WO2020134777A1 - 一种正极补锂材料及其制备方法和用途 - Google Patents

一种正极补锂材料及其制备方法和用途 Download PDF

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WO2020134777A1
WO2020134777A1 PCT/CN2019/120547 CN2019120547W WO2020134777A1 WO 2020134777 A1 WO2020134777 A1 WO 2020134777A1 CN 2019120547 W CN2019120547 W CN 2019120547W WO 2020134777 A1 WO2020134777 A1 WO 2020134777A1
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lithium
positive electrode
containing compound
supplementary material
present
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PCT/CN2019/120547
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English (en)
French (fr)
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王凡
刘晓梅
郑先锋
王国宝
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宁德时代新能源科技股份有限公司
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Priority to ES19904932T priority Critical patent/ES2932152T3/es
Priority to EP19904932.1A priority patent/EP3796432B1/en
Publication of WO2020134777A1 publication Critical patent/WO2020134777A1/zh
Priority to US17/135,504 priority patent/US20210126241A1/en

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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
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    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
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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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • 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 invention relates to the field of electrochemistry, in particular to a positive electrode lithium supplement material, its preparation method and use.
  • Lithium ion batteries have been widely used in portable power supplies, electric vehicles, drones and other fields. However, the energy density and cycle life of lithium ion batteries have reached the bottleneck, and there is an urgent need to develop higher energy density lithium ion batteries.
  • the object of the present invention is to provide a positive electrode lithium supplement material and its preparation method and use, to solve the problems in the prior art.
  • one aspect of the present invention provides a positive electrode lithium supplementary material, including a first lithium-containing compound, the first lithium-containing compound is selected from one of the compounds of formula I or Various combinations:
  • A is selected from C, N, O, P, S, 0 ⁇ x, y ⁇ 3, and the compound of formula I is not Li 2 O;
  • the outer layer of the positive electrode lithium-filling material includes a second lithium-containing compound, and the second lithium-containing compound has lower activity in reacting with water than the first lithium-containing compound.
  • the positive electrode sheet including a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector.
  • the positive electrode active material layer includes a positive electrode active material, a binder, a conductive agent, and the Lithium anode material.
  • Another aspect of the present invention provides a lithium ion battery including the positive electrode tab.
  • the present invention has the following beneficial effects:
  • the positive electrode lithium supplementary material provided by the present invention can effectively prevent the gel phenomenon in the preparation process of the slurry, and can also slow down the inactivation of the lithium supplementary material caused by the reaction of the pole piece with the moisture and carbon dioxide in the air during storage. To a great extent, the manufacturability of lithium-ion lithium-ion batteries is improved, and the energy density and electrochemical performance of lithium-ion batteries are also improved.
  • FIG. 1 shows a schematic diagram of an SEM photograph of a positive electrode lithium supplement material prepared in Example 1 of the present invention.
  • FIG. 2 shows a schematic diagram of an SEM photograph of the positive electrode lithium supplement material prepared in Example 1 of the present invention.
  • the lithium ion battery of the present invention and its preparation method are described in detail below.
  • a first aspect of the present invention provides a positive electrode lithium supplementary material, which includes a first lithium-containing compound, and the first lithium-containing compound is selected from one or a combination of compounds of the formula I:
  • A is selected from C, N, O, P, S, 0 ⁇ x, y ⁇ 3, and the compound of formula I is not Li 2 O;
  • the outer layer of the positive electrode lithium-filling material includes a second lithium-containing compound, and the second lithium-containing compound has lower activity in reacting with water than the first lithium-containing compound.
  • the second lithium-containing compound has lower activity in reacting with water than the first lithium-containing compound.
  • it is an effective method to pre-complement lithium for the battery's positive or negative electrode.
  • Such lithium-containing compounds have a very high capacity and a suitable decomposition voltage, but such lithium-containing compounds are relatively active and easily react with H 2 O to form LiOH.
  • Li 3 Lithium-containing compounds such as N, Li 2 O 2 and Li 2 C 2 are used as lithium-compensating substances.
  • the positive electrode lithium supplementary material containing the second lithium-containing compound outer layer the reaction of the relatively active lithium supplementary material with the outside world can be effectively prevented.
  • the surface-treated positive electrode lithium supplementing material can also slow down the reaction of the highly active lithium supplementing material with water during the preparation and storage of the pole piece, resulting in inactivation.
  • the first lithium-containing compound generally has a higher lithium content and an appropriate decomposition voltage, which is beneficial to increase the energy density of the battery, for example, the lithium of the first lithium-containing compound
  • the content is usually 25% to 60%, 25% to 30%, 30% to 40%, 40% to 50%, or 50% to 60%
  • the theoretical decomposition voltage is usually 1 to 4V, 1 to 2V, 2 to 3V , Or 3 to 4V;
  • the first lithium-containing compound may include but is not limited to a combination of one or more of the compounds shown in Formula I, more specifically, the first lithium-containing compound It may be a combination of one or more of LiN 3 , Li 2 O 2 , Li 2 C 2 and the like, including but not limited to.
  • the mass percentage of the first lithium-containing compound may be 70% to 99%, 70% to 75%, 75% to 80%, 80% to 85%, 85% to 90%, 90% to 92%, 92%-94%, 94%-96%, 96%-98%, or 98%-99%, preferably 90%-98%; the content of the first lithium-containing compound in the positive electrode lithium supplement material can be determined by XRD, ICP And other methods for quantitative testing. If the mass percentage of the first lithium-containing compound is too low, it is generally not conducive to the improvement of the energy density of the cell, and at the same time, the internal resistance of the cell will also increase significantly.
  • the second lithium-containing compound may be an inert material relative to water, and the inert material relative to water specifically refers to environmental conditions during storage, production, battery operation, etc. (For example, it can be exposed to air, and for example, it can be in a dispersion system that does not require strict control of the water content), those that react with water are less active than the first lithium-containing compound, and more preferably refer to Substances that are not easy to absorb moisture and basically do not chemically react with water.
  • the second lithium-containing compound generally has higher chemical stability, and when reacted with H 2 O, the reactivity is generally lower than that of the first lithium-containing compound.
  • the second lithium-containing compound usually also has a higher lithium capacity, so that the entire positive electrode lithium supplementation material has a high lithium supplementation efficiency, but due to its oxidation potential and/or capacity, the lithium supplementation effect is higher than that of the first lithium-containing compound.
