CN115347170A - Lithium supplement additive, preparation method thereof and secondary battery - Google Patents

Lithium supplement additive, preparation method thereof and secondary battery Download PDF

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CN115347170A
CN115347170A CN202210980858.3A CN202210980858A CN115347170A CN 115347170 A CN115347170 A CN 115347170A CN 202210980858 A CN202210980858 A CN 202210980858A CN 115347170 A CN115347170 A CN 115347170A
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lithium
organic
formula
lithium supplement
additive
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朱成奔
万远鑫
孔令涌
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Shenzhen Dynanonic Innovazone New Energy Technology Co Ltd
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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • 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 provides a lithium supplement additive, a preparation method thereof and a secondary battery, wherein the lithium supplement additive comprises a lithium-rich material core and a coating layer arranged on the lithium-rich material core, the coating layer comprises an organic phosphorus compound, the organic phosphorus compound comprises organic phosphoric acid or organic phosphate, and/or the organic phosphorus compound comprises organic hypophosphorous acid or organic hypophosphite; the substituents in the organic phosphoric acid or organic phosphate, the organic hypophosphorous acid or the organic hypophosphite are independently selected from substituted or unsubstituted alkyl or silicon-containing groups, and the substituents of the substituted alkyl comprise fluorine atoms, hydroxyl groups, carboxyl groups, amino groups and amide groups. The lithium supplement additive not only can effectively supplement lithium for the lithium secondary battery and improve the primary efficiency of the battery, but also has good stability, is not easy to react in the air, and is beneficial to the production, storage and transportation of the lithium supplement additive.

Description

Lithium supplement additive, preparation method thereof and secondary battery
Technical Field
The application relates to the field of secondary batteries, in particular to a lithium supplement additive, a preparation method thereof and a secondary battery.
Background
In the first charging process of the battery, surface solid electrolyte films (SEI films) can be formed on the surfaces of the positive electrode and the negative electrode, the formation of the SEI films can consume lithium in the battery and convert the lithium into an inactive lithium-containing compound, so that the loss of reversible lithium is caused, the first efficiency is reduced, and the discharge capacity of the battery is reduced.
In order to compensate for lithium loss caused by the SEI film formed by the first charging, the existing method is to add a lithium supplement additive into the anode or the cathode. However, the existing lithium supplement additive has high activity and is easy to react with water in the air, so that the residual alkali content on the surface of the lithium supplement additive is high, the lithium supplement effect is reduced, the capacity loss of the battery is caused, and the deterioration of the lithium supplement material can also cause the gas production of the battery to be increased, which is not favorable for the safety performance of the battery. In order to ensure effective lithium supplement, the existing lithium supplement additive has extremely strict requirements on the environment in the using and storing processes; in addition, in the preparation process, the lithium supplement additive is easy to oxidize and difficult to synthesize in large scale, and is not beneficial to industrial production. Therefore, it is necessary to provide a new lithium supplement additive and a preparation method thereof to solve the problems of poor stability, poor lithium supplement effect and difficulty in industrial production of the existing lithium supplement additive.
Disclosure of Invention
In view of this, the present application provides a lithium supplement additive, which not only can effectively supplement lithium to a lithium secondary battery and improve the primary efficiency of the battery, but also has good stability, is not easy to react in the air, and is beneficial to the production, storage and transportation of the lithium supplement additive. The application also provides a preparation method of the lithium supplement additive.
The first aspect of the application provides a lithium supplement additive, which comprises a lithium-rich material core and a coating layer arranged on the lithium-rich material core, wherein the coating layer comprises an organic phosphorus compound, the organic phosphorus compound comprises organic phosphoric acid with a structural formula shown in a formula (1-1) or organic phosphate thereof, and/or the organic phosphorus compound comprises organic hypophosphorous acid with a structural formula shown in a formula (2-1) or organic hypophosphite thereof;
Figure BDA0003800366300000021
in the formulae (1-1) and (2-1), R 1 、R 2 、R 3 Independently selected from substituted or unsubstituted alkyl or silicon-containing groups, and the substituent of the substituted alkyl comprises fluorine atom, hydroxyl, carboxyl, amino and amido.
In the lithium supplement additive, the lithium-rich material core can make up for the capacity loss of the lithium secondary battery during the first charge and discharge, and the first charge and discharge efficiency is improved; the organic phosphorus compound in the coating layer can form lattice oxygen through strong acting force between P-O, so that the loss of the lattice oxygen on the surface of the core of the lithium-rich material is reduced, and the structural stability of the lithium supplement additive is improved; and the organic phosphorus compound has good hydrophobic property, can reduce the contact between the lithium-rich material core and moisture and effectively isolate air, thereby inhibiting the lithium supplement additive from generating residual alkali, enabling the lithium supplement additive to stably exist in the air, and being beneficial to the production, storage and use of the lithium supplement additive.
Alternatively, the substituted or unsubstituted alkyl group has 3 to 20 carbon atoms.
Optionally, the organic phosphorus compound comprises one or more of the organic hypophosphorous acid and the organic hypophosphite, and the mass percentage of the organic hypophosphorous acid and/or the organic hypophosphite in the coating layer is greater than or equal to 50%.
Optionally, the cation in the organophosphate or the organophosphinate comprises a metal ion,
Figure BDA0003800366300000022
One or more of ions and ammonium ions.
Alternatively, the organophosphorus compound has a melting point of greater than or equal to 50 ℃.
Alternatively, the organophosphorus compound includes one or more of n-hexylphosphoric acid and salts thereof, n-dodecylphosphoric acid and salts thereof, 1-tetradecylphosphoric acid and salts thereof, n-hexadecylphosphoric acid and salts thereof, n-octadecyl phosphoric acid and salts thereof, 11-carboxyundecylphosphoric acid and salts thereof, 11-hydroxyundecylphosphoric acid and salts thereof, diethylhypophosphorous acid and salts thereof, triethyltetradecylphosphine bis (2,4,4-trimethylpentyl) hypophosphorous acid and salts thereof.
