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WO2023108501A1 - Solution électrolytique de sel de calcium et électrolyte, procédé de préparation associé et son application - Google Patents

Solution électrolytique de sel de calcium et électrolyte, procédé de préparation associé et son application Download PDF

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Publication number
WO2023108501A1
WO2023108501A1 PCT/CN2021/138479 CN2021138479W WO2023108501A1 WO 2023108501 A1 WO2023108501 A1 WO 2023108501A1 CN 2021138479 W CN2021138479 W CN 2021138479W WO 2023108501 A1 WO2023108501 A1 WO 2023108501A1
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calcium
electrolyte
salt
calcium salt
preparation
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Chinese (zh)
Inventor
唐永炳
姚文娇
吴南中
兰元其
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H01M10/054—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
    • H01M10/056—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
    • 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 invention relates to the technical field of secondary batteries, in particular to a calcium salt electrolytic solution and electrolyte, a preparation method and application thereof.
  • Lithium-ion batteries with high performance have been widely used in mobile electronic devices, electric vehicles, large-scale energy storage and other fields.
  • the global reserves of lithium are only 14 million tons and the geographical distribution is uneven, making it difficult to support future energy storage needs. Therefore, it is of great significance to develop new energy storage systems, such as calcium ions and other energy storage systems.
  • Calcium ranks fifth in the crustal abundance, about 2,500 times that of lithium, and is not affected by geopolitics. As a divalent ion, calcium ions can react to generate twice as much charge as lithium ions per mole. For this reason, calcium-ion batteries are expected to become a new generation of high-performance, low-cost energy storage technology to fill the energy storage gap.
  • the electrolyte in secondary batteries, greatly affects the performance of the battery.
  • the electrolyte solution of a secondary battery is composed of an organic solvent, an electrolyte (solute), additives, etc., wherein the electrolyte is the most critical component.
  • Electrolytes can be classified according to the type of anion, such as hexafluorophosphate, tetrafluoroborate, perchlorate, etc.
  • electrolytes such as lithium salts, sodium salts, and potassium salts such as hexafluorophosphoric acid, tetrafluoroboric acid, and perchloric acid have perfect industrial production methods.
  • the corresponding magnesium salts are also relatively mature. However, the development of corresponding calcium salts is slow, and there is a lack of efficient and safe production methods.
  • the standard route for the industrial production of alkali metal hexafluorophosphate uses anhydrous hydrofluoric acid (HF) as the medium to react phosphorus pentafluoride (PF 5 ) with metal fluorides (LiF, NaF, KF) in the medium to form the corresponding hexafluorophosphate Fluorophosphate, however, this method cannot synthesize calcium hexafluorophosphate.
  • HF phosphorus pentafluoride
  • LiF, NaF, KF metal fluorides
  • Document J.Solid State Chem.2008,181,2318 uses CaF 2 to react with PF 5 in anhydrous hydrofluoric acid, and the product is Ca(HF 2 ) 2 .
  • the reaction conversion rate depends on the solubility difference of CaCl and AgCl, because both are insoluble substances, the reaction conversion rate is small, the impurity content is high, and the purification cost is high; secondly, because the reaction generates AgCl as The solid-phase product will adhere to the surface of the reactant, further slowing down the reaction rate and reducing the reaction conversion rate; moreover, the noble metal precursor AgPF 6 will bring extremely high production costs, which cannot meet industrial applications.
  • the industrial preparation method of calcium perchlorate is to react calcium nitrate or calcium chloride with perchloric acid solution, then evaporate and cool the solution to obtain calcium perchlorate tetrahydrate, and then decompress and heat to obtain calcium perchlorate .
  • the decompression and heating process are relatively complicated. On the one hand, it is difficult to completely remove the crystal water, resulting in impure products. On the other hand, improper control of the heating process can easily cause explosions.
  • the Chinese patent with application number 201910551846 discloses a calcium perchlorate preparation device and method.
  • the patent only provides a preparation method for calcium perchlorate solution, and includes from the primary electro-oxidation unit to the secondary electro-oxidation unit to the The three-stage electro-oxidation unit has complex devices and cumbersome preparation process.
