WO2018064907A1 - Preparation method for modified positive electrode material and lithium-ion battery - Google Patents

Preparation method for modified positive electrode material and lithium-ion battery Download PDF

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WO2018064907A1
WO2018064907A1 PCT/CN2017/093545 CN2017093545W WO2018064907A1 WO 2018064907 A1 WO2018064907 A1 WO 2018064907A1 CN 2017093545 W CN2017093545 W CN 2017093545W WO 2018064907 A1 WO2018064907 A1 WO 2018064907A1
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acid
positive electrode
ammonium
electrode material
ion battery
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PCT/CN2017/093545
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French (fr)
Chinese (zh)
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唐代春
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宁德时代新能源科技股份有限公司
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Publication of WO2018064907A1 publication Critical patent/WO2018064907A1/en

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 lithium ion batteries, and in particular to a method for preparing a modified cathode material and a lithium ion battery.
  • Lithium-ion batteries are widely used in portable electronic devices, electric vehicles, and military communications because of their high specific energy, good cycle performance, low self-discharge, and no memory effect.
  • Lithium-ion battery cathode materials are key materials that affect battery performance and cost.
  • cathode materials for lithium ion batteries mainly include spinel materials, polyanionic materials and layered materials. Layered materials, particularly high nickel layered positive electrode materials, have received wide attention due to their high specific capacity.
  • the surface structure is gradually unstable, lithium ions are easily removed from the crystal lattice, and react with water and carbon dioxide in the air, resulting in a large amount of lithium carbonate or hydroxide on the surface of the layered positive electrode material.
  • a residual base such as lithium. If the residual alkali is too high, it will easily lead to the expansion of the soft-packed battery core, and the hard-shell battery SSD will be reversed in advance, which seriously affects the service life of the soft and hard-shell batteries.
  • the existing methods for reducing the residual alkali content on the surface of the layered positive electrode material mainly include controlling the synthesis conditions to reduce the surface residual alkali content of the layered positive electrode material, adding a transition metal compound to react with a surface residual base to form a stable compound, and using an organic solvent or water to layer.
  • the positive electrode material is cleaned.
  • the Chinese patent document CN201310079543.2 filed on March 13, 2013 discloses that the lithium salt optimization synthesis process is added twice in the preparation process, and although the residual alkali content on the surface of the positive electrode material can be reduced to some extent, the operation steps are cumbersome and complicated.
  • the long synthesis time has a great influence on the electrochemical performance (the capacity after only 50 cycles is only 140 mAh/g).
  • this method adopts a high-temperature secondary sintering process, which easily causes destruction of the surface structure of the positive electrode material crystal, thereby affecting the performance of the electrochemical performance.
  • the Chinese patent document CN201410191376.5 which is filed on May 7, 2014, uses an organic solvent of one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and propylene carbonate.
  • the mixture cleans the positive electrode material, although the method can reduce the residual alkali on the surface of the positive electrode material to a certain extent, but the method is expensive, the organic solvent volatilizes seriously, and the human body is greatly damaged.
  • an object of the present invention is to provide a method for preparing a modified positive electrode material and a lithium ion battery, which can effectively reduce residual alkali on the surface of the layered positive active material.
  • the content reduces the gas production of the lithium ion battery and improves the service life of the lithium ion battery.
  • the present invention provides a method for preparing a modified positive electrode material, which comprises the steps of: layered positive active material and an acid having a boiling point of not more than 600 ° C and/or a boiling point of not more than After mixing the acid salt of the acid at 600 ° C, heating to above the boiling temperature or sublimation temperature of the acid, or heating to above the decomposition temperature, boiling temperature or sublimation temperature of the acid salt, heat treatment
  • the acid and/or acid salt becomes a gas and reacts with a residual base on the surface of the layered positive electrode active material to lower the residual alkali content, thereby obtaining a modified positive electrode material.
  • the invention provides a lithium ion battery comprising the modified positive electrode material of one aspect of the invention.
  • the preparation method of the modified positive electrode material of the invention can effectively reduce the residual alkali content of the surface of the layered positive electrode active material, and the modified positive electrode material obtained by the method can effectively reduce the production of the lithium ion battery after being applied to the lithium ion battery. Gas, improve the life of lithium-ion batteries.
  • the method for producing a modified positive electrode material according to the first aspect of the present invention comprises the steps of: laminating the layered positive electrode active material with an acid having a boiling point of not more than 600 ° C (corresponding to the "the acid” below) and/or having a small boiling point After mixing the acid salt of the acid at 600 ° C (corresponding to the "acid salt” below), heating to above the boiling temperature or sublimation temperature of the acid, or heating to the decomposition temperature of the acid salt, The heat treatment is carried out above the boiling temperature or the sublimation temperature to cause the acid and/or acid salt to become gaseous and react with the residual alkali on the surface of the layered positive active material to lower the residual alkali content, thereby obtaining a modified positive electrode material.
  • the "decomposition temperature of the acid salt” means the temperature at which the acid salt is decomposed into the corresponding acid.
  • the layered positive electrode active material is physically mixed with the acid and/or acid salt, and then heated to a boiling temperature of the acid. Or above the sublimation temperature, or heated to above the decomposition temperature, boiling temperature or sublimation temperature of the acid salt, so that the acid or acid salt becomes gaseous and sufficiently contacts and reacts with the layered positive active material. Thereby, the residual alkali on the surface of the layered positive electrode active material is consumed, and the content of the residual alkali is lowered.
  • the modified positive electrode material obtained by the method has a lower pH value, and after being applied to a lithium ion battery, the gas production of the lithium ion battery can be reduced, and the service life of the lithium ion battery can be improved.
  • the layered positive electrode active material when the layered positive electrode active material is only mixed with an acid having a boiling point of not more than 600 ° C, it may be heated to a boiling temperature or a sublimation temperature of the acid. Above, the acid is brought into a gaseous state to react with a residual base on the surface of the layered positive electrode active material.
  • the layered positive electrode active material when the layered positive electrode active material is only mixed with an acid salt of an acid having a boiling point of not more than 600 ° C, it may be heated to the acid salt. Above the boiling point temperature or sublimation temperature, the acid salt is brought into a gaseous state to react with a residual base on the surface of the layered positive electrode active material.
  • the layered positive electrode active material when the layered positive electrode active material is simultaneously mixed with an acid having a boiling point of not more than 600 ° C and an acid salt of an acid having a boiling point of not more than 600 ° C, heating is performed.
  • the temperature can be determined to react with the residual base on the surface of the layered positive electrode active material as long as both the acid and the acid salt become gaseous.
  • the layered positive electrode active material has a general formula of Li a Ni x Co y M 1-xy O 2 , 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0.95 ⁇ a ⁇ 1.1, and 0 ⁇ x + y ⁇ 1, M is selected from one or more of Mn, Al, Mg, Ti.
  • the layered positive electrode active material is selected from the group consisting of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiNi 0.6 Co 0.2 Mn 0.2 O. 2 , LiNi 0.3 Co 0.2 Mn 0.5 O 2 , LiNi 0.3 Co 0.3 Mn 0.4 O 2 , LiNi 0.4 Co 0.4 Mn 0.2 O 2 , LiNi 0.2 Co 0.4 Mn 0.2 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 Or several.
  • the total mass of the acid and/or acid salt is from 0.1% to 50% by mass of the layered positive electrode active material.
  • the acid is selected from the group consisting of oxalic acid, nitric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid, pyrophosphoric acid, and trimeric.
  • oxalic acid nitric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid, pyrophosphoric acid, and trimeric.
  • the acid is selected from the group consisting of oxalic acid.
  • the acid salt of the acid having a boiling point of not more than 600 ° C may be an ammonium salt of the acid having a boiling point of not more than 600 ° C, that is, the The acid salt can be an ammonium salt.