Optionally, the coating layer comprises a first coating layer close to the lithium-rich material core and a second coating layer far away from the lithium-rich material core, the first coating layer comprises one or more of lithium organophosphate and lithium hypophosphite, the structural formula of the lithium organophosphate is shown as a formula (3-1) or a formula (3-2), and the structural formula of the lithium hypophosphite is shown as a formula (3-3); the second coating layer comprises one or more of the organic phosphoric acid, the organic hypophosphorous acid or the organic phosphate shown as the formula (1-2);
Figure BDA0003800366300000031
optionally, the average thickness of the coating layer is 2nm to 150nm.
Optionally, D of the lithium-rich material core 50 The grain diameter is 0.5-30 μm.
Optionally, the mass ratio of the lithium-rich material core to the coating layer is 1 (0.01-0.15).
Optionally, the lithium-rich material core comprises an average chemical formula of Li x M y O z The lithium supplement material of (1), wherein x is more than 0.1 and less than 10,0 and more than y is more than 5,2 and less than or equal to z is less than 10; the M comprises one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce or Zr.
Optionally, the lithium-rich material core comprises one or more of primary particles of a lithium-supplement material and secondary particles of a lithium-supplement material.
Optionally, the lithium supplement additive has a total residual alkali content of less than or equal to 1%.
The lithium supplement additive provided by the first aspect of the application can effectively supplement the loss of lithium ions in the first charge-discharge process of the lithium secondary battery, thereby improving the first charge-discharge efficiency of the lithium ion battery, increasing the energy density of the battery, having good stability, being capable of stably existing in the air, having low surface residual alkali amount, and being beneficial to adding the lithium supplement additive into the lithium secondary battery to realize lithium supplement.
In a second aspect, the present application provides a method for preparing a lithium supplement additive, comprising:
providing an average chemical formula of Li x M y O z The lithium supplement material of (1), wherein x is more than 0.1 and less than 10,0 and more than y is more than 5,2 and less than or equal to z is less than 10; the M comprises one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce or Zr; mixing the lithium supplement material with an organic phosphorus compound and then carrying out heat treatment to obtain a lithium supplement additive; the organic phosphorus compound comprises organic phosphoric acid or organic phosphate thereof with a structural formula shown in a formula (1-1), and/or the organic phosphorus compound comprises organic hypophosphorous acid or organic hypophosphite thereof with a structural formula shown in a formula (2-1);
Figure BDA0003800366300000041
in the formulae (1-1) and (2-1), R 1 、R 2 、R 3 Independently selected from substituted or unsubstituted alkyl or silicon-containing groups, and the substituent of the substituted alkyl comprises fluorine atom, hydroxyl, carboxyl, amino and amido.
Optionally, the heat treatment temperature is 50-300 ℃, and the heat treatment time is 1-5 h.
Optionally, mixing the lithium-supplementing material with the organophosphorus compound comprises one or more of solid phase mixing or liquid phase mixing.
Optionally, the solid phase mixing includes one or more of ball milling and stirring.
Optionally, the liquid phase mixing comprises: and mixing the lithium supplement material, the organic phosphorus compound and an organic solvent to form a mixed solution, wherein the solvent comprises one or more of ethanol, N-hexane, cyclohexane, dichloromethane, ethyl acetate, tetrahydrofuran and N-methylpyrrolidone.
Optionally, the mass concentration of the mixed solution is 0.5-20%.
Optionally, the preparation method of the lithium supplement material comprises: mixing a lithium source and a doping source, and sintering to obtain a lithium supplement material, wherein the lithium source comprises one or more of lithium hydroxide, lithium carbonate, lithium oxide, lithium acetate and lithium oxalate; the doping source comprises a doping metal element M, and the doping source can be one or more of oxides, hydroxides or salts of the doping metal element M, and the doping metal element M comprises one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce or Zr.
The third aspect of the present application provides a positive electrode plate, which includes a current collector and an active material layer disposed on the current collector, wherein the active material layer includes the lithium supplement additive as described in the first aspect.
A fourth aspect of the present application provides a secondary battery comprising a lithium supplement additive as described in the third aspect of the present application.
Drawings
FIG. 1 is a schematic structural diagram of a lithium supplement additive provided in accordance with an embodiment of the present disclosure;
FIG. 2 is a schematic structural diagram of a lithium replenishment additive provided in accordance with an embodiment of the present application;
fig. 3 is a schematic structural diagram of a lithium supplement additive according to an embodiment of the present disclosure.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a lithium supplement additive which is used for supplementing lithium to a positive electrode of a lithium secondary battery. Referring to fig. 1, fig. 1 is a schematic structural diagram of a lithium supplement additive according to an embodiment of the present disclosure, in which a lithium supplement additive 100 includes a lithium-rich material core 10 and a coating layer 20 disposed on the lithium-rich material core 10, where the coating layer includes an organic phosphorus compound.
In an embodiment of the present application, the lithium-rich material core comprises an average chemical formula of Li x M y O z The lithium supplement material of (1), wherein x is more than 0.1 and less than 10,0 and less than y is more than 5,2 and less than or equal to z is less than 10, and M comprises one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce or Zr. In the present application, the lithium-rich material core includes one or more of a lithium supplement material primary particle and a lithium supplement material secondary particle. In some embodiments, the lithium-rich material core is a primary particle of a lithium-supplement material, and the schematic structural diagram is shown in fig. 1. Referring to fig. 2, fig. 2 is a schematic structural diagram of a lithium supplement additive according to an embodiment of the present disclosure, in fig. 2, a lithium-rich material core is a secondary particle formed by stacking a plurality of lithium supplement materials, and a coating layer is coated on a surface of the lithium supplement material secondary particle. In some embodiments of the present application, D of the lithium-rich material core 50 The particle diameter is 0.5-30 μm, further 0.5-12 μm, D of lithium-rich material core 50 The particle size may be specifically, but not limited to, 0.5. Mu.m, 1. Mu.m, 3. Mu.m, 5. Mu.m, 8. Mu.m, 10. Mu.m, or 12 μm.
