CN120136908A - A complex for replenishing lithium or sodium, a non-aqueous electrolyte containing the complex, and a battery - Google Patents
A complex for replenishing lithium or sodium, a non-aqueous electrolyte containing the complex, and a battery Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a complex for supplementing lithium or sodium, wherein the chemical general formula of the complex is as follows: Wherein R is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, vinyl, allyl, ethynyl, phenyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, trifluoroethyl or 4-fluorophenyl, A is BF 3 or PF 5, B is S or C, and M is Li or Na. Compared with the prior art, the complex provided by the invention has higher concentration in the organic solvent, and is beneficial to high-capacity lithium supplementation, so that the performances of gram capacity, long-cycle capacity retention rate, capacity recovery rate after high-temperature storage and the like of a lithium ion battery or a sodium ion battery using the complex are obviously improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a complex for supplementing lithium or sodium and a nonaqueous electrolyte and a battery containing the complex.
Background
At present, lithium (sodium) ion batteries are commercialized, and as electrode materials and interfaces are accompanied by irreversible side reactions in the formation stage and the subsequent cycle process, loss of lithium/sodium ions and attenuation of battery capacity are caused. Industry has therefore attempted to solve this problem by supplementing lithium (sodium).
The more mature lithium (sodium) supplementing modes at present include:
1) Adding a lithium (sodium) source (e.g., lithium powder, sodium powder, etc.) to the negative electrode;
2) Adding a lithium (sodium) source (e.g., lithium ferrate, etc.) to the positive electrode;
3) A lithium (sodium) source (e.g., lithium triflate, etc.) is added to the electrolyte.
The lithium supplementing process through the negative electrode has high requirements, high cost and poor safety, and is not beneficial to large-scale production. The lithium/sodium is supplemented by the positive electrode, and byproducts remain in the battery, so that the energy density of the battery is reduced, holes are easily formed in the positive electrode, and the battery cyclicity is reduced. The lithium trifluoromethylsulfinate is added into the electrolyte, and is converted into gas through an electrochemical oxidation-reduction process, the lithium supplementing agent is low in cost and easy to obtain, byproducts are not remained in a battery system, but the solubility of the lithium trifluoromethylsulfinate in the electrolyte is poor, and the lithium supplementing effect is relatively limited.
In view of the above, the present invention aims to provide a complex for lithium or sodium supplementation, which can perform a good lithium supplementation effect in a lithium ion battery or a sodium ion battery and prolong the service life of the battery, and a nonaqueous electrolyte and a battery comprising the complex.
Disclosure of Invention
Aiming at the defects of the prior art, the complex for supplementing lithium or sodium is provided, and can play a good role in supplementing lithium in a lithium ion battery or a sodium ion battery, so that the service life of the battery is prolonged.
In order to solve the problems, the technical scheme of the invention is as follows:
a complex for lithium or sodium supplementation, the complex having the chemical formula:
Wherein R is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, vinyl, allyl, ethynyl, phenyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, trifluoroethyl or 4-fluorophenyl;
a is BF 3 or PF 5;
B is S or C;
m is Li or Na.
As an improvement of the complex for supplementing lithium or sodium, the preparation method of the complex at least comprises the following steps:
firstly, weighing R-group substituted sodium sulfinate or sodium carboxylate, adding concentrated sulfuric acid, stirring, distilling to obtain R-group substituted sulfinic acid or carboxylic acid, then adding water and lithium hydroxide, and drying after the neutralization reaction is finished to obtain R-group substituted lithium sulfinate compound or lithium carboxylate compound, wherein R-group is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, vinyl, allyl, ethynyl, phenyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, trifluoroethyl or 4-fluorophenyl;
Step two, adding the lithium sulfinate compound or the lithium carboxylate compound obtained in the step one into a reaction bottle, then adding an organic solvent, stirring, controlling the temperature, then adding a fluorine boron compound or a phosphorus pentafluoride compound, and stirring;
And step three, filtering to remove insoluble matters to obtain a complex solution.
As an improvement of the complex for lithium or sodium supplementation of the present invention, the organic solvent in the second step is at least one of methyl ethyl carbonate, dimethyl carbonate, ethylene carbonate, ethyl propionate and propyl propionate.
