CN114097113A - Positive electrode lithium supplement material, positive electrode plate containing material and electrochemical device - Google Patents

Positive electrode lithium supplement material, positive electrode plate containing material and electrochemical device Download PDF

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CN114097113A
CN114097113A CN202180004322.1A CN202180004322A CN114097113A CN 114097113 A CN114097113 A CN 114097113A CN 202180004322 A CN202180004322 A CN 202180004322A CN 114097113 A CN114097113 A CN 114097113A
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positive electrode
lithium
supplement material
lithium supplement
present application
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周墨林
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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    • H—ELECTRICITY
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    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • H01M4/00—Electrodes
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application provides a lithium material is mended to positive pole, contains anodal pole piece and electrochemical device of this material, and this lithium material is mended to positive pole includes: xLi2A substrate of O.yM and carbon present on the substrate; wherein x is more than 0, y is more than or equal to 0.4x and less than or equal to 2x, and M comprises at least one of Mn, Fe, Co, Ni, Cu, Cr or V. The positive electrode lithium-supplementing material is stable chemicallyThe performance is strong, and the particle agglomeration phenomenon in the size mixing process can be effectively improved. The positive electrode lithium supplement material is applied to a positive electrode plate, active lithium can be supplemented, and the energy density of an electrochemical device is effectively improved.

Description

Positive electrode lithium supplement material, positive electrode plate containing material and electrochemical device
Technical Field
The application relates to the field of electrochemistry, in particular to a positive electrode lithium supplement material, a positive electrode plate containing the material and an electrochemical device.
Background
The lithium ion secondary battery has the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, good safety and the like, and is widely applied to various fields of electric energy storage, mobile electronic equipment, electric automobiles, aerospace equipment and the like. As mobile electronic devices and electric vehicles enter a high-speed development stage, the market places increasingly higher requirements on energy density, cycle performance, dynamic performance and the like of lithium ion secondary batteries.
During the first charge and discharge process of the lithium ion secondary battery, a large amount of Solid Electrolyte Interphase (SEI) films are generated on the surface of the negative electrode, so that limited lithium ions and Electrolyte in the lithium ion secondary battery are consumed, irreversible capacity loss is caused, and the energy density of the lithium ion secondary battery is reduced. In cells using graphite cathodes, the first cycle consumes about 10% of the active lithium source; the consumption of the active lithium source is further exacerbated when high specific capacity anode materials are employed, such as alloys (silicon, tin, etc.), oxides (silicon oxide, tin oxide, etc.), and amorphous carbon anodes. Therefore, an appropriate lithium supplementing method is important for improving the energy density of the lithium ion secondary battery.
Disclosure of Invention
The application aims to provide a positive electrode lithium supplement material, a positive electrode plate containing the material and an electrochemical device, so as to improve the energy density of the electrochemical device.
In the present application, the present application is explained by taking a lithium ion secondary battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion secondary battery.
The specific technical scheme is as follows:
first of the present applicationIn one aspect, a positive electrode lithium supplement material is provided, which comprises xLi2A substrate of O.yM and carbon present on the substrate; wherein x is more than 0, y is more than or equal to 0.4x and less than or equal to 2x, and M comprises at least one of Mn, Fe, Co, Ni, Cu, Cr or V.
xLi of the present application2In the matrix of O.yM: x is more than 0, y is more than or equal to 0.4x and less than or equal to 2 x; preferably 3. ltoreq. x.ltoreq.12, 0.5 x. ltoreq. y.ltoreq.1.6 x. M may include at least one of Mn, Fe, Co, Ni, Cu, Cr, or V, etc., and M may preferably include at least one of Mn, Fe, Co, or Ni, etc. Wherein, the valence of M may be 0. Those skilled in the art can select x, y and M according to actual needs to obtain the xLi capable of achieving the purpose of the application2The matrix of O.yM, for example, may include but is not limited to 4Li2O·3Co、Li2O·Co、5Li2O·4Co、3Li2O·2Fe、7Li2O·3Co·2Fe、12Li2O·3Co·2Fe·2V、2Li2O.Mn or Li2O.Ni, and the like. By limiting the above range, the xLi of the present application is obtained2The matrix of O.yM can remove a large amount of lithium ions in the process of first charging, has high specific capacity and can greatly improve the energy density of the lithium ion secondary battery.