In the present application, the coating layer on the surface of the lithium-rich material core comprises an organic phosphorus compound, and the organic phosphorus compound comprises one or more of organic phosphoric acid, organic phosphate, organic hypophosphorous acid and organic hypophosphite. Wherein the structural formula of the organic phosphoric acid is shown as a formula (1-1), the structural formula of the organic phosphate is shown as a formula (1-2) or a formula (1-3), the structural formula of the organic hypophosphorous acid is shown as a formula (2-1), and the structural formula of the organic hypophosphite is shown as a formula (2-2):
Figure BDA0003800366300000061
in the formula (1-1), the formula (1-2), the formula (1-3), the formula (2-1) and the formula (2-2), R 1 、R 2 、R 3 Independently selected from substituted or unsubstituted alkyl or silicon-containing groups, the substituent of the substituted alkyl comprises fluorine atom, hydroxyl, carboxyl, amino, amido, M 1 + Comprises metal ions,
Figure BDA0003800366300000062
The metal ion may be any of lithium ion, sodium ion, aluminum ion, and magnesium ion, for example. In some embodiments, the number of carbon atoms of the substituted or unsubstituted alkyl group is 3 to 20, and controlling the number of carbon atoms of the alkyl group to be 3 to 20 can ensure good hydrophobicity of the organophosphorus compound. The number of carbon atoms of the substituted or unsubstituted alkyl group may specifically be, but not limited to, 3, 5, 8, 10, 12, 15, 17 or 20.
In the lithium supplement additive, the organic phosphorus compound in the coating layer contains hydrophobic functional groups such as alkyl and silicon-containing groups, the organic phosphorus compound with the structure can improve the moisture resistance of the lithium supplement additive and inhibit the permeation of moisture, and the coating layer can also isolate the inner core of a lithium-rich material from the outside, so that the stability of the lithium supplement additive in the air is improved, the lithium supplement additive has an excellent lithium supplement effect, and the production and storage costs of the lithium supplement additive are reduced; in addition, the organophosphorus compound can form lattice oxygen through strong P-O force, so that the loss of the lattice oxygen on the surface of the lithium supplement core particle is reduced, and the phenomenon that the particle structure collapses due to the diffusion of oxygen vacancies formed on the surface into the particle is avoided, thereby improving the structural stability of the lithium supplement material.
In some embodiments of the present application, the substituent of the substituted alkyl group includes one or more of a hydroxyl group, a carboxyl group, or an amino group, and the hydroxyl group, the carboxyl group, or the amino group in the organophosphorus compound helps to increase the interaction force between the coating layer and the lithium-rich material core, thereby enhancing the coating effect. In some embodiments, the substituent group of the substituted alkyl group includes a fluorine atom, and the fluorine atom in the organic phosphorus compound can provide good hydrophobicity to the coating layer to inhibit moisture from permeating into the lithium supplement additive.
In some embodiments of the present application, the melting point of the organophosphorus compound is 50 ℃ or higher and the decomposition temperature of the organophosphorus compound is 100 ℃ or higher. The organic phosphorus compound in the lithium supplement additive coating layer is solid at room temperature, so that a solid phase coating layer with a stable structure can be formed, and the storage stability and the processing performance are better.
In the embodiment of the application, the organic phosphorus compound can also react with residual alkali on the surface of the lithium-rich material core so as to reduce the amount of the residual alkali, thereby ensuring that the lithium supplement additive has a good lithium supplement effect. In some embodiments, the organic phosphorus compound comprises one or more of organic phosphoric acid, organic hypophosphorous acid and organic phosphate with a structural formula shown as formula (1-2), and the organic phosphorus compound with the structure can also form salt with residual alkali on the surface of the lithium-rich material core, so that the amount of the residual alkali is reduced, and the lithium supplement additive has a good lithium supplement effect. Referring to fig. 3, fig. 3 is a schematic structural diagram of a lithium supplement additive according to an embodiment of the present disclosure, in which a coating layer 20 on a surface of a lithium-rich material core includes a first coating layer 21 and a second coating layer 22, where the first coating layer includes one or more of lithium organophosphate and lithium organophosphate, a structural formula of the lithium organophosphate is represented by formula (3-1) or formula (3-2), and a structural formula of the lithium organophosphate is represented by formula (3-3):
Figure BDA0003800366300000071
the second coating layer comprises one or more of organic phosphoric acid, organic hypophosphorous acid and organic phosphate shown in the formula (1-2), organic lithium phosphate or organic lithium hypophosphite in the first coating layer is obtained by reacting organic phosphoric acid, organic hypophosphorous acid and organic phosphate shown in the formula (1-2) in a structural formula with residual alkali (lithium oxide and lithium hydroxide) on the surface of the lithium-rich material inner core, and the lithium supplement material with the structure has low residual alkali on the surface, so that the side reaction of the lithium supplement material and electrolyte is reduced, and the battery performance is improved. In some embodiments of the present disclosure, the total alkali residue of the lithium supplement additive is less than or equal to 1%, and further, the total alkali residue of the lithium supplement additive is less than or equal to 0.3%.
