CN111834673B - Alkaline earth metal hexafluorophosphate electrolyte and preparation method of electrolyte - Google Patents

Alkaline earth metal hexafluorophosphate electrolyte and preparation method of electrolyte Download PDF

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CN111834673B
CN111834673B CN201910318608.1A CN201910318608A CN111834673B CN 111834673 B CN111834673 B CN 111834673B CN 201910318608 A CN201910318608 A CN 201910318608A CN 111834673 B CN111834673 B CN 111834673B
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electrolyte
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hexafluorophosphate
ethyl
calcium
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唐永炳
吴南中
姚文娇
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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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to the field of secondary batteries, and particularly provides a calcium hexafluorophosphate electrolyte, an electrolyte and a preparation method thereof, a magnesium hexafluorophosphate electrolyte, an electrolyte and a preparation method thereof, and a calcium ion battery and a magnesium ion battery containing the electrolyte or the electrolyte. The electrolyte or electrolyte can be used as an active material of a calcium ion battery or a magnesium ion battery. The preparation method adopts cheap and easily-obtained reaction raw materials; the preparation method is simple and has strong operability; the prepared electrolyte and electrolyte have high purity and good stability, and the problem that the electrolyte and the electrolyte required by a calcium ion battery and a magnesium ion battery are difficult to obtain is effectively solved; and the by-products of the preparation method can be recycled and have high added value.

Description

Alkaline earth metal hexafluorophosphate electrolyte and preparation method of electrolyte
Technical Field
The invention relates to the field of secondary batteries, in particular to an electrolyte of calcium hexafluorophosphate and magnesium hexafluorophosphate and a preparation method thereof, an electrolyte and a preparation method thereof, and a calcium ion battery and a magnesium ion battery containing the electrolyte or the electrolyte.
Background
Energy storage technology is an important link in energy application. Compared with a primary battery, the secondary battery has the advantages of resource recycling, economy, environmental protection and the like; lithium ion batteries with high performance are widely applied in the fields of mobile electronic equipment, electric automobiles and the like. However, the global reserve of lithium is only 1400 million tons and is not geographically distributed, which is difficult to support the future energy storage demand. Therefore, the development of novel energy storage systems, such as sodium ions, potassium ions, magnesium ions, calcium ions and the like, has great significance.
Calcium and magnesium ions act as divalent ions and react to produce twice the amount of charge as lithium ions per mole of ion. In addition, the abundance of the crust of the calcium element is ranked fifth, the abundance of the crust of the magnesium element is ranked eighth, and the natural reserves are all far higher than that of the lithium. Therefore, the calcium ion battery and the magnesium ion battery are expected to become a new generation of energy storage technology with high performance and low cost.
In a secondary battery, an electrolyte, which is one of the main components of the battery, greatly affects the performance of the battery. Generally, an electrolytic solution of a secondary battery is composed of an organic solvent, an electrolyte (solute), an additive, and the like, wherein the electrolyte is the most critical component. The commonly used electrolyte includes hexafluorophosphate, tetrafluoroborate, perchlorate, and the like, classified according to the kind of anion. Hexafluorophosphate electrolytes have numerous outstanding advantages over other electrolytes, such as: better stability; good compatibility with conventional organic solvents; higher solubility in conventional organic solvents; the electrolyte composed of the material has good conductivity and ion mobility; the current collector is not corroded; and so on. Based on the above advantages, lithium hexafluorophosphate and an electrolyte thereof have been widely used in lithium ion batteries. Accordingly, alkaline earth metal electrolytes, in particular hexafluorophosphate electrolytes, such as: calcium hexafluorophosphate, magnesium hexafluorophosphate and electrolyte thereof are of great importance to the development of calcium ion batteries and magnesium ion batteries.
For calcium ion and magnesium ion energy storage systems, correspondingly, electrolytes and electrolytes have not been prepared well. The document chem. mater.2015,27,8442 reports a calcium hexafluorophosphate (Ca (PF)6)2) The synthesis method comprises the following steps: silver hexafluorophosphate (AgPF) using acetonitrile as solvent6) With calcium chloride (CaCl)2) As reactants, and the predicted reaction:
Figure BDA0002033944130000021
and (4) drying the filtrate in vacuum to finally obtain a solid product. However, this report only verifies that the solid product contains hexafluorophosphate ions, and does not verify the kind and purity of cations in the product and whether it contains a crystallization solvent molecule. Silver chloride (AgCl) generated by the reaction is a solid-phase productThey adhere to the surface of the reactant and prevent the reaction from continuing, so that it is not guaranteed that the reaction can proceed completely. In addition, the noble metal precursor AgPF6This would result in extremely high production costs.
