WO2023087212A1 - Procédé de préparation d'électrolyte polymère en gel composé d'une charge mésoporeuse - Google Patents

Procédé de préparation d'électrolyte polymère en gel composé d'une charge mésoporeuse Download PDF

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Publication number
WO2023087212A1
WO2023087212A1 PCT/CN2021/131484 CN2021131484W WO2023087212A1 WO 2023087212 A1 WO2023087212 A1 WO 2023087212A1 CN 2021131484 W CN2021131484 W CN 2021131484W WO 2023087212 A1 WO2023087212 A1 WO 2023087212A1
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preparation
solvent
polymer
lithium
electrolyte
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PCT/CN2021/131484
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Chinese (zh)
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孙洪广
郭健
宁大泽
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青岛科技大学
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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
    • 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

Definitions

  • the invention relates to the technical field of secondary batteries, in particular to a filler composite gel polymer electrolyte secondary battery.
  • Lithium metal batteries have the highest theoretical specific capacity (3860mAh ⁇ g -1 ) and the lowest redox potential (-3.040Vvs. hydrogen electrode).
  • Conventional liquid organic electrolytes not only have good ionic conductivity but also have good compatibility with electrodes, which play an important role in lithium metal batteries.
  • using liquid organic electrolytes can easily lead to leakage and burning.
  • uncontrollable short circuits can seriously affect battery life and even lead to explosion.
  • Solid polymer electrolytes can be used as a substitute for liquid electrolytes to address the safety issues of liquid electrolytes due to their good processability and flexibility.
  • the low room temperature conductivity of solid polymer electrolytes limits the room temperature applications of lithium metal batteries.
  • Gel polymer electrolytes which combine the advantages of liquid electrolytes and solid polymers, are considered to be an exploration direction for practical applications of Li metal batteries and have received much attention. Their good interface with electrodes and strong organic solvent reserve can effectively suppress liquid leakage and thus enhance safety. More excitingly, the flexible gel polymer electrolyte can withstand the volume change and infiltration caused by Li dendrite growth. Therefore, gel polymer electrolytes are considered to be the best choice to improve the overall performance of lithium metal batteries.
  • the polymer matrix usually used to make gel polymer electrolyte mainly includes polyimide, PEO, PAN, PVDF-HFP and other polymers.
  • polyimide polyimide
  • PEO polyethylene glycol
  • PAN polyacrylonitrile-butadiene
  • PVDF-HFP polyvinyl-N
  • inorganic nanoparticles into the polymer matrix is a simple and effective strategy to solve the problem of low ionic conductivity and weak mechanical properties of gel polymer electrolytes, because it combines the advantages of inorganic and organic electrolytes and can significantly improve the Bulk properties of gel polymer electrolytes.
  • a significant advantage of this approach is that the nanofillers have uniform distributed stress and excellent thermodynamic properties, which can enhance their mechanical properties and thermal stability.
  • the stable Lewis acid-base effect between the polymer host and the surface chemical groups of ceramic nanoparticles can promote the dissociation of salts, thereby increasing the number of free Li ions. Therefore, the design of high specific surface area filler-filled gel polymer electrolytes is a reasonable direction.
  • the uniform dispersion of fillers can not only improve the mechanical properties of gel polymer electrolytes, but also improve the electrochemical performance by reducing the crystallinity of the polymers.
  • the high specific surface area can provide more opportunities for Lewis acid-base reactions and increase the number of lithium ion migrations.
  • more filler-polymer interfaces can be generated due to abundant mesoporous channels. The more lithium ions there are, the more optimized the lithium ion migration channel is, and the better the performance of the battery will be.
  • the present invention provides a method for preparing a novel composite gel polymer electrolyte.
  • the appropriate composite structure of the polymer electrolyte has excellent stability, good economic benefits, long service life, and excellent battery performance.
  • a method for preparing a special structural filler for a lithium battery composite gel electrolyte includes wormhole-shaped or walnut-shaped nano-inorganic particles, and flower-shaped nano-inorganic particles;
  • the preparation process of wormhole-like nano-inorganic particles is as follows:
  • the molar ratio of the silane precursor, micellar agent, mineralizer and solvent is 1:(0.02-0.06):(7-12):80
  • the precursor is one or more of the following substances: methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, tetrapropyl orthosilicate, methyl triethoxy silane, dimethyldiethoxysilane, tetrakis (2-methoxy-1-methylethyl) silicate;
  • the solvent is one or more of the following substances: water, methanol, ethanol, propanol, butanol, pentanol, cyclohexane, cyclopentane;
