CN116154122A - Porous silicon-based anode material, solid electrode and preparation method - Google Patents
Porous silicon-based anode material, solid electrode and preparation method Download PDFInfo
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Abstract
The invention relates to the technical field of solid-state batteries, in particular to a porous silicon-based anode material, a solid-state battery and a preparation method thereof, wherein the porous silicon-based anode material comprises the following components: the porous silicon-based anode material comprises porous silicon and sulfide solid electrolyte, wherein the sulfide solid electrolyte is coated on the outer surface and the inner surface of a hole of the porous silicon, the content of the sulfide solid electrolyte is 0.5-1% based on the mass of the porous silicon-based anode material being 100%, and the pore diameter of the porous silicon is 30-100 nm. The porous silicon-based anode material provided by the invention has high ionic conductivity and tight contact between solid particles; the obtained solid electrode is applied to a solid battery, can relieve the volume expansion effect, improve the transmission efficiency of lithium ions, reduce the impedance of the battery, improve the coulomb efficiency of the battery and improve the multiplying power performance and the cycle performance.
Description
Technical Field
The invention relates to the field of solid-state batteries, in particular to a porous silicon-based anode material, a solid-state electrode and a preparation method.
Background
The solid-state battery has the advantages of high safety performance, high energy density (which is expected to reach 300-400 Wh/kg or even higher), long cycle life (which is expected to avoid the problem that SEI films and lithium dendrites formed in the process of charging and discharging liquid electrolyte penetrate through a diaphragm), wide working temperature range (good needling and high-temperature stability), high production efficiency, good flexibility and the like. Therefore, solid-state batteries are one of the main directions of future battery development.
In order to meet the excellent performances of high energy density, long cycle life and the like of the solid-state battery, researchers have performed optimization on three materials of the solid-state battery: 1) Solid electrolyte sulfide solid electrolyte with high ionic conductivity (such as Li found in 2010 10 GeP 2 S 12 Material, room temperature ion guide 12mS cm -1 (Nature materials,2011,10 (9): 682.) and Li found in 2015 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 Room temperature ion guide 25mS cm -1 (Nature Energy,2016,1 (4): 16030.)): 2) The positive electrode material is selected from ternary positive electrode materials (the theoretical specific capacity can reach 200mAh/g and above) and lithium-rich manganese-based positive electrode materials (the theoretical specific capacity can reach 250mAh/g and above); 3) The cathode material is selected from silicon cathode material (theoretical specific capacity can reach 4200 mAh/g). However, for silicon anodes, the silicon particles undergo a relatively high volume expansion (300%) during lithium deintercalation, resulting in pulverization of the silicon particles, destruction of the electrode structure, and SThe continuous rupture of the EI film, which causes serious capacity fade of the silicon negative electrode, is a major factor limiting the widespread use of silicon materials. In addition, the electron conductivity and the ion conductivity of the silicon are low, which is unfavorable for the transmission of electrons and lithium ions, thus leading to low coulomb efficiency and poor cycle performance of the silicon cathode.
