CN116722212A - Application of propylene carbonate in polymer gel electrolyte for solid sodium ion battery, solid sodium ion battery and preparation method of solid sodium ion battery - Google Patents

Application of propylene carbonate in polymer gel electrolyte for solid sodium ion battery, solid sodium ion battery and preparation method of solid sodium ion battery Download PDF

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CN116722212A
CN116722212A CN202310622441.4A CN202310622441A CN116722212A CN 116722212 A CN116722212 A CN 116722212A CN 202310622441 A CN202310622441 A CN 202310622441A CN 116722212 A CN116722212 A CN 116722212A
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sodium ion
ion battery
propylene carbonate
battery
sodium
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徐雄文
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Hunan Nafang New Energy Technology 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/058—Construction or manufacture
    • 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

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Abstract

The invention discloses application of propylene carbonate in polymer gel electrolyte for a solid sodium ion battery, the solid sodium ion battery and a preparation method thereof. According to the invention, propylene carbonate is used as a single solvent to prepare the polymer gel electrolyte for the solid sodium ion battery, so that the problem of solvent co-embedding with an amorphous carbon negative electrode is avoided, and the cycle performance of the battery is ensured. Meanwhile, due to the fact that propylene carbonate has no chain structure, the polymerization degree can be improved, no liquid solvent remains after polymerization, and due to the high boiling point attribute of propylene carbonate, the battery has excellent high-temperature thermal stability.

Description

Application of propylene carbonate in polymer gel electrolyte for solid sodium ion battery, solid sodium ion battery and preparation method of solid sodium ion battery
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to application of propylene carbonate in polymer gel electrolyte for solid sodium ion batteries, the solid sodium ion batteries and a preparation method thereof.
Background
The performance and stability of the battery are largely dependent on the quality of the electrolyte solution, and solvents are used in the electrolyte solution manufacturing process, and the selection and use of solvents are important links not to be ignored in the battery manufacturing process. Common solvents include ethylene glycol dimethyl ether (DME), cyanide, carbonate, etc., DME is widely used in lithium ion batteries and fuel cells, and carbonate is currently mainly used in nickel hydrogen batteries and nickel cadmium batteries. The new trend shows that the mixed solvent of carbonate and carboxylate is applied to the lithium battery, so that the potential of the SEI film formed by the negative electrode is high in the first charging process of the lithium ion battery pack, the solvent is prevented from being reduced, the safety of the battery is ensured, and the capacity retention rate and the high-rate charge-discharge capacity of the low-temperature battery are improved.
Propylene carbonate (C) 4 H 6 O 3 ) Is an excellent polar solvent with boiling point: 248 deg.c/760 mmHg. The catalyst is mainly used for macromolecule operation, gas separation process and electrochemistry, in particular for absorbing carbon dioxide in synthetic ammonia raw materials of natural gas and petrochemical plants, and can also be used as plasticizers, spinning solvents, olefin and aromatic hydrocarbon extractants and the like. In the battery industry, the lithium ion battery electrolyte is mixed with other solvents to be used as the solvent of the lithium ion battery electrolyte. There is currently no report on the use of the same as a single solvent for the preparation of battery electrolyte solutions.
Lithium resources are extremely low in reserves in the crust and are unevenly distributed, so that the healthy development of the whole lithium battery industry is difficult to support. Compared with lithium resources, sodium resources are abundant in reserves and uniformly distributed, and have been widely paid attention to the market in recent two years. However, in most lithium ion batteries and sodium ion batteries, liquid electrolyte is used as an electrolyte, and the liquid electrolyte is heated at a high temperature, and then a solvent is easily sprayed out to cause combustion, so that serious safety accidents are caused.
In order to solve the safety problem of the liquid electrolyte, attempts are made to replace the liquid electrolyte with an inorganic solid electrolyte, but a great interface impedance exists between the inorganic solid electrolyte and the positive and negative electrode plates of the battery, so that the room-temperature conductivity is extremely low, and the practical application is difficult. Accordingly, one shifts the focus of attention to polymer gel solid state electrolytes, confining the electrolyte to the polymer network reduces the risk of solvent leakage. The choice of solvent is still a current technical problem. How to select excellent solvent, ensure higher polymerization degree in the preparation process of electrolyte solution, ensure no liquid solvent residue after polymerization, and avoid the problem of solvent co-embedding between the solvent and the amorphous carbon cathode, thereby ensuring the cycle performance and the high-temperature thermal stability of the battery, which is a technical problem yet to be overcome in the field.
