CN115312692A - Positive lithium-rich composite pole piece and preparation method and application thereof - Google Patents

Positive lithium-rich composite pole piece and preparation method and application thereof Download PDF

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Publication number
CN115312692A
CN115312692A CN202210227035.3A CN202210227035A CN115312692A CN 115312692 A CN115312692 A CN 115312692A CN 202210227035 A CN202210227035 A CN 202210227035A CN 115312692 A CN115312692 A CN 115312692A
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lithium
positive
rich
positive electrode
pole piece
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钟泽钦
万远鑫
孔令涌
赵中可
朱成奔
张於财
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Shenzhen Dynanonic Innovazone New Energy Technology Co Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 application relates to the technical field of lithium ion battery anode materials, in particular to a positive electrode lithium-rich composite pole piece and a preparation method and application thereof; the positive lithium-rich composite pole piece comprises a positive current collector and a positive composite substance layer positioned on the positive current collector, wherein lithium-rich materials are distributed in the positive composite substance layer, at least hydrophobic organic materials are distributed on the surface layer of the positive composite substance layer, and the hydrophobic organic materials are selected from hydrophobic organic materials capable of being dissolved in electrolyte; the contained hydrophobic organic material can play a role in isolating harmful components such as water and carbon dioxide in the air, so that the stability of the lithium-rich material contained in the positive electrode composite material layer is effectively ensured, the lithium-rich material can be dissolved in the electrolyte, the effect of supplementing lithium to the battery positive electrode is achieved, and the stability of the electrochemical performance of the battery positive electrode is improved.

Description

Positive lithium-rich composite pole piece and preparation method and application thereof
Technical Field
The application belongs to the technical field of lithium ion battery anode materials, and particularly relates to an anode lithium-rich composite pole piece and a preparation method and application thereof.
Background
The oil energy crisis problem in the 60 and 70 th 20 th century forced people to find new alternative new energy. The lithium ion battery is considered to be one of the most promising energy sources due to its advantages of high working voltage and energy density, relatively small self-discharge level, no memory effect, no pollution of heavy metal elements such as lead and cadmium, and ultra-long cycle life.
In the first charging process of the lithium ion battery, the surface of a negative electrode is usually accompanied with the formation of an SEI (solid electrolyte film) film, and a large amount of Li + is consumed in the process, which means that the Li + separated from a positive electrode material is irreversibly consumed, and the reversible specific capacity of a corresponding battery cell is reduced. The cathode material, in particular a silicon-based cathode material, further consumes Li +, resulting in a first too low coulombic efficiency.
In order to solve the problem of low coulombic efficiency caused by irreversible loss of the negative electrode, the requirement of high energy density can be met by supplementing lithium to the positive electrode besides pre-lithiating the negative electrode material and the pole piece. The lithium-iron-rich material has a theoretical capacity of 867mAh/g, a working voltage window consistent with that of a conventional lithium ion battery, does not basically participate in an electrochemical process at a later stage, and is a lithium supplement additive with a wide prospect. However, the positive electrode is filled with lithium material Li 5 FeO 4 The method has harsh environmental adaptability, and is easy to contact and react with environmental moisture to form a large amount of residual alkali on the surface layer; although CN 110459748 discloses a carbon-coated lithium ferrite material and a preparation method thereof. Isolating the outer ring by gas phase coating with a carbon sourceThe contact between the lithium ferrite and water in the air is relieved, so that the stability of the material is improved; nevertheless, the coating layer is difficult to completely isolate from water in the air, so that the material and the battery pole piece are deteriorated and invalid, and the wide application is not facilitated.
Disclosure of Invention
The application aims to provide a positive lithium-rich composite pole piece and a preparation method and application thereof, and aims to solve the problems that in the prior art, a positive composite pole piece material containing rich lithium is easy to absorb water and is deteriorated and ineffective due to oxidation.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a positive lithium-rich composite electrode sheet, which includes a positive current collector and a positive composite material layer on the positive current collector, wherein the positive composite material layer includes a lithium-rich material, and at least a hydrophobic organic material is distributed on a surface layer of the positive composite material layer, and the hydrophobic organic material is selected from hydrophobic organic materials capable of being dissolved in an electrolyte.
In a second aspect, the present application provides a method for preparing a positive lithium-rich composite pole piece, including the following steps:
preparing positive active slurry for forming a positive composite material layer; wherein the positive active slurry comprises a lithium-rich material and a hydrophobic organic material;
and coating the positive active slurry on the surface of a positive current collector, and sequentially performing rolling and drying treatment to obtain the positive lithium-rich composite pole piece.
In a third aspect, the present application provides a secondary battery comprising a positive lithium-rich composite pole piece.
