M At least one of (a); wherein X is selected from one of Cl, br and I, Y is selected from one of Sn, si, in, ge and Pb, and Z is selected from one of As and Sb; n is more than 0 and less than or equal to 2, M is more than 0 and less than or equal to 2, A is more than 0 and less than or equal to 2, V is more than 0 and less than or equal to 2; b is more than or equal to 0 and less than or equal to 1, and C is more than or equal to 0 and less than or equal to 1.
A method for producing a sulfide solid electrolyte, comprising the steps of:
mixing raw materials corresponding to the molecular formula of the sulfide solid electrolyte according to a preset stoichiometric ratio, and then carrying out high-speed stirring treatment to obtain precursor powder;
and (3) putting the precursor powder into an atmosphere furnace, continuously introducing inert gas, heating to 350-550 ℃, and reacting for 1-12h to obtain the sulfide solid electrolyte.
The preparation method of the sulfide solid electrolyte comprises the steps of preparing the sulfide solid electrolyte from Li 7- N PS 6-N X N 、Li 7-M-A PS 6-M-A Cl A I M 、Li 7-A-V PS 6-A-V Cl A Br V 、Li 7-M-V PS 6-M-V Br V I M 、Li 7-N+B P 1-B Y B S 6-N X N 、Li 7- N P 1-C Z C S 6-N X N 、Li 7-A-V+B P 1-B Y B S 6-A-V Cl A Br V 、Li 7-M-A+B P 1-B Y B S 6-M-A Cl A I M 、Li 7-M-V+B P 1-B Y B S 6-M-V Br V I M 、Li 7-A-V P 1-C Y C S 6-A-V Cl A Br V 、Li 7-M-A P 1-C Y C S 6-M-A Cl A I M 、Li 7-M-V P 1-C Y C S 6-M-V Br V I M At least one of; wherein X is selected from one of Cl, br and I, Y is selected from one of Sn, si, in, ge and Pb, and Z is selected from one of As and Sb; n is more than 0 and less than or equal to 2, M is more than 0 and less than or equal to 2, A is more than 0 and less than or equal to 2, V is more than 0 and less than or equal to 2; b is more than or equal to 0 and less than or equal to 1, and C is more than or equal to 0 and less than or equal to 1.
The preparation method of the sulfide solid electrolyte comprises the following steps of preparing LiCl and Li as raw materials 2 S、P 2 S 5 、LiI、SnS 2 、LiBr、SiS 2 、In 2 S 3 、GeS 2 、PbS、As 2 S 3 Or Sb 2 S 3 One or more of (a).
The preparation method of the sulfide solid electrolyte is characterized in that the rotating speed of the high-speed stirring treatment is 20000-40000 r/min, and the time of the high-speed stirring treatment is 10-30 min.
The preparation method of the sulfide solid electrolyte comprises the step of heating to 350-550 ℃, wherein the heating rate is 3 ℃/min.
The preparation method of the sulfide solid electrolyte comprises the following steps after the reaction is finished: cooling to room temperature at a rate of 2 deg.C/min.
The preparation method of the sulfide solid electrolyte comprises the step of preparing the sulfide solid electrolyte, wherein the inert gas comprises one or more of argon, helium, neon or nitrogen.
The application of the sulfide solid electrolyte is to prepare an all-solid-state lithium ion battery.
An all-solid-state lithium ion battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the sulfide solid-state electrolyte or the sulfide solid-state electrolyte prepared by the preparation method of the sulfide solid-state electrolyte.
