WO2022198660A1 - Positive electrode lithium supplementing material, and positive electrode plate and electrochemical device including same - Google Patents
Positive electrode lithium supplementing material, and positive electrode plate and electrochemical device including same Download PDFInfo
- Publication number
- WO2022198660A1 WO2022198660A1 PCT/CN2021/083385 CN2021083385W WO2022198660A1 WO 2022198660 A1 WO2022198660 A1 WO 2022198660A1 CN 2021083385 W CN2021083385 W CN 2021083385W WO 2022198660 A1 WO2022198660 A1 WO 2022198660A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- lithium
- supplement material
- present application
- lithium supplement
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000000463 material Substances 0.000 title claims abstract description 99
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
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- 239000011159 matrix material Substances 0.000 claims abstract description 32
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the field of electrochemistry, and in particular, to a positive electrode lithium supplement material, a positive electrode pole piece comprising the material, and an electrochemical device.
- Lithium-ion secondary batteries have the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, and good safety. They are widely used in various fields such as electrical energy storage, mobile electronic equipment, electric vehicles, and aerospace equipment. With the rapid development of mobile electronic devices and electric vehicles, the market has put forward higher and higher requirements for the energy density, cycle performance and kinetic performance of lithium-ion secondary batteries.
- Solid Electrolyte Interphase SEI
- SEI Solid Electrolyte Interphase
- the purpose of the present application is to provide a positive electrode lithium supplement material, a positive electrode electrode sheet and an electrochemical device comprising the material, so as to improve the energy density of the electrochemical device.
- the present application is explained by taking a lithium ion secondary battery as an example of the electrochemical device, but the electrochemical device of the present application is not limited to the lithium ion secondary battery.
- the specific technical solutions are as follows:
- a first aspect of the present application provides a positive electrode lithium supplement material, which includes a matrix of xLi 2 O ⁇ yM and carbon existing on the matrix; wherein x>0, 0.4x ⁇ y ⁇ 2x, and M includes Mn , at least one of Fe, Co, Ni, Cu, Cr or V.
- M may include at least one of Mn, Fe, Co, Ni, Cu, Cr, V, etc., and M may preferably include at least one of Mn, Fe, Co, Ni, and the like. Among them, the valence state of M can be 0.
- xLi 2 O.yM a matrix of xLi 2 O.yM that can achieve the purpose of the present application, such as but not limited to 4Li 2 O.3Co, Li 2 O.Co, Any of 5Li2O.4Co , 3Li2O.2Fe , 7Li2O.3Co.2Fe , 12Li2O.3Co.2Fe.2V , 2Li2O.Mn , Li2O.Ni , and the like.
- the xLi 2 O ⁇ yM matrix of the present application is obtained, which can release a large amount of lithium ions during the first charging process, has a high specific capacity, and can greatly improve the performance of lithium ion secondary batteries. Energy Density.
- the inventor unexpectedly found that the presence of carbon on the xLi 2 O yM matrix can not only effectively enhance the chemical stability of the xLi 2 O yM matrix, but also improve the stability of the positive electrode slurry, making it more difficult to agglomerate and more convenient for the positive electrode.
- the preparation and storage of the slurry and its coating on the positive electrode plate can improve the processability of the positive electrode slurry, and can also improve the energy density of the lithium ion secondary battery.
- the carbon existing on the substrate of xLi 2 O ⁇ yM can wrap the entire surface of the substrate or partially wrap the surface of the substrate.
- This application is not particularly limited, as long as the The purpose of the application is sufficient.
- the positive electrode lithium supplement material provided by the present application includes a matrix of xLi 2 O ⁇ yM and carbon existing on the matrix.
- the positive electrode lithium supplement material has high specific capacity, good chemical stability, moderate conductivity, and no gas is generated during the charging lithium supplement process, which can effectively improve the particle agglomeration phenomenon in the positive electrode slurry mixing process, and improve the positive electrode slurry. Processability. Adding the positive electrode lithium supplement material to the positive electrode plate can supplement the loss of active lithium caused by the generation of SEI, thereby further improving the energy density of the lithium ion secondary battery.
- the mass percentage content of carbon is 0.5% to 3% based on the total mass of the positive electrode lithium supplement material.
- the lower limit of the mass percentage of carbon can be included in the following values: 0.5% or 1%; the upper limit of the carbon mass percentage can be included in the following values: 2%, 2.5% or 3%.
- the mass percentage of carbon is too low (for example, less than 0.5%), it is difficult to enhance the chemical stability of the xLi 2 O yM matrix, and it is difficult to act as a barrier layer to separate the xLi 2 O yM matrix from the positive electrode.
- the mass percentage of carbon is too high (for example, higher than 3%), the impedance increases significantly, and the polarization increases with it, which seriously affects the actual specific capacity of the positive electrode lithium supplement material, which in turn affects the The effect of improving the energy density of lithium-ion secondary batteries.
- the mass percentage content of carbon in the positive electrode lithium supplement material within the above 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.
- the first charge specific capacity of the positive electrode lithium supplement material is ⁇ 450 mAh/g. It shows that the specific capacity of the positive electrode lithium supplementary material is high, and a large amount of lithium ions can be released during the first charge to make up for the loss of active lithium caused by the formation of SEI, and enough lithium ions are inserted back into the positive electrode active material during the first discharge, which effectively improves the lithium ion
- the discharge specific capacity of the ion secondary battery improves the energy density of the lithium ion secondary battery.
- a second aspect of the present application provides a method for preparing the positive electrode lithium supplement material of the present application, comprising the following steps:
- a positive electrode lithium supplement material wherein, the molar ratio of naphthalene to lithium metal is 1: (0.6 to 1), and the molar ratio of naphthalene to oxide M a O b is 1 : (0.1 to 0.5), and the ratio of the mole number of naphthalene to the mass of the inorganic carbon source is 1: (0.05 to 0.3) mol/g.
- the above-mentioned preparation method provided in this application is a preferred method for preparing the positive electrode lithium supplementary material of the present application, and those skilled in the art can also prepare the positive electrode lithium supplementary material of the present application according to other methods. There is no special method for this application. Restrictions, as long as the purpose of the application can be achieved.
- the method for preparing a positive electrode lithium supplementary material provided by the present application is a homogeneous reaction at room temperature. Compared with the conventional solid-phase sintering method, the method has higher safety, more uniform and sufficient reaction, and the obtained product morphology and particles. Controllable.
- the preparation method is simple in principle, convenient in operation, excellent in effect, and has good compatibility with the existing preparation process.
- the type of solvent is not particularly limited, as long as the purpose of the present application can be achieved.
- it may be an aprotic solvent, including at least one of tetrahydrofuran, ethylene glycol dimethyl ether, and the like.
- the type of oxide M a O b is not particularly limited, as long as the purpose of the present application can be achieved.
- the oxide MaOb may include MnO , Mn2O3 , MnO2 , FeO , Fe2O3 , CoO , Co2O3 , Co3O4 , NiO , Ni2O3 , Cu2O , At least one of CuO, CrO, Cr 2 O 3 , CrO 3 , VO, V 2 O 3 , VO 2 or V 2 O 5 and the like.
- the inorganic carbon source may include at least one of carbon black, carbon gel, Ketjen black, acetylene black, carbon nanotubes, graphene, and the like.
- the temperature and time of calcination in step (4) are not particularly limited, as long as the purpose of the present application can be achieved.
- the calcination temperature may be 600°C to 700°C
- the calcination time may be 4h to 8h.
- a third aspect of the present application provides a positive electrode sheet, including a positive electrode lithium supplement material, and the positive electrode lithium supplement material is the positive electrode lithium supplement material described in any one of the above embodiments.
- the application of the positive electrode lithium supplement material of the present application to the positive electrode plate can realize the effective supplement of active lithium and improve the energy density of the lithium ion secondary battery.
- the positive electrode sheet in the present application is not particularly limited, as long as the purpose of the present application can be achieved.
- a positive electrode sheet typically 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 purpose of the present application can be achieved, for example, it may include aluminum foil, aluminum alloy foil, or composite current collector.
- the positive electrode active material layer includes a positive electrode active material and a positive electrode lithium supplement material.
- the type of positive active material is not particularly limited, as long as it can achieve the purpose of the present application, for example, it can include nickel cobalt lithium manganate (811, 622, 523, 111), nickel cobalt lithium aluminate, lithium iron phosphate, lithium rich manganese At least one of base material, lithium cobaltate, lithium manganate, lithium iron manganese phosphate or lithium titanate.
- the positive electrode lithium supplement material is at least one of the positive electrode lithium supplement materials provided in this application.
- the thicknesses of the positive electrode current collector and the positive electrode active material layer are not particularly limited as long as the purpose of the present application can be achieved.
- the thickness of the positive electrode current collector is 5 ⁇ m to 20 ⁇ m, preferably 6 ⁇ m to 18 ⁇ m, and more preferably 8 ⁇ m to 16 ⁇ m.
- the thickness of the positive electrode material layer is 30 ⁇ m to 120 ⁇ m.
- the positive electrode active material layer may be provided on one surface (the first surface) of the positive electrode current collector in the thickness direction, or may be provided on both surfaces (the first surface and the second surface) in the thickness direction of the positive electrode current collector )superior.
- the “surface” here can be the entire area of the positive electrode current collector, or a partial area of the positive electrode current collector, which is not particularly limited in this application, as long as the purpose of the application can be achieved.
- the positive electrode sheet may further comprise a conductive layer, and the conductive layer is located 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.
- the mass percentage content of the positive electrode lithium supplement material may be 1% to 10%, preferably 3% to 10%.
- the mass percentage content of the positive electrode lithium supplement material may include: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and the like.
- the positive electrode lithium supplement material may be directly added to the slurry during the positive electrode material slurry mixing process to form a positive electrode slurry containing the positive electrode lithium supplement material of the present application, which is coated on the surface of the positive electrode current collector. It is also possible to pre-deposit a positive electrode lithium supplement material film on the surface of the positive electrode current collector. It is also possible to deposit a positive electrode lithium supplement material film on the surface of the positive electrode active material after the positive electrode active material of the positive electrode sheet is coated.
- the lithium ion secondary battery is assembled after the positive electrode lithium supplement material is added. During the first charging process, the positive electrode lithium supplement material is delithiated and the lithium supplement effect can be exerted.
- the above-mentioned "surface" may be the entire area of the positive electrode current collector/positive electrode active material, or may be a partial area of the positive electrode current collector/positive electrode active material, which is not particularly limited in this application, as long as the purpose of the application can be achieved. Can.
- the negative electrode sheet of the present application is not particularly limited, as long as the purpose of the present application can be achieved.
- a negative electrode sheet typically 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 it can achieve the purpose of the present application.
- the anode active material layer includes an anode active material, a conductive agent, and a thickener.
- the negative electrode active material of the present application may include natural graphite, artificial graphite, mesophase microcarbon beads (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, SiO x (0 ⁇ x ⁇ 2), Li-Sn At least one of alloys, Li-Sn-O alloys, Sn, SnO, SnO 2 , spinel-structured lithium titanate Li 4 Ti 5 O 12 , Li-Al alloys, metallic lithium, and the like.
- MCMB mesophase microcarbon beads
- the thickness of the negative electrode current collector and the negative electrode active material layer is not particularly limited, as long as the purpose of the present application can be achieved, for example, the thickness of the negative electrode current collector is 6 ⁇ m to 10 ⁇ m, and the thickness of the negative electrode active material layer is 30 ⁇ m to 120 ⁇ m.
- the thickness of the negative electrode sheet is not particularly limited, as long as the purpose of the present application can be achieved, for example, the thickness of the negative electrode sheet is 50 ⁇ m to 150 ⁇ m.
