CN114388803B - Passivation layer sulfide solid electrolyte and preparation method and application thereof - Google Patents
Passivation layer sulfide solid electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a passivation layer sulfide solid electrolyte and a preparation method and application thereof, wherein the method comprises the following steps: providing an initial sulfide solid electrolyte powder; and placing the initial sulfide solid electrolyte powder in a tube furnace, continuously introducing inert gas passing through tin tetrachloride liquid, heating to 300-550 ℃, reacting for 1-10h, and generating an in-situ doped tin sulfide solid electrolyte layer on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte. According to the invention, tin tetrachloride vapor is taken out through inert gas, and a layer of tin-doped sulfide solid electrolyte layer (passivation layer) is generated by reaction on the surface of the initial sulfide solid electrolyte powder, the passivation layer has good air stability and high conductivity, and the problem of poor stability of the sulfide solid electrolyte to water is successfully solved on the premise of not influencing the conductivity of the sulfide solid electrolyte.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a passivation layer sulfide solid electrolyte and a preparation method and application thereof.
Technical Field
With the rapid development of portable mobile devices and new energy vehicles and the construction of future energy storage systems, people need more efficient energy storage devices to meet the ever-increasing demands. At present, the lithium ion battery becomes the main force of energy storage equipment by virtue of the advantages of high energy density, high working voltage and long cycle life. However, the commercialized lithium ion battery uses ester or ether organic substances as electrolyte solvents, and such organic substances are easy to generate side reactions with electrode materials in the electrochemical cycle process of the battery, generate flatulence and have potential safety hazards of ignition. Compared with the lithium ion battery made of the liquid electrolyte, the solid electrolyte has the advantages of non-volatility, nonflammability, no corrosion, high mechanical strength and the like, and the all-solid-state battery made of the solid electrolyte has extremely high safety.
At present, there are three main types of solid electrolytes, namely, polymer solid electrolyte, oxide solid electrolyte, and sulfide solid electrolyte. The polymer solid electrolyte has good film-forming property, but the lithium ion conductivity is low; the oxide solid electrolyte is insensitive to water oxygen and has moderate conductivity, but has poor surface interface contact with the electrode material; the sulfide solid electrolyte has ion conductivity comparable to that of liquid electrolyte, ion migration number close to 1, good wettability with electrode materials, and is the most promising direction of all-solid-state batteries. However, sulfide solid electrolytes are unstable and easily react with water and oxygen in the air atmosphere, resulting in extremely severe processing conditions. The reason why the sulfide solid electrolyte is easily reacted with water is that the bond energy of S and P is weak and easily broken by the-OH bond attack in water, and according to the theory of hard and soft acids and bases, P is a strong acid and S is a weak base, and generally the bond energy of the strong acid and strong base, the weak acid and weak base is higher than that of the strong acid and weak base, the weak acid and strong base. Therefore, replacing P with a weak acid or S with a strong base can significantly increase the stability of the solid electrolyte to water. However, the reason why the sulfide solid electrolyte has higher ion conductivity than the oxide solid electrolyte is also that P — S bond energy is weak, providing a good lithium ion transport channel. That is, direct selection of O element substitution decreases the ionic conductivity of the sulfide solid electrolyte.
Chinese patent CN 112020787A discloses the manufacture of a sulfide solid electrolyte material, and the invention providesA method for synthesizing a sulfide solid electrolyte capable of suppressing a decrease in lithium ion conductivity due to moisture, which comprises a Li element, a P element, a S element and an O element. The invention is realized by adding lithium sulfide (Li) 2 S), phosphorus pentasulfide (P) 2 S 5 ) In which part of phosphorus pentoxide (P) is used 2 O 5 ) Replacement of P 2 S 5 To obtain Li (3+x) PS (4-y) O (y) The structure of the sulfide solid electrolyte (wherein x is more than or equal to 0 and less than or equal to 0.2, and y is more than or equal to 0.8 and less than or equal to 1.2). Although the maintenance rate of the ionic conductivity of the sulfide solid electrolyte prepared by the process is improved in a high-humidity environment, the initial ionic conductivity of the synthesized sulfide solid electrolyte is low directly after the O element is doped, and the method cannot effectively isolate moisture.