Has the advantages that: the invention provides a sulfide solid electrolyte, a preparation method thereof and an all-solid-state lithium ion battery. The sulfide solid electrolyte adopts a high-speed stirring mode which is high in efficiency and can be produced in large batch to prepare a precursor, the applicable sulfide material system is wide, the sulfide solid electrolyte material can furthest retain the valence state of S under the preparation of the method, and the valence change of an S element caused by improper energy in a ball milling mode is avoided, so that the generation of a sintered heterogeneous phase is reduced, the crystallinity of the sulfide solid electrolyte is improved, a pure phase is obtained as far as possible, the ionic conductivity and the stability of the sulfide solid electrolyte at room temperature are improved, and the sulfide solid electrolyte has ultrahigh ionic conductivity (the>2×10 -4 S/cm) and low electron conductivity (< 1X 10) -8 S/cm), the first-turn coulombic efficiency, the cycle stability, the cycle life and the stable cycle capability under high voltage of the all-solid-state lithium battery can be improved.
Drawings
Fig. 1 is a flowchart of producing a sulfide solid state electrolyte material according to an embodiment of the present invention;
FIG. 2 shows Li prepared by high-speed stirring in an example of the present invention 5.4 PS 4.4 Cl 1.6 The microstructure of (a);
fig. 3 is XRD patterns of solid electrolytes prepared from samples a, I and L in examples 1 to 4 of the present invention at different doping values;
FIG. 4 is a graph of the AC impedance of a symmetrical cell assembled from electrolytes prepared in samples A, I and L of examples 1-4 of the present invention;
FIG. 5 is a first-turn charge-discharge curve diagram of an all-solid lithium ion battery assembled by the electrolyte of sample A in example 1 according to the present invention at a rate of 0.1C;
FIG. 6 is a first-turn charge-discharge curve diagram of an all-solid lithium ion battery assembled by the electrolyte of sample I in example 3 according to the present invention at a rate of 0.1C;
fig. 7 is a first-turn charge-discharge curve diagram of an all-solid-state lithium ion battery assembled by the electrolyte of sample L in example 4 of the present invention at a rate of 0.1C.
Detailed Description
The invention provides a sulfide solid electrolyte, a preparation method thereof and an all-solid-state lithium ion battery, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a sulfide solid electrolyte which comprises Li 7-N PS 6- N X N 、Li 7-M-A PS 6-M-A Cl A I M 、Li 7-A-V PS 6-A-V Cl A Br V 、Li 7-M-V PS 6-M-V Br V I M 、Li 7-N+B P 1-B Y B S 6-N X N 、Li 7-N P 1- C Z C S 6-N X N 、Li 7-A-V+B P 1-B Y B S 6-A-V Cl A Br V 、Li 7-M-A+B P 1-B Y B S 6-M-A Cl A I M 、Li 7-M-V+B P 1-B Y B S 6-M-V Br V I M 、Li 7-A- V P 1-C Y C S 6-A-V Cl A Br V 、Li 7-M-A P 1-C Y C S 6-M-A Cl A I M 、Li 7-M-V P 1-C Y C S 6-M-V Br V I M At least one of; wherein X is selected from one of Cl, br and I, Y is selected from one of Sn, si, in, ge and Pb, and Z is selected from one of As and Sb; n is more than 0 and less than or equal to 2, M is more than 0 and less than or equal to 2, A is more than 0 and less than or equal to 2, V is more than 0 and less than or equal to 2; b is more than or equal to 0 and less than or equal to 1, and C is more than or equal to 0 and less than or equal to 1.
The sulfide solid electrolyte provided by the embodiment of the invention comprises a Geranite structure Li 7-N PS 6-N X N And associated P-bit and S-bit doping, but is not so limited. In some embodiments, the sulfide solid state electrolyte further comprises a halogen doping, such as Br or I; carbon group element doping such as Sn, si, ge, or Pb, and doping of other elements, and the like. The embodiment of the invention can effectively dope the elements into the structure of the Geranite, broaden the lattice spacing, increase the mixed discharging degree of anions, broaden the transmission channel of lithium ions and greatly improve the ionic conductivity.
In some embodiments, the formula Li 7-N PS 6-N Cl N N in (1) is preferably 0.5<N<1.6; when N is in this range, the conductivity of the sulfide solid state electrolyte material can be optimized. In particular, said N =0.5, 0.75, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6. However, N is not limited to the above numerical values, and other numerical values not listed in this range are also applicable.