The inventors have surprisingly found that xLi2The presence of carbon on the O.yM matrix not only effectively enhances xLi2The chemical stability of the O.yM matrix improves the stability of the anode slurry, is not easy to agglomerate, and is more convenient for the preparation and storage of the anode slurry and the coating of the anode slurry on the anode plate, thereby improving the processing performance of the anode slurry and improving the energy density of the lithium ion secondary battery. This may be due to xLi2Li in O.yM matrix2Poor chemical stability to moisture and CO in the air2Is extremely sensitive and is highly susceptible to the occurrence of Li2O+H2O ═ LiOH and Li2O+CO2＝Li2CO3The reaction of (A) produces surface "residual alkali" LiOH and Li2CO3In xLi2The presence of carbon on O.yM matrix can inhibit LiOH and Li2CO3And can block xLi as a barrier layer2Substrate and positive electrode slurry of O.yMThe contact of the binder in the slurry improves the stability of the slurry and ensures Li2Specific capacity of O. In the present application, it will be understood by those skilled in the art that the presence of xLi is present2The carbon on the O · yM substrate may cover the entire surface of the substrate or partially cover the surface of the substrate, and the present application is not particularly limited as long as the object of the present application can be achieved.
The positive electrode lithium supplement material generates xLi during first charging2O+M–2xe-＝MOx+2xLi+The lithium removal reaction plays a role in lithium supplement. Meanwhile, because the anode lithium-supplementing material is arranged at the anode, the potential of the anode is difficult to be lowered to generate MO (metal oxide) in the subsequent discharging processx+2xLi++2xe-＝xLi2The O + M reacts at 0V to 2V, so that active lithium is not consumed in the subsequent discharging process, and the net supplement of the active lithium is realized.
In general, the positive electrode lithium supplement material provided by the application comprises xLi2A substrate of O.yM, and carbon present on the substrate. The positive electrode lithium supplement material has high specific capacity, good chemical stability and moderate conductivity, does not generate gas in the process of charging and lithium supplement, can effectively improve the particle agglomeration phenomenon in the slurry mixing process of positive electrode slurry, and improves the processing performance of the positive electrode slurry. The positive electrode lithium supplement material is added into a positive electrode plate, so that the loss of active lithium caused by SEI generation can be supplemented, and the energy density of the lithium ion secondary battery is further improved.
In one embodiment of the present application, the carbon is present in an amount of 0.5 to 3% by mass, based on the total mass of the positive electrode lithium supplement material. For example, the lower limit of the mass percentage of carbon may be included in the following values: 0.5% or 1%; the upper limit value of the mass percentage of carbon can be included in the following numerical values: 2%, 2.5% or 3%. Without being bound by any theory, it is difficult to enhance xLi if the carbon content is too low (e.g., less than 0.5 percent by mass)2Chemical stability of O.yM substrate, and difficulty in blocking xLi as a barrier layer2Contacting the substrate of O.yM with the binder in the positive electrode slurry; too high a mass percentage of carbon (e.g. above 3%), a significant increase in impedance, and extremeThe actual specific capacity of the anode lithium supplement material is seriously influenced along with the increase of the lithium ion battery capacity, and the effect of improving the energy density of the lithium ion secondary battery is further influenced. By controlling the mass percentage of carbon in the positive electrode lithium supplement material within the range, the stability of the positive electrode slurry can be effectively improved, and the energy density of the lithium ion secondary battery can be improved.
In one embodiment of the present application, the first charge specific capacity of the positive electrode lithium supplement material is greater than or equal to 450 mAh/g. The specific capacity of the positive electrode lithium supplement material is high, a large amount of lithium ions can be removed to make up for the loss of active lithium caused by SEI generation during first charging, and enough lithium ions are re-embedded into the positive electrode active material during first discharging, so that the discharging specific capacity of the lithium ion secondary battery is effectively improved, and the energy density of the lithium ion secondary battery is further improved.
A second aspect of the present application provides a method of preparing a positive electrode lithium supplement material of the present application, comprising the steps of:
(1) dispersing naphthalene in a solvent, slowly adding lithium metal fragments or powder, and uniformly reacting to obtain a naphthalene lithium solution;
(2) oxide MaObSlowly adding the solution into the naphthalene lithium solution, uniformly stirring the solution for reaction, filtering and drying the solution to obtain the xLi2A substrate of O.yM;
(3) ball-milling and mixing the matrix and an inorganic carbon source, and uniformly dispersing to obtain a mixture;
(4) calcining the mixture in an inert atmosphere to obtain a positive electrode lithium supplement material; wherein the molar ratio of naphthalene to lithium metal is 1: (0.6 to 1), naphthalene and oxide MaObIn a molar ratio of 1: (0.1 to 0.5), the ratio of the number of moles of naphthalene to the mass of the inorganic carbon source is 1: (0.05 to 0.3) mol/g.
The above-described preparation method provided in the present application is a preferred method for preparing the positive electrode lithium supplement material of the present application, and a person skilled in the art can also prepare the positive electrode lithium supplement material of the present application by other methods.