Further, a good solvent is selected to prepare a polymer gel solid electrolyte, while the interfacial resistance is reduced to a certain extent, the cycle performance and the high-temperature stability of the battery are also ensured, but the interface contact condition between the novel polymer gel solid electrolyte and the pole piece is required to be further improved, a preparation method of a lithium ion battery adopting an organic-inorganic composite gel polymer electrolyte is disclosed in the prior art, surface functionalized inorganic oxide nano particles are uniformly fixed on the surface and an inner pore canal of a diaphragm, the modified diaphragm is clamped between positive and negative electrode materials, an electrolyte mixed with a functionalized oligomer and an initiator is injected, and then the oligomer is initiated to undergo in-situ polymerization crosslinking by heating, so that a gel electrolyte is formed by gelation of liquid substances in the battery, but a large amount of solvent is usually remained in the battery, so that the thermal stability of the gel electrolyte is poor, and thermal runaway of the battery is extremely easy to occur under the high-temperature condition.
Disclosure of Invention
The invention aims to provide an application of propylene carbonate in polymer gel electrolyte for solid sodium ion batteries, which aims at overcoming the defects of the existing polymer gel electrolyte preparation technology, in particular to the defects of the polymer gel electrolyte for solid sodium ion batteries in terms of solvent selection and application.
The invention further aims to overcome the technical defects of the existing solid sodium ion battery in the preparation of the polymer gel solid electrolyte and the structure of the polymer gel solid electrolyte and the pole piece based on the application of the solvent, and provides a preparation method of the solid sodium ion battery.
It is a further object of the present invention to provide a solid state sodium ion battery.
The above object of the present invention is achieved by the following technical scheme:
the invention protects the application of propylene carbonate as a single solvent in preparing polymer gel electrolyte for solid sodium ion batteries.
The polymer gel electrolyte for the solid sodium ion battery is prepared by polymerization reaction. The preferable amount of propylene carbonate to be used in the reaction system is determined in accordance with the mass ratio thereof to the monomer in the polymerization reaction.
Optionally, the mass ratio of the monomer to the propylene carbonate is (10-20): 80-90. Specifically, (10-17): (73-80), 13:77, 10:80 or 17:73.
Specifically, the preparation raw materials of the polymer gel electrolyte for the solid sodium ion battery comprise a solvent, sodium salt, a monomer and an initiator;
the solvent only adopts propylene carbonate as the only one solvent;
the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, naFSI and NaTFSI;
the monomer contains unsaturated bonds and comprises one or more of polyethylene glycol diacrylate, methyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, vinyl acetate and vinyl sulfite;
the initiator is azo initiator.
Specifically, the application process comprises the following steps: and injecting the mixed solution of the solvent, the sodium salt, the monomer and the initiator into a battery core of the battery, heating the mixed solution at a high temperature after soaking uniformly to enable the mixed solution to perform in-situ polymerization reaction to form gel electrolyte which is dispersed in the positive electrode, the negative electrode and the diaphragm of the battery and is polymerized in-situ between the positive electrode and the diaphragm and between the negative electrode and the diaphragm.
Preferably, at least one side of the separator is coated with a sodium ion-conducting solid electrolyte layer having a thickness of 2 to 5 μm.
Preferably, the positive electrode sheet includes a current collector and a positive electrode active layer including a sodium ion-conducting solid electrolyte.
The invention also provides a preparation method of the solid sodium ion battery, which comprises the following steps:
s1, a bare cell is obtained through lamination and/or winding of a positive pole piece, a diaphragm and a negative pole piece, and then the bare cell is obtained through encapsulation;
s2, uniformly mixing a monomer containing unsaturated bonds, a solvent, sodium salt and an initiator, and then injecting the mixture into the battery cell in the S1, uniformly soaking, and carrying out in-situ polymerization reaction to obtain the solid sodium ion battery;
wherein the solvent in S2 is a single solvent and is propylene carbonate.
Optionally, the mass ratio of the unsaturated bond-containing monomer to propylene carbonate in the S2 is (10-20) (80-90), the temperature of the in-situ polymerization in the S2 is 60-100 ℃, and the polymerization time is 1-5 h. Specifically, (10-17): (73-80), 13:77, 10:80 or 17:73.