  • the literature Dalton Transactions, 2010, 32 (40), 9696 reports calcium salt perchlorate in benzonitrile solvent, yet the obtained solid product contains inseparable organic solvent molecules and surrounds calcium ions.
  • the perchlorate calcium salt reported in the literature Russian Journal of General Chemistry 2004,74,1150 and Z.Anorg.Allg.Chem.2004,630,914 not only contains organic solvent molecules, but also additionally contains water molecules. The presence of these organic solvent molecules and water molecules seriously affects its performance as an organic system electrolyte, related electrolytes and calcium ion energy storage devices.
  • the present invention provides calcium salt electrolytes and electrolytes and their preparation methods and applications, aiming to solve various problems existing in the existing calcium salt electrolytes and electrolyte preparation methods, and to improve the performance of calcium ion batteries .
  • the present invention provides a method for preparing a calcium salt electrolyte, comprising the following steps:
  • the organic solvent, metallic calcium and a salt containing cations that can be reduced by metallic calcium are placed in the same container, and reacted completely under the protection of an inert gas to obtain a calcium salt electrolyte.
  • the salt comprising a cation reducible by metallic calcium is cuprous or ammonium tetraacetonitrile.
  • said salt comprising a cation reducible by metallic calcium also comprises a stabilizing anionic group
  • the anion group is hexafluorophosphate, tetrafluoroborate, perchlorate, bisfluorosulfonamide, bis(trifluoromethylsulfonyl)imide, trifluoromethylsulfonate, perfluoroalkyl Any one of sulfonate, fluorosulfonate, chlorosulfonate, carborane cluster, and tetrakis(hexafluoroisopropyl)borate.
  • the amount of calcium metal is excessive to ensure the purity of the product and shorten the reaction time
  • the amount of the metal calcium substance is not less than half of tetraacetonitrile cuprous salt or ammonium salt.
  • the organic solvent includes one or more of esters, sulfones, ethers, nitrile organic solvents or ionic liquids.
  • the organic solvent comprises 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), ethyl acetate (EA), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOL), 4-methyl -1,3-dioxolane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone ( MSM), dimethyl
  • the present invention provides a method for preparing a calcium salt electrolyte, comprising the following steps:
  • the calcium salt electrolyte is prepared by the method for preparing the calcium salt electrolyte as described above;
  • the organic solvent is then removed, or the solubility of the calcium salt in the organic solvent is reduced to precipitate the calcium salt solute.
  • the present invention also provides a calcium salt electrolyte, which is prepared by the above-mentioned preparation method of the calcium salt electrolyte.
  • the present invention also provides a calcium salt electrolyte, which is prepared by the above-mentioned preparation method of the calcium salt electrolyte;
  • the above-mentioned calcium salt electrolyte can be redissolved in other organic solvents.
  • the present invention also provides a calcium-ion battery, including a negative electrode of the battery, an electrolyte, a diaphragm, and a positive electrode of the battery, and the electrolyte is the above-mentioned calcium salt electrolyte.
  • the present invention also provides an energy storage device, including the above-mentioned calcium ion battery.
  • the present invention also provides an electrical device, including the above-mentioned calcium-ion battery.
  • the preparation method of the calcium salt electrolyte and electrolyte solution of the present invention solves the existing problems such as complex synthesis routes, high cost, low efficiency, and low product purity.
  • the preparation method and products of calcium hexafluorophosphate electrolyte and electrolyte solution the use of highly toxic and highly corrosive raw materials such as HF and PF 5 in the industry is avoided, and the process is safer, more environmentally friendly, and more operable.
  • the use of commercially available cheap metal calcium and cuprous tetraacetonitrile or ammonium salt as raw materials avoids the use of expensive precursors, and the cost is low.
  • the by-products of the reaction are metal copper or ammonia and hydrogen, which are of high purity, easy to separate, and have recycling value.
  • the preparation method has the advantages of short time, high efficiency, thorough reaction and high purity.
  • the calcium salt electrolyte of the present invention has high purity, good chemical stability, good compatibility with conventional electrode materials, and high ion conductivity and ion mobility.
  • the calcium salt electrolyte of the present invention has high purity and high solubility in conventional organic solvents.
  • the electrolyte solution obtained after the electrolyte is dissolved has a high concentration, good chemical stability, good compatibility with conventional electrode materials, and high ion conductivity and ion mobility.