Document J.Am.chem.Soc.2016,138,8682 Nitrosofluorophosphate (NOPF) using acetonitrile as solvent6) With magnesium metal as a reactant, magnesium hexafluorophosphate (Mg (PF) is prepared6)2) And post-treating to obtain solid product Mg (PF) containing crystallization solvent molecules6)2(CH3CN)6. However, this document only produces magnesium hexafluorophosphate electrolyte in acetonitrile, failing to provide electrolytes of other organic solvent systems such as: magnesium hexafluorophosphate electrolyte of esters, ethers, sulfones and the like, and the electrochemical window of acetonitrile is relatively narrow, thus limiting the application of the electrolyte. In addition, if Mg (PF) is used6)2(CH3CN)6The solid is used as an electrolyte, other conventional organic solvents are used as solvents, and dissolving 1mol of magnesium source brings 6mol of acetonitrile molecules, so that the obvious solvent pollution is caused.
Chem. Commun.2017,53,4573 to refer to the above method, use NOPF6As a precursor, reacting with metallic calcium to prepare the calcium hexafluorophosphate electrolyte. However, the experiment proves that the method can cause the oxidative decomposition of hexafluorophosphate ions to generate difluorophosphate ions (PO) as an impurity2F2 -). This is due to the use of NOPF6When the precursor is used, the strongly oxidizing gas NO generated by the reaction can oxidize hexafluorophosphate ions.
Another Ca (PF)6)2The preparation method of the electrolyte comprises the following steps: using alkali metal hexafluorophosphates, e.g. potassium hexafluorophosphate (KPF)6) The solution is used as a precursor, and the alkali metal cation is replaced by ion exchange resin. The disadvantages of this method are: the ion exchange resin has high cost and can not be repeatedly utilized, the method can not ensure the purity of cations in the electrolyte, and the prepared electrolyte contains a large amount of impurity ions.
The most mainstream of the industrial production of alkali metal hexafluorophosphate electrolyteThe method adopts anhydrous hydrofluoric acid (HF) and phosphorus Pentafluoride (PF)5) Gas and metal fluorides (lithium fluoride, sodium fluoride, potassium fluoride) as reactants. At present, the industrial production method of alkali metal hexafluorophosphate is not used for preparing the alkaline earth metal hexafluorophosphate. The reason for this is that: there is an intrinsic difference between alkali metal elements and alkaline earth metal elements. The outermost electron orbit of the alkali metal atom has only one electron, the outermost electron of the atomic nucleus has small attraction, and the outermost electron is easily lost and becomes a positive ion with one positive charge; while the outermost electron orbital of the alkaline earth atom has two electrons, such paired electrons reduce the energy of the electron orbital. Thus, the alkaline earth metal nuclei are more attractive to the outermost orbital electrons, which require more energy to break free of the nuclei. This intrinsic difference causes a large difference in physical and chemical properties of the alkali metal species and the alkaline earth metal species in terms of atomic radius, first ionization energy, and chemical reactivity. For this reason, it is unpredictable whether the process for the preparation of alkali metal hexafluorophosphates can be carried over to alkaline earth metal hexafluorophosphates.
The preparation of the hexafluorophosphate electrolyte or the electrolyte of the calcium ion and magnesium ion system has not been reported.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of calcium hexafluorophosphate and magnesium hexafluorophosphate electrolyte, which has the advantages of low cost, simple process, high product purity and high utilization rate of substances.
The second purpose of the 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 to the current collector.
A third object of the present invention is to provide a method for preparing a calcium hexafluorophosphate electrolyte and a magnesium hexafluorophosphate electrolyte, which has the same advantages as the above-described method for preparing an electrolyte solution.
A fourth object of the present invention is to provide a calcium hexafluorophosphate electrolyte and a magnesium hexafluorophosphate electrolyte, and an electrolytic solution prepared using the same has the same advantages as the above electrolytic solution.
The fifth object of the present invention is to provide a calcium ion battery or a magnesium ion battery, which comprises the above-mentioned calcium hexafluorophosphate electrolyte or electrolyte, or the above-mentioned magnesium hexafluorophosphate electrolyte or electrolyte.
The sixth purpose of the invention is to provide an energy storage system, which comprises the calcium ion battery or the magnesium ion battery.