In some embodiments, the formula Li 7-N+B P 1-B Sn B S 6-N Cl N B in (1) is preferably 0<B<0.5; n is preferably 0.5<N<1.6; at this range, the conductivity of the sulfide solid state electrolyte material>1×10 -4 S/cm. Specifically, said B =0.05, 0.1, 0.2, 0.3, 0.4, 0.5; the N =1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6. However, B and N are not limited to the above-mentioned values, and other values not listed in the range are also applicable.
The embodiment of the invention also provides a preparation method of the sulfide solid electrolyte, which comprises the following steps as shown in figure 1:
s10, mixing raw materials corresponding to the molecular formula of the sulfide solid electrolyte according to a preset stoichiometric ratio, and then carrying out high-speed stirring treatment to obtain precursor powder;
s20, placing the precursor powder in an atmosphere furnace, continuously introducing inert gas, heating to 350-550 ℃, and reacting for 1-12h to obtain the sulfide solid electrolyte.
The preparation method of the sulfide solid electrolyte is different from the traditional ball milling mode, the uniform precursor can be obtained by adopting high-efficiency high-speed stirring treatment for dozens of minutes even dozens of minutes, and then the sulfide solid electrolyte can be obtained by one-time large-batch sintering, and has ultrahigh room-temperature ionic conductivity and high stability. Moreover, the microstructure of the sulfide solid electrolyte sample prepared by the embodiment of the invention is basically consistent with the microstructure of powder prepared by the traditional ball milling, and the sintered particles are large and the crystallinity is good.
In some embodiments, the speed of the high speed stirring treatment is 20000 to 40000 rpm, and the time of the high speed stirring treatment is 10 to 30 minutes. Under the high-speed stirring speed and time, the raw materials can be fully ground, and powder with uniform particle size can be obtained. If the processing time is not enough, the material mixing is not uniform, the particle sizes of the powder are different, the particle size difference is large, raw material residues are easy to occur after sintering, and the obtained sulfide solid electrolyte material has unstable performance and low ionic conductivity; if the treatment time is too long, the initial sulfide solid state electrolyte material is destroyed, the proportion of the hetero-phase after sintering increases, and the ionic conductivity also decreases. Specifically, the high-speed stirring treatment may be carried out at a rotation speed of 40000 rpm for 10 minutes or at a rotation speed of 30000 rpm for 20 minutes. The processing time required by different material systems is different, and can be specifically adjusted according to different types of precursors.
In some embodiments, the high-speed stirring treatment can be performed for 1 minute every 5 minutes due to the heat dissipation factor, and the process is circulated.
In some embodiments, the high-speed stirring adopts a rotating blade, and the rotating blade for high-speed stirring is 3 layers of double heads and is slightly smaller than the inner diameter of the cavity.
In some embodiments, the particle size distribution D50 of the sulfide solid electrolyte precursor is 90 μm. Specifically, the rotation speed and the time of the high-speed stirring treatment can be appropriately adjusted according to different precursors and particle sizes.
According to the preparation method provided by the embodiment of the invention, the sulfide solid electrolyte precursor is stirred at a high speed by the rotary blade, the traditional high-energy ball milling mode is replaced, the ball milling time is shortened to within half an hour from several hours to more than ten hours, and meanwhile, the preparation of kilogram-grade precursors can be carried out at one time, so that the preparation efficiency is greatly improved. Specifically, compared with the traditional ball milling mode, the method can form initial sulfide solid electrolyte precursor powder very quickly by a high-speed stirring mode, and cannot further damage the initial powder like ball milling; and for the doped elements, the mode can enable the doped elements to enter crystal lattices to the maximum extent, and the generation of a hetero-phase ratio is reduced. Meanwhile, the preparation method forms uniform amorphous material to obtain higher ionic conductivity (>3×10 -4 S/cm) and low electron conductivity (< 1X 10) -8 S/cm), the ultra-high ionic conductivity and electrolyte stability can reduce the occurrence of side reactions, and improve the first-loop coulombic efficiency, the cycle stability and the cycle life of the all-solid-state lithium battery.