  • Calcium ion battery, energy storage equipment and electrical equipment of the present invention comprise above-mentioned electrolytic solution or electrolyte, all have higher operating voltage and capacity.
  • Fig. 1 is the 19 F and 31 P nuclear magnetic resonance (NMR) spectra of the calcium hexafluorophosphate electrolyte prepared by embodiment 1;
  • Fig. 2 is the powder X-ray diffraction (XRD) spectrum of reaction by-product in embodiment 1;
  • Fig. 3 is the energy dispersive X-ray (EDX) spectrum of the calcium hexafluorophosphate electrolyte prepared by embodiment 2;
  • Fig. 4 is the 1 H nuclear magnetic resonance (NMR) spectrum of the calcium hexafluorophosphate electrolyte prepared by embodiment 3;
  • Fig. 5 is the constant current charge and discharge curve figure of the calcium ion battery prepared by embodiment 5;
  • Fig. 6 is the structural representation of a kind of calcium ion battery provided by the present invention.
  • Icons 1-negative electrode current collector; 2-negative electrode active material layer; 3-diaphragm; 4-electrolyte; 5-positive electrode active material layer; 6-positive electrode current collector.
  • the “range” disclosed in the present invention takes the form of lower limit and upper limit, and may respectively have one or more lower limits, and one or more upper limits.
  • each reaction or operation step may be performed sequentially or not.
  • the methods herein are performed sequentially.
  • the present invention provides a method for preparing a calcium salt electrolyte, comprising the following steps: placing an organic solvent, a salt containing a stable anionic group, and metal calcium in the same container under the protection of an inert gas, and waiting for the reaction to complete , to obtain calcium salt electrolyte.
  • the salts containing stable anionic groups contain cations that can be reduced by metallic calcium.
  • the cations are tetraacetonitrile cuprous ions and ammonium ions
  • the reduction products are metal copper, ammonia and hydrogen.
  • the amount of calcium metal should not be less than one-half of that of tetraacetonitrile cuprous ion salt and ammonium ion salt.
  • the method avoids the use of highly toxic and highly corrosive raw materials such as HF and PF 5 , and the process is safer, more environmentally friendly, and more operable, and solves the difficult problem of calcium salt electrolyte and electrolyte solution being difficult to obtain.
  • the use of commercially available cheap metal calcium and cuprous tetraacetonitrile or ammonium salt as raw materials avoids the use of expensive precursors, and the cost is low.
  • the by-products of the reaction are metal copper or ammonia and hydrogen, which are of high purity, easy to separate, and have recycling value.
  • the preparation method has the advantages of short time, high efficiency, thorough reaction and high purity.
  • the organic solvent is not particularly limited, and may be organic solvents 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 (
  • the present invention also provides a method for preparing a calcium salt electrolyte, comprising the following steps: removing the organic solvent from the calcium salt electrolyte prepared by the above method; or reducing the solubility of the calcium salt in the solvent to obtain calcium salt electrolyte.
  • the method for removing the organic solvent is not particularly limited. Specifically, methods such as heating evaporation, reduced pressure evaporation, and normal temperature evaporation can be used.
  • the method for reducing the solubility of the calcium salt in the solvent is not particularly limited. Specifically, methods such as freezing, passing through weak polar or non-polar solvents, and the like can be used.
  • the present invention also provides a calcium salt electrolyte obtained by the above preparation method of the calcium salt electrolyte.
  • the electrolyte is of high purity and has high solubility in conventional organic solvents.
  • the electrolyte solution obtained after the electrolyte is dissolved has a high concentration, good chemical stability, good compatibility with conventional electrode materials, and high ion conductivity and ion mobility.
  • the present invention also provides a calcium salt electrolyte obtained by the above preparation method of the calcium salt electrolyte. Alternatively, it can be obtained by redissolving the above calcium salt electrolyte in other organic solvents.
  • the calcium salt electrolyte has high purity, good chemical stability, good compatibility with conventional electrode materials, and high ion conductivity and ion mobility.
  • the present invention also provides a calcium-ion battery, including a positive electrode, a separator, a negative electrode and the above-mentioned calcium salt electrolyte.