The utility model provides a hydrophobic organic material distributes on the surface layer of the positive pole composite material layer of positive pole rich lithium composite pole piece that this application first aspect provided, it plays the effect of harmful components such as water and carbon dioxide in the isolated air, thereby effectively guarantee the stability ability of rich lithium material that positive pole composite material layer contains, thereby improved the effect that positive pole rich lithium composite pole piece is isolated with steam in the storage process, improve its electrochemical properties's stability, and this hydrophobic organic material is selected from the hydrophobic organic material that can dissolve in electrolyte, after the equipment forms the battery, can dissolve in the electrolyte, reach the effect of mending lithium to the battery positive pole, guarantee not to influence the lithium of rich lithium material and deviate from, improve the life of battery, keep the abundance of lithium ion in the battery system, improve the first effect and the whole electrochemical properties of battery, it accords with the easy water absorption metamorphism problem to have solved rich lithium material pole piece, pole piece processing stability has been improved, the gram capacity performance of rich lithium composite pole piece has been guaranteed, realize the high-efficient lithium of true meaning.
The preparation method of the positive electrode lithium-rich composite pole piece provided by the second aspect of the application is simple and convenient, the prepared positive electrode active slurry is coated on the surface of a positive electrode current collector, in the coating process, the hydrophobic organic material floats to the surface of the positive electrode pole piece along with the evaporation of the solvent of the positive electrode active slurry, an organic hydrophobic isolation layer is formed on the surface of the obtained positive electrode lithium-rich composite pole piece, the positive electrode lithium-rich composite pole piece can be protected to the maximum extent from being contacted with water vapor and carbon dioxide in the air before the battery is assembled and packaged, and the stability of the lithium supplementing performance of the lithium-rich material in the positive electrode lithium-rich composite pole piece is ensured.
The secondary battery provided by the third aspect of the application comprises the provided positive lithium-rich composite pole piece, and the positive lithium-rich composite pole piece comprises the hydrophobic organic material, so that the positive lithium-rich composite pole piece is not influenced by water vapor and carbon dioxide in the air before the secondary battery is formed by packaging, the lithium ions in the obtained secondary battery system are stable, the overall electrochemical performance of the battery is improved, the better cycle performance and lithium supplement performance are realized, and the wide application is facilitated.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a positive lithium-rich composite pole piece provided in an embodiment of the present application.
Fig. 2 is a schematic structural diagram of a positive lithium-rich composite pole piece provided in an embodiment of the present application.
Fig. 3 is a schematic structural diagram of a positive lithium-rich composite pole piece provided in an embodiment of the present application.
Fig. 4 is a schematic structural diagram of a positive lithium-rich composite pole piece provided in an embodiment of the present application.
Fig. 5 is a schematic structural diagram of a positive lithium-rich composite pole piece provided in an embodiment of the present application.
Wherein, in the figures, the respective reference numerals:
1-positive current collector;
2-positive electrode composite material layer;
21-positive electrode active material layer;
22-a layer of lithium-rich material;
3-organic hydrophobic barrier.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry such as g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present application provides a positive electrode lithium-rich composite pole piece, which includes a positive electrode current collector and a positive electrode composite material layer on the positive electrode current collector, wherein the positive electrode composite material layer includes a lithium-rich material, and at least a hydrophobic organic material is further distributed on a surface layer of the positive electrode composite material layer, and the hydrophobic organic material is selected from hydrophobic organic materials that can be dissolved in an electrolyte.
The embodiment of the application provides a positive pole lithium-rich composite pole piece's that positive pole lithium-rich composite pole piece's top layer distributes and has hydrophobic organic material, it plays the effect of harmful ingredients such as water and carbon dioxide in the isolated air, thereby effectively guarantee the stability ability of the rich lithium material that positive pole composite substance layer contains, thereby the effect of positive pole lithium-rich composite pole piece isolated with steam in processing and storage process has been improved, improve its electrochemical performance's stability, and this hydrophobic organic material is selected from the hydrophobic organic material that can dissolve in electrolyte, after the equipment forms the battery, in the electrolyte, can dissolve the effect of lithium is mended to the battery positive pole, guarantee not to influence the lithium of positive pole lithium-rich material and deviate from, improve the life of battery, the abundance of lithium ion in the battery system, improve battery first efficiency and whole electrochemical performance, it accords with the pole piece and easily absorbs water the rotten problem to have solved the rich lithium material, pole piece processing stability has been improved, the gram capacity performance of rich lithium composite pole piece has been guaranteed, realize the high-efficient lithium of true meaning.
In some embodiments, the hydrophobic organic material is distributed on the surface layer of the positive electrode composite material layer, the organic hydrophobic isolation layer is formed on the surface layer of the positive electrode composite material layer, and the formed isolation layer can isolate water vapor and carbon dioxide in the air, so that the positive electrode lithium-rich composite pole piece cannot be easily contacted with the water vapor and the carbon dioxide when the battery is not packaged, and the maximum activity of the lithium-rich material in the positive electrode lithium-rich composite pole piece can be maintained.
