WO2020211081A1 - Électrolyte et solution électrolytique à base d'hexafluoro phosphate de métal alcalino-terreux et procédés de préparation s'y rapportant - Google Patents

Électrolyte et solution électrolytique à base d'hexafluoro phosphate de métal alcalino-terreux et procédés de préparation s'y rapportant Download PDF

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WO2020211081A1
WO2020211081A1 PCT/CN2019/083464 CN2019083464W WO2020211081A1 WO 2020211081 A1 WO2020211081 A1 WO 2020211081A1 CN 2019083464 W CN2019083464 W CN 2019083464W WO 2020211081 A1 WO2020211081 A1 WO 2020211081A1
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electrolyte
hexafluorophosphate
alkaline earth
earth metal
magnesium
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PCT/CN2019/083464
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English (en)
Chinese (zh)
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唐永炳
吴南中
姚文娇
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深圳先进技术研究院
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Priority to PCT/CN2019/083464 priority Critical patent/WO2020211081A1/fr
Publication of WO2020211081A1 publication Critical patent/WO2020211081A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/455—Phosphates containing halogen
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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 present invention relates to the field of secondary batteries, in particular to electrolytes of calcium hexafluorophosphate and magnesium hexafluorophosphate, and preparation methods thereof, electrolytes and preparation methods thereof, and calcium ion batteries and magnesium ions containing the electrolytes or electrolytes battery
  • Energy storage technology is an important part of energy application. Compared with primary batteries, secondary batteries have advantages in resource recycling, economy, and environmental protection; high-performance lithium-ion batteries are widely used in mobile electronic equipment, electric vehicles and other fields.
  • the global reserve of lithium is only 14 million tons and the geographical distribution is uneven, which is difficult to support future energy storage demand. Therefore, it is of great significance to develop new energy storage systems, such as sodium ion, potassium ion, magnesium ion, calcium ion and other energy storage systems.
  • Calcium ions and magnesium ions are divalent ions, and each mole of ions can react to produce twice the charge of lithium ions.
  • the electrolyte is one of the main components of the battery, which greatly affects the performance of the battery.
  • the electrolyte of a secondary battery is composed of organic solvents, electrolytes (solutes), additives, etc., among which the electrolyte is the most critical component.
  • electrolytes classified according to the type of anion, commonly used electrolytes include hexafluorophosphate, tetrafluoroborate, perchlorate, etc.
  • hexafluorophosphate electrolyte has many excellent advantages, such as: better stability; good compatibility with conventional organic solvents; higher solubility in conventional organic solvents; electrolyte composed of it Has good conductivity and ion mobility; does not corrode the current collector; etc.
  • lithium hexafluorophosphate and its electrolyte have been widely used in lithium ion batteries.
  • its alkaline earth metal electrolytes especially hexafluorophosphate electrolytes such as calcium hexafluorophosphate, magnesium hexafluorophosphate and their electrolytes, are crucial to the development of calcium ion batteries and magnesium ion batteries.
  • Literature Chem. Commun. 2017, 53, 4573 intends to learn from the above method, using NOPF6 as a precursor, and reacting with metallic calcium to prepare calcium hexafluorophosphate electrolyte.
  • this method will cause the oxidative decomposition of hexafluorophosphate ions to generate impurity difluorophosphate ions (PO2F2-). This is because when NOPF6 is used as a precursor, the strong oxidizing gas NO produced by the reaction can oxidize hexafluorophosphate ions.
  • Another Ca(PF6)2 electrolyte and electrolyte preparation method is to use alkali metal hexafluorophosphate, such as potassium hexafluorophosphate (KPF6), as the precursor, and replace the alkali metal cations with ion exchange resins.
  • KPF6 potassium hexafluorophosphate
  • the disadvantages of this method are that the ion exchange resin has high cost and cannot be reused, and the method cannot guarantee the purity of the cations in the electrolyte, and the prepared electrolyte contains a large amount of impurity ions.
