CN112421119A - Preparation method of all-solid-state sulfide electrolyte for lithium ion battery - Google Patents

Preparation method of all-solid-state sulfide electrolyte for lithium ion battery Download PDF

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CN112421119A
CN112421119A CN202011319195.8A CN202011319195A CN112421119A CN 112421119 A CN112421119 A CN 112421119A CN 202011319195 A CN202011319195 A CN 202011319195A CN 112421119 A CN112421119 A CN 112421119A
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solid electrolyte
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陈庆
廖健淞
司文彬
白涛
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Chengdu New Keli Chemical Science Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H—ELECTRICITY
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Abstract

The invention provides a preparation method of an all-solid-state sulfide electrolyte for a lithium ion battery, wherein the all-solid-state sulfide electrolyte is prepared by mixing Li2S、P2S5Mixing with the doped powder, heating in a vacuum silicon tube, performing hydrophobic modification by using perfluorodecyl trichlorosilane, performing ultrasonic dispersion, filtering and drying to obtain the product. According to the all-solid-state sulfide electrolyte provided by the invention, an inorganic phase which is not easy to be compounded with sulfide is attached to the surface of the particle through hydrophobic modification to form a hydrophobic coating, so that the corrosion of moisture to the sulfide particle is effectively inhibited, the durability to the moisture is improved, and the cycle performance of a solid-state lithium battery is improved.

Description

Preparation method of all-solid-state sulfide electrolyte for lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of an all-solid sulfide electrolyte for a lithium ion battery.
Background
A lithium ion battery is a type of rechargeable battery that mainly relies on lithium ions moving between a positive electrode and a negative electrode to operate. During charging and discharging, Li+Intercalation and deintercalation to and from two electrodes: in the case of rechargeable batteries, Li +The lithium ion battery is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. The lithium ion battery has high and stable energy densityThe device has strong qualitative property, no memory effect and long cycle life, and is widely applied as a commercial high-efficiency energy storage device.
The electrolyte is an important component of the lithium ion battery, and the electrolyte used in the traditional lithium ion battery is liquid lithium hexafluorophosphate, is easy to decompose to cause battery inflation due to the extreme instability of the electrolyte, and is extremely easy to combust and explode at high temperature, short circuit, overcharge or physical collision. Despite the protection mechanism added by the external encapsulation, it still has a large safety hazard.
The solid lithium ion battery uses the solid electrolyte to replace the liquid electrolyte, so that the safety problem and the use temperature zone problem of the liquid lithium ion battery can be fundamentally solved, and meanwhile, the corrosion of the electrolyte to the positive electrode and the negative electrode can be effectively reduced. However, the current solid-state battery has several serious problems, namely how to effectively improve the lithium ion transport capability of the electrolyte, how to realize good interface contact between the electrode layer and the electrolyte layer, and how to solve the problem of poor mechanical properties of the solid-state electrolyte layer. One of the mainstream materials is inorganic sulfide electrolyte, and the ion conduction capability of the solid electrolyte can be effectively improved in the lithium-sulfur battery. It is extremely moisture sensitive and generates large amounts of hydrogen sulfide gas to corrode the electrodes and cause gassing. Therefore, the method has very important practical significance for controlling the moisture in the preparation process of the solid sulfide electrolyte.
Chinese patent application No. 201711200731.0 discloses an oxide-modified sulfide solid electrolyte and a preparation method thereof, wherein the oxide-modified sulfide solid electrolyte is prepared by using one or more compounds of lithium-oxygen, phosphorus-oxygen and lithium-phosphorus-oxygen to form beta-phase Li3PS4Sulfide solid electrolyte Li to be modified3PS4-xOxWherein 0 is<x<4, and provides an organic liquid solvent dispersion method for preparing the oxide modified sulfide solid electrolyte at low temperature and high efficiency. The Chinese patent application No. 201710676381.9 discloses an oxygen-doped inorganic sulfide solid electrolyte and a preparation method thereof, and the oxygen-doped inorganic sulfide solid electrolyte is characterized in that Li9.54Si1.74P1.44S11.2O0.5Cl0.3The conductivity thereof is 1.1X 10-3s/cm, the oxygen-doped inorganic sulfide solid electrolyte has cheap and easily-obtained raw materials and simple and easy preparation process.