  • the acid salt is selected from the group consisting of ammonium oxalate, ammonium hydrogen oxalate, ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium hydrogen fluoride, ammonium bromide.
  • ammonium iodide ammonium sulfite, ammonium sulfide, ammonium hydrogen sulfide, ammonium acetate, ammonium formate, ammonium propionate, ammonium butyrate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium lactate, ammonium benzoate, ammonium acrylate, One or more of ammonium oleate.
  • the acid salt is selected from one or both of ammonium oxalate and ammonium hydrogen oxalate.
  • the acid or acid salt of the present invention acts on a residual alkali on the surface of the layered positive electrode active material, if the product after the reaction is insoluble in the electrolyte, the product adheres to the surface of the layered positive electrode active material, and the layered positive electrode active is isolated.
  • the contact between the substance and the electrolyte further suppresses the gas production of the lithium ion battery and improves the service life of the lithium ion battery.
  • PF 5 in the electrolyte has a direct influence on the gas production of the lithium ion battery.
  • the oxalic acid formed by the reaction is formed.
  • Lithium can capture two moles of PF 5 in the electrolyte to form LiPF 4 C 2 O 4 and LiPF 6 , which helps to further inhibit the gas production of the lithium ion battery and improve the service life of the lithium ion battery.
  • the heat treatment temperature is from 80 ° C to 600 ° C.
  • the heat treatment process may be directly heated to perform one-step treatment.
  • the heat treatment may be carried out in two steps.
  • the heat treatment may be first performed at a low temperature of 80 ° C to 300 ° C for a period of time, and then the temperature is raised to 400 ° C. Further heat treatment was carried out at 600 °C.
  • Step-by-step heat treatment avoids direct heat The process damages the surface structure of the layered positive active material, thereby minimizing the effect of the heat treatment temperature on the electrochemical performance of the lithium ion battery.
  • the heat treatment time is from 2 h to 72 h.
  • the heat treatment is performed in an oxygen atmosphere or an air atmosphere.
  • the residual base includes one or both of Li 2 CO 3 and LiOH.
  • a lithium ion battery according to a second aspect of the present invention includes a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film disposed on the positive electrode current collector, wherein the positive electrode film includes a modified positive electrode material,
  • the modified positive electrode material is obtained by the method for preparing the modified positive electrode material according to the first aspect of the invention.
  • the negative electrode sheet includes a negative electrode current collector and an negative electrode film disposed on the negative electrode current collector.
  • the negative electrode membrane includes a negative electrode material.
  • the specific type of the negative electrode material is not specifically limited, and can be selected according to requirements.
  • the negative electrode material may be selected from metallic lithium, and the negative electrode material may also be selected from materials capable of intercalating lithium when the electrode potential of the Li/Li + equilibrium potential is ⁇ 2V.
  • the anode material may be selected from natural graphite, artificial graphite, mesophase micro carbon sphere (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn alloy, Li-Sn- One or more of an O alloy, Sn, SnO, SnO 2 , a lithiated lithiated TiO 2 -Li 4 Ti 5 O 12 , Li-Al alloy.
  • natural graphite artificial graphite, mesophase micro carbon sphere (abbreviated as MCMB)
  • hard carbon soft carbon
  • silicon silicon-carbon composite
  • Li-Sn alloy Li-Sn- One or more of an O alloy, Sn, SnO, SnO 2 , a lithiated lithiated TiO 2 -Li 4 Ti 5 O 12 , Li-Al alloy.
  • the specific kind of the separator is not particularly limited, and may be any separator material used in the existing lithium ion battery, such as polyethylene or polypropylene. , polyvinylidene fluoride and multilayer composite films thereof, but are not limited thereto.
  • the electrolyte solution includes a lithium salt, an organic solvent, and an optional additive, wherein specific types of the additive are not specifically limited, and may be selected according to requirements.
  • the lithium salt may be selected from the group consisting of LiPF 6 , LiBF 4 , LiN(SO 2 F) 2 (abbreviated as LiFSi), LiN(CF 3 SO 2 ) 2 (abbreviated as LiTFSi), LiClO 4 , LiAsF 6 , LiB (C 2 ) One or more of O 4 ) 2 (abbreviated as LiBOB), LiBF 2 C 2 O 4 (abbreviated as LiDFOB), and LiPO 2 F 2 .
  • the organic solvent may be selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ⁇ -butyrolactone.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • BL methyl formate
  • MF methyl formate
  • MA ethyl formate
  • EA ethyl propionate
  • PP propyl propionate
  • DMSO dimethyl sulfoxide
  • TMSO sulfolane
  • MSM dimethyl sulfone
  • THF tetrahydrofuran
  • the positive active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 and oxalic acid are mixed at a mass ratio of 1:0.05, and then ball-dried and dry-mixed for 1 hour to prepare a mixture; the mixture prepared above is placed In the muffle furnace, the temperature was raised to 100 ° C under air flow, and the temperature was raised for 5 h, then the temperature was raised to 450 ° C, and the temperature was kept for 5 h, and then cooled to room temperature to obtain a modified positive electrode material.
  • the modified positive electrode material, the binder polyvinylidene fluoride and the conductive agent acetylene black are mixed at a mass ratio of 98:1:1, N-methylpyrrolidone (NMP) is added, and the mixture is stirred under a vacuum mixer until the system is uniform.
  • NMP N-methylpyrrolidone
  • the positive electrode slurry was obtained in a transparent form; the positive electrode slurry was uniformly coated on a positive electrode current collector aluminum foil having a thickness of 12 ⁇ m; the aluminum foil was air-dried at room temperature, transferred to an oven at 120 ° C for 1 hour, and then subjected to cold pressing and slitting to obtain a positive electrode. sheet.
  • the negative electrode material artificial graphite, thickener sodium carboxymethyl cellulose (CMC), binder styrene-butadiene rubber were mixed at a mass ratio of 98:1:1, deionized water was added, and the negative electrode slurry was obtained under the action of a vacuum mixer.
  • the negative electrode slurry was uniformly coated on a negative electrode current collector copper foil having a thickness of 8 ⁇ m; the copper foil was air-dried at room temperature, transferred to an oven at 120 ° C for 1 hour, and then subjected to cold pressing and slitting to obtain a negative electrode sheet.
  • a polypropylene microporous membrane was used as the separator.
  • the positive electrode sheet, the separator film and the negative electrode sheet are stacked in order, so that the separator is in a role of isolation between the positive and negative electrode sheets, and then wound to obtain a bare cell; the bare cell is placed in the outer packaging foil, The prepared electrolyte solution is injected into the dried bare cell, and subjected to vacuum encapsulation, standing, formation, shaping, and the like to obtain a lithium ion battery.
  • the preparation process of the lithium ion battery was the same as that of Example 1, except that in the preparation of the positive electrode sheet, the positive electrode active material was LiNi 0.6 Co 0.2 Mn 0.2 O 2 .
  • the preparation process of the lithium ion battery was the same as that of Example 1, except that in the preparation of the positive electrode sheet, the positive electrode active material was LiNi 0.8 Co 0.15 Al 0.05 O 2 .
  • the preparation process of the lithium ion battery was the same as that of Example 2, except that in the preparation of the positive electrode sheet, the mass ratio of LiNi 0.6 Co 0.2 Mn 0.2 O 2 to oxalic acid was 1:0.01.
  • the preparation process of the lithium ion battery was the same as in Example 2, except that in the preparation of the positive electrode sheet, the mass ratio of LiNi 0.6 Co 0.2 Mn 0.2 O 2 to oxalic acid was 1:0.5.
  • the preparation process of the lithium ion battery was the same as in Example 1, except that in the preparation of the positive electrode sheet, oxalic acid was replaced with ammonium oxalate.