- the negative electrode sheet may further comprise a conductive layer, and the conductive layer is 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.
- the conductive agent may include conductive carbon black (Super P), carbon nanotubes (CNTs), carbon nanofibers, flake graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, or graphene, among others. at least one.
- the above-mentioned binder is not particularly limited, and any binder known in the art can be used as long as the purpose of the present application can be achieved.
- the binder may include polyacryl alcohol, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyimide, polyamideimide, styrene butadiene rubber (SBR), polyvinyl alcohol ( PVA), polyvinylidene fluoride, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), water-based acrylic resin, carboxymethyl cellulose (CMC) or carboxymethyl At least one of sodium cellulose (CMC-Na) and the like.
- SBR styrene butadiene rubber
- PVA polyvinyl alcohol
- PVDF polyvinylidene fluoride
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PVB polyvinyl butyral
- water-based acrylic resin carboxymethyl cellulose (CMC) or carboxymethyl At least one of sodium cellulose (CMC-Na)
- the separator in the present application is not particularly limited as long as the purpose of the present application can be achieved.
- polyethylene (PE), polypropylene (PP)-based polyolefin (PO) separators polyester films (such as polyethylene terephthalate (PET) films), cellulose films, polyimide Amine film (PI), polyamide film (PA), spandex or aramid film, woven film, non-woven film (non-woven fabric), microporous film, composite film, diaphragm paper, rolled film, spinning film, etc. at least one of.
- the release film may include a substrate layer and a surface treatment layer.
- the substrate layer can be a non-woven fabric, film or composite film with a porous structure, and the material of the substrate layer can include at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide, etc. kind.
- polypropylene porous membranes, polyethylene porous membranes, polypropylene non-woven fabrics, polyethylene non-woven fabrics, or polypropylene-polyethylene-polypropylene porous composite membranes may be used.
- at least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance.
- the inorganic layer includes inorganic particles and a binder
- the inorganic particles are not particularly limited, and can be selected from aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, ceria, nickel oxide, for example , at least one of zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate.
- the binder is not particularly limited, for example, it can be selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyethylene One or a combination of rolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
- the polymer layer contains a polymer, and the material of the polymer includes polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly( At least one of vinylidene fluoride-hexafluoropropylene) and the like.
- the lithium ion secondary battery of the present application further includes an electrolyte, and the electrolyte may be at least one of a gel electrolyte, a solid electrolyte, and an electrolytic solution, and the electrolytic solution includes a lithium salt and a non-aqueous solvent.
- the lithium salt may include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2. At least one of LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB or lithium difluoroborate.
- LiPF 6 may be chosen as the lithium salt because it gives high ionic conductivity and improves cycling characteristics.
- the non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof.
- the above-mentioned carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof.
- Examples of the above-mentioned chain carbonate compound are dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), carbonic acid Methyl ethyl ester (MEC) and combinations thereof.
- Examples of cyclic carbonate compounds are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylethylene carbonate (VEC), and combinations thereof.
- fluorocarbonate compounds are fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate Ethyl carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-dicarbonate Fluoro-1-methylethylene, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, and combinations thereof.
- FEC fluoroethylene carbonate
- 1,2-difluoroethylene carbonate 1,1-difluoroethylene carbonate
- 1,1,2-trifluoroethylene carbonate Ethyl carbonate 1,1,2,2-tetrafluoroethylene carbonate
- 1-fluoro-2-methylethylene carbonate 1-fluoro-1-methylethylene carbonate
- 1,2-dicarbonate Fluoro-1-methylethylene 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethyl
- carboxylate compounds are methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone , caprolactone, valerolactone, mevalonolactone, caprolactone, and combinations thereof.
- ether compounds examples include dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethyl ether Oxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof.
- Examples of the above-mentioned other organic solvents are dimethyl sulfoxide, 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 including the positive electrode plate provided by the present application, and the electrochemical device has good energy density.
- the electrochemical device of the present application is not particularly limited, and it may include any device in which an electrochemical reaction occurs.
- 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, or a lithium ion polymer secondary battery, and the like.
- the present application also provides an electronic device comprising the electrochemical device described in the embodiments of the present application, and the electronic device has good energy density.
- the electronic device of the present application is not particularly limited, and it may be used for any electronic device known in the prior art.
- electronic devices may include, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large-scale household storage batteries and lithium-ion capacitors, etc.
- an electrochemical device can be manufactured by the following process: overlapping the positive electrode and the negative electrode through a separator, wrapping them, folding them, etc., and putting them into the casing as needed, injecting the electrolyte into the casing and sealing it, wherein
- the separator used is the aforementioned separator provided in this application.
- an overcurrent preventing element, a guide plate, etc. may be placed in the case to prevent pressure rise and overcharge and discharge inside the electrochemical device.
- the present application provides a positive electrode lithium supplement material, a positive electrode electrode sheet comprising the material, and an electrochemical device.
- the positive electrode lithium supplement material includes: a matrix of xLi 2 O ⁇ yM, and carbon existing on the matrix; wherein, x >0, 0.4x ⁇ y ⁇ 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 slurry mixing process. Applying the positive electrode lithium supplement material in the positive electrode plate can realize the supplement of active lithium and effectively improve the energy density of the electrochemical device.
- Fig. 1 is the XRD (X-ray diffraction) pattern of the positive electrode lithium supplement material of Example 1 of the application;
- Fig. 2 is the SEM (scanning electron microscope) image of the positive electrode lithium supplement material of Example 1 of the application;
- Fig. 3 is the cobalt element EDS (X-ray energy dispersive analysis) spectrum in the positive electrode lithium supplement material of Example 1 of the application;
- Fig. 4 is the oxygen element EDS spectrum in the positive electrode lithium supplement material of Example 1 of the application;
- FIG. 5 is an EDS spectrum of carbon element in the positive electrode lithium supplement material of Example 1 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 the XRD pattern of the positive electrode lithium supplement material of Example 1 of the present application.
- (a) in FIG. 1 is the spectrum of the positive electrode lithium supplement material
- (b) in FIG. 1 is a Co standard diffraction card
- (c) in FIG. 1 is a Li 2 O standard diffraction card.
- FIG. 2 shows a SEM image of the positive electrode lithium supplement material of Example 1 of the present application. As shown in FIG. 2 , the particle size distribution of the positive electrode lithium supplement material is uniform.
- 3 shows the EDS spectrum of cobalt element in the positive electrode lithium supplement material of Example 1 of the present application, indicating that the positive electrode lithium supplement material of the present application contains cobalt element and is uniformly distributed in the positive electrode lithium supplement material.
- FIG. 4 shows the EDS spectrum of oxygen element in the positive electrode lithium supplement material of Example 1 of the present application, indicating 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.
- 5 shows the EDS spectrum of carbon element in the positive electrode lithium supplement material of Example 1 of the present application, indicating that the positive electrode lithium supplement material of the present application contains carbon element and is uniformly distributed in the positive electrode lithium supplement material.
- the positive electrode lithium supplement material to be tested, the conductive agent conductive carbon black (Super P) and the binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 80:10:10, and N-methylpyrrolidone (NMP) was added as The solvent was mixed and prepared into a slurry with a solid content of 40%, and a coating of 100 ⁇ m thickness was applied on the current collector aluminum foil with a scraper. A 1cm-diameter disk was formed, a metal lithium sheet was used as a counter electrode in a glove box, a ceglard composite membrane was selected as the separator, and an electrolyte solution was added to assemble to obtain a button battery.
- Super P conductive agent conductive carbon black
- PVDF binder polyvinylidene fluoride
- NMP N-methylpyrrolidone
- the electrolyte is ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) in a mass ratio of 30:50:20 to obtain an organic solution, and then add lithium salt lithium hexafluorophosphate to the organic solvent to dissolve and mix uniform, and an electrolyte solution with a lithium salt concentration of 1.15 mol/L was obtained.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- Wuhan Blue Electric CT2001A system is used to test the specific charging capacity.
- the button-type battery to be tested containing the positive electrode lithium supplementary material is allowed to stand for 30min in the environment of 25 ⁇ 3°C, and the rate of 0.1C (the theoretical gram of the positive electrode lithium supplementary material)
- the capacity was calculated at 600mAh/g) with constant current charging to a voltage of 4.45V, followed by constant voltage charging to a current of 0.025C, and the first charging capacity was recorded.
- the charging specific capacity of the button battery of the positive electrode lithium supplement material the first charging capacity/the quality of the positive electrode lithium supplement material.
- the lithium ion secondary battery to be tested containing the positive electrode lithium supplement material was left standing for 30min in the environment of 25 ⁇ 3°C, charged with a constant current of 600mA (rated capacity in 2000mAh) to a voltage of 4.4V, and then charged with a constant voltage to 4.4V.
- the current was 50mA, and it was allowed to stand for 5min, and the discharge capacity was recorded for the first time by constant current discharge at a current of 600mA to a termination voltage of 3.0V.
- the positive electrode active material lithium cobalt oxide (LiCoO 2 ), the positive electrode lithium supplement material prepared above, the conductive agent Super P, and the binder PVDF are mixed according to the mass ratio of 95:2:1.5:1.5, and NMP is added as a solvent.
- the slurry was uniformly coated on one surface of a positive electrode current collector aluminum foil with a thickness of 10 ⁇ m, and dried at 130° C. to obtain a positive electrode sheet with a coating thickness of 110 ⁇ m.
- the single-side coating of the positive electrode sheet is completed.
- the above steps are repeated on the other surface of the positive electrode sheet to obtain a positive electrode sheet coated with positive active material on both sides.
- the positive pole piece is cut into a size of 74mm ⁇ 867mm, and the tabs are welded for use.
- the graphite, the negative electrode active material SiO, the conductive agent nano-conductive carbon black, and the binder polyacryl alcohol (PAA) were mixed according to the mass ratio of 78:15:3:4, and deionized water was added as a solvent to prepare a solid content of 60 % slurry, and stir evenly, then add an appropriate amount of deionized water, adjust the viscosity of the slurry to 5000 Pa ⁇ s, and prepare a negative electrode slurry.
- the slurry was uniformly coated on the negative current collector copper foil with a thickness of 8 ⁇ m, dried at 110°C, and cold pressed to obtain a single-sided negative electrode sheet with an active material layer coated with an active material layer with a thickness of 100 ⁇ m.
- these steps are also completed on the back side of the negative electrode pole piece by the same method, that is, the negative pole piece with double-sided coating is obtained.
- the negative pole piece is cut into a size of 76mm ⁇ 851mm, and the tabs are welded for use.
- organic solvents EC, EMC and DEC were mixed in a mass ratio of 30:50:20 to obtain an organic solution, and then a lithium salt lithium hexafluorophosphate was added to the organic solvent to dissolve and mix evenly to obtain a lithium salt concentration of 1.15mol /L of electrolyte.
- a polypropylene (PP) film (supplied by Celgard) with a thickness of 14 ⁇ m was used.
- the positive electrode, the separator and the negative electrode prepared above are stacked in sequence, so that the separator is placed between the positive and negative electrodes to play a role of isolation, and the electrode assembly is obtained by winding.
- the electrode assembly is put into an aluminum-plastic film packaging bag, and the moisture is removed at 80°C, and the prepared electrolyte is injected.