  • the most mainstream method of industrial production of alkali metal hexafluorophosphate electrolyte is to use anhydrous hydrofluoric acid (HF), phosphorus pentafluoride (PF5) gas and metal fluorides (lithium fluoride, sodium fluoride, potassium fluoride) as Reactant.
  • HF hydrofluoric acid
  • PF5 phosphorus pentafluoride
  • metal fluorides lithium fluoride, sodium fluoride, potassium fluoride
  • alkali metal hexafluorophosphate The outermost electron orbit of an alkali metal atom has only one electron, and the attraction of the outermost electron of the nucleus is very small, and it is easy to lose the outermost electron and become a positively charged cation; while the outermost electron orbit of an alkaline earth metal atom With two electrons, this pair of electrons reduces the energy of the electron orbit. Therefore, alkaline earth metal nuclei have greater attraction to the outermost orbital electrons, and the outermost electrons require more energy to get rid of the bondage of the nucleus. This intrinsic difference results in a large difference in physical and chemical properties such as atomic radius, first ionization energy, and chemical reaction activity between alkali metal substances and alkaline earth metal substances. For this reason, it is impossible to predict whether the preparation method of alkali metal hexafluorophosphate can be applied to alkaline earth metal hexafluorophosphate.
  • the first object of the present invention is to provide a method for preparing calcium hexafluorophosphate and magnesium hexafluorophosphate electrolyte, which has low cost, simple process, high product purity and high material utilization.
  • the second object of the present invention is to provide a calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte prepared by the above electrolyte preparation method, which has high purity, good chemical stability, high ion mobility, and no corrosion. Current collector.
  • the third object of the present invention is to provide a method for preparing calcium hexafluorophosphate electrolyte and magnesium hexafluorophosphate electrolyte, which has the same advantages as the above-mentioned electrolyte preparation method.
  • the fourth object of the present invention is to provide a calcium hexafluorophosphate electrolyte and a magnesium hexafluorophosphate electrolyte, and the electrolyte prepared by using the electrolyte has the same advantages as the above-mentioned electrolyte.
  • the fifth object of the present invention is to provide a calcium ion battery or magnesium ion battery, comprising the above-mentioned calcium hexafluorophosphate electrolyte or electrolyte, or the above-mentioned magnesium hexafluorophosphate electrolyte or electrolyte.
  • the sixth object of the present invention is to provide an energy storage system, including the above-mentioned calcium ion battery or magnesium ion battery.
  • the seventh object of the present invention is to provide an electrical equipment including the above-mentioned calcium ion battery or magnesium ion battery.
  • the present invention provides a method for preparing an electrolyte of calcium hexafluorophosphate and magnesium hexafluorophosphate.
  • the reaction formula is as follows:
  • MH2 is MgH2 or CaH2
  • the solvent is a non-aqueous organic solvent.
  • the preparation method includes the following steps: placing an organic solvent, ammonium hexafluorophosphate, and alkaline earth metal hydride in the same container under the protection of an inert gas, and after the reaction is completed, an alkaline earth metal hexafluorophosphate electrolyte is obtained.
  • the alkaline earth metal hydride is calcium hydride or magnesium hydride
  • the amount (number of moles) of the alkaline earth metal hydride should not be less than half of the amount of ammonium hexafluorophosphate;
  • the present invention provides a calcium hexafluorophosphate electrolyte and magnesium hexafluorophosphate electrolyte prepared by the above-mentioned electrolyte preparation method.
  • the present invention provides a method for preparing calcium hexafluorophosphate electrolyte and magnesium hexafluorophosphate electrolyte, including the following steps: removing the organic solvent from the above-mentioned calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte , Or reduce the solubility of calcium hexafluorophosphate or magnesium hexafluorophosphate in the solvent to obtain calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte.
  • the present invention provides a calcium hexafluorophosphate electrolyte and a magnesium hexafluorophosphate electrolyte prepared by the above electrolyte preparation method.