In some embodiments, the obtained positive electrode lithium-rich composite pole piece includes a positive electrode current collector 1 and a positive electrode composite material layer 2 disposed on the surface of the positive electrode current collector 1, as shown in fig. 1. Further, as shown in fig. 2, the hydrophobic organic material forms an organic hydrophobic barrier layer 3 on the surface layer of the positive electrode composite material layer.
In some embodiments, as shown in fig. 3, the positive electrode composite layer 2 is selected from a positive electrode active material layer 21 bonded to the surface of the positive electrode current collector 1 and a lithium-rich material layer 22 bonded to the surface of the positive electrode active material layer facing away from the positive electrode current collector.
In some embodiments, as shown in fig. 4, the positive electrode composite layer 2 is selected from a lithium-rich material layer 22 bonded on the surface of the positive electrode current collector 1 and a positive electrode active material layer 21 bonded on the surface of the lithium-rich material layer away from the surface of the positive electrode current collector.
In some embodiments, as shown in fig. 5, the positive electrode composite layer 2 is selected from a positive electrode active material layer distributed with a lithium-rich material, and the lithium-rich material is mixed with the positive electrode active material to obtain a "lithium-rich material-positive electrode active material" mixed layer 2'.
In some embodiments, the positive current collector has a thickness of 8-20 μm.
In some embodiments, the thickness of the positive electrode composite material layer is 120-250 μm, and the thickness of the positive electrode composite material layer is moderate, which is beneficial for mixing the positive electrode active material to act, and if the thickness of the positive electrode composite material layer is too thin, the assembly is not beneficial to form the battery.
In some embodiments, the thickness of the organic hydrophobic isolation layer is 50nm-1 μm, the thickness of the organic hydrophobic isolation layer is controlled to be moderate, and the effect of isolating harmful components such as water and carbon dioxide in the air can be ensured, so that the stability of the lithium-rich material contained in the positive electrode composite material layer can be effectively ensured, and the lithium-rich material can be quickly dissolved in the electrolyte after being assembled to form a battery, so that the lithium removal of the positive electrode lithium supplement material is not influenced, the service life of the battery is prolonged, and the abundance of lithium ions in a battery system is maintained; if the thickness of the organic hydrophobic isolation layer is too thin, the organic hydrophobic isolation layer cannot play a role in isolating harmful components such as water, carbon dioxide and the like in the air; if the thickness of the organic hydrophobic isolation layer is too thick, the organic hydrophobic isolation layer is not beneficial to being quickly dissolved in electrolyte when the organic hydrophobic isolation layer is assembled to form a battery, and the lithium supplementing effect of the positive electrode lithium supplementing material can be influenced.
In some embodiments, the hydrophobic organic material is selected from hydrophobic organic materials capable of being dissolved in electrolyte, and in the process of forming the battery by using the formed positive electrode lithium-rich composite pole piece through encapsulation and injection, an organic hydrophobic isolation layer formed by the hydrophobic organic material is dissolved in the electrolyte, so that an electrode interface is reopened to achieve the effect of supplementing lithium to the positive electrode of the battery, lithium removal of the positive electrode lithium-supplementing material is not affected, the service life of the battery is prolonged, the abundance of lithium ions in a battery system is kept, and the first effect and the overall electrochemical performance of the battery are improved.
In some embodiments, the hydrophobic organic material includes, but is not limited to, at least one of an alkane tar, a fluorine-containing organic, a silicon-containing organic, a lipid waxy material.
In some embodiments, the hydrophobic organic material is selected from alkane tar, and the alkane tar has stable properties and certain hydrophobicity, and can effectively isolate water vapor and carbon dioxide in air. Wherein, the alkane tar comprises but not limited to at least one of coal tar, waxy tar and aromatic tar.
In some embodiments, the hydrophobic organic material is selected from fluorine-containing organic substances, the fluorine-containing organic substances are stable in property, and the carbon-fluorine and carbon-hydrogen containing alternative chemical bond energy is higher, so that the formed organic hydrophobic isolation layer is high in compactness, not easy to damage and good in isolation effect; and the carbon-fluorine bond has higher lipophilicity, can be quickly dissolved in the electrolyte and is beneficial to use. Wherein, the fluorine-containing organic matter comprises but is not limited to at least one of fluoroethylene carbonate and perfluorodecalin.
In some embodiments, the hydrophobic organic material is selected from, but not limited to, silicon-containing organic substances, where the silicon-containing organic substances refer to compounds that contain Si — C bonds and at least one organic group is directly connected to a silicon atom, and may effectively perform a hydrophobic function, and the connected organic substances may be rapidly dissolved in the electrolyte, thereby facilitating release of the positive lithium particles. Wherein, the silicon-containing organic matter includes but is not limited to at least one of polydimethylsiloxane and octadecyl trimethoxy silane.
