CN113036106A - Composite lithium supplement additive and preparation method and application thereof - Google Patents
Composite lithium supplement additive and preparation method and application thereof Download PDFInfo
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- CN113036106A CN113036106A CN202110257371.8A CN202110257371A CN113036106A CN 113036106 A CN113036106 A CN 113036106A CN 202110257371 A CN202110257371 A CN 202110257371A CN 113036106 A CN113036106 A CN 113036106A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- 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
Abstract
The invention provides a composite lithium supplement additive and a preparation method and application thereof, wherein the composite lithium supplement additive comprises a composite lithium supplement material and a coating layer positioned on the surface of the composite lithium supplement material, and the composite lithium supplement material comprises Li2O and LixMOyM comprises any one or the combination of at least two of Ni, Co, Mn, Mo, Al, Fe, Ti, Cu, Mg or V, x is more than or equal to 2 and less than or equal to 6, y is more than or equal to 2 and less than or equal to 4, and LixMOyCan be used as a catalyst and Li in the charging and discharging process2O reacts in situ and can catalyze Li2O releases more active lithium ions at a lower potential, and provides higher lithium supplement capacity; the chemical stability of the lithium supplement material in the air is improved by the shell coating layer, the composite lithium supplement material forms a core-shell structure in a coating mode, and the moisture in the air can be effectively separated from the moisture in the airThe carbon dioxide and the inner core lithium supplement material are in contact reaction, so that the stability of the lithium supplement material is protected.
Description
Technical Field
The invention belongs to the technical field of energy storage devices, and relates to a composite lithium supplement additive and a preparation method and application thereof.
Background
Lithium ion batteries have the advantages of high voltage, high specific energy, good safety performance, and the like, and have been widely used in portable electronic products and electric vehicles. With the rapid development of new energy automobiles, smart grids and distributed energy storage, higher requirements are put forward on the energy density of new energy devices, and high-capacity electrode materials are urgently needed to be researched. High-capacity electrode materials are often accompanied by lower first effect, and in the first charge and discharge process of a lithium ion battery, with the formation of SEI films on the surfaces of positive and negative electrodes, limited active lithium ions in the battery can be inevitably consumed, so that the total active lithium ions are reduced, the capacity and performance of the electrode materials cannot be fully exerted, and the energy density of the battery is difficult to further improve.
The pre-lithiation technology is an effective method for reducing irreversible capacity loss and improving coulombic efficiency, lithium is supplemented to an electrode material through pre-lithiation, active lithium loss caused by SEI film formation is counteracted, and irreversible capacity loss of the first circle is relieved, so that the total capacity and energy density of the battery are improved. The pre-lithiation of the negative electrode is a common lithium supplement scheme aiming at improving the coulombic efficiency of the battery, but at present, the lithium supplement scheme is still limited by a plurality of problems in the battery manufacturing process: the lithium foil lithium supplement requires development of new lithium supplement equipment, and has higher requirements on the environment; the principle of the stabilized lithium metal powder is that the lithium metal is dispersed in an organic solvent and then applied to the surface of a negative electrode, and the requirements on environment and equipment are harsh; the use of metallic lithium is incompatible with production environment, conventional solvent, binder, heat treatment process and the like, and unstable reaction products caused by continuous demand on an active lithium source in the charging and discharging process after lithium supplement enable the lithium supplement of the negative electrode to be bushy, so that as an alternative technical route, the lithium supplement additive for the positive and negative electrode materials is not only in the research category.
CN109546226A mentions that Li is a lithium-supplementing substance5FeO4Positive electrode active materialThe mass, the conductive agent, the binder and the non-aqueous solvent are mixed to form slurry, the slurry is coated on a positive current collector, a novel positive plate is obtained by baking and cutting, and then the novel positive plate and a negative plate are paired, wound and assembled into a shell to prepare the 18650 battery, and the capacity of a battery core is obviously improved. But also causes the residue of non-lithium source components in the lithium supplement material, leaves more impurities, and causes the problems of serious self-discharge of the battery cell, reduced discharge capacity and the like.
