CN110690440A - Metal ion supplementing additive and preparation method and application thereof - Google Patents

Metal ion supplementing additive and preparation method and application thereof Download PDF

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CN110690440A
CN110690440A CN201911158138.3A CN201911158138A CN110690440A CN 110690440 A CN110690440 A CN 110690440A CN 201911158138 A CN201911158138 A CN 201911158138A CN 110690440 A CN110690440 A CN 110690440A
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metal ion
additive
battery
supplement additive
protective layer
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CN110690440B (en
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黄杰
张坤
李群
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Beijing WeLion New Energy Technology Co ltd
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Beijing WeLion 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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 invention provides a metal ion supplement additive and a preparation method and application thereof, the metal ion supplement additive has an inorganic passivation layer shell and has the characteristic of stable existence in air and in a battery preparation process, so that when the metal ion supplement additive is applied to a rechargeable metal ion battery, the current mainstream preparation processes of a positive plate, a diaphragm and the battery can not be changed, and the metal ion supplement additive has the advantages of high stability and low cost. When the metal ions are supplemented for the battery, the metal ion supplementing additive does not contain transition metal elements, so that the problems of transition metal dissolution and dendritic crystal generation are avoided, and the effect of supplementing the metal ions corresponding to the metal ions of the battery anode is obvious, so that the excellent metal ion supplementing effect can be realized at lower cost, and the performance and the energy density of the battery are improved.

Description

Metal ion supplementing additive and preparation method and application thereof
Technical Field
The invention relates to the technical field of rechargeable metal ion batteries, in particular to a metal ion supplementing additive and a preparation method and application thereof.
Background
The rechargeable metal ion battery mainly comprises a lithium ion battery, a sodium ion battery, a potassium ion battery and the like, wherein the lithium ion battery is the most mature in research and the most widely applied, and is widely applied to consumer electronics, energy storage systems, power systems and the like at present, but how to improve the energy density becomes one of the technical bottlenecks which limit the further application and development of the rechargeable metal ion battery.
For a lithium ion battery, active lithium ions of the lithium ion battery mainly originate from lithium ions in a positive electrode material, a negative electrode material, and an electrolyte, and the number of active lithium ions is limited as a whole. However, in the first charge and discharge process of the lithium ion battery, with the formation of the SEI film on the surfaces of the positive and negative electrodes, the limited amount of active lithium ions in the battery is inevitably consumed, so that the total amount of active lithium ions is reduced, and the capacity and performance of the electrode material cannot be fully exerted, thereby making it difficult to further improve the energy density of the battery. Meanwhile, as the number of battery cycles is increased, limited lithium ions are consumed continuously, so that the energy density is reduced continuously, and the service life of the battery is shortened. Therefore, it is a current research and development hotspot to find an effective technical means for the battery to meet the requirement of the battery on the amount of active lithium ions during the use process.
The most direct method in the prior art is to add metallic lithium to the positive electrode or negative electrode material, and to make the positive electrode material lithiate in advance to supplement the consumption of lithium ions, as disclosed in patent CN 1830110A. However, the problem that this method is not negligible is that the lithium metal is very active in chemical properties and has high requirements for environmental conditions, making it difficult to reduce the cost. Meanwhile, the direct use of lithium metal for the prelithiation of the positive electrode material also results in the destruction of the original structure of the positive electrode material and deterioration of the performance without improvement.
Even if the lithium supplement source is replaced by the organic lithium to supplement lithium for the battery (patent CN102916165A), the limitation exists because the organic lithium is sensitive to moisture during use and needs protection of inert gas.
In view of the disadvantages of the two methods, a lithium supplement additive xLi is reported in the patent literature (US8835027B2)2O·yMOz(x is more than 0 and less than or equal to 4, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 3, and M is transition metal), although the compound has higher specific capacity, the material is rich in Li, has high residual alkali content, is unstable in air, and is easy to react with water and CO2The reaction and decomposition occur, and the environmental requirements of use and storage are extremely strict. Meanwhile, because the lithium ion battery contains transition metal elements, the problems of transition metal dissolution and dendritic crystal generation can be introduced in the charging process, and the performance of the battery is influenced.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a metal ion supplementing additive and a preparation method and application thereof. The metal ion supplement additive has an inorganic passivation layer shell and has the characteristic of stable existence in the air and in the battery preparation process, so that when the metal ion supplement additive is applied to a rechargeable metal ion battery, the current mainstream preparation processes of a positive plate, a diaphragm and the battery can not be changed, and the metal ion supplement additive has the advantages of high stability and low cost. When the metal ions are supplemented for the battery, the metal ion supplementing additive does not contain transition metal elements, so that the problem of dendritic crystal caused by the dissolution of transition metal is avoided, and the effect of supplementing the metal ions corresponding to the metal ions of the battery anode is obvious, so that the excellent metal ion supplementing effect can be realized at lower cost, and the performance and the energy density of the battery are improved.
In order to achieve the above purpose, the invention provides the following technical scheme:
the metal ion supplementing additive comprises composite particle powder, wherein the composite particles are AxByThe core structure comprises a core with a structure and a protective layer M coated on the surface of the core, wherein A is one of Li, Na and K; b is Mg, Ca, Al, Ge, Sn, Sb, Zn, Si/C composite material, SiOz、SiOzComposite material of/C and SiO2Composite material of/Si and SiO2Composite material of/Si/C, SnSu、SnOuThe protective layer M is an inorganic passivation layer; wherein, A isxByAn alloy or solid solution composed of an element a and an element B; x is more than 0, y is more than 0, z is more than 0 and less than 2, and u is more than 0 and less than or equal to 2.