Compared with the conventional solid-phase sintering method, the method for preparing the anode lithium supplement material has higher safety, more uniform and sufficient reaction and controllable appearance and particles of the prepared product. The preparation method has the advantages of simple principle, convenient operation, excellent effect and good compatibility with the existing preparation process.
In one embodiment of the present application, the kind of the solvent is not particularly limited as long as the object of the present application can be achieved. For example, an aprotic solvent may be used, including at least one of tetrahydrofuran or ethylene glycol dimethyl ether, and the like.
In one embodiment of the present application, p-oxide MaObThe kind of (b) is not particularly limited as long as the object of the present application can be achieved. For example, oxide MaObMay include MnO, Mn2O3、MnO2、FeO、Fe2O3、CoO、Co2O3、Co3O4、NiO、Ni2O3、Cu2O、CuO、CrO、Cr2O3、CrO3、VO、V2O3、VO2Or V2O5And the like.
In one embodiment of the present application, the kind of the inorganic carbon source is not particularly limited as long as the object of the present application can be achieved. For example, the inorganic carbon source may include at least one of carbon black, carbon gel, ketjen black, acetylene black, carbon nanotubes, graphene, or the like.
In one embodiment of the present application, the temperature and time of calcination in step (4) are not particularly limited as long as the object of the present application can be achieved. For example, the temperature of calcination may be 600 ℃ to 700 ℃ and the time of calcination may be 4h to 8 h.
A third aspect of the present application provides a positive electrode plate, including a positive electrode lithium supplement material, where the positive electrode lithium supplement material is the positive electrode lithium supplement material described in any one of the above embodiments. The positive electrode lithium supplement material is applied to the positive electrode plate, so that active lithium can be effectively supplemented, and the energy density of the lithium ion secondary battery is improved.
The positive electrode sheet in the present application is not particularly limited as long as the object of the present application can be achieved. For example, the positive electrode tab generally includes a positive electrode current collector and a positive electrode active material layer. The positive electrode current collector is not particularly limited as long as the object of the present invention can be achieved, and may include, for example, an aluminum foil, an aluminum alloy foil, a composite current collector, or the like. The positive electrode active material layer includes a positive electrode active material and a positive electrode lithium supplement material. The kind of the positive electrode active material is not particularly limited as long as the object of the present application can be achieved, and for example, at least one of lithium nickel cobalt manganese oxide (811, 622, 523, 111), lithium nickel cobalt aluminate, lithium iron phosphate, a lithium rich manganese-based material, lithium cobalt oxide, lithium manganese oxide, lithium iron manganese phosphate, or lithium titanate may be included. The positive electrode lithium supplement material is at least one of the positive electrode lithium supplement materials provided by the application. In the present application, the thicknesses of the positive electrode current collector and the positive electrode active material layer are not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the positive electrode current collector is 5 μm to 20 μm, preferably 6 μm to 18 μm, and more preferably 8 μm to 16 μm. The thickness of the positive electrode material layer is 30 μm to 120 μm. In the present application, the positive electrode active material layer may be provided on one surface (first surface) in the thickness direction of the positive electrode current collector, and may also be provided on both surfaces (first surface and second surface) in the thickness direction of the positive electrode current collector. The "surface" herein may be the entire region of the positive electrode current collector or a partial region of the positive electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. Optionally, the positive electrode sheet may further include a conductive layer between the positive electrode current collector and the positive electrode material layer. The composition of the conductive layer is not particularly limited, and may be a conductive layer commonly used in the art. The conductive layer includes a conductive agent and a binder.
In one embodiment of the present application, the positive electrode lithium supplement material may be present in an amount of 1 to 10% by mass, preferably 3 to 10% by mass, based on the total mass of the positive electrode active material layer. For example, the positive electrode lithium supplement material may include, by mass: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. By controlling the content of the positive electrode lithium supplement material in the positive electrode active material layer within the range, the positive electrode plate has good structural stability, and the capacity loss and volume change caused by lithium removal of the positive electrode lithium supplement material can be reduced. The mass percentage of the positive electrode lithium supplement material is controlled in the preferable range, so that the positive electrode plate has better structural stability, and the capacity of the battery can be improved to a greater extent.