CN1290209C reports that a battery is prepared by mixing lithium metal, a negative electrode material and a nonaqueous liquid to form a slurry, coating the slurry on a negative electrode current collector, and drying the slurry, which can improve the first efficiency, but because of the high reactivity of lithium metal, the whole operation needs to be performed in an environment of anhydrous drying, resulting in difficult operation and high equipment cost investment.
The above scheme has the problems of low capacity, high cost, low capacity retention rate and the like, so it is urgently needed to develop a lithium supplement additive with high capacity, low cost and high capacity retention rate, and the lithium supplement additive is applied to a lithium ion battery.
Disclosure of Invention
The invention aims to provide a composite lithium supplement additive and a preparation method and application thereof, wherein the composite lithium supplement additive comprises a composite lithium supplement material and a coating layer positioned on the surface of the composite lithium supplement material, and the composite lithium supplement material comprises Li2O and LixMOyM comprises any one or the combination of at least two of Ni, Co, Mn, Mo, Al, Fe, Ti, Cu, Mg or V, x is more than or equal to 2 and less than or equal to 6, y is more than or equal to 2 and less than or equal to 4, and LixMOyCan be used as a catalyst and Li in the charging and discharging process2O reacts in situ and can catalyze Li2O releases more active lithium ions at a lower potential, and provides higher lithium supplement capacity; the chemical stability of the lithium supplement material in the air is improved by the shell coating layer, the composite lithium supplement material forms a core-shell structure in a coating mode, the contact reaction of moisture and carbon dioxide in the air and the lithium supplement material in the core can be effectively blocked, and the stability of the lithium supplement material is protected.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a composite lithium supplement additive, which comprises a composite lithium supplement material and a coating layer positioned on the surface of the composite lithium supplement material, wherein the composite lithium supplement material comprises Li2O and LixMOyM comprises any one or combination of at least two of Ni, Co, Mn, Mo, Al, Fe, Ti, Cu, Mg or V, x is more than or equal to 2 and less than or equal to 6, for example: 2. 3, 4, 5 or 6, etc., 2 ≦ y ≦ 4, such as: 2. 3 or 4, etc.
In the composite lithium supplement additive of the invention, the LixMOyCan be used as a catalyst and Li in the charging and discharging process2O reacts in situ and can catalyze Li2O releases more active lithium ions at a lower potential, and provides higher lithium supplement capacity; the chemical stability of the lithium supplement material in the air is improved by the shell coating layer, the composite lithium supplement material forms a core-shell structure in a coating mode, the contact reaction of moisture and carbon dioxide in the air and the lithium supplement material in the core can be effectively blocked, and the stability of the lithium supplement material is protected.
The composite lithium supplement additive is added into a lithium ion positive electrode material, so that high initial efficiency and good cycle stability can be shown under the condition of less addition amount, the performance of a lithium ion battery is improved, the used preparation process is compatible with the existing preparation process, an excellent lithium supplement effect can be obtained under the condition of not obviously increasing the manufacturing cost of the battery, the cost of the lithium ion battery is reduced, and the composite lithium supplement additive is suitable for industrial production.
Preferably, the chemical formula of the composite lithium supplement material is aLi2O @ bLixMOy, wherein 0<a.ltoreq.1, for example: 0.1, 0.3, 0.5, 0.7 or 1, etc., preferably 0<a≤0.45，0<b.ltoreq.1, for example: 0.1, 0.2, 0.5, 0.8 or 1, etc., preferably 0.55. ltoreq. b<1。
Preferably, the coating layer includes any one of a polymer electrolyte, a solid electrolyte, or a carbon material, or a combination of at least two thereof.
Preferably, the polymer electrolyte includes any one of polypyrrole, a modified polypyrrole, polythiophene, a modified polythiophene, polyamide, a modified polyamide, polyethylene oxide, a modified polyethylene oxide, polyvinylidene fluoride, a modified polyvinylidene fluoride, a polyacrylate polymer, a modified polyacrylate polymer, a polyacrylonitrile polymer, a modified polyether polymer, polysiloxane, a modified polysiloxane, or a polyanionic single-ion conductor type polymer, or a combination of at least two thereof.