In order to improve the characteristic that the solid sulfide electrolyte used for the lithium ion battery is extremely sensitive to moisture and improve the durability to moisture, a novel all-solid-state sulfide electrolyte is needed to be provided, and the cycle performance of the solid-state battery to moisture is further improved.
Disclosure of Invention
Aiming at the defect that the solid sulfide electrolyte used for the lithium ion battery at present is extremely sensitive to moisture, the invention provides a preparation method of the all-solid-state sulfide electrolyte used for the lithium ion battery, so that the durability of the solid electrolyte to the moisture is effectively improved, and the cycle performance of the solid battery is further improved.
In order to solve the problems, the invention adopts the following technical scheme:
a process for preparing the all-solid sulfide electrolyte used for Li-ion battery2S、P2S5The preparation method comprises the following steps of mixing the mixture with doped powder, heating the mixture in a vacuum silicon tube, performing hydrophobic modification by using perfluorodecyl trichlorosilane, performing ultrasonic dispersion, filtering and drying, and specifically comprises the following steps:
(1) mixing Li2S、P2S5Uniformly mixing the doped solid electrolyte particles with the doped powder according to a stoichiometric proportion, adding the mixture into a vacuum silicon tube, and performing heating treatment by using micro-arc oxidation discharge to obtain doped solid electrolyte particles;
(2) uniformly mixing the doped solid electrolyte particles with epoxy resin and nano-silica, adding a coupling agent, and stirring to coat the particles by coupling the epoxy resin with the nano-silica to obtain coated doped solid electrolyte particles;
(3) adding perfluorodecyl trichlorosilane and tetrahydrofuran solvent into the coated doped solid electrolyte particles, and continuing stirring to realize hydrophobic modification of the doped solid electrolyte particles to obtain a hydrophobic modified doped solid electrolyte dispersion liquid;
(4) and carrying out ultrasonic dispersion on the hydrophobically modified doped solid electrolyte dispersion solution, and then filtering and drying to obtain the all-solid sulfide electrolyte for the lithium ion battery.
Preferably, the metal element of the doped powder in the step (1) is one or a combination of more than two of magnesium, germanium, gallium, selenium and titanium.
Preferably, in the preparation of the doped solid electrolyte particles in step (1), Li2S、P2S5The mol ratio of the doped powder is 1:0.5-0.9: 0.1-0.5.
Preferably, the output voltage of the micro-arc oxidation discharge in the step (1) is 500-700V, the temperature is 80-90 ℃, and the time is 50-60 min.
Preferably, the coupling agent in step (2) is one or a combination of more than two of isopropyl triisostearate titanate, isopropyl tri (dioctylphosphato) titanate and bis (dioctyloxypyrophosphate) ethylene titanate.
Preferably, in the preparation of the coated doped solid electrolyte particles in the step (2), the mass ratio of the doped solid electrolyte particles, the epoxy resin, the nano-silica and the coupling agent is 100:10-20:8-12: 1-3.
Preferably, the rotation speed of the stirring in the step (2) is 200-300rpm, and the time is 40-50 min.
Preferably, in the preparation of the hydrophobically modified doped solid electrolyte dispersion in the step (3), the mass ratio of the coated doped solid electrolyte particles to the perfluorodecyl trichlorosilane is 100: 5-8.
Preferably, the temperature of the drying in the step (4) is 40-50 ℃.