The adding mode of the positive electrode lithium supplement material is not particularly limited, and a person skilled in the art can select the material according to actual needs as long as the purpose of the application can be achieved. For example, the positive electrode material may be directly added to the slurry during the slurry preparation process of the positive electrode material to form a positive electrode slurry containing the positive electrode material, and the positive electrode slurry may be applied to the surface of the positive electrode current collector. The positive electrode lithium-supplementing material film can be deposited on the surface of the positive electrode current collector in advance. Or after the positive active material of the positive pole piece is coated, a positive lithium-supplement material film is deposited on the surface of the positive active material. And assembling the lithium ion secondary battery after the positive electrode lithium supplement material is added, and in the first charging process, removing lithium from the positive electrode lithium supplement material to exert the lithium supplement effect. The "surface" may be the entire region of the positive electrode collector/positive electrode active material or a partial region of the positive electrode collector/positive electrode active material, and the present application is not particularly limited as long as the object of the present application can be achieved.
The negative electrode sheet of the present application is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode tab generally includes a negative electrode current collector and a negative electrode active material layer. The negative electrode current collector is not particularly limited as long as the object of the present invention can be achieved, and may include, for example, a copper foil, a copper alloy foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a composite current collector, or the like. The negative electrode active material layer includes a negative electrode active material, a conductive agent, and a thickener. The negative active material of the present application may include natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composite, SiOx(0<x<2) Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2Lithium titanate Li of spinel structure4Ti5O12At least one of Li-Al alloy and metallic lithium. In the present application, the thickness of the negative electrode current collector and the negative electrode active material layer is not particularly limited as long as the object of the present application can be achieved, and for example, the thickness of the negative electrode current collector is 6 μm to 10 μm and the thickness of the negative electrode active material layer is 30 μm to 120 μm. In the present application, the thickness of the negative electrode tab is not particularly limited as long as the object of the present application can be achieved, and for example, the thickness of the negative electrode tab is 50 μm to 150 μm. Optionally, the negative electrode sheet may further comprise a conductive layer located between the negative electrode current collector and the negative electrode material layer. The composition of the conductive layer is not particularly limited, and may be a conductive layer commonly used in the art. The conductive layer includes a conductive agent and a binder.
The conductive agent is not particularly limited as long as the object of the present application can be achieved. For example, the conductive agent may include at least one of conductive carbon black (Super P), Carbon Nanotubes (CNTs), carbon nanofibers, flake graphite, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, or the like. The above-mentioned binder is not particularly limited, and any binder known in the art may be used as long as the object of the present application can be achieved. For example, the binder may include at least one of polyvinyl alcohol, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyamideimide, styrene-butadiene rubber (SBR), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), aqueous acrylic resin, carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (CMC-Na), or the like.
The separator in the present application is not particularly limited as long as the object of the present application can be achieved. For example, at least one of a Polyolefin (PO) separator mainly composed of Polyethylene (PE) and polypropylene (PP), a polyester film (for example, a polyethylene terephthalate (PET) film), a cellulose film, a polyimide film (PI), a polyamide film (PA), a spandex or aramid film, a woven film, a nonwoven film (nonwoven fabric), a microporous film, a composite film, a separator paper, a roll film, a spun film, and the like. For example, the release film may include a base material layer and a surface treatment layer. The substrate layer may be a non-woven fabric, a film or a composite film having a porous structure, and the material of the substrate layer may include at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide, and the like. Optionally, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite film may be used. Optionally, a surface treatment layer is disposed on at least one surface of the substrate layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance. For example, the inorganic layer includes inorganic particles and a binder, and the inorganic particles are not particularly limited and may be, for example, at least one selected from the group consisting of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium sulfate, and the like. The binder is not particularly limited, and may be, for example, one or a combination of several selected from polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, and polyhexafluoropropylene. The polymer layer contains a polymer, and the material of the polymer comprises at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and the like.
The lithium ion secondary battery of the present application further includes an electrolyte, which may be at least one of a gel electrolyte, a solid electrolyte, and an electrolytic solution including a lithium salt and a non-aqueous solvent. In some embodiments herein, the lithium salt may include LiPF6、LiBF4、LiAsF6、LiClO4、LiB(C6H5)4、LiCH3SO3、LiCF3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiSiF6At least one of LiBOB or lithium difluoroborate. For example, the lithium salt may be LiPF6Since it can give high ionic conductivity and improve cycle characteristics. The non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvent, or a combination thereof. The carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluoro carbonate compound, or a combination thereof. Examples of the above chain carbonate compound are dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Methyl Ethyl Carbonate (MEC), and combinations thereof. Examples of the cyclic carbonate compound are Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), Vinyl Ethylene Carbonate (VEC), and combinations thereof. Examples of the fluoro carbonate compound are fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1,2, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, and combinations thereof. Examples of the above carboxylic acid ester compounds are methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ -butyrolactone, decalactone, valerolactone, mevalonolactone, caprolactone, and combinations thereof. Examples of the above ether compounds are dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof. Examples of such other organic solvents are dimethylsulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate and phosphate esters and combinations thereof.
