CN116589494A - Magnesium/calcium borate, and preparation method and application thereof - Google Patents

Magnesium/calcium borate, and preparation method and application thereof Download PDF

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CN116589494A
CN116589494A CN202310236192.5A CN202310236192A CN116589494A CN 116589494 A CN116589494 A CN 116589494A CN 202310236192 A CN202310236192 A CN 202310236192A CN 116589494 A CN116589494 A CN 116589494A
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magnesium
metal
calcium
calcium borate
borohydride
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陆盈盈
李思远
程豪
张世超
张嘉辉
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ZJU Hangzhou Global Scientific and Technological Innovation Center
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ZJU Hangzhou Global Scientific and Technological Innovation Center
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • 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
    • 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

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Abstract

The application relates to the technical field of metal magnesium batteries or metal calcium batteries, and discloses a magnesium/calcium borate salt, a preparation method and application thereof. The preparation method comprises the following steps: step 1, reacting borohydride containing metal M with an alcohol compound in a solvent to prepare a first intermediate product; wherein M is a metal element with activity lower than that of metal magnesium or metal calcium; step 2, reacting the first intermediate product with magnesium metal or calcium metal in a solvent to prepare a second intermediate product; and step 3, reacting the second intermediate product with the alcohol compound used in the step 1 to obtain the magnesium/calcium borate, wherein the purity of the magnesium/calcium borate synthesized by the preparation method is high and can reach 99.85 percent at most.

Description

Magnesium/calcium borate, and preparation method and application thereof
Technical Field
The application relates to the technical field of metal magnesium batteries or metal calcium batteries, in particular to magnesium/calcium borate and a preparation method and application thereof.
Background
The lithium ion battery has wide application in the aspects of smart phones, unmanned aerial vehicles, hybrid electric vehicles and the like, but along with the development of society, the traditional lithium ion battery is difficult to meet the requirements of high-energy/high-power devices in terms of price and performance. Thus, researchers have begun to study the next generation of high energy density metal-based batteries. Because the content of magnesium (2 wt%)/calcium (3 wt%) element in the crust is far higher than that of lithium element (0.0065%), the material cost price of metal magnesium battery or metal calcium battery is far lower than that of current lithium ion battery system, but the development of both batteries is limited by electrolyte system.
The electrolyte material of magnesium or calcium comprises magnesium/calcium salt such as chlorine-containing Grignard reagent, mg (BH) 4 ) 2 And carbon boron cluster anions such as magnesium salt/calcium salt, for example, CN 114380855A discloses a salt with heteroatom-containing compound coordination anions or with heteroatom-containing compound and anions having Lewis acid alkali effect, wherein the radius of the central atom of the anions is larger, the steric hindrance of the anions bonded with the anions is smaller, so that the central atom can be further coordinated with the heteroatom-containing compound or act with Lewis acid alkali, the orbital energy level of the central atom is changed, a layer of magnesium-conducting ion SEI film containing inorganic matters is easily formed on the surface of magnesium metal in situ, reversible magnesium deposition/dissolution can be carried out, and further passivation of a magnesium cathode and side reaction of the magnesium cathode and electrolyte are inhibited. In addition, the use of magnesium chloride or grignard reagent magnesium/calcium salt can effectively improve the deposition reversibility of magnesium metal (ACS appl. Mate. Interfaces 2019,11,9062-9072), but the positive and negative electrode components and the shell of the battery are at risk of being corroded due to the existence of a large amount of free chloride ions in the electrolyte. Magnesium borohydride/calcium borohydride electrolyte salts can remove impurities on the surface of magnesium calcium metal through borohydride, so that the cycle reversibility is improved, but the anions of the magnesium/calcium borohydride electrolyte salts have strong reducibility and low oxidation resistance, so that the magnesium/calcium borohydride electrolyte salts have limited wide use.
Among them, magnesium/calcium borate is the most commonly used electrolyte for a polyvalent metal magnesium/calcium battery, and has excellent properties. On the one hand, however, the synthesis method is usually carried out by adopting magnesium borohydride as a raw material, but the synthetic raw material is difficult to obtain(e.g., magnesium borohydride was not commercially available on a commercial platform since 2020), complex synthesis, making the electrolyte system costly, e.g., mg (CB 11 H 11 F) 2 And Mg [ B (HFIP) 4 ] 2 (HFIP hexafluoroisopropoxy, -OCH (CF) 3 ) 2 ) On the other hand, the synthesis requires strict protocols and certain intermediates and end products are unstable at ambient conditions and decompose in the presence of moisture. This has hindered the further development of magnesium/calcium metal batteries and the need to develop new magnesium/calcium borate synthesis methods has been felt.