In some embodiments, the hydrophobic organic material is selected from, but not limited to, lipid waxy materials, wherein the lipid waxy materials are connected by carbon-oxygen bonds, so that a dense film layer is formed, and the ester bonds are non-covalent bonds and do not react with water, so that the formed organic hydrophobic insulating layer has high compactness and can effectively insulate water vapor and carbon dioxide in the air; and after the battery is assembled and packaged, the ester group can be dissolved in the organic solvent and can be dissolved in the electrolyte, so that the effect of supplementing lithium to the battery anode is achieved, and the service life of the battery is prolonged. Wherein the lipid waxy material includes but is not limited to at least one of sorbitan monostearate, polyethylene glycol, polypropylene, stigmasterol and cholesterol.
In some embodiments, the hydrophobic organic material is present in an amount of 0.5 to 20% by mass, based on 100% by mass of the total mass of the positive electrode composite layer.
In a specific embodiment, the content of the hydrophobic organic material is selected from 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% by mass based on 100% by mass of the total mass of the positive electrode composite material layer.
In some embodiments, lithium-rich materials are distributed in the positive electrode composite layer, after the positive electrode lithium-rich composite pole piece is assembled to form the battery, a film layer formed by hydrophobic organic materials can be dissolved in electrolyte, so that the lithium-rich materials can fully supplement lithium, the service life of the battery is further prolonged, the abundance of lithium ions in a battery system is kept, the first effect and the overall electrochemical performance of the battery are improved, the gram capacity of the lithium-rich composite pole piece is guaranteed, and the high-efficiency lithium supplement in the true sense is realized.
In some embodiments, the lithium-rich material comprises Li x M y O z 、Li w A、Li 1+a N b G c H d O e At least one of (a); wherein x is more than 0 and less than or equal to 8, y is more than 0 and less than or equal to 3, z is more than 0 and less than or equal to 6, and w is more than 0 and less than or equal to 5; a is more than 0 and less than or equal to 1, b is more than 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, e is more than or equal to 1.8 and less than or equal to 3; m is at least one element of Fe, co, ni, mn, si, sn, cu, mo, al and Ti, A is at least one element of C, N, O, P, S, F, B and Se; n is at least one element of Fe and Mn; g is at least one element of Ni, co, A1, mg, ti, fe, cu, cr, mo, zr, ru and Sn; h is at least one element of S, P, B or F.
In some embodiments, the lithium-rich material has the general structural formula Li x M y O z When, including but not limited to Li 2 MnO 2 、Li 6 MnO 4 、Li 6 CoO 4 、Li 2 NiO 2 、Li 4 SiO 4 、Li 8 SnO 6 At least one of (a).
In some embodiments, the lithium-rich material has the general structural formula Li w When A, including but not limited to Li 2 S、Li 3 N、LiF、Li 3 B、Li 2 O、Li 3 P、Li 2 At least one of Se.
In some embodiments, the lithium-rich material has the general structural formula Li 1+a N b G c H d O e The lithium-rich material is selected from lithium-rich iron-based materials, and the lithium-rich iron-based materials include fLiFeO 2 ·gLi 2 O·hG i O j Wherein, 15f + g is more than or equal to 0.98, h is less than or equal to 0.02, g/h is more than or equal to 1.8 and less than or equal to 2.1, f, g and h are mole numbers; j/i is more than or equal to 1 and less than or equal to 2.5; and G includes at least one element of Ni, co, A1, mg, ti, fe, cu, cr, mo, zr, ru, sn.
In some embodiments, the lithium-rich material is present in an amount of 0.5 to 30% by mass, based on 100% by mass of the total mass of the positive electrode composite layer.
In a specific embodiment, the content of the lithium-rich material is selected from 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% by mass based on 100% by mass of the total mass of the positive electrode composite material layer.
In some embodiments, the positive electrode composite layer further comprises: a positive electrode active material, a conductive agent, and a binder; the positive electrode composite material layer comprises the following components in percentage by mass based on 100% of the total mass of the positive electrode composite material layer:
the mass percentage of the positive active material is 60-99%,
the mass percentage of the conductive agent is 0.2-20%,
the mass percentage of the binder is 0.5-3%.
In some embodiments, the positive lithium-rich composite pole piece comprises, based on 100% of the total mass of the positive composite layer: the mass percentage of the positive electrode active material is 65%, the mass percentage of the lithium-rich material is 25%, the mass percentage of the conductive agent is 2%, the mass percentage of the hydrophobic organic material is 3%, and the mass percentage of the binder is 5%.
In some embodiments, the positive electrode lithium-rich composite pole piece comprises, based on 100% of the total mass of the positive electrode composite layer: the mass percentage of the positive electrode active material is 65%, the mass percentage of the lithium-rich material is 25%, the mass percentage of the conductive agent is 4%, the mass percentage of the hydrophobic organic material is 1%, and the mass percentage of the binder is 5%.