  • the preparation process of the lithium ion battery was the same as that of Example 1, except that in the preparation of the positive electrode sheet, hydrochloric acid was used instead of oxalic acid.
  • the preparation process of the lithium ion battery was the same as in Example 1, except that in the preparation of the positive electrode sheet, ammonium chloride was used instead of oxalic acid.
  • the preparation process of the lithium ion battery is the same as that in the first embodiment, except that in the preparation of the positive electrode sheet, the conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 is used as the positive electrode material, and the residual alkali is not removed by heat treatment.
  • the preparation process of the lithium ion battery was the same as that in Example 2, except that in the preparation of the positive electrode sheet, LiNi 0.6 Co 0.2 Mn 0.2 O 2 was used as the positive electrode material, and the residual alkali was not removed by heat treatment.
  • the preparation process of the lithium ion battery was the same as that in Example 3, except that in the preparation of the positive electrode sheet, LiNi 0.8 Co 0.15 Al 0.05 O 2 was used as the positive electrode material, and the residual alkali was not removed by heat treatment.
  • the preparation process of the lithium ion battery was the same as that of Example 2, except that in the preparation of the positive electrode sheet, the mass ratio of LiNi 0.6 Co 0.2 Mn 0.2 O 2 to oxalic acid was 1:0.6.
  • the lithium ion battery is charged at a constant current of 1 C to a voltage of 4.2 V, and then charged at a constant voltage of 4.2 V until the current reaches 0.05 C. At this time, the volume of the lithium ion battery is tested by the drainage method and recorded as V 0 . Then, the lithium ion battery was placed in an oven at 60 ° C for two months, and the volume of the ion battery was measured by the drainage method and recorded as V 1 .
  • the volume expansion ratio (%) of the lithium ion battery after storage at 60 ° C for two months [(V 1 - V 0 ) / V 0 ] ⁇ 100%.
  • the lithium ion battery was subjected to a 1 C constant current charge and discharge cycle at 280 V for 200 weeks at 60 ° C, and finally the capacity retention of the lithium ion battery was calculated.
  • Example 1-8 From the correlation data analysis of Table 1, it is known that the acid salt having an boiling point of not more than 600 ° C or an acid having a boiling point of not more than 600 ° C in Example 1-8 reduces the residual alkali content of the surface of the layered positive electrode active material, lithium ion battery
  • the volume expansion ratio after storage at 60 ° C for two months was significantly improved compared to Comparative Examples 1-3.
  • Example 2 Examples 4-5 and Comparative Example 4
  • the acid salt of the acid having a boiling point of not more than 600 ° C or an acid having a boiling point of not more than 600 ° C in Examples 1-8 can reduce the residual alkali content on the surface of the layered positive electrode active material, and the appropriate amount of acid or acid salt is not It may deteriorate the cycle performance and even improve the cycle performance, but referring to Comparative Example 4, it is known that excessive acid or acid salt has a significant deterioration effect on the cycle performance.

Abstract

A preparation method for a modified positive electrode material and a lithium-ion battery. The preparation method for the modified positive electrode material comprises the steps of: mixing a layered positive electrode active substance with an acid of which the boiling point is no greater than 600 °C and/or an acid salt of the acid of which the boiling point is no greater than 600 °C, then heating beyond the boiling point temperature or sublimation temperature of the acid, or heating beyond the decomposition temperature, the boiling point temperature, or the sublimation temperature of the acidic salt for heat processing, thereby allowing the acid and/or the acidic salt to transition into the gaseous state and to react with any residual alkaline on the surface of the layered positive electrode active substance, thus reducing the content of the residual alkaline, and producing the modified positive electrode material. When the modified positive electrode material produced per the present method is applied in a lithium-ion battery, gas production of the lithium-ion battery is reduced, and the service life of the lithium-ion battery is increased.

Description

改性正极材料的制备方法及锂离子电池Method for preparing modified cathode material and lithium ion battery 技术领域Technical field
本发明涉及锂离子电池领域，具体涉及一种改性正极材料的制备方法及锂离子电池。The invention relates to the field of lithium ion batteries, and in particular to a method for preparing a modified cathode material and a lithium ion battery.
背景技术Background technique
锂离子电池因具有比能量高、循环性能好、自放电小、无记忆效应等优点而广泛应用于便携式电子设备、电动车及军用通信等领域。锂离子电池正极材料是影响电池性能和成本的关键材料。目前锂离子电池正极材料主要包括尖晶石材料、聚阴离子型材料和层状材料。层状材料，特别是高镍层状正极材料以其比容量高而受到广泛关注。Lithium-ion batteries are widely used in portable electronic devices, electric vehicles, and military communications because of their high specific energy, good cycle performance, low self-discharge, and no memory effect. Lithium-ion battery cathode materials are key materials that affect battery performance and cost. At present, cathode materials for lithium ion batteries mainly include spinel materials, polyanionic materials and layered materials. Layered materials, particularly high nickel layered positive electrode materials, have received wide attention due to their high specific capacity.
层状正极材料随着镍含量的增加，表面结构逐渐不稳定，锂离子容易从晶格中脱出，并与空气中的水和二氧化碳反应，导致层状正极材料表面存在大量的碳酸锂或氢氧化锂等残余碱。残余碱过高，容易导致软包电芯产气鼓胀，硬壳电芯SSD提前翻转，严重影响了软包和硬壳电芯的使用寿命。As the nickel content increases, the surface structure is gradually unstable, lithium ions are easily removed from the crystal lattice, and react with water and carbon dioxide in the air, resulting in a large amount of lithium carbonate or hydroxide on the surface of the layered positive electrode material. A residual base such as lithium. If the residual alkali is too high, it will easily lead to the expansion of the soft-packed battery core, and the hard-shell battery SSD will be reversed in advance, which seriously affects the service life of the soft and hard-shell batteries.
现有降低层状正极材料表面残余碱含量的方法主要有控制合成条件降低层状正极材料的表面残余碱含量、添加过渡金属化合物与表面残余碱反应生成稳定化合物、采用有机溶剂或水对层状正极材料进行清洗。例如2013年3月13日申请的中国专利文献CN201310079543.2公开了在制备过程中分两次加入锂盐优化合成工艺，虽然能够一定程度上降低正极材料表面残余碱含量，但操作步骤繁琐复杂，合成时间长，对电化学性能有很大影响(其循环50次后的容量只有140mAh/g)。又例如2012年9月15日申请的中国专利文献CN201210359842.7公开了在高镍正极材料LiNixCoyMzO2(其中，0.6≤x≤1，0≤y≤0.4,0≤z≤0.4，且x+y+z＝1)的表面均匀包覆锂离子导体化合物LiAlO2、Li4Ti5O12、Li2ZrO3中的一种或多种，该方法不仅消耗了残余碱，而且包覆层具有高的锂离子电导率，有利于锂离子在电极界面的传输。但是该方法采用高温二次烧结工艺，容易造成正极材料晶体表面结构的破坏，从 而影响电化学性能的发挥。再例如2014年5月7日申请的中国专利文献CN201410191376.5采用有机溶剂为碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸丙烯酯中的一种或两种以上的混合物清洗正极材料，虽然该方法一定程度上能够降低正极材料表面残余碱，但该方法价格昂贵，有机溶剂挥发严重，对人体伤害大。The existing methods for reducing the residual alkali content on the surface of the layered positive electrode material mainly include controlling the synthesis conditions to reduce the surface residual alkali content of the layered positive electrode material, adding a transition metal compound to react with a surface residual base to form a stable compound, and using an organic solvent or water to layer. The positive electrode material is cleaned. For example, the Chinese patent document CN201310079543.2 filed on March 13, 2013 discloses that the lithium salt optimization synthesis process is added twice in the preparation process, and although the residual alkali content on the surface of the positive electrode material can be reduced to some extent, the operation steps are cumbersome and complicated. The long synthesis time has a great influence on the electrochemical performance (the capacity after only 50 cycles is only 140 mAh/g). For example, Chinese patent document CN201210359842.7, filed on September 15, 2012, discloses a high nickel positive electrode material LiNi x Co y M z O 2 (where 0.6 ≤ x ≤ 1, 0 ≤ y ≤ 0.4, 0 ≤ z ≤ 0.4, and the surface of x+y+z=1) uniformly coats one or more of the lithium ion conductor compounds LiAlO 2 , Li 4 Ti 5 O 12 , Li 2 ZrO 3 , which not only consumes residual alkali, Moreover, the cladding layer has high lithium ion conductivity, which facilitates the transport of lithium ions at the electrode interface. However, this method adopts a high-temperature secondary sintering process, which easily causes destruction of the surface structure of the positive electrode material crystal, thereby affecting the performance of the electrochemical performance. For example, the Chinese patent document CN201410191376.5, which is filed on May 7, 2014, uses an organic solvent of one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and propylene carbonate. The mixture cleans the positive electrode material, although the method can reduce the residual alkali on the surface of the positive electrode material to a certain extent, but the method is expensive, the organic solvent volatilizes seriously, and the human body is greatly damaged.