In order to improve the defect of the silicon material, the nano-crystallization, the silicon particle coating and the compounding of the silicon material are proposed, so that the electrochemical performance of the silicon cathode is improved to a great extent. CN110071280a discloses a preparation method of silicon negative electrode material coated with oxide solid electrolyte, which mainly comprises the following preparation processes: dispersing a silicon anode material in an ammonium formate buffer solution, adding an oxide precursor, stirring, uniformly coating the surface of the silicon substrate with the oxide, centrifuging and drying to obtain an oxide-coated silicon composite material; mixing the obtained silicon composite material coated with the oxide with lithium hydroxide monohydrate, grinding uniformly to obtain mixed powder, reacting the mixed powder at high temperature under inert atmosphere, and cooling to room temperature after the reaction is finished to obtain the silicon composite material coated with the oxide. The invention relieves the volume expansion of silicon in the lithium intercalation process to a certain extent, but has the following defects: 1) The silicon composite material and the lithium hydroxide monohydrate are mechanically grinded, so that the grinding uniformity is difficult to ensure; 2) The solid electrolyte coating amount is more than 10wt%, and the ionic conductivity and the electronic conductivity of the composite electrode are low due to the fact that the ionic conductivity and the electronic conductivity of the oxide are low. CN107579239B discloses a graphene/solid electrolyte coated silicon composite material and a preparation method thereof, wherein the preparation process mainly comprises the following steps: and coating a layer of graphene on the silicon-based material by using a chemical vapor deposition method, and then coating the silicon-based material with oxide by using an oxide ester precursor and concentrated ammonia water to obtain the silicon anode material co-coated with the oxide and the graphene. And lithiating the composite material by using lithium hydroxide monohydrate to finally prepare the graphene/solid electrolyte composite coated silicon composite material. The invention has the following defects: 1) The preparation process is complex; 2) There is also a problem that the ion conductivity and the electron conductivity of the composite electrode are low due to a large coating amount of the oxide. CN107240688A discloses a silicon/sulfur-based solid electrolyte composite anode material with high cycle performance and a preparation method thereof, wherein the main preparation process is as follows: (1) Mixing sulfide in mortar in certain proportion; (2) Adding silicon powder and sulfide after physical mixing into an organic solvent according to a certain proportion, and magnetically stirring at a certain temperature; (3) Removing the organic solvent by suction filtration or rotary evaporation, drying under certain conditions and heat treating to obtain the silicon/sulfur-based solid electrolyte composite anode material. The invention has the following defects: 1) The sulfur-based solid electrolyte only coats the outer layer of the silicon particles, and the sulfur-based solid electrolyte does not exist for the pores inside the porous silicon material; 2) Physical mixing is difficult to ensure uniformity. The current methods of preparing silicon-based composites suitable for use in solid state batteries are not ideal. Furthermore, the above-described invention is proposed only for a liquid battery, and there is no report on the application of the porous silicon material-coated method to a solid battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a porous silicon-based anode material, a solid electrode and a preparation method.
In a first aspect, the porous silicon-based anode material provided by the invention comprises porous silicon and sulfide solid electrolyte, wherein the sulfide solid electrolyte is coated on the outer surface and the inner surface of a hole of the porous silicon, and the content of the sulfide solid electrolyte is 0.5-1% based on the mass of the porous silicon-based anode material being 100%. According to the porous silicon-based anode material provided by the invention, the sulfide uniformly coats the surfaces of porous silicon particles and the surfaces in the holes, so that the solid-solid contact area can be increased; furthermore, sulfide ion conductivity is high, so that the surface and the inside of the composite material have ion conductivity; meanwhile, the sulfide has low elastic modulus, and can buffer stress generated by the volume change of silicon particles. In addition, the invention is generated in situ, sulfide is tightly contacted with silicon particles, and is not easy to separate from sulfide in the process of volume expansion and contraction of the silicon particles, so that the ion conductivity can be further ensured. The porous silicon-based anode material provided by the invention has high ionic conductivity and tight contact between solid particles; the obtained solid electrode is applied to a solid battery, can relieve the volume expansion effect, improve the transmission efficiency of lithium ions, reduce the impedance of the battery, improve the coulomb efficiency of the battery and improve the multiplying power performance and the cycle performance.
Preferably, the porous silicon comprises mesopores or macropores, and the pore diameter of the porous silicon is less than 500nm; preferably, the pore diameter of the porous silicon is between 30 and 100 nm. In the invention, the pore diameter of the porous silicon is preferably 30-100nm, so that the electrochemical performance of the electrode can be improved, and the cycling performance of the solid-state battery is better.
Preferably, the sulfide solid state electrolyte includes glassy Li 2 S·P 2 S 5 System, glassy ceramic Li-P-S system or crystalline Li 6 PS 5 M x M is Cl, br or I.
Further preferably, the sulfide solid state electrolyte is Li 6 PS 5 Cl x (X is more than or equal to 0.5 and less than or equal to 2.0), and the conductivity is optimal when X is more than or equal to 1.0 and less than or equal to 1.6.
Preferably, the mass ratio of the porous silicon to the sulfide solid state electrolyte is 99.5:0.5 to 99:1, preferably 99.4:0.6 to 99.2:0.8.