- Example 15 ⁇ preparation of positive electrode lithium supplement material>, ⁇ preparation of positive electrode pole piece>, ⁇ preparation of negative electrode pole piece>, ⁇ preparation of electrolyte>, ⁇ preparation of separator> and The preparation steps of ⁇ Preparation of Lithium Ion Secondary Battery> are the same as those in Example 1, and the changes of relevant preparation parameters are shown in Table 1:
- the negative electrode active material graphite, nano-conductive carbon black, styrene-butadiene rubber and sodium carboxymethyl cellulose are mixed according to the mass ratio of 95:2:2:1, and deionized water is added as a solvent to prepare a slurry with a solid content of 70%. ingredients and mix well.
- the slurry was uniformly coated on the negative current collector copper foil with a thickness of 8 ⁇ m, dried at 110° C., and cold pressed to obtain a negative electrode pole piece with an active material layer of 150 ⁇ m in thickness on one side coated with an active material layer.
- these steps are also completed on the back side of the negative electrode pole piece by the same method, that is, the negative pole piece with double-sided coating is obtained.
- the negative pole piece is cut into a size of 76mm ⁇ 851mm, and the tabs are welded for use.
- Comparative Example 1 Comparative Example 2, Comparative Example 3 and Comparative Example 4, ⁇ Preparation of Positive Electrode Sheet>, ⁇ Preparation of Negative Electrode Sheet>, ⁇ Preparation of Electrolyte>, ⁇ Preparation of Separator> and ⁇ Lithium Ion Preparation of secondary battery>
- the preparation steps are the same as in Example 1.
- Comparative Example 2 Comparative Example 3 and Comparative Example 4, ⁇ Preparation of positive electrode lithium supplement material> is the same as Example 1, and the changes in relevant preparation parameters are as follows: As shown in Table 2:
- 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.
- the preparation parameters of Example 14, Example 15, Example 16, Example 17, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5 are shown in Table 3:
- Example 1 Example 6, Example 7, Example 8, Example 9, Example 10, Example 11, Example 12 and Comparative Example 1 and Comparative Example 5 that the same components and The content of the inorganic carbon source wraps the matrix with different components to form different cathode lithium supplement materials.
- the composition of the matrix is different, as long as the composition of the matrix is within the scope of the present application, the chemical stability of the positive electrode lithium supplement material can be effectively improved, and the particle agglomeration phenomenon during the slurry mixing process of the positive electrode can be effectively suppressed.
- the application of the above-mentioned positive electrode lithium supplement material in the positive electrode plate can effectively supplement the active lithium, so that the energy density of the lithium ion secondary battery can be effectively improved.
- Example 1 Example 2, Example 3 and Comparative Example 2 and Comparative Example 3 that the positive electrode lithium supplementary material with the carbon content of the present application can effectively improve the first charge specific capacity of the positive electrode lithium supplementary material, and can achieve The active lithium is effectively supplemented, so that the energy density of the lithium-ion secondary battery is effectively improved.
- the calcination temperature, calcination time and the type of inorganic carbon source of the positive electrode lithium supplement material usually also affect the first charge specific capacity of the positive electrode lithium supplement material. It can be seen from Examples 1, 4 and 5 that as long as the above preparation is used If the parameters are within the scope of the present application, the first charge specific capacity of the positive electrode lithium supplementary material and the energy density of the lithium ion secondary battery can be effectively improved.
- Example 1 Example 13, Example 14, Example 15, Example 16 and Comparative Example 4 that the content of the positive electrode lithium supplementary material is within the scope of the application, which can effectively improve the first charge of the positive electrode lithium supplementary material Specific capacity and energy density of lithium-ion secondary batteries.
- the mass percentage of the positive electrode lithium supplement material is preferably 3% to 10%, for example, Example 13, Example 14, Example 15, Example 16, can more effectively improve the energy of the lithium ion secondary battery density.
- the cathode lithium supplement material provided by the present application includes a matrix of xLi 2 O ⁇ yM and carbon existing on the matrix.
- the positive electrode lithium supplement material has strong chemical stability, and can effectively improve the particle agglomeration phenomenon in the slurry mixing process. Applying the cathode lithium supplement material to an electrochemical device can effectively supplement active lithium and effectively improve the energy density of the electrochemical device.
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Abstract
Provided are a positive electrode lithium supplementing material, and a positive electrode plate and an electrochemical device including same. The positive electrode lithium supplementing material comprises: an xLi2O·yM matrix and carbon present on the matrix, wherein x＞0, 0.4x≤y≤2x, and M comprises at least one of Mn, Fe, Co, Ni, Cu, Cr or V. The positive electrode lithium supplementing material has a high chemical stability and can effectively improve the phenomenon of particle aggregation during a paste mixing process. The positive electrode lithium supplementing material is applied to the positive electrode plate, such that active lithium can be supplemented, and the energy density of the electrochemical device can be effectively improved.
Description
本申请涉及电化学领域，具体涉及一种正极补锂材料、包含该材料的正极极片和电化学装置。The present application relates to the field of electrochemistry, and in particular, to a positive electrode lithium supplement material, a positive electrode pole piece comprising the material, and an electrochemical device.
锂离子二次电池具有储能密度大、开路电压高、自放电率低、循环寿命长、安全性好等优点，广泛应用于电能储存、移动电子设备、电动汽车和航天航空设备等各个领域。随着移动电子设备和电动汽车进入高速发展阶段，市场对锂离子二次电池的能量密度、循环性能和动力学性能等都提出了越来越高的要求。Lithium-ion secondary batteries have the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, and good safety. They are widely used in various fields such as electrical energy storage, mobile electronic equipment, electric vehicles, and aerospace equipment. With the rapid development of mobile electronic devices and electric vehicles, the market has put forward higher and higher requirements for the energy density, cycle performance and kinetic performance of lithium-ion secondary batteries.
由于锂离子二次电池在首次充放电过程中，负极表面会产生大量的固体电解质界面膜(Solid Electrolyte Interphase，SEI)，消耗锂离子二次电池中有限的锂离子和电解液，造成不可逆容量损失，降低锂离子二次电池的能量密度。在使用石墨负极的电池中，首次循环会消耗大约10％的活性锂源；当采用高比容量的负极材料，如合金类(硅、锡等)、氧化物类(氧化硅、氧化锡等)和无定形碳负极时，活性锂源的消耗将进一步加剧。因此，一种合适的补锂方法对锂离子二次电池的能量密度的提高显得尤为重要。During the first charge and discharge process of the lithium-ion secondary battery, a large amount of solid electrolyte interface film (Solid Electrolyte Interphase, SEI) will be produced on the surface of the negative electrode, which consumes the limited lithium ions and electrolyte in the lithium-ion secondary battery, resulting in irreversible capacity loss. , reducing the energy density of lithium-ion secondary batteries. In batteries using graphite anodes, about 10% of the active lithium source is consumed in the first cycle; when using anode materials with high specific capacity, such as alloys (silicon, tin, etc.), oxides (silicon oxide, tin oxide, etc.) and amorphous carbon anode, the consumption of active lithium source will be further exacerbated. Therefore, a suitable lithium replenishment method is particularly important to improve the energy density of lithium ion secondary batteries.
发明内容SUMMARY OF THE INVENTION
本申请的目的在于提供一种正极补锂材料、包含该材料的正极极片和电化学装置，以提高电化学装置的能量密度。The purpose of the present application is to provide a positive electrode lithium supplement material, a positive electrode electrode sheet and an electrochemical device comprising the material, so as to improve the energy density of the electrochemical device.
需要说明的是，本申请的内容中，以锂离子二次电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子二次电池。具体技术方案如下：It should be noted that, in the content of the present application, the present application is explained by taking a lithium ion secondary battery as an example of the electrochemical device, but the electrochemical device of the present application is not limited to the lithium ion secondary battery. The specific technical solutions are as follows:
本申请的第一方面提供了一种正极补锂材料，其包括xLi
2O·yM的基体、及存在于该基体上的碳；其中，x＞0，0.4x≤y≤2x，M包括Mn、Fe、Co、Ni、Cu、Cr或V中的至少一种。
A first aspect of the present application provides a positive electrode lithium supplement material, which includes a matrix of xLi 2 O·yM and carbon existing on the matrix; wherein x>0, 0.4x≤y≤2x, and M includes Mn , at least one of Fe, Co, Ni, Cu, Cr or V.
本申请的xLi
2O·yM的基体中：x＞0，0.4x≤y≤2x；优选3≤x≤12、0.5x≤y≤1.6x。M可以包括Mn、Fe、Co、Ni、Cu、Cr或V等中的至少一种，M优选可以包括Mn、Fe、Co或Ni等中的至少一种。其中，M的价态可以为0价。本领域技术人员可以根据实际需 要对x、y和M进行选择，得到能够实现本申请目的的xLi
2O·yM的基体，例如可以包括但不限于4Li
2O·3Co、Li
2O·Co、5Li
2O·4Co、3Li
2O·2Fe、7Li
2O·3Co·2Fe、12Li
2O·3Co·2Fe·2V、2Li
2O·Mn或Li
2O·Ni等中的任一种。通过对上述范围的限定，得到本申请的xLi
2O·yM的基体，该基体在首次充电的过程中可脱出大量的锂离子，比容量很高，可极大的提升锂离子二次电池的能量密度。
In the matrix of xLi 2 O·yM of the present application: x>0, 0.4x≤y≤2x; preferably 3≤x≤12, 0.5x≤y≤1.6x. M may include at least one of Mn, Fe, Co, Ni, Cu, Cr, V, etc., and M may preferably include at least one of Mn, Fe, Co, Ni, and the like. Among them, the valence state of M can be 0. Those skilled in the art can select x, y and M according to actual needs to obtain a matrix of xLi 2 O.yM that can achieve the purpose of the present application, such as but not limited to 4Li 2 O.3Co, Li 2 O.Co, Any of 5Li2O.4Co , 3Li2O.2Fe , 7Li2O.3Co.2Fe , 12Li2O.3Co.2Fe.2V , 2Li2O.Mn , Li2O.Ni , and the like. By limiting the above range, the xLi 2 O·yM matrix of the present application is obtained, which can release a large amount of lithium ions during the first charging process, has a high specific capacity, and can greatly improve the performance of lithium ion secondary batteries. Energy Density.
发明人意外地发现，xLi
2O·yM基体上存在碳时，不仅能够有效增强xLi
2O·yM的基体的化学稳定性，使正极浆料的稳定性得以提升，更加不易团聚，更加便于正极浆料的制备、存储及其在正极极片上的涂覆，从而改善正极浆料的加工性能，还能够提高锂离子二次电池的能量密度。这可能是由于xLi
2O·yM基体中Li
2O化学稳定性差，对空气中的水分和CO
2异常敏感，极易发生Li
2O+H
2O＝LiOH和Li
2O+CO
2＝Li
2CO
3的反应产生表面“残碱”LiOH和Li
2CO
3，而在xLi
2O·yM基体上存在碳，能够抑制LiOH和Li
2CO
3的生成，并且能够作为阻隔层隔断xLi
2O·yM的基体与正极浆料中的粘结剂的接触，提高了浆料的稳定性，并且保证了Li
2O的比容量。在本申请中，本领域技术人员应当理解，存在于xLi
2O·yM的基体上的碳，可以将基体表面全部包裹，也可以将基体表面部分包裹，本申请没有特别限制，只要能够实现本申请目的即可。
The inventor unexpectedly found that the presence of carbon on the xLi 2 O yM matrix can not only effectively enhance the chemical stability of the xLi 2 O yM matrix, but also improve the stability of the positive electrode slurry, making it more difficult to agglomerate and more convenient for the positive electrode. The preparation and storage of the slurry and its coating on the positive electrode plate can improve the processability of the positive electrode slurry, and can also improve the energy density of the lithium ion secondary battery. This may be due to the poor chemical stability of Li 2 O in the xLi 2 O·yM matrix, which is extremely sensitive to moisture and CO 2 in the air, and is prone to Li 2 O+H 2 O=LiOH and Li 2 O+CO 2 =Li The reaction of 2CO3 produces surface "residual bases" LiOH and Li2CO3, and the presence of carbon on the xLi2O · yM matrix can suppress the formation of LiOH and Li2CO3, and can act as a barrier to block xLi2O The contact between the yM matrix and the binder in the positive electrode slurry improves the stability of the slurry and ensures the specific capacity of Li 2 O. In this application, those skilled in the art should understand that the carbon existing on the substrate of xLi 2 O·yM can wrap the entire surface of the substrate or partially wrap the surface of the substrate. This application is not particularly limited, as long as the The purpose of the application is sufficient.