In some embodiments, the feedstock comprises LiCl, li 2 S、P 2 S 5 、LiI、SnS 2 、LiBr、SiS 2 、In 2 S 3 、GeS 2 、PbS、As 2 S 3 Or Sb 2 S 3 One or more of (a). The corresponding raw materials can be selected according to different sulfide solid electrolytes. For example, for preparing electrolyte LPSC, liCl and Li can be selected 2 S and P 2 S 5 (ii) a For preparing electrolyte LPSCI, liCl and Li can be selected 2 S, liI and P 2 S 5 (ii) a Preparing electrolyte LPSnSCI, liCl and Li can be selected 2 S、LiI、SnS 2 And P 2 S 5 Etc., and can be appropriately selected as needed. Meanwhile, it should be noted that,the present invention does not require any special source of the raw material, and commercially available ones can be used.
In some specific embodiments, the preparation of the sulfide solid electrolyte LPSC comprises the steps of:
s100, liCl and P 2 S 5 And Li 2 S, weighing stoichiometric ratio according to different chemical formulas, mixing and carrying out high-speed stirring treatment to obtain mixed powder;
s200, placing the mixed powder in an atmosphere furnace, continuously introducing inert gas, heating to 300-550 ℃, reacting for 1-10h, reducing the temperature to room temperature, crushing and collecting to obtain the sulfide solid electrolyte LPSC.
Specifically, the rotating speed of the high-speed stirring treatment is 20000-40000 r/min, and the time of the high-speed stirring treatment is 10-30 min.
In some embodiments, in the step of raising the temperature to 350-550 ℃, the temperature raising rate is 3 ℃/min.
In some embodiments, the method further comprises the following steps after the temperature is increased to 300-550 ℃ and the reaction is carried out for 1-10 h: cooling to room temperature at a rate of 2 deg.C/min.
In some embodiments, the inert gas comprises one or more of argon, helium, neon, or nitrogen.
In some embodiments, in step S20, the container for performing the high-temperature sintering reaction is made of alumina, a quartz crucible, or a titanium pot.
The preparation method of the sulfide solid electrolyte provided by the embodiment of the invention replaces the traditional ball milling mode, adopts a high-efficiency and large-batch high-speed stirring mode to prepare precursor powder, uses a large container to contain the prepared sulfide, places the sulfide in an atmosphere furnace, continuously introduces inert gas, heats the sulfide to 350-550 ℃, reacts for 1-10 hours, and finally crushes and collects the prepared sulfide solid electrolyte. The sulfide solid electrolyte material can furthest retain the valence state of S under the preparation of the method, and the valence change of an S element caused by improper energy in a ball milling mode is avoided, so that the generation of a sintered impure phase is reduced, the crystallinity of the sulfide solid electrolyte is improved, a pure phase is obtained as far as possible, and the ionic conductivity and the stability of the sulfide solid electrolyte at room temperature are improved. Meanwhile, the method is simple and easy to operate, is suitable for large-scale production, can obtain initial sulfide solid electrolyte powder only by mixing materials at a high speed within half an hour, and can obtain kilogram-level sulfide solid electrolyte by subsequently using a large-capacity alumina crucible to contain the alumina crucible and heating the alumina crucible under inert gas.
The embodiment of the invention also provides application of the sulfide solid electrolyte, and the sulfide solid electrolyte prepared by the sulfide solid electrolyte or the sulfide solid electrolyte prepared by the sulfide solid electrolyte preparation method is applied to preparation of an all-solid-state lithium ion battery.