Further, the protective layer M is any one of carbon, Mg, Ca, Al, Ge, Sn, Sb, Zn and Si or oxide, carbonate, silicate, sulfate, sulfite, stannate of any one of the elements, or the protective layer M and the AxByThe A element in the inner core is one or a mixture of more than two of oxide, carbonate, silicate, stannate, sulfate and sulfite of the A element.
Further, in the composite particle, AxByThe content of the element A in the alloy is within 90wt percent.
Further, in the composite particle, AxByThe content of the element A is 8-50 wt%.
Further, the particle size of the inner core is within 100 μm.
Further, the average thickness of the protective layer M is within 1 μ M.
The invention also discloses a preparation method of the metal ion supplement additive, which comprises the step of coating or depositing the protective layer M on the surface AxByAnd (3) surface of the inner core.
Further, when the protective layer M is carbon, carbon coating is carried out by utilizing a chemical deposition method, a mechanical composite method or a carbon-containing organic matter high-temperature pyrolysis method;
when the protective layer M is carbon, Mg, Ca, Al,Ge. Coating the protective layer M on the substrate A by using an evaporation method, a magnetron sputtering method, an atomic layer deposition method or an electron beam deposition method when Sn, Sb, Zn or Si is one of the materialsxByA core surface;
when the protective layer M is an oxide, carbonate, silicate, sulfate, sulfite, stannate or A including any one of Mg, Ca, Al, Ge, Sn, Sb, Zn and SixByWhen the oxide, carbonate, silicate, stannate, sulfate, sulfite of the element A in the core is any one or a mixture of two or more of them, the protective layer M may be coated or deposited on the element A by any one of the following methods ① and ②xBySurface of the core:
① will AxByCarrying out heat treatment on the inner core under a specific atmosphere;
② is prepared by vapor deposition, magnetron sputtering, atomic layer deposition or electron beam depositionxByCoating any one of carbon, Mg, Ca, Al, Ge, Sn, Sb, Zn and Si on the surface of the inner core, and then carrying out heat treatment in a specific atmosphere;
wherein the specific atmosphere in the methods ① and ② is a gas atmosphere containing at least one of oxygen, carbon dioxide, sulfur monoxide, sulfur dioxide, and dry air.
Further, the heat treatment temperature in the methods ① and ② is 25-800 ℃, and the heat treatment time is 0.01-24 h.
The invention also discloses a positive pole piece which comprises the metal ion supplement additive or the metal ion supplement additive prepared by the preparation method.
Further, the positive pole piece comprises 80-100 wt% of positive pole active material, 0-20 wt% of first conductive agent and 0-20 wt% of first binder, and the content of the metal ion supplement additive is 0.1-20 wt% of the positive pole active material.
The invention also discloses a preparation method of the positive pole piece, which is prepared by the following method a:
the method a comprises the following steps: and weighing the positive active material, the first conductive agent, the first binder and the metal ion supplement additive according to the proportion, mixing to form positive slurry, then uniformly coating the positive slurry on the surface of a positive substrate, and drying and curing.
The positive pole piece can also be prepared by a method b, wherein the method b comprises the following steps:
s1: weighing a positive electrode active material, a first conductive agent and a first binder according to a proportion, uniformly mixing to form mixed slurry, and coating the mixed slurry on the surface of a positive electrode substrate to form a positive electrode slurry layer;
s2: weighing the metal ion supplementing additive, the second binder and the second conductive agent according to the proportion, uniformly mixing to form a mixture, and coating the mixture on the surface of the positive electrode slurry layer prepared in S1;
the positive pole piece can also be prepared by a method c, wherein the method c comprises the following steps:
(1) weighing the metal ion supplementing additive, the second binder and the second conductive agent according to the proportion, uniformly mixing to form a mixture, and coating the mixture on the surface of the anode substrate to form a coating layer;
(2) weighing the positive electrode active material, the first conductive agent and the first binder according to the proportion, uniformly mixing to form mixed slurry, and coating the mixed slurry on the surface of the coating layer prepared in the step (1).
A composite membrane comprises a substrate, wherein the surface of the substrate is coated with the metal ion supplement additive or the metal ion supplement additive prepared by the preparation method.
The invention also discloses a rechargeable metal ion battery which comprises the positive pole piece or the positive pole piece prepared by the preparation method of the positive pole piece and/or the composite diaphragm.
Compared with the prior art, the invention has the following beneficial effects:
taking a lithium battery as an example, the lithium supplementing principle of the metal supplementing additive provided by the invention is as follows:
in the lithium battery containing the lithium ion supplement additive, no matter the lithium ion supplement additive is distributed between the positive active materials, or between the surface of the positive pole piece, or between the positive base material and the positive slurry layer, or the surface of the diaphragm facing to one side of the positive pole piece, after the lithium battery is assembled, the electrolyte fully infiltrates the positive active materials and the metal ion supplement additive, under the charging action, lithium elements in the ion supplement additive are released into the electrolyte to supplement lithium ions lost in the working process of the battery, and the lithium removal potential of the positive material is still kept at the normal charge-discharge potential (between 1.0 and 5.0V). The surface protection layer M of the lithium supplement additive can protect internal active metal elements in the slurry mixing process, so that the internal active metal elements are relieved or do not react with air and a solvent, the stability of the lithium supplement additive in the air and in the battery preparation process is improved, and the conduction of lithium ions in the charging process is not hindered, so that the lithium supplement additive has excellent lithium supplement performance, the first lithium removal capacity of the battery can be obviously improved, and additional active lithium ions can be provided. In addition, because the lithium supplement additive does not contain transition metal elements, the problems of transition metal dissolution and transition metal dendrite generation in the battery cycle process can not be caused, and further, the negative effects on the safety and cycle performance can not be caused to the battery performance.