Preferably, the solid electrolyte includes any one of lithium fluoride, aluminum fluoride, lithium metaphosphate, aluminum metaphosphate, perovskite type lithium lanthanum titanyl phosphate (LLTO), NASICON type lithium ion conductor titanium aluminum phosphate (LATP), or garnet type lithium ion conductor Lithium Lanthanum Zirconium Oxide (LLZO) or a combination of at least two thereof.
Preferably, the carbon material includes any one of graphite, graphene, carbon nanotubes, carbon fibers, acetylene black, soft carbon, hard carbon, or amorphous carbon, or a combination of at least two thereof.
Preferably, the average thickness of the coating layer is 0.1 to 2 μm, for example: 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 1.5 μm, 2 μm, or the like.
Preferably, the mass fraction of the composite lithium supplement material is 95-99.5% based on 100% of the mass of the composite lithium supplement additive, such as: 95%, 95.5%, 96%, 96.5%, 97%, 98%, 99% or 99.5%, etc., preferably 98 to 99%.
Preferably, the mass fraction of the coating layer is 0.5-5%, such as: 0.5%, 1%, 2%, 3%, 4%, 5%, etc., preferably 1 to 2%.
Preferably, the particle size of the composite lithium supplement material is 0.1-5 μm, for example: 0.1 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, or the like.
Preferably, the de-intercalation potential of the composite lithium supplement additive is 1.5-4.2V, such as: 1.5V, 1.8V, 2V, 2.5V, 3V, 3.5V, 4.2V, etc.
Preferably, the lithium removal capacity of the composite lithium supplement additive is 400-1200 mAh, for example: 400mAh, 500mAh, 600mAh, 800mAh, 1000mAh or 1200mAh, etc.
In a second aspect, the present invention provides a method for preparing the composite lithium supplement additive according to the first aspect, the method comprising the following steps:
(1) mixing a lithium source and an M metal source, and carrying out primary heat treatment to obtain LixMOy；
(2) Li obtained in the step (1)xMOyMixing with metal lithium, and performing secondary heat treatment to obtain a composite lithium supplement material;
(3) and (3) coating the composite lithium supplement material obtained in the step (2) to obtain the composite lithium supplement additive.
Preferably, the lithium source in step (1) comprises any one of lithium carbonate, lithium hydroxide monohydrate, anhydrous lithium hydroxide or lithium oxide or a combination of at least two thereof.
Preferably, the M metal source comprises a metal oxide of M and/or a metal salt of M.
Preferably, the temperature of the primary heat treatment is 300-1000 ℃, for example: 300 deg.C, 500 deg.C, 600 deg.C, 800 deg.C or 1000 deg.C, etc.
Preferably, the temperature rise rate of the primary heat treatment is 1-5 ℃/min, for example: 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min or 5 deg.C/min, etc.
Preferably, the time of the primary heat treatment is 2-30 h, for example: 2h, 5h, 10h, 20h or 30h and the like.
Preferably, the temperature of the secondary heat treatment in the step (2) is 200-800 ℃, for example: 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 800 ℃ or the like.
Preferably, the temperature rise rate of the secondary heat treatment is 1-5 ℃/min, for example: 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min or 5 deg.C/min, etc.
Preferably, the time of the secondary heat treatment is 1-5 h, for example: 1h, 2h, 3h, 4h or 5h and the like.
Preferably, the coating treatment of step (3) comprises liquid phase polymerization and/or mechanical compounding.
In a third aspect, the present invention provides a positive electrode plate, wherein the positive electrode plate comprises the composite lithium supplement additive according to the first aspect.