  • the calcium-ion battery has a relatively high working voltage and capacity.
  • the calcium ion battery provided by the present invention has two working principles, one is: during the charging process, calcium ions are desorbed or desorbed from the positive electrode and enter the electrolyte, and the calcium ions in the electrolyte migrate to the negative electrode and intercalate or absorb In the negative electrode active material; during the discharge process, calcium ions either desorb or desorb from the negative electrode material and enter the electrolyte, and the calcium ions in the electrolyte migrate to the positive electrode and intercalate or adsorb in the positive electrode active material.
  • the second is: during the charging process, the anions in the electrolyte migrate to the positive electrode and embed or adsorb in the positive active material, and the calcium ions in the electrolyte migrate to the negative electrode and embed or adsorb in the negative active material; during the discharge process, the anions from the positive electrode Desorb or desorb and enter the electrolyte, calcium ions desorb or desorb 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 conductor and a positive electrode binder, the content of the positive electrode active material is 50-99wt%, and the content of the positive electrode conductor is 0.5-30wt%, the content of positive electrode binder is 0.5-20wt%.
  • the positive electrode active material includes at least one of carbon materials, organic substances, metals, alloys, oxides, sulfides, nitrides or carbides.
  • 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 50-99wt%, and the content of the negative electrode conductive agent is 0.5-30wt%, the content of the negative electrode binder is 0.5-20wt%.
  • the negative electrode active material includes at least one of carbon materials, organic substances, metals, alloys, oxides, sulfides, nitrides or carbides.
  • the positive electrode conductive agent or the negative electrode conductive agent includes at least one of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene or reduced graphene oxide.
  • the positive electrode binder or negative electrode binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber (Styrene Butadiene Rubber, styrene-butadiene rubber) or polyolefins .
  • the positive or negative current collector is any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth or germanium; or, the positive or negative current collector It is an alloy including at least any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth or germanium; or, the positive electrode collector or the negative electrode collector is at least including A composite material of any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth or germanium; or, the positive current collector or negative current collector is a carbon material.
  • Alloy refers to a substance with metallic properties synthesized by two or more metals and metals or nonmetals by a certain method.
  • Metal composite material refers to a metal-based composite conductive material formed by combining metal and other non-metallic materials. Typical but non-limiting metal composites include graphene-metal composites, carbon fiber-metal composites, ceramic-metal composites, and the like.
  • the electrolytic solution includes the above-mentioned calcium salt electrolytic solution.
  • the electrolyte solution further includes additives, and the content of the additives is preferably 0.1-20 wt%.
  • the additive is added in the electrolyte, and the additive can form a stable solid electrolyte film on the surface of the electrode and improve the service life of the battery.
  • the additives include at least one of esters, sulfones, ethers, nitriles or olefins.
  • Additives include fluoroethylene carbonate, vinylene carbonate, ethylene 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, metadiazepine, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorinated chain ether, difluoromethylethylene carbonate, Trifluoromethylethylene carbonate, chloroethylene carbonate, bromoethylene carbonate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate, phosphi
  • the diaphragm includes porous polymer film or inorganic porous film, preferably at least one of porous polypropylene film, porous polyethylene film, porous composite polymer film, glass fiber paper or porous ceramic diaphragm.
  • the structure of a calcium ion battery provided by the present invention includes 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 a positive electrode current collector 6 .
  • the preparation method of the calcium ion battery includes: assembling the positive electrode, the separator, the negative electrode and the electrolyte.
  • the above preparation method has simple process and low manufacturing cost, and the calcium ion battery prepared by the method has the advantages of high discharge voltage and high charge and discharge capacity.
  • the preparation method of calcium ion battery comprises the following steps:
  • Electrolyte preparation the electrolyte prepared by the above method for preparing the calcium salt electrolyte, or the electrolyte prepared by dissolving the electrolyte prepared by the above method for preparing the calcium salt electrolyte in an organic solvent;
  • the assembly process is as follows: in an inert atmosphere or a dry environment, the prepared positive electrode, separator, and negative electrode are tightly stacked or wound in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then packaged into the case to complete the calcium ion process. Assembly of the battery.
  • the form of the calcium-ion battery of the present invention is not limited to button batteries, and can also be designed into square shells, cylinders, soft packs, etc. according to the core components.