A fourth aspect of the present application provides an electrochemical device comprising the positive electrode sheet provided by the present application, which has good energy density. The electrochemical device of the present application is not particularly limited, and may include any device in which electrochemical reactions occur. In some embodiments, the electrochemical device may include, but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery (lithium ion battery), a lithium polymer secondary battery, a lithium ion polymer secondary battery, or the like.
The present application also provides an electronic device comprising the electrochemical device described in the embodiments of the present application, which has good energy density. The electronic device of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile machine, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a handheld cleaner, a portable CD player, a mini-disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable recorder, a radio, a backup power source, an electric motor, an automobile, a motorcycle, a power-assisted bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large household battery, a lithium ion capacitor, and the like.
The process for preparing the electrochemical device is well known to those skilled in the art, and the present application is not particularly limited. For example, the electrochemical device may be manufactured by the following process: the positive pole piece and the negative pole piece are overlapped through the isolating film, the positive pole piece and the negative pole piece are placed into the shell after being wound, folded and the like according to needs, electrolyte is injected into the shell and the shell is sealed, wherein the isolating film is the isolating film provided by the application. In addition, an overcurrent prevention element, a guide plate, or the like may be placed in the case as necessary to prevent a pressure rise and overcharge/discharge inside the electrochemical device.
The application provides a lithium material is mended to positive pole, contains anodal pole piece and electrochemical device of this material, and this lithium material is mended to positive pole includes: xLi2A substrate of O.yM and carbon present on the substrate; wherein x is more than 0, y is more than or equal to 0.4x and less than or equal to 2x,m includes at least one of Mn, Fe, Co, Ni, Cu, Cr, or V. The positive electrode lithium supplement material has strong chemical stability, and can effectively improve the particle agglomeration phenomenon in the size mixing process. The positive electrode lithium supplement material is applied to a positive electrode plate, active lithium can be supplemented, and the energy density of an electrochemical device is effectively improved.
Drawings
In order to illustrate the technical solutions of the present application and the prior art more clearly, the following briefly introduces examples and figures that need to be used in the prior art, it being obvious that the figures in the following description are only some examples of the present application.
Fig. 1 is an XRD (X-ray diffraction) pattern of the positive electrode lithium supplement material of example 1 of the present application;
fig. 2 is an SEM (scanning electron microscope) image of the positive electrode lithium supplement material of example 1 of the present application;
fig. 3 is an EDS (X-ray spectroscopy) spectrum of cobalt element in the positive electrode lithium supplement material of example 1 of the present application;
fig. 4 is an EDS spectrum of an oxygen element in the positive electrode lithium supplement material of example 1 of the present application;
fig. 5 is an EDS spectrum of carbon element in the positive electrode lithium supplement material of example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail below with reference to the accompanying drawings and examples. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other technical solutions obtained by a person of ordinary skill in the art based on the embodiments in the present application belong to the scope of protection of the present application.
In the embodiments of the present application, the present application is explained by taking a lithium ion secondary battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion secondary battery.
Fig. 1 shows an XRD spectrum of the positive electrode lithium supplement material of example 1 of the present application. Wherein (a) in FIG. 1 is a diagram of a positive electrode lithium-supplementing materialSpectrum, (b) in fig. 1 is Co standard diffraction card, and (c) in fig. 1 is Li2O standard diffraction cards. As shown in fig. 1, (a) the map can see: diffraction peaks with 2 theta of 44.2 degrees and 51.5 degrees appear, and the diffraction peaks correspond to the diffraction peaks of Co; diffraction peaks with 2 theta of 33.1 DEG, 38.4 DEG, 55.4 DEG, 66.0 DEG and 69.4 DEG appear, corresponding to Li2Diffraction peak of O, indicating the presence of Co and Li in the positive electrode lithium-supplement material of example 1 of the present application2O。
Fig. 2 shows an SEM image of the positive electrode lithium supplement material of example 1 of the present application, and as shown in fig. 2, the particle size distribution of the positive electrode lithium supplement material is uniform. Fig. 3 shows an EDS spectrum of cobalt in the positive electrode lithium supplement material of example 1 of the present application, which shows that the positive electrode lithium supplement material of the present application contains cobalt and is uniformly distributed in the positive electrode lithium supplement material. Fig. 4 shows an EDS spectrum of oxygen element in the positive electrode lithium supplement material of example 1 of the present application, which indicates that the positive electrode lithium supplement material of the present application contains oxygen element and is uniformly distributed in the positive electrode lithium supplement material. Fig. 5 shows an EDS spectrum of carbon in the positive electrode lithium supplement material of example 1 of the present application, which shows that the positive electrode lithium supplement material of the present application contains carbon and is uniformly distributed in the positive electrode lithium supplement material.