CN105047987a discloses a chloride-free electrolyte for magnesium batteries and a method of converting a magnesium electrolyte into a chloride-free electrolyte, which converts water-stable borate-type or carboborate-type anions into metal salts of alkali metals or silver by ion exchange and then into magnesium salts free of chloride by another ion exchange. However, the end point of the exchange process is difficult to judge, the risk of magnesium halide in the product is high, and meanwhile, the cost of silver element in the raw material is high, so that the industrial production and recovery are not easy.
Disclosure of Invention
Aiming at the problems of difficult source of synthetic raw materials and high preparation cost of magnesium/calcium borate, the application provides a brand-new magnesium/calcium borate preparation method, which adopts low-cost raw materials to prepare magnesium/calcium borate under mild conditions, has higher yield and purity and excellent product performance, and can be applied to a magnesium metal full battery scene of more than 3V.
In order to achieve the above purpose, the application adopts the following technical scheme:
a preparation method of magnesium/calcium borate comprises the following steps:
step 1, reacting borohydride containing metal M with an alcohol compound in a solvent to prepare a first intermediate product; wherein M is a metal element with activity lower than that of metal magnesium or metal calcium; when preparing magnesium borates, M should be less active than metallic magnesium; when preparing calcium borates, M should be less active than metallic calcium;
step 2, reacting the first intermediate product with magnesium metal or calcium metal in a solvent to prepare a second intermediate product; when preparing magnesium borate, adding metal magnesium; when preparing calcium borate, adding metal calcium;
step 3, reacting the second intermediate product with the alcohol compound used in step 1 to obtain the magnesium/calcium borate.
The preparation method of magnesium borate/calcium salt provided by the application comprises the steps of firstly synthesizing borate containing target anions through borate precursors with low metal activity, then obtaining an intermediate reaction product through substitution reaction of high-activity metal magnesium or calcium, and finally carrying out secondary reaction on a second intermediate product and an alcohol compound, and further removing residual borohydride in the second intermediate product to obtain pure target magnesium borate/calcium salt. In the prior art, magnesium borohydride is used for directly synthesizing magnesium borate, and although the steps are simpler, the solid phase method is often remained in raw materials for synthesizing the remained chloride, which can affect the purity of the product and the high-voltage application. The method can solve the defects of expensive raw materials such as magnesium borohydride or calcium borohydride, low purity and difficult purchase, and can solve the problems of low product purity and more byproducts.
In some embodiments, M is selected from any of an alkaline earth metal or a transition metal.
In some embodiments, the alkaline earth metal comprises beryllium or magnesium, and the transition metal comprises titanium, vanadium, chromium, manganese, iron, cobalt, nickel, tin, copper, or zinc.
In some embodiments, M is selected from any one of zinc, tin, beryllium, nickel, magnesium.
When preparing the calcium borate salt, magnesium borohydride can be used as a raw material, the reaction condition is mild, byproducts are few, and the product purity is high.
In some embodiments, the borohydride of metal M is zinc borohydride.
In some embodiments, the alcohol compound is a C1-C12 substituted or unsubstituted monohydric or polyhydric alcohol; wherein, when substituted, the substituents are each independently selected from halogen, such as fluorine, chlorine, bromine or iodine; preferably fluorine;
in some embodiments, the monohydric alcohol comprises at least one of the compounds represented by formula I,
R 1 -OH formula I
Wherein R is 1 Selected from the group consisting of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C7-C12 aralkyl, substituted or unsubstituted C3-C10 alicyclic hydrocarbon, substituted or unsubstituted C3-C12 heterocyclic, preferably selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C7-C10 aralkyl, wherein, when substituted, the substituents are each independently selected from the group consisting of halogen, preferably fluorine;
in some embodiments, the polyol comprises at least one of the compounds represented by formula II,
wherein R is 2 、R 3 、R 4 And R is 5 Each independently selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C7-C12 aralkyl, substituted or unsubstituted C3-C10 alicyclic hydrocarbon, substituted or unsubstituted C3-C12 heterocyclic, preferably selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C7-C10 aralkyl, wherein, when substituted, each substituent is independently selected from halogen, preferably fluorine; n is an integer between 0 and 6, for example 0, 1,2, 3, 4,5 or 6. The method comprises the steps of carrying out a first treatment on the surface of the
In the present application, the C1-C10 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or n-hexyl.