The invention adopts the preferable sulfide solid electrolyte type and the proportion of the sulfide solid electrolyte type and the porous silicon, can better relieve the volume expansion effect of the silicon negative electrode, has better ionic conductivity, further improves the coulombic efficiency of the battery, reduces the internal resistance of the battery and improves the multiplying power performance and the cycle performance.
In a second aspect, the preparation method of the porous silicon-based anode material provided by the invention comprises the following steps:
1) Adding porous silica powder and sulfide solid electrolyte into an organic solvent according to a proportion, and stirring;
2) Removing the organic solvent and performing heat treatment at 60-110 ℃.
Preferably, the method comprises the following steps:
1) Adding porous silica powder and sulfide solid electrolyte into excessive organic solvent in proportion, and magnetically stirring for 2-3 h at room temperature;
2) Removing the organic solvent by suction filtration or rotary evaporation, and performing heat treatment at 90-100 ℃ for 20-40 min.
According to the preparation method, the silicon-based anode material with the sulfide uniformly coated on the inner and outer surfaces of the porous silicon particles is obtained, so that the transmission of lithium ions can be promoted, and the interface impedance can be reduced.
Further preferably, the organic solvent is one or more of alcohols, ethers and nitriles, preferably acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, n-butyl ether, isobutyl ether or isopropyl ether, more preferably n-butyl ether. The adoption of the preferred organic solvent in the invention can lead the prepared porous silicon-based anode material to have better performance.
In a third aspect, the solid electrode provided by the invention comprises the silicon-based anode material or the silicon-based anode material obtained by the preparation method.
In a fourth aspect, the present invention provides a method for preparing the solid state electrode, comprising:
1) Mixing the porous silicon-based anode material, the solid electrolyte, the conductive agent, the binder and the organic solvent in proportion to obtain slurry;
2) Coating the slurry on a current collector to obtain a pole piece;
3) And drying the pole piece at 75-90 ℃, preferably 80 ℃ to obtain the solid electrode.
Preferably, the mass ratio of the anode material to the solid electrolyte is 60:40-80:20; the mass of the slurry is 100 percent, the conductive agent is 1 to 5 percent, and the binder is 1 to 5 percent.
In a fifth aspect, the present invention provides a solid state battery comprising said silicon-based negative electrode material or said solid state electrode.
The invention has the advantages that: compared with the prior art, the method is simple and effective, and the obtained porous silicon-based anode material has high ionic conductivity and tight contact between solid particles; the obtained solid electrode is applied to a solid battery, can relieve the volume expansion effect, improve the transmission efficiency of lithium ions, reduce the impedance of the battery, improve the coulomb efficiency of the battery and improve the multiplying power performance and the cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing charge and discharge curves of a porous silicon-based negative electrode material electrode coated with a sulfur-based solid electrolyte according to an embodiment of the present invention;
FIG. 2 is a graph showing the cycling profile of a porous silicon-based negative electrode material coated with a sulfur-based solid state electrolyte in accordance with an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, which are used for illustrating the present invention but are not intended to limit the scope of the present invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the embodiment of the invention, the sulfide solid state electrolyte is Li 6 PS 5 Cl x (0.5.ltoreq.X.ltoreq.2.0), with Li being the specific material 6 PS 5 Cl x (1.0≤X≤1.6)。
Example 1
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.2 Adding the mixture into excessive n-butyl ether according to the mass ratio of 99.5:0.5, magnetically stirring the mixture for 2 hours at room temperature, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 2
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.2 Adding the mixture into excessive n-butyl ether according to the mass ratio of 99.4:0.6, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 3
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested. Fig. 1-2 show the charge-discharge curve and the electrode cycle curve of the porous silicon-based anode material coated with the sulfur-based solid electrolyte according to the present embodiment.
