WO2020206884A1 - 正极材料的回收方法、得到的正极材料及其用途 - Google Patents

正极材料的回收方法、得到的正极材料及其用途 Download PDF

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WO2020206884A1
WO2020206884A1 PCT/CN2019/099177 CN2019099177W WO2020206884A1 WO 2020206884 A1 WO2020206884 A1 WO 2020206884A1 CN 2019099177 W CN2019099177 W CN 2019099177W WO 2020206884 A1 WO2020206884 A1 WO 2020206884A1
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optionally
positive electrode
cathode material
sintering
electrode material
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PCT/CN2019/099177
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English (en)
French (fr)
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岳海峰
席小兵
杨顺毅
黄友元
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深圳市贝特瑞纳米科技有限公司
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Priority to JP2021534414A priority Critical patent/JP7220360B2/ja
Priority to US17/286,284 priority patent/US20220115718A1/en
Priority to EP19923985.6A priority patent/EP3832782A4/en
Priority to KR1020217011469A priority patent/KR20210059763A/ko
Publication of WO2020206884A1 publication Critical patent/WO2020206884A1/zh

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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
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/58—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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • This application belongs to the field of recycling of waste lithium ion batteries, and relates to a method for recycling a positive electrode material, the obtained positive electrode material and its use.
  • Lithium-ion batteries have the advantages of high charging voltage, large specific energy, long cycle life, good safety performance, no memory effect, and small self-discharge. Since their commercialization in the 1990s, they have been widely used in mobile phones and notebook computers. , Video cameras, digital cameras, medical equipment and other portable electronic products. In recent years, as the prices of consumer electronic products such as mobile phones and notebook computers have dropped significantly, the penetration rate of these products has greatly increased, which has led to an increase in the demand for lithium-ion batteries in my country. At present, my country has become the largest producer, consumer and exporter of lithium-ion batteries.
  • the recycling of lithium battery materials is an inevitable step to open up the closed loop of the industry.
  • the cathode material is a key part of the lithium battery, and its recycling and reuse is the top priority.
  • the cumulative decommissioning in the following five years will be greater than 100 GWh.
  • the corresponding lithium battery material market that needs to be scrapped and recycled in the future will also increase. . Open up the closed-circuit cycle of lithium battery materials in the industry, so that new energy materials always remain green, instead of changing from green to black after the end of the life cycle, which has significant social and environmental benefits.
  • CN108306071A discloses a waste lithium ion battery cathode material recovery process, which includes the following steps: (1) disassemble and slit the waste lithium ion battery, and treat at high temperature in a tube furnace; (2) immerse the obtained cathode material Dissolve in the acidic solution and filter to obtain the filtrate; (3) Use D2EHPA to perform countercurrent cascade extraction of the filtrate; (4) Add the raffinate in (3) to the manganese source according to the set precursor element ratio, according to the design The element ratio of the precursor of the positive electrode material is adjusted to the composition of the raw material. Ammonia solution is added to the raw material and placed in the co-precipitation reactor. Then sodium hydroxide solution is added to adjust the pH to 10-12.
  • CN102751549B discloses a full-component resource recovery method for waste lithium ion battery cathode materials: (1) A fluorine-containing organic acid aqueous solution is used to separate the active material and aluminum foil in the waste lithium ion battery cathode material, and the liquid-solid-solid separation obtains the leachate , Lithium-containing active materials and aluminum foil; (2) Lithium-containing active materials are respectively subjected to high-temperature roasting and lye removal treatment; (3) The leaching solution is respectively subjected to acid distillation to recover fluorine-containing organic acid, adding alkali to precipitate impurity ions, and ammonium carbonate.
  • Precipitation preparation of nickel-cobalt-manganese carbonate ternary precursor (4) Adjust the components of the processed active material and nickel-cobalt-manganese carbonate ternary precursor mixture, mix with a certain proportion of lithium carbonate and then high-temperature solid-phase sintering Then prepare nickel cobalt lithium manganate ternary composite cathode material.
  • the preparation method has a wide application range, but the prepared cathode material has a low purity.
  • CN107699692A discloses a method for recycling and regenerating cathode materials of waste lithium ion batteries, which belongs to the field of waste recycling.
  • the method is: the anode material of the waste lithium ion battery obtained after the treatment of the waste lithium ion battery is mixed with an organic acid, and when a solution containing metal ions is obtained, the water-soluble salt of the metal ion is added, the pH is adjusted, and the gel is dried. Afterwards, it is calcined and ground to obtain a regenerated lithium ion battery positive electrode material; when the precipitate is obtained, a lithium source is added, and the regenerated lithium ion battery positive electrode material is obtained by calcination and grinding.
  • the leaching process of the method does not produce secondary pollution, the leaching efficiency is high, and the cost is low, but the purity of the prepared cathode material is low.
  • the recycling method of waste cathode materials has not yet involved the regulation of carbon content.
  • the recovered cathode materials still contain various carbon sources such as conductive agents and binders added during slurrying, and may also be accompanied by
  • the carbon content in the recovered positive electrode material is significantly higher, the effective active material content is lower, and the energy density is lowered. Therefore, there is a need in the art to develop a cathode material recovery method, which can effectively control the carbon content in the recovered cathode material, has a simple preparation process, can be industrially produced, and the prepared cathode material has good electrochemical performance .
  • One of the objectives of the present application is to provide a method for recycling cathode materials, the method includes the following steps:
  • the gas in the oxidizing atmosphere includes CO 2 .
  • an oxidizing atmosphere containing CO 2 is used as the basic oxidant to remove excess carbon components in the recovered cathode material.
  • the basic chemical reaction is: CO 2 +C ⁇ 2CO, thereby realizing the controlled removal of waste cathode materials. carbon.
  • the preparation method proposed in the present application enables the oxidative decarburization and the sintering repair process of the material crystal structure to be performed simultaneously, which can save energy consumption and cost.
  • the partial pressure ratio P of CO 2 in the oxidizing atmosphere is 0.1 to 1, optionally 0.8 to 1, such as 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9.
  • P P CO2 / P total
  • P the partial pressure of CO2 of CO 2 in the oxidizing atmosphere
  • P-oxidizing atmosphere is a total of all the total gas pressure.
  • the oxidizing atmosphere further includes any one or a mixture of at least two of a protective gas and a strong oxidizing gas; for example, the oxidizing atmosphere is a CO 2 mixed protective gas, and the oxidizing atmosphere is a CO 2 mixed Strong oxidizing gas, or the oxidizing atmosphere is a mixture of CO 2 , protective gas and trace strong oxidizing gas, this application realizes the controlled decarburization of waste cathode materials by controlling the oxidizing property of the mixed gas.
  • This application controls the oxidability of the mixed gas by adjusting the proportion of CO 2 and the partial pressure of strong oxidizing gas or protective gas, thereby achieving controllable decarburization of waste cathode materials.