  • the present invention provides a calcium ion battery and a magnesium ion battery, comprising the above-mentioned calcium hexafluorophosphate electrolyte or electrolyte, or the above-mentioned magnesium hexafluorophosphate electrolyte or electrolyte.
  • the present invention provides an energy storage system, including the above-mentioned calcium ion battery or magnesium ion battery.
  • the present invention provides an electrical equipment including the above-mentioned calcium ion battery or magnesium ion battery.
  • the method for preparing calcium hexafluorophosphate electrolyte and electrolyte, and magnesium hexafluorophosphate electrolyte and electrolyte uses industrial inexpensive precursors NH4PF6 and metal hydride as raw materials, and avoids the use of toxic and corrosive raw materials HF and PF5;
  • the method is simple and does not require complicated equipment; the preparation method has nothing to do with organic solvents, and the solvent can be freely selected; the prepared product has high purity; the by-products are all gases to ensure the complete reaction; the by-products NH3 and H2 are stable reducing gases ,
  • by-product NH3 is the raw material for industrial production of nitrogen fertilizer, and by-product H2 is a clean energy.
  • the calcium hexafluorophosphate electrolyte and electrolyte, the magnesium hexafluorophosphate electrolyte and the electrolyte provided by the invention have higher purity and better chemical stability; they have good compatibility with conventional electrode materials; conductivity and ion migration High rate; does not corrode the current collector.
  • the calcium hexafluorophosphate electrolyte and the magnesium hexafluorophosphate electrolyte provided by the present invention have high solubility in conventional organic solvents; the electrolyte obtained after the electrolyte is dissolved has high concentration, good conductivity and ion mobility; Corrosion current collector.
  • the calcium ion battery and magnesium ion battery provided by the present invention contain the above-mentioned electrolyte or electrolyte, and the calcium ion battery and magnesium ion battery have higher working voltage and capacity.
  • the energy storage system provided by the present invention includes the aforementioned calcium ion battery and magnesium ion battery, and therefore has at least the same advantages as the aforementioned calcium ion battery and magnesium ion battery, and has a higher discharge voltage and charge and discharge capacity.
  • the electrical equipment provided by the present invention includes the aforementioned calcium ion battery and magnesium ion battery, and therefore has at least the same advantages as the aforementioned calcium ion battery and magnesium ion battery, and has the advantages of high discharge voltage and high charge and discharge capacity. It can work longer, reduce the number of charging, extend the service life, and use more convenient.
  • Figure 1 shows the NMR spectrum (a) of 19F and the NMR spectrum (b) of 31P of the electrolyte solution obtained in Example 1;
  • Example 2 is a mass spectrum of the gas produced by the reaction in Example 1;
  • Figure 3 is an EDX diagram of the electrolyte obtained in Example 2.
  • Example 4 is a constant current charge-discharge curve diagram of a double-carbon calcium ion battery composed of Example 3.
  • FIG. 5 is a schematic structural diagram of a calcium ion battery or a magnesium ion battery provided by the present invention.
  • Icon 1- negative electrode current collector; 2- negative electrode active material layer; 3- separator; 4- electrolyte; 5- positive electrode active material layer; 6- positive electrode current collector.
  • the form of the lower limit and upper limit of the "range" disclosed in the present invention may be one or more lower limits and one or more upper limits, respectively.
  • each reaction or operation step may be carried out in sequence or out of sequence.
  • the reaction method herein is carried out sequentially.
  • a method for preparing a calcium hexafluorophosphate electrolyte or an electrolyte of magnesium hexafluorophosphate includes the following steps: putting an organic solvent, ammonium hexafluorophosphate, and alkaline earth metal hydride in an inert Placed in the same container under gas protection, and after the reaction is complete, an alkaline earth metal hexafluorophosphate electrolyte is obtained.