C2-C10 alkenyl includes vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1, 3-butadienyl, 3-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl or cyclohexenyl.
C2-C10 alkynyl includes ethynyl, 1-propynyl, 2-propynyl, 1 dimethyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-pentynyl, 3-pentynyl, 2-hexynyl or 3-hexynyl.
C6-C12 aryl includes phenyl, methylphenyl, ethylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, n-pentylphenyl, isopentylphenyl or n-hexylphenyl.
C7-C12 aralkyl includes phenethyl, phenylpropyl, benzyl or phenylbutyl.
Fluoro-substituted C1-C6 alkyl groups include fluoromethyl, fluoroethyl, fluoro-n-propyl, fluoroisopropyl, fluoro-n-butyl, fluoroisobutyl, fluoro-t-butyl, fluoro-n-pentyl, fluoroisopentyl or fluoro-n-hexyl, wherein fluoro means that at least one hydrogen atom in the C1-C6 alkyl group is replaced by a fluorine atom. In some embodiments, the fluoro-substituted C1-C6 alkyl is selected from the group consisting of monofluoromethyl, difluoromethyl, trifluoromethyl, difluoroethyl, trifluoroethyl, pentafluoroethyl, hexafluoroisopropyl, or perfluoro-tert-butyl.
Fluoro-substituted C6-C10 aryl groups include fluorophenyl, fluoromethylphenyl, fluoroethylphenyl, fluoroisopropylphenyl, fluoro-n-butylphenyl, fluoroisobutylphenyl, fluoro-t-butylphenyl, fluoro-n-pentylphenyl, fluoroisopentylphenyl or fluoro-n-hexylphenyl groups, wherein fluoro represents that at least one hydrogen atom of the C6-C10 aryl group is replaced by a fluorine atom. In some embodiments, the fluoro-substituted C6-C10 aryl is selected from the group consisting of monofluorophenyl, difluorophenyl, trifluorophenyl, monofluoromethylphenyl, difluoromethylphenyl, trifluoromethylphenyl, difluoroethylphenyl, trifluoroethylphenyl, pentafluoroethylphenyl, hexafluoroisopropylphenyl, or perfluoro-tert-butylphenyl.
The fluoro-substituted C7-C10 aralkyl group includes a fluorophenylethyl group, a fluorophenylpropyl group, a fluorobenzyl group or a fluorobutyl group, wherein fluoro represents that at least one hydrogen atom in the C7-C10 aralkyl group is substituted with a fluorine atom. In some embodiments, the fluoro-substituted C7-C10 aralkyl is selected from the group consisting of 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl alcohol, 2, 3-difluorobenzyl, 2, 4-difluorobenzyl, 2, 6-difluorobenzyl, 2,4, 6-trifluorobenzyl, perfluorobenzyl, 4-fluorophenylethyl, 2, 6-difluorophenethyl, perfluorophenethyl, 4-fluorophenylpropyl, 2, 6-difluorophenylpropyl, perfluorophenylpropyl, 4-fluorobutyl, 2, 6-difluorophenylbutyl, and perfluorophenylbutyl.
In some embodiments, the alcohol compound includes at least one of ethanol, trifluoroethanol, 3-fluoropropanol, 1-trifluoro-2-propanol, 4-fluorobenzyl alcohol, 2, 6-difluorobenzyl alcohol, hexafluoroisopropanol, perfluoro-t-butanol, and hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-butanediol.
In some embodiments, the solvents in step 1 and step 2 are each independently selected from ether solvents including one or more of ethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
In some embodiments, in step 1, the molar ratio of borohydride of metal M to alcohol compound is 1 (2-10); such as 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or any value therebetween.
In the reaction, the molar ratio of H in the borohydride of the metal M to hydroxyl in the alcohol compound is 1 (0.8-1.2), so that the waste of raw materials can be avoided.
In some embodiments, the amount of magnesium metal or calcium metal added is such that the metal M in the first intermediate product is fully displaced as a benchmark. In the step 2, the molar ratio of the metal magnesium or the metal calcium to the borohydride of the metal M is (1-4): 1; such as 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or any value therebetween. The slightly excessive metal magnesium/calcium can effectively replace low-activity metal elements in the solution, and the purity of the product is improved.
In some embodiments, in step 3, the molar ratio of alcohol compound to borohydride of the metal M is (0.5-2): 1; such as 1:1, 1.5:1, or any value therebetween. The alcohol compound in the limited range is added again, so that the residual borohydride in the step 1 can be further removed, and the purity of the product is improved.