  • proportion of CO 2 partial pressure is less than 0.1 , The oxidizing atmosphere of the oxidizing atmosphere is too strong or too weak, and the controllability of the oxidizing atmosphere is low.
  • the oxidizing atmosphere described in this application uses the method of mixing CO 2 with protective gas or strong oxidizing gas to control the oxidizing property of the mixed gas, that is, the mixed gas prepared by mixing CO 2 with strong oxidizing gas has strong oxidizing property ,
  • the mixed gas prepared by mixing CO 2 and the protective gas has weak oxidability, and then controllable decarburization of the waste cathode material is achieved by controlling the oxidability of the mixed gas, and the carbon content of the obtained cathode material is less than or equal to 2.86 wt%.
  • the oxidizing atmosphere includes CO 2 and a protective gas
  • the partial pressure of the protective gas accounts for ⁇ 0.95, such as 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 Or 0.95 etc.
  • the oxidizing atmosphere includes CO 2 and a strong oxidizing gas, and the proportion of the partial pressure of the strong oxidizing gas is ⁇ 0.2, for example, 0.01, 0.05, 0.1, 0.12, 0.15, or 0.2.
  • the proportion of the partial pressure of the strong oxidizing gas in the oxidizing atmosphere described in this application is ⁇ 0.2.
  • the cathode material is lithium iron phosphate
  • the oxidizing atmosphere used will not cause Fe 2+ in the lithium iron phosphate to be oxidized to Fe 3 + .
  • the strong oxidizing gas includes any one or a combination of at least two of oxygen, chlorine, fluorine, nitrogen dioxide, ozone, and sulfur trioxide, and optional oxygen, such as oxygen, chlorine, and fluorine. Wait.
  • the protective gas includes any one or a combination of at least two of nitrogen, argon, helium, neon, krypton, and xenon, and optional nitrogen, such as nitrogen, argon, helium, etc. .
  • the particle size distribution D50 of the positive electrode material to be recovered is 0.5 to 5.0 ⁇ m, for example, 0.8 ⁇ m, 1.0 ⁇ m, 1.5 ⁇ m, 1.8 ⁇ m, 2.0 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4.0 ⁇ m, 4.5 ⁇ m, or 4.8 ⁇ m and so on.
  • the cathode material to be recovered includes carbon-coated lithium iron phosphate to be recovered.
  • This application does not specifically limit the positive electrode material to be recycled.
  • the positive electrode material that needs carbon removal during the recycling process is applicable to this application. It can be selected to contain excess carbon and variable metal elements at the same time, and the carbon needs to be oxidized and removed in a low-priced state.
  • the cathode material to be recovered in which the metal is not oxidized to a high valence state is exemplified by the carbon-coated lithium iron phosphate to be recovered.
  • the water content in the positive electrode material to be recovered is 50-5000 ppm, such as 100 ppm, 300 ppm, 500 ppm, 1000 ppm, 1200 ppm, 1500 ppm, 2000 ppm, 2500 ppm, 3000 ppm, 3500 ppm, 4000 ppm or 4500 ppm.
  • the sintering temperature is 650-800°C, optionally 730-780°C, such as 680°C, 700°C, 730°C, 750°C, or 780°C.
  • the sintering temperature described in this application is less than 650°C, the decarburization effect is not obvious; when the sintering temperature is greater than 800°C, the original structure of the lithium iron phosphate is affected, and even impurity phases appear.
  • the sintering time is 5-20h, optionally 10-15h, such as 8h, 10h, 12h, 15h, 17h or 19h.
  • the gas flow rate of the sintering process is 2-20m 3 /h, optionally 5-15m 3 /h, such as 3m 3 /h, 5m 3 /h, 8m 3 /h, 10m 3 /h, 12m 3 /h, 15m 3 /h, 17m 3 /h or 19m 3 /h, etc.
  • the sintering method is dynamic sintering or static sintering.
  • the dynamic sintering is rotary kiln sintering.
  • the static sintering includes any one or a combination of at least two of box furnace sintering, tube furnace sintering, roller kiln sintering, and pusher kiln sintering.
  • the charging container in static sintering is a graphite crucible.
  • the charge thickness of the static sintering is 1-100 mm, and may be 10-50 mm, for example, 5 mm, 10 mm, 20 mm, 30 mm, 50 mm, 70 mm, 80 mm or 90 mm.
  • the preparation method of the positive electrode material to be recycled includes: stripping the waste positive electrode material from the pole pieces of the waste battery, and then crushing it to obtain the positive electrode material to be recycled.
  • the peeling includes wet immersion peeling or dry calcining peeling.
  • the wet soaking and stripping includes: immersing the used battery pole pieces in the solution and performing separation treatment.
  • the separation treatment includes any one or a combination of at least two of heating, stirring and ultrasonic treatment.
  • the heating temperature is 20-90°C, optionally 50-80°C, such as 30°C, 40°C, 50°C, 60°C, 70°C, or 80°C.
  • the heating time is 20 to 120 minutes, for example, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, etc.
  • the rotational speed of the stirring is 200-1000r/min, optionally 300-500r/min, such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min or 900r /min etc.
  • the stirring time is 20 to 120 minutes, for example, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, etc.
  • the frequency of the ultrasonic treatment is 20-40KHz, such as 25KHz, 30KHz or 35KHz.
  • the ultrasonic treatment time is 10-60 minutes, and may be 20-40 minutes, for example, 15 minutes, 20 minutes, 30 minutes, 40 minutes, or 50 minutes.
  • the solution is an alkaline solution or an organic solvent.
  • the pH of the alkaline solution is 7-14, optionally 9-11, such as 8, 9, 10, 11, 12, or 13, etc.
  • the organic solvent includes any one or a combination of at least two of N, N dimethyl acetamide, dimethyl sulfoxide, tetramethyl urea, and trimethyl phosphate, such as N, N Dimethylacetamide or dimethylsulfoxide, etc.
  • the dry calcination stripping includes: putting the waste battery pole pieces into a heating reactor and calcination in a nitrogen atmosphere or an argon atmosphere.
  • the calcination temperature is 400-600°C, optionally 450-550°C, such as 420°C, 450°C, 480°C, 500°C, 520°C, 550°C, or 580°C.
  • the calcination time is 1-10h, optionally 1-3h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9h.
  • the heating reactor includes any one of a box furnace, a tube furnace, a roller hearth furnace, a pusher furnace or a rotary furnace.
  • the peeling method is dry calcination peeling
  • the crushing method is mechanical crushing or jet crushing.
  • the peeling method is wet immersion peeling
  • the crushing method is wet ball milling or sand milling.
  • the stripping method is wet immersion stripping, and the crushed positive electrode material is dried to obtain the positive electrode material to be recovered.
  • the drying method includes any one or a combination of at least two of suction filtration, pressure filtration and spray drying.
  • the air inlet temperature of the spray drying is 200-260°C, such as 210°C, 220°C, 230°C, 240°C, or 250°C.
  • the air outlet temperature of the spray drying is 70-130°C, such as 80°C, 90°C, 100°C, 110°C, or 120°C.