  • the method uses industrialized cheap precursors NH 4 PF 6 and metal hydrides; avoids the use of toxic and corrosive raw materials HF and PF 5 ; the preparation method is simple and does not require complicated equipment; the preparation method has nothing to do with the solvent, and the solvent can be freely selected;
  • the prepared product has high purity; the by-products are all gases to ensure the complete reaction; the by-products NH 3 and H 2 are stable reducing gases to avoid the oxidation and decomposition of hexafluorophosphate ion; the by-product NH 3 is the raw material for the industrial production of nitrogen fertilizer , H 2 is a clean energy.
  • the organic solvent is not particularly limited, and may be an organic solvent such as esters, sulfones, ethers, nitriles or ionic liquids. Specifically, including propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), acetonitrile (ACN), methyl formate (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), acetic acid Ethyl ester (EA), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOL), 4-methyl-1,3 -Dioxolane (4MeDOL), dimethoxymethane (DM
  • the alkaline earth metal hydride is calcium hydride or magnesium hydride
  • the amount (number of moles) of the alkaline earth metal hydride should not be less than half of the amount of ammonium hexafluorophosphate;
  • a calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte is provided, which is obtained by the above-mentioned preparation method of calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte.
  • the electrolyte has good chemical stability, high ion mobility, and does not corrode the current collector.
  • a method for preparing calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte is provided in at least one embodiment.
  • the above-mentioned calcium hexafluorophosphate or magnesium hexafluorophosphate electrolyte is removed from the organic solvent, or the solubility of calcium hexafluorophosphate and magnesium hexafluorophosphate in the solvent is reduced to obtain calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte.
  • the method of removing the organic solvent is not particularly limited. Specifically, methods such as heating evaporation, reduced pressure evaporation, and room temperature volatilization can be used.
  • the method of reducing the solubility of calcium hexafluorophosphate and magnesium hexafluorophosphate in the solvent is not particularly limited. Specifically, methods such as freezing, introducing weakly polar or non-polar solvents, etc. can be used.
  • a calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte is provided, which is obtained by the above-mentioned preparation method of calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte.
  • a calcium ion battery or a magnesium ion battery which includes a positive electrode, a separator, a negative electrode, and the above-mentioned calcium hexafluorophosphate electrolyte or electrolyte, or the above-mentioned magnesium hexafluorophosphate electrolyte or electrolyte.
  • the calcium ion battery or magnesium ion battery provided by the present invention has two working principles, one of which is: during the charging process, calcium ions or magnesium ions are extracted from the positive electrode and enter the electrolyte, and the calcium ions or magnesium ions in the electrolyte Migrate to the negative electrode and be embedded in the negative electrode active material; during the discharge process, calcium ions or magnesium ions are extracted from the negative electrode material and enter the electrolyte, and the calcium ions or magnesium ions in the electrolyte migrate to the positive electrode and be embedded in the positive electrode active material .
  • the second is: during the charging process, the anions in the electrolyte migrate to the positive electrode and be embedded in the positive electrode active material, and the calcium ions or magnesium ions in the electrolyte migrate to the negative electrode and be embedded in the negative electrode active material; during the discharge process, the anions are removed from the positive electrode And into the electrolyte, calcium ions or magnesium ions are extracted from the negative electrode and enter the electrolyte.
  • the positive electrode includes a positive electrode active material layer and a positive electrode current collector.
  • the positive electrode active material layer includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder.
  • the content of the positive electrode active material is 60-95 wt%, and the content of the positive electrode conductive agent is 2-30wt%, and the content of the positive electrode binder is 2-10wt%.
  • the positive electrode active material includes at least one of carbon material, metal, alloy, sulfide, nitride, oxide, or carbide.
  • the positive electrode current collector or the negative electrode current collector is any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, or germanium, preferably aluminum;
  • the positive electrode current collector or the negative electrode current collector is an alloy including at least any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, or germanium;
  • the positive electrode current collector or the negative electrode current collector is a composite material including at least any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, or germanium.