In some embodiments, the positive lithium-rich composite pole piece comprises, based on 100% of the total mass of the positive composite layer: the mass percentage of the positive electrode active material is 65%, the mass percentage of the lithium-rich material is 25%, the mass percentage of the conductive agent is 4.5%, the mass percentage of the hydrophobic organic material is 0.5%, and the mass percentage of the binder is 5%.
In some embodiments, the positive lithium-rich composite pole piece comprises, based on 100% of the total mass of the positive composite layer: the mass percentage of the positive electrode active material is 65%, the mass percentage of the lithium-rich material is 25%, the mass percentage of the conductive agent is 3%, the mass percentage of the hydrophobic organic material is 2%, and the mass percentage of the binder is 5%.
In some embodiments, the positive lithium-rich composite pole piece comprises, based on 100% of the total mass of the positive composite layer: the mass percentage of the positive electrode active material is 65%, the mass percentage of the lithium-rich material is 25%, the mass percentage of the conductive agent is 4%, the mass percentage of the hydrophobic organic material is 1%, and the mass percentage of the binder is 5%.
In some embodiments, the positive active material includes at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium nickel cobalt aluminate, lithium cobalt oxide.
In some embodiments, the binder comprises at least one of polyimide, polyvinylidene fluoride, polyamide.
In some embodiments, the conductive agent comprises at least one of conductive carbon black, carbon nanotubes, carbon nanofibers, graphite flakes, graphene.
In some embodiments, the positive electrode current collector includes, but is not limited to, at least one of aluminum foil and copper foil, and the metal material may be selected as required.
The second aspect of the embodiments of the present application provides a method for preparing a positive lithium-rich composite pole piece, including the following steps:
s01, preparing positive active slurry for forming a positive composite material layer; wherein the positive active slurry comprises a lithium-rich material and a hydrophobic organic material;
s02, coating the positive active slurry on the surface of the positive current collector, and sequentially performing rolling and drying treatment to obtain the positive lithium-rich composite pole piece.
The preparation method of the positive electrode lithium-rich composite pole piece provided by the second aspect of the embodiment of the application is simple and convenient, the prepared positive electrode active slurry is coated on the surface of a positive electrode current collector, in the coating process, the hydrophobic organic material floats upwards to the surface of the positive electrode pole piece along with the evaporation of the solvent of the positive electrode active slurry, and an organic hydrophobic isolation layer is formed on the surface of the obtained positive electrode lithium-rich composite pole piece, so that the positive electrode lithium-rich composite pole piece can be protected from being contacted with water vapor and carbon dioxide in the air before being assembled and packaged, and the stability of the lithium supplementing performance of the lithium-rich material in the positive electrode lithium-rich composite pole piece is ensured.
In step S01, a positive electrode active slurry for forming a positive electrode composite material layer is prepared; wherein the positive active slurry includes a lithium-rich material and a hydrophobic organic material.
In some embodiments, the positive current collector, the positive active material, the lithium-rich material, the binder, the conductive agent, and the hydrophobic organic material are provided separately according to the positive lithium-rich composite pole piece.
In some embodiments, the hydrophobic organic material comprises at least one of an alkane tar, a fluorine-containing organic, a silicon-containing organic, a lipid waxy material.
In some alternative embodiments, the hydrophobic organic material comprises at least one of coal tar, fluoroethylene carbonate, perfluorodecalin, polydimethylsiloxane, octadecyltrimethoxysilane, sorbitan monostearate.
In some embodiments, the lithium-rich material comprises Li x M y O z 、Li w A、Li 1+a N b G c H d O e At least one of; wherein x is more than 0 and less than or equal to 8, y is more than 0 and less than or equal to 3, z is more than 0 and less than or equal to 6, and w is more than 0 and less than or equal to 5; a is more than 0 and less than or equal to 1, b is more than 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, e is more than or equal to 1.8 and less than or equal to 3; (ii) a M is at least one element of Fe, co, ni, mn, si, sn, cu, mo, al and Ti, A is at least one element of C, N, O, P, S, F, B and Se; n is at least one element of Fe and Mn; g is at least one element of Ni, co, A1, mg, ti, fe, cu, cr, mo, zr, ru and Sn; h is at least one element of S, P, B and F.
In some alternative embodiments, the lithium-rich material includes, but is not limited to, li 2 MnO 2 、Li 6 MnO 4 、Li 6 CoO 4 、Li 2 NiO 2 、Li 4 SiO 4 、Li 8 SnO 6、 Li 2 S、Li 3 N、LiF、Li 3 B、Li 2 O、Li 3 P、Li 2 At least one of Se.
In some embodiments, the positive active material, the lithium-rich material, the binder, the conductive agent, and the hydrophobic organic material are mixed to obtain a positive active slurry.