  • the compressed air inlet air pressure of the spray drying is 0.1-0.8 MPa, for example, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa or 0.7 MPa.
  • the air inlet flow rate of the spray drying is 1-15m 3 /h, for example, 2m 3 /h, 5m 3 /h, 8m 3 /h, 10m 3 /h, 12m 3 /h or 14m 3 /h Wait.
  • the feed rate of the spray drying is 0.5-10L/h, for example, 1L/h, 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h h or 9L/h etc.
  • the solid content of the spray-dried slurry is 5%-40%, such as 7%, 8%, 10%, 15%, 20%, 25%, 30% or 35%.
  • the method for recycling a cathode material described in this application includes the following steps:
  • the cathode material to be recovered is sintered in a tube furnace at a temperature of 730 to 780° C. for 10 to 15 hours with a gas flow rate of 5 to 15 m 3 /h to obtain the recovered cathode material ,
  • the partial pressure of CO 2 in the oxidizing atmosphere containing CO 2 accounts for 0.1-1.
  • the second objective of the present application is to provide a cathode material, which is obtained by the cathode material recovery method described in one of the objectives.
  • the positive electrode material prepared by this application can increase its gram capacity by 5% to 10%.
  • the positive electrode material prepared by this application has excellent cycle performance, and the capacity retention rate of 200 cycles at 1C rate is ⁇ 99 %.
  • the positive electrode material includes lithium iron phosphate.
  • the particle size distribution D50 of the positive electrode material is 0.2-5 ⁇ m, optionally 0.5-2 ⁇ m, such as 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, or 4 ⁇ m.
  • the carbon content of the positive electrode material is 2-5wt%, for example 2.5wt%, 2.6wt%, 2.8wt%, 3wt%, 3.4wt%, 3.5wt%, 3.8wt%, 4wt%, 4.5wt% % Or 4.7% by weight, etc.
  • the carbon in the cathode material to be recycled includes coated carbon and uncoated carbon sources.
  • the uncoated carbon includes carbon sources such as CNTs or graphene.
  • the application will A proper amount of residual uncoated carbon and coated carbon will be further carbonized during the sintering process to repair the coated carbon and improve the electrochemical performance of the material.
  • the third objective of this application is to provide a use of the positive electrode material as described in the second objective.
  • the positive electrode material is used in the battery field, and optionally in the field of lithium ion battery positive electrode materials.
  • the fourth object of the present application is to provide a lithium ion battery including the positive electrode material described in the second object.
  • the recovery method for waste cathode materials has not yet involved quantitative control of carbon content.
  • the carbon content in the recovered cathode materials is significantly higher, the effective active material content is lower, and the energy density is lowered.
  • This application adopts An oxidizing atmosphere containing CO 2 is used as an oxidant to remove excess carbon components in the recovered cathode material, and the carbon content of the obtained cathode material is less than or equal to 2.86% by weight.
  • the oxidizing atmosphere adopted in this application will not cause Fe 2+ in the lithium iron phosphate to be oxidized to Fe 3+ .
  • the oxidizing atmosphere used in this application uses CO 2 as the basic oxidant, and then mixes with protective gas or strong oxidizing gas and CO 2 controls the partial pressure of the gas. Oxidizing.
  • the preparation method proposed in the application allows the process of oxidative decarburization and sintering repair to be carried out simultaneously, which can save energy and cost.
  • the capacity of the positive electrode material prepared by decarburization can be increased by 5 % ⁇ 10%, the positive electrode material prepared in this application has excellent cycle performance, and the capacity retention rate of 200 cycles at 1C rate is ⁇ 99%.
  • a method for recycling cathode materials includes the following steps:
  • step (2) the oxidizing atmosphere is a mixed atmosphere of CO 2 and O 2 , the partial pressure of CO 2 accounts for 0.8, and the partial pressure of O 2 accounts for 0.2.
  • the gas in the oxidizing atmosphere in step (2) is a mixed gas of CO 2 and O 2 , the partial pressure of CO 2 is 0.9, and the partial pressure of O 2 is 0.1.
  • step (2) the oxidizing atmosphere is a mixed atmosphere of CO 2 and O 2 , the partial pressure of CO 2 is 0.7, and the partial pressure of O 2 is 0.3.
  • step (2) the oxidizing atmosphere is a mixed atmosphere of CO 2 and nitrogen, the partial pressure of CO 2 accounts for 0.9, and the partial pressure of nitrogen accounts for 0.1.
  • step (2) the oxidizing atmosphere is a mixed atmosphere of CO 2 and nitrogen, the partial pressure of CO 2 is 0.1, and the partial pressure of nitrogen is 0.9.
  • step (2) the oxidizing atmosphere is a mixed atmosphere of CO 2 and nitrogen, the partial pressure of CO 2 is 0.05, and the partial pressure of nitrogen is 0.95.
  • Example 2 The difference from Example 1 is that the sintering temperature in step (2) is 730°C.
  • step (2) The difference from Example 1 is that the sintering temperature in step (2) is 780°C.
  • a method for recycling cathode materials includes the following steps:
  • a method for recycling cathode materials includes the following steps:
  • step (2) is: sintering the cathode material to be recovered obtained in step (1) at 750° C. for 12 hours in a nitrogen atmosphere without performing an oxidation process in an oxidizing atmosphere.
  • Example 1 The difference from Example 1 is that the oxidizing atmosphere in step (2) is a nitrogen dioxide atmosphere, and the partial pressure ratio of nitrogen dioxide is 1.
  • the positive electrode material prepared in this application is made into a positive pole piece, the negative electrode is a metal lithium sheet, the separator is Celgard 2400, and the electrolyte is 1 mol/L LiPF 6 , dimethyl carbonate and ethyl methyl carbonate Mixed solution (volume ratio 1:1:1), assembled into CR2025 button battery.
  • the preparation process of the positive pole piece includes: mixing the prepared positive electrode material, conductive agent acetylene black, binder PVDF (polyvinylidene fluoride) in a mass ratio of 93:2:3, and mixing N-methylpyrrolidone NMP as a solvent After the slurry is made, it is coated on aluminum foil.
  • the coated aluminum foil is slowly dried in a common oven at 50°C, and then transferred to a vacuum oven to dry at 110°C for 10 hours to obtain the required electrode pads, which are rolled and punched A disc with a diameter of 8.4mm is used as the positive pole piece;
  • Electrochemical test The button battery is tested on the LAND battery test system of Wuhan Jinnuo Electronics Co., Ltd. under normal temperature conditions.