  • Lithium compounds usually have certain limitations.
  • the outer layer of the positive lithium supplement material may include a second lithium-containing compound, and the second lithium-containing compound may include but is not limited to Li 2 CO 3 , Li 3 PO4, Li 2 O, Li 2 SO 4 , and sulfurous acid A combination of one or more of lithium, lithium oxalate, lithium ascorbate, and the like.
  • the second lithium-containing compound may be formed by reacting the first lithium-containing compound. The above reaction method should be known to those skilled in the art.
  • the first lithium-containing compound may be added to an acid and/or In the presence of CO 2 , a second lithium-containing compound is formed on its surface.
  • the mass percentage of the second lithium-containing compound may be 1 to 30%, 1 to 5%, 5 to 10%, 10 to 15%, 15 to 20%, 20 to 25%, or 25 to 30%, the preferred mass percentage may be 2 to 10%, and the content of the second lithium-containing compound in the positive electrode lithium supplement material may be quantitatively tested by XRD, ICP, or other methods. If the mass percentage of the second lithium-containing compound is too high, it is generally not conducive to the improvement of the energy density of the cell, and at the same time, the internal resistance of the cell will also increase significantly; and if the mass percentage of the second lithium-containing compound is too low, it cannot It plays the role of fully protecting the first lithium-containing compound with high inner layer activity.
  • the outer layer of the positive electrode lithium supplementary material generally refers to a thickness range corresponding to the surface of 0.5-100 nm, 0.5-1 nm, 1-2 nm, 2-5 nm, 5-10 nm, 10
  • the portion of -20 nm, 20-30 nm, 30-50 nm, 50-70 nm, or 70-100 nm is preferably 2-50 nm.
  • the thickness of the outer layer of the positive electrode lithium supplement material can be characterized by element mapping methods such as SEM, TEM, and STEM.
  • the thickness of the inert outer layer is too high, it is generally not conducive to the improvement of the energy density of the cell, and at the same time, the internal resistance of the cell will also increase significantly; while if the thickness of the inert outer layer is too low, it will not be able to fully protect the inner layer The role of the first active lithium-containing compound.
  • the particle size distribution range of the positive electrode lithium supplementary material may be 0.05 to 10um, 0.05 to 0.1um, 0.1 to 0.2um, 0.2 to 0.3um, 0.3 to 0.5um, 0.5 to 1um, 1-2um, 2-3um, 3-4um, 4-6um, 6-8um, or 8-10um, preferably 0.1-6um, more preferably 0.2-4um.
  • the activity of the positive electrode lithium supplement material increases with the decrease in particle size, and it is more likely to react with the moisture, binder and solvent in the environment to accelerate the slurry gel; however, the large particle lithium supplement material has poor dynamics, resulting in its The lithium efficiency is reduced, so the particle size of the lithium supplement material needs to be moderate, preferably 0.1 to 6 um.
  • the lithium iron phosphate system has a smaller particle size, while the ternary, lithium manganate and other systems have a larger particle size.
  • the lithium supplement material is further preferably 0.2 to 4um, which can improve the stability of the slurry, at the same time, it is conducive to improving the lithium efficiency of the lithium supplement material, and further improving the energy density and electrochemical performance of the battery.
  • a second aspect of the present invention provides a method for preparing a positive electrode lithium supplementary material provided in the first aspect of the present invention, comprising: providing first lithium-containing compound particles; and forming a second lithium-containing compound on the surface of the first lithium-containing compound particles.
  • a person skilled in the art may select a suitable method to form a second lithium-containing compound on the surface of the first lithium-containing compound particles to provide the desired lithium supplementary material for preparation.
  • the first lithium-containing compound may be added in an acid and/or In the presence of CO 2 , a second lithium-containing compound is formed on the surface thereof to form an outer layer of the positive electrode lithium supplementary material including the second lithium-containing compound, more specifically, in an organic solvent in which the first lithium-containing compound is dispersed , A suitable amount of CO 2 is added, and a certain concentration of acid (for example, sulfuric acid, phosphoric acid, etc.) is added to form a second lithium-containing compound on the surface thereof, so as to form an outer layer of a positive electrode lithium supplement material including the second lithium-containing compound.
  • acid for example, sulfuric acid, phosphoric acid, etc.
  • a third aspect of the present invention provides the use of the positive electrode lithium supplementary material provided in the first aspect of the present invention in the preparation of a positive electrode tab for a lithium ion (secondary) battery and/or a lithium ion (secondary) battery.
  • the positive-electrode lithium supplementary material may be located in the positive-electrode active material layer of the positive-electrode sheet, and further assembled to prepare a battery.
  • the positive-electrode lithium supplementary material may be mixed with the positive-electrode active material, a binder, a conductive agent, etc., thereby It is used to prepare the positive electrode active material layer; it can also be mixed with a binder and a conductive agent to prepare a lithium supplementary material layer, placed between the positive electrode sheet and the positive electrode material layer or on the surface of the positive electrode material layer, and further assembled to prepare a battery.
  • a fourth aspect of the present invention provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a binder, a conductive agent and the present invention
  • the cathode supplement lithium material provided in the first aspect can reduce the activity of reacting with water, so that the lithium can be effectively supplemented to the battery after the positive electrode active material layer is formed.
  • a person skilled in the art may select a suitable method to prepare the positive electrode sheet. For example, the method may include the steps of: mixing and coating a positive electrode active material, a binder, a conductive agent, and a positive electrode lithium supplement material provided in the first aspect of the present invention It is distributed on the positive electrode current collector.
  • the binder generally includes a fluorine-containing polyolefin-based binder
  • the fluorine-containing polyolefin-based binder may include but is not limited to polyvinylidene fluoride (PVDF), Vinylidene fluoride copolymers, etc. or their modified (for example, modified by carboxylic acid, acrylic acid, acrylonitrile, acrylate, acrylamide, etc.) derivatives, etc.
  • PVDF polyvinylidene fluoride
  • VDF polyvinylidene fluoride copolymers
  • modified for example, modified by carboxylic acid, acrylic acid, acrylonitrile, acrylate, acrylamide, etc.
  • a person skilled in the art can adjust the content of the binder in the positive electrode active material layer according to the parameters of the positive electrode sheet bonding force, electrode sheet resistance, electrode sheet processing performance, etc.