Examples
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
The test method and the test equipment are as follows:
testing the first charging specific capacity:
< preparation of button cell >
Mixing a positive electrode lithium supplement material to be tested, conductive carbon black (Super P) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder according to a mass ratio of 80:10:10, adding N-methylpyrrolidone (NMP) as a solvent, stirring and blending to obtain slurry with the solid content of 40%, coating a coating with the thickness of 100 microns on a current collector aluminum foil by using a scraper, drying the coating in a vacuum drying box for 12 hours at the temperature of 130 ℃, cutting the coating into a wafer with the diameter of 1cm in a drying environment by using a punching machine, taking a metal lithium sheet as a counter electrode in a glove box, selecting a ceglard composite membrane as an isolating membrane, and adding electrolyte to assemble the button cell. The electrolyte is prepared by mixing Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) in a mass ratio of 30:50:20 to obtain an organic solution, adding lithium salt lithium hexafluorophosphate into the organic solvent, dissolving and uniformly mixing to obtain the electrolyte with the concentration of lithium salt being 1.15 mol/L.
< measurement of specific Capacity for first Charge >
The method adopts a Wuhan blue electricity CT2001A system to carry out charging specific capacity test, the button cell to be tested containing the positive electrode lithium supplement material is kept stand for 30min in an environment with the temperature of 25 +/-3 ℃, the constant current charging is carried out with the multiplying power of 0.1C (the theoretical gram capacity of the positive electrode lithium supplement material is calculated by 600 mAh/g) until the voltage is 4.45V, then the constant voltage charging is carried out until the current is 0.025C, and the first charging capacity is recorded.
The button cell charging specific capacity of the positive electrode lithium supplement material is equal to the initial charging capacity/the quality of the positive electrode lithium supplement material.
First discharge capacity test:
standing the lithium ion secondary battery to be tested containing the positive electrode lithium supplement material in an environment with the temperature of 25 +/-3 ℃ for 30min, charging the lithium ion secondary battery to be tested to the voltage of 4.4V by using the current of 600mA (the rated capacity is calculated by 2000 mAh) in a constant current manner, then charging the lithium ion secondary battery to the current of 50mA in a constant voltage manner, standing the lithium ion secondary battery for 5min, discharging the lithium ion secondary battery to the final voltage of 3.0V by using the current of 600mA in a constant current manner, and recording the first discharge capacity.
Example 1
< preparation of Positive electrode lithium-doped Material >
Dispersing 128.17g of naphthalene in 1L of tetrahydrofuran solvent, slowly adding 5.55g of lithium metal fragments, and uniformly reacting to obtain a naphthalene lithium solution; 24.08g of Co oxide was weighed3O4Slowly adding the mixture into the naphthalene lithium solution, uniformly stirring the mixture for reaction, filtering and drying the mixture to obtain 4Li2A substrate of O.3Co; 10g of the above-mentioned 4Li2Carrying out ball milling mixing on the O.3Co substrate and 0.05g of inorganic carbon source carbon black, and uniformly dispersing to obtain a mixture; calcining the mixture at 600 ℃ for 8h in an inert atmosphere to obtain 4Li2And a positive electrode lithium-supplementing material in which carbon is present on an O.3Co substrate. Based on positive pole is mendedThe mass percentage of carbon in the total mass of the lithium material is 0.5%.
< preparation of Positive electrode sheet >
The positive electrode active material lithium cobaltate (LiCoO)2) Mixing the prepared positive electrode lithium supplement material, the conductive agent Super P and the binder PVDF according to the mass ratio of 95:2:1.5:1.5, adding NMP as a solvent, preparing into slurry with the solid content of 75%, and uniformly stirring. And uniformly coating the slurry on one surface of an aluminum foil of the positive current collector with the thickness of 10 mu m, and drying at 130 ℃ to obtain a positive pole piece with the coating thickness of 110 mu m. And finishing the single-side coating of the positive pole piece after the steps are finished. And then, repeating the steps on the other surface of the positive pole piece to obtain the positive pole piece with the positive active material coated on the two surfaces. After coating, cutting the positive pole piece into a size of 74mm × 867mm, and welding a tab for standby.