发明内容Summary of the invention
鉴于背景技术中存在的问题，本发明的目的在于提供一种改性正极材料的制备方法及锂离子电池，所述改性正极材料的制备方法能够有效地降低层状正极活性物质表面的残余碱含量，降低锂离子电池的产气，提高锂离子电池的使用寿命。In view of the problems in the prior art, an object of the present invention is to provide a method for preparing a modified positive electrode material and a lithium ion battery, which can effectively reduce residual alkali on the surface of the layered positive active material. The content reduces the gas production of the lithium ion battery and improves the service life of the lithium ion battery.
为了达到上述目的，在本发明的一方面，本发明提供了一种改性正极材料的制备方法，其包括步骤：将层状正极活性物质与沸点不大于600℃的酸和/或沸点不大于600℃的酸的酸式盐混合后，加热至所述酸的沸点温度或升华温度之上，或加热至所述酸式盐的分解温度、沸点温度或升华温度之上进行热处理，使所述酸和/或酸式盐变成气体与所述层状正极活性物质表面的残余碱反应，降低残余碱的含量，即得到改性正极材料。In order to achieve the above object, in one aspect of the invention, the present invention provides a method for preparing a modified positive electrode material, which comprises the steps of: layered positive active material and an acid having a boiling point of not more than 600 ° C and/or a boiling point of not more than After mixing the acid salt of the acid at 600 ° C, heating to above the boiling temperature or sublimation temperature of the acid, or heating to above the decomposition temperature, boiling temperature or sublimation temperature of the acid salt, heat treatment The acid and/or acid salt becomes a gas and reacts with a residual base on the surface of the layered positive electrode active material to lower the residual alkali content, thereby obtaining a modified positive electrode material.
在本发明的另一方面，本发明提供了一种锂离子电池，其包括本发明一方面所述的改性正极材料。In another aspect of the invention, the invention provides a lithium ion battery comprising the modified positive electrode material of one aspect of the invention.
相对于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
本发明改性正极材料的制备方法能够有效地降低层状正极活性物质表面的残余碱含量，当采用此方法得到的改性正极材料应用到锂离子电池中后，能够有效降低锂离子电池的产气，提高锂离子电池的使用寿命。The preparation method of the modified positive electrode material of the invention can effectively reduce the residual alkali content of the surface of the layered positive electrode active material, and the modified positive electrode material obtained by the method can effectively reduce the production of the lithium ion battery after being applied to the lithium ion battery. Gas, improve the life of lithium-ion batteries.
具体实施方式detailed description
下面详细说明根据本发明的改性正极材料的制备方法及锂离子电池。Hereinafter, a method of preparing a modified positive electrode material and a lithium ion battery according to the present invention will be described in detail.
首先说明根据本发明第一方面的改性正极材料的制备方法。First, a method of preparing the modified positive electrode material according to the first aspect of the present invention will be explained.
根据本发明第一方面的改性正极材料的制备方法包括步骤：将层状正极活性物质与沸点不大于600℃的酸(对应下面的“所述酸”)和/或沸点不大 于600℃的酸的酸式盐(对应下面的“所述酸式盐”)混合后，加热至所述酸的沸点温度或升华温度之上，或加热至所述酸式盐的分解温度、沸点温度或升华温度之上进行热处理，使所述酸和/或酸式盐变成气态与所述层状正极活性物质表面的残余碱反应，降低残余碱的含量，即得到改性正极材料。其中，“所述酸式盐的分解温度”是指酸式盐分解为对应的酸的温度。The method for producing a modified positive electrode material according to the first aspect of the present invention comprises the steps of: laminating the layered positive electrode active material with an acid having a boiling point of not more than 600 ° C (corresponding to the "the acid" below) and/or having a small boiling point After mixing the acid salt of the acid at 600 ° C (corresponding to the "acid salt" below), heating to above the boiling temperature or sublimation temperature of the acid, or heating to the decomposition temperature of the acid salt, The heat treatment is carried out above the boiling temperature or the sublimation temperature to cause the acid and/or acid salt to become gaseous and react with the residual alkali on the surface of the layered positive active material to lower the residual alkali content, thereby obtaining a modified positive electrode material. Here, the "decomposition temperature of the acid salt" means the temperature at which the acid salt is decomposed into the corresponding acid.
在根据本发明第一方面所述的改性正极材料的制备方法中，通过将所述层状正极活性物质与所述酸和/或酸式盐物理混合，然后加热至所述酸的沸点温度或升华温度之上，或加热至所述酸式盐的分解温度、沸点温度或升华温度之上，使所述酸或者酸式盐变成气态充分与所述层状正极活性物质接触并反应，从而消耗掉层状正极活性物质表面的残余碱，降低残余碱的含量。通过此方法得到的改性正极材料具有较低的pH值，将其应用到锂离子电池中后，能够降低锂离子电池的产气，提高锂离子电池的使用寿命。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the layered positive electrode active material is physically mixed with the acid and/or acid salt, and then heated to a boiling temperature of the acid. Or above the sublimation temperature, or heated to above the decomposition temperature, boiling temperature or sublimation temperature of the acid salt, so that the acid or acid salt becomes gaseous and sufficiently contacts and reacts with the layered positive active material. Thereby, the residual alkali on the surface of the layered positive electrode active material is consumed, and the content of the residual alkali is lowered. The modified positive electrode material obtained by the method has a lower pH value, and after being applied to a lithium ion battery, the gas production of the lithium ion battery can be reduced, and the service life of the lithium ion battery can be improved.
在根据本发明第一方面所述的改性正极材料的制备方法中，当将层状正极活性物质仅与沸点不大于600℃的酸混合时，可加热至所述酸的沸点温度或升华温度之上，使所述酸变成气态与层状正极活性物质表面的残余碱进行反应。In the method for producing a modified positive electrode material according to the first aspect of the present invention, when the layered positive electrode active material is only mixed with an acid having a boiling point of not more than 600 ° C, it may be heated to a boiling temperature or a sublimation temperature of the acid. Above, the acid is brought into a gaseous state to react with a residual base on the surface of the layered positive electrode active material.
在根据本发明第一方面所述的改性正极材料的制备方法中，当将层状正极活性物质仅与沸点不大于600℃的酸的酸式盐混合时，可加热至所述酸式盐的沸点温度或升华温度之上，使所述酸式盐变成气态与层状正极活性物质表面的残余碱进行反应。In the method for producing a modified positive electrode material according to the first aspect of the present invention, when the layered positive electrode active material is only mixed with an acid salt of an acid having a boiling point of not more than 600 ° C, it may be heated to the acid salt. Above the boiling point temperature or sublimation temperature, the acid salt is brought into a gaseous state to react with a residual base on the surface of the layered positive electrode active material.