Likewise, corresponding to AxByThe inner core can supplement corresponding A metal elements for corresponding A metal element batteries so as to optimize the charge and discharge performance and stability of the metal element batteries, and can supplement potassium metal ions for potassium-containing metal batteries when A is K.
The metal ion supplement additive provided by the invention has the following advantages:
1. the composition particles of the metal ion supplement additive of the invention consist of AxByThe inner core of the structure and a protective layer M coated on the surface of the inner core, wherein AxByThe surface protective layer M improves the stability of the metal ion supplement additive in the air and in the battery preparation process.
2. The metal ion supplementing additive can be applied to rechargeable metal ion batteries, particularly can be applied to positive pole pieces and diaphragms of the batteries, is compatible with the existing preparation process, and can achieve excellent metal ion supplementing effect under the condition of not obviously increasing the manufacturing cost of the batteries.
3. The residue of the metal ion supplementing additive of the invention after metal ion supplementation is AnBy@ M, where 0<n<And x does not contain transition metal elements, so that the problems of transition metal dissolution and generation of transition metal dendrites are avoided, and the battery can obtain better performance.
Drawings
FIG. 1 shows A of composite particle H1xBySEM image of kernel;
FIG. 2 is an SEM image of composite particles H1 coated with a protective layer M;
FIG. 3 is a graph showing the first cycle charge and discharge curves of comparative example 7, which contains only H1 and does not contain lithium cobaltate active material;
FIG. 4 is a first cycle charge and discharge curve of example 2 and comparative example 6;
FIG. 5 is an SEM image of the positive electrode plate in example 2 when not charged and discharged;
FIG. 6 is an SEM photograph of the positive electrode plate in example 2 after 10 cycles of charging and discharging;
fig. 7 is an optical picture of the S2 septum used in example 8.
Detailed Description
The invention aims to provide a metal ion supplementing additive, and a preparation method and application thereof. The metal ion supplement additive has an inorganic passivation layer shell and has the characteristic of stable existence in the air and in the battery preparation process, so that when the metal ion supplement additive is applied to a rechargeable metal ion battery, the current mainstream preparation processes of a positive plate, a diaphragm and the battery can not be changed, and the metal ion supplement additive has the advantages of high stability and low cost. When the metal ions are supplemented for the battery, the metal ion supplementing additive does not contain transition metal elements, so that the problems of transition metal dissolution and dendritic crystal generation are avoided, and the effect of supplementing the metal ions corresponding to the metal ions of the battery anode is obvious, so that the excellent metal ion supplementing effect can be realized at lower cost, and the performance and the energy density of the battery are improved. The specific technical scheme of the invention is as follows:
the metal ion supplementing additive comprises composite particle powder, wherein the composite particles are AxByThe core structure comprises a core with a structure and a protective layer M coated on the surface of the core, wherein A is one of Li, Na and K; b is Mg, Ca, Al, Ge, Sn, Sb, Zn, Si/C composite material, SiOz、SiOzComposite material of/C and SiO2Composite material of/Si and SiO2Composite material of/Si/C, SnSu、SnOuThe protective layer M is an inorganic passivation layer; wherein, A isxByAn alloy or solid solution composed of an element a and an element B; x is more than 0, y is more than 0, z is more than 0 and less than 2, and u is more than 0 and less than or equal to 2.
Specifically, the protective layer M is any one of carbon, Mg, Ca, Al, Ge, Sn, Sb, Zn and Si or oxide, carbonate, silicate, sulfate, sulfite, stannate of any one of the elements, or the protective layer M is mixed with the AxByThe A element oxide, carbonate, silicate, stannate, sulfate, sulfite or their mixture, such as: including but not limited to MgO, CaO, Al2O3、GeO、GeO2、SnO、SnO2、SbO2、ZnO、SiO2、Li2O、Na2CO3、MgCO3、CaCO3、Li2SiO3、Li2SnO3、K2SO3、Na2SO4And the like.
Preferably, in the composite particle, AxByThe content of the element A in the inner core is within 90 wt%, and 8-50 wt% is preferable; a. thexByThe particle size of the core is within 100 μm, preferably within 20 μm, because if it is applied to a battery, the particle size of the core is too large to achieve uniform distribution in the battery; the action mechanism of the metal ion supplement additive is as follows: when applied to a battery, during charging, AxByThe A ions released from the inner core reach the electrolyte through a transmission route formed by the protective layer M, if the thickness of the protective layer M is too high, the difficulty of a transmission path for releasing the A ions into the electrolyte is increased, the transmission resistance is increased,it is preferable that the thickness of the protective layer M is within 1 μ M, more preferably within 100 nm.