  • the binder in the positive electrode active material layer The mass percentage content may be 0.5% to 5%, 0.5% to 1%, 1% to
  • the mass percentage of the positive electrode lithium supplement material in the positive electrode active material layer may be 0.2% to 10%, 0.2% to 0.5%, 0.5% to 1%, 1% to 2% , 2% to 4%, 4% to 6%, 6% to 8%, or 8% to 10%.
  • a person skilled in the art can appropriately adjust the content of the positive electrode lithium supplement material in the positive pole piece according to the actual use function of the battery cell. Generally speaking, increasing the mass percentage content of the lithium supplement material can increase the active lithium available in the battery cell Content, which can increase the cycle life of the battery.
  • the positive electrode active material may be various positive electrode active materials suitable for lithium ion (secondary) batteries in the art, for example, may include but not limited to layered positive electrode active materials, sharp A combination of one or more of spar-type cathode active material, olivine-type cathode active material, metal sulfide, etc.
  • the cathode material can also be modified, and the method of modifying the cathode material should be known to those skilled in the art, for example, the cathode material can be modified by coating, doping, etc.
  • the material used in the modification treatment may be, but not limited to, a combination of one or more of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, etc.
  • the weight of the positive electrode active material may account for 80% to 99%, 90% to 97%, 80% to 85%, 85% to 90%, 90% to 95%, 95% to 97% of the total mass of the positive electrode active material layer , Or 97% ⁇ 99%.
  • a person skilled in the art can adjust the content of the positive electrode active material according to the actual use of the battery cell.
  • the higher the positive electrode active material ratio, the lower the proportion of the lithium supplement material, and the higher the capacity density of the battery cell The increase in cycle life will be reduced to a certain extent; on the contrary, the lower the proportion of positive electrode active material, the proportion of lithium supplementary materials will increase accordingly, the energy density of the battery will decrease, and the increase in cycle life will increase accordingly.
  • the conductive agent may be various conductive agents suitable for lithium ion (secondary) batteries in the art, for example, may include but not limited to acetylene black, conductive carbon black, carbon fiber (VGCF), carbon nanotubes (CNT), Ketjen Black, etc. one or more combinations.
  • the weight of the conductive agent may account for 0.1% to 5%, 0.2% to 3%, 0.5% to 2%, 0.1% to 0.2%, 0.2% to 0.3%, 0.3% to 0.5% of the total mass of the positive electrode active material layer , 0.5% to 1%, 1% to 2%, 2% to 3%, 3% to 4%, or 4% to 5%.
  • the amount of conductive agent in the positive electrode active material mainly affects the internal resistance of the cell and the energy density of the cell.
  • the proportion of the positive electrode active material and the lithium-compensating material increases accordingly, the greater the resistance of the pole piece, and the energy density of the cell will be improved to a certain extent.
  • the positive electrode current collector may generally be a layered body, the positive electrode current collector may generally be a structure or part capable of collecting current, and the positive electrode current collector may be suitable for various
  • the material of the positive electrode current collector of the lithium ion battery for example, the positive electrode current collector may include but not limited to metal foil and the like, and more specifically may include but not limited to copper foil, aluminum foil and the like.
  • a fifth aspect of the present invention provides a lithium ion (secondary) battery including the positive electrode tab as described in the fourth aspect of the present invention.
  • the lithium-ion battery may also include other components that can be used in the lithium-ion battery. For example, it may also include a negative pole piece, a battery separator, an electrolyte, an external electrode, a tab, a packaging case, and the like.
  • the method for preparing the lithium-ion battery should be known to those skilled in the art.
  • the positive pole piece, the separator, and the negative pole piece can each be a layered body, so that they can be cut to the target size in turn Stacked, it can be further wound to a target size for forming a battery cell, and can be further combined with an electrolyte to form a lithium ion battery.
  • the specific type of the lithium-ion battery is not specifically limited, and for example, it may include but is not limited to a cylindrical battery, an aluminum battery or a soft-pack battery.
  • the negative electrode tab generally includes a negative electrode current collector and a negative electrode active material layer on the surface of the negative electrode current collector, and the negative electrode active material layer generally includes a negative electrode active material.
  • the negative electrode active material may be various materials suitable for negative electrode active materials of lithium ion batteries in the art, for example, may include but not limited to graphite, soft carbon, hard carbon, carbon fiber, mesophase carbon microspheres, silicon-based materials , Tin-based materials, lithium titanate or other metals that can form alloys with lithium, etc.
  • the graphite may be selected from one or more of artificial graphite, natural graphite and modified graphite;
  • the silicon-based material may be selected from one of elemental silicon, silicon oxide compound, silicon carbon composite, silicon alloy One or more species;
  • the tin-based material may be selected from one or more of elemental tin, tin oxide compounds, and tin alloys.
  • the negative electrode current collector is usually a structure or part that collects current.
  • the negative electrode current collector may be various materials suitable for use as a negative electrode current collector of a lithium ion battery in the art.
  • the negative electrode current collector may include but is not limited to The metal foil and the like may more specifically include but not limited to copper foil and the like.
  • the separator may be a variety of materials suitable for lithium ion battery separators in the art, for example, it may include but not limited to polyethylene, polypropylene, polyvinylidene fluoride, aramid , Polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester and natural fiber, one or more combinations.
  • the electrolyte may be various electrolytes suitable for lithium ion batteries in the art.
  • the electrolyte generally includes an electrolyte and a solvent, and the electrolyte may generally include a lithium salt and the like.
  • the lithium salt may It is an inorganic lithium salt and/or an organic lithium salt, etc., and may specifically include but not limited to lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluorooxalate phosphate, LiN(SO 2 RF) 2 , LiN(SO 2 F)(SO 2 RF), one or more of bistrifluoromethanesulfonimide, lithium bis(fluorosulfonyl)imide, lithium bisoxalate borate, lithium difluorooxalate borate, etc. The combination.
  • the concentration of the electrolyte may be between 0.5M and 1.5M.
  • the solvent may be any solvent suitable for an electrolyte of a lithium ion battery in the art.
  • the solvent of the electrolyte is usually a non-aqueous solvent, preferably an organic solvent, and may specifically include but not limited to ethylene carbonate, carbonic acid Propylene ester, butylene carbonate, pentenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propylene Propionate, ethyl butyrate, ethyl propionate, propyl butyrate, vinylene carbonate, vinyl sulfite, propylene sulfite, ⁇ -butyrolactone, tetrahydrofuran, etc. or their halogenated derivatives One or more combinations.