In some embodiments, the reaction temperature of step 1 is 10-80 ℃ and the reaction time is 0.5-48 hours; for example, the reaction temperature is 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃ or any value therebetween, and the reaction time is 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 24h, 28h, 30h, 35h, 40h, 46h or any value therebetween. In some embodiments, no foaming occurs during the first reaction in step 1, indicating that the first reaction is complete.
In some embodiments, the reaction temperature in step 2 is 10-80 ℃ and the reaction time is 0.5-48 hours; for example, the reaction temperature is 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃ or any value therebetween, and the reaction time is 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 24h, 28h, 30h, 35h, 40h, 46h or any value therebetween. In some embodiments, in step 2, the second reaction is completed when no solid, such as black solid, is precipitated on the metal surface during the second reaction.
In some embodiments, the reaction temperature of step 3 is 10-80 ℃ and the reaction time is 0.5-24 hours. For example, the reaction temperature is 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃ or any value between them, and the reaction time is 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or any value between them.
In some embodiments, the second intermediate product produced in step 2 is filtered to remove displaced metal, followed by the reaction of step 3.
The post-treatment of the magnesium/calcium borate prepared in the step 3 comprises precipitation, centrifugation or filtration, and drying to remove the solvent, thus obtaining pure magnesium/calcium borate;
in some embodiments, the poor solvent used for the precipitation is selected from at least one of cyclohexane, n-hexane, n-pentane, pyridine; the drying temperature is preferably 45-80deg.C for 0.5-12 hr. The volume of the precipitating agent is not lower than the volume of the reaction liquid to be treated.
In some embodiments, the magnesium/calcium borate salt is produced in a yield of no less than 75% and at a purity of no less than 95%. In some embodiments, the yield is no less than 78%, 80%, 82%, 83%, 85%, or any value thereof, and the purity is no less than 96%, 97%, 98%, 99%, or any value therebetween.
The application also provides a magnesium/calcium borate which is prepared according to the preparation method of the magnesium/calcium borate. The product has high purity and excellent performance, and can be applied to a magnesium metal full battery scene with the voltage of more than 3V.
The application also provides application of the magnesium/calcium borate in a secondary battery.
In some embodiments, the positive electrode material of the secondary battery comprises one or more of copper sulfide, pyrene-4, 5,9, 10-tetraketone and quinone materials, and the negative electrode material is magnesium metal or calcium metal respectively.
In some embodiments, a secondary battery electrolyte includes the magnesium/calcium borate.
In some embodiments, the magnesium/calcium borate salt molar concentration in the electrolyte is 0.5mol/L to 3mol/L, or 0.5mol/L to 2mol/L, or 0.8mol/L to 1.5mol/L.
In some embodiments, the electrolyte comprises a solvent that is common to electrolytes in the art, including one or more of ethylene glycol dimethyl ether (DME), ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), butylene Carbonate (BC), fluoroethylene carbonate (FEC), methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), sulfolane (SF), dimethylsulfone (MSM), methylsulfone (EMS), and diethylsulfone (ESE).
In some embodiments, additives are optionally also included in the liquid electrolyte. For example, the additives may include negative electrode film-forming additives, or may include positive electrode film-forming additives, or may include additives that improve certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high temperature performance of the battery, additives that improve the low temperature performance of the battery, and the like.
The present application also provides an apparatus comprising at least one of the above secondary battery, battery module or battery pack.
In some embodiments, the apparatus includes, but is not limited to: electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric storage systems, and the like. To meet the device's demand for high power and high energy density, a battery pack or battery module may be employed.
In other embodiments, the device may be a cell phone, tablet, notebook, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Compared with the prior art, the application has the following beneficial effects:
the preparation method of magnesium/calcium borate provided by the application synthesizes borate containing target anions through borate precursors with low metal activity (such as Zn, ni, sn, be and the like), and then obtains the target borate through substitution reaction of high-activity metal magnesium/calcium.
Drawings
FIG. 1 shows liquid nuclear magnetic NMR spectra of example 1 and example 7.
FIG. 2 is an elemental purity analysis ICP chart of example 1.
FIG. 3 shows liquid nuclear magnetic NMR spectra of example 2 and example 8.
FIG. 4 shows liquid nuclear magnetic NMR spectra of example 3 and example 9.
FIG. 5 is a liquid nuclear magnetic NMR spectrum of example 4 and example 10.
