CN113725481A - Synthesis of novel nano solid electrolyte and preparation method of composite solid electrolyte - Google Patents

Synthesis of novel nano solid electrolyte and preparation method of composite solid electrolyte Download PDF

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Publication number
CN113725481A
CN113725481A CN202111030172.XA CN202111030172A CN113725481A CN 113725481 A CN113725481 A CN 113725481A CN 202111030172 A CN202111030172 A CN 202111030172A CN 113725481 A CN113725481 A CN 113725481A
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electrolyte
solid electrolyte
lithium
sulfide
composite
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Inventor
韩乃旺
郭鑫
张仁柏
娄忠良
刘昊
郁星星
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Tianneng Shuai Fude Energy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of solid lithium ion batteries, and particularly relates to a synthesis method of a novel nano solid electrolyte and a preparation method of a composite solid electrolyte, wherein Li is selected2S, lithium halide, P4S6The three inorganic substances are used for preparing a precursor of the sulfide electrolyte by a sol-gel method, and then the sulfide electrolyte at a nanometer level is synthesized by magnetically stirring a solid phase in an inert gas environment. Firstly, adding the prepared sulfide electrolyte and PVP into the synthesis process of a polymer ion conductor, then uniformly coating the composite electrolyte on a lithium ion battery pole piece and drying to obtain the composite solid electrolyte. The solid electrolyte synthesized and prepared by the method can be in close contact with the pole piece, so that the interface impedance is effectively reduced, and the ionic conductivity is improved; nano sulfide electrolyteThe lithium ion battery electrolyte can provide enough strength for the electrolyte, cannot be penetrated by lithium dendrites, and has higher ionic conductivity, better safety performance, and more excellent cycle life and rate capability.

Description

Synthesis of novel nano solid electrolyte and preparation method of composite solid electrolyte
Technical Field
The invention belongs to the technical field of solid lithium ion batteries, and particularly relates to a synthesis method of a novel nano solid electrolyte and a preparation method of a composite solid electrolyte.
Background
At present, liquid carbonate organic solvents and lithium salts are used as transmission media of lithium ions in lithium ion batteries applied in large scale, and the liquid electrolyte is used as the transmission media of the lithium battery, so that the lithium ion batteries have the advantage of higher ionic conductivity and can meet the requirements of high-rate charge and discharge and long cycle of the batteries; however, the carbonate solvents are combustible, and when short circuit occurs in the lithium battery and some sparks occur, the electrolyte is easy to ignite, so that great potential safety hazard is brought to the battery. In order to solve the safety problem caused by the electrolyte, the research application of the solid electrolyte gradually enters the field of people. The solid electrolyte is one of the most promising schemes for solving the safety problem of the lithium ion battery, the diaphragm and the electrolyte in the traditional lithium battery are replaced by the solid electrolyte, the interior of the battery is not easy to burn, and the safety is ensured. The solid electrolyte includes inorganic electrolytes, gel polymer electrolytes and organic-inorganic composite electrolytes. The inorganic solid electrolyte has higher conductivity (more than or equal to 10-3S/cm), low conductive activation energy (E is less than or equal to 0.5eV) and good high-temperature resistance; however, these materials are very brittle and difficult to process, and the interfacial resistance with the electrode active material is a great obstacle to the application of these materials. The interfacial impedance of the electrode and the electrolyte is a key problem restricting the development of the solid-state lithium ion battery, which not only limits the rate performance of the battery, but also causes the cycle performance to be greatly reduced. In addition, poor contact at the interface also leads to mechanical failure and deterioration of the ion-conductive interface layer due to interface change during charging and discharging overcharge of the battery.