The invention also discloses a preparation method of the metal ion supplement additive, which comprises the following steps:
when the protective layer M is carbon, performing carbon coating in a carbon source environment by using a chemical deposition method, a mechanical composite method or a carbon-containing organic matter high-temperature pyrolysis method; wherein, the carbon source of the vapor deposition method can be alcohols, aldehydes, alkanes, alkenes or alkynes; the carbon source of the mechanical composite method can be directly selected from one or more of acetylene black, Super P, CNT and Super S; the carbon source for the high-temperature pyrolysis of the carbon-containing organic matter is selected from one or more of glucose, starch, aldehyde, organic acid, phenol and carbon-containing fluoride.
When the protective layer M is one of Mg, Ca, Al, Ge, Sn, Sb, Zn and Si, the protective layer M is coated on the substrate A by adopting an evaporation method, a magnetron sputtering method, an atomic layer deposition method or an electron beam deposition methodxByA core surface;
when the protective layer M is an oxide, carbonate, silicate, sulfate, sulfite, stannate or A including any one of Mg, Ca, Al, Ge, Sn, Sb, Zn and SixByWhen the element A is an oxide, carbonate, silicate, stannate, sulfate, sulfite, or a mixture of two or more thereof, the protective layer M may be coated or deposited on the element A by any of the following methods ① and ②xBySurface of the core:
① will AxByCarrying out heat treatment on the inner core under a specific atmosphere;
② coating the protective layer M on the substrate A by evaporation, magnetron sputtering, atomic layer deposition or electron beam depositionxByThe surface of the inner core is firstly treated by the AxByCoating any one of Mg, Ca, Al, Ge, Sn, Sb, Zn and Si on the surface of the inner core, and then carrying out heat treatment in a specific atmosphere;
the specific atmosphere in the methods ① and ② is a gas atmosphere containing any one of oxygen, carbon dioxide, sulfur monoxide, sulfur dioxide, and dry air.
Wherein the heat treatment temperature of the method ① or the method ② is 25-800 ℃, preferably 80-400 ℃, and the heat treatment time is 0.01-24h, preferably 20min-4 h;
wherein, when oxygen is contained in a specific atmosphere, oxide and silicate components can be generated; when the specific atmosphere contains sulfur dioxide and sulfur monoxide, sulfite and sulfate components can be generated; when carbon dioxide is contained in a specific atmosphere, a carbonate component may be generated.
Wherein A isxByThe inner core can be obtained by commercial purchase, or can be obtained by heating x parts of A and y parts of B under the protection of inert gas, wherein the heating temperature is 80-800 ℃, and the heating time is 1-12 h.
The invention also provides a positive pole piece, which comprises the metal ion supplement additive, wherein the metal ion supplement additive can be distributed among positive active material particles, can also be distributed on the surface of the positive pole piece, or can be distributed between a positive base material and a positive slurry layer.
Specifically, when the metal ion supplement additive is distributed among the positive electrode active material particles, the metal ion supplement additive, the positive electrode active material, the first conductive agent and the first binder can be mixed and added in the mixing process, and the positive electrode plate containing the metal ion supplement additive is obtained through processes of mixing, coating, baking, rolling, cutting and the like, wherein the positive electrode plate comprises 80-100 wt% of the positive electrode active material, 0-20 wt% of the first conductive agent and 0-20 wt% of the first binder (the sum of the mass percentages of the positive electrode active material, the first conductive agent and the first binder is 100%), the content of the metal ion supplement additive is 0.1-20 wt% of the positive electrode active material, and the content of the specific lithium supplement additive is determined according to the requirement of battery design.
When the metal ion supplement additive is distributed on the surface of the positive pole piece, the positive pole slurry can be coated on the surface of the positive pole base material, namely, a common positive pole piece is prepared firstly, slurry containing the metal ion supplement additive, a second binder and a second conductive agent is prepared at the same time, and the prepared slurry is coated on the surface of the positive pole piece by using the process for preparing the positive pole piece, so that the positive pole piece containing the metal ion supplement additive is obtained; the positive electrode slurry contains 80-100 wt% of positive electrode active material, 0-20 wt% of first conductive agent and 0-20 wt% of first binder (wherein the sum of the mass percentages of the positive electrode active material, the first conductive agent and the first binder is 100%), and the content of the metal ion supplement additive is 0.1-20 wt% of the positive electrode active material; the dosage of the particularly preferred metal ion supplementing additive is determined according to the design requirement of the battery; in the mixed slurry composed of the metal ion supplement additive, the second binder and the second conductive agent, the content of the metal ion supplement additive is 80-99 wt%, the content of the second adhesive is 0.5-10 wt%, and the content of the second conductive agent is 0.5-10 wt%.
When the metal ion supplement additive is distributed between the anode substrate and the anode slurry layer, firstly coating mixed slurry containing the metal particle supplement additive on the surface of the anode substrate (in the mixed slurry, the content of the metal ion supplement additive is 80-99 wt%, the content of the second adhesive is 0.5-10 wt%, and the content of the second conductive agent is 0.5-10 wt%), baking, and then coating the prepared anode slurry on the mixed slurry to obtain the anode piece with the lithium ion supplement additive distributed between the anode substrate and the anode slurry layer.
Because the metal ion supplement additive has better chemical stability in the air, the whole pole piece preparation process can adopt the existing pole piece preparation process to prepare, and the base material of the used positive pole piece is the common base material of the cell pole piece base material such as aluminum foil, carbon-coated aluminum foil and the like, which can not be repeated.