  • one or more of the method steps mentioned in the present invention does not exclude that there may be other method steps before or after the combination step or that other method steps may be inserted between these explicitly mentioned steps unless otherwise Explained; It should also be understood that the combined connection relationship between one or more devices/devices mentioned in the present invention does not exclude that there may be other devices/devices or those mentioned explicitly in these before and after the combined device/device Other devices/apparatuses can also be inserted between the two devices/apparatuses unless otherwise stated.
  • each method step is only a convenient tool to identify each method step, not to limit the order of each method step or to limit the scope of the present invention, the change or adjustment of its relative relationship, in If the technical content is not substantially changed, it should be regarded as the scope of the invention.
  • Li 2 O 2 , Li 2 C 2 and Li 3 N materials of different specifications are selected, the positive electrode slurry is prepared, coated into a positive pole piece, and then assembled into a soft-packed lithium ion battery, and the battery is tested 1C/1C cycle performance at 45°C.
  • Li 2 O 2 in diethyl carbonate and pass CO 2 gas to prepare Li with a surface containing 3% Li 2 CO 3 /Li 2 O, a thickness of about 1 nm, and a particle size of about 0.2um 2 O 2 lithium supplement material, SEM photos of powder see Figure 1 and Figure 2.
  • This Li 2 O 2 lithium supplement material, positive electrode active material LiFePO 4 , conductive agent Super P (conductive carbon, SP), and binder PVDF are dissolved in a solvent NMP in a weight ratio of 2:95:1.5:1.5 and obtained by stirring Even slurry.
  • step (2) The slurry prepared in step (1) is evenly coated on the positive electrode current collector aluminum foil with a coating weight of 0.02 g/cm 2 , and the positive electrode sheet containing Li 2 O 2 is obtained by cold pressing and slitting ;
  • the preparation steps of the batteries and batteries of Examples 2 to 6 are the same as those of Example 1, except that the first lithium-containing compound, the second lithium-containing compound, the thickness of the inert outer layer, the particle size of the lithium supplement material, and the lithium supplement material are used.
  • the content is different, the specific parameters are shown in Table 1.
  • the preparation steps of the battery cell and battery of Comparative Example 1 are the same as those in Example 1, except that the lithium supplementary material used is Li 2 C 2 directly, and there is no second lithium-containing compound and inert outer layer.
  • the content of lithium supplement materials is different, and the specific parameters are shown in Table 1.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6 Comparative Example 1 LixAy Li 2 O 2 Li 3 N Li 2 C 2 Li 2 C 2 Li 2 C 2 Li 2 C 2 Li 2 C 2
  • Type of second lithium-containing compound Li 2 CO 3 Li 2 SO 3 Lithium oxalate Li 2 O Li 3 PO 4 Li 2 CO 3 -
  • Second lithium-containing compound content (%) 1 5 10 15 8 8 - Inert outer layer thickness (nm) 1 2 50 80 150 30 - Lithium supplement material size (um) 0.2 0.2 4 2 10 2 2
  • the slurry prepared in step (1) in each example and comparative example in a 500mL beaker, place it in an environment with a humidity environment of 1.0 ⁇ 0.2%, and record the state of the slurry every 1h until the slurry gels As the viscosity of the slurry first rose to 50000mPa.s as a gel, the specific anti-gelation time is shown in Table 2.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6 Comparative Example 1
  • Anti-gel time (h) 16 20 twenty four 30
  • m ⁇ Battery internal resistance (m ⁇ ) 0.36 0.37 0.40 0.42 0.44 0.38 - Cycle life 7520 7624 7764 7538 7569 7812 -
  • the charging capacity of the formed cell is directly measured by the measuring device.
  • the cell active material mass refers to the mass of LiFePO 4 in the cell.
  • the additive mass in the battery cell refers to the total mass of the lithium supplementary additive added in the battery cell, and includes the first lithium-containing compound and the second lithium-containing compound.
  • purity mass of the first lithium-containing compound/total mass of the lithium-compensating material.
  • Additive lithium efficiency (charge capacity of the formed cell-mass of active material of the cell * gram capacity of the active material) / (additive mass in the cell * purity * gram capacity of the additive) * 100%.
  • the lithium efficiency of the lithium supplement material with the coating layer is significantly higher than that of the uncoated lithium supplement material, which is mainly due to the During the production process of the core, due to the higher activity, the deactivation rate is also higher, resulting in a decrease in lithium efficiency.
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.