The existing solid electrolyte of the lithium battery is extremely sensitive to moisture and poor in moisture durability, so that the application of the solid electrolyte is limited. In view of this, the invention provides a method for preparing all-solid-state sulfide electrolyte for lithium ion battery, which is prepared by mixing Li2S、P2S5According to the chemical formula of the doped powderAfter mixing the components according to the mass ratio, carrying out heating treatment by using micro-arc oxidation discharge, then mixing the particles with epoxy resin and nano-silica, adding a coupling agent, stirring, coating the particles by using epoxy resin coupled nano-silica, and finally adding perfluorodecyl trichlorosilane for modification treatment to obtain the hydrophobic sulfide electrolyte. According to the all-solid-state sulfide electrolyte provided by the invention, the hydrophobic coating is formed on the sulfide surface through micro-arc oxidation discharge and hydrophobic modification, so that the corrosion of moisture to sulfide particles is effectively inhibited, the durability of moisture is improved, and the cycle performance of a solid-state lithium battery is improved.
Compared with the prior art, the invention provides a preparation method of an all-solid-state sulfide electrolyte for a lithium ion battery, which has the outstanding characteristics and excellent effects that:
1. according to the invention, the doped powder is used for doping sulfide, the doped phase and lithium form an alloy phase with a micron-sized coarse structure in the micro-arc oxidation discharge process, the conductivity of an electrolyte is improved, and a hydrophobic coating is formed on the coarse surface through hydrophobic modification, so that the corrosion of moisture on sulfide particles is effectively inhibited.
2. According to the invention, the sulfide electrolyte particles are modified by the hydrophobic coating, so that the durability of the sulfide electrolyte particles to moisture is effectively improved, and the cycle performance of the solid-state battery is improved.
Drawings
Fig. 1 is a schematic flow diagram of the synthesis of an all-solid sulfide electrolyte of the present invention, wherein 1-doped solid electrolyte particles, 2-epoxy and nanosilica mixture, 3-doped solid electrolyte particles coated with 4-coated doped solid electrolyte particles, hydrophobic modification of 5-fluorodecyl trichlorosilane, 6-all-solid sulfide electrolyte.
FIG. 2 is a schematic structural view of the all-solid-state sulfide electrolyte of the present invention, wherein: 6-1 is LPS electrolyte, 6-2 is a coating layer, and 6-3 is a hydrophobic layer.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Mixing Li2S、P2S5Uniformly mixing the doped solid electrolyte powder and the doped powder according to a stoichiometric proportion, then adding the mixture into a vacuum silicon tube, and carrying out heating treatment by using micro-arc oxidation discharge to obtain doped solid electrolyte powder; the metal elements of the doped powder are magnesium and germanium; in the preparation of doped solid electrolyte particles, Li2S、P2S5The molar ratio of the doped powder is 1:0.7: 0.3; the output voltage of micro-arc oxidation discharge is 580V, the temperature is 86 ℃, and the time is 56 min;
(2) uniformly mixing the doped solid electrolyte particles with epoxy resin and nano-silica, adding a coupling agent, and stirring to coat the particles by coupling the epoxy resin with the nano-silica to obtain coated doped solid electrolyte particles; the coupling agent is isopropyl triisostearate; in the preparation of the coated doped solid electrolyte particles, the mass ratio of the doped solid electrolyte particles, the epoxy resin, the nano silicon dioxide and the coupling agent is 100:14:11: 2; the stirring speed is 260rpm, and the time is 44 min;
(3) adding perfluorodecyl trichlorosilane and tetrahydrofuran solvent into the coated doped solid electrolyte particles, and continuing stirring to realize hydrophobic modification of the doped solid electrolyte particles to obtain a hydrophobic modified doped solid electrolyte dispersion liquid; in the preparation of the hydrophobically modified doped solid electrolyte dispersion liquid, the mass ratio of the coated doped solid electrolyte particles to the perfluorodecyl trichlorosilane is 100: 7;
(4) carrying out ultrasonic dispersion on the hydrophobically modified doped solid electrolyte dispersion liquid, and then filtering and drying to prepare an all-solid sulfide electrolyte for the lithium ion battery; the temperature of drying was 45 ℃.