The seventh purpose of the invention is to provide an electric device, which comprises the calcium ion battery or the magnesium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a preparation method of a calcium hexafluorophosphate and magnesium hexafluorophosphate electrolyte, wherein the reaction formula is as follows:
Figure BDA0002033944130000041
wherein MH2Is MgH2Or CaH2The solvent is a non-aqueous organic solvent. The preparation method comprises the following steps: and (3) placing the organic solvent, ammonium hexafluorophosphate and alkaline earth metal hydride in the same container under the protection of inert gas, and obtaining the alkaline earth metal hexafluorophosphate electrolyte after the reaction is completed.
As a further preferable technical solution, the alkaline earth metal hydride is calcium hydride or magnesium hydride;
preferably, the amount (moles) of alkaline earth metal hydride species should not be less than one-half the amount of ammonium hexafluorophosphate species;
in a second aspect, the invention provides a calcium hexafluorophosphate electrolyte and a magnesium hexafluorophosphate electrolyte prepared by the above electrolyte preparation method.
In a third aspect, the present invention provides a method for preparing a calcium hexafluorophosphate electrolyte and a magnesium hexafluorophosphate electrolyte, comprising the steps of: and removing the organic solvent from the calcium hexafluorophosphate electrolyte or the magnesium hexafluorophosphate electrolyte, or reducing the solubility of the calcium hexafluorophosphate or the magnesium hexafluorophosphate in the solvent to obtain the calcium hexafluorophosphate electrolyte or the magnesium hexafluorophosphate electrolyte.
In a fourth aspect, the invention provides a calcium hexafluorophosphate electrolyte and a magnesium hexafluorophosphate electrolyte prepared by the above electrolyte preparation method.
In a fifth aspect, the present invention provides a calcium ion battery and a magnesium ion battery, which comprise the above calcium hexafluorophosphate electrolyte or electrolyte, or the above magnesium hexafluorophosphate electrolyte or electrolyte.
In a sixth aspect, the invention provides an energy storage system comprising the above calcium ion battery or magnesium ion battery.
In a seventh aspect, the present invention provides an electric device, including the above calcium ion battery or magnesium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of calcium hexafluorophosphate electrolyte, magnesium hexafluorophosphate electrolyte and magnesium hexafluorophosphate electrolyte, which uses industrial cheap precursor NH4PF6And metal hydride is used as raw material, so that the use of toxic and strong corrosive raw materials HF and PF is avoided5(ii) a The preparation method is simple, and complex instruments and equipment are not needed; the preparation method is independent of organic solvents, and the solvents can be freely selected; the prepared product has high purity; the byproducts are all gases, so that the reaction is ensured to be completely carried out; by-product NH3And H2The stable reducing gas is used for preventing hexafluorophosphate ions from being oxidized and decomposed; by-product NH3Is a raw material for industrially producing nitrogenous fertilizer and a byproduct H2Is a clean energy source.
The calcium hexafluorophosphate electrolyte and the magnesium hexafluorophosphate electrolyte provided by the invention have higher purity and better chemical stability; the electrode material has good compatibility with the conventional electrode material; the conductivity and the ion mobility are high; the current collector is not corroded.
The calcium hexafluorophosphate electrolyte and the magnesium hexafluorophosphate electrolyte provided by the invention have higher solubility in the conventional organic solvent; the electrolyte obtained after the electrolyte is dissolved has higher concentration, good conductivity and ion mobility; the current collector is not corroded.
The calcium ion battery and the magnesium ion battery provided by the invention contain the electrolyte or the electrolyte, and the calcium ion battery and the magnesium ion battery have higher working voltage and capacity.
The energy storage system provided by the invention comprises the calcium ion battery and the magnesium ion battery, so that the energy storage system at least has the same advantages as the calcium ion battery and the magnesium ion battery, and has higher discharge voltage and charge-discharge capacity.
The electric equipment provided by the invention comprises the calcium ion battery and the magnesium ion battery, so that the electric equipment at least has the advantages of being the same as those of the calcium ion battery and the magnesium ion battery, and has the advantages of high discharge voltage and high charge-discharge capacity.
Drawings
FIG. 1 shows an electrolyte obtained in example 119NMR spectra (a) and (b) of F31NMR spectrum (b) of P;
FIG. 2 is a mass spectrum of the gas produced by the reaction of example 1;
FIG. 3 is an EDX diagram of the electrolyte obtained in example 2;
fig. 4 is a constant current charge and discharge curve diagram of the two-carbon calcium ion battery formed in 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 current collector; 2-a negative electrode active material layer; 3-a separator; 4-an electrolyte; 5-positive electrode active material layer; 6-positive electrode current collector.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features and preferred features mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may or may not be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
In a first aspect, in at least one embodiment, there is provided a method of preparing a calcium hexafluorophosphate electrolyte or a magnesium hexafluorophosphate electrolyte, comprising the steps of: and (3) placing the organic solvent, ammonium hexafluorophosphate and alkaline earth metal hydride in the same container under the protection of inert gas, and obtaining the alkaline earth metal hexafluorophosphate electrolyte after the reaction is completed.