It is also preferable that at least one side of the separator is coated with a sodium ion-conducting solid electrolyte layer having a thickness of 2 to 5 μm.
Preferably, the positive electrode sheet includes a current collector and a positive electrode active layer including a sodium ion-conducting solid electrolyte.
In a specific embodiment, the solid electrolyte for guiding sodium ions has a particle size of 0.3 to 3 μm.
Specifically, the positive electrode active layer comprises a positive electrode active material, a conductive agent, an adhesive and a sodium ion-conducting solid electrolyte; the positive electrode active material includes layered oxides, prussian blue, prussian white, polyanion positive electrodes (including phosphates such as sodium vanadium phosphate, sulfates such as sodium iron sulfate, pyrophosphates such as sodium iron phosphate, and fluoro-or fluorooxo-compounds of the above); the conductive agent is a commonly used carbon conductive agent, such as one or more of conductive graphite, carbon black, carbon fiber, carbon nanotube and graphene; the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile and polyimide; sodium ion conducting solid state electrolytes comprising beta-Al 2 O 3 And NASICON-type electrolytes.
In a specific embodiment, the positive electrode active material: conductive agent: and (2) a binder: the mass ratio of the solid electrolyte of sodium ions is (87-96.5:1-3:1.5-5:1-5).
Preferably, the negative electrode tab includes a current collector and a negative electrode active layer including a sodium ion-conducting solid electrolyte.
In a specific embodiment, the solid electrolyte for guiding sodium ions has a particle size of 0.2 to 2 μm.
Specifically, the anode active layer includes an anode active material, a conductive agent, a binder, and a sodium ion-conductive solid electrolyte; the negative electrode active material includes amorphous carbon such as soft carbon and hard carbon; the conductive agent is a commonly used carbon conductive agent, such as one or more of conductive graphite, carbon black, carbon fiber, carbon nanotube and graphene; the binder is one or more of polyacrylic acid, polyacrylonitrile, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyvinylidene fluoride and polytetrafluoroethylene; sodium ion conducting solid state electrolytes comprising beta-Al 2 O 3 And NASICON-type electrolytes.
In a specific embodiment, the negative electrode active material: conductive agent: and (2) a binder: the mass ratio of the solid electrolyte of sodium ions is (87-96.5:1-3:1.5-5:1-5).
The sodium ion-conductive solid electrolyte in the positive electrode active layer or the negative electrode active layer not only plays a role of sodium ion conduction, but also can be uniformly dispersed in pores among active material particles, so that the compaction density of the positive electrode material and the negative electrode material is improved, and the energy density and the safety of the solid-state battery are further improved. According to the invention, the research shows that the sodium ion guiding effect and the pore filling effect of the sodium ion guiding solid electrolyte can be better exerted when the particle size of the sodium ion guiding solid electrolyte in the positive electrode active layer is 0.3-3 mu m or the particle size of the sodium ion guiding solid electrolyte in the negative electrode active layer is 0.2-2 mu m.
Optionally, the monomer containing unsaturated bond is one or more of polyethylene glycol diacrylate, methyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, vinyl acetate and vinyl sulfite; the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, naFSI and NaTFSI.
Specifically, the initiator is an azo initiator, and the mass fraction of the initiator relative to the monomer containing unsaturated bonds is 0.1-1%.
The solid sodium ion battery prepared by the preparation method of the solid sodium ion battery is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention creatively proposes that propylene carbonate is only used as a single solvent in the gel electrolyte for the solid sodium ion battery, and unexpected good effect is obtained. In the technical scheme of the invention, propylene carbonate cannot be co-embedded with the amorphous carbon cathode, so that good cycle performance of the battery is ensured, and deterioration cannot occur; the single propylene carbonate is used as the solvent, no other chain ester exists, the polymerization degree can be improved, no liquid solvent residue exists, and the battery has excellent high-temperature heat stability due to the high-boiling-point attribute of the propylene carbonate.
The invention uses the monomer containing unsaturated bond, propylene carbonate, sodium salt and initiator to polymerize in situ to form polymer gel electrolyte, wherein propylene carbonate can be well crosslinked with the monomer to participate in the formation of polymer network, further improving the polymerization degree and reducing the residual liquid solvent. A good polymer gel solid state electrolyte is obtained, limiting the electrolyte to the polymer network reduces the risk of solvent leakage while well reducing the interfacial resistance.