The invention also discloses a composite diaphragm, which comprises a base film, wherein the surface of the base film is coated with a metal ion supplement additive; specifically, the base film is a single-layer polypropylene (PP) film, a Polyethylene (PE) film, a PP/PE composite film, a polyvinylidene fluoride (PVDF) film, a polyimide film, or a multi-layer diaphragm, each layer of which independently comprises at least one of PE, polypropylene, PVDF and polyimide, or the membrane with Al2O3Or a single or multilayer film of boehmite coating; the sheetThe total thickness of the layer film or the multilayer film is 0.1-50 μm, and the porosity is 5-80%; the thickness of each layer in the multilayer film is 0.1-30 μm independently.
The preparation method of the composite diaphragm comprises the following steps: mixing 80-98.5 wt% of metal ion supplement additive and 1.5-20 wt% of third binder to form slurry, then uniformly coating the slurry on one surface of the base film, drying and curing to form the composite diaphragm; specifically, the sizing agent is coated on the surface of a base film in a mode of extrusion coating, micro-concave coating or coating transfer, and then baking is carried out to volatilize a solvent in the sizing agent to obtain the coating agent; the process of coating the mixed slurry containing the alkali metal supplement particle additive on the surface of the base film to prepare the mixed diaphragm is the same as the coating process of the current diaphragm with the coating, and detailed description is omitted here.
The first binder, the second binder and the third binder are commonly used binders for the positive pole piece of the lithium ion battery, and preferably one or more of PVDF, polyimide and PVDF-HFP are mixed; the first conductive agent and the second conductive agent are preferably one or a mixture of two or more of acetylene black, conductive carbon black, Super P, Ketjen black and carbon nanotubes.
Specifically, when the composite diaphragm is applied to a battery, one side of the composite diaphragm, which is provided with the metal ion supplement additive, faces to the positive pole piece, and the metal ion supplement additive has certain conductivity, the width of a covering region on one side of a base film needs to meet the requirement of (W-2 x n) mm, wherein n is the width between two sides of the base film coating region and the edge of the base film, n is 0.1-3mm, and W is the width of the base film. When the metal ion supplement membrane is applied to a battery cell, full coating is required to be unavailable, the coverage area of the metal ion supplement additive coating is consistent with the positive pole piece area and is not exceeded, and a certain distance is required to be reserved at the edges of two sides of the membrane along the length direction, so that the short circuit of the battery cell is avoided.
A rechargeable metal-ion battery comprising a positive electrode sheet and/or a composite separator as described above.
In the rechargeable metal-ion battery, after the metal ion supplement additive supplements active lithium ions to the battery, axByIn @ M, part of metal A ions are removed to generate AnByResidue of @ M, wherein 0<n<x, therefore, the residue after the metal ion supplementing additive supplements metal ions to the battery, namely A, can be observed and detected on the surface of the positive pole piece and/or the composite diaphragm facing to the positive pole in the use process of the metal ion batterynBy@ M, where 0<n<x. Specifically, distinguishing and verification can be performed according to the difference of the shapes of the lithium ion supplement additive and the active material, ICP elemental analysis and other modes.
The technical solutions in the embodiments of the present invention are clearly and completely described below by taking a lithium battery as an example and combining with the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, 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 invention.
Preparation of composite particles
Composite particles H1, H2, H3, H4, H5 and H6 are prepared, wherein the core structure and the protective layer M of each composite particle are shown in Table 1, and the preparation method and conditions are shown in Table 2.
Table 1 shows parameter information of composite particles
Figure BDA0002285357050000091
TABLE 2 preparation conditions and preparation method parameter information of composite particles
Figure BDA0002285357050000101
In the composite particles, as shown in fig. 1 and 2, the results of observation using a scanning electron microscope before and after coating the protective layer with H1 composite particles are shown in fig. 1 as H1 composite particlesComposite particles AxByThe SEM image before the inner core is coated with the protective layer M, and fig. 2 is the SEM image after the H1 composite particles are coated with the protective layer M.
Wherein fig. 2 is an SEM image of the lithium ion supplement additive H1, it can be seen that the H1 particle surface has many protrusions with unevenness, while the surface of the comparative sample (see fig. 1) without the M protective layer is smoother, and it can be seen by comparison that after the surface protective layer M is prepared, the H1 particle surface becomes rough and uneven, which is a result of the surface protective layer M, which can increase the chemical stability of the lithium ion supplement additive in the air, so that the properties thereof in the air and in the battery preparation process are stable.
A in Table 1xByThe core material is commercially available.
Preparation of positive pole piece
Mixing lithium cobaltate, SP, CNT and polyvinylidene fluoride according to a mass ratio of 96: 1: 1: 2, mixing, adding N-methyl pyrrolidone, stirring the mixture at a high speed to obtain uniform anode slurry, coating the anode slurry on a 12um aluminum foil, drying to obtain an anode sheet, and rolling and die-cutting for later use. Wherein the surface density of the positive electrode plate is 160g/m2。
It should be noted that the positive electrode sheet in the examples and the positive electrode sheet in the comparative examples have the same positive active material, conductive agent, first binder and solvent, and the same preparation process of the positive electrode sheet, except for the type of the lithium supplement additive, and the components and constituents of the positive electrode slurry, as shown in table 3.
Table 3 information about the different positive electrode sheets.