在根据本发明第一方面所述的改性正极材料的制备方法中，将层状正极活性物质同时与沸点不大于600℃的酸以及沸点不大于600℃的酸的酸式盐混合时，加热的温度只要保证所述酸和所述酸式盐均变成气态能与层状正极活性物质表面的残余碱进行反应。In the method for producing a modified positive electrode material according to the first aspect of the present invention, when the layered positive electrode active material is simultaneously mixed with an acid having a boiling point of not more than 600 ° C and an acid salt of an acid having a boiling point of not more than 600 ° C, heating is performed. The temperature can be determined to react with the residual base on the surface of the layered positive electrode active material as long as both the acid and the acid salt become gaseous.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述层状正极活性物质的通式为LiaNixCoyM1-x-yO2，0≤x＜1，0≤y≤1，0.95≤a≤1.1，且0≤x+y≤1，M选自Mn、Al、Mg、Ti中的一种或几种。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the layered positive electrode active material has a general formula of Li a Ni x Co y M 1-xy O 2 , 0 ≤ x < 1, 0 ≤ y ≤ 1, 0.95 ≤ a ≤ 1.1, and 0 ≤ x + y ≤ 1, M is selected from one or more of Mn, Al, Mg, Ti.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述层状正极活性物质选自LiNi1/3Co1/3Mn1/3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.3Co0.2Mn0.5O2、LiNi0.3Co0.3Mn0.4O2、LiNi0.4Co0.4Mn0.2O2、LiNi0.2Co0.4Mn0.2O2、 LiNi0.8Co0.15Al0.05O2中的一种或几种。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the layered positive electrode active material is selected from the group consisting of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiNi 0.6 Co 0.2 Mn 0.2 O. 2 , LiNi 0.3 Co 0.2 Mn 0.5 O 2 , LiNi 0.3 Co 0.3 Mn 0.4 O 2 , LiNi 0.4 Co 0.4 Mn 0.2 O 2 , LiNi 0.2 Co 0.4 Mn 0.2 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 Or several.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述酸和/或酸式盐的总质量为所述层状正极活性物质的质量的0.1％～50％。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the total mass of the acid and/or acid salt is from 0.1% to 50% by mass of the layered positive electrode active material.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述酸选自草酸、硝酸、盐酸、氢氟酸、氢溴酸、氢碘酸、亚硫酸、焦磷酸、三聚磷酸、偏磷酸、硫化氢、醋酸、甲酸、丙酸、丁酸、异丁酸、磷酸、乳酸、苯甲酸、丙烯酸、油酸中的一种或几种。优选地，所述酸选自草酸。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the acid is selected from the group consisting of oxalic acid, nitric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid, pyrophosphoric acid, and trimeric. One or more of phosphoric acid, metaphosphoric acid, hydrogen sulfide, acetic acid, formic acid, propionic acid, butyric acid, isobutyric acid, phosphoric acid, lactic acid, benzoic acid, acrylic acid, and oleic acid. Preferably, the acid is selected from the group consisting of oxalic acid.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述沸点不大于600℃的酸的酸式盐可为所述沸点不大于600℃的酸的铵盐，即所述酸式盐可为铵盐。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the acid salt of the acid having a boiling point of not more than 600 ° C may be an ammonium salt of the acid having a boiling point of not more than 600 ° C, that is, the The acid salt can be an ammonium salt.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述酸式盐选自草酸铵、草酸氢铵、硝酸铵、氯化铵、氟化铵、氟化氢铵、溴化铵、碘化铵、亚硫酸铵、硫化铵、硫化氢铵、醋酸铵、甲酸铵、丙酸铵、丁酸铵、磷酸二氢铵、磷酸氢二铵、乳酸铵、苯甲酸铵、丙烯酸铵、油酸铵中的一种或几种。优选地，所述酸式盐选自草酸铵、草酸氢铵中的一种或两种。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the acid salt is selected from the group consisting of ammonium oxalate, ammonium hydrogen oxalate, ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium hydrogen fluoride, ammonium bromide. , ammonium iodide, ammonium sulfite, ammonium sulfide, ammonium hydrogen sulfide, ammonium acetate, ammonium formate, ammonium propionate, ammonium butyrate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium lactate, ammonium benzoate, ammonium acrylate, One or more of ammonium oleate. Preferably, the acid salt is selected from one or both of ammonium oxalate and ammonium hydrogen oxalate.
当本发明的酸或者酸式盐与层状正极活性物质表面的残余碱作用时，如果反应后的产物不溶于电解液，该产物会附着在层状正极活性物质的表面，隔离层状正极活性物质与电解液的接触，从而进一步抑制锂离子电池的产气，提高了锂离子电池的使用寿命。此外，电解液中的PF5对锂离子电池的产气有直接影响，当用草酸、草酸铵、草酸氢铵中的一种或几种对层状正极活性物质进行处理时，反应生成的草酸锂能够捕获电解液中两摩尔的PF5反应生成LiPF4C2O4和LiPF6，从而有助于进一步抑制锂离子电池的产气，提高锂离子电池的使用寿命。When the acid or acid salt of the present invention acts on a residual alkali on the surface of the layered positive electrode active material, if the product after the reaction is insoluble in the electrolyte, the product adheres to the surface of the layered positive electrode active material, and the layered positive electrode active is isolated. The contact between the substance and the electrolyte further suppresses the gas production of the lithium ion battery and improves the service life of the lithium ion battery. In addition, PF 5 in the electrolyte has a direct influence on the gas production of the lithium ion battery. When the layered positive electrode active material is treated with one or more of oxalic acid, ammonium oxalate or ammonium hydrogen oxalate, the oxalic acid formed by the reaction is formed. Lithium can capture two moles of PF 5 in the electrolyte to form LiPF 4 C 2 O 4 and LiPF 6 , which helps to further inhibit the gas production of the lithium ion battery and improve the service life of the lithium ion battery.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述热处理温度为80℃～600℃。In the method of producing a modified positive electrode material according to the first aspect of the present invention, the heat treatment temperature is from 80 ° C to 600 ° C.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述热处理工艺可直接加热进行一步处理。In the method of producing a modified positive electrode material according to the first aspect of the present invention, the heat treatment process may be directly heated to perform one-step treatment.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述热处理也可分两步进行，例如可首先在80℃～300℃低温下热处理一段时间，然后升温至400℃～600℃进行进一步热处理。分步热处理的方法可避免了直接热处 理过程对层状正极活性物质表面结构的破坏，从而将热处理温度对锂离子电池的电化学性能的影响降到最低。In the method for preparing a modified positive electrode material according to the first aspect of the present invention, the heat treatment may be carried out in two steps. For example, the heat treatment may be first performed at a low temperature of 80 ° C to 300 ° C for a period of time, and then the temperature is raised to 400 ° C. Further heat treatment was carried out at 600 °C. Step-by-step heat treatment avoids direct heat The process damages the surface structure of the layered positive active material, thereby minimizing the effect of the heat treatment temperature on the electrochemical performance of the lithium ion battery.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述热处理的时间为2h～72h。In the method for producing a modified positive electrode material according to the first aspect of the present invention, the heat treatment time is from 2 h to 72 h.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述热处理在氧气气氛或空气气氛中进行。In the method of producing a modified positive electrode material according to the first aspect of the present invention, the heat treatment is performed in an oxygen atmosphere or an air atmosphere.
在根据本发明第一方面所述的改性正极材料的制备方法中，所述残余碱包括Li2CO3、LiOH中的一种或两种。In the method of producing a modified positive electrode material according to the first aspect of the present invention, the residual base includes one or both of Li 2 CO 3 and LiOH.