On the basis, the invention further optimizes and improves the interface contact condition between the new polymer gel solid electrolyte and the pole piece, and the preparation raw material of the polymer gel electrolyte is injected into the battery core of the battery in a liquid state, so that the polymer gel solid electrolyte can be better filled between active material particles of the positive pole and the negative pole, and the polymer gel solid electrolyte formed by in-situ polymerization is tightly contacted with the positive pole and the negative pole, thereby remarkably improving the contact performance between the electrolyte and the positive pole and the negative pole.
Drawings
FIG. 1 is a schematic diagram of the gel electrolyte of example 1 after polymerization;
FIG. 2 is a physical diagram of the gel electrolyte of comparative example 1 after polymerization;
FIG. 3 is a physical diagram of the gel electrolyte of comparative example 2 after polymerization.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The conventional positive electrode plate, negative electrode plate and solid electrolyte membrane (or diaphragm) in the field can be used in the invention, and for convenience in explanation of the technical effects of the invention, the following positive electrode plate, negative electrode plate and solid electrolyte membrane are specifically selected for experiments.
Example 1
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (polyethylene glycol diacrylate, mn is 700), propylene carbonate and sodium salt (sodium hexafluorophosphate) with the mass ratio of 13:77:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization at a high temperature (60-100 ℃) to obtain the solid sodium ion battery.
Wherein, the positive pole piece in S1 is prepared by the following preparation method:
positive electrode active material (nickel-iron-manganese layered oxide, model Na001A, manufactured by Zhenhua New Material), conductive agent (SP+CNT, mass ratio of 1:1), binder (PVDF) and sodium ion-conductive solid electrolyte (Na) 3 Zr 2 PSi 2 O 12 Particle size of 1 μm) in a mass ratio of 94:2:2:2, adding the mixture into N-methylpyrrolidone (NMP), and uniformly stirring to obtain anode slurry; uniformly coating the positive electrode slurry on two sides of an aluminum foil by using a coating machine, and rolling and cutting the aluminum foilAnd obtaining a positive plate, and finally baking and vacuum drying for later use.
The negative electrode plate in S1 is prepared by the following preparation method:
a negative electrode active material (hard carbon), a conductive agent (SP), a binder (CMC+SBR) and a sodium ion conductive solid electrolyte (Na 3 Zr 2 PSi 2 O 12 Particle size of 1 μm) in mass ratio of 92:3:3:2, adding into deionized water, and stirring to obtain negative electrode slurry; and uniformly coating the negative electrode slurry on two sides of an aluminum foil by using a coating machine, rolling and cutting to obtain a negative electrode plate, and finally baking and vacuum drying for later use.
The solid electrolyte membrane in S1 is prepared by the following preparation method:
solid electrolyte (Na) 3 Zr 2 PSi 2 O 12 Particle size of 0.5 μm) and an adhesive (acrylic ester) according to a mass ratio of 90:10, and then adding the mixture into deionized water, uniformly stirring, and uniformly coating the mixture on the surfaces of two sides of a diaphragm to form a solid electrolyte layer with a single-side thickness of 2 μm.
Example 2
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerized monomer (pentaerythritol triacrylate), propylene carbonate and sodium salt (sodium hexafluorophosphate) containing unsaturated bonds according to a mass ratio of 13:77:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization at a high temperature (60-100 ℃) to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Example 3
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (methyl methacrylate), propylene carbonate and sodium salt (sodium hexafluorophosphate) containing unsaturated bonds according to a mass ratio of 13:77:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization at a high temperature (60-100 ℃) to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Example 4
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (polyethylene glycol diacrylate, mn is 700), propylene carbonate and sodium salt (sodium hexafluorophosphate) with the mass ratio of 10:80:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization at a high temperature (60-100 ℃) to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Example 5
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (polyethylene glycol diacrylate, mn is 700), propylene carbonate and sodium salt (sodium hexafluorophosphate) with the mass ratio of 17:73:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization at a high temperature (60-100 ℃) to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Example 6
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (polyethylene glycol diacrylate, mn is 700), propylene carbonate and sodium salt (sodium hexafluorophosphate) with the mass ratio of 18:72:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization under the high-temperature condition to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Example 7
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (polyethylene glycol diacrylate, mn is 700), propylene carbonate and sodium salt (sodium hexafluorophosphate) with the mass ratio of 9:81:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization at a high temperature (60-100 ℃) to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Example 8
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (polyethylene glycol diacrylate, mn is 700), propylene carbonate and sodium salt (sodium hexafluorophosphate) with the mass ratio of 13:77:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization at a high temperature (60-100 ℃) to obtain the solid sodium ion battery. Wherein, the positive pole piece in S1 is prepared by the following preparation method:
mixing an anode active substance (nickel-iron-manganese layered oxide, model Na001A, produced by Zhenhua new materials), a conductive agent (SP+CNT, mass ratio of 1:1) and a binder (PVDF) in a mass ratio of 96:2:2, adding into N-methylpyrrolidone (NMP), and uniformly stirring to obtain anode slurry; and uniformly coating the positive electrode slurry on two sides of an aluminum foil by using a coating machine, rolling and cutting to obtain a positive electrode plate, and finally baking and vacuum drying for later use.