The embodiment of the invention also provides an all-solid-state lithium ion battery which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the sulfide solid-state electrolyte or the sulfide solid-state electrolyte prepared by the preparation method of the sulfide solid-state electrolyte.
The sulfide solid electrolyte, the preparation method thereof and the all-solid-state lithium ion battery of the present invention are further explained by the following specific examples:
example 1 Synthesis of LPSC
In a glove box, weighing:
sample a:21.4gLi 2 S、20.7gP 2 S 5 、7.9gLiCl(Li 6 PS 5 Cl)
Sample B:20.57gLi 2 S、20.73gP 2 S 5 、8.69gLiCl(Li 5.9 PS 4.9 Cl 1.1 )
Sample C:19.74gLi 2 S、20.75gP 2 S 5 、9.5gLiCl(Li 5.8 PS 4.8 Cl 1.2 )
The raw materials in various proportions are respectively poured into a powder grinding machine cavity to be stirred at a high speed, the stirring time is 15 minutes, and the precursor can be obtained by resting for 1 minute every 5 minutes due to the heat dissipation factor.
And putting the precursor into an alumina crucible, heating to 560 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 8h, the heating rate is 3 ℃/min, and the cooling rate is 2 ℃/min. After sintering, the samples were collected and ground thoroughly in a glove box and sieved using a 30 micron mesh screen to obtain LPSC samples of the corresponding molecular formula.
Example 2 Synthesis of LPSC
In a glove box, weighing:
sample D:18.9gLi 2 S、20.78gP 2 S 5 、10.30gLiCl(Li 5.7 PS 4.7 Cl 1.3 )
Sample E:18.07gLi 2 S、20.81gP 2 S 5 、11.11gLiCl(Li 5.6 PS 4.6 Cl 1.4 )
Sample F:17.23gLi 2 S、20.84gP 2 S 5 、11.9gLiCl(Li 5.5 PS 4.5 Cl 1.5 )
Sample G:16.39gLi 2 S、20.87gP 2 S 5 、12.73gLiCl(Li 5.4 PS 4.4 Cl 1.6 )
The raw materials in various proportions are respectively poured into a powder grinding machine cavity to be stirred at a high speed, the stirring time is 10 minutes, and the precursor can be obtained by resting for 1 minute every 5 minutes due to the heat dissipation factor.
And (3) putting the precursor into an alumina crucible, heating to 520 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 8h, the heating rate is 3 ℃/min, and the cooling rate is 2 ℃/min. After sintering, the samples were collected and ground thoroughly in a glove box and sieved using a 30 micron mesh screen to obtain LPSC samples of the corresponding molecular formula.
Example 3 Synthesis of LPCSI
In a glove box, weighing:
sample H:21.04gLi 2 S、20.35gP 2 S 5 、7.37gLiCl、1.23gLiI(Li 6 PS 5 Cl 0.95 I 0.05 )
Sample I:21.69gLi 2 S、20.02gP 2 S 5 、6.87gLiCl、2.41gLiI(Li 6 PS 5 Cl 0.9 I 0.1 )
Sample J:20.03gLi 2 S、19.38gP 2 S 5 、5.91gLiCl、4.66gLiI(Li 6 PS 5 Cl 0.8 I 0.2 )
The raw materials in various proportions are respectively poured into a powder grinding machine cavity to be stirred at a high speed, the stirring time is 18 minutes, and the precursor can be obtained by resting for 1 minute every 5 minutes due to the heat dissipation factor.
And putting the precursor into an alumina crucible, heating to 550 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 12h, the heating rate is 3 ℃/min, and the cooling rate is 2 ℃/min. After sintering, the samples were collected and ground thoroughly in a glove box and sieved using a 30 micron mesh screen to obtain LPSC samples of the corresponding molecular formula.