Introduction of an electrolytic solution into a high molecular polymer has been developed into a gel polymer electrolyte, also referred to as a semi-solid electrolyte. The gel electrolyte was first proposed by feurlade et al, which was further characterized by Abraham et al. The electrolyte composed of the ternary components of the macromolecular compound, the lithium salt and the polar organic solvent is also solid, but has obvious difference from the traditional solid electrolyte in performance and structure, so the electrolyte is called as a gel polymer electrolyte. The polymer compound is usually Polyacrylonitrile (PAN), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), or the like. Common organic solvents are diethyl carbonate (DEC), Propylene Carbonate (PC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), etc. In gel polymer electrolytes, mechanical strength and electrical conductivity are a pair of contradictions. The mechanical strength can be increased by increasing the polymer/solvent ratio, but the conductivity is reduced. Meanwhile, in the preparation of the polymer gel electrolyte, two problems are caused due to the absorption of a large amount of solvent: (1) the electrolyte lacks sufficient mechanical strength to prevent short circuiting between the electrodes; (2) the thermal stability is poor during charge and discharge. The organic framework of these materials does not fundamentally solve the flammability problem and the battery is prone to thermal runaway.
The inorganic-organic composite electrolyte integrates inorganic electrolyte and polymer electrolyte, possibly makes use of the advantages of the inorganic electrolyte and the polymer electrolyte, and has the advantages of good toughness, high conductivity, good thermal stability, easy processing, wide electrochemical window and the like. Scrosati reports a Nano-Materials composite polymer electrolyte, and the addition of an inorganic material not only greatly improves the machining performance of a composite system, but also destroys the crystal region structure in a polymer, increases the content of an amorphous region and enables the ionic conductivity of the electrolyte to reach 10-5S/cm. Professor of hamgongdang and dong goose modifies the inorganic nanophase by in-situ polymerization of methyl methacrylate on the surface of the inorganic nanoparticles. Tests show that polymethyl methacrylate can not be uniformly coated on the surface of inorganic nanoparticles, and meanwhile, the grafting rate is low, so that the synthesis of nanoparticles with uniform core-shell morphology can not be really realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a synthesis method of a novel nano solid electrolyte and a preparation method of a composite solid electrolyte.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a synthesis method of a novel nano solid electrolyte comprises the following steps:
(1) preparation of sulfide precursor
Respectively dissolving Li in volatile organic solvent2S, lithium halide, P4S6And then Li is respectively added under the temperature condition of 20-30 DEG C2S, lithium halide, P4S6Stirring until the solution is completely dissolved and no precipitate is generated, and obtaining Li2S solution, lithium halide solution, P4S6A solution;
mixing Li2S solution, lithium halide solution, P4S6Adding the solution into a container, mixing, and stirring and mixing by using a magnetic bar at the rotating speed of 100-150 r/min;
introducing nitrogen or argon with the purity of more than 99.999 percent into the container, heating the mixed solution after the reaction is in an inert atmosphere, controlling the temperature between 70 and 78 ℃, and simultaneously arranging an exhaust hole on the container to discharge the inert gas and the volatilized organic solvent. After the organic solvent in the container is volatilized, obtaining precursor powder of the sulfide;
(2) synthesis of sulfide electrolyte
Sealing the container, keeping the interior of the container in inert atmosphere, increasing the rotation speed of magnetic stirring to 200-250 r/min, and reacting for 5-10 h at 200-300 ℃ to ensure that reactants slowly grow to nano level and ensure complete crystal form;
and stopping heating after the reaction is finished, and cooling to room temperature to obtain the nano sulfide electrolyte.
Preferably, the whole synthesis environment of the novel nano solid electrolyte requires that the moisture content is less than or equal to 10 ppm.
Preferably, the volatile organic solvent is selected from one of absolute ethyl alcohol, acetone, pyridine, diethyl ether and tetrahydrofuran.
Preferably, the Li2S, lithium halide, P4S6The molar ratio of (A) to (B) is 1 to (0-0.9) to (0.2-1).
Preferably, the lithium halide is one of lithium chloride, lithium fluoride, lithium bromide and lithium iodide.