In a fourth aspect, the invention further provides a lithium ion battery, where the lithium ion battery includes the positive electrode sheet described in the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the composite lithium supplement additive of the invention, the LixMOyCan be used as a catalyst and Li in the charging and discharging process2O reacts in situ and can catalyze Li2O releases more active lithium ions at a lower potential, and provides higher lithium supplement capacity; the coating layer of the shell improves the chemical stability of the lithium supplement material in the air.
(2) According to the invention, the composite lithium supplement material forms a core-shell structure in a coating mode, so that the contact reaction between moisture and carbon dioxide in the air and the core lithium supplement material can be effectively blocked, and the stability of the lithium supplement material is protected.
(3) The composite lithium supplement additive is added into a lithium ion positive electrode material, so that high initial efficiency and good cycle stability can be shown under the condition of less addition amount, the performance of a lithium ion battery is improved, the used preparation process is compatible with the existing preparation process, an excellent lithium supplement effect can be obtained under the condition of not obviously increasing the manufacturing cost of the battery, the cost of the lithium ion battery is reduced, and the composite lithium supplement additive is suitable for industrial production.
(4) The battery prepared by using the composite lithium supplement additive has the first cycle charging specific capacity of more than 226.5mAh/g, the first cycle discharging specific capacity of more than 198.3mAh/g, the first efficiency of more than 84.3 percent and the capacity retention rate of more than 94.1 percent after 100 cycles.
Drawings
FIG. 1 is a schematic structural diagram of the composite lithium supplement additive according to example 1 of the present invention, where 100 is LixMOy200 is Li2O, 300 is a coating layer.
FIG. 2 is an SEM image of a composite lithium supplement additive of example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a composite lithium supplement additive, which is prepared by the following method:
(1) mixing Li2CO3And Mn2O3Uniformly mixing the materials according to a molar ratio of 2:1, putting the obtained mixture into a chamber furnace, heating the mixture to 650 ℃ at a heating rate of 5 ℃/min under the protection of argon for heat treatment for 10 hours to obtain a lithium-rich material Li4Mn2O5；
(2) Sintering the lithium-rich material Li obtained in the step (1)4Mn2O5Mixing with metal lithium at a molar ratio of 6.5:3.5 in inert atmosphere, heating to 300 deg.C at a temperature of 2 deg.C/min in mixed atmosphere of argon and oxygen for 5 hr to obtain 0.35Li2[email protected]4Mn2O5The composite lithium supplement material of (1);
(3) adding LATP glycol dispersion liquid according to the coating amount of 2 wt%, mixing with the composite lithium supplement material, carrying out ball milling, and drying to obtain the composite lithium supplement additive.
The schematic structure of the composite lithium supplement additive is shown in figure 1.
The SEM image of the composite lithium supplement additive is shown in FIG. 2.
Example 2
The embodiment provides a composite lithium supplement additive, which is prepared by the following method:
(1) mixing Li2CO3And Mn2O3Uniformly mixing the materials according to a molar ratio of 2:1, putting the obtained mixture into a chamber furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the protection of argon, and carrying out heat treatment for 12h to obtain a lithium-rich material Li4Mn2O5；
(2) Sintering the lithium-rich material Li obtained in the step (1)4Mn2O5Mixing with metal lithium at a molar ratio of 5.5:4.5 in inert atmosphere, and adding argonHeating to 350 ℃ at a heating rate of 3 ℃/min for heat treatment for 4h under the mixed atmosphere of oxygen and the obtained product to obtain 0.45Li2[email protected]4Mn2O5The composite lithium supplement material of (1);
(3) adding 1 wt% of graphene NMP dispersion liquid, mixing with the composite lithium supplement material at a high speed, and preparing the composite lithium supplement additive by spray drying.