其次说明根据本发明第二方面的锂离子电池。Next, a lithium ion battery according to a second aspect of the present invention will be described.
根据本发明第二方面所述的锂离子电池包括正极片、负极片、隔离膜、电解液。A lithium ion battery according to a second aspect of the present invention includes a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte.
在根据本发明第二方面所述的锂离子电池中，所述正极片包括正极集流体和设置于所述正极集流体上的正极膜片，其中，所述正极膜片包括改性正极材料，所述改性正极材料通过本发明第一方面所述的改性正极材料的制备方法得到。In the lithium ion battery according to the second aspect of the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode film disposed on the positive electrode current collector, wherein the positive electrode film includes a modified positive electrode material, The modified positive electrode material is obtained by the method for preparing the modified positive electrode material according to the first aspect of the invention.
在根据本发明第二方面所述的锂离子电池中，所述负极片包括负极集流体和设置于所述负极集流体上的负极膜片。所述负极膜片包括负极材料。其中，所述负极材料的具体种类均不受到具体的限制，可根据需求进行选择。所述负极材料可以选自金属锂，所述负极材料也可以选自相对于Li/Li+平衡电位的电极电位＜2V时可以嵌入锂的材料。具体地，所述负极材料可选自天然石墨、人造石墨、中间相微碳球(简称为MCMB)、硬碳、软碳、硅、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO2、尖晶石结构的锂化TiO2-Li4Ti5O12、Li-Al合金中的一种或几种。In the lithium ion battery according to the second aspect of the present invention, the negative electrode sheet includes a negative electrode current collector and an negative electrode film disposed on the negative electrode current collector. The negative electrode membrane includes a negative electrode material. The specific type of the negative electrode material is not specifically limited, and can be selected according to requirements. The negative electrode material may be selected from metallic lithium, and the negative electrode material may also be selected from materials capable of intercalating lithium when the electrode potential of the Li/Li + equilibrium potential is <2V. Specifically, the anode material may be selected from natural graphite, artificial graphite, mesophase micro carbon sphere (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn alloy, Li-Sn- One or more of an O alloy, Sn, SnO, SnO 2 , a lithiated lithiated TiO 2 -Li 4 Ti 5 O 12 , Li-Al alloy.
在根据本发明第二方面所述的锂离子电池中，所述隔离膜的具体种类并不受到具体的限制，可以是现有锂离子电池中使用的任何隔离膜材料，例如聚乙烯、聚丙烯、聚偏氟乙烯以及它们的多层复合膜，但不仅限于这些。In the lithium ion battery according to the second aspect of the present invention, the specific kind of the separator is not particularly limited, and may be any separator material used in the existing lithium ion battery, such as polyethylene or polypropylene. , polyvinylidene fluoride and multilayer composite films thereof, but are not limited thereto.
在根据本发明第二方面所述的锂离子电池中，所述电解液包括锂盐、有机溶剂以及可选的添加剂，其中所述添加剂的具体种类均不受到具体的限制，可根据需求进行选择。所述锂盐可选自LiPF6、LiBF4、LiN(SO2F)2(简 写为LiFSi)、LiN(CF3SO2)2(简写为LiTFSi)、LiClO4、LiAsF6、LiB(C2O4)2(简写为LiBOB)、LiBF2C2O4(简写为LiDFOB)、LiPO2F2中的一种或几种。所述有机溶剂可选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、γ-丁内酯(BL)、甲酸甲酯(MF)、甲酸乙酯(MA)、乙酸乙酯(EA)、丙酸乙酯(EP)、丙酸丙酯(PP)、二甲基亚砜(DMSO)、环丁砜(TMSO)、二甲基砜(MSM)、四氢呋喃(THF)中的一种或几种。In the lithium ion battery according to the second aspect of the present invention, the electrolyte solution includes a lithium salt, an organic solvent, and an optional additive, wherein specific types of the additive are not specifically limited, and may be selected according to requirements. . The lithium salt may be selected from the group consisting of LiPF 6 , LiBF 4 , LiN(SO 2 F) 2 (abbreviated as LiFSi), LiN(CF 3 SO 2 ) 2 (abbreviated as LiTFSi), LiClO 4 , LiAsF 6 , LiB (C 2 ) One or more of O 4 ) 2 (abbreviated as LiBOB), LiBF 2 C 2 O 4 (abbreviated as LiDFOB), and LiPO 2 F 2 . The organic solvent may be selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), γ-butyrolactone. (BL), methyl formate (MF), ethyl formate (MA), ethyl acetate (EA), ethyl propionate (EP), propyl propionate (PP), dimethyl sulfoxide (DMSO), One or more of sulfolane (TMSO), dimethyl sulfone (MSM), tetrahydrofuran (THF).
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。在以下实施例中，所用到的材料、试剂以及仪器如没有特殊说明，均可从商业途径购买获得。The present application is further illustrated below in conjunction with the embodiments. It is to be understood that the examples are not intended to limit the scope of the application. In the following examples, the materials, reagents, and instruments used were commercially available unless otherwise specified.
实施例1Example 1
(1)正极片的制备(1) Preparation of positive electrode sheet
将正极活性物质LiNi1/3Co1/3Mn1/3O2和草酸按质量比为1:0.05的比例混合，然后球磨干混1h制得混合料；将上述制得的混合料置于马弗炉中，在通入空气的条件下升温至100℃，保温5h，然后升温至450℃，保温5h，之后冷却到室温，即得到改性正极材料。The positive active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 and oxalic acid are mixed at a mass ratio of 1:0.05, and then ball-dried and dry-mixed for 1 hour to prepare a mixture; the mixture prepared above is placed In the muffle furnace, the temperature was raised to 100 ° C under air flow, and the temperature was raised for 5 h, then the temperature was raised to 450 ° C, and the temperature was kept for 5 h, and then cooled to room temperature to obtain a modified positive electrode material.
将上述改性正极材料、粘结剂聚偏氟乙烯、导电剂乙炔黑按照质量比98:1:1进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系成均一透明状，获得正极浆料；将正极浆料均匀涂覆于厚度为12μm的正极集流体铝箔上；将铝箔在室温晾干后转移至120℃烘箱干燥1h，然后经过冷压、分切得到正极片。The modified positive electrode material, the binder polyvinylidene fluoride and the conductive agent acetylene black are mixed at a mass ratio of 98:1:1, N-methylpyrrolidone (NMP) is added, and the mixture is stirred under a vacuum mixer until the system is uniform. The positive electrode slurry was obtained in a transparent form; the positive electrode slurry was uniformly coated on a positive electrode current collector aluminum foil having a thickness of 12 μm; the aluminum foil was air-dried at room temperature, transferred to an oven at 120 ° C for 1 hour, and then subjected to cold pressing and slitting to obtain a positive electrode. sheet.
(2)负极片的制备(2) Preparation of negative electrode sheet
将负极材料人造石墨、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶按照质量比98:1:1进行混合，加入去离子水，在真空搅拌机作用下获得负极浆料；将负极浆料均匀涂覆在厚度为8μm的负极集流体铜箔上；将铜箔在室温晾干后转移至120℃烘箱干燥1h，然后经过冷压、分切得到负极片。The negative electrode material artificial graphite, thickener sodium carboxymethyl cellulose (CMC), binder styrene-butadiene rubber were mixed at a mass ratio of 98:1:1, deionized water was added, and the negative electrode slurry was obtained under the action of a vacuum mixer. The negative electrode slurry was uniformly coated on a negative electrode current collector copper foil having a thickness of 8 μm; the copper foil was air-dried at room temperature, transferred to an oven at 120 ° C for 1 hour, and then subjected to cold pressing and slitting to obtain a negative electrode sheet.