  • the micelles are one or more of the following substances: sodium lauryl sulfate, cetyltrimethylammonium bromide, cetyltrimethylammonium toluenesulfonate, Cetyl pyridinium bromide;
  • the amine mineralizer is one or more of the following substances: ammonia water, triethanolamine, ethylamine, propylamine, butylamine, diethylamine, diethylammonia, triethylamine Ammonium, urea, etc.;
  • the range of heating condition temperature and heating reaction time of the mixed system is: 30°C-120°C, 1-12h;
  • the post-treatment method of the prepared substance is at least one of the following methods: suction filtration, rotary evaporation, centrifugation, and vacuum drying.
  • the molar ratio of the silane precursor, micelle, mineralizer and solvent is 1:(0.01-0.04):(0.015-0.035):80; further, the precursor is the following substances One or more of: methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, tetrapropyl orthosilicate, methyltriethoxysilane, dimethyldiethoxysilane, Tetrakis(2-methoxy-1-methylethyl)silicate;
  • the solvent is one or more of the following substances: water, methanol, ethanol, propanol, butanol, pentanol, cyclohexane, cyclopentane;
  • the micelles are one or more of the following substances: sodium lauryl sulfate, cetyltrimethylammonium bromide, cetyltrimethylammonium toluenesulfonate, Cetyl pyridinium bromide;
  • the amine mineralizer is one or more of the following substances: ammonia water, triethanolamine, ethylamine, propylamine, butylamine, diethylamine, diethylammonia, triethylamine Ammonium, urea, etc.;
  • the range of heating condition temperature and heating reaction time of the mixed system is: 30°C-120°C, 1-12h;
  • the post-treatment method of the prepared substance is at least one of the following methods: suction filtration, rotary evaporation, centrifugation, and vacuum drying.
  • the solvent is one or more of the following substances: water, methanol, ethanol, propanol, butanol, pentanol, cyclohexane, cyclopentane;
  • the precursor is one or more of the following substances: methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, tetrapropyl orthosilicate, methyl triethoxy silane, dimethyldiethoxysilane, tetrakis (2-methoxy-1-methylethyl) silicate;
  • the micelles are one or more of the following substances: sodium lauryl sulfate, cetyltrimethylammonium bromide, cetyltrimethylammonium toluenesulfonate, Cetyl pyridinium bromide;
  • heating condition temperature and heating reaction time range of the mixed system are 80°C-180°C, 0.5h-12h;
  • the post-treatment method of the prepared substance is at least one of the following methods: suction filtration, rotary evaporation, centrifugation, and vacuum drying.
  • the present invention also claims to protect a preparation method of lithium battery composite gel electrolyte, comprising the following steps:
  • the prepared lithium battery composite gel electrolyte is added with special structural fillers for blending; heat treatment is carried out during and after blending.
  • the preparation method of the polymer solution mainly includes a polymer and a solvent that can dissolve the polymer: first, the polymer is added to the solvent that can dissolve the polymer according to a certain amount ; The mixed solution is then formed into a film by the action of the mold; enters the heat treatment process and obtains the final required polymer;
  • the polymer is at least one selected from the following: polyacrylonitrile, polyoxypropylene, polyvinyl chloride, polyvinylidene fluoride, polyethylene oxide, various copolymers such as PVDF-HFP ⁇ PAN-PMMA;
  • the polymer-soluble solvent is at least one selected from the following: acetone, tetrahydrofuran, N,N-dimethylacetamide, N-methylpyrrolidone;
  • heat treatment temperature and time range are: 40°C-120°C, 1-24h;
  • the amount of the polymer added to the solvent is 1-20 parts, based on 100 parts by weight of the mixture of the polymer and the solvent.
  • the temperature range of the mold in step (3) is: 30°C to 120°C;
  • the addition amount of the nano-inorganic particle filler is 1-20 parts, based on 100 parts by weight of the mixture of the polymer and the filler.
  • the preparation method of the battery electrolyte mainly includes an electrolyte salt and a solvent that can dissolve the electrolyte salt: directly adding the electrolyte salt to the single or mixed mixture of the soluble electrolyte salt according to a certain amount. in the solvent;
  • the electrolyte salt is at least one selected from the following substances: lithium bis-fluorosulfonimide (LiTFSI), lithium perchlorate (LiClCO4), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate ( LiAsF6) lithium tetrafluoroborate (LiBF4), lithium trifluoromethanesulfonate (LiCFSO3);
  • LiTFSI lithium bis-fluorosulfonimide
  • LiClCO4 lithium perchlorate
  • LiPF6 lithium hexafluorophosphate
  • LiAsF6 lithium hexafluoroarsenate
  • LiBF4 lithium tetrafluoroborate
  • LiCFSO3 lithium trifluoromethanesulfonate
  • the solvent for dissolving the electrolyte salt is a mixed system of at least two substances selected from the following: dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), ethylene carbonate (EC), ethyl methyl carbonate (EMC), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, ethylene glycol bispropionitrile ether, diphenyl ether , crown ether, diethylene glycol dimethyl ether, dioxolane;
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether ethylene glycol bispropionitrile ether