Example 3
The embodiment provides a composite lithium supplement additive, which is prepared by the following method:
(1) mixing Li2CO3And Mn2O3Uniformly mixing the materials according to a molar ratio of 2:1, putting the obtained mixture into a chamber furnace, heating to 650 ℃ at a heating rate of 5 ℃/min under the protection of argon, and sintering for 10h to obtain a lithium-rich material Li4Mn2O5；
(2) Sintering the lithium-rich material Li obtained in the step (1)4Mn2O5Mixing with metal lithium at a molar ratio of 8.5:1.5 in inert atmosphere, heating to 300 deg.C at a temperature of 2 deg.C/min in mixed atmosphere of argon and oxygen, and sintering for 2 hr to obtain 0.15Li2[email protected]4Mn2O5The composite lithium supplement material of (1);
(3) adding 1 wt% of graphene NMP dispersion liquid, mixing with the composite lithium supplement material at a high speed, and preparing the composite lithium supplement additive by spray drying.
Example 4
The embodiment provides a composite lithium supplement additive, which is prepared by the following method:
(1) mixing Li2Mixing O and NiO uniformly according to the mol ratio of 2:1, putting the obtained mixture into a chamber furnace, heating to 550 ℃ at the heating rate of 5 ℃/min under the protection of argon, and sintering for 8h to obtain the lithium-rich material Li4Mn2O5；
(2) Sintering the lithium-rich material Li obtained in the step (1)4Mn2O5Mixing with metal lithium at a molar ratio of 4:1 in an inert atmosphereUniformly heating to 500 ℃ at a heating rate of 2 ℃/min under the mixed atmosphere of argon and oxygen, and sintering for 2h to obtain 0.2Li2[email protected]4Mn2O5The composite lithium supplement material of (1);
(3) adding 1.2 wt% of the coating amount into lithium metaphosphate ethanol dispersion, mixing with the composite lithium supplement material, carrying out ball milling, and drying to obtain the composite lithium supplement additive.
Example 5
The embodiment provides a composite lithium supplement additive, which is prepared by the following method:
(1) mixing Li2Mixing O and CoO uniformly according to the mol ratio of 3:1, putting the obtained mixture into a chamber furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the protection of argon, and sintering for 18h to obtain the lithium-rich material Li6CoO4；
(2) Sintering the lithium-rich material Li obtained in the step (1)6CoO4Uniformly mixing the lithium powder and the metal lithium in an inert atmosphere according to the mass ratio of 8:2, heating to 500 ℃ at the heating rate of 2 ℃/min in the mixed atmosphere of argon and oxygen, and sintering for 2 hours to obtain 0.2Li2[email protected]6CoO4The composite lithium supplement material of (1);
(3) adding 2 wt% of coating amount of silane coupling agent NMP dispersion liquid, mixing with the composite lithium supplement material, ball milling, and drying to obtain the composite lithium supplement additive.
Example 6
The embodiment provides a composite lithium supplement additive, which is prepared by the following method:
(1) mixing Li2O and Fe2O3Uniformly mixing the materials according to a molar ratio of 5:1, putting the obtained mixture into a chamber furnace, heating to 750 ℃ at a heating rate of 5 ℃/min under the protection of argon, and sintering for 20h to obtain a lithium-rich material Li5FeO4；
(2) Sintering the lithium-rich material Li obtained in the step (1)5FeO4Uniformly mixing the lithium metal and the lithium metal in an inert atmosphere according to the mass ratio of 7:3, and heating at the temperature of 2 ℃/min in the mixed atmosphere of argon and oxygenThe temperature is increased to 500 ℃ at a speed and the sintering is carried out for 2h to obtain 0.3Li2[email protected]5FeO4The composite lithium supplement material of (1);
(3) adding 1 wt% of LATP glycol dispersion liquid, mixing with the composite lithium supplement material, ball milling, and drying to obtain the composite lithium supplement additive.
Example 7
This example differs from example 1 only in that the sintering temperature in step (1) is 300 ℃, and the other conditions and parameters are exactly the same as those in example 1.
Example 8
This example differs from example 1 only in that the sintering temperature in step (1) is 1000 ℃ and the other conditions and parameters are exactly the same as in example 1.
Example 9
This example differs from example 1 only in that the sintering temperature in step (2) is 200 ℃, and the other conditions and parameters are exactly the same as those in example 1.