Figure BDA0002285357050000111
In table 3, "in-sheet" in the column of "distribution state of lithium ion supplement additive" is to mix the lithium ion supplement additive with the positive electrode active material, the conductive agent and the first binder to form positive electrode slurry and coat the positive electrode slurry on the surface of the positive electrode substrate; the positive pole piece is prepared on the surface of the pole piece, then the slurry for supplementing the lithium ion additive is prepared, and the slurry is coated on the surface of the positive pole piece. The method comprises the steps of firstly preparing a metal ion supplement additive coating on a base material, then preparing anode slurry, and coating the anode slurry on the surface of the metal ion supplement additive coating.
Preparation of negative pole piece
Mixing silicon-oxygen-carbon material, acetylene black, styrene butadiene rubber and sodium carboxymethylcellulose according to a mass ratio of 95: 2: 2: 1, adding deionized water, stirring the mixture at a high speed to obtain uniform negative electrode slurry, coating the uniform negative electrode slurry on 8um copper foil, drying to obtain a negative electrode plate, and rolling and die-cutting the negative electrode plate for later use, wherein the surface density is 150g/m 2.
When metallic lithium is used for the negative electrode, the metallic lithium used is commercially available metallic lithium foil.
Preparation of battery diaphragm
The preparation method of the battery diaphragm comprises the following steps: mixing 95 wt% of lithium ion supplementing additive and 5 wt% of third binder to form slurry, and then coating the slurry on the surface of the diaphragm substrate.
In some examples and comparative examples, the separator substrate used was a commercially available 16um PE separator substrate and a 16+4um alumina coated PE separator substrate; in some embodiments, the separator substrate used was a 16umPE substrate coated on one side with a lithium ion supplement additive, as shown in table 4.
Table 4 information on the separators used in the examples and comparative examples.
Figure BDA0002285357050000112
Figure BDA0002285357050000121
Preparation of lithium battery
Stacking the prepared positive plate, the diaphragm and the negative plate in sequenceInjecting proper amount of 1M LiPF6The cell button was assembled in a glove box under argon atmosphere with the electrolyte solution of EC-EMC-DEC (volume ratio 1: 1: 1), and the cell information of examples and comparative examples is shown in table 5. It should be noted that, when the separators S2 and S3 are used, since the positive electrode sheet and the negative electrode sheet are used as single-sided sheets, the battery separator having a lithium ion supplement additive loading region is selected, and the battery operation is not affected, so that no margin space is left in the battery separator used in the related example; in addition, when the separators S2 and S3 were used, the side having the lithium ion supplement additive faced the positive electrode sheet.
Table 5 battery information and test data information for examples 1-12 and comparative examples 1-7.
Figure BDA0002285357050000122
Figure BDA0002285357050000131
Sixthly, the button cells prepared in the above examples 1 to 12 and comparative examples 1 to 7 are tested for relevant performance, and the test method and the result are as follows:
(1) the test method of the battery comprises the following steps: connecting the button cell with a charge-discharge test instrument at 25 ℃, if the cathode adopts a pure metal lithium cathode, setting the cell to carry out constant-current constant-voltage charging at a current of 0.1 ℃, setting the cutoff voltage to be 4.5V and the cutoff current to be 0.01C, standing for 10min, then discharging to 2.75V at a constant current of 0.1C, and standing for 10 min; performing cycle test by constant current and constant voltage charging at 0.1C, with cut-off voltage of 4.5V and cut-off current of 0.1C, standing for 10 min; discharging with constant current of 0.1C to 2.75V, standing for 10min, and circulating for 50 weeks; if the negative electrode adopts silicon-oxygen-carbon, setting the battery to carry out constant-current constant-voltage charging at a current of 0.1C, setting the cut-off voltage to be 4.4V and the cut-off current to be 0.01C, standing for 10min, then discharging at a constant current of 0.1C to 2.75V, and standing for 10 min; and in the cycle test, constant-current constant-voltage charging is carried out at the current of 0.1C, the cut-off voltage is 4.4V, the cut-off current is 0.1C, standing for 10min, constant-current discharging is carried out at the current of 0.1C until the voltage reaches 2.75V, standing for 10min, and the cycle lasts for 50 weeks.
The above tests involve the following calculation:
specific charge capacity is charge capacity/mass of positive electrode active material;
specific discharge capacity is discharge capacity/mass of positive active material;
first coulombic efficiency-first cycle discharge capacity/first cycle charge capacity 100%.
(2) The results of the cell-related performance tests of examples 1 to 12 and comparative examples 1 to 7 are shown in table 6:
table 6 results of performance test on batteries prepared in examples 1 to 12 and comparative examples 1 to 7
Figure BDA0002285357050000132
Figure BDA0002285357050000141
FIG. 3 is a first cycle charge and discharge curve diagram of comparative example 7, which contains only H1 and does not contain lithium cobaltate, wherein the charge and discharge voltage range is 1-4.5V, the charge and discharge current is 0.05C, the pole piece shows 507.7mAh/g of charge capacity, lithium ions can be extracted from the pole piece between 2.75V and 4.5V, the charge and discharge range of the positive pole material is better, almost no discharge capacity exists between 4.5V and 2.75V, when the discharge is continued to 1V, the discharge capacity is only 65.9mAh/g, the lithium ions extracted from H1 can not be reversibly inserted back into H1 between 3V and 4.5V, and the released active lithium ions can be used for compensating the loss of lithium ions in the charge and discharge process of the lithium battery. It should be noted that fig. 3 shows that H1 can extract lithium ions between 2.75V and 4.5V, but does not represent that lithium in H1 is completely extracted, and some lithium therein may not reach the extraction potential, i.e. when the charging voltage range of the battery is within the extraction potential range of H1, H1 may still contain some lithium which is not extracted.