The test method comprises the following steps:
the all-solid-state sulfide electrolyte prepared in the embodiment is subjected to performance testing, the prepared all-solid-state sulfide electrolyte is taken and tested by a KRUSS Germany Kruss contact angle measuring instrument, and the water contact angle of the electrolyte surface is measured, so that the obtained result is shown in Table 1;
the all-solid sulfide electrolyte prepared in the embodiment is subjected to cycle performance test, and LiFePO is added4Uniformly mixing carbon black and PVDF according to a mass ratio of 91:3:6, smearing, drying in vacuum to prepare a positive plate, taking lithium as a negative electrode, taking the all-solid sulfide electrolyte obtained in the embodiment, packaging the electrolyte into a battery in a glove box filled with argon, testing the charge-discharge cycle test of the assembled battery sample by adopting a CHI660a electrochemical workstation, testing the first specific capacity by using a 0.1C multiplying power, placing the battery sample in an environment with the relative humidity of 80% for 15 days, testing, calculating the specific capacities when the battery sample is subjected to charge-discharge cycles for 50 times, 100 times and 200 times, and calculating the capacity retention rate to obtain the result shown in Table 1.
Example 2
(1) Mixing Li2S、P2S5Uniformly mixing the doped solid electrolyte powder and the doped powder according to a stoichiometric proportion, then adding the mixture into a vacuum silicon tube, and carrying out heating treatment by using micro-arc oxidation discharge to obtain doped solid electrolyte powder; the metal elements of the doped powder are gallium and selenium; in the preparation of doped solid electrolyte particles, Li2S、P2S5The molar ratio of the doped powder is 1:0.5: 0.1; the output voltage of micro-arc oxidation discharge is 500V, the temperature is 80 ℃, and the time is 60 min;
(2) uniformly mixing the doped solid electrolyte particles with epoxy resin and nano-silica, adding a coupling agent, and stirring to coat the particles by coupling the epoxy resin with the nano-silica to obtain coated doped solid electrolyte particles; the coupling agent is isopropyl tri (dioctyl phosphate acyloxy) titanate; in the preparation of the coated doped solid electrolyte particles, the mass ratio of the doped solid electrolyte particles, the epoxy resin, the nano silicon dioxide and the coupling agent is 100:10:8: 1; the stirring speed is 200rpm, and the time is 50 min;
(3) adding perfluorodecyl trichlorosilane and tetrahydrofuran solvent into the coated doped solid electrolyte particles, and continuing stirring to realize hydrophobic modification of the doped solid electrolyte particles to obtain a hydrophobic modified doped solid electrolyte dispersion liquid; in the preparation of the hydrophobically modified doped solid electrolyte dispersion liquid, the mass ratio of the coated doped solid electrolyte particles to the perfluorodecyl trichlorosilane is 100: 5;
(4) carrying out ultrasonic dispersion on the hydrophobically modified doped solid electrolyte dispersion liquid, and then filtering and drying to prepare an all-solid sulfide electrolyte for the lithium ion battery; the drying temperature was 40 ℃.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 3
(1) Mixing Li2S、P2S5Uniformly mixing the doped solid electrolyte powder and the doped powder according to a stoichiometric proportion, then adding the mixture into a vacuum silicon tube, and carrying out heating treatment by using micro-arc oxidation discharge to obtain doped solid electrolyte powder; the metal elements of the doped powder are magnesium, selenium and titanium; in the preparation of doped solid electrolyte particles, Li2S、P2S5The molar ratio of the doped powder is 1:0.9: 0.5; the output voltage of micro-arc oxidation discharge is 700V, the temperature is 90 ℃, and the time is 50 min;