本申请的正极补锂材料在首次充电时发生xLi
2O+M–2xe
-＝MO
x+2xLi
+的脱锂反应，起到补锂的作用。同时，由于该正极补锂材料在正极，后续的放电过程中正极电位很难会低到可以发生MO
x+2xLi
++2xe
-＝xLi
2O+M反应的0V至2V，因此后续放电过程中不会消耗活性锂，从而对活性锂实现了净补充。
The cathode lithium-supplementing material of the present application undergoes a delithiation reaction of xLi 2 O+M-2xe − =MO x +2xLi + during the first charging, and plays the role of supplementing lithium. At the same time, since the positive electrode lithium supplement material is at the positive electrode, it is difficult for the positive electrode potential to be so low that the reaction of MO x +2xLi + +2xe - =xLi 2 O+M can occur from 0V to 2V during the subsequent discharge process. Therefore, in the subsequent discharge process No active lithium is consumed, resulting in a net replenishment of active lithium.
整体而言，本申请提供的正极补锂材料，包括xLi
2O·yM的基体、及存在于该基体上的碳。该正极补锂材料的比容量高、化学稳定性好、导电性适中、且在充电补锂过程中无气体产生，能够有效改善正极浆料调浆过程中的颗粒团聚现象，提高正极浆料的加工性能。将该正极补锂材料添加到正极极片中，能够补充因生成SEI造成的活性锂损失，从而进一步提升锂离子二次电池的能量密度。
In general, the positive electrode lithium supplement material provided by the present application includes a matrix of xLi 2 O·yM and carbon existing on the matrix. The positive electrode lithium supplement material has high specific capacity, good chemical stability, moderate conductivity, and no gas is generated during the charging lithium supplement process, which can effectively improve the particle agglomeration phenomenon in the positive electrode slurry mixing process, and improve the positive electrode slurry. Processability. Adding the positive electrode lithium supplement material to the positive electrode plate can supplement the loss of active lithium caused by the generation of SEI, thereby further improving the energy density of the lithium ion secondary battery.
在本申请的一种实施方案中，基于正极补锂材料的总质量，碳的质量百分含量为0.5％至3％。例如，碳的质量百分含量的下限值可以包括以下数值中：0.5％或1％；碳的质量百分含量的上限值可以包括以下数值中：2％、2.5％或3％。不限于任何理论，碳的质量百分含量过低(例如低于0.5％)，难以增强xLi
2O·yM的基体的化学稳定性，也难以作为阻隔层隔断xLi
2O·yM的基体与正极浆料中的粘结剂的接触；碳的质量百分含量过高(例如高 于3％)，阻抗显著增加，极化随之增长，严重影响正极补锂材料的实际比容量，进而影响对锂离子二次电池能量密度的提升效果。通过将正极补锂材料中的碳的质量百分含量控制在上述范围内，能够有效提升正极浆料的稳定性、提升锂离子二次电池的能量密度。
In an embodiment of the present application, the mass percentage content of carbon is 0.5% to 3% based on the total mass of the positive electrode lithium supplement material. For example, the lower limit of the mass percentage of carbon can be included in the following values: 0.5% or 1%; the upper limit of the carbon mass percentage can be included in the following values: 2%, 2.5% or 3%. Without being limited to any theory, if the mass percentage of carbon is too low (for example, less than 0.5%), it is difficult to enhance the chemical stability of the xLi 2 O yM matrix, and it is difficult to act as a barrier layer to separate the xLi 2 O yM matrix from the positive electrode. The contact of the binder in the slurry; the mass percentage of carbon is too high (for example, higher than 3%), the impedance increases significantly, and the polarization increases with it, which seriously affects the actual specific capacity of the positive electrode lithium supplement material, which in turn affects the The effect of improving the energy density of lithium-ion secondary batteries. By controlling the mass percentage content of carbon in the positive electrode lithium supplement material within the above 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.
在本申请的一种实施方案中，正极补锂材料的首次充电比容量≥450mAh/g。表明正极补锂材料的比容量高，在首次充电时可脱出大量的锂离子来弥补生成SEI造成的活性锂损失，首次放电时有足够的锂离子回嵌至正极活性材料中，有效提升了锂离子二次电池的放电比容量，进而提升了锂离子二次电池的能量密度。In an embodiment of the present application, the first charge specific capacity of the positive electrode lithium supplement material is ≥450 mAh/g. It shows that the specific capacity of the positive electrode lithium supplementary material is high, and a large amount of lithium ions can be released during the first charge to make up for the loss of active lithium caused by the formation of SEI, and enough lithium ions are inserted back into the positive electrode active material during the first discharge, which effectively improves the lithium ion The discharge specific capacity of the ion secondary battery improves the energy density of the lithium ion secondary battery.
本申请的第二方面提供了一种制备本申请的正极补锂材料的方法，其包括以下步骤：A second aspect of the present application provides a method for preparing the positive electrode lithium supplement material of the present application, comprising the following steps:
(1)将萘分散于溶剂中，缓慢加入锂金属碎片或粉末，均匀反应得到萘锂溶液；(1) dispersing naphthalene in a solvent, slowly adding lithium metal fragments or powder, and uniformly reacting to obtain a lithium naphthalene solution;
(2)将氧化物M
aO
b缓慢加入上述萘锂溶液中，搅拌反应均匀后过滤烘干，得到xLi
2O·yM的基体；
(2) slowly adding oxide M a O b into the above-mentioned lithium naphthalene solution, stirring and reacting evenly, filtering and drying to obtain a matrix of xLi 2 O yM;
(3)将上述基体与无机碳源进行球磨混合，分散均匀，得到混合物；(3) carrying out ball milling mixing with above-mentioned matrix and inorganic carbon source, disperse uniformly, obtain mixture;
(4)将上述混合物在惰性气氛中煅烧，即得到正极补锂材料；其中，萘与锂金属的摩尔比为1：(0.6至1)，萘与氧化物M
aO
b的摩尔比为1：(0.1至0.5)，萘的摩尔数与无机碳源的质量的比例为1：(0.05至0.3)mol/g。
(4) calcining the above 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), and the molar ratio of naphthalene to oxide M a O b is 1 : (0.1 to 0.5), and the ratio of the mole number of naphthalene to the mass of the inorganic carbon source is 1: (0.05 to 0.3) mol/g.
需要说明的是，本申请提供的上述制备方法为制备本申请的正极补锂材料的优选方法，本领域技术人员也可以根据其他方法制备得到本申请的正极补锂材料，本申请对此没有特别限制，只要能够实现本申请目的即可。It should be noted that the above-mentioned preparation method provided in this application is a preferred method for preparing the positive electrode lithium supplementary material of the present application, and those skilled in the art can also prepare the positive electrode lithium supplementary material of the present application according to other methods. There is no special method for this application. Restrictions, as long as the purpose of the application can be achieved.
本申请提供的制备正极补锂材料的方法是一种室温下的均相反应，相较于常规的固相烧结法，其安全性更高、反应更加均匀充分、制备得到的产物形貌和颗粒可控。该制备方法原理简单、操作方便、效果极佳，且与现有制备工艺间的兼容性好。The method for preparing a positive electrode lithium supplementary material provided by the present application is a homogeneous reaction at room temperature. Compared with the conventional solid-phase sintering method, the method has higher safety, more uniform and sufficient reaction, and the obtained product morphology and particles. Controllable. The preparation method is simple in principle, convenient in operation, excellent in effect, and has good compatibility with the existing preparation process.
在本申请的一种实施方案中，对溶剂的种类没有特别限制，只要能够实现本申请目的即可。例如，可以为非质子溶剂，包括四氢呋喃或乙二醇二甲醚等中的至少一种。In one embodiment of the present application, the type of solvent is not particularly limited, as long as the purpose of the present application can be achieved. For example, it may be an aprotic solvent, including at least one of tetrahydrofuran, ethylene glycol dimethyl ether, and the like.
在本申请的一种实施方案中，对氧化物M
aO
b的种类没有特别限制，只要能够实现本申请目的即可。例如，氧化物M
aO
b可以包括MnO、Mn
2O
3、MnO
2、FeO、Fe
2O
3、CoO、Co
2O
3、Co
3O
4、NiO、Ni
2O
3、Cu
2O、CuO、CrO、Cr
2O
3、CrO
3、VO、V
2O
3、VO
2或V
2O
5 等中的至少一种。
In an embodiment of the present application, the type of oxide M a O b is not particularly limited, as long as the purpose of the present application can be achieved. For example, the oxide MaOb may include MnO , Mn2O3 , MnO2 , FeO , Fe2O3 , CoO , Co2O3 , Co3O4 , NiO , Ni2O3 , Cu2O , At least one of CuO, CrO, Cr 2 O 3 , CrO 3 , VO, V 2 O 3 , VO 2 or V 2 O 5 and the like.
在本申请的一种实施方案中，对无机碳源的种类没有特别限制，只要能够实现本申请目的即可。例如，无机碳源可以包括炭黑、碳凝胶、科琴黑、乙炔黑、碳纳米管或石墨烯等中的至少一种。In an embodiment of the present application, there is no particular limitation on the type of the inorganic carbon source, as long as the purpose 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, and the like.
在本申请的一种实施方案中，对步骤(4)中煅烧的温度和时间没有特别限制，只要能够实现本申请目的即可。例如，煅烧的温度可以为600℃至700℃，煅烧的时间可以为4h至8h。In an embodiment of the present application, the temperature and time of calcination in step (4) are not particularly limited, as long as the purpose of the present application can be achieved. For example, the calcination temperature may be 600°C to 700°C, and the calcination time may be 4h to 8h.
本申请的第三方面提供了一种正极极片，包括正极补锂材料，该正极补锂材料为上述任一实施方案所述的正极补锂材料。将本申请的正极补锂材料应用于正极极片中，能够实现活性锂地有效补充，提升锂离子二次电池的能量密度。A third aspect of the present application provides a positive electrode sheet, including a positive electrode lithium supplement material, and the positive electrode lithium supplement material is the positive electrode lithium supplement material described in any one of the above embodiments. The application of the positive electrode lithium supplement material of the present application to the positive electrode plate can realize the effective supplement of active lithium and improve the energy density of the lithium ion secondary battery.