  • the present invention also provides an energy storage device comprising the calcium-ion battery described above, thus having at least the same advantages as the calcium-ion battery described above, and having a higher working voltage and capacity.
  • the above-mentioned energy storage devices refer to power storage devices that mainly use calcium-ion batteries as power storage sources, including but not limited to household energy storage systems or distributed energy storage systems.
  • power storage devices that mainly use calcium-ion batteries as power storage sources, including but not limited to household energy storage systems or distributed energy storage systems.
  • a home energy storage system electric power is stored in a calcium ion battery serving as a power storage source, and as needed, the electric power stored in the calcium ion battery is consumed to enable use of various devices such as home appliances.
  • the present invention also provides an electrical device, including the above-mentioned calcium-ion battery, thus having at least the same advantages as the above-mentioned calcium-ion battery, and having a higher working voltage and capacity.
  • the aforementioned electrical equipment includes but is not limited to electronic products, electric tools, or electric vehicles.
  • Electronic products are electronic devices that perform various functions, such as playing music, using a calcium-ion battery as an operating power source.
  • a power tool is an electric tool that uses a calcium-ion battery as a driving power source for moving parts such as a drill.
  • Electric vehicles are electric vehicles (including electric bicycles, electric cars) that run on calcium ion batteries as a driving power source, and may be automobiles equipped with other driving sources in addition to calcium ion batteries, including hybrid vehicles.
  • the obtained calcium hexafluorophosphate electrolyte was characterized by nuclear magnetic resonance (NMR) of 19 F and 31 P, and the results are shown in Figure 1, 19 F shows a doublet, and 31 P shows a septet, which are PF 6 -ions . Characteristic lines. No other peak shapes of 19 F and 31 P were seen, indicating that PF 6 - is a single species of F and P elements, and PF 6 - ion does not decompose.
  • NMR nuclear magnetic resonance
  • reaction reduction product is metal copper
  • Ca(OH) 2 originate from metal calcium raw material, because Ca(OH) 2 in organic It does not dissolve in the solvent and does not pollute the prepared electrolyte.
  • the calcium hexafluorophosphate electrolyte prepared in Example 1 was taken and vacuum-dried for 24 hours to obtain the calcium hexafluorophosphate electrolyte.
  • the obtained calcium hexafluorophosphate electrolyte was characterized by energy dispersive X-ray spectroscopy (EDX). The results are shown in Figure 3. Only calcium, phosphorus, and fluorine element signals were seen, but no copper element signal was seen, indicating that the reaction was complete and the product was of high purity.
  • the calcium hexafluorophosphate electrolyte prepared in Example 3 was taken and vacuum-dried for 24 hours to obtain the calcium hexafluorophosphate electrolyte.
  • a calcium ion battery its preparation process is as follows:
  • the glass fiber film was cut into discs with a diameter of 16 mm and used as the separator for later use.
  • the constant current charge and discharge curve of the battery is shown in Figure 5.
  • the charge specific capacity of the calcium ion battery is 67.3mAh/g, and the discharge specific capacity is 55.5mAh/g.
  • a calcium ion battery the difference from Example 5 is that the electrolyte used is: the calcium hexafluorophosphate electrolyte prepared in Example 2 is dissolved in EC+PC+DMC+EMC (volume ratio is 2:2:3 :3) in, make the calcium hexafluorophosphate electrolyte that concentration is 0.6mol/L.
  • the rest are the same as in Embodiment 5, and will not be repeated here.
  • Embodiment 7-66 provides the method for preparing calcium hexafluorophosphate electrolyte and electrolyte, and the difference with embodiment 1-2 is, the quality of tetraacetonitrile cuprous hexafluorophosphate used, the quality of metal calcium, the kind of organic solvent , reaction time, and electrolyte preparation methods are different, as shown in Table 1.
  • Embodiment 67-126 provides the method for preparing calcium hexafluorophosphate electrolyte and electrolyte, and the difference from embodiment 3-4 is that the quality of ammonium hexafluorophosphate used, the quality of metallic calcium, the type of organic solvent, the length of reaction, the electrolyte The preparation methods are different, as shown in Table 2.