Example 10
This example differs from example 1 only in that the sintering temperature in step (2) is 800 ℃, and the other conditions and parameters are exactly the same as those in example 1.
Example 11
This example differs from example 1 only in that the coating amount of LATP in step (3) is 5 wt%, and other conditions and parameters are exactly the same as those in example 1.
Example 12
This example differs from example 1 only in that the coating amount of LATP in step (3) is 0.5 wt%, and the other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example is different from example 1 only in that the coating treatment of step (2) is not performed, and other conditions and parameters are exactly the same as those of example 1.
Comparative example 2
This comparative example differs from example 1 only in that no Mn is added in step (1)2O3Other conditions and parameters were exactly the same as those in example 1.
And (3) performance testing:
the lithium supplement additive obtained in the examples 1-12 and the comparative examples 1-2, NCM811, polyvinylidene fluoride (PVDF), carbon black conductive agent (super-P) and Carbon Nano Tube (CNT) are weighed according to the mass ratio of 1:96:2.0:0.5:0.5, NMP with a proper amount is added to be stirred at a high speed for 60 minutes to obtain uniform anode slurry, the anode slurry is coated on an aluminum foil with the diameter of 12 mu m, and the anode slurry is dried, rolled and then punched into a wafer with the diameter of phi 14 mm. At 1.0mol/L LiPF6The method comprises the following steps of (1: 1 volume ratio)/EC + DEC (0.5 vol.% VC +1 vol.% FEC) as an electrolyte, using silicon-oxygen-carbon 500 as a counter electrode, using a ceramic coated diaphragm as the diaphragm, assembling the diaphragm into a button cell in a glove box filled with argon, connecting the prepared button cell with a blue testing instrument at room temperature, using metal lithium as a negative electrode, setting the cell to perform constant-current and constant-voltage charging at a current of 0.2C, setting a charge cut-off voltage to be 4.5V, standing for 10min, performing constant-current and constant-voltage discharging at a current of 0.2C, and setting a discharge cut-off voltage to be 2.5V, wherein the test results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the battery prepared by using the composite lithium supplement additive has the first cycle specific charge capacity of more than 226.5mAh/g, the first cycle specific discharge capacity of more than 198.3mAh/g, the first efficiency of more than 84.3 percent and the capacity retention rate of more than 94.1 percent after 100 cycles.
By comparing the embodiment 1 with the embodiments 7-8, the sintering temperature in the step (1) can influence the effect of the prepared composite lithium supplement additive, and the sintering temperature is controlled to be 300-1000 ℃, so that the lithium-rich compound Li with better effect can be preparedxMoy。
As can be seen from comparison of example 1 with examples 9-10, the sintering temperature in step (2) affects the resulting composite lithium supplement additiveThe sintering temperature is controlled to be 200-800 ℃, and Li can be better treatedxMOyAnd the lithium-oxygen composite material is combined with a metal lithium-oxygen compound, and the composite lithium-supplementing material with better effect is obtained under sintering.
By comparing the embodiment 1 with the embodiments 11 to 12, the quality fraction of the coating layer can influence the effect of the composite lithium supplement additive, and the quality fraction of the coating layer is controlled to be 0.5 to 5 percent, so that the composite lithium supplement additive with better effect can be prepared.
Compared with the comparative example 1, the embodiment 1 has the advantages that the composite lithium supplement material forms a core-shell structure in a coating mode, so that the contact reaction between moisture and carbon dioxide in the air and the core lithium supplement material can be effectively blocked, and the stability of the lithium supplement material is protected.
From comparison of example 1 with comparative example 2, the LixMOyCan be used as a catalyst and Li in the charging and discharging process2O reacts in situ and can catalyze Li2O releases more active lithium ions at a lower potential, and provides higher lithium supplement capacity; the coating layer of the shell improves the chemical stability of the lithium supplement material in the air.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The composite lithium supplement additive is characterized by comprising a composite lithium supplement material and a coating layer positioned on the surface of the composite lithium supplement material, wherein the composite lithium supplement material comprises Li2O and LixMOyM comprises any one or the combination of at least two of Ni, Co, Mn, Mo, Al, Fe, Ti, Cu, Mg or V, x is more than or equal to 2 and less than or equal to 6, and y is more than or equal to 2 and less than or equal to 4.