(3)电解液的制备(3) Preparation of electrolyte
在含水量<10ppm的氩气气氛手套箱中，将EC、PC、DEC按照体积比 为EC:PC:DEC＝1:1:1进行混合，接着将充分干燥的锂盐LiPF6溶解于混合有机溶剂中，混合均匀后获得电解液。In an argon atmosphere glove box having a water content of <10 ppm, EC, PC, and DEC were mixed at a volume ratio of EC:PC:DEC = 1:1:1, followed by dissolving the sufficiently dried lithium salt LiPF 6 in a mixed organic In the solvent, the mixture was uniformly mixed to obtain an electrolytic solution.
(4)隔离膜的制备(4) Preparation of separator
以聚丙烯微孔膜作为隔离膜。A polypropylene microporous membrane was used as the separator.
(5)锂离子电池的制备(5) Preparation of lithium ion battery
将正极片、隔离膜、负极片按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕得到裸电芯；将裸电芯置于外包装箔中，将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、整形等工序，获得锂离子电池。The positive electrode sheet, the separator film and the negative electrode sheet are stacked in order, so that the separator is in a role of isolation between the positive and negative electrode sheets, and then wound to obtain a bare cell; the bare cell is placed in the outer packaging foil, The prepared electrolyte solution is injected into the dried bare cell, and subjected to vacuum encapsulation, standing, formation, shaping, and the like to obtain a lithium ion battery.
实施例2Example 2
锂离子电池的制备过程同实施例1，区别在于：在正极片的制备中，正极活性物质为LiNi0.6Co0.2Mn0.2O2。The preparation process of the lithium ion battery was the same as that of Example 1, except that in the preparation of the positive electrode sheet, the positive electrode active material was LiNi 0.6 Co 0.2 Mn 0.2 O 2 .
实施例3Example 3
锂离子电池的制备过程同实施例1，区别在于：在正极片的制备中，正极活性物质为LiNi0.8Co0.15Al0.05O2。The preparation process of the lithium ion battery was the same as that of Example 1, except that in the preparation of the positive electrode sheet, the positive electrode active material was LiNi 0.8 Co 0.15 Al 0.05 O 2 .
实施例4Example 4
锂离子电池的制备过程同实施例2，区别在于：在正极片的制备中，LiNi0.6Co0.2Mn0.2O2与草酸的质量比为1:0.01。The preparation process of the lithium ion battery was the same as that of Example 2, except that in the preparation of the positive electrode sheet, the mass ratio of LiNi 0.6 Co 0.2 Mn 0.2 O 2 to oxalic acid was 1:0.01.
实施例5Example 5
锂离子电池的制备过程同实施例2，区别在于：在正极片的制备中，LiNi0.6Co0.2Mn0.2O2与草酸的质量比为1:0.5。The preparation process of the lithium ion battery was the same as in Example 2, except that in the preparation of the positive electrode sheet, the mass ratio of LiNi 0.6 Co 0.2 Mn 0.2 O 2 to oxalic acid was 1:0.5.
实施例6Example 6
锂离子电池的制备过程同实施例1，区别在于：在正极片的制备中，用草酸铵替代草酸。 The preparation process of the lithium ion battery was the same as in Example 1, except that in the preparation of the positive electrode sheet, oxalic acid was replaced with ammonium oxalate.
实施例7Example 7
锂离子电池的制备过程同实施例1，区别在于：在正极片的制备中，用盐酸替代草酸。The preparation process of the lithium ion battery was the same as that of Example 1, except that in the preparation of the positive electrode sheet, hydrochloric acid was used instead of oxalic acid.
实施例8Example 8
锂离子电池的制备过程同实施例1，区别在于：在正极片的制备中，用氯化铵替代草酸。The preparation process of the lithium ion battery was the same as in Example 1, except that in the preparation of the positive electrode sheet, ammonium chloride was used instead of oxalic acid.
对比例1Comparative example 1
锂离子电池的制备过程同实施例1，区别在于：在正极片的制备中，以常规LiNi1/3Co1/3Mn1/3O2为正极材料，未进行热处理消除残余碱。The preparation process of the lithium ion battery is the same as that in the first embodiment, except that in the preparation of the positive electrode sheet, the conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 is used as the positive electrode material, and the residual alkali is not removed by heat treatment.
对比例2Comparative example 2
锂离子电池的制备过程同实施例2，区别在于：在正极片的制备中，以LiNi0.6Co0.2Mn0.2O2为正极材料，未进行热处理消除残余碱。The preparation process of the lithium ion battery was the same as that in Example 2, except that in the preparation of the positive electrode sheet, LiNi 0.6 Co 0.2 Mn 0.2 O 2 was used as the positive electrode material, and the residual alkali was not removed by heat treatment.
对比例3Comparative example 3
锂离子电池的制备过程同实施例3，区别在于：在正极片的制备中，以LiNi0.8Co0.15Al0.05O2为正极材料，未进行热处理消除残余碱。The preparation process of the lithium ion battery was the same as that in Example 3, except that in the preparation of the positive electrode sheet, LiNi 0.8 Co 0.15 Al 0.05 O 2 was used as the positive electrode material, and the residual alkali was not removed by heat treatment.
对比例4Comparative example 4
锂离子电池的制备过程同实施例2，区别在于：在正极片的制备中，LiNi0.6Co0.2Mn0.2O2与草酸的质量比为1:0.6。The preparation process of the lithium ion battery was the same as that of Example 2, except that in the preparation of the positive electrode sheet, the mass ratio of LiNi 0.6 Co 0.2 Mn 0.2 O 2 to oxalic acid was 1:0.6.
接下来说明锂离子电池的测试过程。Next, the test process of the lithium ion battery will be described.
(1)锂离子电池的高温存储性能(1) High-temperature storage performance of lithium-ion batteries
在25℃下，将锂离子电池以1C恒流充电至电压为4.2V，然后以4.2V恒压充电至电流为到0.05C，此时采用排水法测试锂离子电池的体积并记为V0；然后将锂离子电池置于60℃烘箱中存储两个月后取出，采用排水法测试此时离子电池的体积并记为V1。 At 25 ° C, the lithium ion battery is charged at a constant current of 1 C to a voltage of 4.2 V, and then charged at a constant voltage of 4.2 V until the current reaches 0.05 C. At this time, the volume of the lithium ion battery is tested by the drainage method and recorded as V 0 . Then, the lithium ion battery was placed in an oven at 60 ° C for two months, and the volume of the ion battery was measured by the drainage method and recorded as V 1 .
锂离子电池60℃存储两个月后的体积膨胀率(％)＝[(V1-V0)/V0]×100％。The volume expansion ratio (%) of the lithium ion battery after storage at 60 ° C for two months = [(V 1 - V 0 ) / V 0 ] × 100%.
(2)锂离子电池的高温循环性能(2) High temperature cycle performance of lithium ion battery
在60℃下，将锂离子电池在2.8V～4.2V之间以1C恒流充放电循环进行200周，最后计算锂离子电池的容量保持率。The lithium ion battery was subjected to a 1 C constant current charge and discharge cycle at 280 V for 200 weeks at 60 ° C, and finally the capacity retention of the lithium ion battery was calculated.