  • Alloy refers to a substance with metallic characteristics synthesized by a certain method from two or more metals and metals or non-metals.
  • Metal composite material refers to a metal matrix composite conductive material formed by the combination of metal and other non-metal materials.
  • Typical but non-limiting metal composite materials include graphene-metal composite materials, carbon fiber-metal composite materials and ceramic-metal composite materials.
  • the negative electrode includes a negative electrode active material layer and a negative electrode current collector.
  • the negative electrode active material layer includes a negative electrode active material, a negative electrode conductive agent and a negative electrode binder.
  • the content of the negative electrode active material is 60-90 wt%, and the content of the negative electrode conductive agent is 5-30wt%, and the content of the negative electrode binder is 5-10wt%.
  • the negative active material includes at least one of a carbon material, a metal, an alloy, a sulfide, a nitride, an oxide, or a carbide.
  • the positive electrode conductive agent or the negative electrode conductive agent includes at least one of conductive carbon black, conductive carbon balls, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene, or reduced graphene oxide.
  • the positive electrode binder or the negative electrode binder includes polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber (Styrene Butadiene Rubber, styrene butadiene rubber) or polyolefins. At least one.
  • the electrolyte includes the above-mentioned calcium hexafluorophosphate electrolyte or electrolyte, or the magnesium hexafluorophosphate electrolyte or electrolyte.
  • the electrolyte further includes additives, and the content of the additives is preferably 0.1-20 wt%. Adding additives to the electrolyte can form a stable solid electrolyte membrane on the electrode surface and improve the battery life.
  • the additives include at least one of esters, sulfones, ethers, nitriles, or olefins.
  • Additives include fluoroethylene carbonate, vinylene carbonate, vinyl ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfate Ester, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide , Diazabenzene, meta-diazepine, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorinated chain ether, difluoromethyl ethylene carbonate, Trifluoromethyl ethylene carbonate, chloroethylene carbonate, bromoethylene carbonate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate,
  • the separator includes a porous polymer film or an inorganic porous film, and preferably includes at least one of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper, or a porous ceramic separator.
  • Fig. 5 is a schematic diagram of the structure of a calcium ion battery or a magnesium ion battery provided by the present invention, including a negative electrode current collector 1, a negative electrode active material layer 2, a separator 3, an electrolyte 4, a positive electrode active material layer 5 and Positive current collector 6.
  • the preparation method of the above-mentioned calcium ion battery or magnesium ion battery includes: assembling a positive electrode, a separator, a negative electrode, and an electrolyte.
  • the above-mentioned preparation method has simple process and low manufacturing cost.
  • the calcium ion battery or magnesium ion battery prepared by the method has the advantages of high discharge voltage and high charge and discharge capacity.
  • the method includes the following steps:
  • the negative electrode active material, the negative electrode conductive agent and the negative electrode binder are made into a negative electrode slurry, and then the negative electrode slurry is coated on the surface of the negative electrode current collector, dried and cut to obtain a negative electrode of the required size; or , Press the negative electrode active material on the surface of the negative electrode current collector, and cut to obtain the negative electrode of the required size;
  • the positive electrode active material, the positive electrode conductive agent and the positive electrode binder are made into a positive electrode slurry, and then the positive electrode slurry is coated on the surface of the positive electrode current collector, dried and cut to obtain a positive electrode of the required size;
  • step (e) Assemble the negative electrode obtained in step (a), the electrolyte obtained in step (b), the separator obtained in step (c), and the positive electrode obtained in step (d).
  • the assembly specifically includes: under an inert environment, the prepared negative electrode, separator, and positive electrode are tightly stacked or wound in sequence, and electrolyte is dripped to make the separator completely infiltrated, and then packaged into the casing to complete the calcium ion battery or magnesium Assembly of ion battery.
  • the shape of the calcium ion battery or the magnesium ion battery of the present invention is not limited to the button battery, and can also be designed into a flat shape, a cylindrical shape, etc. according to the core components.