In some embodiments, a solvent is provided, and the positive electrode active material, the lithium-rich material, the binder, the conductive agent, and the hydrophobic organic material are dissolved by the solvent and subjected to a mixing, ball-milling, and stirring process to obtain a positive electrode active slurry.
In some embodiments, the solvent is at least one selected from butyl acetate, NMP, n-hexane, and cyclohexane, and the solvent is provided to disperse the materials of the positive electrode, and the organic solvent can not be affected by the aqueous solution without adding water.
And step S02, coating the positive active slurry on the surface of the positive current collector, and sequentially performing rolling and drying treatment to obtain the positive lithium-rich composite pole piece.
In some embodiments, in the step of drying, the temperature of the drying is 100 ℃ to 130 ℃ and the time of the drying is 20 to 24 hours.
In a third aspect of the embodiments of the present application, a secondary battery is provided, where the secondary battery includes a positive lithium-rich composite pole piece.
The secondary battery provided by the third aspect of the embodiment of the application includes the positive lithium-rich composite pole piece, and the positive lithium-rich composite pole piece includes the hydrophobic organic material, so that before the secondary battery is formed by packaging, the positive lithium-rich composite pole piece is not influenced by water vapor and carbon dioxide in the air, lithium ions in the obtained secondary battery system are stable, the overall electrochemical performance of the battery is improved, and the secondary battery has good cycle performance and lithium supplement performance, and is favorable for wide application.
In some embodiments, in the packaging process of the secondary battery, at least part of the organic hydrophobic isolation layer on the surface of the positive lithium-rich composite pole piece is dissolved in the electrolyte, so that in the using process of the positive lithium-rich composite pole piece, the release of lithium ions of a lithium-containing core material can be excited, the high-efficiency lithium supplement in the true sense is realized, and the integral conductivity of the material is improved; the obtained battery material has the characteristics of high capacity and long cycle.
In some embodiments, the secondary battery further comprises an electrolyte, a separator, and a negative electrode tab.
In some embodiments, the electrolyte is selected from the group consisting of ethylene carbonate, ethyl methyl carbonate, and LiPF 6 Wherein the volume ratio of ethylene carbonate to ethyl methyl carbonate is 3:7,LiPF 6 The concentration of (2) is 1mol/L.
In some embodiments, the separator includes, but is not limited to, at least one of a polypropylene microporous separator, a PP film, a PE film.
In some embodiments, the negative electrode sheet includes, but is not limited to, a lithium sheet.
The following description will be given with reference to specific examples.
Example A1
Positive lithium-rich composite pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black, hydrophobic organic materials fluoroethylene carbonate and polyvinylidene fluoride in a ratio of 65: 25: 2:3:5, mixing, ball-milling and stirring to obtain positive active slurry, coating the positive active slurry on the surface of a positive current collector aluminum foil, rolling, and drying in an air oven at 110 ℃ overnight to obtain the positive lithium-rich composite pole piece.
Example A2
Positive lithium-rich composite pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black, hydrophobic organic materials polydimethylsiloxane and polyvinylidene fluoride in a ratio of 65: 25: 4:1:5, mixing, ball-milling and stirring to obtain positive active slurry, coating the positive active slurry on the surface of a positive current collector aluminum foil, rolling, and drying in an air oven at 110 ℃ overnight to obtain the positive lithium-rich composite pole piece.
Example A3
Positive lithium-rich composite pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black, hydrophobic organic material coal tar and polyvinylidene fluoride in a ratio of 65: 25: 4.5:0.5:5, mixing, ball-milling and stirring to obtain positive active slurry, coating the positive active slurry on the surface of the positive current collector aluminum foil, rolling, and drying in an air oven at 110 ℃ overnight to obtain the positive lithium-rich composite pole piece.
Example A4
Positive lithium-rich composite pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black, hydrophobic organic materials of sorbitan monostearate and polyvinylidene fluoride in a ratio of 65: 25: 3:2:5, mixing, ball-milling and stirring to obtain positive active slurry, and coating the positive active slurry on an aluminum foil surface of a positive current collectorAnd (4) rolling, and drying in an air oven at 110 ℃ overnight to obtain the positive lithium-rich composite pole piece.
Example A5
Positive lithium-rich composite pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black, hydrophobic organic materials of octadecyl trimethoxy silane and polyvinylidene fluoride are mixed according to the weight ratio of 65: 25: 4.5:0.5:5, mixing, ball-milling and stirring to obtain positive active slurry, coating the positive active slurry on the surface of a positive current collector aluminum foil, rolling, and drying in an air oven at 110 ℃ overnight to obtain the positive lithium-rich composite pole piece.