FIG. 6 shows the coulombic efficiency of the organic magnesium borate salt electrolytes synthesized in examples 1-4.
FIG. 7 shows the coulombic efficiency of the organic calcium borate salt electrolytes synthesized in examples 7-12.
FIG. 8 is a 3V full cell cycle life and graph of the organic magnesium borate salt electrolyte synthesized in example 1.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
Example 1
Zinc borohydride Zn (BH 4 ) 2 And hexafluoroisopropanol at 1:4.5 molar ratio into ethylene glycol dimethyl ether solution, and reacting at 25deg.C for 6 hr until no bubbles are generated, and adding metal magnesium (molar ratio, mg: zn (BH 4 ) 2 =1.5:1) is put into the solution for reaction until no black object is separated out from the surface of magnesium metal, and metallic zinc is removed by filtration to obtain a reaction solution; to this was added hexafluoroisopropanol (molar ratio, hexafluoroisopropanol: zn (BH 4 ) 2 =1:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Mg [ OBHFIP ]]2。
The nuclear magnetic resonance spectrum of the liquid is shown in figure 1, the purity of the product is high, no obvious impurity is found, the yield is 79.3% by ICP element analysis (table 1, figure 2) and calculation, the purity is 99.75%, and the purity and yield are summarized in table 1.
Example 2
Zinc borohydride and perfluoro-tert-butanol were reacted at 1:4 molar ratio, and fully reacting for 6 hours at 25 ℃ until no bubbles are generated. Then the metal magnesium (molar ratio Mg: zn (BH) 4 ) 2 =1.5:1) is put into the reaction solution to react until no black substance is separated out from the surface of magnesium metal, metallic zinc is removed by filtration,obtaining a reaction solution; to which perfluoro-tert-butanol (molar ratio: perfluoro-tert-butanol: zn (BH) 4 ) 2 =1:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane and obtain the target salt Mg [ OBpftb ]]2, the yield and purity are shown in Table 1.
Example 3
Zinc borohydride and ethanol were combined at 1:4 molar ratio into ethylene glycol dimethyl ether solution, and reacting at 25deg.C for 6 hr until no bubble is generated to obtain precursor, and adding metal magnesium (molar ratio Mg: zn (BH) 4 ) 2 =1.5:1) was put into the solution to react until no black substance was precipitated on the magnesium metal surface, metallic zinc was removed by filtration to obtain a reaction solution, to which ethanol (molar ratio: ethanol Zn (BH) 4 ) 2 =1.5:1) to bubble free, the post-reaction solution was precipitated by adding 2 volumes of cyclohexane, filtered and dried to remove the cyclohexane target salt Mg [ OBEt]2, the yield and purity are shown in Table 1.
Example 4
Zinc borohydride and trifluoroethanol were combined at 1:4 molar ratio into ethylene glycol dimethyl ether solution, and reacting at 25deg.C for 6 hr until no bubble is generated to obtain precursor, and adding metal magnesium (molar ratio Mg: zn (BH) 4 ) 2 =1.5:1) was added to the solution to react until no black substance was precipitated on the magnesium metal surface, and metallic zinc was removed by filtration to obtain a reaction solution, to which trifluoroethanol (molar ratio: trifluoroethanol Zn (BH) 4 ) 2 =1.5:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Mg [ obtge ]]2. The yields and purities are shown in Table 1.
Example 5
Zinc borohydride and 1, 1-trifluoro-2-propanol were combined in an amount of 1:4.5 molar ratio into ethylene glycol dimethyl ether solution, and reacting at 25deg.C for 6 hr until no bubble is generated to obtain precursor, and adding metal magnesium (molar ratio Mg: zn (BH) 4 ) 2 =1.5:1) is put into the solution for reaction until no black substance is precipitated on the surface of magnesium metal, and metallic zinc is removed by filtration to obtain a reaction solution, and the reaction solution is added into the reaction solution1, 1-trifluoro-2-propanol (molar ratio: 1, 1-trifluoro-2-propanol: zn (BH) 4 ) 2 =1.5:1) to bubble free, adding 2 volumes of cyclohexane to the solution after reaction to precipitate, filtering and drying to remove cyclohexane to obtain the target salt Mg [ OBtf1p ]]2. The yields and purities are shown in Table 1.