  • an energy storage system including the calcium ion battery or the magnesium ion battery described above.
  • the energy storage system includes the aforementioned calcium ion battery or magnesium ion battery, and therefore has at least the same advantages as the aforementioned calcium ion battery or magnesium ion battery, and has a higher discharge voltage and charge-discharge capacity.
  • the aforementioned energy storage system refers to a power storage system that mainly uses calcium ion batteries or magnesium ion batteries as a power storage source, including but not limited to household energy storage systems or distributed energy storage systems.
  • a household energy storage system electricity is stored in a calcium ion battery or a magnesium ion battery used as a power storage source, and the electricity stored in the calcium ion battery or magnesium ion battery is consumed as needed to be able to use such as household electronics Various devices of the product.
  • an electrical equipment including the above-mentioned calcium ion battery or magnesium ion battery.
  • the electrical equipment includes the calcium ion battery or magnesium ion battery described above, and therefore has at least the same advantages as the calcium ion battery or magnesium ion battery described above, and has the advantages of high discharge voltage and high charge and discharge capacity. Under the same discharge current, it can Work longer, reduce charging times, extend service life, and use more convenient.
  • the aforementioned electrical equipment includes, but is not limited to, electronic devices, electric tools, or electric vehicles.
  • the electronic device is an electronic device that uses a calcium ion battery or a magnesium ion battery as an operating power source to perform various functions (for example, playing music).
  • An electric tool is an electric tool that uses calcium ion batteries or magnesium ion batteries as a driving power source for moving parts (for example, drill bits).
  • Electric vehicles are electric vehicles (including electric bicycles and electric cars) that rely on calcium-ion batteries or magnesium-ion batteries as driving power sources, and can be vehicles equipped with other driving sources in addition to calcium-ion batteries or magnesium-ion batteries (including Hybrid vehicles).
  • This embodiment provides a calcium hexafluorophosphate electrolyte and a preparation method thereof, including the following steps:
  • the reaction product for mass spectrometry (MS) characterization.
  • MS mass spectrometry
  • the gas product contains a large amount of H 2 and NH 3 , which proves that the reaction produces gas products H 2 and NH 3 .
  • the rest of the mass spectrum signal comes from the volatile molecules of the solvent dimethyl carbonate DMC and the argon in the glove box.
  • This embodiment provides a calcium hexafluorophosphate electrolyte and a preparation method thereof, including the following steps:
  • This embodiment provides a calcium ion battery, which is prepared according to the following steps:
  • the constant current charge and discharge curve of the battery is shown in Fig. 4.
  • the specific charge capacity of the calcium ion battery is 65.6 mAh/g, and the specific discharge capacity is 54.1 mAh/g.
  • This embodiment provides a calcium ion battery, which is different from embodiment 3 in that the electrolyte used is: the calcium hexafluorophosphate electrolyte obtained in embodiment 2 is dissolved in EC+DMC+EMC (the volume ratio is 4: 3:2) to prepare a calcium hexafluorophosphate electrolyte with a concentration of 0.6 mol/L.
  • the rest is the same as Embodiment 3, and will not be repeated here.
  • Example 5-65 provides methods for preparing calcium hexafluorophosphate electrolyte and electrolyte. The difference from Example 1-2 is that the amount of calcium hydride used, the type of organic solvent, the reaction time, and the method of removing the organic solvent are shown in Table 1.
  • Examples 66-126 provide the preparation method of the magnesium hexafluorophosphate electrolyte and the electrolyte.
  • the difference from Example 5-55 is that the amount of magnesium hydride used, the type of organic solvent, the reaction time, and the method of removing the organic solvent are shown in Table 2.
  • Examples 127-156 provide methods for preparing calcium ion batteries and magnesium ion batteries.
  • the difference from Example 3-4 is that the electrolytes used in Examples 127-131 are from the calcium hexafluorophosphate electrolytes obtained in Examples 5-9, and the electrolytes used in Examples 132-136 are respectively Examples 5-9.