The invention also provides a non-aqueous electrolyte which comprises conductive sodium salt or conductive lithium salt, a non-aqueous organic solvent and an additive, and is characterized by further comprising the lithium-supplementing or sodium-supplementing complex.
As an improvement of the nonaqueous electrolyte, the mass percentage of the complex in the electrolyte is 0.1% -40%.
As an improvement of the nonaqueous electrolyte, the mass percentage of the complex in the electrolyte is 0.3% -30%.
As an improvement of the nonaqueous electrolyte of the present invention, the conductive lithium salt includes at least one of LiBF4、LiPF6、LiPO2F2、LiAsF6、LiClO4、LiSO3CF3、LiB(C2O4)2、LiBF2C2O4、LiN(SO2CF3)2、LiN(SO2F)2 and the conductive sodium salt includes at least one of NaBF4、NaPF6、NaPO2F2、NaAsF6、NaClO4、NaSO3CF3、NaB(C2O4)2、NaBF2C2O4、NaN(SO2CF3)2、NaN(SO2F)2;
The nonaqueous organic solvent is at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate;
the additive is at least one of ethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, succinonitrile, adiponitrile, 1, 2-cyanoethoxyethane and hexane-tricarbonitrile.
The invention also provides a battery, which comprises a positive plate, a negative plate, a diaphragm and the non-aqueous electrolyte.
As an improvement of the battery of the present invention, both the positive electrode sheet and the negative electrode sheet contain an active material, a conductive agent, a current collector, and a binder that binds the active material and the conductive agent to the current collector;
The positive plate comprises a positive active material capable of reversibly intercalating/deintercalating lithium or sodium ions, the positive active material is a lithium or sodium composite metal oxide, and the metal oxide comprises oxides of nickel, cobalt, manganese elements and any proportion combination thereof;
The negative electrode sheet comprises a negative electrode active material capable of receiving or releasing lithium or sodium ions, wherein the negative electrode active material comprises lithium or sodium metal, lithium or sodium alloy, crystalline carbon, amorphous carbon, carbon fiber, hard carbon and soft carbon, the crystalline carbon comprises natural graphite, graphitized coke, graphitized MCMB and graphitized mesophase pitch carbon fiber, and the lithium or sodium alloy comprises lithium or sodium and aluminum, zinc, silicon, tin, gallium and antimony metal.
As an improvement of the battery, the positive electrode active material further comprises at least one of chemical elements including Mg, al, ti, sn, V, ge, ga, B, zr, cr, fe, sr and rare earth elements, and further comprises a polyanion lithium compound LiM x(PO4)y, wherein M is Ni, co, mn, fe, ti, V, x is more than or equal to 0 and less than or equal to 5, and y is more than or equal to 0 and less than or equal to 5.
Compared with the prior art, the complex provided by the invention has higher concentration in the organic solvent, and is beneficial to high-capacity lithium supplementation, so that the performances of gram capacity, long-cycle capacity retention rate, capacity recovery rate after high-temperature storage and the like of a lithium ion battery or a sodium ion battery using the complex are obviously improved.
Drawings
FIG. 1 is a cyclic voltammetry test curve of a lithium triflate boron trifluoride complex battery in example 2-1 of the present invention.
Detailed Description
The invention provides a complex for supplementing lithium or sodium, which has a chemical general formula:
Wherein R is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, vinyl, allyl, ethynyl, phenyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, trifluoroethyl or 4-fluorophenyl;
A is BF 3 or PF 5, B is S or C, and M is Li or Na.
Wherein, the preparation method of the complex at least comprises the following steps:
firstly, weighing R-group substituted sodium sulfinate or sodium carboxylate, adding concentrated sulfuric acid, stirring, distilling to obtain R-group substituted sulfinic acid or carboxylic acid, then adding water and lithium hydroxide, and drying after the neutralization reaction is finished to obtain R-group substituted lithium sulfinate compound or lithium carboxylate compound, wherein R-group is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, vinyl, allyl, ethynyl, phenyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, trifluoroethyl or 4-fluorophenyl;
Step two, adding the lithium sulfinate compound or the lithium carboxylate compound obtained in the step one into a reaction bottle, then adding an organic solvent, stirring, controlling the temperature, then adding a fluorine boron compound or a phosphorus pentafluoride compound, and stirring;
And step three, filtering to remove insoluble matters to obtain a complex solution.