The method uses an industrial cheap precursor NH4PF6And metal hydrides; avoid using HF and PF which are toxic and strong corrosive raw materials5(ii) a The preparation method is simple, and complex instruments and equipment are not needed; the preparation method is independent of the solvent, and the solvent can be freely selected; the prepared product has high purity; the byproducts are all gases, so that the reaction is ensured to be completely carried out; by-product NH3And H2Is stable reducing gas, and can prevent hexafluorophosphate radical ion from oxidationDecomposing; by-product NH3As a raw material for the industrial production of nitrogen fertilizers, H2Is a clean energy source.
The organic solvent is not particularly limited, and may be: esters, sulfones, ethers, nitriles or ionic liquid. Specifically, 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-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), γ -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), dimethylsulfone (MSM), dimethyl ether (DME), Ethylene Sulfite (ES), sulfurous acid (ES), ethylene glycol (m), and propylene carbonate (DMC), Propylene Sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), crown ether (12-crown-4), 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, sodium salt, potassium salt, sodium chloride, etc. and sodium chloride, etc. is added, 1-butyl-1-methylimidazole-bis (trifluoromethylsulfonyl) imide salt, N-butyl-N-methylpyrrolidine-bis (trifluoromethylsulfonyl) imide salt, 1-butyl-1-methylpyrrolidine-bis (trifluoromethylsulfonyl) imide salt, N-methyl-N-propylpyrrolidine-bis (trifluoromethylsulfonyl) imide salt, N-methyl, propylpiperidine-bis (trifluoromethylsulfonyl) imide salt, N-methyl, butylpiperidine-bis (trifluoromethylsulfonyl) imide salt.
Preferably, the alkaline earth metal hydride is calcium hydride or magnesium hydride;
preferably, the amount (moles) of alkaline earth metal hydride species should not be less than one-half the amount of ammonium hexafluorophosphate species;
in a second aspect, in at least one embodiment, there is provided a calcium hexafluorophosphate electrolyte or a magnesium hexafluorophosphate electrolyte obtained by the above method for producing a calcium hexafluorophosphate electrolyte or a magnesium hexafluorophosphate electrolyte. The electrolyte has good chemical stability, high ion mobility and no corrosion to a current collector.
In a third aspect, in at least one embodiment, a method of making a calcium hexafluorophosphate electrolyte or a magnesium hexafluorophosphate electrolyte is provided. And removing the organic solvent from the calcium hexafluorophosphate or magnesium hexafluorophosphate electrolyte, or reducing the solubility of the calcium hexafluorophosphate and magnesium hexafluorophosphate in the solvent to obtain the calcium hexafluorophosphate electrolyte or magnesium hexafluorophosphate electrolyte.
The method for removing the organic solvent is not particularly limited. Specifically, the solvent may be evaporated by heating, evaporation under reduced pressure, or evaporation at room temperature.
The method for reducing the solubility of calcium hexafluorophosphate or magnesium hexafluorophosphate in the solvent is not particularly limited. Specifically, the solvent may be frozen or passed through a weakly polar or nonpolar solvent.
In a fourth aspect, in at least one embodiment, there is provided a calcium hexafluorophosphate electrolyte or a magnesium hexafluorophosphate electrolyte obtained by the above method for producing a calcium hexafluorophosphate electrolyte or a magnesium hexafluorophosphate electrolyte.
In a fifth aspect, there is provided in at least one embodiment a calcium ion battery or a magnesium ion battery comprising a positive electrode, a separator, a negative electrode and the above calcium hexafluorophosphate electrolyte or the above magnesium hexafluorophosphate electrolyte.
The calcium ion battery or the magnesium ion battery provided by the invention has two working principles, one of which is as follows: in the charging process, calcium ions or magnesium ions are removed from the positive electrode and enter the electrolyte, and the calcium ions or the magnesium ions in the electrolyte are transferred to the negative electrode and embedded into the negative electrode active material; during discharge, 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 are embedded in the positive electrode active material. The second method comprises the following steps: in the charging process, anions in the electrolyte migrate to the positive electrode and are embedded into the positive electrode active material, and calcium ions or magnesium ions in the electrolyte migrate to the negative electrode and are embedded into the negative electrode active material; during the discharge process, anions are extracted from the positive electrode and enter the electrolyte, and calcium ions or magnesium ions are extracted from the negative electrode and enter the electrolyte.