2. The composite lithium supplementing additive of claim 1 whereinThe chemical formula of the composite lithium supplement material is aLi2O @ bLixMOy, wherein a is more than or equal to 0 and less than or equal to 1, preferably a is more than or equal to 0 and less than or equal to 0.45, b is more than or equal to 0 and less than or equal to 1, preferably b is more than or equal to 0.55 and less than or equal to 1;
preferably, the coating layer comprises any one of a polymer electrolyte, a solid electrolyte or a carbon material, or a combination of at least two of them;
preferably, the polymer electrolyte comprises any one of polypyrrole, modified polypyrrole, polythiophene, modified polythiophene, polyamide, modified polyethylene oxide, polyvinylidene fluoride, modified polyvinylidene fluoride, polyacrylate polymer, modified polyacrylate polymer, polyacrylonitrile polymer, modified polyether polymer, polysiloxane, modified polysiloxane, or polyanionic single-ion conductor type polymer, or a combination of at least two of them;
preferably, the solid electrolyte includes any one of lithium fluoride, aluminum fluoride, lithium metaphosphate, aluminum metaphosphate, perovskite type lithium ion conductor LLTO, NASICON type lithium ion conductor LATP, or garnet type lithium ion conductor LLZO or a combination of at least two thereof;
preferably, the carbon material includes any one or a combination of at least two of graphite, graphene, carbon nanotubes, carbon fibers, acetylene black, soft carbon, hard carbon, or amorphous carbon;
preferably, the average thickness of the coating layer is 0.1-2 μm.
3. The composite lithium supplement additive according to claim 1 or 2, wherein the mass fraction of the composite lithium supplement material is 95-99.5%, preferably 98-99%, based on 100% of the mass of the composite lithium supplement additive;
preferably, the mass fraction of the coating layer is 0.5-5%, preferably 1-2%;
preferably, the particle size of the composite lithium supplement material is 0.1-5 μm.
4. The composite lithium supplement additive according to any one of claims 1 to 3, wherein the composite lithium supplement additive has a lithium deintercalation potential of 1.5 to 4.2V;
preferably, the lithium removal capacity of the composite lithium supplement additive is 400-1200 mAh.
5. A method for preparing the composite lithium supplement additive according to any one of claims 1 to 4, wherein the method comprises the following steps:
(1) mixing a lithium source and an M metal source, and carrying out primary heat treatment to obtain LixMOy；
(2) Li obtained in the step (1)xMOyMixing with metal lithium, and performing secondary heat treatment to obtain a composite lithium supplement material;
(3) and (3) coating the composite lithium supplement material obtained in the step (2) to obtain the composite lithium supplement additive.
6. The method of claim 5, wherein the lithium source of step (1) comprises any one of lithium carbonate, lithium hydroxide monohydrate, lithium hydroxide anhydrous, or lithium oxide, or a combination of at least two thereof;
preferably, the M metal source comprises a metal oxide of M and/or a metal salt of M;
preferably, the temperature of the primary heat treatment is 300-1000 ℃;
preferably, the temperature rise speed of the primary heat treatment is 1-5 ℃/min;
preferably, the time of the primary heat treatment is 2-30 h.
7. The method according to claim 5 or 6, wherein the temperature of the secondary heat treatment in the step (2) is 200 to 800 ℃;
preferably, the temperature rise speed of the secondary heat treatment is 1-5 ℃/min;
preferably, the time of the secondary heat treatment is 1-5 h.
8. The method according to any one of claims 5 to 7, wherein the coating treatment of step (3) comprises liquid phase polymerization and/or mechanical compounding.
9. A positive electrode plate, characterized in that the positive electrode plate comprises the composite lithium supplement additive according to any one of claims 1 to 4.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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