  • the charge and discharge voltage range is 3.0 ⁇ 4.3V, and the 1C current density is defined as 170mA/ g, test the capacity retention rate under 1C current density for 200 weeks, and the rate performance under 0.1C, 0.3C, 0.5C, 1C, 2C, 3C, 5C, 10C;
  • Compaction density test use compaction density tester to test, the pressure is 6600 pounds, the cross-sectional area is 1.3cm 2 ;
  • Example 1 161.4 158.1 149.5 140.5 135.8 130.5 110.6 101.2
  • Example 2 159.5 156.9 146.2 136.5 130.6 126.6 107.4 99.3
  • Example 3 160.5 157.9 148.2 138.5 132.6 128.6 108.4 100.3
  • Example 4 158.5 152.9 145.3 135.4 128.4 125.4 104.5 95.4
  • Example 5 160.9 157.9 149.2 140.2 135.4 129.4 109.4 100.5
  • Example 6 160.0 157.1 148.0 137.9 130.8 127.5 106.8 94.6
  • Example 7 156.5 154.2 145.6 134.8 128.4 126.4 105.2 92.1
  • Example 8 159.1 156.5 147.3 138.1 133.4 128.1 108.7 99.8
  • Example 9 160.0 157.1 148.2 139.0 134.5 128.9 109.1 100.2
  • Example 10 162.2 157.6 148.8 139.8 133.4 129.1 105.8 95.6
  • Example 11 161.0 157.2 148.2 139.6 132.9 128.8 105.2 95.0
  • Comparative example 1 158.3 151.6 133.7 127.5 118.7 106.2 76.2 1.0
  • Comparative example 2 159.6 152.8 134.4 125.6 109.5 98.1 72.6 0.5
  • this application uses an oxidizing atmosphere containing CO 2 as the basic oxidant.
  • the oxygen potential of the atmosphere is adjusted by adding oxygen or nitrogen, and the recovery is controlled by oxidative decarburization.
  • the carbon component in the obtained positive electrode material, the prepared positive electrode material has less carbon content, and the carbon content is less than or equal to 2.86 wt%.
  • the oxidizing atmosphere of the present application is relatively weak, and will not make the positive electrode material lithium iron phosphate Fe 2+ is oxidized to Fe 3+ , and the prepared cathode material has good cycle stability and rate performance, and the 200-week capacity retention rate is ⁇ 99.0%.
  • Example 4 cycle stability and rate performance of Example 4 is poorer than that of Example 1, and the Fe 3+ /Fe 2+ value is larger, which may be due to the CO 2 content in Example 4 If the pressure is too small, the partial pressure of O 2 is too large, and the oxidizing atmosphere is more oxidizing, which not only removes the excess carbon component in the waste lithium iron phosphate pole piece, but also removes the lithium iron phosphate in the waste lithium iron phosphate material.
  • the carbon component of the outer coating is stripped, and part of the Fe 2+ in the waste lithium iron phosphate is oxidized to Fe 3+ at the same time, so that the cycle stability and rate performance of the cathode material are poor, and the Fe 3+ /Fe 2+ value Larger.
  • Example 7 has higher C content, poorer rate performance, and lower gram capacity. This may be because the partial pressure of CO 2 in Example 7 is too small and nitrogen The partial pressure is too large, and the oxidizing atmosphere of the oxidizing atmosphere is weaker, and the carbon content in the prepared positive electrode material is higher, and the active material content in the prepared positive electrode material is lower and the capacity is lower.