Example 4 LPSnSCI
Sample K:20.55gLi 2 S、18.7gP 2 S 5 、6.75gLiCl、2.37gLiI、1.62gSnS 2 (Li 6.05 Sn 0.05 P 0.95 S 5 Cl 0.9 I 0.1 )
Sample L:20.41gLi 2 S、17.42gP 2 S 5 、6.64gLiCl、2.33gLiI、3.18gSnS 2 (Li 6.1 Sn 0.1 P 0.9 S 5 Cl 0.9 I 0.1 )
Sample M:20.14gLi 2 S、14.99gP 2 S 5 、6.43gLiCl、2.25gLiI、6.16gSnS 2 (Li 6.2 Sn 0.2 P 0.8 S 5 Cl 0.9 I 0.1 )
The raw materials in various proportions are respectively poured into a powder grinding machine cavity to be stirred at a high speed, the stirring time is 20 minutes, and the precursor can be obtained by resting for 1 minute every 5 minutes due to the heat dissipation factor.
And putting the precursor into an alumina crucible, heating to 500 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 12h, the heating rate is 3 ℃/min, and the cooling rate is 2 ℃/min. After sintering, the samples were collected and ground thoroughly in a glove box and sieved using a 30 micron mesh screen to obtain LPSC samples of the corresponding molecular formula.
Test example 1
For sample G (Li) obtained in example 2 5.4 PS 4.4 Cl 1.6 ) The microstructure was observed and shown in FIG. 2. As can be seen from the figure, the sample prepared by the embodiment of the scheme has the microscopic morphology basically consistent with that of powder prepared by the traditional ball milling, and the sintered particles are large and have good crystallinity.
The sulfide solid electrolyte samples a, I, and L prepared in the above examples 1 to 4 were subjected to X-ray diffraction at angles of 20 to 70 °, and XRD results are shown in fig. 3. As can be seen from the figure, XRD in the embodiment has a very pure Geranite structure, high main peak intensity and few miscellaneous peaks.
Test example 2
The electrochemical properties of the sulfide solid electrolytes prepared in the above examples 1 to 4 were tested:
and (3) ion conductivity test: the thickness of the obtained solid electrolyte wafer is measured by using an electrochemical workstation to measure an alternating current impedance spectrum, the measuring range is 10-1000000 Hz, the measuring temperature is 25 ℃, 0.3g of solid electrolyte powder is poured into a sleeve with the diameter of 10mm, tabletting is carried out under a tabletting machine, the pressure is 200MPa, the pressure maintaining time is 1min, and the thickness of the obtained solid electrolyte wafer is measured by using a micrometer. A piece of carbon-coated copper foil (with the carbon end facing the solid electrolyte) is respectively placed at two ends of the solid electrolyte sheet to form a blocking battery of carbon-coated aluminum foil/electrolyte sheet/carbon-coated aluminum foil, and the blocking battery is placed into a conductivity test kit, pressurized at 200Mpa and connected with an electrochemical workstation for EIS test, wherein the test range is 10-1000000 Hz, direct current voltage of 200mV is applied, and the test temperature is 25 ℃, and the result is shown in FIG. 4. As can be seen, at room temperature, the impedances of samples A, I and L were 53.2. Omega., 28.9. Omega., and 43.0. Omega., respectively, and the corresponding conductivities were 3.8ms/cm,4.1ms/cm, and 5.2ms/cm, respectively.