Example A6
Positive lithium-rich composite pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black, hydrophobic organic materials perfluorodecalin and polyvinylidene fluoride are mixed according to a ratio of 65: 25: 4:1:5, mixing, ball-milling and stirring to obtain positive active slurry, coating the positive active slurry on the surface of the positive current collector aluminum foil, rolling, and drying in an air oven at 110 ℃ overnight to obtain the positive lithium-rich composite pole piece.
Comparative example A1
Positive pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black and polyvinylidene fluoride in a ratio of 65: 25: 5:5, mixing, ball-milling and stirring to obtain anode slurry, coating the anode slurry on the surface of the aluminum foil, rolling, and carrying out vacuum drying at 110 ℃ overnight to obtain the anode piece.
Comparative example A2
Positive pole piece and preparation method thereof
Lithium iron phosphate and lithium-rich material Li 5 FeO 4 Conductive carbon black and polyvinylidene fluoride in a ratio of 65: 25: 4:1 to obtain positive slurry, coating the positive slurry on the surface of an aluminum foil, rolling, and carrying out vacuum drying at 110 ℃ overnight to obtain the positive pole piece.
Example B1
Lithium secondary battery and preparation thereof
The positive electrode lithium-rich composite pole piece obtained in example A1 was provided,
ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 3 6 Forming an electrolyte, liPF 6 The concentration of (2) is 1mol/L. And (2) assembling the positive lithium-rich composite pole piece obtained in the example A1, the polypropylene microporous separator, the lithium piece and the electrolyte to obtain the lithium secondary battery.
The lithium secondary batteries of examples B2 to B6 were prepared in exactly the same manner as in example B1, except that "the positive electrode lithium-rich composite electrode sheet obtained in example A1" was replaced with "the positive electrode lithium-rich composite electrode sheet obtained in the corresponding examples A2 to A8".
The lithium secondary batteries of comparative examples A1 to A2 were prepared in exactly the same manner as in example B1, except that "the positive electrode lithium-rich composite electrode sheet obtained in example A1" was replaced with "the positive electrode lithium-rich composite electrode sheet obtained in comparative examples A1 to A2".
Property testing
The electrochemical performance of the lithium secondary batteries of examples B1 to B6 and comparative examples B1 to B2 was tested under the following conditions: and (3) placing the assembled battery at room temperature for 24 hours, and then carrying out charge-discharge test, wherein the charge-discharge voltage is 2.0-4.3V.
Analysis of results
The electrochemical properties of the lithium secondary batteries of examples B1 to B6 and comparative examples B1 to B2 are shown in Table 1.
TABLE 1
Figure BDA0003536282060000151
As can be seen from table 1, in the lithium secondary batteries of embodiments B1 to B6 of the present application, since the hydrophobic organic material is added, after the batteries are assembled to form a battery, lithium ions are released more sufficiently, a lithium supplement effect can be effectively achieved, and the positive electrode can have higher first charge capacity exertion and lower first efficiency, thereby compensating for a decrease in energy density due to first negative electrode irreversible lithium loss.
Experiments of a comparative example show that the lithium supplement material in the comparative example 1 has serious failure due to no protection of a hydrophobic layer, and the lithium supplement is not effectively realized; although comparative example 2 isolates moisture interference by vacuum drying, the influence of moisture is also inevitably introduced during coating, resulting in the occurrence of side reactions and partial consumption of active lithium.
In conclusion, the secondary battery comprises the provided positive lithium-rich composite pole piece, and the positive lithium-rich composite pole piece comprises the hydrophobic organic material, so that the positive lithium-rich composite pole piece is not influenced by water vapor and carbon dioxide in the air before the secondary battery is packaged and formed, lithium ions in an obtained secondary battery system are stable, the overall electrochemical performance of the battery is improved, and the secondary battery has good cycle performance and lithium supplement performance, and is favorable for wide application.
The above description is only a preferred embodiment of the present application and should not be taken as limiting the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (14)

1. The positive lithium-rich composite pole piece is characterized by comprising a positive current collector and a positive composite substance layer positioned on the positive current collector, wherein the positive composite substance layer comprises a lithium-rich material, at least the surface layer of the positive composite substance layer is also distributed with a hydrophobic organic material, and the hydrophobic organic material is selected from hydrophobic organic materials capable of being dissolved in electrolyte.
2. The positive electrode lithium-rich composite pole piece according to claim 1, wherein the hydrophobic organic material forms an organic hydrophobic isolation layer on the surface layer of the positive electrode composite material layer.
3. The positive lithium-rich composite pole piece according to claim 1, wherein the positive composite layer is selected from a positive active material layer bonded on the surface of the positive current collector and a lithium-rich material layer bonded on the surface of the positive active material layer away from the surface of the positive current collector; and/or the presence of a gas in the gas,
the positive electrode composite layer is selected from a lithium-rich material layer combined on the surface of the positive electrode current collector and a positive electrode active material layer combined on the surface of the lithium-rich material layer away from the surface of the positive electrode current collector; and/or the presence of a gas in the atmosphere,
the positive electrode compound material layer is selected from a positive electrode active material layer distributed with a lithium-rich material.