  • Comparative Example 1 has higher C content, lower 200-week capacity retention, poorer rate performance, and lower gram capacity, which may be due to the
  • the positive electrode material is not subjected to the oxidation and carbon removal process, and the obtained positive electrode material has a higher carbon content and a lower active material content.
  • the capacity of Example 1 is increased by 5%-10% relative to 1 gram of the comparative example.

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Abstract

一种正极材料的回收方法，所述方法包括如下步骤：将待回收正极材料在氧化性气氛下烧结，得到正极材料；所述氧化性气氛中的气体包括CO 2。得到的正极材料中碳含量较少，循环稳定性和倍率性能良好，碳含量≤2.86wt％，200周容量保持率≥99.0％。

Description

正极材料的回收方法、得到的正极材料及其用途 技术领域
本申请属于废旧锂离子电池回收领域，涉及正极材料的回收方法、得到的正极材料及其用途。
背景技术
锂离子电池由于具有充电电压高、比能量大、循环寿命长、安全性能好、无记忆效应、自放电小等优点，自20世纪90年代实现商品化以来，已广泛应用于移动电话、笔记本电脑、摄像机、数码相机、医疗器械等便携式电子产品领域。近年来，随着移动电话、笔记本电脑等消费类电子产品价格大幅降低，使得这些产品普及率大大提高，进而导致我国锂离子电池需求量逐年递增。目前，我国已成为锂离子电池的最大生产、消费和出口国。
面对即将到来的大规模锂电池退役，锂电材料循环利用是打通行业闭环的必然步骤。其中正极材料作为锂电池的关键部分，其回收再利用是重中之重。到2020年我国退役动力电池退役约24GWh，随后5年累计退役量将大于100GWh，而伴随着未来锂电池装机量不断增加，将来相应的需要报废、循环利用的锂电材料市场也会越来越大。打通锂电材料在行业中的闭路循环，使新能源材料始终保持绿色，而不是使用周期结束后由绿色变为黑色，具有显著的社会效益和环境效益。
CN108306071A公开了一种废旧锂离子电池正极材料回收工艺，包括如下步骤：(1)将废旧锂离子电池进行拆分并进行分切，管式炉中高温处理；(2)将得到的正极材料浸入酸性溶解液中溶解后过滤，得到滤液；(3)利用D2EHPA对滤液进行逆流串级萃取；(4)将(3)中的萃余液按照所设定前驱体元素比例 加入锰源，按照设计的正极材料前躯体的元素比例调整原料组成，向原料中加入氨水溶液共同置入共沉淀反应釜内，然后加入氢氧化钠溶液，调整pH值为10～12，反应8～24h后过滤、洗涤沉淀得到正极材料的沉淀。所述回收工艺实现了对正极材料以及正极集流体的完全回收利用，但是制备过程复杂难以工业化回收废旧锂离子电池正极材料。
CN102751549B公开了一种废旧锂离子电池正极材料全组分资源化回收方法：(1)采用含氟有机酸水溶液分离废旧锂离子电池正极材料中的活性物质与铝箔，液-固-固分离得到浸出液、含锂活性物质和铝箔；(2)含锂活性物质分别进行高温焙烧、碱液除杂处理；(3)浸出液分别进行加酸蒸馏回收含氟有机酸、加碱沉淀杂质离子、碳酸铵共沉淀制备镍钴锰碳酸盐三元前驱体；(4)将处理后的活性物质和镍钴锰碳酸盐三元前驱体混合物组分调控，配入一定比例的碳酸锂后高温固相烧结再制备镍钴锰酸锂三元复合正极材料。所述制备方法适用范围广，但制得的正极材料纯度较低。
CN107699692A公开了一种回收及再生废旧锂离子电池正极材料的方法，属于废物资源化的领域。所述方法为：废旧锂离子电池处理后得到的废旧锂离子电池正极材料与有机酸混合，当得到含有金属离子的溶液时，加入金属离子的水溶性盐，调pH，搅拌至形成凝胶干燥后，煅烧研磨，得到再生的锂离子电池正极材料；当得到沉淀时，加入锂源，煅烧研磨，得到再生的锂离子电池正极材料。所述方法浸出过程不产生二次污染，浸出效率高，且成本较低，但制得的正极材料纯度较低。
在相关技术中，对于废旧正极材料的回收方法尚未涉及对碳含量的调控，回收得到的正极材料中依然存在调浆时加入的导电剂和粘结剂等多种碳源，同 时还可能伴有包覆碳脱离，需后处理碳包覆的情况，进而回收得到的正极材料中碳含量显著偏高，有效活性物质含量偏低，拉低能量密度。因此，本领域需要开发一种正极材料的回收方法，所述方法能有效控制回收得到的正极材料中的碳含量，并且制备过程简单，可工业化生产，制备得到的正极材料具有良好的电化学性能。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的之一在于提供一种正极材料的回收方法，所述方法包括如下步骤：
将待回收正极材料在氧化性气氛下烧结，得到回收的正极材料；
所述氧化性气氛中的气体包括CO 2。
本申请采用含有CO 2的氧化性气氛作为基础氧化剂，来脱除回收得到的正极材料中多余的碳组分，基本化学反应为：CO 2+C→2CO，进而实现废旧正极材料的可控脱碳。
本申请提出的制备方法可使氧化脱碳与材料晶体结构的烧结修复过程同时进行，可节省能耗与成本。
可选地，所述氧化性气氛中CO 2的分压占比P为0.1～1，可选0.8～1，例如0.2、0.3、0.4、0.5、0.6、0.7、0.8或0.9等。
所述P＝P CO2/P 总，P CO2为氧化性气氛中CO 2的分压，P 总为氧化性气氛中所有气体总压力。
可选地，所述氧化性气氛还包括保护性气体与强氧化性气体中的任意一种 或至少两种的混合；例如氧化性气氛为CO 2混合保护性气体，氧化性气氛为CO 2混合强氧化性气体，或者氧化性气氛为CO 2、保护性气体和微量强氧化性气体混合，本申请通过控制混合气体的氧化性实现废旧正极材料的可控脱碳。
本申请通过调控CO 2与强氧化性气体或保护性气体性的分压占比来控制混合气体的氧化性，进而实现废旧正极材料的可控脱碳，CO 2的分压占比小于0.1时，氧化性气氛的氧化性过强或过弱，氧化性气氛的可控性较低。
本申请所述的氧化性气氛采用CO 2与保护性气体或强氧化性气体混合的方法来调控混合气体的氧化性，即采用CO 2与强氧化性气体混合制得的混合气体氧化性较强，采用CO 2与保护性气体混合制得的混合气体氧化性较弱，进而通过控制混合气体的氧化性实现废旧正极材料的可控脱碳，得到的正极材料碳含量≤2.86wt％。
可选地，所述氧化性气氛包括CO 2和保护性气体，所述保护性气体的分压占比≤0.95，例如0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9或0.95等。
可选地，所述氧化性气氛包括CO 2和强氧化性气体，所述强氧化性气体的分压占比≤0.2，例如0.01、0.05、0.1、0.12、0.15或0.2等。
本申请所述氧化性气氛中强氧化性气体的分压占比≤0.2，对于正极材料为磷酸铁锂时，采用的氧化性气氛不会使磷酸铁锂中的Fe 2+被氧化为Fe 3+。
可选地，所述强氧化性气体包括氧气、氯气、氟气、二氧化氮、臭氧、三氧化硫中的任意一种或至少两种的组合，可选氧气，例如氧气、氯气、氟气等。
可选地，所述保护性气体包括氮气、氩气、氦气、氖气、氪气和氙气中的任意一种或至少两种的组合，可选氮气，例如氮气、氩气、氦气等。