Based on one general inventive concept, another object of the present invention is to provide a method of preparing a composite solid electrolyte, including the steps of:
(1) adding the prepared nano sulfide electrolyte and polyvinylpyrrolidone into the synthesis process of the polymer ion conductor to obtain a composite electrolyte;
(2) and uniformly coating the composite electrolyte on a pole piece of a lithium ion battery, and drying at the temperature of 100-120 ℃ to obtain the composite solid electrolyte.
Preferably, the weight ratio of the nano sulfide electrolyte to the polyvinylpyrrolidone to the polymer is (10-80) to (1-5) to (20-90).
Preferably, the polymer is one selected from the group consisting of polyether polymers, polyacrylonitrile polymers, polymethacrylate polymers, polyvinylidene fluoride polymers, polyvinyl chloride polymers and polyamine polymers.
Preferably, the conductivity of the composite solid electrolyte is more than or equal to 5.1 x 10-3S/cm。
The invention selects Li2S, LiR (halogen such as F, Cl, Br, I), P4S6The three inorganic substances are used for preparing a precursor of the sulfide electrolyte by a sol-gel method, and then the nano-grade sulfide electrolyte is synthesized by magnetically stirring the precursor in a solid phase at 200-300 ℃ in an inert gas environment. Adding 10-80% of the prepared sulfide electrolyte and 1-5% of PVP (polyvinylpyrrolidone) into a synthesis process of a polymer ion conductor, wherein the polymer accounts for 20-90%, and finally uniformly coating the composite electrolyte on a lithium ion battery pole piece and drying at 100-120 ℃ to obtain the composite solid electrolyte.
The solid electrolyte synthesized and prepared by the method can not only form close contact with the pole piece, effectively reduce the interface impedance and improve the ionic conductivity, and the conductivity can reach 5.1 multiplied by 10-3More than S/cm;the addition of the nanosulfide electrolyte thereto also provides sufficient strength of the electrolyte not penetrated by the lithium dendrites. Therefore, the conductive material has higher ionic conductivity, better safety performance, and more excellent cycle life and rate performance.
Compared with the prior art, the invention has the following innovation points:
(1) the inorganic electrolyte of the invention adopts a sulfide system with higher conductivity and a molecular general formula of LixByAz(A ═ S; B ═ F, Cl, Br, I and other halogens; x/y/z is the corresponding stoichiometric ratio) from Li2S, lithium halide, P4S6The three parts are as follows;
in the prior art, P, Si, Ge, Sn or Ag, Zn, Al, etc. are usually selected as sulfide electrolyte B (as in the patent publication No. CN 101013753A), and the reason why lithium halide is selected as the raw material in the present invention is that: sulfides containing Ge, Sn, Ag, Zn and Al are unstable when contacting with metallic lithium, and can be reduced by lithium to form an interface layer at an interface, and the interface layer can increase interface impedance and influence ionic conductivity; and the above metals combined with lithium form an electronically conductive alloy, which aggravates the degradation of battery capacity. In order to avoid negative effects caused by using excessive cations, the lithium halide is used as a synthesis component, so that the stability of the solid electrolyte can be improved on one hand, and the conductivity of lithium ions can be improved on the other hand due to the larger radius of halogen atoms.
The invention also relates to the commonly used P2S5By changing to P4S6Due to the fact that in the process of synthesis, P2S5Poor thermal stability and easy decomposition to generate toxic and harmful gas H2S, and use P4S6The structure is more stable, the decomposition is not easy to occur when the catalyst is heated, and the synthesized product is stable and complete.
(2) The invention provides a sol-gel-low-temperature stirring solid-phase synthesis method for synthesizing nano sulfide for the first time, and has the advantages of low cost, simpler process and high yield.