Chinese patent CN 110400967A discloses a sulfide solid electrolyte with a three-layer core-shell structure and a preparation method thereof, wherein Li-Argyrodite solid electrolyte or LGPS-type solid electrolyte and P are mixed 2 S 5 Mixing, heat treating to obtain intermediate powder, and adding O 2 The multilayer sulfide solid electrolyte is placed in the atmosphere for 0 to 100 hours, and the multilayer sulfide solid electrolyte which takes Li-Argyrodite solid electrolyte or LGPS-type solid electrolyte as a core, li-P-S as an intermediate layer and Li-P-S-O as a shell layer is prepared. Although the invention has the effect of improving the reduction amplitude of the conductivity after exposure in a high humidity atmosphere, the improvement capability is directly proportional to the doping amount of the O element, and the performance parameter of the sulfide solid electrolyte body after excessive doping of the O element is obviously influenced by the ionic conductivity.
Chinese patent CN 106099178A discloses a sulfide solid electrolyte and a preparation method thereof, which improves the stability of a sulfide/oxide composite solid electrolyte in air by coating an oxide-based ion conductor on the surface of the sulfide solid electrolyte. However, the composite solid electrolyte according to the present invention causes a problem of an interface between the solid electrolyte and the battery positive electrode due to the high hardness of the oxide-based ion conductor, and thus, practical application of the solid electrolyte is limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a passivation layer sulfide solid electrolyte, and a preparation method and application thereof, and aims to solve the problems of low conductivity and poor water stability of the conventional sulfide solid electrolyte.
The technical scheme of the invention is as follows:
a preparation method of a passivation layer sulfide solid electrolyte comprises the following steps:
providing an initial sulfide solid electrolyte powder;
and placing the initial sulfide solid electrolyte powder in a tube furnace, continuously introducing inert gas passing through tin tetrachloride liquid, heating to 300-550 ℃, reacting for 1-10h, and generating an in-situ doped tin sulfide solid electrolyte layer on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
The preparation method of the passivation layer sulfide solid electrolyte comprises the step of preparing an initial sulfide solid electrolyte powder, wherein the initial sulfide solid electrolyte powder is one of LPSC, LGPS and LPS, and the chemical formula of LPSC is Li 6-x PS 5-x Cl 1+x X is more than or equal to 0 and less than or equal to 0.8; LGPS has the formula Li 11-y M 2-y P 1+y S 12 M = one of Ge and Si, y is more than or equal to 0.5 and less than or equal to 1.5; LPS has the chemical formula of 75Li 2 S-25P 2 S 5 。
The preparation method of the passivation layer sulfide solid electrolyte comprises the step of preparing a passivation layer sulfide solid electrolyte, wherein the flow rate of inert gas is 0.05-1L/min.
The preparation method of the passivation layer sulfide solid electrolyte comprises the following step of preparing a passivation layer sulfide solid electrolyte, wherein the inert gas is one or more of argon, helium, neon and nitrogen.
The preparation method of the passivation layer sulfide solid electrolyte comprises the step of heating to 300-550 ℃ for reaction for 1-10 hours, wherein the heating rate is 3 ℃/min.
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps of heating to 300-550 ℃ and reacting for 1-10 hours: the temperature is reduced to room temperature at the speed of 2 ℃/min.
The invention discloses a passivation layer sulfide solid electrolyte, which is prepared by the preparation method of the passivation layer sulfide electrolyte.
The invention relates to an application of a passivation layer sulfide solid electrolyte, wherein the passivation layer sulfide solid electrolyte is used for preparing a lithium ion battery.
Has the advantages that: the invention provides a preparation method of a passivation layer sulfide solid electrolyte, which takes tin tetrachloride vapor out through inert gas, and generates a layer of sulfide solid electrolyte layer (passivation layer) containing doped tin on the surface of initial sulfide solid electrolyte powder through reaction.
Drawings
FIG. 1 is a flow chart of a preparation method of a passivation layer sulfide solid electrolyte.