本申请中的正极极片没有特别限制，只要能够实现本申请目的即可。例如，正极极片通常包含正极集流体和正极活性材料层。其中，正极集流体没有特别限制，只要能够实现本申请目的即可，例如，可以包含铝箔、铝合金箔或复合集流体等。正极活性材料层包括正极活性材料和正极补锂材料。正极活性材料的种类没有特别限制，只要能够实现本申请目的即可，例如，可以包含镍钴锰酸锂(811、622、523、111)、镍钴铝酸锂、磷酸铁锂、富锂锰基材料、钴酸锂、锰酸锂、磷酸锰铁锂或钛酸锂中的至少一种。正极补锂材料为本申请提供的正极补锂材料中的至少一种。在本申请中，正极集流体和正极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，正极集流体的厚度为5μm至20μm，优选为6μm至18μm，更优选为8μm至16μm。正极材料层的厚度为30μm至120μm。在本申请中，正极活性材料层可以设置于正极集流体厚度方向上的一个表面(第一表面)上，也可以设置于正极集流体厚度方向上的两个表面(第一表面和第二表面)上。需要说明，这里的“表面”可以是正极集流体的全部区域，也可以是正极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。任选地，所述正极极片还可以包含导电层，所述导电层位于正极集流体和正极材料层之间。所述导电层的组成没有特别限制，可以是本领域常用的导电层。所述导电层包括导电剂和粘结剂。The positive electrode sheet in the present application is not particularly limited, as long as the purpose of the present application can be achieved. For example, a positive electrode sheet typically includes a positive electrode current collector and a positive electrode active material layer. Among them, the positive electrode current collector is not particularly limited, as long as the purpose of the present application can be achieved, for example, it may include aluminum foil, aluminum alloy foil, or composite current collector. The positive electrode active material layer includes a positive electrode active material and a positive electrode lithium supplement material. The type of positive active material is not particularly limited, as long as it can achieve the purpose of the present application, for example, it can include nickel cobalt lithium manganate (811, 622, 523, 111), nickel cobalt lithium aluminate, lithium iron phosphate, lithium rich manganese At least one of base material, lithium cobaltate, lithium manganate, lithium iron manganese phosphate or lithium titanate. The positive electrode lithium supplement material is at least one of the positive electrode lithium supplement materials provided in this 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 purpose 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 (the first surface) of the positive electrode current collector in the thickness direction, or may be provided on both surfaces (the first surface and the second surface) in the thickness direction of the positive electrode current collector )superior. It should be noted that the “surface” here can be the entire area of the positive electrode current collector, or a partial area of the positive electrode current collector, which is not particularly limited in this application, as long as the purpose of the application can be achieved. Optionally, the positive electrode sheet may further comprise a conductive layer, and the conductive layer is located 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.
在本申请的一种实施方案中，基于正极活性材料层的总质量，正极补锂材料的质量百分含量可以为1％至10％，优选为3％至10％。例如，正极补锂材料的质量百分含量可以包括：1％、2％、3％、4％、5％、6％、7％、8％、9％、10％等。通过将正极活性材料层中正 极补锂材料的含量控制在上述范围内，使正极极片具有良好的结构稳定性，可减少正极补锂材料脱锂所造成的容量损失和体积变化。将正极补锂材料的质量百分含量控制在上述优选范围内，能够使正极极片具有更好的结构稳定性，也能更大限度地提升电池的容量。In an embodiment of the present application, based on the total mass of the positive electrode active material layer, the mass percentage content of the positive electrode lithium supplement material may be 1% to 10%, preferably 3% to 10%. For example, the mass percentage content of the positive electrode lithium supplement material may include: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and the like. By controlling the content of the positive electrode lithium supplementing material in the positive electrode active material layer within the above range, the positive electrode pole piece has good structural stability, and the capacity loss and volume change caused by the delithiation of the positive electrode lithium supplementing material can be reduced. Controlling the mass percentage content of the positive electrode lithium supplement material within the above-mentioned preferred range can make the positive electrode pole piece have better structural stability, and can also maximize the capacity of the battery.
本申请对正极补锂材料的添加方式没有特别限制，本领域技术人员可以根据实际需要进行选择，只要能实现本申请目的即可。例如，可以是在正极材料调浆过程中直接向浆料中添加正极补锂材料，形成包含本申请正极补锂材料的正极浆料，涂覆于正极集流体表面。也可以是在正极集流体表面上预先沉积正极补锂材料薄膜。还可以是在正极极片的正极活性材料涂布完成后，在正极活性材料表面再沉积正极补锂材料薄膜。正极补锂材料添加之后组装锂离子二次电池，在首次充电过程中，正极补锂材料脱锂即可发挥补锂效果。需要说明的是，上述的“表面”可以是正极集流体/正极活性材料的全部区域，也可以是正极集流体/正极活性材料的部分区域，本申请没有特别限制，只要能实现本申请目的即可。There is no particular limitation on the method of adding the positive electrode lithium supplement material in the present application, and those skilled in the art can select according to actual needs, as long as the purpose of the present application can be achieved. For example, the positive electrode lithium supplement material may be directly added to the slurry during the positive electrode material slurry mixing process to form a positive electrode slurry containing the positive electrode lithium supplement material of the present application, which is coated on the surface of the positive electrode current collector. It is also possible to pre-deposit a positive electrode lithium supplement material film on the surface of the positive electrode current collector. It is also possible to deposit a positive electrode lithium supplement material film on the surface of the positive electrode active material after the positive electrode active material of the positive electrode sheet is coated. The lithium ion secondary battery is assembled after the positive electrode lithium supplement material is added. During the first charging process, the positive electrode lithium supplement material is delithiated and the lithium supplement effect can be exerted. It should be noted that the above-mentioned "surface" may be the entire area of the positive electrode current collector/positive electrode active material, or may be a partial area of the positive electrode current collector/positive electrode active material, which is not particularly limited in this application, as long as the purpose of the application can be achieved. Can.
本申请的负极极片没有特别限制，只要能够实现本申请目的即可。例如，负极极片通常包含负极集流体和负极活性材料层。其中，负极集流体没有特别限制，只要能够实现本申请目的即可，例如，可以包含铜箔、铜合金箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜或复合集流体等。负极活性材料层包括负极活性材料、导电剂和增稠剂。本申请的负极活性材料可以包括天然石墨、人造石墨、中间相微碳球(MCMB)、硬碳、软碳、硅、硅-碳复合物、SiO
x(0<x<2)、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO
2、尖晶石结构的钛酸锂Li
4Ti
5O
12、Li-Al合金及金属锂等中的至少一种。在本申请中，对负极集流体和负极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可，例如，负极集流体的厚度为6μm至10μm，负极活性材料层的厚度为30μm至120μm。本申请中，负极极片的厚度没有特别限制，只要能够实现本申请目的即可，例如，负极极片的厚度为50μm至150μm。任选地，所述负极极片还可以包含导电层，所述导电层位于负极集流体和负极材料层之间。所述导电层的组成没有特别限制，可以是本领域常用的导电层。所述导电层包括导电剂和粘结剂。
The negative electrode sheet of the present application is not particularly limited, as long as the purpose of the present application can be achieved. For example, a negative electrode sheet typically 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 it can achieve the purpose of the present application. The anode active material layer includes an anode active material, a conductive agent, and a thickener. The negative electrode active material of the present application may include natural graphite, artificial graphite, mesophase microcarbon beads (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, SiO x (0<x<2), Li-Sn At least one of alloys, Li-Sn-O alloys, Sn, SnO, SnO 2 , spinel-structured lithium titanate Li 4 Ti 5 O 12 , Li-Al alloys, metallic lithium, and the like. 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 purpose of the present application can be achieved, 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 120μm. In the present application, the thickness of the negative electrode sheet is not particularly limited, as long as the purpose of the present application can be achieved, for example, the thickness of the negative electrode sheet is 50 μm to 150 μm. Optionally, the negative electrode sheet may further comprise a conductive layer, and the conductive layer is 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.
上述导电剂没有特别限制，只要能够实现本申请目的即可。例如，导电剂可以包括导电炭黑(Super P)、碳纳米管(CNTs)、碳纳米纤维、鳞片石墨、乙炔黑、炭黑、科琴黑、碳点、碳纳米管或石墨烯等中的至少一种。上述所述粘结剂没有特别限制，可以使用本领域公知的任何粘结剂，只要能够实现本申请目的即可。例如，粘结剂可以包括聚丙烯醇、聚丙烯酸钠、聚丙烯酸钾、聚丙烯酸锂、聚酰亚胺、聚酰亚胺、聚酰胺酰亚胺、丁苯橡胶 (SBR)、聚乙烯醇(PVA)、聚偏氟乙烯、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚乙烯醇缩丁醛(PVB)、水性丙烯酸树脂、羧甲基纤维素(CMC)或羧甲基纤维素钠(CMC-Na)等中的至少一种。The above-mentioned 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 conductive carbon black (Super P), carbon nanotubes (CNTs), carbon nanofibers, flake graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, or graphene, among others. at least one. The above-mentioned binder is not particularly limited, and any binder known in the art can be used as long as the purpose of the present application can be achieved. For example, the binder may include polyacryl alcohol, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyimide, polyamideimide, styrene butadiene rubber (SBR), polyvinyl alcohol ( PVA), polyvinylidene fluoride, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), water-based acrylic resin, carboxymethyl cellulose (CMC) or carboxymethyl At least one of sodium cellulose (CMC-Na) and the like.
本申请中的隔离膜没有特别限制，只要能够实现本申请目的即可。例如，聚乙烯(PE)、聚丙烯(PP)为主的聚烯烃(PO)类隔膜，聚酯膜(例如聚对苯二甲酸二乙酯(PET)膜)、纤维素膜、聚酰亚胺膜(PI)、聚酰胺膜(PA)，氨纶或芳纶膜、织造膜、非织造膜(无纺布)、微孔膜、复合膜、隔膜纸、碾压膜、纺丝膜等中的至少一种。例如，隔离膜可以包括基材层和表面处理层。基材层可以为具有多孔结构的无纺布、膜或复合膜，基材层的材料可以包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯和聚酰亚胺等中的至少一种。任选地，可以使用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。任选地，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。例如，无机物层包括无机颗粒和粘结剂，所述无机颗粒没有特别限制，例如可以选自氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙和硫酸钡等中的至少一种。所述粘结剂没有特别限制，例如可以选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯和聚六氟丙烯中的一种或几种的组合。聚合物层中包含聚合物，聚合物的材料包括聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)等中的至少一种。The separator in the present application is not particularly limited as long as the purpose of the present application can be achieved. For example, polyethylene (PE), polypropylene (PP)-based polyolefin (PO) separators, polyester films (such as polyethylene terephthalate (PET) films), cellulose films, polyimide Amine film (PI), polyamide film (PA), spandex or aramid film, woven film, non-woven film (non-woven fabric), microporous film, composite film, diaphragm paper, rolled film, spinning film, etc. at least one of. For example, the release film may include a substrate layer and a surface treatment layer. The substrate layer can be a non-woven fabric, film or composite film with a porous structure, and the material of the substrate layer can include at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide, etc. kind. Optionally, polypropylene porous membranes, polyethylene porous membranes, polypropylene non-woven fabrics, polyethylene non-woven fabrics, or polypropylene-polyethylene-polypropylene porous composite membranes may be used. Optionally, at least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can 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, the inorganic particles are not particularly limited, and can be selected from aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, ceria, nickel oxide, for example , at least one of zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate. The binder is not particularly limited, for example, it can be selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyethylene One or a combination of rolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene. The polymer layer contains a polymer, and the material of the polymer includes polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly( At least one of vinylidene fluoride-hexafluoropropylene) and the like.