可选地，所述待回收正极材料的粒度分布D50为0.5～5.0μm，例如0.8μm、 1.0μm、1.5μm、1.8μm、2.0μm、2.5μm、3μm、3.5μm、4.0μm、4.5μm或4.8μm等。
可选地，所述待回收正极材料包括待回收碳包覆磷酸铁锂。
本申请对待回收正极材料不做具体限定，回收过程中需要进行碳脱除的正极材料都适用于本申请，可选为同时含有多余碳和变价金属元素，需要将碳氧化脱除且低价态金属不被氧化至高价态的待回收正极材料，示例性的为待回收碳包覆磷酸铁锂。
可选地，所述待回收正极材料中水含量为50～5000ppm，例如100ppm、300ppm、500ppm、1000ppm、1200ppm、1500ppm、2000ppm、2500ppm、3000ppm、3500ppm、4000ppm或4500ppm等。
可选地，所述烧结的温度为650～800℃，可选730～780℃，例如680℃、700℃、730℃、750℃或780℃等。
本申请所述烧结的温度小于650℃时，则脱碳效果不明显；烧结的温度大于800℃时，则磷酸铁锂原有结构受影响，甚至出现杂质相。
可选地，所述烧结的时间为5～20h，可选10～15h，例如8h、10h、12h、15h、17h或19h等。
可选地，所述烧结过程的气流量为2～20m 3/h，可选5～15m 3/h，例如3m 3/h、5m 3/h、8m 3/h、10m 3/h、12m 3/h、15m 3/h、17m 3/h或19m 3/h等。
可选地，所述烧结的方式为动态烧结或静态烧结。
可选地，所述动态烧结为回转窑炉烧结。
可选地，所述静态烧结包括箱式炉烧结、管式炉烧结、辊道窑炉烧结和推板窑炉烧结中的任意一种或至少两种的组合。
可选地，所述静态烧结中装料容器为石墨坩埚。
可选地，所述静态烧结的装料厚度为1～100mm，可选10～50mm，例如5mm、10mm、20mm、30mm、50mm、70mm、80mm或90mm等。
可选地，所述待回收正极材料的制备方法包括：将废旧电池极片中废旧正极材料剥离后，进行破碎，得到待回收正极材料。
可选地，所述剥离包括湿法浸泡剥离或干法煅烧剥离。
可选地，所述湿法浸泡剥离包括：将废旧电池极片浸泡在溶液中，并进行分离处理。
可选地，所述分离处理包括加热、搅拌和超声波处理中的任意一种或至少两种的组合。
可选地，所述加热的温度为20～90℃，可选50～80℃，例如30℃、40℃、50℃、60℃、70℃或80℃等。
可选地，所述加热的时间为20～120min，例如40min、50min、60min、70min、80min、90min、100min或110min等。
可选地，所述搅拌的转速为200～1000r/min，可选300～500r/min，例如300r/min、400r/min、500r/min、600r/min、700r/min、800r/min或900r/min等。
可选地，所述搅拌的时间为20～120min，例如40min、50min、60min、70min、80min、90min、100min或110min等。
可选地，所述超声波处理的频率为20～40KHz，例如25KHz、30KHz或35KHz等。
可选地，所述超声波处理的时间为10～60min，可选20～40min，例如15min、20min、30min、40min或50min等。
可选地，所述溶液为碱性溶液或有机溶剂。
可选地，所述碱性溶液的pH为7～14，可选9～11，例如8、9、10、11、12或13等。
可选地，所述有机溶剂包括N,N二甲基乙酰胺、二甲基亚砜、四甲基脲、和磷酸三甲酯中的任意一种或至少两种的组合，例如N,N二甲基乙酰胺或二甲基亚砜等。
可选地，所述干法煅烧剥离包括：将废旧电池极片放入加热反应器中，在氮气气氛或氩气气氛下煅烧。
可选地，所述煅烧的温度为400～600℃，可选450～550℃，例如420℃、450℃、480℃、500℃、520℃、550℃或580℃等。
可选地，所述煅烧的时间为1～10h，可选1～3h，例如2h、3h、4h、5h、6h、7h、8h或9h等。
可选地，所述加热反应器包括箱式炉、管式炉、辊道窑炉、推板窑炉或回转窑炉中的任意一种。
可选地，所述剥离的方式为干法煅烧剥离，所述破碎的方式为机械破碎或气流粉碎。
可选地，所述剥离的方式为湿法浸泡剥离，所述破碎的方式为湿法球磨或砂磨。
可选地，所述剥离的方式为湿法浸泡剥离，所述破碎后的正极材料干燥后得到待回收正极材料。
可选地，所述干燥的方式包括抽滤、压滤和喷雾干燥中的任意一种或至少两种的组合。
可选地，所述喷雾干燥的进风口温度为200～260℃，例如210℃、220℃、230℃、240℃或250℃等。
可选地，所述喷雾干燥的出风口温度为70～130℃，例如80℃、90℃、100℃、110℃或120℃等。
可选地，所述喷雾干燥的压缩空气进气气压为0.1～0.8MPa，例如0.2MPa、0.3MPa、0.4MPa、0.5MPa、0.6MPa或0.7MPa等。
可选地，所述喷雾干燥的进气流速为1～15m 3/h，例如2m 3/h、5m 3/h、8m 3/h、10m 3/h、12m 3/h或14m 3/h等。
可选地，所述喷雾干燥的进料速率为0.5～10L/h，例如1L/h、2L/h、3L/h、4L/h、5L/h、6L/h、7L/h、8L/h或9L/h等。
可选地，所述喷雾干燥的浆料固含量为5％～40％，例如7％、8％、10％、15％、20％、25％、30％或35％等。
作为可选技术方案，本申请所述一种正极材料的回收方法，所述方法包括如下步骤：
(1)将废旧电池极片放入管式炉中，在氮气气氛下450～550℃煅烧1～3h，得到剥离后的废旧正极材料，然后将干法煅烧剥离后的废旧正极材料进行机械破碎，得到粒度分布D50为0.5～5.0μm的待回收正极材料；
(2)在含有CO 2的氧化性气氛下，将所述待回收正极材料在730～780℃温度下管式炉烧结10～15h，气流量为5～15m 3/h，得到回收的正极材料，所述含有CO 2的氧化性气氛中CO 2的分压占比为0.1～1。
本申请的目的之二是提供一种正极材料，所述正极材料通过目的之一所述一种正极材料回收的方法得到。
本申请通过脱碳制备得到的正极材料相对于未脱碳的正极材料，克容量可提升5％～10％，本申请制备的正极材料循环性能优异，1C倍率下循环200周容量保持率≥99％。
可选地，所述正极材料包括磷酸铁锂。
可选地，所述正极材料的粒度分布D50为0.2～5μm，可选0.5～2μm，例如0.5μm、1μm、2μm、3μm或4μm等。
可选地，所述正极材料的碳含量为2～5wt％，例如2.5wt％、2.6wt％、2.8wt％、3wt％、3.4wt％、3.5wt％、3.8wt％、4wt％、4.5wt％或4.7wt％等。
待回收正极材料中的碳包括包覆碳和非包覆碳源，所述非包覆碳包括CNTs或石墨烯等碳源，本申请在对多余的碳组分进行脱除的过程中，会适量残留非包覆碳和包覆碳，进而在烧结过程中，非包覆碳会进一步碳化，修复包覆碳，提高材料的电化学性能。
本申请目的之三是提供一种如目的之二所述正极材料的用途，所述正极材料应用于电池领域，可选用于锂离子电池正极材料领域。
本申请目的之四是提供一种锂离子电池，所述锂离子电池包括目的之二所述的正极材料。
与相关技术相比，本申请具有如下有益效果：
(1)相关技术中，对于废旧正极材料的回收方法尚未涉及对碳含量的定量调控，回收得到的正极材料中碳含量显著偏高，有效活性物质含量偏低，拉低能量密度，本申请采用含有CO 2的氧化性气氛作为氧化剂，来脱除回收得到的正极材料中多余的碳组分，得到的正极材料碳含量≤2.86wt％。