Positive electrode
The positive electrode comprises a positive active material layer and a positive current collector, wherein the positive active material layer comprises a positive active material, a positive conductive agent and a positive binder, the content of the positive active material is 60-95 wt%, the content of the positive conductive agent is 2-30 wt%, and the content of the positive binder is 2-10 wt%.
Preferably, the positive electrode active material includes at least one of a carbon material, a metal, an alloy, a sulfide, a nitride, an oxide, or a carbide.
Preferably, 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;
or the positive current collector or the negative current collector is an alloy at least comprising any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth or germanium;
or the positive current collector or the negative current collector is a composite material at least comprising any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth or germanium.
The term "alloy" means a substance having a metallic property which is synthesized from two or more metals and metals or nonmetals by a certain method.
"Metal composite" refers to a metal matrix composite conductive material formed by combining a metal with other non-metallic materials. Typical, but non-limiting, metal composites include graphene-metal composites, carbon fiber-metal composites, ceramic-metal composites, and the like.
Negative electrode
The negative electrode comprises a negative electrode active material layer and a negative electrode current collector, wherein the negative electrode active material layer comprises 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%, the content of the negative electrode conductive agent is 5-30 wt%, and the content of the negative electrode binder is 5-10 wt%.
Preferably, the negative electrode active material includes at least one of a carbon material, a metal, an alloy, a sulfide, a nitride, an oxide, or a carbide.
Further, 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.
Further, the positive electrode binder or the negative electrode binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR Rubber (Styrene Butadiene Rubber), or polyolefin.
Electrolyte solution
The electrolyte comprises the calcium hexafluorophosphate electrolyte or the magnesium hexafluorophosphate electrolyte.
Furthermore, the electrolyte also comprises an additive, and the content of the additive is preferably 0.1-20 wt%. And an additive is added in the electrolyte, and the additive can form a stable solid electrolyte membrane on the surface of the electrode, so that the service life of the battery is prolonged.
The additive comprises at least one of esters, sulfones, ethers, nitriles or olefins.
The additive comprises fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, difluoro methyl vinyl carbonate, trifluoro methyl vinyl carbonate, chloroethylene carbonate, bromo vinyl carbonate, trifluoroethyl phosphonic acid, bromo butyrolactone, fluoro acetoxy ethane, phosphate ester, phosphite ester, phosphazene, ethanolamine, carbonized dimethylamine, At least one of cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide or lithium carbonate.
Diaphragm
The separator comprises a porous polymer film or an inorganic porous film, and preferably comprises 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 structural diagram of a calcium ion battery or a magnesium ion battery with a structure provided by the present invention, and the calcium ion battery or the magnesium ion battery 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.
Illustratively, the preparation method of the calcium ion battery or the magnesium ion battery comprises the following steps: the positive electrode, the separator, the negative electrode, and the electrolyte were assembled. The preparation method has the advantages of simple process and low manufacturing cost, and the calcium ion battery or the magnesium ion battery prepared by the method has the advantages of high discharge voltage and high charge-discharge capacity.
Further preferably, the method comprises the steps of:
(a) preparing a negative electrode: preparing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder into negative electrode slurry, coating the negative electrode slurry on the surface of a negative electrode current collector, drying and cutting to obtain a negative electrode with a required size; or pressing the negative electrode active material on the surface of the negative electrode current collector, and cutting to obtain a negative electrode with a required size;
(b) preparing an electrolyte: the electrolyte prepared by the preparation method of the calcium hexafluorophosphate electrolyte and the magnesium hexafluorophosphate electrolyte or the electrolyte prepared by the preparation method of the calcium hexafluorophosphate electrolyte and the magnesium hexafluorophosphate electrolyte is dissolved in an organic solvent.
(c) Preparing a diaphragm: taking a porous polymer film or an inorganic porous film with a required size as a diaphragm for standby;
(d) preparing a positive electrode: preparing a positive electrode active material, a positive electrode conductive agent and a positive electrode binder into positive electrode slurry, coating the positive electrode slurry on the surface of a positive electrode current collector, drying and cutting to obtain a positive electrode with a required size;
(e) assembling the negative electrode obtained in the step (a), the electrolyte obtained in the step (b), the separator obtained in the step (c), and the positive electrode obtained in the step (d).
Preferably, the assembling specifically comprises: and tightly stacking or winding the prepared cathode, the diaphragm and the anode in turn in an inert environment, dripping electrolyte to completely infiltrate the diaphragm, and then packaging into a shell to complete the assembly of the calcium ion battery or the magnesium ion battery.