本申请的锂离子二次电池还包括电解质，电解质可以是凝胶电解质、固态电解质和电解液中的至少一种，电解液包括锂盐和非水溶剂。在本申请一些实施方案中，锂盐可以包括LiPF
6、LiBF
4、LiAsF
6、LiClO
4、LiB(C
6H
5)
4、LiCH
3SO
3、LiCF
3SO
3、LiN(SO
2CF
3)
2、LiC(SO
2CF
3)
3、LiSiF
6、LiBOB或二氟硼酸锂中的至少一种。举例来说，锂盐可以选用LiPF
6，因为它可以给出高的离子导电率并改善循环特性。非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。上述碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。上述链状碳酸酯化合物的实例为碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。环状碳酸酯化合物的实例为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)及其组合。氟代碳酸 酯化合物的实例为碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯及其组合。上述羧酸酯化合物的实例为甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯及其组合。上述醚化合物的实例为二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃及其组合。上述其它有机溶剂的实例为二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯和磷酸酯及其组合。
The lithium ion secondary battery of the present application further includes an electrolyte, and the electrolyte may be at least one of a gel electrolyte, a solid electrolyte, and an electrolytic solution, and the electrolytic solution includes a lithium salt and a non-aqueous solvent. In some embodiments of the present application, the lithium salt may include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2. At least one of LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB or lithium difluoroborate. For example, LiPF 6 may be chosen as the lithium salt because it gives high ionic conductivity and improves cycling characteristics. The non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof. The above-mentioned carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof. Examples of the above-mentioned chain carbonate compound are dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), carbonic acid Methyl ethyl ester (MEC) and combinations thereof. Examples of cyclic carbonate compounds are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylethylene carbonate (VEC), and combinations thereof. Examples of fluorocarbonate compounds are fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate Ethyl carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-dicarbonate Fluoro-1-methylethylene, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, and combinations thereof. Examples of the above-mentioned carboxylate compounds are methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ-butyrolactone , caprolactone, valerolactone, mevalonolactone, caprolactone, and combinations thereof. Examples of the above ether compounds are dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethyl ether Oxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof. Examples of the above-mentioned other organic solvents are dimethyl sulfoxide, 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.
本申请的第四方面提供了一种电化学装置，包括本申请提供的正极极片，该电化学装置具有良好的能量密度。本申请的电化学装置没有特别限制，其可以包括发生电化学反应的任何装置。在一些实施例中，电化学装置可以包括但不限于：锂金属二次电池、锂离子二次电池(锂离子电池)、锂聚合物二次电池或锂离子聚合物二次电池等。A fourth aspect of the present application provides an electrochemical device including the positive electrode plate provided by the present application, and the electrochemical device has good energy density. The electrochemical device of the present application is not particularly limited, and it may include any device in which an electrochemical reaction occurs. 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, or a lithium ion polymer secondary battery, and the like.
本申请还提供了一种电子装置，包含本申请实施方案中所述的电化学装置，该电子装置具有良好的能量密度。本申请的电子装置没有特别限制，其可以是用于现有技术中已知的任何电子装置。在一些实施例中，电子装置可以包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。The present application also provides an electronic device comprising the electrochemical device described in the embodiments of the present application, and the electronic device has good energy density. The electronic device of the present application is not particularly limited, and it may be used for any electronic device known in the prior art. In some embodiments, electronic devices may include, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large-scale household storage batteries and lithium-ion capacitors, etc.
电化学装置的制备过程为本领域技术人员所熟知的，本申请没有特别的限制。例如电化学装置可以通过以下过程制造：将正极极片和负极极片经由隔离膜重叠，并根据需要将其卷绕、折叠等操作后放入壳体内，将电解液注入壳体并封口，其中所用的隔离膜为本申请提供的上述隔离膜。此外，也可以根据需要将防过电流元件、导板等置于壳体中，从而防止电化学装置内部的压力上升、过充放电。The preparation process of the electrochemical device is well known to those skilled in the art, and the present application is not particularly limited. For example, an electrochemical device can be manufactured by the following process: overlapping the positive electrode and the negative electrode through a separator, wrapping them, folding them, etc., and putting them into the casing as needed, injecting the electrolyte into the casing and sealing it, wherein The separator used is the aforementioned separator provided in this application. In addition, if necessary, an overcurrent preventing element, a guide plate, etc. may be placed in the case to prevent pressure rise and overcharge and discharge inside the electrochemical device.
本申请提供了一种正极补锂材料、包含该材料的正极极片和电化学装置，该正极补锂材料包括：xLi
2O·yM的基体、及存在于该基体上的碳；其中，x＞0，0.4x≤y≤2x，M包 括Mn、Fe、Co、Ni、Cu、Cr或V中的至少一种。该正极补锂材料化学稳定性强，能够有效改善调浆过程中的颗粒团聚现象。将该正极补锂材料应用在正极极片中，能够实现活性锂地补充，有效提升电化学装置的能量密度。
The present application provides a positive electrode lithium supplement material, a positive electrode electrode sheet comprising the material, and an electrochemical device. The positive electrode lithium supplement material includes: a matrix of xLi 2 O·yM, and carbon existing on the matrix; wherein, x >0, 0.4x≤y≤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 slurry mixing process. Applying the positive electrode lithium supplement material in the positive electrode plate can realize the supplement of active lithium and effectively improve the energy density of the electrochemical device.
为了更清楚地说明本申请和现有技术的技术方案，下面对实施例和现有技术中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例。In order to illustrate the technical solutions of the present application and the prior art more clearly, the following briefly introduces the drawings required in the embodiments and the prior art. Obviously, the drawings in the following description are only for the present application. some examples.
图1为本申请的实施例1的正极补锂材料的XRD(X射线衍射)图谱；Fig. 1 is the XRD (X-ray diffraction) pattern of the positive electrode lithium supplement material of Example 1 of the application;
图2为本申请的实施例1的正极补锂材料的SEM(扫描电子显微镜)图；Fig. 2 is the SEM (scanning electron microscope) image of the positive electrode lithium supplement material of Example 1 of the application;
图3为本申请的实施例1的正极补锂材料中的钴元素EDS(X射线能谱分析)图谱；Fig. 3 is the cobalt element EDS (X-ray energy dispersive analysis) spectrum in the positive electrode lithium supplement material of Example 1 of the application;
图4为本申请的实施例1的正极补锂材料中的氧元素EDS图谱；Fig. 4 is the oxygen element EDS spectrum in the positive electrode lithium supplement material of Example 1 of the application;
图5为本申请的实施例1的正极补锂材料中的碳元素EDS图谱。FIG. 5 is an EDS spectrum of carbon element in the positive electrode lithium supplement material of Example 1 of the present application.
为使本申请的目的、技术方案、及优点更加清楚明白，以下参照附图和实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员所获得的所有其他技术方案，都属于本申请保护的范围。In order to make the objectives, technical solutions, and advantages of the present application more clear, the present application will be further described in detail below with reference to the accompanying drawings and embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all of the embodiments. All other technical solutions obtained by those of ordinary skill in the art based on the embodiments in this application fall within the protection scope of this application.
需要说明的是，本申请的具体实施方式中，以锂离子二次电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子二次电池。It should be noted that, in the specific embodiment 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.
图1示出了本申请的实施例1的正极补锂材料的XRD图谱。其中，图1中的(a)为正极补锂材料的图谱，图1中的(b)为Co标准衍射卡片，图1中的(c)为Li
2O标准衍射卡片。如图1所示，(a)图谱中可以看到：出现了2θ为44.2°和51.5°的衍射峰，对应Co的衍射峰；出现了2θ为33.1°、38.4°、55.4°、66.0°和69.4°的衍射峰，对应Li
2O的衍射峰，表明本申请实施例1的正极补锂材料中存在Co和Li
2O。
FIG. 1 shows the XRD pattern of the positive electrode lithium supplement material of Example 1 of the present application. Wherein, (a) in FIG. 1 is the spectrum of the positive electrode lithium supplement material, (b) in FIG. 1 is a Co standard diffraction card, and (c) in FIG. 1 is a Li 2 O standard diffraction card. As shown in Figure 1, it can be seen in the spectrum (a) that there are diffraction peaks with 2θ of 44.2° and 51.5°, corresponding to the diffraction peaks of Co; 2θ of 33.1°, 38.4°, 55.4°, 66.0° and The diffraction peak at 69.4° corresponds to the diffraction peak of Li 2 O, indicating that Co and Li 2 O exist in the positive electrode lithium supplement material of Example 1 of the present application.
图2示出了本申请的实施例1的正极补锂材料的SEM图，如图2所示，正极补锂材料的颗粒度分布均匀。图3示出了本申请的实施例1的正极补锂材料中的钴元素EDS图谱， 表明本申请的正极补锂材料中含有钴元素，且均匀分布于正极补锂材料中。图4示出了本申请的实施例1的正极补锂材料中的氧元素EDS图谱，表明本申请的正极补锂材料中含有氧元素，且均匀分布于正极补锂材料中。图5示出了本申请的实施例1的正极补锂材料中的碳元素EDS图谱，表明本申请的正极补锂材料中含有碳元素，且均匀分布于正极补锂材料中。FIG. 2 shows a SEM image of the positive electrode lithium supplement material of Example 1 of the present application. As shown in FIG. 2 , the particle size distribution of the positive electrode lithium supplement material is uniform. 3 shows the EDS spectrum of cobalt element in the positive electrode lithium supplement material of Example 1 of the present application, indicating that the positive electrode lithium supplement material of the present application contains cobalt element and is uniformly distributed in the positive electrode lithium supplement material. FIG. 4 shows the EDS spectrum of oxygen element in the positive electrode lithium supplement material of Example 1 of the present application, indicating 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. 5 shows the EDS spectrum of carbon element in the positive electrode lithium supplement material of Example 1 of the present application, indicating that the positive electrode lithium supplement material of the present application contains carbon element and is uniformly distributed in the positive electrode lithium supplement material.
实施例Example
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。另外，只要无特别说明，“份”、“％”为质量基准。Hereinafter, the embodiment of the present application will be described more specifically with reference to Examples and Comparative Examples. Various tests and evaluations were performed according to the following methods. In addition, unless otherwise specified, "parts" and "%" are based on mass.
测试方法和设备：Test methods and equipment:
首次充电比容量测试：First charge specific capacity test:
<扣式电池的制备><Preparation of button battery>
将待测试正极补锂材料、导电剂导电炭黑(Super P)和粘结剂聚偏二氟乙烯(PVDF)按照质量比80:10:10进行混合，加入N-甲基吡咯烷酮(NMP)作为溶剂，经过搅拌调配成为固含量为40％的浆料，利用刮刀在集流体铝箔上涂覆100μm厚度的涂层，130℃下经过12h真空干燥箱烘干后，利用冲压机在干燥环境中切成直径为1cm的圆片，在手套箱中以金属锂片作为对电极，隔离膜选择ceglard复合膜，加入电解液组装得到扣式电池。电解液为碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)以质量比30:50:20混合得到有机溶液，然后向有机溶剂中加入锂盐六氟磷酸锂溶解并混合均匀，得到锂盐的浓度为1.15mol/L的电解液。The positive electrode lithium supplement material to be tested, the conductive agent conductive carbon black (Super P) and the binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 80:10:10, and N-methylpyrrolidone (NMP) was added as The solvent was mixed and prepared into a slurry with a solid content of 40%, and a coating of 100 μm thickness was applied on the current collector aluminum foil with a scraper. A 1cm-diameter disk was formed, a metal lithium sheet was used as a counter electrode in a glove box, a ceglard composite membrane was selected as the separator, and an electrolyte solution was added to assemble to obtain a button battery. The electrolyte is ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) in a mass ratio of 30:50:20 to obtain an organic solution, and then add lithium salt lithium hexafluorophosphate to the organic solvent to dissolve and mix uniform, and an electrolyte solution with a lithium salt concentration of 1.15 mol/L was obtained.