Wherein the organic solvent in the second step is at least one of methyl ethyl carbonate, dimethyl carbonate, ethylene carbonate, ethyl propionate and propyl propionate.
The invention also provides a non-aqueous electrolyte which comprises conductive sodium salt or conductive lithium salt, a non-aqueous organic solvent and an additive, and is characterized by further comprising the lithium-supplementing or sodium-supplementing complex.
Wherein the mass percentage of the complex in the electrolyte is 0.1% -40%, preferably 0.3% -30%.
The conductive lithium salt comprises at least one of LiBF4、LiPF6、LiPO2F2、LiAsF6、LiClO4、LiSO3CF3、LiB(C2O4)2、LiBF2C2O4、LiN(SO2CF3)2、LiN(SO2F)2, the conductive sodium salt comprises at least one of NaBF4、NaPF6、NaPO2F2、NaAsF6、NaClO4、NaSO3CF3、NaB(C2O4)2、NaBF2C2O4、NaN(SO2CF3)2、NaN(SO2F)2;
the nonaqueous organic solvent is at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate;
The additive is at least one of ethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, succinonitrile, adiponitrile, 1, 2-cyanoethoxyethane and hexane tri-nitrile.
The invention also provides a battery, which comprises a positive plate, a negative plate, a diaphragm and the non-aqueous electrolyte.
As an improvement of the battery of the present invention, both the positive electrode sheet and the negative electrode sheet contain an active material, a conductive agent, a current collector, and a binder that binds the active material and the conductive agent to the current collector;
The positive plate comprises a positive electrode active material capable of reversibly intercalating/deintercalating lithium or sodium ions, the positive electrode active material is a composite metal oxide of lithium or sodium, and the metal oxide comprises oxides of nickel, cobalt, manganese elements and any proportion combination thereof;
The negative electrode sheet comprises a negative electrode active material capable of accepting or releasing lithium or sodium ions, wherein the negative electrode active material comprises lithium or sodium metal, lithium or sodium alloy, crystalline carbon, amorphous carbon, carbon fiber, hard carbon and soft carbon, the crystalline carbon comprises natural graphite, graphitized coke, graphitized MCMB and graphitized mesophase pitch carbon fiber, and the lithium or sodium alloy comprises lithium or sodium and aluminum, zinc, silicon, tin, gallium and antimony metal.
The positive electrode active material further comprises at least one of chemical elements including Mg, al, ti, sn, V, ge, ga, B, zr, cr, fe, sr and rare earth elements, and further comprises a polyanion lithium compound LiM x(PO4)y, wherein M is Ni, co, mn, fe, ti, V, x is more than or equal to 0 and less than or equal to 5, and y is more than or equal to 0 and less than or equal to 5.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application. Although the following examples only show some of the substances, it should be emphasized that all the substances listed in the present application are applicable.
The experimental methods used in the embodiment of the application are conventional methods unless otherwise specified.
In the examples and comparative examples described below, all starting materials were prepared synthetically or were commercially available by conventional methods unless otherwise specified.
Example 1-1
The embodiment provides a preparation method of a complex for lithium supplementation, which comprises the following chemical principles:
A1000 mL reaction flask was charged with 70g (0.5 mol) of lithium trifluoromethylsulfinate, 243 g of dimethyl carbonate, 34g (0.5 mol) of boron trifluoride was introduced thereinto, the temperature was controlled at 25℃and the reaction was stirred for 8 hours. Filtration under reduced pressure gave a clear solution, 104g of a product, in which the concentration of lithium triflate boron trifluoride complex was 30%.
The preparation method of the lithium trifluoromethylsulfinate comprises the following steps:
and weighing sodium trifluoromethylsulfinate, adding concentrated sulfuric acid, stirring, distilling to obtain the trifluoromethylsulfinic acid, adding water and lithium hydroxide, and drying after the neutralization reaction is finished to obtain the lithium trifluoromethylsulfinate.
Examples 1 to 2
The embodiment provides a preparation method of a complex for lithium supplementation, which comprises the following chemical principles:
A1000 mL reaction flask was charged with 70g (0.5 mol) of lithium trifluoromethylsulfinate, 214g of diethyl carbonate was added thereto, 63g (0.5 mol) of phosphorus pentafluoride was introduced thereinto, the temperature was controlled at 25℃and the reaction was stirred for 8 hours. Filtration under reduced pressure gave 113g of a clear solution product, in which the concentration of lithium trifluoromethylsulfinate phosphorus pentafluoride complex was 30%.