Test example 3
For the sulfide solid electrolyte Li provided in the above example 1 6 PS 5 Cl (sample A) and sulfide solid electrolyte Li provided in example 3 6 PS 5 Cl 0.9 I 0.1 (sample I) sulfide solid electrolyte Li provided in example 4 6.1 Sn 0.1 P 0.9 S 5 Cl 0.9 I 0.1 (sample L) the first coulombic efficiency and discharge capacity test was performed using a New Wille tester, comprising the specific steps of:
1) Taking a certain amount of the electrolyte material, and tabletting under the pressure of 40MPa to obtain an LPSC solid electrolyte sheet;
2) Adding a certain mass of ternary cathode material and sulfide solid electrolyte into one side of the solid electrolyte sheet prepared in the step 1) to obtain a cathode material; adding a negative electrode material prepared by mixing graphite and sulfide solid electrolyte on the other side of the solid electrolyte; pressing under 300MPa to obtain the all-solid-state lithium ion battery;
3) Respectively carrying out 0.1C charge and discharge on the all-solid-state lithium battery obtained in the step 2), wherein the voltage range is 3-4.2V vs + 。
The first-turn coulombic efficiency of the all-solid-state battery assembled by the sample A, the sample I and the sample L is shown in fig. 5-7, and it can be seen from the graphs that the first-turn coulombic efficiency of the battery composed of the sulfide solid-state electrolyte material prepared by the embodiment of the invention is up to more than 82%, and the charge and discharge of the electrolyte with high conductivity and stability prepared by the method are shown, so that the reversible capacity is greatly improved; meanwhile, the charge and discharge capacity of the battery composed of the sulfide electrolyte material prepared by the embodiment of the invention is higher, even up to 175mAh/g.
In summary, the invention provides a sulfide solid electrolyte, a preparation method thereof and an all-solid-state lithium ion battery. The preparation method replaces the traditional ball milling mode, adopts a high-efficiency and large-batch high-speed stirring mode to prepare the precursor, and uses a large container to contain the prepared sulfidePlacing the mixture in an atmosphere furnace after being filled, continuously introducing inert gas, heating to 350-550 ℃, reacting for 1-10h, and finally crushing and collecting the prepared sulfide solid electrolyte. The sulfide solid electrolyte material can furthest retain the valence state of S under the preparation of the method, and the valence change of an S element caused by improper energy in a ball milling mode is avoided, so that the generation of a sintered impure phase is reduced, the crystallinity of the sulfide solid electrolyte is improved, a pure phase is obtained as far as possible, and the ionic conductivity and the stability of the sulfide solid electrolyte at room temperature are improved. The uniform sulfide solid electrolyte precursor is prepared by high-speed stirring, and the sulfide solid electrolyte prepared by sintering has ultrahigh ionic conductivity (>2×10 -4 S/cm) and low electron conductivity (< 1X 10) -8 S/cm), for example, the solid electrolyte material Li of the present invention 5.4 PS 4.4 Cl 1.6 At 25 deg.C, the ionic conductivity is more than 1 × 10 -2 S/cm，Li 6 PS 5 Ionic conductivity of Cl is more than 4X 10 -3 S/cm, which can improve the first-turn coulombic efficiency, the cycle stability, the cycle life and the stable cycle capability under high voltage of the all-solid-state lithium battery. Meanwhile, the sulfide prepared by the preparation method can form a complete precursor within half an hour, and the preparation of hundreds of grams or even kilograms of precursors can be carried out simultaneously, so that the time cost is greatly reduced due to high-efficiency preparation time and large-batch treatment capacity, and the commercialization process of the sulfide solid electrolyte material is improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. A sulfide solid state electrolyte, characterized in that the sulfide solid state electrolyte comprises Li 7-N PS 6-N X N 、Li 7-M-A PS 6-M-A Cl A I M 、Li 7-A-V PS 6-A-V Cl A Br V 、Li 7-M-V PS 6-M-V Br V I M 、Li 7-N+B P 1-B Y B S 6-N X N 、Li 7-N P 1-C Z C S 6- N X N 、Li 7-A-V+B P 1-B Y B S 6-A-V Cl A Br V 、Li 7-M-A+B P 1-B Y B S 6-M-A Cl A I M 、Li 7-M-V+B P 1-B Y B S 6-M-V Br V I M 、Li 7-A-V P 1- C Y C S 6-A-V Cl A Br V 、Li 7-M-A P 1-C Y C S 6-M-A Cl A I M 、Li 7-M-V P 1-C Y C S 6-M-V Br V I M At least one of; wherein X is selected from one of Cl, br and I, Y is selected from one of Sn, si, in, ge and Pb, and Z is selected from one of As and Sb; n is more than 0 and less than or equal to 2, M is more than 0 and less than or equal to 2, A is more than 0 and less than or equal to 2, V is more than 0 and less than or equal to 2; b is more than or equal to 0 and less than or equal to 1, and C is more than or equal to 0 and less than or equal to 1.