In some embodiments of the present application, the organic phosphorus compound includes one or more of organic hypophosphorous acid and organic hypophosphite, and the organic hypophosphorous acid and the organic hypophosphite have reducibility, and can absorb active oxygen generated by the lithium supplement additive during charging and discharging processes, inhibit gas generation reaction caused by the active oxygen, and effectively improve the safety performance of the battery. In some embodiments of the present application, the mass percentage of the organic hypophosphorous acid and/or organic hypophosphite in the coating layer is 50% to 100%, and the mass percentage of the organic hypophosphorous acid and/or organic hypophosphite in the coating layer may be specifically, but not limited to, 50%, 60%, 70%, 80%, 90%, or 100%. That is, when the organic phosphorus compound includes organic hypophosphorous acid, the mass percentage content of the organic hypophosphorous acid in the coating layer is 50-100%; when the organic phosphorus compound comprises organic hypophosphite, the mass percentage content of the organic hypophosphite in the coating layer is 50-100%; when the organic phosphorus compound comprises organic hypophosphorous acid and organic hypophosphite, the mass percentage of the organic hypophosphorous acid and the organic hypophosphite in the coating layer is 50-100%.
In some embodiments of the present application, the organophosphorus compound comprises one or more of n-hexylphosphoric acid and salts thereof, n-dodecylphosphoric acid and salts thereof, 1-tetradecylphosphoric acid and salts thereof, n-hexadecylphosphoric acid and salts thereof, n-octadecyl phosphoric acid and salts thereof, 11-carboxyundecylphosphoric acid and salts thereof, 11-hydroxyundecylphosphoric acid and salts thereof, diethylhypophosphorous acid and salts thereof, triethyltetradecylphosphine bis (2,4,4-trimethylpentyl) hypophosphorous acid and salts thereof. In some embodiments, the organophosphorus compound comprises one or more of diethyl aluminum hypophosphite, triethyltetradecylphosphine bis (2,4,4-trimethylpentyl) hypophosphite. The organic phosphorus compound has good stability, and when the organic phosphorus compound is applied to a battery, the coating layer can also inhibit the side reaction of electrolyte and a lithium-rich material, so that the lithium supplementing performance of the lithium supplementing material is ensured.
In some embodiments of the present application, the average thickness of the coating layer is 2nm to 150nm, and the average thickness of the coating layer may be, but is not limited to, 2nm, 5nm, 10nm, 30nm, or 40nm. In some embodiments, the average thickness of the coating layer is 2nm to 40nm. When the coating layer is in the thickness range, the effective protection of the lithium-rich material inner core can be realized, and the kinetic transmission of ions and electrons is not influenced, so that the effective lithium supplement of the battery is realized. In some embodiments of the present application, the mass ratio of the lithium-rich material core to the coating layer is (1), (0.01-0.15), and further is (0.01-0.1), and the mass ratio of the lithium-rich material core to the coating layer may specifically be, but is not limited to, 1. The thickness of the protective layer can be adjusted by controlling the mass ratio of the lithium-rich material core to the coating layer, so that the coating layer can effectively protect the lithium-rich material core; lithium ions in the lithium-rich material core have moderate extraction rate, so that effective lithium supplement can be realized; in addition, the low mass ratio of the coating layer can also ensure that the lithium supplement additive has high lithium supplement capacity.
In the lithium supplement additive provided by the application, the lithium-rich material kernel can supplement lithium ions consumed by a battery to form an SEI film in the first charging and discharging process, the first charging gram capacity of the battery is improved, the surface interface stability of the lithium supplement material can be improved by the coating layer, the storage life of the lithium supplement material is prolonged, and the weight ratio of the coating layer in the lithium supplement material is low, so that the lithium supplement additive has higher specific capacity; the surface interface of the lithium supplement material has the characteristics of hydrophobicity and stability, and the production and the storage of the lithium supplement material do not need harsh operating environment, thereby being beneficial to large-scale production.
The application also provides a preparation method of the lithium supplement additive, which comprises the following steps:
providing an average formula of Li x M y O z The lithium supplement material of (1), wherein x is more than 0.1 and less than 10,0 and more than y is more than 5,2 and less than or equal to z is less than 10; m comprises one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce or Zr; and mixing the lithium supplement material with an organic phosphorus compound, and then carrying out heat treatment to obtain the lithium supplement additive. The organic phosphorus compound comprises one or more of organic phosphoric acid, organic phosphate, organic hypophosphorous acid and organic hypophosphite. Wherein the structural formula of the organic phosphoric acid is shown as a formula (1-1), the structural formula of the organic phosphate is shown as a formula (1-2) or a formula (1-3), the structural formula of the organic hypophosphorous acid is shown as a formula (2-1), and the structural formula of the organic hypophosphite is shown as a formula (2-2):
Figure BDA0003800366300000091
in the formula (1-1), the formula (1-2), the formula (1-3), the formula (2-1) and the formula (2-2),R 1 、R 2 、R 3 independently selected from substituted or unsubstituted alkyl or silicon-containing groups, the substituent of the substituted alkyl group comprises fluorine atom, hydroxyl, carboxyl, amino and amido, M 1 + Comprises metal ions,
Figure BDA0003800366300000092
The metal ion may be any of lithium ion, sodium ion, aluminum ion, and magnesium ion, for example.
In the embodiment of the present application, the mixing of the lithium-supplementing material and the organic phosphorus compound may be solid-phase mixing or liquid-phase mixing, and the mass ratio of the lithium-supplementing material to the organic phosphorus compound is 1 (0.01 to 0.15) at the time of mixing. In some embodiments of the present application, the solid phase mixing comprises one or more of ball milling, stirring. In some embodiments of the present application, the liquid phase mixing is to mix a lithium supplement material, an organic phosphorus compound, and a solvent to form a mixed solution, wherein the solvent is a non-aqueous solvent that does not react with the lithium supplement material and can dissolve the organic phosphorus compound, and the mass concentration of the mixed solution is 0.5% to 20%. In some embodiments, the liquid phase mixed solvent comprises one or more of ethanol, N-hexane, cyclohexane, dichloromethane, ethyl acetate, tetrahydrofuran, N-methylpyrrolidone.