The preparation method of the lithium trifluoromethylsulfinate comprises the following steps:
and weighing sodium trifluoromethylsulfinate, adding concentrated sulfuric acid, stirring, distilling to obtain the trifluoromethylsulfinic acid, adding water and lithium hydroxide, and drying after the neutralization reaction is finished to obtain the lithium trifluoromethylsulfinate.
Examples 1 to 3
The embodiment provides a preparation method of a complex for lithium supplementation, which comprises the following chemical principles:
a1000 mL reaction flask was charged with 60g (0.5 mol) of lithium trifluoroacetate, 243 g of dimethyl carbonate was added, 34g (0.5 mol) of boron trifluoride was introduced, the temperature was controlled at 25℃and the reaction was stirred for 8 hours. Filtration under reduced pressure gave a clear solution, which gave 94g of a product having a lithium trifluoroacetate boron trifluoride complex concentration of 30%.
The preparation method of the lithium trifluoroacetate comprises the following steps:
And weighing sodium trifluoroacetate, adding concentrated sulfuric acid, stirring, distilling to obtain trifluoroacetic acid, adding water and lithium hydroxide, and drying after the neutralization reaction is finished to obtain lithium trifluoroacetate.
Examples 1 to 4
The embodiment provides a preparation method of a complex for lithium supplementation, which comprises the following steps:
Firstly, weighing sodium phenylsulfinate, adding concentrated sulfuric acid, stirring, distilling to obtain phenylsulfinic acid, then adding water and lithium hydroxide, and drying after the neutralization reaction is finished to obtain lithium phenylsulfinate;
step two, adding the lithium phenylsulfinate obtained in the step one into a reaction bottle, then adding ethyl propionate, stirring, controlling the temperature, adding a phosphorus pentafluoride compound, and stirring for 6 hours at 35 ℃;
And step three, filtering to remove insoluble matters to obtain a complex solution.
Examples 1 to 5
The embodiment provides a preparation method of a complex for lithium supplementation, which comprises the following steps:
Firstly, weighing sodium isopropylsulfinate, adding concentrated sulfuric acid, stirring, distilling out isopropylsulfinic acid, then adding water and lithium hydroxide, and drying after the neutralization reaction is finished to obtain lithium isopropylsulfinate;
Step two, adding the lithium isopropylsulfinate obtained in the step one into a reaction bottle, then adding methyl ethyl carbonate, stirring, controlling the temperature, adding a phosphorus pentafluoride compound, and stirring for 4 hours at the temperature of 30 ℃;
And step three, filtering to remove insoluble matters to obtain a complex solution.
Example 2-1
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
(1) Preparation of electrolyte
In a glove box in argon atmosphere (H 2 O <1 ppm), preparing electrolyte with the following formula of 12.5% of LiPF 6,2％VC,0.5％PS,5％CF3SO2Li·BF3, EC/DMC/EMC=40/40/20, and fully and uniformly stirring to obtain the lithium secondary battery electrolyte (free acid <15ppm, water content <10 ppm).
(2) Preparation of positive electrode plate
And (3) dissolving polyvinylidene fluoride (PVDF) with the mass percentage of 3% in NMP solution, adding 94% of lithium iron phosphate, 2% of conductive agent and 1% of dispersing agent into the solution, uniformly mixing, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain the positive plate. Other cathode materials LiMn2O4、LiCoO2、LiNi0.5Co0.3Mn0.2、LiNi0.3Co0.3Mn0.3 were prepared in the same manner.
(3) Preparation of negative electrode plate
And (3) dissolving the SBR binder with the mass percentage of 4% and the CMC thickener with the mass percentage of 1% in an aqueous solution, adding the graphite with the mass percentage of 95% into the solution, uniformly mixing, coating the mixed slurry on two sides of a copper foil, and drying and rolling to obtain the negative electrode plate.
(4) Manufacturing of lithium ion battery
And (3) preparing the prepared positive pole piece, negative pole piece and isolating film into a square battery core in a winding mode, packaging by adopting a polymer, pouring the prepared electrolyte, and preparing the lithium ion battery through processes such as formation and the like.