  • diphenyl ether , crown ether, diethylene glycol di
  • the electrolyte salt is added in an amount of 1 to 20 parts by mass, based on 100 parts by weight of the mixture of the electrolyte solvent and the electrolyte salt.
  • the preparation method of the negative electrode material and/or positive electrode material first, the slurry of the positive/negative electrode material is coated on a current collector, and the initial positive/negative electrode is prepared after drying and removing the solvent.
  • the final available electrode size and shape are prepared by pressing, cutting and other processes; the slurry contains a positive/negative electrode material, a binder, a solvent, and a conductive material;
  • the positive electrode material is at least one material selected from the following: lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium iron oxide;
  • the negative electrode material is at least one material selected from the following: graphitized mesocarbon microspheres (MCMB), amorphous carbon, silicon, tin, natural graphite, artificial graphite;
  • MCMB graphitized mesocarbon microspheres
  • the binder is at least one material selected from the following: PVDF, LA-132, LA-133, CMC, SBR, pectin, etc.;
  • the conductive material is conductive carbon black.
  • the present invention also claims to protect a method for assembling a lithium battery, which includes putting the positive/negative electrode, the composite gel polymer electrolyte, and an electrolyte solution into the battery shell in a certain order; the An electrolyte solution needs to be in contact with the surface and/or interior of the positive/negative electrode, the surface and/or interior of the composite gel polymer electrolyte.
  • the present invention has the following beneficial effects: the present invention uses mesoporous silicon dioxide nanoparticles with special structure as filler, prepares a composite gel polymer electrolyte through a pouring method, and assembles a lithium metal battery.
  • the composite gel polymer electrolyte provided by the invention also has the following advantages:
  • a lithiation reaction can occur between the filler and the lithium dendrite, and the filler has good mechanical strength. These factors can effectively inhibit the growth of the lithium dendrite and improve the cycle stability of the lithium battery.
  • Fig. 1 is the scanning electron microscope picture that uses the composite gel polymer electrolyte filler of embodiment 1;
  • Fig. 2 is the scanning electron microscope picture that uses the composite gel polymer electrolyte filler of embodiment 2;
  • Fig. 3 is the scanning electron microscope picture that uses the composite gel polymer electrolyte filler of embodiment 3;
  • Fig. 4 is the scanning electron microscope picture using the composite gel polymer electrolyte filler of comparative example 2;
  • Fig. 5 is to use the composite gel polymer electrolyte of embodiment 1 to assemble into the cycle performance of battery;
  • Figure 7 is the cycle performance of a battery assembled using the composite gel polymer electrolyte of Example 3.
  • Figure 8 is the cycle performance of a battery assembled using the composite gel polymer electrolyte of Comparative Example 1;
  • Figure 9 shows the cycle performance of batteries assembled using the composite gel polymer electrolyte of Comparative Example 2.
  • Fig. 10 is the tensile stress-strain curves of various embodiments and comparative examples.
  • the raw materials used in the following examples are all commercially available products except for the wormhole-shaped, walnut-shaped and flower-shaped mesoporous silica fillers.
  • Composite gel polymer electrolytes were prepared using the wormhole-shaped, walnut-shaped and flower-shaped nano-silica particles prepared above.
  • the method for preparing the lithium metal battery assembled by the composite gel polymer electrolyte of Example 1 is carried out in the following steps:
  • Step 1 Accurately weigh 3.52g cetyltrimethylammonium bromide, 2.38g sodium lauryl sulfate and 5.27g triethanolamine with electronic analytical balance, take 100ml deionized water with measuring cylinder, and cetyl Trimethylammonium bromide, sodium lauryl sulfate and triethanolamine were all dissolved in distilled water and transferred to a 250mL three-necked flask. Mechanical stirring was carried out at a speed of 800 rpm for 10.0 h. Afterwards, 5.6 mL of ethyl orthosilicate was accurately weighed with a pipette and added into a three-neck flask for stirring, and the reaction time was 20.0 h. Then, the nano-silicon particle solution is concentrated by rotary evaporation to obtain a stable nano-silicon particle dispersion, which is then dried to obtain wormhole-like nano-silicon particles with a super-high specific surface area.
  • Step 2 Make a solution with 0.12g of required silicon dioxide and 0.8g of acetone, sonicate for 1.0h, stir with 1.3g of PVDFHFP and 4.3g of acetone at 50°C to make a solution, mix the two and continue to stir at 50°C After 2.0h, add 0.2g of water and continue to stir for 5.0h, drop the mixed solution on a glass plate with a 200 ⁇ m spatula to form a film, dry it at room temperature for 1.0h, gently peel it off with tweezers and spread it on a glass plate, put it in 60 °C vacuum oven for 24h to remove the residue.
  • Step 3 First, dry LiCoO 2 (LCO) powder and carbon black (Super P) in a vacuum oven at 120° C. for 24 hours to remove residual water.