(2)在进一步可选的技术方案中，对于正极材料为磷酸铁锂，本申请采用 的氧化性气氛不会使磷酸铁锂中的Fe 2+被氧化为Fe 3+。
(3)在进一步可选的技术方案中，本申请采用的氧化性气氛以CO 2作为基础氧化剂，再通过与保护性气体或强氧化性气体混合并CO 2控制分压的方法来调控气体的氧化性。
(4)申请提出的制备方法可使氧化脱碳与烧结修复的过程同时进行，可节省能耗与成本，通过脱碳制备得到的正极材料相对于未脱碳的正极材料，克容量可提升5％～10％，本申请制备的正极材料循环性能优异，1C倍率下循环200周容量保持率≥99％。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
一种正极材料的回收方法包括如下步骤：
(1)将废旧磷酸铁锂极片放入管式炉中，在氮气气氛下500℃煅烧2h，得到剥离后的废旧磷酸铁锂材料，然后将干法煅烧剥离后的废旧磷酸铁锂材料进行气流粉碎，得到粒度分布D50为1.5μm的待回收正极材料；
(2)将所述待回收正极材料放置于CO 2的分压占比为1的氧化性气氛中，待回收正极材料在石墨坩埚中的铺料厚度为30mm，750℃烧结12h，得到粒径D50为2.1μm的正极材料。
实施例2
与实施例1的区别在于，步骤(2)氧化性气氛为CO 2和O 2的混合气氛中， CO 2的分压占比为0.8，O 2分压占比为0.2。
实施例3
与实施例1的区别在于，步骤(2)氧化性气氛中气体为CO 2和O 2的混合气体，CO 2的分压占比为0.9，O 2的分压占比为0.1。
实施例4
与实施例1的区别在于，步骤(2)氧化性气氛为CO 2和O 2的混合气氛中，CO 2的分压占比为0.7，O 2的分压占比为0.3。
实施例5
与实施例1的区别在于，步骤(2)氧化性气氛为CO 2和氮气的混合气氛中，CO 2的分压占比为0.9，氮气的分压占比为0.1。
实施例6
与实施例1的区别在于，步骤(2)氧化性气氛为CO 2和氮气的混合气氛中，CO 2的分压占比为0.1，氮气的分压占比为0.9。
实施例7
与实施例1的区别在于，步骤(2)氧化性气氛为CO 2和氮气的混合气氛中，CO 2的分压占比为0.05，氮气的分压占比为0.95。
实施例8
与实施例1的区别在于，步骤(2)中烧结温度为730℃。
实施例9
与实施例1的区别在于，步骤(2)中烧结温度为780℃。
实施例10
一种正极材料的回收方法包括如下步骤：
(1)将废旧磷酸铁锂极片浸泡在二甲基亚砜中，并进行20KHz超声波处理10min，得到湿法剥离后的正极材料，将所述正极材料进行湿法球磨，球磨至D50为0.8μm，然后将破碎的正极材料喷雾干燥，所述喷雾干燥的浆料固含量为5％，得到待回收正极材料的粒径D50为1.0μm；
(2)将所述待回收正极材料放置于CO 2的分压占比为1的氧化性气氛中，待回收正极材料在石墨坩埚中的铺料厚度为30mm，780℃烧结10h，得到粒径D50为1.8μm的正极材料。
实施例11
一种正极材料的回收方法包括如下步骤：
(1)将废旧磷酸铁锂极片浸泡在N,N二甲基乙酰胺中，并进行40KHz超声波处理60min，得到湿法剥离后的正极材料，将所述正极材料进行湿法球磨，球磨至D50为0.8μm，然后将破碎的正极材料喷雾干燥，所述喷雾干燥的浆料固含量为40％，得到待回收正极材料的粒径D50为1.0μm；
(2)将所述待回收正极材料放置于CO 2的分压占比为1的氧化性气氛中，待回收正极材料在石墨坩埚中的铺料厚度为30mm，730℃烧结15h，得到粒径D50为1.5μm的正极材料。
对比例1
与实施例1的区别在于，步骤(2)为：将步骤(1)得到的待回收正极材料在氮气气氛下750℃烧结12h，不在氧化性气氛中进行氧化过程。
对比例2
与实施例1的区别在于，步骤(2)中氧化性气氛为二氧化氮气氛，二氧化氮的分压占比为1。
性能测试：
将制备得到的正极材料进行如下性能测试：
(1)电池组装：将本申请制得的正极材料制成正极极片，负极为金属锂片，隔膜是Celgard2400，电解液是1mol/L的LiPF 6、碳酸二甲酯和碳酸乙基甲酯混合液(体积比1:1:1)，组装成CR2025型钮扣电池。正极极片的制备过程包括：将制备得到的正极材料、导电剂乙炔黑、粘结剂PVDF(聚偏氟乙烯)按照93:2:3的质量比，以N-甲基吡咯烷酮NMP作溶剂混合制成浆料后涂覆在铝箔上，将涂覆后的铝箔于普通烘箱50℃缓慢烘干，之后转入真空烘箱于110℃干燥10h，得到所需的电极极片，碾压并冲切成直径为8.4mm的圆片作为正极极片；
(2)电化学测试：在常温条件，将制得的钮扣电池在武汉金诺电子有限公司LAND电池测试系统上进行测试，充放电电压区间为3.0～4.3V，定义1C电流密度为170mA/g，测试1C电流密度下循环200周的容量保持率，以及0.1C、0.3C、0.5C、1C、2C、3C、5C、10C下的倍率性能；
(3)压实密度测试：采用压实密度测试仪进行测试，压力为6600磅，横截面积为1.3cm 2；
(4)元素百分含量测试：采用电感耦合等离子体光谱仪进行测试。
所得测试结果分别列于表1、表2。
表1各实施例成品理化性能
Figure PCTCN2019099177-appb-000001
Figure PCTCN2019099177-appb-000002
表2各实施例成品倍率性能(mAh/g)
  0.1C 0.3C 0.5C 1C 2C 3C 5C 10C
实施例1 161.4 158.1 149.5 140.5 135.8 130.5 110.6 101.2
实施例2 159.5 156.9 146.2 136.5 130.6 126.6 107.4 99.3
实施例3 160.5 157.9 148.2 138.5 132.6 128.6 108.4 100.3
实施例4 158.5 152.9 145.3 135.4 128.4 125.4 104.5 95.4
实施例5 160.9 157.9 149.2 140.2 135.4 129.4 109.4 100.5
实施例6 160.0 157.1 148.0 137.9 130.8 127.5 106.8 94.6
实施例7 156.5 154.2 145.6 134.8 128.4 126.4 105.2 92.1
实施例8 159.1 156.5 147.3 138.1 133.4 128.1 108.7 99.8
实施例9 160.0 157.1 148.2 139.0 134.5 128.9 109.1 100.2
实施例10 162.2 157.6 148.8 139.8 133.4 129.1 105.8 95.6
实施例11 161.0 157.2 148.2 139.6 132.9 128.8 105.2 95.0
对比例1 158.3 151.6 133.7 127.5 118.7 106.2 76.2 1.0
对比例2 159.6 152.8 134.4 125.6 109.5 98.1 72.6 0.5
通过表1和表2可以看出，实施例1～11中本申请采用含有CO 2的氧化性气氛作为基础氧化剂，通过加入氧气或氮气来调控气氛的氧势，进而通过氧化脱碳来控制回收得到的正极材料中的碳组分，制得的正极材料中碳含量较少，碳含量≤2.86wt％，本申请的氧化性气氛的氧化性较弱，不会使正极材料磷酸铁锂中的Fe 2+被氧化为Fe 3+，制得的正极材料的循环稳定性和倍率性能良好，200周容量保持率≥99.0％。