  • Examples 127-146 respectively provide calcium tetrafluoroborate, calcium perchlorate, calcium bisfluorosulfonyl imide, calcium bis(trifluoromethylsulfonyl)imide, calcium trifluoromethanesulfonate, perfluoroalkane Calcium sulfonate, calcium fluorosulfonate, calcium chlorosulfonate, carborane cluster calcium, tetrakis(hexafluoroisopropyl)calcium borate electrolyte and preparation method of electrolyte solution.
  • Examples 127-136 and Examples 1-2 The difference between Examples 127-136 and Examples 1-2 is that the type of cuprous tetraacetonitrile used is different, and the amount of the substance is equal to that described in Example 1.
  • the difference between Examples 137-146 and Examples 3-4 is that the types of ammonium salts used are different, and the amount of the substances is equal to that described in Example 3, see Table 3 for details.
  • Embodiment 147-196 provides the preparation method of calcium ion battery, and the difference with embodiment 5-6 is:
  • the electrolyte used in Examples 147-151 comes from the calcium hexafluorophosphate electrolyte obtained in Examples 7-11 respectively;
  • the electrolyte used in Examples 152-156 is the 0.8mol/L calcium hexafluorophosphate electrolyte prepared from the calcium hexafluorophosphate electrolyte obtained in Examples 7-11;
  • the electrolyte used in Examples 157-161 is the 0.6mol/L calcium hexafluorophosphate electrolyte prepared from the calcium hexafluorophosphate electrolyte obtained in Examples 7-11;
  • the electrolytes used in Examples 162-166 are respectively from the calcium hexafluorophosphate electrolytes obtained in Examples 67-71;
  • the electrolyte used in Examples 167-171 is the 0.8mol/L calcium hexafluorophosphate electrolyte prepared from the calcium hexafluorophosphate electrolyte obtained in Examples 67-71;
  • the electrolytes used in Examples 172-176 were 0.6 mol/L calcium hexafluorophosphate electrolytes prepared from the calcium hexafluorophosphate electrolytes obtained in Examples 67-71, respectively.
  • the electrolytes used in Examples 177-196 are 0.4 mol/L calcium salt electrolytes prepared from the calcium salt electrolytes obtained in Examples 127-146, respectively.
  • Examples 197-211 provide calcium-ion batteries and their preparation methods. The difference from Examples 5-6 lies in the use of different electrolytes and positive electrode active materials, as shown in Table 4.
  • Comparative Example 1-4 and Examples 1-2 and 5-6 The difference between Comparative Example 1-4 and Examples 1-2 and 5-6 is that the amount of tetraacetonitrile copper hexafluorophosphate used is 9 grams, and the anhydrous acetonitrile used is 60 milliliters, and the rest are the same as in Example 1-4, except Let me repeat.
  • Comparative Example 5-6 The difference between Comparative Example 5-6 and Example 3-4 is that the amount of ammonium hexafluorophosphate used is 5 grams, the amount of anhydrous acetonitrile used is 60 ml, and the rest is the same as that of Example 1-2, and will not be repeated here.
  • Comparative Example 7-8 The difference between Comparative Example 7-8 and Example 5-6 is that the electrolyte used is the electrolyte obtained in Comparative Example 5, the electrolyte used is the electrolyte obtained in Comparative Example 6, and the rest is the same as that of Example 5-6, and will not be repeated here.
  • Example First cycle discharge specific capacity (mAh/g) Stable discharge specific capacity (mAh/g) Example 5 52.9 55.5
  • Example 6 58.7 57.3
  • Example 148 57.5 41.7
  • Example 149 58.3 57.5
  • Example 150 43.2 41.1
  • Example 152 71.0 71.9
  • Example 153 55.4 51.4
  • Example 157 49.1 51.2 Example 158 55.6 39.6
  • Example 159 69.5 56.6
  • Example 160 46.9 48.8
  • Example 161 50.6 41.9
  • Example 162 56.9 46.0
  • Example 164 67.9 69.3 Example 165 74.6 75.7
  • Example 167 48.3 49.0
  • Example 169 53.1 48.6 Example 170 74.1
  • the calcium ion battery of the embodiment of the present invention has significantly improved initial discharge specific capacity and stable discharge specific capacity.