Example 4
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.2 Adding the mixture into excessive n-butyl ether according to the mass ratio of 99.2:0.8, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode is to make the porous silicon-based negative electrodeMixing the material, sulfide solid electrolyte, conductive agent and binder according to the mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 5
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.1:0.9, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 6
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.2 Adding the mixture into excessive n-butyl ether according to the mass ratio of 99.0:1.0, magnetically stirring the mixture for 2 hours at room temperature, and removing the n-butyl ether by a suction filtration methodAnd (3) performing heat treatment at the temperature of 100 ℃ for 30min, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 7
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 100nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 8
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte and a preparation method of the porous silicon-based anode materialThe solid-state electrode and the solid-state battery of (2) specifically include: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 90nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 9
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 50nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is positive electrode, and sulfide isThe intermediate electrolyte layer and the lithium-indium alloy are used as a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 10
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 30nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 11
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 0.5 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode is to make the porous silicon-based negative electrodeMixing the material, sulfide solid electrolyte, conductive agent and binder according to the mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 12
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.0 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 13
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 1.6 Adding the mixture into excessive n-butyl ether according to the mass ratio of 99.3:0.7, magnetically stirring the mixture for 2 hours at room temperature, and removing the n-butyl ether by a suction filtration methodAnd (3) performing heat treatment at the temperature of 100 ℃ for 30min, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Example 14
The embodiment provides a porous silicon-based anode material coated with a sulfur-based solid electrolyte, a solid electrode prepared from the porous silicon-based anode material, and a solid battery, which specifically comprise: in a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 2.0 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Comparative example 1
In a drying room (the dew point is lower than-50 ℃), adding nano silicon powder with the pore diameter of 80nm into excessive n-butyl ether, magnetically stirring for 2 hours at room temperature, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Comparative example 2
In a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 500nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Comparative example 3
In a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 10nm and Li are mixed 6 PS 5 Cl 1.2 Adding excessive n-butyl ether at a mass ratio of 99.3:0.7, magnetically stirring at room temperature for 2 hr, removing n-butyl ether by suction filtration, and heat treating at 100deg.C for 30minAnd drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Comparative example 4
In a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Adding Br into excessive n-butyl ether according to the mass ratio of 99.3:0.7, magnetically stirring for 2 hours at room temperature, removing the n-butyl ether by using a suction filtration method, performing heat treatment at 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Comparative example 5
In a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 0.3 Adding the mixture into excessive n-butyl ether according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at 100 ℃ for 30 minutes, and drying the mixture to obtain the porous coated with the sulfur-based solid electrolyteSilicon-based negative electrode material. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
Comparative example 6
In a drying room (dew point is lower than-50 ℃), nano silicon powder with aperture of 80nm and Li are mixed 6 PS 5 Cl 2.2 Adding excessive n-butyl ether into the mixture according to the mass ratio of 99.3:0.7, magnetically stirring the mixture at room temperature for 2 hours, removing the n-butyl ether by using a suction filtration method, performing heat treatment at the temperature of 100 ℃ for 30 minutes, and drying the mixture to obtain the porous silicon-based anode material coated with the sulfur-based solid electrolyte. Preparing a solid electrode and a solid battery by using the porous silicon-based anode material and sulfide solid electrolyte according to the proportion of 70:30; the preparation of the solid electrode comprises the steps of mixing the porous silicon-based anode material, sulfide solid electrolyte, a conductive agent and a binder according to a mass ratio of 70:30:3:3, and adding a proper amount of solvent to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; drying the pole piece at 80 ℃ to obtain a solid electrode; the solid-state electrode in the solid-state battery is a positive electrode, sulfide is an intermediate electrolyte layer, and lithium-indium alloy is a negative electrode. The solid-state battery capacity and cycle performance were tested.
The performance of the batteries in examples and comparative examples was tested, and the results thereof are shown in tables 1 to 3.
Table 1 comparison of solid state battery performance at different ratios of nano silicon to LPSCl
Table 2 comparison table of solid state battery performance under different pore diameters of nano silicon
Table 3 comparison of solid state battery performance with different sulfide choices
According to table 1, the electrochemical performance of the solid-state battery shows a trend of increasing and decreasing with decreasing ratio of nano silicon to LPSCl; the method is characterized in that when the LPSCl is low, the inner and outer surfaces of the nano silicon cannot be uniformly coated, the transmission performance of lithium ions is poor, and the interface impedance of the battery is high; when LPSCl is higher, the coating layers on the inner and outer surfaces of the nano silicon are later, which rather hinders the transmission of lithium ions, and the battery performance is reduced.