Detailed Description
The invention provides a passivation layer sulfide solid electrolyte and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a method for preparing a passivation layer sulfide solid electrolyte according to the present invention, which includes the steps of:
s10, providing initial sulfide solid electrolyte powder;
and S20, placing the initial sulfide solid electrolyte powder in a tube furnace, continuously introducing inert gas passing through tin tetrachloride liquid, heating to 300-550 ℃, reacting for 1-10h, and generating an in-situ doped tin sulfide solid electrolyte layer on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Specifically, compared with the doping of oxygen element, the influence of the doping of Sn element on the conductivity of the initial sulfide solid electrolyte powder is small; the method is a solid/gas reaction, and the tin-doped sulfide solid electrolyte layer generated in situ on the surface of the initial sulfide solid electrolyte powder can be made to be nano-scale in thickness, so that the influence of a passivation layer on the ion conductivity of the internal sulfide solid electrolyte is reduced to the maximum extent while the water oxygen invasion in the environment is blocked; further, since the present invention is only tin-doped on the surface of the initial sulfide solid electrolyte powder, the initial sulfide solid electrolyte powder itself is not hardened as compared with directly coating an oxide layer, thereby ensuring the advantage that the initial sulfide solid electrolyte can more easily obtain a good active material/solid electrolyte interface.
The preparation method of the passivation layer sulfide solid electrolyte provided by the invention is simple in process, only the initial sulfide solid electrolyte powder finished product is heated under inert gas, tin tetrachloride vapor is brought out through the inert gas, and a layer of tin-doped sulfide solid electrolyte layer (passivation layer) is generated on the surface of the initial sulfide solid electrolyte powder through reaction.
In some embodiments, the initial sulfide solid electrolyte powder is one of LPSC, LGPS, and LPS, but is not limited thereto. In this embodiment, the chemical formula of the LPSC is Li 6-x PS 5-x Cl 1+x X is more than or equal to 0 and less than or equal to 0.8; LGPS has the formula Li 11-y M 2-y P 1+y S 12 M = one of Ge and Si, y is more than or equal to 0.5 and less than or equal to 1.5; LPS has the chemical formula of 75Li 2 S-25P 2 S 5 。
In some embodiments, the preparation of the LPSC comprises the steps of:
in a glove box under argon atmosphere, li 2 S、P 2 S 5 LiCl with the chemical formula Li 6-x PS 5-x Cl 1+x (wherein x is more than or equal to 0 and less than or equal to 0.8) taking 10g of raw materials with corresponding stoichiometric ratio, putting the raw materials and 400g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and then carrying out ball milling at 550rpm for 9 hours to obtain the precursor. And putting the precursor into an alumina crucible, heating to 450-590 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 1-20h, the heating rate is 3 ℃/min, and the cooling rate is 1.5 ℃/min. After sintering, collecting Li 6-x PS 5-x Cl 1+x The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh.
In some embodiments, the preparation of the LGPS comprises the steps of:
in a glove box under argon atmosphere, li 2 S、MS 2 、P 2 S 5 With the chemical formula Li 11-y M 2-y P 1+y S 12 (wherein M = at least one of Ge and Si, and y is more than or equal to 0.5 and less than or equal to 1.5) 5g of raw material with corresponding stoichiometric ratio is taken, the raw material and 400g of 10mm zirconia ball milling beads are put into a 500mL zirconia ball milling pot, ball milling is carried out for one hour at 300rpm, and ball milling is carried out for 16 hours at 450rpm, thus obtaining the precursor. And putting the precursor into an alumina crucible, heating to 400-550 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 1-20h, the heating rate is 2 ℃/min, and the cooling rate is 3 ℃/min. After sintering, collecting Li 11-y M 2-y P 1+y S 12 The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh.
In some embodiments, the preparation of the LPS comprises the steps of:
in a glove box under argon atmosphere, li 2 S、P 2 S 5 In the chemical formula of 75Li 2 S-25P 2 S 5 Taking 5g of raw materials with corresponding stoichiometric ratio, putting the raw materials and 300g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and then carrying out ball milling at 450rpm for 12 hours to obtain a precursor. And putting the precursor into an alumina crucible, heating to 250-400 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 1-20h, the heating rate is 2 ℃/min, and the cooling rate is 5 ℃/min. BakingAfter completion, 75Li was collected 2 S-25P 2 S 5 The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh. In this example, the 75Li 2 S-25P 2 S 5 Refers to Li 2 S and P 2 S 5 In a molar ratio of 3.