In the preparation method of the lithium supplement additive, the organic phosphorus compound is melted at a certain temperature in the heat treatment process and then coated on the surface of the lithium supplement material to form a uniform and compact coating layer. In some embodiments of the present application, the temperature of the heat treatment is 50 ℃ to 300 ℃ and the time of the heat treatment is 1h to 5h, wherein the temperature of the heat treatment may be, but not limited to, 50 ℃, 80 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃, and the time of the heat treatment may be, but not limited to, 1h, 2h, 3h, 4h or 5h. It is to be noted that, in the present application, the heat treatment temperature is lower than the decomposition temperature of the organic phosphorus compound, and for example, when the decomposition temperature of the organic phosphorus compound is 250 ℃, the heat treatment may be 200 ℃; when the decomposition temperature of the organic phosphorus compound is 150 ℃, the heat treatment may be 100 ℃.
In some embodiments of the present application, when the organic phosphorus compound is any one of organic phosphoric acid, organic hypophosphorous acid and organic phosphate having a structural formula shown in formula (1-2), during the heat treatment process, the organic phosphorus compound reacts with residual alkali on the surface of the lithium supplement material, such as lithium oxide or lithium hydroxide, to generate corresponding lithium organic phosphate or lithium organic hypophosphite, so as to reduce the amount of residual alkali, and form a lithium supplement additive having a first coating layer and a second coating layer structure as shown in fig. 3, wherein the structural formula of the lithium organic phosphate is shown in formula (3-1) or formula (3-2), and the structural formula of the lithium organic hypophosphite is shown in formula (3-3):
Figure BDA0003800366300000101
the lithium supplement material with the structure has low surface residual alkali content, is beneficial to reducing the side reaction of the lithium supplement material and electrolyte, and improves the battery performance.
In some embodiments of the present application, the preparing of the lithium supplement material comprises: and mixing the lithium source and the doping source, and sintering to obtain the lithium supplement material. In embodiments of the present application, the sintering is performed in a non-oxidizing atmosphere comprising one or more of nitrogen, helium, and argon. In some embodiments of the present application, after mixing the lithium source and the doping source according to a molar ratio, sintering the mixture at 250-500 ℃ for 4-10 h, then heating the mixture to 700-900 ℃ for sintering for 6-24 h, and cooling the mixture along with the furnace to obtain the lithium supplement material. In the embodiment of the present application, the sintering equipment may be any one of a rotary furnace, a box furnace, a tube furnace, a roller kiln, a pusher kiln, or a fluidized bed. In some embodiments of the present disclosure, the product is further granulated after sintering, so as to obtain secondary particles of the lithium supplement material. In some embodiments of the present disclosure, the lithium source includes one or more of lithium hydroxide, lithium carbonate, lithium oxide, lithium acetate, and lithium oxalate, the dopant source includes a doping metal element M, the dopant source may be one or more of an oxide, a hydroxide, or a salt of the doping metal element M, and the doping metal element M includes one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce, or Zr.
The preparation method of the lithium supplement additive is simple in process and convenient and fast to operate, and the obtained lithium supplement additive is good in stability and suitable for large-scale production.
The application also provides a positive pole piece, and this positive pole piece includes the mass flow body and sets up the active material layer on the mass flow body, and the active material layer includes the benefit lithium additive of this application. In some embodiments of the present application, the current collector includes any one of a copper foil and an aluminum foil. In some embodiments, the active material layer includes an electrode active material, a lithium supplement additive, a binder, and a conductive agent. In the embodiment of the present application, the binder includes one or more of polyvinylidene chloride, soluble polytetrafluoroethylene, styrene-butadiene rubber, hydroxypropylmethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivative. In an embodiment of the present application, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fiber, C60, and carbon nanotube. In the embodiment of the present application, the electrode active material includes one or more of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadium fluorophosphate, lithium titanate, lithium nickel cobalt manganese oxide, and lithium nickel cobalt aluminate. In some embodiments of the present application, the preparation process of the positive electrode sheet is: mixing an electrode active material, a lithium supplement additive, a conductive agent and a binder to obtain electrode slurry, coating the electrode slurry on a current collector, and drying, rolling, die-cutting and the like to prepare the positive pole piece.
The application also provides a secondary battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises the positive pole piece provided by the application. The secondary battery provided by the application has better cycle performance and safety performance due to the adoption of the lithium supplement additive, and is beneficial to the application of the secondary battery in various fields.
The following will further describe the embodiments of the present application by dividing into a plurality of examples.
Example 1
A lithium supplementing additive comprises a lithium-rich material core and a lithium-rich materialA coating layer on the surface of the core, wherein the lithium-rich material core comprises an average chemical formula of Li 6 MnO 4 The coating layer of the lithium supplement material comprises tetradecyl phosphoric acid, and the mass percentage of the organic phosphorus compound in the lithium supplement additive is 4%.
1) Preparation of lithium-supplementing material
According to the weight ratio of Li: and (2) weighing a certain amount of lithium oxide and manganese carbonate according to the molar ratio of Mn =6.0 6 MnO 4 And (5) supplementing lithium materials.
2) Preparation of lithium supplement additive
And (3) adding 0.12g of tetradecyl phosphoric acid into 3g of the lithium supplementing material prepared in the step (1), uniformly mixing, and carrying out heat treatment at 250 ℃ for 2h in a nitrogen atmosphere to obtain the lithium supplementing additive.