(3) The composite electrolyte is finally obtained by adding nano sulfide and PVP (polyvinylpyrrolidone) in the process of preparing the high-molecular conductive polymer for the first time. Because the nano sulfide is easy to agglomerate, the surfactant such as PVP is added to prevent the agglomeration of nano particles, so that the sulfide electrolyte is more uniformly dispersed among chain segment structures of the high molecular polymer. In addition, ion transmission in the polymer electrolyte mainly occurs in an amorphous region, and the unmodified polymer has high crystallinity at room temperature, so that the ionic conductivity is low, and the large-current charge and discharge capacity is seriously influenced. The method for reducing the crystallinity can improve the moving capability of a polymer chain segment, so that the conductivity of a system is improved, at present, more inorganic fillers are researched, including Al2O3, SiO2, MgO and other metal oxide nano particles, zeolite, montmorillonite and the like, the addition of the inorganic particles disturbs the order of the polymer chain segment in a matrix, the crystallinity of the polymer chain segment is reduced, and the interaction generated among the polymer, lithium salt and the inorganic particles increases a lithium ion transmission channel, so that the conductivity and the ion mobility are improved. The inorganic filler can also play a role in adsorbing trace impurities (such as moisture) in the composite electrolyte and improving the mechanical property. In order to further improve the conductivity of the polymer, the order of chain segments in the matrix is disturbed by introducing the nano sulfide, the crystallinity of the chain segments is reduced, and the interaction generated between the polymer and the sulfide increases a lithium ion transmission channel, so that the conductivity and the ion transference number are improved.
Drawings
FIG. 1 is a transmission electron micrograph of a nano-sulfide electrolyte synthesized according to the present invention;
FIG. 2 scanning electron micrographs of polymers in the examples of the invention.
Detailed Description
The present invention will be further described with reference to specific embodiments for making the objects, technical solutions and advantages of the present invention more apparent, but the present invention is not limited to these examples. It should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment. In the invention, all parts and percentages are mass units, and the adopted equipment, raw materials and the like can be purchased from the market or are commonly used in the field. The methods in the following examples are conventional in the art unless otherwise specified.
The following is a detailed description of specific embodiments of the invention.
Examples
Process for preparing nano sulfide
1. Preparation of sulfide precursor
The whole synthesis environment requires that the water content is less than or equal to 10ppm, and the superior pure absolute ethyl alcohol is used as a solvent to respectively dissolve Li2S, lithium halide (LiCl in the present example), P4S6Separately reacting Li at a temperature of 25 DEG C2S, lithium halide, P4S6Stirring until the solution is completely dissolved and no precipitate is generated, and obtaining Li2S solution, lithium halide solution, P4S6A solution; wherein Li2S：LiCl：P4S6The mol ratio between the two is 1: 0.2: 0.6;
mixing Li2S solution, lithium halide solution, P4S6Adding the solution into a container, mixing, and starting stirring by using a magnetic bar at the rotating speed of 125 r/min; introducing high-purity N into the container2(purity is more than 99.999%) or high-purity argon, the reaction is in an inert atmosphere, the solution is heated, the temperature is controlled to be 74 +/-1 ℃, meanwhile, the container is provided with an exhaust hole, the inert gas and the volatilized absolute ethyl alcohol are discharged, and after the volatilization of the absolute ethyl alcohol in the container is finished, the precursor powder of the sulfide is obtained.
2. Synthesis of sulfide electrolyte
And sealing the container, keeping the inside of the container in an inert atmosphere, increasing the rotating speed of magnetic stirring to 225r/min, keeping the reaction temperature at 250 +/-5 ℃, reacting for 7.5 hours, slowly growing the reactants to the nano level, ensuring the completeness of the crystal form, stopping heating after the reaction is finished, and cooling to room temperature to obtain the nano sulfide electrolyte.