In some embodiments, the inert gas is one or more of argon, helium, neon, and nitrogen, but is not limited thereto.
In some embodiments, the initial sulfide solid electrolyte powder is placed in an alumina crucible, the alumina crucible is placed in a tube furnace under argon atmosphere, and argon is continuously introduced/discharged at a flow rate of 0.05-1L/min, and tin tetrachloride (SnCl) is passed before the argon is introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 300-550 ℃ at the speed of 3 ℃/min by using steam, keeping the temperature for 1-10h, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating an in-situ tin-doped sulfide solid electrolyte layer on the surface of the initial sulfide solid electrolyte powder to prepare the passivation layer sulfide solid electrolyte.
In some embodiments, the passivation layer sulfide solid electrolyte is prepared by the preparation method of the passivation layer sulfide electrolyte.
In some embodiments, the invention also provides application of the passivation layer sulfide solid electrolyte, wherein the passivation layer sulfide solid electrolyte is used for preparing a lithium ion battery.
The invention is further illustrated by the following specific examples:
comparative example 1
Synthetic method of LPSC
In a glove box under argon atmosphere, li 2 S、P 2 S 5 LiCl with the chemical formula Li 6 PS 5 And taking 10g of raw materials with the corresponding stoichiometric ratio by Cl, putting the raw materials and 400g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and then carrying out ball milling at 550rpm for 9 hours to obtain a precursor. Putting the precursor into oxygenAnd (3) melting the aluminum crucible, heating to 590 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 8h, the heating rate is 3 ℃/min, and the cooling rate is 1.5 ℃/min. After sintering, collecting Li 6-x PS 5-x Cl 1+x The samples were ground thoroughly in a glove box and sieved using a sieve with a pore size of 30 microns.
Comparative example 2
Synthetic method of LPSC
In a glove box under argon atmosphere, li 2 S、P 2 S 5 LiCl with the chemical formula Li 5.5 PS 4.5 Cl 1.5 Taking 10g of raw materials with the corresponding stoichiometric ratio, putting the raw materials and 400g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and then carrying out ball milling at 550rpm for 9 hours to obtain a precursor. And putting the precursor into an alumina crucible, heating to 550 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 10h, the heating rate is 3 ℃/min, and the cooling rate is 1.5 ℃/min. After sintering, collecting Li 6-x PS 5-x Cl 1+x The samples were ground thoroughly in a glove box and sieved using a sieve with a pore size of 30 microns.
Comparative example 3
Synthetic method of LPSC
In a glove box under argon atmosphere, li 2 S、P 2 S 5 LiCl with the chemical formula Li 5.2 PS 4.2 Cl 1.8 Taking 10g of raw materials with the corresponding stoichiometric ratio, putting the raw materials and 400g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and then carrying out ball milling at 550rpm for 9 hours to obtain a precursor. And putting the precursor into an alumina crucible, heating to 500 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 14h, the heating rate is 3 ℃/min, and the cooling rate is 1.5 ℃/min. After sintering, collecting Li 6-x PS 5-x Cl 1+x The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh.
Comparative example 4
The synthesis method of LGPS comprises the following steps:
in a glove box under argon atmosphere, li 2 S、MS 2 、P 2 S 5 In the chemical formula Li 10 GeP 2 S 12 Taking 5g of raw materials with corresponding stoichiometric ratio, putting the raw materials and 400g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and carrying out ball milling at 450rpm for 16 hours to obtain a precursor. And (3) putting the precursor into an alumina crucible, heating to 550 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 10h, the heating rate is 2 ℃/min, and the cooling rate is 3 ℃/min. After sintering, collecting Li 11-y M 2-y P 1+y S 12 The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh.
Comparative example 5
The synthesis method of LGPS comprises the following steps:
in a glove box under argon atmosphere, li 2 S、MS 2 、P 2 S 5 In the chemical formula Li 10.5 Ge 1.5 P 1.5 S 12 Taking 5g of raw materials with corresponding stoichiometric ratio, putting the raw materials and 400g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and carrying out ball milling at 450rpm for 16 hours to obtain a precursor. And putting the precursor into an alumina crucible, heating to 450 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 14h, the heating rate is 2 ℃/min, and the cooling rate is 3 ℃/min. After sintering, collecting Li 11-y M 2-y P 1+y S 12 The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh.