(2) uniformly mixing the doped solid electrolyte particles with epoxy resin and nano-silica, adding a coupling agent, and stirring to coat the particles by coupling the epoxy resin with the nano-silica to obtain coated doped solid electrolyte particles; the coupling agent is bis (dioctyloxy pyrophosphate) ethylene titanate; in the preparation of the coated doped solid electrolyte particles, the mass ratio of the doped solid electrolyte particles, the epoxy resin, the nano silicon dioxide and the coupling agent is 100: 20: 12: 3; the stirring speed is 300rpm, and the time is 40 min;
(3) adding perfluorodecyl trichlorosilane and tetrahydrofuran solvent into the coated doped solid electrolyte particles, and continuing stirring to realize hydrophobic modification of the doped solid electrolyte particles to obtain a hydrophobic modified doped solid electrolyte dispersion liquid; in the preparation of the hydrophobically modified doped solid electrolyte dispersion liquid, the mass ratio of the coated doped solid electrolyte particles to the perfluorodecyl trichlorosilane is 100: 8;
(4) carrying out ultrasonic dispersion on the hydrophobically modified doped solid electrolyte dispersion liquid, and then filtering and drying to prepare an all-solid sulfide electrolyte for the lithium ion battery; the temperature of drying was 50 ℃.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 4
(1) Mixing Li2S、P2S5Uniformly mixing the doped solid electrolyte powder and the doped powder according to a stoichiometric proportion, then adding the mixture into a vacuum silicon tube, and carrying out heating treatment by using micro-arc oxidation discharge to obtain doped solid electrolyte powder; the metal elements of the doped powder are gallium, selenium and titanium; in the preparation of doped solid electrolyte particles, Li2S、P2S5The molar ratio of the doped powder is 1:0.8: 0.3; the output voltage of micro-arc oxidation discharge is 600V, the temperature is 85 ℃, and the time is 55 min;
(2) uniformly mixing the doped solid electrolyte particles with epoxy resin and nano-silica, adding a coupling agent, and stirring to coat the particles by coupling the epoxy resin with the nano-silica to obtain coated doped solid electrolyte particles; the coupling agent is isopropyl triisostearate; in the preparation of the coated doped solid electrolyte particles, the mass ratio of the doped solid electrolyte particles, the epoxy resin, the nano silicon dioxide and the coupling agent is 100:15:10: 2; the stirring speed is 250rpm, and the time is 45 min;
(3) adding perfluorodecyl trichlorosilane and tetrahydrofuran solvent into the coated doped solid electrolyte particles, and continuing stirring to realize hydrophobic modification of the doped solid electrolyte particles to obtain a hydrophobic modified doped solid electrolyte dispersion liquid; in the preparation of the hydrophobically modified doped solid electrolyte dispersion liquid, the mass ratio of the coated doped solid electrolyte particles to the perfluorodecyl trichlorosilane is 100: 6;
(4) carrying out ultrasonic dispersion on the hydrophobically modified doped solid electrolyte dispersion liquid, and then filtering and drying to prepare an all-solid sulfide electrolyte for the lithium ion battery; the temperature of drying was 45 ℃.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Comparative example 1
Comparative example 1 compared with example 1, the all-solid sulfide electrolyte prepared without hydrophobic modification was tested by the method of example 1, and the test results are shown in table 1.
Table 1:
Figure 874188DEST_PATH_IMAGE002
according to the detection results of the examples 1 to 4 and the comparative example 1, the hydrophobic performance of the examples 1 to 4 is better than that of the comparative example 1, which shows that the hydrophobic treatment has a certain effect, in a capacity cycling performance test, because the hydrophobic layer on the surface inhibits the moisture from infiltrating into the electrolyte, compared with the comparative example without hydrophobic modification, the cycling performance of the batteries of the examples 1 to 4 is obviously better, and the hydrophobic modification can effectively inhibit the moisture from infiltrating into the electrolyte membrane.