  • the obtained calcium hexafluorophosphate electrolyte was prepared with 0.8mol/L calcium hexafluorophosphate electrolyte.
  • the electrolyte used in Examples 137-141 was 0.5mol/L prepared with the calcium hexafluorophosphate electrolyte obtained in Examples 5-9.
  • the electrolytes used in Examples 152-156 are 0.4mol/L magnesium hexafluorophosphate electrolyte prepared with the magnesium hexafluorophosphate electrolyte obtained in Examples 66-70. liquid.
  • Examples 157-170 provide methods for preparing calcium ion batteries and magnesium ion batteries.
  • the difference from Example 3-4 lies in the electrolyte and the positive electrode active material used, as shown in Table 3.
  • Example Electrolyte Cathode material 157 Example 5 CaCo 2 O 4 158 Example 5 CaMn 2 O 4 159 Example 5 Ca 3 Co 2 O 6 160 Example 5 CaMoO 3 161 Example 5 Prussian blue analog 162 Example 9 S 163 Example 5 V 2 O 5 164 Example 7 Prussian blue analog 165 Example 8 Prussian blue analog 166 Example 66 Mo 3 S 4 167 Example 66 S 168 Example 66 V 2 O 5 169 Example 66 MnO 2 170 Example 67 Mo 3 S 4
  • Examples 171-184 provide methods for preparing calcium ion batteries and magnesium ion batteries.
  • the difference from Example 3-4 is the electrolyte used.
  • the electrolyte used is obtained by blending the original solution and the blending solution, as shown in Table 4.
  • Comparative Example 1-4 The difference between Comparative Example 1-4 and Example 1-4 is that the amount of ammonium hexafluorophosphate used is 1.63 g (10 mmol), the dimethyl carbonate DMC used is 25 ml, and the rest is the same as that of Example 1-4. No longer.
  • Comparative Example 5-8 The difference between Comparative Example 5-8 and Example 1-4 is that the amount of ammonium hexafluorophosphate used is 1.63 g (10 mmol), the amount of magnesium hydride used is 0.05 g (2 mmol), and the amount of dimethyl carbonate used DMC is 25 ml, and the rest is the same as in Examples 1-4, and will not be repeated.
  • Elemental analysis of the electrolytes and electrolytes prepared in Comparative Examples 1-2 and 5-6 shows that the cations in the samples include not only calcium/magnesium ions but also a large amount of ammonium ions, indicating that the corresponding preparation methods are not perfect.
  • the resulting electrolyte and electrolyte have low purity.
  • Example 3 72 54
  • Example 4 110 75
  • Example 127 102 65
  • Example 128 108 68
  • Example 129 99 59
  • Example 130 107 72
  • Example 131 106 70
  • Example 132 130 86
  • Example 134 127 81
  • Example 135 160 90
  • Example 136 145 89 Example 137 123 78
  • Example 138 120 75
  • Example 140 125 74
  • Example 141 114 76
  • Example 142 118 72
  • Example 143 117 73
  • Example 144 124 79
  • Example 146 120
  • Example 147 124 82
  • Example 148 123 83
  • Example 149 130
  • Example 150 110 78
  • Example 151 114 79
  • Example 152 100
  • Example 153 105
  • Example 156 96 68
  • Example 157 74 54
  • Example 158 66
  • Example 159 90
  • Example 160 97 89
  • Example 161 102 85
  • Example 162 123
  • Example 163 56
  • Example 164 84 74
  • Example 165 85
  • Example 166 64 45
  • Example 167 100
  • Example 168 60
  • Example 169 60
  • Example 170 70
  • Example 171 45
  • Example 172 80
  • Example 173 89
  • Example 175 55
  • Example 178 46 34
  • Example 179 60
  • Example 180 67
  • Example 181 105 92
  • Example 182 84 43
  • Example 183 71 51
  • Example 184 76 52
  • Comparative example 3 35 twenty one Comparative example 4
  • Comparative example 7 20
  • Comparative example 8 25 15
  • the preferred embodiments of the present invention have higher initial discharge specific capacity and higher initial discharge capacity than Comparative Examples 3-4 and 7-8. Stable discharge specific capacity. Therefore, the preferred embodiments of the present invention can provide more effective methods for preparing calcium hexafluorophosphate electrolytes and electrolytes, magnesium hexafluorophosphate electrolytes and electrolytes, and calcium ion batteries and magnesium ion batteries with better performance.