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Abstract

本发明涉及电化学领域，特别是涉及一种正极补锂材料及其制备方法和用途。本发明提供一种正极补锂材料，包括第一含锂化合物，所述第一含锂化合物选自化学式如式I所示的化合物中的一种或多种的组合，所述正极补锂材料的外层包括第二含锂化合物，所述第二含锂化合物与水反应的活性低于第一含锂化合物。本发明所提供的正极补锂材料可以有效地防止浆料制备过程中的凝胶现象，还能够减缓极片在存放过程中，与空气中的水分及二氧化碳反应而导致补锂材料的失活，很大程度的提升补锂锂离子电池的可制造性，同时提升锂离子电池的能量密度与电化学性能。

Description

一种正极补锂材料及其制备方法和用途 技术领域
本发明涉及电化学领域，特别是涉及一种正极补锂材料及其制备方法和用途。
背景技术
锂离子电池已广泛应用于便携式电源、电动车、无人机等领域。然而目前锂离子电池的能量密度、循环寿命等已达瓶颈，急需开发更高能量密度的锂离子电池。
在锂离子电池首次充电过程中，负极表面形成固态电解质膜(SEI)会消耗大量的活性锂，从而造成可循环利用的锂减少，降低电池的首次库伦效率和电池容量。特别是对于使用高比容的负极材料，如合金硅、氧化硅、锡、氧化锡、氧化钛等，活性锂消耗进一步加剧，大大降低电池的能量密度。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种正极补锂材料及其制备方法和用途，用于解决现有技术中的问题。
为实现上述目的及其他相关目的，本发明一方面提供一种正极补锂材料，包括第一含锂化合物，所述第一含锂化合物选自化学式如式I所示的化合物中的一种或多种的组合：
Li xA y   式I
其中，A选自C、N、O、P、S，0<x，y≤3，且式I化合物不为Li 2O；
所述正极补锂材料的外层包括第二含锂化合物，所述第二含锂化合物与水反应的活性低于第一含锂化合物。
本发明另一方面提供一种正极极片，包含正极集流体和位于所述正极集流体上的正极活性物质层，所述正极活性物质层包括正极活性物质、粘结剂、导电剂和所述的正极补锂材料。
本发明另一方面提供一种锂离子电池的，含有所述的正极极片。
相对于现有技术，本发明具有以下有益效果：
本发明所提供的正极补锂材料可以有效地防止浆料制备过程中的凝胶现象，还能够减缓极片在存放过程中，与空气中的水分及二氧化碳反应而导致补锂材料的失活，很大程度的提升补锂锂离子电池的可制造性，同时提升锂离子电池的能量密度与电化学性能。
附图说明
图1显示为本发明实施例1制备获得的正极补锂材料的SEM照片示意图。
图2显示为本发明实施例1制备获得的正极补锂材料的SEM照片示意图。
具体实施方式
下面详细说明本发明的锂离子电池及其制备方法。
本发明第一方面提供一种正极补锂材料，包括第一含锂化合物，所述第一含锂化合物选自化学式如式I所示的化合物中的一种或多种的组合：
Li xA y   式I
其中，A选自C、N、O、P、S，0<x，y≤3，且式I化合物不为Li 2O；
所述正极补锂材料的外层包括第二含锂化合物，所述第二含锂化合物与水反应的活性低于第一含锂化合物。为了针对电池首次库伦效率和电池容量降低的问题，对电池正极或者负极进行预补锂是一种有效的方法，然而在实际测试研究中可以发现诸如Li 3N、Li 2O 2和Li 2C 2这类含锂化合物具有很高的容量及合适的分解电压，但是此类含锂化合物相对较为活泼，极易与H 2O反应形成LiOH。由于锂离子电池正极中使用的大多都是含氟聚烯烃类高分子粘结剂，此类粘结剂容易受到碱性基团的攻击，发生交联反应导致浆料发生凝胶，因此，Li 3N、Li 2O 2和Li 2C 2这类含锂化合物作为补锂物质，用于正极片制备时，在很短的时间内便与粘结剂作用形成凝胶，限制了其实际应用。而本发明中，通过使用含有第二含锂化合物外层的正极补锂材料，可以有效阻止相对活泼的补锂材料与外界的反应。另外，表面处理后的正极补锂材料还能够减缓极片在制备、存放等过程中，活性程度较高的补锂材料与水反应而导致失活。
本发明所提供的正极补锂材料中，所述第一含锂化合物通常具有较高的锂含量和适当的分解电压，从而有利于提升电池能量密度，例如，所述第一含锂化合物的锂含量通常为25％～60％、25％～30％、30％～40％、40％～50％、或50％～60％，理论分解电压通常为1～4V、1～2V、2～3V、或3～4V；再例如，所述第一含锂化合物可以是包括但不限于如式I所示的化合物中的一种或多种的组合，更具体的，所述第一含锂化合物可以是包括但不限于LiN 3、Li 2O 2、Li 2C 2等中的一种或多种的组合。所述第一含锂化合物所占的质量百分比可以为70％～99％、70％～75％、75％～80％、80％～85％、85％～90％、90％～92％、92％～94％、94％～96％、96％～98％、或98％～99％，优选为90％～98％；正极补锂材料中第一含锂化合物的含量可以通过XRD、ICP等方法进行定量测试。第一含锂化合物的质量百分比如果过低，通常不利于电 芯能量密度的提升，同时，电芯的内阻也会明显增加。
本发明所提供的正极补锂材料中，所述第二含锂化合物可以是相对于水的惰性材料，所述相对于水的惰性材料具体指在存储、生产、电池的工作等过程的环境条件下(例如，可以是暴露于空气的条件下，再例如，可以是在不需要严苛地控制水含量的分散体系中)，那些与水反应的活性低于第一含锂化合物，更优选指那些不易吸湿、基本上不与水发生化学反应的物质。所述第二含锂化合物通常具有更高的化学稳定性，与H 2O作用时，反应活性通常低于第一含锂化合物。另外，第二含锂化合物通常也具有较高的锂容量，从而可以使整个正极补锂材料具有很高的补锂效率，但是因其氧化电位和/或容量，补锂效果相对于第一含锂化合物通常会有一定的局限性。所述正极补锂材料的外层可以包括第二含锂化合物，所述第二含锂化合物可以是包括但不限于Li 2CO 3、Li 3PO4、Li 2O、Li 2SO 4、亚硫酸锂、草酸锂、抗坏血酸锂等中的一种或多种的组合。所述第二含锂化合物可以由所述第一含锂化合物经反应形成，上述反应方法对于本领域技术人员来说应该是已知的，例如，可以将第一含锂化合物在酸和/或CO 2存在的条件下，在其表面形成第二含锂化合物。