<首次充电比容量的测试><Test of specific capacity for first charge>
本申请采用武汉蓝电CT2001A***进行充电比容量测试，将含有正极补锂材料的待测扣式电池在25±3℃环境中静置30min，以0.1C的倍率(正极补锂材料的理论克容量以600mAh/g计)恒流充电至电压为4.45V，随后恒压充电至电流为0.025C，记录首次充电容量。In this application, Wuhan Blue Electric CT2001A system is used to test the specific charging capacity. The button-type battery to be tested containing the positive electrode lithium supplementary material is allowed to stand for 30min in the environment of 25±3℃, and the rate of 0.1C (the theoretical gram of the positive electrode lithium supplementary material) The capacity was calculated at 600mAh/g) with constant current charging to a voltage of 4.45V, followed by constant voltage charging to a current of 0.025C, and the first charging capacity was recorded.
正极补锂材料的扣式电池充电比容量＝首次充电容量/正极补锂材料的质量。The charging specific capacity of the button battery of the positive electrode lithium supplement material = the first charging capacity/the quality of the positive electrode lithium supplement material.
首次放电容量测试：First discharge capacity test:
将含有正极补锂材料的待测锂离子二次电池在25±3℃环境中静置30min，以600mA(额定容量以2000mAh计)的电流恒流充电至电压为4.4V，随后恒压充电至电流为50mA，静置5min，以600mA的电流恒流放电至终止电压3.0V，记录首次放电容量。The lithium ion secondary battery to be tested containing the positive electrode lithium supplement material was left standing for 30min in the environment of 25±3℃, charged with a constant current of 600mA (rated capacity in 2000mAh) to a voltage of 4.4V, and then charged with a constant voltage to 4.4V. The current was 50mA, and it was allowed to stand for 5min, and the discharge capacity was recorded for the first time by constant current discharge at a current of 600mA to a termination voltage of 3.0V.
实施例1Example 1
<正极补锂材料的制备><Preparation of positive electrode lithium supplement material>
将128.17g萘分散于1L四氢呋喃溶剂中，缓慢加入5.55g锂金属碎片，均匀反应得到萘锂溶液；称取24.08g的氧化物Co
3O
4，缓慢加入上述萘锂溶液中，搅拌反应均匀后过滤烘干，得到4Li
2O·3Co的基体；将10g上述4Li
2O·3Co的基体与0.05g无机碳源炭黑进行球磨混合，分散均匀，得到混合物；将上述混合物在惰性气氛中，于600℃煅烧8h，得到4Li
2O·3Co的基体上存在碳的正极补锂材料。基于正极补锂材料的总质量，碳的质量百分含量为0.5％。
Disperse 128.17g of naphthalene in 1L of tetrahydrofuran solvent, slowly add 5.55g of lithium metal fragments, and uniformly react to obtain a lithium naphthalene solution; weigh 24.08g of oxide Co 3 O 4 , slowly add it to the above-mentioned lithium naphthalene solution, and stir to react evenly. Filter and dry to obtain a 4Li 2 O 3Co matrix; 10 g of the above 4Li 2 O 3Co matrix and 0.05 g of inorganic carbon source carbon black are ball-milled and mixed, and the mixture is uniformly dispersed to obtain a mixture; the above mixture is placed in an inert atmosphere in After calcining at 600°C for 8h, a positive electrode lithium supplement material with carbon on the matrix of 4Li 2 O·3Co was obtained. Based on the total mass of the positive electrode lithium supplement material, the mass percentage of carbon is 0.5%.
<正极极片的制备><Preparation of positive electrode sheet>
将正极活性材料钴酸锂(LiCoO
2)、上述制备得到的正极补锂材料、导电剂Super P、粘结剂PVDF按照质量比95:2:1.5:1.5进行混合，加入NMP作为溶剂，调配成为固含量为75％的浆料，并搅拌均匀。将浆料均匀涂覆在厚度为10μm的正极集流体铝箔的一个表面上，130℃条件下烘干，得到涂层厚度为110μm的正极极片。以上步骤完成后，即完成正极极片的单面涂布。之后，在该正极极片的另一个表面上重复以上步骤，即得到双面涂布正极活性材料的正极极片。涂布完成后，将正极极片裁切成74mm×867mm的规格并焊接极耳待用。
The positive electrode active material lithium cobalt oxide (LiCoO 2 ), the positive electrode lithium supplement material prepared above, the conductive agent Super P, and the binder PVDF are mixed according to the mass ratio of 95:2:1.5:1.5, and NMP is added as a solvent. A slurry with a solid content of 75%, and stir well. The slurry was uniformly coated on one surface of a positive electrode current collector aluminum foil with a thickness of 10 μm, and dried at 130° C. to obtain a positive electrode sheet with a coating thickness of 110 μm. After the above steps are completed, the single-side coating of the positive electrode sheet is completed. After that, the above steps are repeated on the other surface of the positive electrode sheet to obtain a positive electrode sheet coated with positive active material on both sides. After the coating is completed, the positive pole piece is cut into a size of 74mm×867mm, and the tabs are welded for use.
<负极极片的制备><Preparation of negative pole piece>
将石墨、负极活性材料SiO、导电剂纳米导电炭黑、粘结剂聚丙烯醇(PAA)按照质量比78:15:3:4进行混合，加入去离子水作为溶剂，调配成为固含量为60％的浆料，并搅拌均匀，再加入适量的去离子水，调节浆料的粘度为5000Pa·s，制成负极浆料。将浆料均匀涂覆在在厚度为8μm的负极集流体铜箔上，110℃条件下烘干，冷压后得到活性材料层厚度为100μm的单面涂覆活性材料层的负极极片。以上步骤完成后，采用同样的方法在该负极极片背面也完成这些步骤，即得到双面涂布完成的负极极片。涂布完成后，将负极极片裁切成规格为76mm×851mm的规格并焊接极耳待用。The graphite, the negative electrode active material SiO, the conductive agent nano-conductive carbon black, and the binder polyacryl alcohol (PAA) were mixed according to the mass ratio of 78:15:3:4, and deionized water was added as a solvent to prepare a solid content of 60 % slurry, and stir evenly, then add an appropriate amount of deionized water, adjust the viscosity of the slurry to 5000 Pa·s, and prepare a negative electrode slurry. The slurry was uniformly coated on the negative current collector copper foil with a thickness of 8 μm, dried at 110°C, and cold pressed to obtain a single-sided negative electrode sheet with an active material layer coated with an active material layer with a thickness of 100 μm. After the above steps are completed, these steps are also completed on the back side of the negative electrode pole piece by the same method, that is, the negative pole piece with double-sided coating is obtained. After the coating is completed, the negative pole piece is cut into a size of 76mm×851mm, and the tabs are welded for use.
<电解液的制备><Preparation of Electrolyte>
在干燥氩气气氛中，将有机溶剂EC、EMC和DEC以质量比30:50:20混合得到有机溶液，然后向有机溶剂中加入锂盐六氟磷酸锂溶解并混合均匀，得到锂盐的浓度为1.15mol/L的电解液。In a dry argon atmosphere, organic solvents EC, EMC and DEC were mixed in a mass ratio of 30:50:20 to obtain an organic solution, and then a lithium salt lithium hexafluorophosphate was added to the organic solvent to dissolve and mix evenly to obtain a lithium salt concentration of 1.15mol /L of electrolyte.
<隔离膜的制备><Preparation of separator>
采用厚度为14μm的聚丙烯(PP)薄膜(Celgard公司提供)。A polypropylene (PP) film (supplied by Celgard) with a thickness of 14 μm was used.
<锂离子二次电池的制备><Preparation of lithium ion secondary battery>
将上述制备的正极、隔离膜、负极按顺序叠好，使隔离膜处于正负极中间起到隔离的作用，并卷绕得到电极组件。将电极组件装入铝塑膜包装袋中，并在80℃下脱去水分，注入配好的电解液，经过真空封装、静置、化成、整形等工序得到锂离子二次电池。The positive electrode, the separator and the negative electrode prepared above are stacked in sequence, so that the separator is placed between the positive and negative electrodes to play a role of isolation, and the electrode assembly is obtained by winding. The electrode assembly is put into an aluminum-plastic film packaging bag, and the moisture is removed at 80°C, and the prepared electrolyte is injected.
实施例2、实施例3、实施例4、实施例5、实施例6、实施例7、实施例8、实施例9、实施例10、实施例11、实施例12、实施例13、实施例14、实施例15和实施例16中，<正极补锂材料的制备>、<正极极片的制备>、<负极极片的制备>、<电解液的制备>、<隔离膜的制备>及<锂离子二次电池的制备>的制备步骤均与实施例1相同，相关制备参数的变化如表1中所示：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. In Example 15 and Example 16, <preparation of positive electrode lithium supplement material>, <preparation of positive electrode pole piece>, <preparation of negative electrode pole piece>, <preparation of electrolyte>, <preparation of separator> and The preparation steps of <Preparation of Lithium Ion Secondary Battery> are the same as those in Example 1, and the changes of relevant preparation parameters are shown in Table 1:
表1Table 1
实施例17Example 17
<负极极片的制备><Preparation of negative pole piece>
将负极活性材料石墨、纳米导电炭黑、丁苯橡胶和羧甲基纤维素钠按照质量比95:2:2:1进行混合，加入去离子水作为溶剂，调配成为固含量为70％的浆料，并搅拌均匀。将浆料均匀涂覆在厚度为8μm的负极集流体铜箔上，110℃条件下烘干，冷压后得到活性材料层厚度为150μm的单面涂覆活性材料层的负极极片。以上步骤完成后，采用同样的方法在该负极极片背面也完成这些步骤，即得到双面涂布完成的负极极片。涂布完成后，将负极极片裁切成规格为76mm×851mm的规格并焊接极耳待用。The negative electrode active material graphite, nano-conductive carbon black, styrene-butadiene rubber and sodium carboxymethyl cellulose are mixed according to the mass ratio of 95:2:2:1, and deionized water is added as a solvent to prepare a slurry with a solid content of 70%. ingredients and mix well. The slurry was uniformly coated on the negative current collector copper foil with a thickness of 8 μm, dried at 110° C., and cold pressed to obtain a negative electrode pole piece with an active material layer of 150 μm in thickness on one side coated with an active material layer. After the above steps are completed, these steps are also completed on the back side of the negative electrode pole piece by the same method, that is, the negative pole piece with double-sided coating is obtained. After the coating is completed, the negative pole piece is cut into a size of 76mm×851mm, and the tabs are welded for use.
<正极补锂材料的制备>、<正极极片的制备>、<电解液的制备>、<隔离膜的制备>及<锂离子二次电池的制备>与实施例1相同。<Preparation of Lithium Supplement Material for Positive Electrode>, <Preparation of Positive Electrode Sheet>, <Preparation of Electrolyte Solution>, <Preparation of Separator Film>, and <Preparation of Lithium Ion Secondary Battery> are the same as in Example 1.
对比例1、对比例2、对比例3和对比例4中，<正极极片的制备>、<负极极片的制备>、<电解液的制备>、<隔离膜的制备>及<锂离子二次电池的制备>的制备步骤均与实施例1相同，在对比例2、对比例3和对比例4中，<正极补锂材料的制备>与实施例1相同，相关制备参数的变化如表2中所示：In Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4, <Preparation of Positive Electrode Sheet>, <Preparation of Negative Electrode Sheet>, <Preparation of Electrolyte>, <Preparation of Separator> and <Lithium Ion Preparation of secondary battery> The preparation steps are the same as in Example 1. In Comparative Example 2, Comparative Example 3 and Comparative Example 4, <Preparation of positive electrode lithium supplement material> is the same as Example 1, and the changes in relevant preparation parameters are as follows: As shown in Table 2:
表2Table 2
注：表2中的“/”表示不存在该对应制备参数。Note: "/" in Table 2 indicates that the corresponding preparation parameter does not exist.