Example 6
Zinc borohydride and 3-fluoropropanol were combined in an amount of 1:4.5 molar ratio into ethylene glycol dimethyl ether solution, and reacting at 25deg.C for 6 hr until no bubbles are generated, and adding metal magnesium (molar ratio Mg: zn (BH) 4 ) 2 =1.5:1) was added to the solution to react until no black substance was precipitated on the magnesium metal surface, and metallic zinc was removed by filtration to obtain a reaction solution, to which 3-fluoropropanol (molar ratio: 3-fluoropropanol Zn (BH) 4 ) 2 =1:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Mg [ OBtf2p ]]2. The yields and purities are shown in Table 1.
Example 7
Zinc borohydride Zn (BH 4) 2 And hexafluoroisopropanol at 1: the mixture was poured into a glycol dimethyl ether solution at a molar ratio of 4.5, and the mixture was allowed to react at 25℃for 6 hours until no bubbles were formed. Then the metal calcium (molar ratio, ca: zn (BH) 4 ) 2 =1.5:1) was added to the solution to react until no black substance was precipitated on the surface of the calcium metal, and metallic zinc was removed by filtration to obtain a reaction solution, to which hexafluoroisopropanol (molar ratio: hexafluoroisopropanol Zn (BH) 4 ) 2 =1:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Ca [ OBHFIP ]] 2 . The yields and purities are shown in Table 1.
Example 8
Zinc borohydride and perfluoro-tert-butanol were reacted at 1:4 molar ratio, and fully reacting for 6 hours at 25 ℃ until no bubbles are generated. Then, metallic calcium (molar ratio Ca: zn (BH) 4 ) 2 =1.5:1) is put into the solution for reaction until no black substance is precipitated on the surface of the calcium metal, and metallic zinc is removed by filtration to obtain a reaction solution, and the reaction solution is added toWherein perfluoro-tert-butanol (molar ratio: perfluoro-tert-butanol: zn (BH) 4 ) 2 =1:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Ca [ OBpftb ]]2. The yields and purities are shown in Table 1.
Example 9
Zinc borohydride and ethanol were combined at 1:4 molar ratio, and fully reacting for 6 hours at 25 ℃ until no bubbles are generated. Then, metallic calcium (molar ratio Ca: zn (BH) 4 ) 2 =1.5:1) was put into the solution to react until no black substance was precipitated on the surface of the calcium metal, and metallic zinc was removed by filtration to obtain a reaction solution, to which ethanol (molar ratio: ethanol Zn (BH) 4 ) 2 =1.5:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Ca [ OBEt ]]2. The yields and purities are shown in Table 1.
Example 10
Zinc borohydride and trifluoroethanol were combined at 1:4 molar ratio, and fully reacting for 6 hours at 25 ℃ until no bubbles are generated. Then, metallic calcium (molar ratio Ca: zn (BH) 4 ) 2 =1.5:1) was added to the solution to react until no black substance was precipitated on the surface of the calcium metal, and metallic zinc was removed by filtration to obtain a reaction solution, to which trifluoroethanol (molar ratio: trifluoroethanol Zn (BH) 4 ) 2 =1.5:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Ca [ obtge ]]2. The yields and purities are shown in Table 1.
Example 11
Zinc borohydride and 1, 1-trifluoro-2-propanol were combined in an amount of 1: the mixture was poured into a glycol dimethyl ether solution at a molar ratio of 4.5, and the mixture was allowed to react at 25℃for 6 hours until no bubbles were formed. Then, metallic calcium (molar ratio Ca: zn (BH) 4 ) 2 =1.5:1) was put into solution for reaction until no black material was precipitated on the calcium metal surface. Filtering to remove zinc metal to obtain a reaction solution, and adding 1, 1-trifluoro-2-propanol (molar ratio: 1, 1-trifluoro)-2-propanol Zn (BH) 4 ) 2 =1.5:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Ca [ OBtf1p ]]2. The yields and purities are shown in Table 1.
Example 12
Zinc borohydride and 3-fluoropropanol were combined in an amount of 1: the mixture was poured into a glycol dimethyl ether solution at a molar ratio of 4.5, and the mixture was allowed to react at 25℃for 6 hours until no bubbles were formed. Then, metallic calcium (molar ratio Ca: zn (BH) 4 ) 2 =1.5:1) was added to the solution to react until no black substance was precipitated on the surface of the calcium metal, and metallic zinc was removed by filtration to obtain a reaction solution, to which 3-fluoropropanol (molar ratio: 3-fluoropropanol Zn (BH) 4 ) 2 =1:1) until no bubbles, adding 2 times volume of cyclohexane into the solution after the reaction to precipitate, filtering and drying to remove cyclohexane, and obtaining the target salt Ca [ OBtf2p ]]2. The yields and purities are shown in Table 1.