3) Preparation of lithium Secondary Battery
Mixing N-methyl pyrrolidone, lithium iron phosphate, a lithium supplement additive, super P and polyvinylidene fluoride according to the mass ratio of 100;
uniformly mixing graphite serving as a negative electrode active material, a conductive agent Super P, a thickener carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) serving as a binder in deionized water to prepare negative electrode slurry, wherein the mass ratio of the graphite to the Super P to the CMC to the SBR is 95.5. And coating the negative electrode slurry on a current collector copper foil, and performing drying-rolling-secondary drying procedures to obtain a negative electrode pole piece.
EC (ethylene carbonate) and DEC (diethyl carbonate) were mixed in a volume ratio of 3:7 and LiPF was added 6 Forming an electrolyte, liPF 6 The concentration of (2) is 1mol/L. And assembling the positive pole piece, the negative pole piece, the Polyethylene (PE) diaphragm and the electrolyte to obtain the lithium secondary battery.
Example 2
A lithium supplementing additive comprises a lithium-rich material core and a lithium-rich material coreA coating layer on the surface, wherein the lithium-rich material core comprises Li 6 MnO 4 The coating layer of the lithium supplement material comprises tetradecyl sodium phosphate, and the mass percentage of the organic phosphorus compound in the lithium supplement additive is 4%.
The lithium supplement material was prepared by the same method as in example 1, and the lithium supplement additive was prepared by the following method:
and (3) adding 0.12g of tetradecyl sodium phosphate into 3g of the lithium supplement material prepared in the step (1), uniformly mixing, and carrying out heat treatment at 250 ℃ for 2h in a nitrogen atmosphere to obtain the lithium supplement additive.
A lithium secondary battery was prepared in the same manner as in example 1.
Example 3
A lithium supplementing additive comprises a lithium-rich material core and a coating layer on the surface of the lithium-rich material core, wherein the lithium-rich material core comprises an average chemical formula of Li 6 MnO 4 The coating layer of the lithium supplement material comprises diethyl hypophosphorous acid, and the mass percentage of the organic phosphorus compound in the lithium supplement additive is 4%.
The lithium supplement material was prepared by the same method as in example 1, and the lithium supplement additive was prepared by the following method:
and (3) adding 0.12g of diethyl hypophosphorous acid into 3g of the lithium supplementing material prepared in the step (1), uniformly mixing, and carrying out heat treatment at 200 ℃ for 2h in a nitrogen atmosphere to obtain the lithium supplementing additive.
A lithium secondary battery was prepared in the same manner as in example 1.
Example 4
A lithium supplementing additive comprises a lithium-rich material core and a coating layer on the surface of the lithium-rich material core, wherein the lithium-rich material core comprises an average chemical formula of Li 6 MnO 4 The coating layer of the lithium supplement material comprises diethyl aluminum hypophosphite, and the mass percentage of the organic phosphorus compound in the lithium supplement additive is 4%.
The lithium supplement material was prepared by the same method as in example 1, and the lithium supplement additive was prepared by the following method:
and (3) adding 0.12g of diethyl aluminum hypophosphite into 3g of the lithium supplement material prepared in the step (1), uniformly mixing, and carrying out heat treatment for 2h at 200 ℃ in a nitrogen atmosphere to obtain the lithium supplement additive.
A lithium secondary battery was prepared in the same manner as in example 1.
Example 5
The lithium supplement additive comprises a lithium-rich material core and a coating layer on the surface of the lithium-rich material core, wherein the lithium-rich material core comprises a lithium with an average chemical formula of Li 6 MnO 4 The coating layer of the lithium supplement material comprises tetradecyl phosphoric acid and diethyl hypophosphorous acid, and the mass percentage of the organic phosphorus compound in the lithium supplement additive is 4%.
The lithium supplement material was prepared by the same method as in example 1, and the lithium supplement additive was prepared by the following method:
and (3) adding 0.04g of tetradecyl phosphoric acid and 0.08g of diethyl hypophosphorous acid into 3g of the lithium supplementing material prepared in the step (1), uniformly mixing, and carrying out heat treatment at 220 ℃ for 2h in a nitrogen atmosphere to obtain the lithium supplementing additive.
A lithium secondary battery was prepared in the same manner as in example 1.
Example 6
A lithium supplementing additive comprises a lithium-rich material core and a coating layer on the surface of the lithium-rich material core, wherein the lithium-rich material core comprises an average chemical formula of Li 6 MnO 4 The coating layer of the lithium supplement material comprises tetradecyl phosphoric acid, and the mass percentage of the organic phosphorus compound in the lithium supplement additive is 0.5%.
The lithium supplement material was prepared by the same method as in example 1, and the lithium supplement additive was prepared by the following method:
and (3) adding 0.015g of tetradecyl phosphoric acid into 3g of the lithium supplementing material prepared in the step (1), uniformly mixing, and carrying out heat treatment for 2h at 250 ℃ in a nitrogen atmosphere to obtain the lithium supplementing additive.
A lithium secondary battery was prepared in the same manner as in example 1.
Example 7
The lithium supplementing additive comprises a lithium-rich material core and a coating layer on the surface of the lithium-rich material core, wherein the lithium is richThe core of the material comprises an average chemical formula of Li 6 MnO 4 The coating layer of the lithium supplement material comprises tetradecyl phosphoric acid, and the mass percentage of the organic phosphorus compound in the lithium supplement additive is 20%.
The lithium supplement material was prepared by the same method as in example 1, and the lithium supplement additive was prepared by the following method:
and (2) taking 3g of the lithium supplement material prepared in the step (1), adding 0.60 of tetradecyl phosphoric acid, uniformly mixing, and carrying out heat treatment for 2h at 250 ℃ in a nitrogen atmosphere to obtain the lithium supplement additive.
A lithium secondary battery was prepared in the same manner as in example 1.