对比例5Comparative Example 5
<正极补锂材料的制备><Preparation of positive electrode lithium supplement material>
将金属锂碎片和氧化物Co
3O
4按照摩尔比8:1混合，得到第一混合物；在氩气保护气氛状态下将第一混合物在180℃下烧结4h，得到第二混合物；将第二混合物与Ar、O
2和HF体积比＝3:0.05:96.95的混合气体进行混合并反应，得到正极补锂材料2.1Li
2O·Co·0.5CoO
0.05F
0.1。
The metal lithium fragments and the oxide Co 3 O 4 are mixed according to a molar ratio of 8:1 to obtain a first mixture; the first mixture is sintered at 180° C. for 4 h under an argon protective atmosphere to obtain a second mixture; the second mixture is obtained The mixture is mixed and reacted with a mixed gas with a volume ratio of Ar, O 2 and HF=3:0.05:96.95 to obtain a positive electrode lithium supplement material 2.1Li 2 O·Co·0.5CoO 0.05 F 0.1 .
<正极极片的制备>、<负极极片的制备>、<电解液的制备>、<隔离膜的制备>及<锂离子二次电池的制备>，与实施例1相同。<Preparation of Positive Electrode Sheet>, <Preparation of Negative Electrode Sheet>, <Preparation of Electrolyte Solution>, <Preparation of Separator Film>, and <Preparation of Lithium Ion Secondary Battery> are the same as in Example 1.
实施例1、实施例2、实施例3、实施例4、实施例5、实施例6、实施例7、实施例8、实施例9、实施例10、实施例11、实施例12、实施例13、实施例14、实施例15、实施例16、实施例17、对比例1、对比例2、对比例3、对比例4、对比例5的制备参数如表3所示：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. The preparation parameters of Example 14, Example 15, Example 16, Example 17, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 5 are shown in Table 3:
表3table 3
注：表3中的“/”表示不存在该对应制备参数。Note: "/" in Table 3 indicates that the corresponding preparation parameter does not exist.
从实施例1、实施例6、实施例7、实施例8、实施例9、实施例10、实施例11、实施例12和对比例1、对比例5可以看出，本申请采用相同成分和含量的无机碳源对不同成分的基体进行包裹，形成不同的正极补锂材料。虽然基体成分不同，但是只要基体的成分在本申请范围内，均能有效改善正极补锂材料的化学稳定性，使正极浆料调浆过程中的颗粒团聚现象得到有效抑制。而且，将上述正极补锂材料应用在正极极片中，均能够实现活性锂地有效补充，使锂离子二次电池的能量密度得到有效提升。It can be seen from Example 1, Example 6, Example 7, Example 8, Example 9, Example 10, Example 11, Example 12 and Comparative Example 1 and Comparative Example 5 that the same components and The content of the inorganic carbon source wraps the matrix with different components to form different cathode lithium supplement materials. Although the composition of the matrix is different, as long as the composition of the matrix is within the scope of the present application, the chemical stability of the positive electrode lithium supplement material can be effectively improved, and the particle agglomeration phenomenon during the slurry mixing process of the positive electrode can be effectively suppressed. In addition, the application of the above-mentioned positive electrode lithium supplement material in the positive electrode plate can effectively supplement the active lithium, so that the energy density of the lithium ion secondary battery can be effectively improved.
从实施例1、实施例2、实施例3和对比例2、对比例3可以看出，具有本申请碳含量的正极补锂材料，能有效提升正极补锂材料的首次充电比容量，能够实现活性锂地有效补充，使锂离子二次电池的能量密度得到有效提升。It can be seen from Example 1, Example 2, Example 3 and Comparative Example 2 and Comparative Example 3 that the positive electrode lithium supplementary material with the carbon content of the present application can effectively improve the first charge specific capacity of the positive electrode lithium supplementary material, and can achieve The active lithium is effectively supplemented, so that the energy density of the lithium-ion secondary battery is effectively improved.
正极补锂材料的煅烧温度、煅烧时间以及无机碳源的种类通常也会影响正极补锂材料的首次充电比容量，从实施例1、实施例4、实施例5可以看出，只要使上述制备参数在本申请范围内，就能够有效提升正极补锂材料的首次充电比容量以及锂离子二次电池的能量密度。The calcination temperature, calcination time and the type of inorganic carbon source of the positive electrode lithium supplement material usually also affect the first charge specific capacity of the positive electrode lithium supplement material. It can be seen from Examples 1, 4 and 5 that as long as the above preparation is used If the parameters are within the scope of the present application, the first charge specific capacity of the positive electrode lithium supplementary material and the energy density of the lithium ion secondary battery can be effectively improved.
从实施例1、实施例13、实施例14、实施例15、实施例16和对比例4可以看出，正极补锂材料的含量在本申请范围内，能够有效提升正极补锂材料的首次充电比容量以及锂离子二次电池的能量密度。尤其是正极补锂材料的质量百分含量优选为3％至10％时，例如，实施例13、实施例14、实施例15、实施例16，能更加有效地提升锂离子二次电池的能量密度。It can be seen from Example 1, Example 13, Example 14, Example 15, Example 16 and Comparative Example 4 that the content of the positive electrode lithium supplementary material is within the scope of the application, which can effectively improve the first charge of the positive electrode lithium supplementary material Specific capacity and energy density of lithium-ion secondary batteries. Especially when the mass percentage of the positive electrode lithium supplement material is preferably 3% to 10%, for example, Example 13, Example 14, Example 15, Example 16, can more effectively improve the energy of the lithium ion secondary battery density.
综合上述分析可知，本申请提供的正极补锂材料，包括xLi
2O·yM的基体、及存在于所述基体上的碳。该正极补锂材料的化学稳定性强，能够有效改善调浆过程中的颗粒团聚现象。将该正极补锂材料应用于电化学装置中，能够实现活性锂地有效补充，使电化学装置的能量密度得到有效提升。
Based on the above analysis, it can be seen that the cathode lithium supplement material provided by the present application includes a matrix of xLi 2 O·yM and carbon existing on the matrix. The positive electrode lithium supplement material has strong chemical stability, and can effectively improve the particle agglomeration phenomenon in the slurry mixing process. Applying the cathode lithium supplement material to an electrochemical device can effectively supplement active lithium and effectively improve the energy density of the electrochemical device.
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。The above descriptions are only preferred embodiments of the present application, and are not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection of the present application. within the range.
Claims (10)
- 一种正极补锂材料，其包括xLi 2O·yM的基体、及存在于所述基体上的碳； A positive electrode lithium supplement material, which comprises a matrix of xLi 2 O·yM and carbon existing on the matrix;其中，x＞0，0.4x≤y≤2x，M包括Mn、Fe、Co、Ni、Cu、Cr或V中的至少一种。Wherein, x>0, 0.4x≤y≤2x, and M includes at least one of Mn, Fe, Co, Ni, Cu, Cr or V.
- 根据权利要求1所述的正极补锂材料，其中，所述M包括Mn、Fe、Co或Ni中的至少一种；所述M的价态为0价。The positive electrode lithium supplement material according to claim 1, wherein the M comprises at least one of Mn, Fe, Co or Ni; and the valence state of the M is zero.
- 根据权利要求1所述的正极补锂材料，其中，基于所述正极补锂材料的总质量，所述碳的质量百分含量为0.5％至3％。The positive electrode lithium supplement material according to claim 1, wherein the mass percentage content of the carbon is 0.5% to 3% based on the total mass of the positive electrode lithium supplement material.
- 根据权利要求1所述的正极补锂材料，其中，所述正极补锂材料的首次充电比容量≥450mAh/g。The positive electrode lithium supplement material according to claim 1, wherein the first charge specific capacity of the positive electrode lithium supplement material is greater than or equal to 450mAh/g.
- 一种制备权利要求1至4中任一项所述的正极补锂材料的方法，其包括以下步骤：A method for preparing the positive electrode lithium supplement material according to any one of claims 1 to 4, comprising the following steps:(1)将萘分散于溶剂中，缓慢加入锂金属碎片或粉末，均匀反应得到萘锂溶液；(1) dispersing naphthalene in a solvent, slowly adding lithium metal fragments or powder, and uniformly reacting to obtain a lithium naphthalene solution;(2)将氧化物M aO b缓慢加入所述萘锂溶液中，搅拌反应均匀后过滤烘干，得到xLi 2O·yM的基体； (2) slowly adding oxide M a O b into the lithium naphthalene solution, stirring and reacting evenly, filtering and drying to obtain a matrix of xLi 2 O·yM;(3)将所述基体与无机碳源进行球磨混合，分散均匀，得到混合物；(3) carrying out ball milling mixing of described matrix and inorganic carbon source, disperse uniformly, obtain mixture;(4)将所述混合物在惰性气氛中煅烧，即得到所述正极补锂材料；(4) calcining the mixture in an inert atmosphere to obtain the positive electrode lithium supplement material;其中，所述萘与所述锂金属的摩尔比为1：(0.6至1)，所述萘与所述氧化物M aO b的摩尔比为1：(0.1至0.5)，所述萘的摩尔数与所述无机碳源的质量的比例为1：(0.05至0.3)mol/g。 Wherein, the molar ratio of the naphthalene to the lithium metal is 1:(0.6 to 1), the molar ratio of the naphthalene to the oxide M a O b is 1: (0.1 to 0.5), and the The ratio of the number of moles to the mass of the inorganic carbon source is 1:(0.05 to 0.3) mol/g.
- 根据权利要求5所述的方法，其中，所述溶剂包括四氢呋喃或乙二醇二甲醚中的至少一种；The method of claim 5, wherein the solvent comprises at least one of tetrahydrofuran or ethylene glycol dimethyl ether;所述氧化物M aO b包括MnO、Mn 2O 3、MnO 2、FeO、Fe 2O 3、CoO、Co 2O 3、Co 3O 4、NiO、Ni 2O 3、Cu 2O、CuO、CrO、Cr 2O 3、CrO 3、VO、V 2O 3、VO 2或V 2O 5中的至少一种； The oxide MaOb includes MnO , Mn2O3 , MnO2 , FeO , Fe2O3 , CoO, Co2O3 , Co3O4 , NiO , Ni2O3 , Cu2O , CuO at least one of , CrO, Cr 2 O 3 , CrO 3 , VO, V 2 O 3 , VO 2 or V 2 O 5 ;所述无机碳源包括炭黑、碳凝胶、科琴黑、乙炔黑、碳纳米管或石墨烯中的至少一种；The inorganic carbon source includes at least one of carbon black, carbon gel, Ketjen black, acetylene black, carbon nanotubes or graphene;在步骤(4)中，煅烧的温度为600℃至700℃，煅烧的时间为4h至8h。In step (4), the calcination temperature is 600°C to 700°C, and the calcination time is 4h to 8h.
- 一种正极极片，其包括权利要求1至4中任一项所述的正极补锂材料。A positive electrode plate, comprising the positive electrode lithium supplement material according to any one of claims 1 to 4.
- 根据权利要求7所述的正极极片，其中，基于正极活性材料层的总质量，所述正极补锂材料的质量百分含量为1％至10％。The positive electrode sheet according to claim 7, wherein, based on the total mass of the positive electrode active material layer, the mass percentage content of the positive electrode lithium supplementing material is 1% to 10%.
- 一种电化学装置，其包括权利要求7或8所述的正极极片。An electrochemical device comprising the positive electrode plate of claim 7 or 8.
- 一种电子装置，其包括权利要求9所述的电化学装置。An electronic device comprising the electrochemical device of claim 9 .
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