The shape of the calcium ion battery or the magnesium ion battery is not limited to a button battery, and can be designed into a flat plate shape, a cylindrical shape and the like according to core components.
In a sixth aspect, there is provided in at least one embodiment an energy storage system comprising the above calcium ion battery or magnesium ion battery. The energy storage system comprises the calcium ion battery or the magnesium ion battery, so that the energy storage system at least has the same advantages as the calcium ion battery or the magnesium ion battery, and has higher discharge voltage and charge-discharge capacity.
The energy storage system refers to an electric power storage system mainly using a calcium ion battery or a magnesium ion battery as an electric power storage source, and includes, but is not limited to, a household energy storage system or a distributed energy storage system. For example, in a household energy storage system, electric power is stored in a calcium ion battery or a magnesium ion battery serving as a power storage source, and the electric power stored in the calcium ion battery or the magnesium ion battery is consumed as needed to enable use of various devices such as household electronic products.
In a seventh aspect, in at least one embodiment, there is provided an electric device, comprising the above-described calcium-ion battery or magnesium-ion battery. The electric equipment comprises the calcium ion battery or the magnesium ion battery, so that the electric equipment at least has the same advantages as the calcium ion battery or the magnesium ion battery, has the advantages of high discharge voltage and high charge and discharge capacity, can work for a longer time under the same discharge current, reduces the charging frequency, prolongs the service life and is more convenient to use.
The electric equipment includes, but is not limited to, an electronic device, an electric tool, an electric vehicle, and the like. The electronic device is an electronic device that performs various functions (e.g., playing music) using a calcium ion battery or a magnesium ion battery as an operation power source. The electric tool is an electric tool that uses a calcium ion battery or a magnesium ion battery as a driving power source moving part (e.g., a drill bit). The electric vehicle is an electric vehicle (including an electric bicycle, an electric automobile) that runs on a calcium ion battery or a magnesium ion battery as a driving power source, and may be an automobile (including a hybrid automobile) equipped with another driving source in addition to the calcium ion battery or the magnesium ion battery.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
The embodiment provides a calcium hexafluorophosphate electrolyte and a preparation method thereof, and the method comprises the following steps:
in an argon glove box, 0.652 g (4 mmol) NH was added4PF6With 0.2 g (4.7 mmol) of CaH2Placed in 10 ml of dimethyl carbonate DMC; stirring for 48 hours, and filtering to obtain a clear solution; degassing the clarified solution to obtain Ca (PF)6)2And (3) an electrolyte.
Taking the prepared electrolyte solution to carry out19F and31nuclear Magnetic Resonance (NMR) characterization of P. As shown in the attached figure 1 of the drawings,19f shows a doublet peak,31P shows a seven-fold peak, these are PF6 -Characteristic spectrum of ion, which shows that solution contains PF6 -Ions. Is not shown19F、31Other peak shapes of P, illustrate PF6 -Does not decompose; is not shown14N/15The characteristic peak of N indicates that ammonium hexafluorophosphate has reacted to completion.
And taking the reaction product for Mass Spectrum (MS) characterization. As shown in FIG. 2, the gaseous product contained a large amount of H2And NH3Demonstration of the reaction to form gaseous product H2And NH3. The remaining mass spectrum signals originate from the volatile molecules of the solvent dimethyl carbonate DMC and argon in the glove box.
Taking the prepared electrolyte and droppingDrying the inert substrate, and performing elemental analysis, wherein the results show that the substrate surface contains a large amount of Ca element, which indicates that the electrolyte contains a large amount of Ca2+. Additionally P, F elements are visible.
Example 2
The embodiment provides a calcium hexafluorophosphate electrolyte and a preparation method thereof, and the method comprises the following steps:
the electrolyte prepared in example 1 was dried in vacuum for 24 hours to obtain an organic liquid-free calcium hexafluorophosphate electrolyte.
And (4) taking the prepared calcium hexafluorophosphate electrolyte, and performing energy dispersive X-ray spectroscopy (EDX) characterization. As shown in FIG. 3, it was confirmed that the electrolyte contained Ca, P and F elements.
Example 3
The embodiment provides a calcium ion battery, which is prepared according to the following steps:
(1) preparing a battery cathode: and (2) mixing the mesocarbon microbeads MCMB, the conductive carbon black and the polyvinylidene fluoride PVDF into uniform slurry by using N-methylpyrrolidone NMP according to the mass ratio of 8:1: 1. And (3) uniformly coating the slurry on the surface of an aluminum foil (a negative current collector), and performing vacuum drying. And cutting the dried battery pole piece into a circular sheet with the diameter of 12mm, and compacting the circular sheet to be used as a battery cathode for standby.