  • LCO LiCoO 2
  • Super P carbon black
  • Example 2 The filler of a composite gel polymer electrolyte in this example is walnut-shaped silica nanoparticles.
  • the method for preparing the lithium metal battery assembled by the composite gel polymer electrolyte of Example 2 is carried out in the following steps:
  • Step 1 Accurately weigh 4.08g cetyltrimethylammonium bromide, 2.38g sodium dodecylsulfonate and 5.27g ammonia water with electronic analytical balance, take 130ml deionized water with measuring cylinder, and cetyl Trimethylammonium bromide, sodium dodecylsulfonate and ammonia water were all dissolved in distilled water and transferred to a 250mL three-necked flask. Mechanical stirring was carried out at a speed of 600 rpm for 10.0 h. Afterwards, 7.8 mL of ethyl orthosilicate was accurately weighed with a pipette and added into a three-neck flask for stirring, and the reaction time was 15.0 h. Then, the nano-silicon particle solution is concentrated by rotary evaporation to obtain a stable nano-silicon particle dispersion, which is then dried to obtain ultra-high pore volume walnut-shaped silicon nano-particles.
  • Step 2 Make a solution with 0.21g of the required silica and 1.5g of acetone, sonicate for 1.0h, stir with 2.3g of PVDFHFP and 3.5g of acetone at 50°C to make a solution, mix the two and continue to stir at 50°C After 2.0h, add 0.2g of water and continue to stir for 5.0h, drop the mixed solution on a glass plate with a 200 ⁇ m spatula to form a film, dry it at room temperature for 1.0h, gently peel it off with tweezers and spread it on a glass plate, put it in 60 °C vacuum oven for 24h to remove the residue.
  • Step 3 First, dry LiCoO 2 (LCO) powder and carbon black (Super P) in a vacuum oven at 120° C. for 24 hours to remove residual water.
  • LCO LiCoO 2
  • Super P carbon black
  • Embodiment 3 The filler of a composite gel polymer electrolyte in this embodiment is flower-shaped silica nanoparticles.
  • the method for preparing the lithium metal battery assembled by the composite gel polymer electrolyte of Example 3 is carried out in the following steps:
  • Comparative Example 1 The difference between this example and Example 1 is that there is no filler in the gel polymer electrolyte.
  • Comparative Example 2 The difference between this example and Example 1 is that the filler in the gel polymer electrolyte is ordinary solid silica nanoparticles.
  • the behavior of ionic conductivity was evaluated by performing AC impedance analysis using an Autolab PGSTAT 302N system.
  • the ionic conductivity can be calculated according to equation (4-1) as follows:
  • L, Rb and S are the thickness, impedance and area of GPE, respectively. The results are detailed in Table 1.
  • m 0 is the weight of the dry separator
  • mi is the weight of the separator after immersion in the electrolyte. The results are detailed in Table 1.
  • ⁇ V is the DC polarization voltage (0.005 V) applied in the chronoamperometry step
  • I0 and IS are the initial current and steady-state current in the chronoamperometry step, respectively.
  • Ro and Rs are the initial and steady-state interfacial resistance, respectively.
  • a novel composite gel polymer electrolyte was prepared by exploring the composite process of filler and gel polymer matrix. Those containing gel polymer electrolytes with special structures have high ionic conductivity and lithium ion transfer number.
  • the effective surface area is increased by the uniform distribution and dense microporous structure. This further enhances the strong Lewis acid-base interaction between the electrolyte ion species and the hydroxyl groups on the surface of the ceramic filler, which further dissociates the lithium salt and releases more lithium ions for migration.
  • the ion migration number is the highest, and the reason why the specific capacity of the battery is higher than that of the comparison sample.
  • the structural advantage of high pore volume can effectively increase the filler-polymer interface, which is more conducive to the transport of lithium ions, optimizes the passage of lithium ions during migration, and enables rapid migration of lithium ions
  • polymer batteries containing walnut-like fillers have higher battery specific capacity when the migration number of lithium ions is lower than that of wormholes. Therefore, the optimized migration channel mechanism brought by high pore volume is better than that of high specific surface area structure.
  • Mechanism of salt In the flower-shaped filler battery system, the filler has the characteristics of high specific surface area and ultra-high pore volume, which makes the flower-shaped filler have both walnut-like and wormhole-like structural advantages and possible mechanisms of action. Polymer batteries have higher specific capacity.
  • the lithium ion migration channel of the filler is more optimized, and the lithium ion migration efficiency of the composite gel polymer electrolyte is higher, so that the battery has Excellent cycle performance.
  • the uniform distribution of fillers in the gel polymer electrolyte enables the formation of a stable SEI layer on the Li anode, thereby significantly suppressing Li dendrite growth.
  • the gel-polymer batteries doped with mesoporous fillers exhibit excellent cycle stability in addition to higher mechanical strength and thermal stability.