Comparative example 6
The synthesis method of LGPS comprises the following steps:
in a glove box under argon atmosphere, li 2 S、MS 2 、P 2 S 5 In the chemical formula Li 9.5 Si 0.5 P 2.5 S 12 Taking 5g of raw materials with corresponding stoichiometric ratio, putting the raw materials and 400g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and carrying out ball milling at 450rpm for 16 hours to obtain a precursor. Putting the precursor into an alumina crucible, heating to 400 ℃ in an argon atmosphere, sintering, keeping the temperature for 18h, wherein the heating rate is 2 ℃/min, and coolingThe rate was 3 deg.C/min. After sintering, collecting Li 11-y M 2-y P 1+y S 12 The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh.
Comparative example 7
The LPS synthesis method comprises the following steps:
in a glove box under argon atmosphere, li 2 S、P 2 S 5 With the chemical formula of 75Li 2 S-25P 2 S 5 Taking 5g of raw materials with corresponding stoichiometric ratio, putting the raw materials and 300g of 10mm zirconia ball milling beads into a 500mL zirconia ball milling tank, carrying out ball milling at 300rpm for one hour, and then carrying out ball milling at 450rpm for 12 hours to obtain a precursor. And (3) putting the precursor into an alumina crucible, heating to 350 ℃ in an argon atmosphere, and sintering, wherein the heat preservation time is 2h, the heating rate is 2 ℃/min, and the cooling rate is 5 ℃/min. After sintering, 75Li was collected 2 S-25P 2 S 5 The samples were ground thoroughly in a glove box and sieved using a 30 micron mesh.
Example 1
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LPSC powder in comparative example 1 was placed in an alumina crucible, the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 1L/min, and tin tetrachloride (SnCl) was passed before argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 550 ℃ at the speed of 3 ℃/min, keeping the temperature for 1h, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 2
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LPSC powder in comparative example 2 was placed in an alumina crucible, and the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.8L/min, and tin tetrachloride (SnCl) was passed before argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 520 ℃ at the speed of 3 ℃/min, keeping the temperature for 1h, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 3
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LPSC powder in comparative example 3 was placed in an alumina crucible, the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.6L/min, and tin tetrachloride (SnCl) was passed before argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 480 ℃ at the speed of 3 ℃/min, keeping the temperature for 2 hours, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 4
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LPSC powder in comparative example 3 was placed in an alumina crucible, the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.3L/min, and tin tetrachloride (SnCl) was passed before argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 480 ℃ at the speed of 3 ℃/min, keeping the temperature for 4h, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 5
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LGPS powder in comparative example 4 was placed in an alumina crucible, and the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.5L/min through an argon gas introduction tubeTin tetrachloride (SnCl) is needed to pass through the furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 500 ℃ at the speed of 3 ℃/min, keeping the temperature for 3h, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 6
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LGPS powder of comparative example 4 was placed in an alumina crucible, and the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.1L/min, and tin tetrachloride (SnCl) was passed before argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 500 ℃ at the speed of 3 ℃/min, keeping the temperature for 5 hours, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 7
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LGPS powder of comparative example 5 was placed in an alumina crucible, and the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.05L/min, and tin tetrachloride (SnCl) was passed before argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 420 ℃ at the speed of 3 ℃/min, keeping the temperature for 10 hours, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 8
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LGPS powder in comparative example 6 was placed in an alumina crucible, and the alumina crucible was placed in a tube furnace under argon atmosphere and was continuously charged/dischargedArgon gas with flow rate of 0.8L/min is introduced into the tube furnace via tin tetrachloride (SnCl) 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 350 ℃ at the speed of 3 ℃/min, keeping the temperature for 8 hours, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 9
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LPS powder in comparative example 7 was placed in an alumina crucible, the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.7L/min, and tin tetrachloride (SnCl) was passed before the argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 320 ℃ at the speed of 3 ℃/min, keeping the temperature for 4h, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 10
The preparation method of the passivation layer sulfide solid electrolyte comprises the following steps:
the LPS powder in comparative example 7 was placed in an alumina crucible, the alumina crucible was placed in a tube furnace in an argon atmosphere, and argon gas was continuously introduced/discharged at a flow rate of 0.4L/min, and tin tetrachloride (SnCl) was passed before the argon gas was introduced into the tube furnace 4 ) Carrying-out part SnCl in liquid 4 And (3) heating the tube furnace to 300 ℃ at the speed of 3 ℃/min by using steam, keeping the temperature for 8 hours, cooling the tube furnace to room temperature at the speed of 2 ℃/min, and generating a sulfide solid electrolyte layer doped with tin in situ on the surface of the initial sulfide solid electrolyte powder to obtain the passivation layer sulfide solid electrolyte.