2. A method for producing a sulfide solid electrolyte, comprising the steps of:
mixing raw materials corresponding to the molecular formula of the sulfide solid electrolyte according to a preset stoichiometric ratio, and then carrying out high-speed stirring treatment to obtain precursor powder;
and (3) putting the precursor powder into an atmosphere furnace, continuously introducing inert gas, heating to 350-550 ℃, and reacting for 1-12h to obtain the sulfide solid electrolyte.
3. The method according to claim 2, wherein the sulfide solid electrolyte comprises Li 7-N PS 6-N X N 、Li 7-M-A PS 6-M-A Cl A I M 、Li 7-A-V PS 6-A-V Cl A Br V 、Li 7-M-V PS 6-M-V Br V I M 、Li 7-N+ B P 1-B Y B S 6-N X N 、Li 7-N P 1-C Z C S 6-N X N 、Li 7-A-V+B P 1-B Y B S 6-A-V Cl A Br V 、Li 7-M-A+B P 1-B Y B S 6-M-A Cl A I M 、Li 7-M-V+ B P 1-B Y B S 6-M-V Br V I M 、Li 7-A-V P 1-C Y C S 6-A-V Cl A Br V 、Li 7-M-A P 1-C Y C S 6-M-A Cl A I M 、Li 7-M-V P 1-C Y C S 6-M-V Br V I M At least one of; wherein X is selected from one of Cl, br and I, Y is selected from one of Sn, si, in, ge and Pb, and Z is selected from one of As and Sb; n is more than 0 and less than or equal to 2, M is more than 0 and less than or equal to 2, A is more than 0 and less than or equal to 2, V is more than 0 and less than or equal to 2; b is more than or equal to 0 and less than or equal to 1, and C is more than or equal to 0 and less than or equal to 1.
4. The method according to claim 3, wherein the raw material comprises LiCl, li 2 S、P 2 S 5 、LiI、SnS 2 、LiBr、SiS 2 、In 2 S 3 、GeS 2 、PbS、As 2 S 3 Or Sb 2 S 3 One or more of (a).
5. The method according to claim 2, wherein the rotation speed of the high-speed stirring treatment is 20000 to 40000 rpm, and the time of the high-speed stirring treatment is 10 to 30 minutes.
6. The method according to claim 2, wherein in the step of raising the temperature to 350 to 550 ℃, the temperature raising rate is 3 ℃/min.
7. The method for producing a sulfide solid electrolyte according to claim 2, further comprising, after completion of the reaction, the steps of: cooling to room temperature at a rate of 2 deg.C/min.
8. The method of producing a sulfide solid state electrolyte according to claim 2, wherein the inert gas includes one or more of argon, helium, neon, or nitrogen.
9. Use of a sulfide solid electrolyte according to claim 1 or a sulfide solid electrolyte prepared by the method according to any one of claims 2 to 8 for the preparation of an all-solid lithium ion battery.
10. An all-solid-state lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the sulfide solid-state electrolyte according to claim 1 or the sulfide solid-state electrolyte prepared by the method for preparing the sulfide solid-state electrolyte according to any one of claims 2 to 8.
CN202211182287.5A 2022-09-27 2022-09-27 Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium ion battery Pending CN115579511A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN117199507A (en) * 2023-08-14 2023-12-08 国联汽车动力电池研究院有限责任公司 Inorganic sulfide solid electrolyte and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117199507A (en) * 2023-08-14 2023-12-08 国联汽车动力电池研究院有限责任公司 Inorganic sulfide solid electrolyte and preparation method thereof

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