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Abstract

La présente invention concerne la préparation et l'application d'un électrolyte polymère en gel composé d'une charge mésoporeuse. Dans la présente invention, des nanoparticules de dioxyde de silicium ayant des structures mésoporeuses spéciales sont conçues, et elles sont mélangées avec un électrolyte polymère en gel pour préparer un électrolyte polymère en gel composé d'une charge mésoporeuse ; de plus, une résistance mécanique élevée et une bonne stabilité électrochimique sont maintenues. Par comparaison avec l'échantillon vierge et les électrolytes composés de nanoparticules de dioxyde de silicium solides, l'électrolyte polymère de gel composé de charge mésoporeuse selon la présente invention présente une quantité d'absorption de liquide supérieure et une conductivité ionique supérieure, et a également une mobilité d'ions lithium plus élevée. En raison de la bonne compatibilité entre une charge mésoporeuse et un métal lithium, une couche SEI stable peut être générée. De plus, une batterie au lithium-métal assemblée par l'électrolyte polymère en gel composé de charge mésoporeuse présente une bonne performance de cycle.
PCT/CN2021/131484 2021-11-18 2021-11-18 Procédé de préparation d'électrolyte polymère en gel composé d'une charge mésoporeuse WO2023087212A1 (fr)

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Citations (4)

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CN102005609A (zh) * 2010-10-20 2011-04-06 浙江工业大学 一种复合凝胶型聚合物电解质膜及其应用
CN104692399A (zh) * 2015-02-09 2015-06-10 齐鲁工业大学 一种高度有序放射状球形具皱介孔二氧化硅材料及其制备方法
CN110550638A (zh) * 2019-09-25 2019-12-10 东北大学 一种单分散大孔径的介孔二氧化硅纳米粒子的制备方法
CN110931851A (zh) * 2019-11-27 2020-03-27 北京航空航天大学 一种锂硫电池用复合电解质及其制备方法和应用

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CN102005609A (zh) * 2010-10-20 2011-04-06 浙江工业大学 一种复合凝胶型聚合物电解质膜及其应用
CN104692399A (zh) * 2015-02-09 2015-06-10 齐鲁工业大学 一种高度有序放射状球形具皱介孔二氧化硅材料及其制备方法
CN110550638A (zh) * 2019-09-25 2019-12-10 东北大学 一种单分散大孔径的介孔二氧化硅纳米粒子的制备方法
CN110931851A (zh) * 2019-11-27 2020-03-27 北京航空航天大学 一种锂硫电池用复合电解质及其制备方法和应用

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Title
郭健 (GUO, JIAN): "介孔二氧化硅微球的制备及其凝胶复合电解质应用研究 (Preparation of Mesoporous Silica Microspheres and Study on Gel Polymerization Dielectric Composite System)", 中国优秀博硕士学位论文数据库(硕士)工程科技I辑 (ENGINEERING SCIENCE AND TECHNOLOGY I, CHINA DOCTORAL DISSERTATIONS/MASTER'S THESES FULL-TEXT DATABASE), no. 01, 15 January 2021 (2021-01-15), ISSN: 1674-0246 *

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