As shown in the information in tables 5 and 6, the difference between example 1 and comparative example 5 is that H1 supplementary metallic lithium additive is contained only in the positive electrode sheet of example 1, and comparison of their first cycle charge and discharge test data shows that the first cycle charge capacity of example 1 is 239.5mAh/g, which is significantly higher than that of comparative example 5(192.6mAh/g) without any special treatment, indicating that H1 benefits from M protective layer, so that the chemical properties are stable during the preparation of battery, lithium element is released through M protective layer during the charging process, and has higher lithium supplementary capacity, since the specific charge capacity is calculated based on the positive electrode active material, the charge capacity of battery is significantly improved, and at the same time, the first cycle discharge capacity of example 1 is equivalent to comparative example 5, indicating that the residue after H1 releases lithium ion exerts no significant side effect on the performance of the positive electrode active material, lithium ions released by the lithium supplement additive exist in the electrolyte, so that the lithium ions consumed by the SEI film can be compensated, and the problem of transition metal dendrite generation due to the dissolution of transition metal can be avoided because the components of the electrolyte do not contain transition metal elements.
The lithium supplement effect of the lithium supplement additive H1 was further verified in the full cell, as shown in the first-week charge and discharge curves of example 2 and comparative example 6 of fig. 4, it was found from the first-week charge and discharge data of comparative example 2 and comparative example 6 that the discharge capacity of example 2 was 150.5mAh/g, while the discharge capacity of comparative example 6 was only 135.9mAh, resulting in a lower discharge capacity of comparative example 6 mainly due to the fact that the content of active lithium ions in the full cell was limited, and during the charge and discharge, since the formation of the SEI film consumed part of the active lithium ions, lithium ions that had been intercalated into the negative electrode could not be completely extracted, and thus the discharge capacity was lower. When added to H1 in example 2, the lithium ions consumed by participating in the formation of SEI can be compensated by the additional active lithium ions provided by H1, and thus the reversible discharge capacity of example 2 is significantly higher than that of comparative example 6. In addition, as can be seen from the discharge capacities at 50 weeks of comparative example 2 and comparative example 6, example 2 after the addition of H1 still has a significant advantage in capacity, which is attributed to the beneficial lithium supplementing effect of H1, and the residue thereof does not adversely affect the performance of the positive electrode material. In addition, fig. 5 is an SEM image of the electrode sheet before charging in example 2, and it can be seen that the more rounded and plump particles are lithium cobaltate particles, and the well-defined water chestnut particles are H1 particles (shown in the frame), and the morphology features of the particles are clearly different and can be easily distinguished. After the pole piece of example 2 is subjected to charge and discharge cycles for 10 weeks, the SEM of the pole piece is shown in fig. 6, and the lithium cobaltate particles still exist, and the existence of H1 particles can still be observed, which is distinguished in that the originally dense H1 particles become non-dense, and the surface of the particles has lamellae and pores, because after the H1 particles are subjected to multiple charge and discharge cycles in the battery, the internal lithium is extracted from the H1 to become the lithium ion compensation battery, which meets the lithium ion requirement, and thus the original dense structure has lamellae and pores. The results from the cell data show that the H1 residue did not degrade the performance of the cell.
In addition, the first-cycle charge capacity of examples 4 and 5, and examples 10 and 11, which use the H2-H5 lithium supplement additive, respectively, is also significantly higher than that of comparative example 5, indicating that H2 and H3 also have excellent lithium supplement effects.
Comparative examples 3 and 4 are commercial positive electrode lithium supplement additive Li added to the positive electrode2CuO2(H6, no protective layer M) the amount of H6 added was the same as the amount of H1 added in the C3 tab used in example 1. By comparison, H6 shows a certain lithium supplementing effect, but the specific charge capacity of the battery is lower than that of example 1, and the lithium supplementing effect is not as excellent as that of H1, namely H6 can provide no more lithium ions than H1. Further, when the lithium ion supplement additive of the present invention is applied to a separator, the lithium ion supplement additive can supplement lithium ions to a battery, as in examples 3, 8 and 9, and has a significant lithium supplement effect. Fig. 7 is an optical photograph of the S2 separator used in example 8, wherein the surface of the separator loaded with H1 was black.
In summary, the lithium ion supplement additive of the present invention has an excellent lithium supplement effect, and is applied to a battery for lithium supplement, the specific addition amount needs to be optimally designed according to the lithium ion demand of the battery and the lithium ion amount actually provided by the lithium ion supplement additive, rather than being added randomly, and when the addition amount is too small, the lithium ion provided to the battery cannot meet the battery demand, so the lithium supplement effect is not particularly obvious.
The above embodiments are described specifically with respect to lithium batteries, and the present invention is also applicable to other metals than lithium batteries or lithium ion batteriesWhen the metal ion supplement additive provided by the invention is applied to other metal batteries, AxByThe element A in the inner core is a metal corresponding to the electrolyte free metal ions of the metal battery.