Example 11
The sulfide solid electrolytes prepared in comparative examples 1 to 7 and the passivation layer sulfide solid electrolytes prepared in examples 1 to 10 were tested for their properties:
1. and (3) ion conductivity test: 0.2g 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 300MPa, the pressure maintaining time is 1min, and the thickness of the obtained solid electrolyte wafer is tested by using a micrometer. A piece of carbon-coated copper foil (carbon end facing solid electrolyte) was placed on each end of the solid electrolyte sheet as a blocking electrode, and placed in a conductivity test kit, pressurized at 300Mpa, and connected to an electrochemical workstation for EIS testing, with the results shown in table 1.
2. The EIS was tested as follows: a DC voltage of 50mV was applied and tested using the AC impedance method over the frequency range of 1MHz to 1Hz, and the results are shown in Table 1.
3. Hydrogen sulfide (H) 2 S) measurement of production amount: weighing 100mg of solid electrolyte in a glove box in argon atmosphere, sealing, transferring to a constant temperature and humidity box with gloves, opening the seal after the temperature is stabilized at 25 ℃ and the humidity is stabilized at RH35%, placing in a closable flask with the volume of 1155mL, standing for 10min, and using H 2 S Detector (GX-2009, manufactured by Riken Keiki) tests H in flask 2 S concentration, and calculating H 2 The results of the amount of S gas generated are shown in Table 1.
4. Ion conductivity test after dry air exposure: the ionic conductivity after dry air exposure was measured by EIS test using a dry air replacement glove box having a dew point of-45 ℃ and the products of examples and comparative examples placed and left for 4 hours and then returned to the argon replacement glove box, and the results are shown in Table 1.
TABLE 1 test results
As can be seen from table 1, a tin-doped sulfide solid electrolyte layer (passivation layer) is formed by reaction on the surface of the initial sulfide solid electrolyte powder, so that the passivation layer sulfide solid electrolyte has an excellent effect of blocking water and oxygen attacks, and the influence of the passivation layer on the ion conductivity of the internal sulfide solid electrolyte is minimized.
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 (4)
1. A preparation method of a passivation layer sulfide solid electrolyte is characterized by comprising the following steps:
providing an initial sulfide solid electrolyte powder;
placing the initial sulfide solid electrolyte powder in a tube furnace, continuously introducing inert gas passing through tin tetrachloride liquid, heating to 300-550 ℃, reacting for 1-10h, cooling to room temperature at the speed of 2 ℃/min, and generating an in-situ tin-doped sulfide solid electrolyte layer on the surface of the initial sulfide solid electrolyte powder to prepare the passivation layer sulfide solid electrolyte; the flow rate of the inert gas is 0.05-1L/min, the inert gas is one or more of argon, helium, neon and nitrogen, and in the step of heating to 300-550 ℃ for reaction for 1-10h, the heating rate is 3 ℃/min.
2. The method of preparing the passivation layer sulfide solid electrolyte of claim 1, wherein the initial sulfide solid electrolyte powder is one of LPSC, LGPS and LPS, wherein LPSC has a chemical formula of Li 6-x PS 5-x Cl 1+x X is more than or equal to 0 and less than or equal to 0.8; LGPS has the formula Li 11-y M 2-y P 1+y S 12 M = one of Ge and Si, y is more than or equal to 0.5 and less than or equal to 1.5; LPS has the chemical formula of 75Li 2 S-25P 2 S 5 。
3. A passivated layer sulfide solid electrolyte characterized by being prepared by the method for preparing a passivated layer sulfide solid electrolyte according to any one of claims 1-2.
4. Use of a passivated layer sulfide solid electrolyte according to claim 3 for the production of a lithium ion battery.
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