Comparative example 1
The finished bis (trifluoromethylsulfonyl) imide magnesium Mg (TFSI) 2, a prior art product, was purchased from the microphone reagent.
Comparative example 2
The finished bis (trifluoromethylsulfonyl) calcium imide Ca (TFSI) 2 of the prior art is purchased from the microphone reagent.
Comparative example 3
Finished magnesium borohydride Mg (BH 4 ) 2 Purchased from microphone reagent.
The liquid nuclear magnetic patterns of Mg [ OBpftb ]2 and Ca [ OBpftb ]2 prepared in examples 2 and 8 are shown in FIG. 3, the liquid nuclear magnetic patterns of Mg [ OBEt ]2 and Ca [ OBEt ]2 prepared in examples 3 and 9 are shown in FIG. 4, and the liquid nuclear magnetic patterns of Mg [ OBtge ]2 and Ca [ OBtge ]2 prepared in examples 4 and 10 are shown in FIG. 5, and the purity of the product is high as seen from each figure, and no by-product is produced.
Application example
1. Electrolyte system preparation
The magnesium/calcium salt obtained in examples 1 to 12 was added to a glyme solution at a water oxygen content of less than 0.01ppm, and slowly added to a concentration of 0.5M (mol/L) of the magnesium/calcium salt, to obtain the corresponding example electrolyte.
Under the condition that the water oxygen content is less than 0.01ppm, slowly adding Mg (TFSI) 2 or Ca (TFSI) 2 to 0.5M into ethylene glycol dimethyl ether, and uniformly stirring to obtain the comparative electrolyte.
2. Battery preparation and decomposition voltage test
The magnesium-copper coulomb efficiency test method comprises the following steps: and adopting an Mg/Cu lithium-free negative electrode battery assembly test, assembling according to the sequence of a negative electrode shell, an elastic sheet, a gasket, a lithium sheet, a GFD glass fiber diaphragm, a copper sheet and a positive electrode shell, adding 60-100 microliters of electrolyte into each battery to wet the diaphragm, and finally packaging the battery. The battery was pre-charged and discharged at a current density of 0.1mA/cm2 at a voltage of 0-2V, and then deposited at a current density of 0.67mA/cm2 for 10 minutes at a voltage of 0-1.4V, and then at a current density of 0.67mA/cm 2 Lithium stripping is performed until the voltage is higher than 1.4V, and coulombic efficiency is calculated.
Coulombic efficiency = discharge capacity/charge capacity
The method for testing the calcium copper coulomb efficiency comprises the following steps: and adopting Ca/Cu lithium-free negative electrode battery assembly test, assembling according to the sequence of a negative electrode shell, an elastic sheet, a gasket, a lithium sheet, a GFD glass fiber diaphragm, a copper sheet and a positive electrode shell, adding 60-100 microliters of electrolyte into each battery to wet the diaphragm, and finally packaging the battery. The battery is firstly at 0.1mA/cm under the voltage interval of 0-2V 2 Pre-charging and discharging at a current density of 2mA/cm in a voltage range of 0-2V 2 Is deposited for 3 minutes at a current density of 2mA/cm 2 Lithium stripping is performed until the voltage is higher than 2V, and coulombic efficiency is calculated.
Coulombic efficiency = discharge capacity/charge capacity
The 3V magnesium metal full battery assembly method comprises the following steps: preparing a positive electrode plate: the positive electrode active material pyrene-4, 5,9, 10-tetraketone, conductive carbon black and binder polyvinylidene fluoride (PVDF) are mixed according to the weight ratio of 3:5:2 thoroughly stirring and mixing in a proper amount of N-methyl pyrrolidone (NMP) to form uniform positive electrode slurry; coating the positive electrode slurry on a positive electrode current collector Al foil to obtain a positive electrode plate;
preparing a negative electrode plate: commercial 30 micron magnesium poise; preparation of a separation film: 675 microns GF-D glass fiber diaphragm is selected; preparation of magnesium metal battery: and sequentially stacking the positive electrode plate, the diaphragm and the negative electrode plate, enabling the diaphragm to be positioned between the positive electrode plate and the negative electrode plate to play a role in isolation, adding 60-100 microliters of electrolyte into each battery to wet the diaphragm, and finally packaging the battery.