(5) Battery performance test
And (3) cyclic voltammetry testing conditions, namely, using the coated positive electrode material, selecting lithium as a counter electrode, assembling the positive electrode material into a button cell, testing a CV curve by using an electrochemical workstation, and scanning the open-circuit potential of-4.6V and the scanning speed of 0.1mV/s.
The cycle test condition comprises that the battery is charged and discharged at 1/1C, the battery is charged and discharged at 1C once under the normal temperature, the battery is fully charged at 1C, the battery is stored at high temperature, and the taken-out battery is discharged at 1C after the battery is completely cooled.
Examples 2-2 to 2-6 and comparative examples 3-1 to 3-7 the same procedure as in example 2-1 was followed except for the following parameters.
TABLE 1 examples 2-6 and comparative examples 3-1-3-7
Example 4-1
The embodiment provides a preparation method of a sodium ion battery, which comprises the following steps:
(1) Preparation of electrolyte
In a glove box in argon atmosphere (H 2 O <1 ppm), preparing electrolyte with the following formula of 12.5% NaPF 6,2％VC,0.5％PS,5％CF3SO2Na·BF3, PC/DMC/EMC=40/40/20, and fully and uniformly stirring to obtain the sodium secondary battery electrolyte (free acid <15ppm, water content <10 ppm).
(2) Preparation of positive electrode plate
And (3) dissolving polyvinylidene fluoride (PVDF) with the mass percentage of 3% in NMP solution, adding the polyanion positive electrode material with the mass percentage of 94%, the conductive agent with the mass percentage of 2% and the dispersing agent with the mass percentage of 1% into the solution, uniformly mixing, coating the mixed slurry on two sides of an aluminum foil, drying and rolling to obtain the positive electrode plate.
(3) Preparation of negative electrode plate
And (3) dissolving the SBR binder with the mass percentage of 4% and the CMC thickener with the mass percentage of 1% in an aqueous solution, adding the hard carbon with the mass percentage of 95% into the solution, uniformly mixing, coating the mixed slurry on two sides of a copper foil, and drying and rolling to obtain the negative electrode plate.
(4) Sodium ion battery fabrication
And (3) preparing the prepared positive pole piece, negative pole piece and isolating film into a square battery core in a winding mode, packaging by adopting a polymer, pouring the prepared electrolyte, and preparing the sodium ion battery through processes such as formation and the like.
(5) Battery performance test
Cyclic voltammetry test conditions the cyclic voltammetry test conditions comprise that the coated positive electrode material is used as a counter electrode, lithium is selected to be assembled into a button cell, an electrochemical workstation is used for testing a CV curve, and the scanning range is opened at a potential of-4.6V and the scanning speed is 0.1mV/s.
As can be seen from FIG. 1, after the positive electrode has lithium intercalation/deintercalation potential, the oxidation potential of the lithium triflate boron trifluoride complex appears at about 4.05V, and the oxidation potential of the lithium triflate boron trifluoride complex is higher than that of lithium triflate (about 3.85V), which indicates that the pre-intercalation lithium material has proper lithium deintercalation potential and meets the basic requirement of the pre-intercalation lithium material.
From the results of examples 2-1 to 2-8, comparative examples 3-4~3-7 and comparative examples 3-1 to 3-3, it can be seen that the battery using the lithium sulfinate (carboxylate) complex has significantly improved gram capacity, long-cycle capacity retention and capacity recovery after high-temperature storage in the case where the solvent and additive components are the same. From the results of comparative examples 3-3 and examples 2-3, examples 2-6~2-8, it can be seen that increasing the amount of lithium sulfinate (carboxylate) complex is advantageous for the performance of the battery in gram capacity, long-cycle capacity retention and capacity recovery after high-temperature storage. From the results of examples 1-1 to 1-3, comparative examples 3-8 and comparative examples 3-9, the solubility of lithium trifluoromethylsulfonyl imide and lithium trifluoroacetate in carbonate is not good, generally less than 3%, which is unfavorable for large-capacity lithium supplementation, but lithium trifluoromethylsulfonyl imide complex and lithium trifluoroacetate complex can be as high as 30%, which is favorable for large-capacity lithium supplementation.
The above results indicate that the lithium sulfinate (carboxylate) complex plays a good role in lithium supplementation in batteries.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
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