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Abstract

L'invention concerne un électrolyte et une solution électrolytique à base d'hexafluoro phosphate de calcium ainsi que des procédés de préparation s'y rapportant, un électrolyte et une solution électrolytique à base d'hexafluoro phosphate de magnésium ainsi qu'un procédé de préparation de la solution électrolytique et une batterie au calcium-ion et une batterie au magnésium-ion contenant la solution électrolytique ou l'électrolyte, ce qui concerne principalement le domaine des batteries secondaires. La solution électrolytique ou l'électrolyte peuvent être utilisés en tant que matière active d'une batterie au calcium-ion ou d'une batterie au magnésium-ion. Dans le procédé de préparation, des matières de réaction bon marché et facilement disponibles sont utilisées. Le procédé de fabrication est simple et a une exploitabilité élevée. La solution électrolytique et l'électrolyte préparés ont une pureté élevée et une bonne stabilité, de sorte que le problème consistant en ce que l'électrolyte et la solution électrolytique nécessaires pour des batteries au calcium-ion et des batteries au magnésium-ion sont difficiles à obtenir est efficacement résolu. De plus, les sous-produits issus du procédé de préparation peuvent être recyclés et avoir une haute valeur ajoutée.
PCT/CN2019/083464 2019-04-19 2019-04-19 Électrolyte et solution électrolytique à base d'hexafluoro phosphate de métal alcalino-terreux et procédés de préparation s'y rapportant WO2020211081A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023108501A1 (fr) * 2021-12-15 2023-06-22 深圳先进技术研究院 Solution électrolytique de sel de calcium et électrolyte, procédé de préparation associé et son application

Citations (4)

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Publication number Priority date Publication date Assignee Title
US5496661A (en) * 1993-08-24 1996-03-05 Moli Energy (1990) Limited Simplified preparation of LiPF6 based electolyte for non-aqueous batteries
WO2015122511A1 (fr) * 2014-02-14 2015-08-20 ステラケミファ株式会社 Procédé de fabrication de sel métallique alcalin de dihalophosphate et procédé de fabrication de sel métallique alcalin de difluorophosphate
CN106745096A (zh) * 2017-02-16 2017-05-31 九江天赐高新材料有限公司 六氟磷酸碱金属盐的制备方法
CN108217622A (zh) * 2017-12-21 2018-06-29 珠海市赛纬电子材料股份有限公司 一种六氟磷酸钠的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5496661A (en) * 1993-08-24 1996-03-05 Moli Energy (1990) Limited Simplified preparation of LiPF6 based electolyte for non-aqueous batteries
WO2015122511A1 (fr) * 2014-02-14 2015-08-20 ステラケミファ株式会社 Procédé de fabrication de sel métallique alcalin de dihalophosphate et procédé de fabrication de sel métallique alcalin de difluorophosphate
CN106745096A (zh) * 2017-02-16 2017-05-31 九江天赐高新材料有限公司 六氟磷酸碱金属盐的制备方法
CN108217622A (zh) * 2017-12-21 2018-06-29 珠海市赛纬电子材料股份有限公司 一种六氟磷酸钠的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023108501A1 (fr) * 2021-12-15 2023-06-22 深圳先进技术研究院 Solution électrolytique de sel de calcium et électrolyte, procédé de préparation associé et son application

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