(2) Preparing a battery positive electrode: the expanded graphite, the conductive carbon black and the polyvinylidene fluoride (PVDF) are mixed into uniform slurry by N-methylpyrrolidone (NMP) according to the mass ratio of 8:1: 1. And (3) uniformly coating the slurry on the surface of an aluminum foil (a positive current collector), and drying in vacuum. And cutting the dried battery pole piece into a wafer with the diameter of 10mm, and compacting the wafer to be used as a battery anode for later use.
(3) Preparing a diaphragm: the glass fiber film was cut into a circular piece having a diameter of 16mm and used as a separator.
(4) Assembling the battery: and (3) in a glove box protected by inert gas, tightly stacking the prepared cathode pole piece, diaphragm and anode pole piece in sequence, dropwise adding the electrolyte obtained in the embodiment 1 to completely soak the diaphragm, and then packaging the stacked part into a button cell shell to complete the assembly of the double-carbon calcium ion cell.
The constant-current charge and discharge curve of the calcium ion battery is shown in figure 4, the charge specific capacity of the calcium ion battery is 65.6mAh/g, and the discharge specific capacity of the calcium ion battery is 54.1 mAh/g.
Example 4
This example provides a calcium ion battery, which is different from example 3 in that the electrolyte used is: the calcium hexafluorophosphate electrolyte obtained in example 2 was dissolved in EC + DMC + EMC (volume ratio: 4:3:2) to prepare a calcium hexafluorophosphate electrolyte having a concentration of 0.6 mol/L. The rest is the same as embodiment 3, and is not described again.
Examples 5 to 65
Examples 5-65 provide methods of preparing calcium hexafluorophosphate electrolytes and electrolytes. The differences from example 1-2 were in the amount of calcium hydride used, the type of organic solvent, the length of the reaction, and the method of removing the organic solvent, as shown in Table 1.
Table 1 preparation of calcium hexafluorophosphate electrolytes and electrolytes of examples 5 to 65
Figure BDA0002033944130000151
Figure BDA0002033944130000161
Figure BDA0002033944130000171
Figure BDA0002033944130000181
Figure BDA0002033944130000191
Examples 66 to 126
Examples 66-126 provide magnesium hexafluorophosphate electrolytes and methods of preparing the electrolytes. The differences from examples 5 to 55 were in the amount of magnesium hydride used, the kind of organic solvent, the length of the reaction, and the method of removing the organic solvent, as shown in Table 2.
TABLE 2 preparation of magnesium hexafluorophosphate electrolytes and electrolytes of examples 66 to 126
Figure BDA0002033944130000201
Figure BDA0002033944130000211
Figure BDA0002033944130000221
Figure BDA0002033944130000231
Example 127-
Example 127-156 provides methods for preparing calcium and magnesium ion batteries. The difference from the examples 3-4 is that the electrolytes used in the examples 127-131 are derived from the calcium hexafluorophosphate electrolytes obtained in the examples 5-9, the electrolytes used in the examples 132-136 are 0.8mol/L calcium hexafluorophosphate electrolytes prepared from the calcium hexafluorophosphate electrolytes obtained in the examples 5-9, and the electrolytes used in the examples 137-141 are 0.5mol/L calcium hexafluorophosphate electrolytes prepared from the calcium hexafluorophosphate electrolytes obtained in the examples 5-9; the electrolytes used in the examples 142-146 are respectively magnesium hexafluorophosphate electrolytes prepared in the examples 66-70, the electrolytes used in the examples 147-151 are respectively 0.7mol/L magnesium hexafluorophosphate electrolytes prepared from the magnesium hexafluorophosphate electrolytes prepared in the examples 66-70, and the electrolytes used in the examples 152-156 are respectively 0.4mol/L magnesium hexafluorophosphate electrolytes prepared from the magnesium hexafluorophosphate electrolytes prepared in the examples 66-70.
Example 157-
Example 157-170 provides methods for preparing calcium ion batteries and magnesium ion batteries, which differ from examples 3-4 in the electrolyte and positive electrode active materials used, as shown in table 3.
TABLE 3 preparation of calcium ion battery and magnesium ion battery in example 157-170
Figure BDA0002033944130000241
Figure BDA0002033944130000251
Example 171-
Example 171-184 provides methods for preparing calcium ion batteries and magnesium ion batteries, which differ from examples 3-4 in the electrolyte used. The electrolyte is obtained by blending stock solution and blending solution, as shown in Table 4.