< preparation of negative electrode sheet >
Mixing graphite, a negative electrode active material SiO, a conductive agent nano conductive carbon black and a binder polypropylene alcohol (PAA) according to a mass ratio of 78:15:3:4, adding deionized water as a solvent, blending into slurry with a solid content of 60%, uniformly stirring, adding a proper amount of deionized water, adjusting the viscosity of the slurry to 5000 Pa.s, and preparing into negative electrode slurry. And uniformly coating the slurry on a negative current collector copper foil with the thickness of 8 mu m, drying at 110 ℃, and cold-pressing to obtain the negative pole piece with the active material layer of which the thickness is 100 mu m and the single surface is coated with the active material layer. And after the steps are finished, the steps are also finished on the back surface of the negative pole piece by adopting the same method, and the negative pole piece with the double-sided coating is obtained. After coating, cutting the negative pole piece into a specification of 76mm × 851mm and welding a pole ear for standby.
< preparation of electrolyte solution >
In a dry argon atmosphere, mixing organic solvents EC, EMC and DEC according to a mass ratio of 30:50:20 to obtain an organic solution, adding lithium salt lithium hexafluorophosphate into the organic solvent to dissolve and uniformly mix, and obtaining an electrolyte with the concentration of lithium salt being 1.15 mol/L.
< preparation of separator >
A polypropylene (PP) film (available from Celgard) having a thickness of 14 μm was used.
< preparation of lithium ion Secondary Battery >
And (3) stacking the prepared positive electrode, the prepared isolating membrane and the prepared negative electrode in sequence to enable the isolating membrane to be positioned between the positive electrode and the negative electrode to play an isolating role, and winding to obtain the electrode assembly. And (3) putting the electrode assembly into an aluminum-plastic film packaging bag, dehydrating at 80 ℃, injecting the prepared electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion secondary battery.
In examples 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16, the preparation steps of < preparation of positive electrode lithium-supplementing material >, < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of electrolyte >, < preparation of separator > and < preparation of lithium ion secondary battery > were the same as in example 1, and the changes in the relevant preparation parameters were as shown in table 1:
TABLE 1
Figure BDA0003445974320000131
Example 17
< preparation of negative electrode sheet >
Mixing the negative active material graphite, the nano conductive carbon black, the styrene butadiene rubber and the sodium carboxymethyl cellulose according to the mass ratio of 95:2:2:1, adding deionized water as a solvent, blending into slurry with the solid content of 70%, and uniformly stirring. And uniformly coating the slurry on a negative current collector copper foil with the thickness of 8 mu m, drying at 110 ℃, and cold-pressing to obtain the negative pole piece with the active material layer coated on one side and the thickness of 150 mu m. And after the steps are finished, the steps are also finished on the back surface of the negative pole piece by adopting the same method, and the negative pole piece with the double-sided coating is obtained. After coating, cutting the negative pole piece into a specification of 76mm × 851mm and welding a pole ear for standby.
The preparation of positive electrode lithium-supplement material, the preparation of positive electrode sheet, the preparation of electrolyte, the preparation of separator and the preparation of lithium ion secondary battery were the same as in example 1.
In comparative examples 1,2, 3 and 4, the preparation steps of < preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of electrolyte >, < preparation of separator > and < preparation of lithium ion secondary battery > were the same as in example 1, and in comparative examples 2, 3 and 4, < preparation of positive electrode lithium supplement material > was the same as in example 1, and the changes in the relevant preparation parameters are shown in table 2:
TABLE 2
Figure BDA0003445974320000141
Note: the "/" in table 2 indicates that the corresponding production parameters are not present.
Comparative example 5
< preparation of Positive electrode lithium-doped Material >
Fragmenting metallic lithium and oxide Co3O4Mixing according to a molar ratio of 8:1 to obtain a first mixture; sintering the first mixture at 180 ℃ for 4h under the protection of argon to obtain a second mixture; mixing the second mixture with Ar and O2Mixing the anode and the mixed gas with HF volume ratio of 3:0.05:96.95, and reacting to obtain the cathode lithium supplement material 2.1Li2O·Co·0.5CoO0.05F0.1。
< preparation of positive electrode sheet >, < preparation of negative electrode sheet >, < preparation of electrolyte >, < preparation of separator > and < preparation of lithium ion secondary battery > were the same as in example 1.
The preparation parameters of example 1, example 2, example 3, example 4, example 5, example 6, example 7, example 8, example 9, example 10, example 11, example 12, example 13, example 14, example 15, example 16, example 17, comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5 are shown in table 3:
Figure BDA0003445974320000161
Figure BDA0003445974320000171
as can be seen from examples 1, 6, 7, 8, 9, 10, 11, 12, and 1, 5, the present application uses inorganic carbon sources with the same composition and content to wrap substrates with different compositions to form different positive electrode lithium supplement materials. Although the components of the matrix are different, the chemical stability of the positive electrode lithium supplement material can be effectively improved as long as the components of the matrix are within the range of the application, so that the particle agglomeration phenomenon in the slurry mixing process of the positive electrode slurry is effectively inhibited. And the positive electrode lithium supplement material is applied to the positive electrode plate, so that active lithium can be effectively supplemented, and the energy density of the lithium ion secondary battery is effectively improved.