本发明所提供的正极补锂材料中，所述第二含锂化合物所占的质量百分比可以为1～30％、1～5％、5～10％、10～15％、15～20％、20～25％、或25～30％，优选的质量百分比可以为2～10％，正极补锂材料中第二含锂化合物的含量可以通过XRD、ICP等方法进行定量测试。第二含锂化合物的质量百分比如果过高，通常不利于电芯能量密度的提升，同时，电芯的内阻也会明显增加；而第二含锂化合物的质量百分比如果过低时，则不能起到充分保护内层活性较高的第一含锂化合物的作用。
本发明所提供的正极补锂材料中，所述正极补锂材料的外层通常指对应其表面的厚度范围为0.5～100nm、0.5～1nm、1～2nm、2～5nm、5～10nm、10～20nm、20～30nm、30～50nm、50～70nm、或70～100nm的部分，优选为2～50nm。正极补锂材料的外层的厚度可以通过SEM、TEM、STEM等元素mapping方法进行表征。惰性外层的厚度如果过高，通常不利于电芯能量密度的提升，同时，电芯的内阻也会明显增加；而惰性外层的厚度如果过低时，则不能起到充分保护内层活性较高的第一含锂化合物的作用。
本发明所提供的正极补锂材料中，所述正极补锂材料的粒径分布范围可以为0.05～10um、0.05～0.1um、0.1～0.2um、0.2～0.3um、0.3～0.5um、0.5～1um、1～2um、2～3um、3～4um、4～6um、6～8um、或8～10um，优选为0.1～6um，更优选为0.2～4um。正极补锂材料的活性随颗粒尺寸的减小，活性增加，更易与环境中的水分、粘结剂及溶剂反应，加速浆料凝胶；而大颗粒的补锂材料动力学较差，导致其锂效率降低，因此补锂材料的粒径需要适 中，优选为0.1～6um。在用于常见正极材料补锂时，由于磷酸铁锂体系的颗粒尺寸较小，而三元、锰酸锂等体系颗粒尺寸较大，为了更好的与正极活性颗粒尺寸相匹配，补锂材料的粒径进一步优选为0.2～4um，从而可以在提升浆料稳定性的同时，有利于提升补锂材料锂效率的发挥，进一步提升电池的能量密度和电化学性能。
本发明第二方面提供本发明第一方面所提供的正极补锂材料的制备方法，包括：提供第一含锂化合物颗粒；在第一含锂化合物颗粒表面形成第二含锂化合物。本领域技术人员可选择合适的方法，在第一含锂化合物颗粒表面形成第二含锂化合物，以提供所需制备的正极补锂材料，例如，可以将第一含锂化合物在酸和/或CO 2存在的条件下，在其表面形成第二含锂化合物，以形成包括第二含锂化合物的正极补锂材料的外层，更具体可以是在分散有第一含锂化合物的有机溶剂中，通入适量的CO 2、添加一定浓度的酸(例如，硫酸、磷酸等)，在其表面形成第二含锂化合物，以形成包括第二含锂化合物的正极补锂材料的外层。
本发明第三方面提供本发明第一方面所提供的正极补锂材料在制备锂离子(二次)电池用正极极片和/或锂离子(二次)电池中的用途。所述正极补锂材料可以位于正极极片的正极活性物质层中，并进一步被组装以制备电池，例如，所述正极补锂材料可以与正极活性物质、粘结剂、导电剂等混合，从而被用于制备正极活性物质层；也可以混以粘结剂、导电剂，制备补锂材料层，置于正极片与正极材料层之间或置于正极材料层表面，进一步被组装以制备电池。
本发明第四方面提供一种正极极片，包含正极集流体和位于所述正极集流体上的正极活性物质层，所述正极活性物质层包括正极活性物质、粘结剂、导电剂和本发明第一方面所提供的正极补锂材料。在电极的制备、存储过程中，所述正极补锂材料可以降低与水反应的活性，从而可以在正极活性物质层形成后，有效地对电池进行补锂。本领域技术人员可选择合适的方法制备所述正极极片，例如，可以包括如下步骤：将正极活性物质、粘结剂、导电剂和本发明第一方面所提供的正极补锂材料混合，涂布于正极集流体上。
本发明所提供的正极极片中，所述粘结剂通常包括含氟聚烯烃类粘结剂，所述含氟聚烯烃类粘结剂可以是包括但不限于聚偏氟乙烯(PVDF)、偏氟乙烯共聚物等或它们的改性(例如，羧酸、丙烯酸、丙烯腈、丙烯酸酯、丙烯酰胺等改性)衍生物等。本领域技术人员可根据正极极片的粘结力、极片电阻、极片加工性能等参数，对正极活性物质层中粘结剂的含量进行调整，例如，正极活性物质层中粘结剂的质量百分比含量可以是0.5％～5％、0.5％～1％、1％～2％、2％～3％、3％～4％、或4％～5％。
本发明所提供的正极极片中，所述正极补锂材料在正极活性物质层中的质量百分比可以 为0.2％～10％、0.2％～0.5％、0.5％～1％、1％～2％、2％～4％、4％～6％、6％～8％、或8％～10％。本领域技术人员可以根据电芯的实际使用功能对正极极片中的正极补锂材料的含量进行适当调整，通常来说，提高补锂材料的质量百分比含量可以提高电芯中可利用的活性锂含量，从而可以提升电芯的循环寿命。
本发明所提供的正极极片中，所述正极活性物质可以是本领域各种适用于锂离子(二次)电池的正极活性物质，例如，可以是包括但不限于层状正极活性物质、尖晶石型正极活性物质、橄榄石型正极活性物质、金属硫化物等中的一种或多种的组合，更具体的，所述正极活性物质可以是包括但不限于化学式如Li aNi xCo yM zO 2-bN b(其中0.95≤a≤1.2，x＞0，y≥0，z≥0，且x+y+z＝1，0≤b≤1，M选自Mn、Al中的一种或多种的组合，N选自F、P、S中的一种或多种的组合)所示的化合物中的一种或多种的组合，所述正极活性物质还可以是包括但不限于LiCoO 2、LiNiO 2、LiVO 2、LiCrO 2、LiMn 2O 4、LiCoMnO 4、Li 2NiMn 3O 8、LiNi 0.5Mn 1.5O 4、LiCoPO 4、LiMnPO 4、LiFePO 4、LiNiPO 4、LiCoFSO 4、CuS 2、FeS 2、MoS 2、NiS、TiS 2等中的一种或多种的组合。所述正极材料还可以经过改性处理，对正极材料进行改性处理的方法对于本领域技术人员来说应该是已知的，例如，可以采用包覆、掺杂等方法对正极材料进行改性，改性处理所使用的材料可以是包括但不限于Al、B、P、Zr、Si、Ti、Ge、Sn、Mg、Ce、W等中的一种或多种的组合。所述正极活性物质的重量可以占正极活性物质层总质量80％～99％、90％～97％、80％～85％、85％～90％、90％～95％、95％～97％、或97％～99％。本领域技术人员可根据电芯的实际使用情况对正极活性物质的含量进行调整，通常来说，正极活性物质占比越高，补锂材料的占比自然降低，电芯的能力密度会越高，循环寿命的提升会有一定程度降低；相反，正极活性物质占比越低，补锂材料的占比相应提升，电芯的能量密度会有所下降，而循环寿命的提升则会相应增加。