4. The positive lithium-rich composite pole piece according to claim 1, wherein the hydrophobic organic material comprises at least one of alkane tar, fluorine-containing organic matter, silicon-containing organic matter, and lipid waxy material.
5. The positive lithium-rich composite pole piece according to claim 4, wherein the alkane tar comprises at least one of coal tar, waxy tar and aromatic tar; and/or the presence of a gas in the atmosphere,
the fluorine-containing organic matter comprises at least one of fluoroethylene carbonate and perfluorodecalin; and/or the presence of a gas in the gas,
the silicon-containing organic matter comprises at least one of polydimethylsiloxane and octadecyltrimethoxysilane; and/or the presence of a gas in the gas,
the lipid waxy material comprises at least one of sorbitan monostearate, polyethylene, polypropylene, stigmasterol and cholesterol.
6. The positive electrode lithium-rich composite pole piece according to claim 1, wherein the mass percentage of the hydrophobic organic material is 0.5-20% based on 100% of the total mass of the positive electrode composite layer.
7. The positive lithium-rich composite pole piece according to any one of claims 1 to 5, wherein the lithium-rich material comprises Li x M y O z 、Li w A、Li 1+a N b G c H d O e At least one of; wherein x is more than 0 and less than or equal to 8, y is more than 0 and less than or equal to 3, z is more than 0 and less than or equal to 3W is more than 0 and less than or equal to 5; a is more than 0 and less than or equal to 1, b is more than 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 0.2, e is more than or equal to 1.8 and less than or equal to 3; m is at least one element of Fe, co, ni, mn, si, sn, cu, mo, al and Ti, A is at least one element of C, N, O, P, S, F, B and Se; n is at least one element of Fe and Mn; g is at least one element of Ni, co, A1, mg, ti, fe, cu, cr, mo, zr, ru and Sn; h is at least one element of S, P, B and F.
8. The positive electrode lithium-rich composite pole piece according to claim 7, wherein the lithium-rich material is contained in an amount of 0.5 to 30% by mass based on 100% by mass of the total mass of the positive electrode composite layer.
9. The positive lithium-rich composite pole piece according to any one of claims 1 to 5, wherein the positive composite layer further comprises: a positive electrode active material, a conductive agent, and a binder; the positive electrode active material, the binder and the conductive agent comprise the following components in percentage by mass based on 100% of the total mass of the positive electrode composite material layer:
the mass percentage of the positive active material is 60-99%,
the mass percentage of the conductive agent is 0.2-20%,
the mass percentage of the binder is 0.5-3%.
10. The positive lithium-rich composite pole piece according to claim 9, wherein the positive active material comprises at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium manganese phosphate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, and lithium cobalt oxide.
11. A preparation method of a positive lithium-rich composite pole piece is characterized by comprising the following steps:
preparing positive active slurry for forming a positive composite material layer; wherein the positive active slurry includes a lithium-rich material and a hydrophobic organic material;
and coating the positive active slurry on the surface of the positive current collector, and sequentially performing rolling and drying treatment to obtain the positive lithium-rich composite pole piece.
12. The method for preparing the positive electrode lithium-rich composite pole piece according to claim 11, wherein in the step of drying, the temperature of the drying is 100 ℃ to 130 ℃, and the time of the drying is 20 hours to 24 hours.
13. A secondary battery comprising the positive electrode lithium-rich composite electrode sheet according to any one of claims 1 to 10.
14. The secondary battery of claim 13, wherein during packaging of the secondary battery, at least a portion of the organic hydrophobic barrier layer on the surface layer of the positive electrode lithium-rich composite pole piece is dissolved in the electrolyte.
CN202210227035.3A 2022-03-08 2022-03-08 Positive lithium-rich composite pole piece and preparation method and application thereof Pending CN115312692A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116435459A (en) * 2023-06-08 2023-07-14 合肥国轩高科动力能源有限公司 Positive plate and preparation method thereof, lithium ion battery and preparation method thereof
CN116979018A (en) * 2023-09-22 2023-10-31 宁德时代新能源科技股份有限公司 Modified pole piece, preparation method thereof, secondary battery and power utilization device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116435459A (en) * 2023-06-08 2023-07-14 合肥国轩高科动力能源有限公司 Positive plate and preparation method thereof, lithium ion battery and preparation method thereof
CN116435459B (en) * 2023-06-08 2023-11-24 合肥国轩高科动力能源有限公司 Positive plate and preparation method thereof, lithium ion battery and preparation method thereof
CN116979018A (en) * 2023-09-22 2023-10-31 宁德时代新能源科技股份有限公司 Modified pole piece, preparation method thereof, secondary battery and power utilization device

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