The 3V magnesium metal full battery test method comprises the following steps: the assembled battery is hung on a blue electric test frame, a voltage circulation interval is set to be 1.0V-3.2V, the theoretical specific capacity is 350mAh/g, and charge and discharge circulation is carried out at 4C multiplying power. The results of the tests are shown in Table 1, and FIG. 6 shows the coulombic efficiency of the organic magnesium borate salt electrolytes of examples 1-4, FIG. 7 shows the coulombic efficiency of the organic calcium borate salt electrolytes synthesized in examples 7-12, and FIG. 8 shows the 3V full cell cycle life and curve of the organic magnesium borate salt electrolytes synthesized in example 1. The product prepared by the preparation method of the application has excellent performance, in particular to Mg [ OBHFIP ]2 and Mg [ OBpftb ]2 of examples 1-2, high coulomb efficiency and long service life for 3V magnesium metal batteries.
TABLE 1
As can be seen from Table 1, the yields of magnesium borate/calcium salt obtained by the preparation method of the application are all above 75%, and the purities are all above 95%, which is far higher than that of commercial magnesium borohydride of comparative example 3. While all comparative examples had higher cycle coulombic efficiency and number of turns than commercial comparative examples 1,2.
While certain exemplary embodiments of the application have been illustrated and described, the application is not limited to the disclosed embodiments. Rather, one of ordinary skill in the art will recognize that certain modifications and changes may be made to the described embodiments without departing from the spirit and scope of the present application as described in the appended claims.

Claims (10)

1. A method for preparing magnesium/calcium borate, which is characterized by comprising the following steps:
step 1, reacting borohydride containing metal M with an alcohol compound in a solvent to prepare a first intermediate product; wherein M is a metal element with activity lower than that of metal magnesium or metal calcium;
step 2, reacting the first intermediate product with magnesium metal or calcium metal in a solvent to prepare a second intermediate product;
step 3, reacting the second intermediate product with the alcohol compound used in step 1 to obtain the magnesium/calcium borate.
2. The method for preparing magnesium/calcium borate according to claim 1, wherein the metal M is selected from any one of zinc, tin, beryllium, nickel, magnesium;
and/or the alcohol compound is a C1-C12 substituted or unsubstituted monohydric alcohol or polyhydric alcohol; wherein, when substituted, the substituents are each independently selected from halogen.
3. The method for preparing magnesium/calcium borate according to claim 1, wherein the alcohol compound comprises at least one of ethanol, trifluoroethanol, 3-fluoropropanol, 1-trifluoro-2-propanol, 4-fluorobenzyl alcohol, 2, 6-difluorobenzyl alcohol, hexafluoroisopropanol, perfluoro-t-butanol, and hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-butanediol.
4. The method for preparing magnesium/calcium borate according to claim 1, wherein the solvents in the step 1 and the step 2 are each independently selected from ether solvents including one or more of ethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
5. The method for preparing magnesium/calcium borate according to claim 1, wherein in the step 1, the molar ratio of borohydride of the metal M to the alcohol compound is 1 (2-10);
and/or in step 2, the molar ratio of the metal magnesium or the metal calcium to the borohydride of the metal M is (1-4): 1;
and/or in step 3, the molar ratio of the alcohol compound to the borohydride of the metal M is (0.1-2): 1.
6. The method for preparing magnesium/calcium borate according to claim 1, wherein the reaction temperature of step 1 is 10-80 ℃ and the reaction time is 0.5-48 hours;
and/or the reaction temperature in the step 2 is 10-80 ℃ and the reaction time is 0.5-48h;
and/or the reaction temperature in the step 3 is 10-80 ℃ and the reaction time is 0.5-24h.
7. The method for preparing magnesium/calcium borate according to claim 1, wherein the second intermediate product obtained in the step 2 is filtered and then subjected to the reaction of the step 3;
and/or the post-treatment of the magnesium/calcium borate prepared in the step 3 comprises precipitation, centrifugation or filtration and drying, wherein the precipitating agent is at least one selected from cyclohexane, n-hexane, n-pentane and pyridine.
8. The method for producing magnesium/calcium borate according to claim 1, wherein the yield of the magnesium/calcium borate is not less than 75% and the purity is not less than 95%.
9. Magnesium/calcium borate prepared according to the process of any one of claims 1 to 8.
10. Use of the magnesium/calcium borate according to claim 9 in a secondary battery.
CN202310236192.5A 2023-03-13 2023-03-13 Magnesium/calcium borate, and preparation method and application thereof Pending CN116589494A (en)

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