Claims (9)

1. The preparation method of the all-solid-state sulfide electrolyte for the lithium ion battery is characterized in that the all-solid-state sulfide electrolyte is prepared by mixing Li2S、P2S5The preparation method comprises the following steps of mixing the mixture with doped powder, heating the mixture in a vacuum silicon tube, performing hydrophobic modification by using perfluorodecyl trichlorosilane, performing ultrasonic dispersion, filtering and drying, and specifically comprises the following steps:
(1) mixing Li2S、P2S5Uniformly mixing the doped solid electrolyte particles with the doped powder according to a stoichiometric proportion, adding the mixture into a vacuum silicon tube, and performing heating treatment by using micro-arc oxidation discharge to obtain doped solid electrolyte particles;
(2) uniformly mixing the doped solid electrolyte particles with epoxy resin and nano-silica, adding a coupling agent, and stirring to coat the particles by coupling the epoxy resin with the nano-silica to obtain coated doped solid electrolyte particles;
(3) adding perfluorodecyl trichlorosilane and tetrahydrofuran solvent into the coated doped solid electrolyte particles, and continuously stirring to obtain a hydrophobically modified doped solid electrolyte dispersion liquid;
(4) and carrying out ultrasonic dispersion on the hydrophobically modified doped solid electrolyte dispersion solution, and then filtering and drying to obtain the all-solid sulfide electrolyte for the lithium ion battery.
2. The method according to claim 1, wherein the metal element of the doped powder in step (1) is one or a combination of two or more of magnesium, germanium, gallium, selenium and titanium.
3. The method according to claim 1, wherein in the step (1), Li is added to the doped solid electrolyte particles to prepare the doped solid electrolyte particles2S、P2S5The mol ratio of the doped powder is 1:0.5-0.9: 0.1-0.5.
4. The method as claimed in claim 1, wherein the micro-arc oxidation discharge in step (1) has an output voltage of 500-700V, a temperature of 80-90 ℃ and a time of 50-60 min.
5. The method according to claim 1, wherein the coupling agent in step (2) is one or a combination of two or more of isopropyl triisostearate, isopropyltris (dioctylphosphato) titanate, and bis (dioctyloxypyrophosphate) ethylene titanate.
6. The preparation method of the all-solid-state sulfide electrolyte for the lithium ion battery according to claim 1, wherein in the preparation of the coated doped solid electrolyte particles in the step (2), the mass ratio of the doped solid electrolyte particles, the epoxy resin, the nano-silica and the coupling agent is 100:10-20:8-12: 1-3.
7. The method as claimed in claim 1, wherein the stirring speed in step (2) is 200-300rpm for 40-50 min.
8. The method for preparing the all-solid-state sulfide electrolyte of the lithium ion battery according to claim 1, wherein in the step (3), the doped solid-state electrolyte particles coated with the hydrophobic modified doped solid-state electrolyte dispersion are prepared, and the mass ratio of the doped solid-state electrolyte particles to the perfluorodecyl trichlorosilane is 100: 5-8.
9. The method for preparing an all-solid-state sulfide electrolyte for a lithium ion battery according to claim 1, wherein the temperature for drying in the step (4) is 40 to 50 ℃.
CN202011319195.8A 2020-11-23 2020-11-23 Preparation method of all-solid-state sulfide electrolyte for lithium ion battery Withdrawn CN112421119A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117174988A (en) * 2023-09-01 2023-12-05 哈尔滨工业大学 Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery
WO2024032093A1 (en) * 2022-08-09 2024-02-15 宜宾南木纳米科技有限公司 Hydrophobic solid-state electrolyte prepared by using dry method, as well as preparation method therefor, and use thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024032093A1 (en) * 2022-08-09 2024-02-15 宜宾南木纳米科技有限公司 Hydrophobic solid-state electrolyte prepared by using dry method, as well as preparation method therefor, and use thereof
CN117174988A (en) * 2023-09-01 2023-12-05 哈尔滨工业大学 Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery
CN117174988B (en) * 2023-09-01 2024-04-30 哈尔滨工业大学 Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery

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Application publication date: 20210226