  • Examples 151-152 The calcium-ion battery in 170-171 has the highest initial discharge specific capacity and stable discharge specific capacity, and the best performance. Therefore, it also shows that Examples 151-152 and 170-171 can provide more effective methods for preparing calcium hexafluorophosphate electrolyte and electrolyte, and calcium ion batteries with better performance.
  • the preparation method of the calcium salt electrolyte and electrolyte solution of the present invention solves the existing problems such as complex synthesis routes, high cost, low efficiency, and low product purity.
  • the preparation method and products of calcium hexafluorophosphate electrolyte and electrolyte solution the use of highly toxic and highly corrosive raw materials such as HF and PF 5 in the industry is avoided, and the process is safer, more environmentally friendly, and more operable.
  • the use of commercially available cheap metal calcium and cuprous tetraacetonitrile or ammonium salt as raw materials avoids the use of expensive precursors, and the cost is low.
  • the by-products of the reaction are metal copper or ammonia and hydrogen, which are of high purity, easy to separate, and have recycling value.
  • the preparation method has the advantages of short time, high efficiency, thorough reaction and high purity.
  • the calcium salt electrolyte of the present invention has high purity, good chemical stability, good compatibility with conventional electrode materials, and high ion conductivity and ion mobility.
  • the calcium salt electrolyte of the present invention has high purity and high solubility in conventional organic solvents.
  • the electrolyte solution obtained after the electrolyte is dissolved has a high concentration, good chemical stability, good compatibility with conventional electrode materials, and high ion conductivity and ion mobility.

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Abstract

La présente invention a trait au domaine technique des batteries secondaires, et concerne en particulier une solution d'électrolyte de sel de calcium et un électrolyte, un procédé de préparation associé et son application. La solution d'électrolyte de sel de calcium est obtenue par la mise en réaction complète d'un solvant organique, de calcium métallique et d'un sel contenant des cations pouvant être réduits par le calcium métallique dans le même récipient sous la protection d'un gaz inerte, et l'électrolyte de sel de calcium est obtenu par l'élimination du solvant organique dans la solution d'électrolyte de sel de calcium préparée, ou par une réduction de la solubilité du sel de calcium dans le solvant organique, et la séparation d'un soluté de sel de calcium. Le procédé de préparation, qui utilise des matières premières peu coûteuses et faciles à obtenir, est court, son efficacité est élevée et il permet d'obtenir une réaction complète, une pureté élevée, et une séparation et une récupération aisées du sous-produit. De plus, la pureté de la solution d'électrolyte de sel de calcium préparée et de l'électrolyte est élevée, et l'invention permet de résoudre efficacement le problème de la difficulté d'obtention de l'électrolyte de sel de calcium et de la solution d'électrolyte requis par une batterie au calcium-ion.
PCT/CN2021/138479 2021-12-15 2021-12-15 Solution électrolytique de sel de calcium et électrolyte, procédé de préparation associé et son application Ceased WO2023108501A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102105395A (zh) * 2008-08-08 2011-06-22 斯泰拉化工公司 六氟磷酸盐的制造方法
CN102916220A (zh) * 2011-08-05 2013-02-06 丰田自动车株式会社 镁电池电解液
WO2020211081A1 (fr) * 2019-04-19 2020-10-22 深圳先进技术研究院 Électrolyte et solution électrolytique à base d'hexafluoro phosphate de métal alcalino-terreux et procédés de préparation s'y rapportant
CN111834673A (zh) * 2019-04-19 2020-10-27 深圳先进技术研究院 一种碱土金属六氟磷酸盐电解质及电解液制备方法

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CN102105395A (zh) * 2008-08-08 2011-06-22 斯泰拉化工公司 六氟磷酸盐的制造方法
CN102916220A (zh) * 2011-08-05 2013-02-06 丰田自动车株式会社 镁电池电解液
WO2020211081A1 (fr) * 2019-04-19 2020-10-22 深圳先进技术研究院 Électrolyte et solution électrolytique à base d'hexafluoro phosphate de métal alcalino-terreux et procédés de préparation s'y rapportant
CN111834673A (zh) * 2019-04-19 2020-10-27 深圳先进技术研究院 一种碱土金属六氟磷酸盐电解质及电解液制备方法

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