According to table 2, as the pore diameter of the nano-silicon is reduced, the electrochemical performance of the solid-state battery shows a tendency of increasing and then decreasing; the method is characterized in that when the aperture of the nano silicon is too large, the inner surface and the outer surface of the nano silicon are not easy to be uniformly coated, the contact between solid particles is poor, the lithium ion transmission performance is reduced, and the interface impedance of a battery is increased; when the aperture of the nano silicon is too small, the inner surface of the nano silicon is not easy to be coated, the lithium ion transmission performance is reduced, and the interface impedance of the battery is increased.
According to table 3, the electrochemical performance of the solid-state battery showed a trend of increasing and decreasing with increasing Cl content in LPSCl; this is because the Cl element affects the ionic conductivity of LPSCl, and as the Cl element increases, the ionic conductivity of LPSCl tends to decrease from increasing to decreasing.
Table 1-3 is summarized, with 80nm pore size nano-silicon and Li in example 3 6 PS 5 Cl 1.2 At a ratio of 99.3:0.7, the electrochemical performance of the resulting solid-state battery was optimal.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The porous silicon-based anode material is characterized by comprising porous silicon and sulfide solid electrolyte, wherein the sulfide solid electrolyte is coated on the outer surface and the inner surface of a hole of the porous silicon, and the content of the sulfide solid electrolyte is 0.5-1.0% based on the mass of the porous silicon-based anode material being 100%.
2. The porous silicon-based anode material according to claim 1, wherein the porous silicon comprises mesopores or macropores, and the pore diameter of the porous silicon is less than 500nm; preferably, the pore diameter of the porous silicon is between 30 and 100 nm.
3. The porous silicon-based anode material of claim 1, wherein the sulfide solid state electrolyte comprises glassy Li 2 S·P 2 S 5 System, glassy ceramic Li-P-S system or crystalline Li 6 PS 5 M x M is Cl, br or I, preferably Li 6 PS 5 Cl x (0.5≤X≤2.0)。
4. The porous silicon-based anode material according to claim 1, wherein the mass ratio of the porous silicon to the sulfide solid state electrolyte is 99.5:0.5 to 99.0:1.0, preferably 99.4:0.6 to 99.2:0.8.
5. The method for preparing a porous silicon-based anode material according to any one of claims 1 to 4, comprising the steps of:
1) Adding porous silica powder and sulfide solid electrolyte into an organic solvent according to a proportion, and stirring;
2) Removing the organic solvent and performing heat treatment at 60-110 ℃.
6. The method for preparing a porous silicon-based anode material according to claim 5, comprising the steps of:
1) Adding porous silica powder and sulfide solid electrolyte into excessive organic solvent in proportion, and magnetically stirring for 2-3 h at room temperature;
2) Removing the organic solvent by suction filtration or rotary evaporation, and performing heat treatment at 90-100 ℃ for 20-40 min.
7. The method for producing a porous silicon-based anode material according to claim 5 or 6, wherein the organic solvent is one or more of alcohols, ethers and nitriles, preferably acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, n-butyl ether, isobutyl ether or isopropyl ether, more preferably n-butyl ether.
8. A solid electrode comprising the silicon-based anode material according to claim 1 or the silicon-based anode material obtained by the production method according to any one of claims 5 to 7.
9. A method of making a solid state electrode as defined in claim 8, comprising:
1) Mixing the porous silicon-based anode material, the solid electrolyte, the conductive agent, the binder and the organic solvent in proportion to obtain slurry;
2) Coating the slurry on a current collector to obtain a pole piece;
3) Drying the pole piece at 75-90 ℃, preferably 80 ℃, so as to obtain a solid electrode;
preferably, the mass ratio of the anode material to the solid electrolyte is 60:40-80:20; the mass of the slurry is 100 percent, the conductive agent is 1 to 5 percent, and the binder is 1 to 5 percent.
10. A solid-state battery comprising the silicon-based anode material according to claim 1 or the solid-state electrode according to claim 8.
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