表1实施例1-8和对比例1-4的性能测试结果Table 1 Performance test results of Examples 1-8 and Comparative Examples 1-4
Figure PCTCN2017093545-appb-000001
Figure PCTCN2017093545-appb-000001
从表1的相关数据分析可知，实施例1-8中采用沸点不大于600℃的酸或沸点不大于600℃的酸的酸式盐降低层状正极活性物质表面的残余碱含量，锂离子电池在60℃存储两个月后的体积膨胀率较对比例1-3得到了明显改善。在实施例2、实施例4-5与对比例4的比较中可以看出，随着草酸含量的增加，锂离子电池存储后的体积膨胀率降低，但锂离子电池多次循环后的容量保持率也随之降低。即实施例1-8中采用沸点不大于600℃的酸或沸点不大于600℃的酸的酸式盐可降低层状正极活性物质表面的残余碱含量，适当含量的酸或酸式盐并不会恶化循环性能甚至能改善循环性能，但参照对比例4可知，过多的酸或者酸式盐对循环性能有明显恶化作用。 From the correlation data analysis of Table 1, it is known that the acid salt having an boiling point of not more than 600 ° C or an acid having a boiling point of not more than 600 ° C in Example 1-8 reduces the residual alkali content of the surface of the layered positive electrode active material, lithium ion battery The volume expansion ratio after storage at 60 ° C for two months was significantly improved compared to Comparative Examples 1-3. In the comparison of Example 2, Examples 4-5 and Comparative Example 4, it can be seen that as the oxalic acid content increases, the volume expansion ratio of the lithium ion battery after storage decreases, but the capacity retention of the lithium ion battery after multiple cycles The rate is also reduced. That is, the acid salt of the acid having a boiling point of not more than 600 ° C or an acid having a boiling point of not more than 600 ° C in Examples 1-8 can reduce the residual alkali content on the surface of the layered positive electrode active material, and the appropriate amount of acid or acid salt is not It may deteriorate the cycle performance and even improve the cycle performance, but referring to Comparative Example 4, it is known that excessive acid or acid salt has a significant deterioration effect on the cycle performance.
根据上述说明书的揭示，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。 Based on the above description, those skilled in the art can also make appropriate changes and modifications to the above embodiments. Therefore, the present application is not limited to the specific embodiments disclosed and described herein, and the modifications and variations of the present invention are intended to fall within the scope of the appended claims.

Claims (10)

  1. 一种改性正极材料的制备方法，其特征在于，包括步骤：将层状正极活性物质与沸点不大于600℃的酸和/或沸点不大于600℃的酸的酸式盐混合后，加热至所述酸的沸点温度或升华温度之上，或加热至所述酸式盐的分解温度、沸点温度或升华温度之上进行热处理，使所述酸和/或酸式盐变成气态与所述层状正极活性物质表面的残余碱反应，降低残余碱含量，即得到改性正极材料。A method for preparing a modified cathode material, comprising the steps of: mixing a layered cathode active material with an acid salt having an acidity of not more than 600 ° C and/or an acid having a boiling point of not more than 600 ° C, and heating to Heat-treating above the boiling temperature or sublimation temperature of the acid or heating to a decomposition temperature, a boiling temperature or a sublimation temperature of the acid salt to cause the acid and/or acid salt to become gaseous and The residual alkali reaction on the surface of the layered positive electrode active material reduces the residual alkali content, thereby obtaining a modified positive electrode material.
  2. 根据权利要求1所述的改性正极材料的制备方法，其特征在于，所述层状正极活性物质的通式为LiaNixCoyM1-x-yO2，0≤x＜1，0≤y≤1，0.95≤a≤1.1，且0≤x+y≤1，M选自Mn、Al、Mg、Ti中的一种或几种。The method for preparing a modified positive electrode material according to claim 1, wherein the layered positive electrode active material has a general formula of Li a Ni x Co y M 1-xy O 2 , 0 ≤ x < 1, 0 ≤ y ≤ 1, 0.95 ≤ a ≤ 1.1, and 0 ≤ x + y ≤ 1, M is selected from one or more of Mn, Al, Mg, Ti.
  3. 根据权利要求2所述的改性正极材料的制备方法，其特征在于，所述层状正极活性物质选自LiNi1/3Co1/3Mn1/3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.3Co0.2Mn0.5O2、LiNi0.3Co0.3Mn0.4O2、LiNi0.4Co0.4Mn0.2O2、LiNi0.2Co0.4Mn0.2O2、LiNi0.8Co0.15Al0.05O2中的一种或几种。The method for preparing a modified positive electrode material according to claim 2, wherein the layered positive electrode active material is selected from the group consisting of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.3 Co 0.2 Mn 0.5 O 2 , LiNi 0.3 Co 0.3 Mn 0.4 O 2 , LiNi 0.4 Co 0.4 Mn 0.2 O 2 , LiNi 0.2 Co 0.4 Mn 0.2 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 Or several.
  4. 根据权利要求1所述的改性正极材料的制备方法，其特征在于，所述酸和/或酸式盐的总质量为所述层状正极活性物质的质量的0.1％～50％。The method of producing a modified positive electrode material according to claim 1, wherein the total mass of the acid and/or acid salt is from 0.1% to 50% by mass of the layered positive electrode active material.
  5. 根据权利要求1所述的改性正极材料的制备方法，其特征在于，所述酸选自草酸、硝酸、盐酸、氢氟酸、氢溴酸、氢碘酸、亚硫酸、焦磷酸、三聚磷酸、偏磷酸、硫化氢、醋酸、甲酸、丙酸、丁酸、异丁酸、磷酸、乳酸、苯甲酸、丙烯酸、油酸中的一种或几种，优选地，所述酸选自草酸。The method for preparing a modified positive electrode material according to claim 1, wherein the acid is selected from the group consisting of oxalic acid, nitric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid, pyrophosphoric acid, and trimerization. One or more of phosphoric acid, metaphosphoric acid, hydrogen sulfide, acetic acid, formic acid, propionic acid, butyric acid, isobutyric acid, phosphoric acid, lactic acid, benzoic acid, acrylic acid, oleic acid, preferably, the acid is selected from the group consisting of oxalic acid .
  6. 根据权利要求1所述的改性正极材料的制备方法，其特征在于，所述酸式盐为铵盐。The method of producing a modified positive electrode material according to claim 1, wherein the acid salt is an ammonium salt.
  7. 根据权利要求6所述的改性正极材料的制备方法，其特征在于，所述 酸式盐选自草酸铵、草酸氢铵、硝酸铵、氯化铵、氟化铵、氟化氢铵、溴化铵、碘化铵、亚硫酸铵、硫化铵、硫化氢铵、醋酸铵、甲酸铵、丙酸铵、丁酸铵、磷酸二氢铵、磷酸氢二铵、乳酸铵、苯甲酸铵、丙烯酸铵、油酸铵中的一种或几种，优选地，所述酸式盐选自草酸铵、草酸氢铵中的一种或两种。The method of preparing a modified positive electrode material according to claim 6, wherein said The acid salt is selected from the group consisting of ammonium oxalate, ammonium hydrogen oxalate, ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium hydrogen fluoride, ammonium bromide, ammonium iodide, ammonium sulfite, ammonium sulfide, ammonium hydrogen sulfide, ammonium acetate, ammonium formate. And one or more of ammonium propionate, ammonium butyrate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium lactate, ammonium benzoate, ammonium acrylate, ammonium oleate, preferably, the acid salt is selected from the group consisting of One or two of ammonium oxalate and ammonium hydrogen oxalate.
  8. 根据权利要求1所述的改性正极材料的制备方法，其特征在于，所述热处理温度为80℃～600℃。The method of producing a modified positive electrode material according to claim 1, wherein the heat treatment temperature is from 80 ° C to 600 ° C.
  9. 根据权利要求1所述的改性正极材料的制备方法，其特征在于，所述残余碱包括Li2CO3、LiOH中的一种或两种。The method of producing a modified positive electrode material according to claim 1, wherein the residual base comprises one or both of Li 2 CO 3 and LiOH.
  10. 一种锂离子电池，其特征在于，包括根据权利要求1-9中任一项所述的改性正极材料的制备方法得到的改性正极材料。 A lithium ion battery characterized by comprising the modified positive electrode material obtained by the method for producing a modified positive electrode material according to any one of claims 1-9.
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