As can be seen from examples 1,2, 3, and comparative examples 2 and 3, the positive electrode lithium supplement material having the carbon content of the present application can effectively increase the first charge specific capacity of the positive electrode lithium supplement material, can effectively supplement active lithium, and effectively increase the energy density of the lithium ion secondary battery.
The calcination temperature and the calcination time of the positive electrode lithium supplement material and the type of the inorganic carbon source generally affect the first charge specific capacity of the positive electrode lithium supplement material, and it can be seen from examples 1, 4 and 5 that the first charge specific capacity of the positive electrode lithium supplement material and the energy density of the lithium ion secondary battery can be effectively improved as long as the preparation parameters are within the range of the application.
As can be seen from examples 1, 13, 14, 15, 16 and 4, the content of the positive electrode lithium supplement material in the range of the present application can effectively increase the first charge specific capacity of the positive electrode lithium supplement material and the energy density of the lithium ion secondary battery. Particularly, when the mass percentage of the positive electrode lithium supplement material is preferably 3% to 10%, for example, in examples 13, 14, 15, and 16, the energy density of the lithium ion secondary battery can be more effectively increased.
In summary, the positive electrode lithium supplement material provided by the present application includes xLi2A substrate of O.yM, and carbon present on the substrate. The positive electrode lithium supplement material has strong chemical stability, and can effectively improve the particle agglomeration phenomenon in the size mixing process. The anode lithium supplement material is applied to an electrochemical device, so that active lithium can be effectively supplemented, and the energy density of the electrochemical device is effectively improved.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. The positive electrode lithium supplementing material comprises xLi2A substrate of O.yM, and carbon present on the substrate;
wherein x is more than 0, y is more than or equal to 0.4x and less than or equal to 2x, and M comprises at least one of Mn, Fe, Co, Ni, Cu, Cr or V.
2. The positive electrode lithium supplement material of claim 1, wherein the M comprises at least one of Mn, Fe, Co, or Ni; the valence of M is 0.
3. The positive electrode lithium supplement material according to claim 1, wherein the carbon is contained in an amount of 0.5 to 3% by mass based on the total mass of the positive electrode lithium supplement material.
4. The positive electrode lithium supplement material according to claim 1, wherein the first charge specific capacity of the positive electrode lithium supplement material is not less than 450 mAh/g.
5. A method of preparing the positive electrode lithium supplement material of any one of claims 1 to 4, comprising the steps of:
(1) dispersing naphthalene in a solvent, slowly adding lithium metal fragments or powder, and uniformly reacting to obtain a naphthalene lithium solution;
(2) oxide MaObSlowly adding the solution into the naphthalene lithium solution, uniformly stirring the solution for reaction, filtering and drying the solution to obtain the xLi2A substrate of O.yM;
(3) performing ball milling mixing on the matrix and an inorganic carbon source, and uniformly dispersing to obtain a mixture;
(4) calcining the mixture in an inert atmosphere to obtain the anode lithium supplement material;
wherein the molar ratio of the naphthalene to the lithium metal is 1: (0.6 to 1), said naphthalene and said oxide MaObIn a molar ratio of 1: (0.1 to 0.5), and the ratio of the number of moles of naphthalene to the mass of the inorganic carbon source is 1: (0.05 to 0.3) mol/g.
6. The method of claim 5, wherein the solvent comprises at least one of tetrahydrofuran or ethylene glycol dimethyl ether;
the oxide MaObIncluding MnO and Mn2O3、MnO2、FeO、Fe2O3、CoO、Co2O3、Co3O4、NiO、Ni2O3、Cu2O、CuO、CrO、Cr2O3、CrO3、VO、V2O3、VO2Or V2O5At least one of;
the inorganic carbon source comprises at least one of carbon black, carbon gel, Ketjen black, acetylene black, carbon nanotubes or graphene;
in the step (4), the calcining temperature is 600 ℃ to 700 ℃, and the calcining time is 4h to 8 h.
7. A positive electrode sheet comprising the positive electrode lithium supplement material according to any one of claims 1 to 4.
8. The positive electrode sheet according to claim 7, wherein the positive electrode lithium supplement material is contained in an amount of 1 to 10% by mass based on the total mass of the positive electrode active material layer.
9. An electrochemical device comprising the positive electrode sheet of claim 7 or 8.
10. An electronic device comprising the electrochemical device of claim 9.
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