The negative electrode plate in S1 is prepared by the following preparation method:
mixing a negative electrode active material (hard carbon), a conductive agent (SP) and a binder (CMC+SBR) in a mass ratio of 94:3:3, adding the mixture into deionized water, and uniformly stirring to obtain negative electrode slurry; and uniformly coating the negative electrode slurry on two sides of an aluminum foil by using a coating machine, rolling and cutting to obtain a negative electrode plate, and finally baking and vacuum drying for later use.
The solid electrolyte membrane in S1 is prepared by the following preparation method:
solid electrolyte (Na) 3 Zr 2 PSi 2 O 12 Particle size of 0.5 μm) and an adhesive (acrylic ester) according to a mass ratio of 90:10, and then adding the mixture into deionized water, uniformly stirring, and uniformly coating the mixture on the surfaces of two sides of a diaphragm to form a solid electrolyte layer with a single-side thickness of 2 μm.
Comparative example 1
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerization monomer (polyethylene glycol diacrylate, mn is 700), dimethyl carbonate and sodium salt (sodium hexafluorophosphate) containing unsaturated bonds according to a mass ratio of 13:77:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and carrying out in-situ polymerization reaction for 2 hours at 75 ℃ to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Comparative example 2
The preparation method of the solid sodium ion battery comprises the following steps:
s1, a bare cell is obtained by winding a positive electrode plate, a solid electrolyte membrane and a negative electrode plate, and then the bare cell is packaged to obtain the cell;
s2, uniformly mixing a polymerized monomer (polyethylene glycol diacrylate, mn is 700), propylene carbonate, dimethyl carbonate and sodium salt (sodium hexafluorophosphate) according to a mass ratio of 13:30:47:10, then injecting the mixture into the battery cell in S1, adding an initiator (azo) with the mass of 0.5% of the mass of the unsaturated bond monomer, uniformly soaking, and then carrying out in-situ polymerization reaction for 2 hours at 75 ℃ to obtain the solid sodium ion battery.
Wherein the positive electrode sheet, the negative electrode sheet and the solid electrolyte membrane in S1 are the same as in example 1.
Result detection
As can be seen from fig. 1 to 3, in example 1, pure propylene carbonate is used as a solvent, and the mixed solution is almost completely polymerized to form gel after in-situ polymerization; in comparative example 1, pure chain dimethyl carbonate is used as a solvent, and the mixed solution only exists in a liquid state after in-situ polymerization; in contrast, in comparative example 2, in which propylene carbonate and dimethyl carbonate were used as mixed solvents, a part of gel state was observed after in-situ polymerization, but a large amount of liquid residue was present at the same time. Therefore, propylene carbonate is used as a solvent, and can be well crosslinked with a monomer to participate in the formation of a polymer network, so that the polymerization degree is improved, and the liquid solvent residue is reduced.
The above sodium ion solid-state battery was subjected to an RT (room temperature) 0.5C charge-discharge cycle test (test voltage range of 1.5 to 3.9V), and a 350 ℃ hot plate heating test (specifically, the battery was heated to 350 ℃ on a hot plate and held for 30 min) (charging to 3.9V before the test), respectively, and the test results are shown in table 1.