本发明所提供的正极极片中，所述导电剂可以是本领域各种适用于锂离子(二次)电池的导电剂，例如，可以是包括但不限于乙炔黑、导电炭黑、碳纤维(VGCF)、碳纳米管(CNT)、科琴黑等中的一种或多种的组合。所述导电剂的重量可以占正极活性物质层总质量的0.1％～5％、0.2％～3％、0.5％～2％、0.1％～0.2％、0.2％～0.3％、0.3％～0.5％、0.5％～1％、1％～2％、2％～3％、3％～4％、或4％～5％。导电剂占正极活性物质的量主要影响电芯的内阻和电芯的能量密度。通常来说，导电剂占比越高，正极活性物质和补锂材料的占比相应降低，极片电阻越小，而电芯能量密度会有一定程度的降低；相反，导电剂占比越低，正极活性物质和补锂材料的占比相应提高，极片电阻越大，而电芯能量密度会有一定程度的提升。
本发明所提供的正极极片中，所述正极集流体通常可以为层体，所述正极集流体通常是 可以汇集电流的结构或零件，所述正极集流体可以是本领域各种适用于作为锂离子电池正极集流体的材料，例如，所述正极集流体可以是包括但不限于金属箔等，更具体可以是包括但不限于铜箔、铝箔等。
本发明第五方面提供一种锂离子(二次)电池的，含有如本发明第四方面所述的正极极片。所述锂离子电池中，还可以包括其他可以用于锂离子电池的部件，例如，还可以包括负极极片、电池隔膜、电解液、外接电极、极耳、包装壳等。制备所述锂离子电池的方法对于本领域技术人员来说应该是已知的，例如，所述正极极片、隔离膜和负极极片各自都可以是层体，从而可以裁剪成目标尺寸后依次叠放，还可以进一步卷绕至目标尺寸，以用于形成电芯，并可以进一步与电解液结合以形成锂离子电池。所述锂离子电池的具体类型没有具体限制，例如，可以是包括但不限于圆柱电池、铝壳电池或者软包电池等。
本发明所提供的锂离子电池中，所述负极极片通常包括负极集流体和位于负极集流体表面的负极活性物质层，所述负极活性物质层通常包括负极活性物质。所述负极活性物质可以是本领域各种适用于锂离子电池的负极活性物质的材料，例如，可以是包括但不限于石墨、软碳、硬碳、碳纤维、中间相碳微球、硅基材料、锡基材料、钛酸锂或其他能与锂形成合金的金属等中的一种或几种。其中，所述石墨可选自人造石墨、天然石墨以及改性石墨中的一种或几种；所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅合金中的一种或几种；所述锡基材料可选自单质锡、锡氧化合物、锡合金中的一种或几种。所述负极集流体通常是汇集电流的结构或零件，所述负极集流体可以是本领域各种适用于作为锂离子电池负极集流体的材料，例如，所述负极集流体可以是包括但不限于金属箔等，更具体可以是包括但不限于铜箔等。
本发明所提供的锂离子电池中，所述隔离膜可以是本领域各种适用于锂离子电池隔膜的材料，例如，可以是包括但不限于聚乙烯、聚丙烯、聚偏氟乙烯、芳纶、聚对苯二甲酸乙二醇酯、聚四氟乙烯、聚丙烯腈、聚酰亚胺，聚酰胺、聚酯和天然纤维等中的一种或多种的组合。所述电解液可以是本领域各种适用于锂离子电池的电解液，例如，所述电解液通常包括电解质和溶剂，所述电解质通常可以包括锂盐等，更具体的，所述锂盐可以是无机锂盐和/或有机锂盐等，具体可以是包括但不限于六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、四氟草酸磷酸锂、LiN(SO 2RF) 2、LiN(SO 2F)(SO 2RF)、双三氟甲烷磺酰亚胺、双(氟磺酰)亚胺锂、双草酸硼酸锂、二氟草酸硼酸锂等中的一种或多种的组合。再例如，所述电解质的浓度可以为0.5M～1.5M之间。所述溶剂可以是本领域各种适用于锂离子电池的电解液的溶剂，所述电解液的溶剂通常为非水溶剂，优选可以为有机溶剂，具体可以是包括但不限于碳 酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸戊烯酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲乙酯、甲酸甲酯、甲酸乙酯、乙酸甲酯、乙酸乙酯、丙酸丙酯、丁酸乙酯、丙酸乙酯、丁酸丙酯、碳酸亚乙烯酯、亚硫酸乙烯酯、亚硫酸丙烯酯、γ-丁内酯、四氢呋喃等或它们的卤代衍生物中的一种或多种的组合。
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
须知，下列实施例中未具体注明的工艺设备或装置均采用本领域内的常规设备或装置。
此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明；还应理解，本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备/装置，除非另有说明。而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。
本发明具体实施例中选用不同规格的Li 2O 2、Li 2C 2及Li 3N材料，通过制备正极浆料，涂布成正极极片，然后组装成软包锂离子电池，并测试电池45℃下1C/1C循环性能。
实施例1
正极浆料制备：
(1)将Li 2O 2分散在碳酸二乙酯中，通入CO 2气体，制备得到表面含有3％Li 2CO 3/Li 2O，厚度约为1nm，颗粒尺寸约为0.2um的Li 2O 2补锂材料，粉料SEM照片参见图1和图2。将此Li 2O 2补锂材料、正极活性物质LiFePO 4、导电剂Super P(导电碳，SP)、粘结剂PVDF按重量比2：95：1.5：1.5溶于溶剂NMP中，经搅拌获得均匀的浆料.