While the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (16)

1. The metal ion supplementing additive comprises composite particle powder, and is characterized in that the composite particles are AxByThe core structure comprises a core with a structure and a protective layer M coated on the surface of the core, wherein A is one of Li, Na and K; b is Mg, Ca, Al, Ge, Sn, Sb, Zn, Si/C composite material, SiOz、SiOzComposite material of/C and SiO2Composite material of/Si and SiO2Composite material of/Si/C, SnSu、SnOuThe protective layer M is an inorganic passivation layer; wherein, A isxByIs an alloy or solid solution composed of an element A and an element B; x is more than 0, y is more than 0, z is more than 0 and less than 2, and u is more than 0 and less than or equal to 2.
2. The metal ion supplement additive according to claim 1, wherein the protective layer M is an oxide, carbonate, silicate, sulfate, sulfite, stannate or A of any one or more of carbon, Mg, Ca, Al, Ge, Sn, Sb, Zn, SixByThe A element in the inner core is one or a mixture of more than two of oxide, carbonate, silicate, stannate, sulfate and sulfite of the A element.
3. The metal ion supplement additive of claim 1, wherein in the composite particles, A isxByThe content of element A inWithin 90 wt%.
4. The metal ion supplement additive of claim 3, wherein in the composite particles, A isxByThe content of the element A is 8-50 wt%.
5. The metal ion supplementing additive of claim 1, wherein the particle size of the inner core is within 100 μm.
6. The metal ion supplementing additive according to claim 5, wherein the protective layer M has an average thickness of up to 1 μ M.
7. A method for preparing a metal ion supplement additive, which is characterized by coating or depositing a protective layer M on AxByAnd (3) surface of the inner core.
8. The method for preparing the metal ion supplement additive according to claim 7, wherein when the protective layer M is carbon, the carbon coating is performed by using a chemical deposition method, a mechanical composite method or a high-temperature pyrolysis method of carbon-containing organic matter;
when the protective layer M is one of Mg, Ca, Al, Ge, Sn, Sb, Zn and Si, the protective layer M is coated on the substrate A by adopting an evaporation method, a magnetron sputtering method, an atomic layer deposition method or an electron beam deposition methodxByA core surface;
when the protective layer M is an oxide, carbonate, silicate, sulfate, sulfite, stannate or A including any one of Mg, Ca, Al, Ge, Sn, Sb, Zn and SixByWhen the oxide, carbonate, silicate, stannate, sulfate, sulfite of the element A in the core is any one or a mixture of two or more of them, the protective layer M may be coated or deposited on the element A by any one of the following methods ① and ②xBySurface of the core:
① will AxByCarrying out heat treatment on the inner core under a specific atmosphere;
② is prepared by vapor deposition, magnetron sputtering, atomic layer deposition or electron beam depositionxByCoating any one of carbon, Mg, Ca, Al, Ge, Sn, Sb, Zn and Si on the surface of the inner core, and then carrying out heat treatment in a specific atmosphere;
wherein, the specific atmosphere in the methods ① and ② is a gas atmosphere containing at least one of oxygen, carbon dioxide, sulfur monoxide, sulfur dioxide and dry air.
9. The method of claim 8, wherein the heat treatment temperature in the methods ① and ② is 25-800 ℃ and the heat treatment time is 0.01-24 h.
10. A positive electrode plate, characterized in that the positive electrode plate comprises the metal ion supplement additive according to any one of claims 1 to 6 or the metal particle supplement additive prepared by the preparation method according to any one of claims 7 to 9.
11. The positive pole piece of claim 10, wherein the positive pole piece comprises 80-100 wt% of positive active material, 0-20 wt% of first conductive agent, and 0-20 wt% of first binder, and the content of the metal ion supplement additive is 0.1-20 wt% of the positive active material.
12. The preparation method of the positive pole piece according to claim 11, wherein the positive pole active material, the first conductive agent, the first binder and the metal ion supplement additive are weighed in proportion and mixed to form positive pole slurry, and then the positive pole slurry is uniformly coated on the surface of the positive pole base material and dried and cured.
13. The preparation method of the positive pole piece according to claim 11, comprising the following steps:
s1: weighing the positive active material, the first conductive agent and the first binder according to the proportion, uniformly mixing to form mixed slurry, and coating the mixed slurry on the surface of a positive substrate to form a positive slurry layer;
s2: and weighing the metal ion supplementing additive, the second binder and the second conductive agent according to the proportion, uniformly mixing to form a mixture, and coating the mixture on the surface of the positive electrode slurry layer prepared in the step S1.
14. The preparation method of the positive pole piece according to claim 11, comprising the following steps:
(1) weighing the metal ion supplementing additive, the second binder and the second conductive agent according to the proportion, uniformly mixing to form a mixture, and coating the mixture on the surface of the anode substrate to form a coating layer;
(2) and (2) weighing the positive electrode active material, the first conductive agent and the first binder according to the proportion, mixing to form mixed slurry, and then uniformly coating the surface of the coating layer prepared in the step (1) with the mixed slurry.
15. A composite separator comprising a substrate, wherein the surface of the substrate is coated with the metal ion supplement additive according to any one of claims 1 to 6 or the metal ion supplement additive prepared by the preparation method according to any one of claims 7 to 9.
16. A rechargeable metal-ion battery comprising a positive electrode sheet according to any one of claims 10 to 11 or a positive electrode sheet prepared by the preparation method according to any one of claims 12 to 14 and/or a composite separator according to claim 15.
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