TABLE 1
Numbering device 300-cycle capacity retention rate Heating voltage of 350 ℃ hot plate
Example 1 95.7％ 3.75V
Example 2 95.5％ 3.72V
Example 3 95.7％ 3.74V
Example 4 95.9％ 3.71V
Example 5 95.3％ 3.74V
Example 6 95.0％ 3.71V
Example 7 95.4％ 3.71V
Example 8 95.5％ 3.73V
Comparative example 1 95.6％ 0.5V
Comparative example 2 95.9％ 2.8V
As can be seen from Table 1, the difference of the circulation capacity retention rate of each example is not large, but the voltage after the hot plate at 350 ℃ is obviously different, the voltage of more than 3.7V is still obtained after the experiment of the example is finished, the voltage of the comparative example 1 is reduced to 0.5V, the voltage of the comparative example 2 is also reduced to 2.8V, namely, the comparative example is internally shorted, so that the voltage is obviously reduced, but the example has better thermal stability, does not generate internal short circuit, still has a voltage value close to the initial voltage, and the gel electrolyte prepared by adopting the single propylene carbonate as the solvent is fully proved to have excellent thermal stability, so that the risk of thermal runaway is effectively reduced.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (14)

1. The application of propylene carbonate as a single solvent in preparing polymer gel electrolyte for solid sodium ion battery.
2. The use according to claim 1, wherein the polymer gel electrolyte for the solid sodium ion battery is prepared by polymerization reaction, and the reaction system comprises monomers and propylene carbonate, wherein the mass ratio of the monomers to the propylene carbonate is (10-20): 80-90.
3. The use according to claim 2, wherein the reaction system comprises propylene carbonate, sodium salt, monomer and initiator;
the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, naFSI and NaTFSI;
the monomer contains unsaturated bonds and comprises one or more of polyethylene glycol diacrylate, methyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, vinyl acetate and vinyl sulfite;
the initiator is azo initiator.
4. The use according to claim 1, 2 or 3, characterized in that the mixed solution of the solvent, sodium salt, monomer and initiator is injected into the cell of the battery, and is uniformly soaked, so that the mixed solution undergoes in-situ polymerization reaction to form gel electrolyte which is dispersed in the positive electrode, the negative electrode and the diaphragm of the battery and is polymerized in-situ between the positive electrode and the diaphragm and between the negative electrode and the diaphragm.
5. The preparation method of the solid sodium ion battery is characterized by comprising the following steps of:
s1, a bare cell is obtained through lamination and/or winding of a positive pole piece, a diaphragm and a negative pole piece, and then the bare cell is obtained through encapsulation;
s2, uniformly mixing a monomer containing unsaturated bonds, a solvent, sodium salt and an initiator, and then injecting the mixture into the battery cell of the S1, uniformly soaking, and carrying out in-situ polymerization reaction to obtain the solid sodium ion battery;
wherein the solvent in S2 is a single solvent and is propylene carbonate.
6. The preparation method according to claim 5, wherein the mass ratio of the unsaturated bond-containing monomer to propylene carbonate of S2 is (10-20): 80-90;
the temperature of the in-situ polymerization reaction is 60-100 ℃ and the polymerization reaction time is 1-5 h.
7. The method according to claim 5, wherein at least one side of the separator of S1 is coated with a sodium ion-conducting solid electrolyte layer having a thickness of 2 to 5 μm.
8. The method of claim 5, wherein S1 the positive electrode sheet comprises a current collector and a positive electrode active layer comprising a sodium ion-conducting solid electrolyte.
9. The method according to claim 8, wherein the sodium ion-conducting solid electrolyte has a particle size of 0.3 to 3. Mu.m.
10. The method of claim 5, wherein S1 the negative electrode tab comprises a current collector and a negative electrode active layer comprising a sodium ion conducting solid state electrolyte.
11. The method according to claim 10, wherein the sodium ion-conducting solid electrolyte has a particle size of 0.2 to 2 μm.
12. The method according to claim 5, wherein the monomer is one or more of polyethylene glycol diacrylate, methyl methacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, vinyl acetate and vinyl sulfite.
13. The process according to claim 5, wherein the initiator is an azo initiator, and the mass fraction of the initiator relative to the unsaturated bond-containing monomer is 0.1 to 1%.
14. A solid state sodium ion battery made by the method of any one of claims 5 to 13.
CN202310622441.4A 2023-05-30 2023-05-30 Application of propylene carbonate in polymer gel electrolyte for solid sodium ion battery, solid sodium ion battery and preparation method of solid sodium ion battery Pending CN116722212A (en)

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