补锂电芯和电池的制备：
(2)将步骤(1)中制备的浆料均匀地涂布在正极集流体铝箔上，涂布重量为0.02g/cm 2，经冷压、分条获得含有Li 2O 2的正极极片；
(3)由人造石墨：SP：CMC：SBR＝96.5：1：1：1.5溶解于水中作为负极活性物质层的 浆料，在铜集流体上涂布负极活性物质层，经冷压、分条获得负极极片；
(4)将步骤(2)制备的正极极片、步骤(3)制备的负极极片、厚度10um的聚乙烯材质隔离膜卷绕获得锂离子电芯；
(5)将锂离子电芯装入电池包装中并注入EC：EMC：DEC＝1：1：1电解液，电解液中含有浓度为1mol/L的六氟磷酸锂、2％VC和3％PS；经过化成充电过程，Li 2O 2释放活性锂到负极中，最后经过抽气、密封、整形获得正极补锂后的锂离子电池。
实施例2～6
实施例2～6的电芯和电池的制备步骤同实施例1，不同的是所使用的第一含锂化合物、第二含锂化合物、惰性外层厚度、补锂材料粒径、补锂材料含量有所不同，具体参数如表1中所示。
对比例1
对比例1的电芯和电池的制备步骤同实施例1，不同的是所使用补锂材料直接为Li 2C 2，并没有第二含锂化合物和惰性外层，其补锂材料粒径、补锂材料含量有所不同，具体参数如表1中所示。
表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 对比例1
LixAy Li 2O 2 Li 3N Li 2C 2 Li 2C 2 Li 2C 2 Li 2C 2 Li 2C 2
第二含锂化合物种类 Li 2CO 3 Li 2SO 3 草酸锂 Li 2O Li 3PO 4 Li 2CO 3 -
第二含锂化合物含量(％) 1 5 10 15 8 8 -
惰性外层厚(nm) 1 2 50 80 150 30 -
补锂材料尺寸(um) 0.2 0.2 4 2 10 2 2
粘结剂 PVDF PVDF PVDF PVDF PVDF PVDF PVDF
补锂材料含量(％) 0.5 0.5 20 10 5 5 5
对实施例1～6和对比例1制备的浆料抗凝胶时间以及获得的电池进行性能测试，具体测试方法如下：
浆料抗凝胶时间测试：
将各实施例和对比例中步骤(1)所制备的浆料置于500mL烧杯中，放置在湿度环境为1.0±0.2％的环境中，每隔1h记录浆料状态，至浆料发生凝胶，以浆料粘度首次上升至50000mPa.s视为凝胶，具体的抗胶凝时间如表2所示。
电芯内阻测试：
将各实施例和对比例所制备的锂离子电池将化成后，充电至3.3V，静置12h后，使用内阻仪测试电芯的内阻值，具体结果如表2所示。
电芯循环测试：
将各实施例和对比例所制备的电池放置于高低温箱中，恒温25℃测试，在电压范围2.5V～3.65V之间进行1C倍率的充放电测试，直至电芯容量衰减至起始容量的80％，记录电芯循环次数，具体结果如表2所示。
表2
  实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 对比例1
抗凝胶时间(h) 16 20 24 30 36 26 ＜1
电池内阻(mΩ) 0.36 0.37 0.40 0.42 0.44 0.38 -
循环寿命 7520 7624 7764 7538 7569 7812 -
从上述表2中可以看出，对于不含惰性层的对比例1，浆料在1h内发生凝胶，而实施例1～6的浆料发生凝胶的时间则远远大于对比例1，说明本发明所提供的正极补锂材料所形成的浆料可以有效改善活性较高的补锂材料与水接触后所发生的凝胶现象。另外，实施例1～6对比一定程度说明包覆层厚度增加，会一定程度上增加电池的内阻，因而需要兼顾材料的加工性能和电芯内阻，使用合适厚度的包覆层补锂材料。电芯的循环寿命主要依赖于补锂材料的含量，随补锂材料含量的增加，电芯循环性能会得到提升。
添加剂的锂效率的测试：
化成电芯充电容量通过测量设备直接测量获得。
电芯活性物质质量指电芯中LiFePO 4的质量。
活性材料化成克容量为扣电实测首次充电克容量，计算方法如下：首次充电克容量＝首次充电容量/活性物质质量。
电芯中添加剂质量指电芯中所添加补锂添加剂的总质量，包含第一含锂化合物和第二含锂化合物。
纯度的计算方法如下：纯度＝第一含锂化合物质量/补锂材料总质量。
添加剂克容量为理论值，其计算方法如下：添加剂克容量＝(1mol添加剂锂的摩尔数/添 加剂物质的量)*26802mAh/g。
添加剂锂效率的计算方法如下：添加剂锂效率＝(化成电芯充电容量-电芯活性物质质量*活性材料化成克容量)/(电芯中添加剂质量*纯度*添加剂克容量)*100％。
各参数的结果具体结果如表3所示：
表3
Figure PCTCN2019120547-appb-000001
通过对补锂材料锂效率的计算可以看出，含有包覆层的补锂材料锂效率发挥都明显高于未包覆的补锂材料，这主要是由于不含包覆的补锂材料在电芯生产过程中，由于活性较高，失活速率也较高，从而导致锂效率降低。
综上所述，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (11)

  1. 一种正极补锂材料，包括第一含锂化合物，所述第一含锂化合物选自化学式如式I所示的化合物中的一种或多种的组合：
    Li xA y    式I
    其中，A选自C、N、O、P、S，0<x，y≤3，且式I化合物不为Li 2O；
    所述正极补锂材料的外层包括第二含锂化合物，所述第二含锂化合物与水反应的活性低于第一含锂化合物。
  2. 如权利要求1所述的正极补锂材料，其特征在于，所述Li xA y选自LiN 3、Li 2O 2、Li 2C 2中的一种或多种的组合。
  3. 如权利要求1所述的正极补锂材料，其特征在于，所述第二含锂化合物选自Li 2CO 3、Li 3PO4、Li 2O、Li 2SO 4、亚硫酸锂、草酸锂、抗坏血酸锂中的一种或多种的组合。
  4. 如权利要求1所述的正极补锂材料，其特征在于，所述第二含锂化合物由所述第一含锂化合物经反应形成。
  5. 如权利要求1所述的正极补锂材料，其特征在于，所述正极补锂材料中，所述第二含锂化合物所占的质量百分比为1～30％，优选质量百分比为2～10％。
  6. 如权利要求1所述的正极补锂材料，其特征在于，所述正极补锂材料中，所述正极补锂材料的外层的厚度范围是0.5～100nm，优选为2～50nm。
  7. 如权利要求1所述的正极补锂材料，其特征在于，所述正极补锂材料的粒径分布范围为0.05～10um，优选为0.2～4um。
  8. 一种正极极片，包含正极集流体和位于所述正极集流体上的正极活性物质层，所述正极活性物质层包括正极活性物质、粘结剂、导电剂和如权利要求1-7任一权利要求所述的正极补锂材料。
  9. 如权利要求8所述的正极极片，其特征在于，所述粘结剂包括含氟聚烯烃类粘结剂。
  10. 如权利要求8所述的正极极片，其特征在于，所述正极补锂材料在所述正极活性物质层中的质量百分比为0.2％～10％。
  11. 一种锂离子电池，含有如权利要求8～10任一权利要求所述的正极极片。
PCT/CN2019/120547 2018-12-26 2019-11-25 一种正极补锂材料及其制备方法和用途 WO2020134777A1 (zh)

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