Example 8
A lithium supplementing additive comprises a lithium-rich material core and a coating layer on the surface of the lithium-rich material core, wherein the lithium-rich material core comprises an average chemical formula of Li 6 MnO 4 The coating layer of the lithium supplement material comprises tetradecyl phosphoric acid, and the content of the organic phosphorus compound in the lithium supplement additive is 4 percent by mass.
The lithium supplement material was prepared by the same method as in example 1, and the lithium supplement additive was prepared by the following method:
and (3) adding 0.12g of tetradecyl phosphoric acid into 3g of the lithium supplementing material prepared in the step (1), uniformly mixing, and carrying out heat treatment at 40 ℃ for 1h in a nitrogen atmosphere to obtain the lithium supplementing additive.
A lithium secondary battery was prepared in the same manner as in example 1.
To demonstrate the advantageous effects of the examples of the present application, the following comparative examples were set.
Comparative example 1
Comparative example 1 differs from example 1 in that Li is added 6 MnO 4 The lithium supplement material was directly added to the battery as a lithium supplement additive, and the battery was prepared in the same manner as in example 1.
Effects of the embodiment
1) The lithium supplement additives of examples 1-8 were subjected to particle size testing and morphology characterization using a laser particle sizer and a transmission electron microscope to obtain the structural parameters of the lithium supplement additives of examples 1-8, the specific parameters being shown in table 1.
TABLE 1 structural parameters of the lithium supplement additives of examples 1-8
Experimental group D of the core of lithium-rich Material 50 Particle size (μm) Average thickness of coating (nm)
Example 1 14.94 9.2
Example 2 13.98 9.5
Example 3 15.32 9.1
Example 4 15.82 8.9
Example 5 14.69 9.1
Example 6 15.05 1.3
Examples7 14.42 44.1
Example 8 15.51 4.2
As can be seen from Table 1, the lithium supplement additives of examples 1-5 have moderate surface coating thickness, which is beneficial for the coating to effectively protect the lithium-rich material core; in the lithium supplement additive of example 6, the content of the organic phosphorus compound is too low, and the thickness of the formed coating layer is thin; in the lithium supplement additive of example 7, the content of the organic phosphorus compound was too high, and the thickness of the formed coating layer was thick; in the preparation process of the lithium supplement additive in example 8, the heat treatment temperature is low, the adhesion performance of the organic phosphorus compound to the lithium-rich material core is poor, the uniformity of the formed coating layer is poor, and the average thickness of the coating layer is thin.
2) The residual alkali content of the lithium supplement additives of examples 1 to 8 and comparative example 1 was tested by the following specific test methods: respectively weighing 5g of lithium supplement additives of examples 1-8 and comparative example 1, adding 50mL of ultrapure water from which carbon dioxide is removed, dissolving in a beaker, and ultrasonically oscillating the sample for 5min at an ultrasonic frequency of 5KHz and a power of 50w, and stirring once every 1 min; the mixture was filtered to a 100ml volumetric flask with a quantitative paper and the volume was fixed. Taking the sample solution, carrying out potentiometric titration by using a hydrochloric acid standard solution, and recording the volume V of the consumed hydrochloric acid standard solution 1 And V 2 In which V is 1 The volume of HCl standard solution consumed for titration to the first jump point; v 2 The volume of HCl standard solution consumed from the first jump point to the second jump point. OH was calculated according to the following formula - And CO 3 2- Residual alkali amount:
Figure BDA0003800366300000161
total residual alkali = w (OH) - )+w(CO 3 2- )
Wherein m is the actual mass of the sample, c is the concentration of the HCl standard solution, V 3 Volume of filtrate, V 4 The volume of the filtrate is 100mL after the volume is determined. See table 2 for the results of the total residual alkali test of the lithium supplement additives of examples 1-8 and comparative example 1.
TABLE 2 summary of the total residual alkali content of the lithium supplement additives of examples 1-8 and comparative example 1
Experimental group Total residual alkali (%)
Example 1 0.259
Example 2 0.424
Example 3 0.274
Example 4 0.391
Example 5 0.269
Example 6 0.833
Example 7 0.082
Example 8 0.293
Comparative example 1 1.211
As can be seen from table 2, the total residual alkali amount of the lithium supplement additive for the positive electrode (examples 1-8) containing the organic phosphorus compound is significantly lower than that of comparative example 1, which illustrates that the organic phosphorus compound coating can effectively reduce the residual alkali of the lithium supplement additive, and for each example, the coating layer of example 1 comprises tetradecyl phosphoric acid, i.e., the coating layer comprises organic phosphoric acid, and the coating layer of example 2 comprises sodium tetradecyl phosphate, i.e., the coating layer comprises organic phosphate, and as can be seen from the comparison between example 1 and example 2, the residual alkali amount of the lithium supplement additive can be effectively reduced by using the organic phosphoric acid coating layer, compared with the organic phosphate coating layer, because the organic phosphoric acid can also react with the residual alkali on the surface of the lithium-rich material core to reduce the residual alkali amount; as can be seen from the comparison of example 1 and example 2, the use of organic hypophosphorous acid as the coating layer is effective in reducing the amount of residual base of the lithium supplement additive relative to organic hypophosphorous acid.
3) The electrochemical performance of the lithium secondary batteries of examples 1 to 8 and comparative example 1 was tested under the following conditions: the battery is placed in an environment of 25 ℃, the battery is subjected to charge-discharge circulation by using 0.1C current in a charge-discharge voltage interval of 3.0-4.4V, the gas production is measured by adopting a differential electrochemical mass spectrometer under the same condition, and the test results refer to Table 3.