Table 4 preparation of calcium ion battery and magnesium ion battery in example 171-184
Figure BDA0002033944130000252
Comparative examples 1 to 4
Comparative examples 1 to 4 differ from examples 1 to 4 in that 1.63 g (10 mmol) of ammonium hexafluorophosphate was used and 25 ml of dimethyl carbonate DMC was used, and they were the same as examples 1 to 4 and thus are not repeated.
Comparative examples 5 to 8
Comparative examples 5 to 8 differ from examples 1 to 4 in that the amount of ammonium hexafluorophosphate used was 1.63 g (10 mmol), the amount of magnesium hydride used was 0.05 g (2 mmol), and the amount of dimethyl carbonate DMC used was 25 ml, and they were the same as examples 1 to 4 and thus are not repeated.
Elemental analysis is carried out on the electrolytes and electrolytes prepared in the comparative examples 1-2 and 5-6, and the results show that cations in the sample not only comprise calcium/magnesium ions, but also a large amount of ammonium ions, which indicates that the corresponding preparation method is not perfect and that the prepared electrolytes and electrolytes have low purity.
Performance test
The constant current charge and discharge test was performed on the calcium ion battery and the magnesium ion battery of the above example 127-184 and the comparative examples 3-4 and 7-8; the test results are shown in Table 5.
TABLE 5 results of tests on the performance of calcium ion battery or magnesium ion battery in example 127-156 and comparative examples 3-4 and 7-8
Figure BDA0002033944130000261
Figure BDA0002033944130000271
Figure BDA0002033944130000281
As can be seen from Table 5, the preferred embodiments (e.g., 132-136, 145, 149) of the present invention have higher initial specific discharge capacity and higher stable specific discharge capacity than the comparative examples 3-4, 7-8. Therefore, the preferred embodiments of the present invention can provide more efficient methods for preparing calcium hexafluorophosphate electrolytes and magnesium hexafluorophosphate electrolytes and calcium ion batteries and magnesium ion batteries with better performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. The preparation method of the alkaline earth metal hexafluorophosphate electrolyte is characterized by comprising the following steps of:
placing an organic solvent, ammonium hexafluorophosphate and an alkaline earth metal hydride in the same container under the protection of inert gas, and obtaining an alkaline earth metal hexafluorophosphate electrolyte after the reaction is completed; wherein the alkaline earth metal is magnesium or calcium.
2. The process of claim 1, wherein the alkaline earth metal hydride is present in excess to ensure purity of the product.
3. The production method according to claim 1, wherein the organic solvent is any one of esters, sulfones, ethers, nitriles, and ionic liquids.
4. The method according to claim 1,
the organic solvent is propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, 12-crown-4, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethyl sulfite, 12-crown-4, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-methyl acetate, dimethyl sulfite, dimethyl sulfate, 12-crown-methyl ester, sodium hydrogen carbonate, sodium hydrogen carbonate, sodium carbonate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propyl pyrrolidine-bis-trifluoromethyl sulfonyl imide salt, N-methyl-N-propyl pyrrolidine-bis-trifluoromethyl sulfonyl imide salt, N-methyl-benzyl-ethyl-methyl-benzyl-ethyl-methyl-ethyl-methyl-benzyl-ethyl-methyl-ethyl-methyl-ethyl-propyl-benzyl-ethyl-sulfonyl imide salt, ethyl-methyl-ethyl-methyl-ethyl-butyl-ethyl-methyl-butyl-ethyl-butyl-methyl-butyl-methyl-butyl-methyl-butyl-methyl-and, One or more of N-methyl-N-propyl piperidine-bis (trifluoromethyl) sulfonyl imide salt and N-methyl-N-butyl piperidine-bis (trifluoromethyl) sulfonyl imide salt.
5. An alkaline earth metal hexafluorophosphate electrolyte characterized in that,
the alkaline earth metal hexafluorophosphate electrolyte prepared by the method according to any one of claims 1 to 4.
6. A method for preparing alkaline earth metal hexafluorophosphate electrolyte is characterized in that,
the alkaline earth metal hexafluorophosphate electrolyte prepared by the method according to any one of claims 1 to 4, wherein the removal of the organic solvent or the reduction of the solubility of the calcium hexafluorophosphate or magnesium hexafluorophosphate electrolyte in the solvent gives a calcium hexafluorophosphate electrolyte or a magnesium hexafluorophosphate electrolyte.
7. A calcium ion battery comprising the calcium hexafluorophosphate electrolyte prepared by the method according to any one of claims 1 to 4.
8. A magnesium ion battery comprising the magnesium hexafluorophosphate electrolyte prepared by the method according to any one of claims 1 to 4.
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