Preparation of (di) composite polymer electrolyte
Firstly, adding the prepared nano sulfide electrolyte and polyvinylpyrrolidone into the synthesis process of a polymer ion conductor to obtain a composite electrolyte; wherein the weight ratio of the nano sulfide electrolyte to the polyvinylpyrrolidone to the polymer is 58: 3.5: 38.5, and the polymer is polyvinyl chloride (PVC)
Then the composite electrolyte is evenly coated on a pole piece of the lithium ion battery and dried at the temperature of 110 ℃ to obtain the lithium ion battery with the conductivity of more than or equal to 5.1 multiplied by 10-3S/cm of composite solid electrolyte.
The above embodiments are merely preferred embodiments of the present invention, and any simple modification, modification and substitution changes made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.

Claims (8)

1. A synthesis method of a novel nano solid electrolyte is characterized by comprising the following steps:
(1) preparation of sulfide precursor
Respectively dissolving Li in volatile organic solvent2S, lithium halide, P4S6And then Li is respectively added under the temperature condition of 20-30 DEG C2S, lithium halide, P4S6Stirring until the solution is completely dissolved and no precipitate is generated, and obtaining Li2S solution, lithium halide solution, P4S6A solution;
mixing Li2S solution, lithium halide solution, P4S6Adding the solution into a container, mixing, and stirring and mixing by using a magnetic bar at the rotating speed of 100-150 r/min;
introducing nitrogen or argon with the purity of more than 99.999 percent into the container, heating the mixed solution after the reaction is in an inert atmosphere, controlling the temperature between 70 and 78 ℃, and simultaneously arranging an exhaust hole on the container to discharge the inert gas and the volatilized organic solvent. After the organic solvent in the container is volatilized, obtaining precursor powder of the sulfide;
(2) synthesis of sulfide electrolyte
Sealing the container, keeping the interior of the container in inert atmosphere, increasing the rotation speed of magnetic stirring to 200-250 r/min, and reacting for 5-10 h at 200-300 ℃ to ensure that reactants slowly grow to nano level and ensure complete crystal form;
and stopping heating after the reaction is finished, and cooling to room temperature to obtain the nano sulfide electrolyte.
2. The method for synthesizing a novel nano solid electrolyte according to claim 1, wherein the whole synthesis environment of the novel nano solid electrolyte requires that the moisture content is less than or equal to 10 ppm.
3. The method for synthesizing a novel nano solid electrolyte according to claim 1, wherein the volatile organic solvent is one selected from absolute ethyl alcohol, acetone, pyridine, diethyl ether and tetrahydrofuran.
4. The method of claim 1, wherein the Li is selected from the group consisting of Li, and Li2S, lithium halide, P4S6The molar ratio of (A) to (B) is 1 to (0-0.9) to (0.2-1).
5. The method for synthesizing a novel nano solid electrolyte according to claim 1, wherein the lithium halide is one of lithium chloride, lithium fluoride, lithium bromide and lithium iodide.
6. A preparation method of a composite solid electrolyte is characterized by comprising the following steps:
(1) adding the nano sulfide electrolyte prepared according to any one of claims 1-5 and polyvinylpyrrolidone into the synthesis process of the polymer ion conductor to obtain a composite electrolyte;
(2) and uniformly coating the composite electrolyte on a pole piece of a lithium ion battery, and drying at the temperature of 100-120 ℃ to obtain the composite solid electrolyte.
7. The preparation method of the composite solid electrolyte as claimed in claim 6, wherein the weight ratio of the nano sulfide electrolyte to the polyvinylpyrrolidone to the polymer is (10-80) to (1-5) to (20-90).
8. The method according to claim 7, wherein the polymer is one selected from the group consisting of polyether polymers, polyacrylonitrile polymers, polymethacrylate polymers, polyvinylidene fluoride polymers, polyvinyl chloride polymers, and polyethyleneimine polymers.
CN202111030172.XA 2021-09-03 2021-09-03 Synthesis of novel nano solid electrolyte and preparation method of composite solid electrolyte Pending CN113725481A (en)

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