TABLE 3 TABLE of Performance parameters of the batteries of examples 1-8 and comparative example 1
Figure BDA0003800366300000171
As can be seen from table 3, the lithium ion batteries of examples 1 to 8 of the present application have excellent electrochemical properties compared with the lithium ion battery of comparative example 1, and the first charge specific capacity, the first discharge specific capacity, and the first effect are all significantly higher than those of the lithium ion battery of comparative example 1, which indicates that the positive electrode lithium supplement additive provided by the present application has a more excellent lithium supplement effect; in addition, it can be seen from the gas production test result that the lithium ions Chi Chanqi in the embodiments 1 to 8 are fewer, which fully indicates that the organic phosphorus compound coating can effectively reduce the loss of lattice oxygen on the surface of the lithium-rich material core, inhibit the gas production phenomenon caused by the release of active oxygen, and improve the structural stability and safety of the lithium supplement additive.
For each embodiment, the organic hypophosphorous acid or the organic hypophosphite with reducing property is adopted as the coating layer in the embodiments 3 to 5, so that the active oxygen generated by the lithium supplement additive in the charging and discharging process can be absorbed more favorably, and the gas generation reaction caused by the active oxygen can be inhibited; in the embodiment 6, the content of the organic phosphorus compound is lower, the residual alkali content on the surface of the lithium supplement additive is high, the lithium supplement effect is reduced, the first effect of the battery is reduced, and the gas generation is more; in example 7, the content of the organic phosphorus compound is too high, and although the lithium-rich material core can be effectively protected to reduce gas generation, the lithium supplement capacity of the lithium supplement additive is reduced due to the lower mass ratio of the lithium-rich material core; the lithium supplement additive of example 8 has a lower heat treatment temperature during the preparation process, a coating layer with poor uniformity and low density, weakens the protection effect on the lithium-rich material core, and has a lower first effect and more gas production.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent application shall be subject to the appended claims.

Claims (11)

1. The lithium supplement additive is characterized by comprising a lithium-rich material core and a coating layer arranged on the lithium-rich material core, wherein the coating layer comprises an organic phosphorus compound, the organic phosphorus compound comprises organic phosphoric acid with a structural formula shown in a formula (1-1) or organic phosphate thereof, and/or the organic phosphorus compound comprises organic hypophosphorous acid with a structural formula shown in a formula (2-1) or organic hypophosphite thereof;
Figure FDA0003800366290000011
in the formulae (1-1) and (2-1), R 1 、R 2 、R 3 Independently selected from substituted or unsubstituted alkyl or silicon-containing groups, and the substituent of the substituted alkyl comprises fluorine atom, hydroxyl, carboxyl, amino and amido.
2. The lithium supplement additive of claim 1, wherein the organophosphorus compound comprises one or more of the organic hypophosphorous acid and the organic hypophosphite, and the organic hypophosphorous acid and/or the organic hypophosphite accounts for 50% or more by mass of the coating layer.
3. The lithium supplement additive of claim 1, wherein the organophosphorus compound has a melting point of 50 ℃ or greater.
4. The lithium supplement additive of claim 1, wherein the coating comprises a first coating proximate to the lithium-rich material core and a second coating distal to the lithium-rich material core, the first coating comprising one or more of a lithium organophosphate having a formula as shown in formula (3-1) or formula (3-2) and a lithium hypophosphite having a formula as shown in formula (3-3); the second coating layer comprises one or more of the organic phosphoric acid, the organic hypophosphorous acid or the organic phosphate shown as the formula (1-2);
Figure FDA0003800366290000012
Figure FDA0003800366290000021
5. the lithium supplement additive according to claim 1, wherein the average thickness of the clad layer is 2nm to 150nm.
6. The lithium supplement additive according to claim 1, wherein the mass ratio of the lithium-rich material core to the coating layer is 1 (0.01-0.15).
7. The lithium replenishment additive of claim 1 wherein the total residual alkali content of the lithium replenishment additive is less than or equal to 1%.
8. The lithium supplement additive of claim 1, wherein the lithium rich material core comprises an average chemical formula of Li x M y O z Wherein x is more than 0.1 and less than 10,0 and more than y is more than 5,2 and is more than or equal to z is less than 10; the M comprises one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce or Zr.
9. A preparation method of a lithium supplement additive is characterized by comprising the following steps:
providing an average chemical formula of Li x M y O z The lithium supplement material of (1), wherein x is more than 0.1 and less than 10,0 and more than y is more than 5,2 and less than or equal to z is less than 10; the M comprises one or more of Mn, fe, cr, co, ni, cu, zn, mg, ti, si, sn, ce or Zr; mixing the lithium supplement material with an organic phosphorus compound and then carrying out heat treatment to obtain a lithium supplement additive; the organic phosphorus compound comprises organic phosphoric acid with a structural formula shown as a formula (1-1) or organic phosphate thereof, and/or the organic phosphorus compound comprises a structural formulaAn organic hypophosphorous acid represented by the formula (2-1) or an organic hypophosphite thereof;
Figure FDA0003800366290000022
in the formulae (1-1) and (2-1), R 1 、R 2 、R 3 Independently selected from substituted or unsubstituted alkyl or silicon-containing groups, and the substituent of the substituted alkyl comprises fluorine atom, hydroxyl, carboxyl, amino and amido.
10. A positive electrode sheet comprising a current collector and an active material layer disposed on the current collector, wherein the active material layer comprises the lithium supplement additive according to any one of claims 1 to 8.
11. A secondary battery comprising the positive electrode sheet according to claim 10.
CN202210980858.3A 2022-08-16 2022-08-16 Lithium supplement additive, preparation method thereof and secondary battery Pending CN115347170A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117059804A (en) * 2023-10-13 2023-11-14 瑞浦兰钧能源股份有限公司 Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117059804A (en) * 2023-10-13 2023-11-14 瑞浦兰钧能源股份有限公司 Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery
CN117059804B (en) * 2023-10-13 2024-03-19 瑞浦兰钧能源股份有限公司 Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery

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Inventor after: Lin Lvhuan

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