通过表1和表2可以看出，实施例4相对于实施例1的循环稳定性和倍率性能较差，Fe 3+/Fe 2+数值较大，可能是因为实施例4中CO 2的分压过小，O 2的分压过大，进而氧化性气氛的氧化性较强，不仅除去了废旧磷酸铁锂极片中多余的碳组分，而且还将废旧磷酸铁锂材料中磷酸铁锂外包覆的碳组分剥离，同时还将废旧磷酸铁锂中部分Fe 2+氧化为Fe 3+，进而制得正极材料的循环稳定性和倍率性能较差，Fe 3+/Fe 2+数值较大。
通过表1和表2可以看出，实施例7相对于实施例1，C含量较高，倍率性能较差，克容量较低，可能是因为实施例7中CO 2的分压过小，氮气的分压过大，进而氧化性气氛的氧化性较弱，制得正极材料中碳含量较高，进而制得正极材料中活性物质含量较低，容量较低。
通过表1和表2可以看出，对比例1相对于实施例1，C含量较高，200周容量保持率较低，倍率性能较差，克容量较低，可能是因为对比例1中的正极 材料没有进行氧化除碳过程，得到的正极材料中碳含量较高，活性物质含量较低，实施例1相对于对比例1克容量提升5％～10％。
通过表1和表2可以看出，对比例2相对于实施例1的循环稳定性和倍率性能较差，可能是因为对比例2中的氧化性气氛为二氧化氮，氧化性较强，在高温时将正极材料磷酸铁锂中的Fe 2+氧化为Fe 3+，而且还将废旧磷酸铁锂材料中磷酸铁锂外包覆的碳组分剥离，进而制得的正极材料的循环稳定性和倍率性能较差。
申请人声明，本申请通过上述实施例来说明本申请的详细工艺设备和工艺流程，但本申请并不局限于上述详细工艺设备和工艺流程，即不意味着本申请必须依赖上述详细工艺设备和工艺流程才能实施。

Claims (14)

  1. 一种正极材料的回收方法，其中，所述方法包括如下步骤：
    将待回收正极材料在氧化性气氛下烧结，得到回收的正极材料；
    所述氧化性气氛中的气体包括CO 2。
  2. 如权利要求1所述的方法，其中，所述氧化性气氛中CO 2的分压占比P为0.1～1，可选0.8～1；
    可选地，所述
    Figure PCTCN2019099177-appb-100001
    为氧化性气氛中CO 2的分压，P 总为氧化性气氛中所有气体总压力。
  3. 如权利要求1或2所述的方法，其中，所述氧化性气氛还包括保护性气体与强氧化性气体中的任意一种或至少两种的混合；
    可选地，所述氧化性气氛包括CO 2和强氧化性气体，所述强氧化性气体的分压占比≤0.2；
    可选地，所述氧化性气氛包括CO 2和保护性气体，所述保护性气体的分压占比≤0.95；
    可选地，所述强氧化性气体包括氧气、氯气、氟气、二氧化氮、臭氧、三氧化硫中的任意一种或至少两种的组合，可选氧气；
    可选地，所述保护性气体包括氮气、氩气、氦气、氖气、氪气和氙气中的任意一种或至少两种的组合，可选氮气。
  4. 如权利要求1-3中任一项所述的方法，其中，所述待回收正极材料的粒度分布D50为0.5～5.0μm；
    可选地，所述待回收正极材料包括待回收碳包覆磷酸铁锂；
    可选地，所述待回收正极材料中水含量为50～5000ppm。
  5. 如权利要求1-4之一所述的方法，其中，所述烧结的温度为650～800℃， 可选730～780℃；
    可选地，所述烧结的时间为5～20h，可选10～15h；
    可选地，所述烧结过程的气流量为2～20m 3/h，可选5～15m 3/h；
    可选地，所述烧结的方式为动态烧结或静态烧结；
    可选地，所述动态烧结为回转窑炉烧结；
    可选地，所述静态烧结包括箱式炉烧结、管式炉烧结、辊道窑炉烧结和推板窑炉烧结中的任意一种或至少两种的组合；
    可选地，所述静态烧结中装料容器为石墨坩埚；
    可选地，所述静态烧结的装料厚度为1～100mm，可选10～50mm。
  6. 如权利要求1-5之一所述的方法，其中，所述待回收正极材料的制备方法包括：将废旧电池极片中废旧正极材料剥离后，进行破碎，得到待回收正极材料；
    可选地，所述剥离包括湿法浸泡剥离或干法煅烧剥离；
    可选地，所述湿法浸泡剥离包括：将废旧电池极片浸泡在溶液中，并进行分离处理；
    可选地，所述分离处理包括加热、搅拌和超声波处理中的任意一种或至少两种的组合；
    可选地，所述加热的温度为20～90℃，可选50～80℃；
    可选地，所述加热的时间为20～120min；
    可选地，所述搅拌的转速为200～1000r/min，可选300～500r/min；
    可选地，所述搅拌的时间为20～120min；
    可选地，所述超声波处理的频率为20～40KHz；
    可选地，所述超声波处理的时间为10～60min，可选20～40min；
    可选地，所述溶液为碱性溶液或有机溶剂；
    可选地，所述碱性溶液的pH为7～14，可选9～11；
    可选地，所述有机溶剂包括N,N二甲基乙酰胺、二甲基亚砜、四甲基脲、和磷酸三甲酯中的任意一种或至少两种的组合；
    可选地，所述干法煅烧剥离包括：将废旧电池极片放入加热反应器中，在氮气气氛或氩气气氛下煅烧；
    可选地，所述煅烧的温度为400～600℃，可选450～550℃；
    可选地，所述煅烧的时间为1～10h，可选1～3h；
    可选地，所述加热反应器包括箱式炉、管式炉、辊道窑炉、推板窑炉或回转窑炉中的任意一种。
  7. 如权利要求1-6之一所述的方法，其中，所述剥离的方式为干法煅烧剥离，所述破碎的方式为机械破碎或气流粉碎；
    可选地，所述剥离的方式为湿法浸泡剥离，所述破碎的方式为湿法球磨或砂磨；
    可选地，所述剥离的方式为湿法浸泡剥离，所述破碎后的正极材料经干燥后得到待回收正极材料；
    可选地，所述干燥的方式包括抽滤、压滤和喷雾干燥中的任意一种或至少两种的组合；
    可选地，所述喷雾干燥的进风口温度为200～260℃；
    可选地，所述喷雾干燥的出风口温度为70～130℃；
    可选地，所述喷雾干燥的压缩空气进气气压为0.1～0.8MPa；
    可选地，所述喷雾干燥的进气流速为1～15m 3/h；
    可选地，所述喷雾干燥的进料速率为0.5～10L/h；
    可选地，所述喷雾干燥的浆料固含量为5％～40％。
  8. 一种如权利要求1-7之一所述的正极材料的回收方法，其中，所述方法包括如下步骤：
    (1)将废旧电池极片放入管式炉中，在氮气气氛下450～550℃煅烧1～3h，得到剥离后的废旧正极材料，然后将干法煅烧剥离后的废旧正极材料进行机械破碎，得到粒度分布D50为0.5～5.0μm的待回收正极材料；
    (2)在含有CO 2的氧化性气氛下，将所述待回收正极材料在730～780℃温度下管式炉烧结10～15h，气流量为5～15m 3/h，得到回收的正极材料，所述含有CO 2的氧化性气氛中CO 2的分压占比为0.1～1。
  9. 一种正极材料，其中，所述正极材料通过如权利要求1-8之一所述的正极材料的回收方法得到；
  10. 如权利要求9所述的正极材料，其中，所述正极材料包括磷酸铁锂。
  11. 如权利要求9所述的正极材料，其中，所述正极材料的粒度分布D50为0.2～5μm，可选0.5～2μm；
    可选地，所述正极材料的碳含量为2～5wt％。
  12. 一种如权利要求9-11中任一项所述正极材料的用途，其中，所述正极材料应用于电池领域。
  13. 如权利要求12所述的正极材料的用途，其中，所述正极材料用于锂离子电池正极材料领域。
  14. 一种锂离子电池，其中，所述锂离子电池包括如权利要求9-11中任一 项所述的正极材料。
PCT/CN2019/099177 2019-04-09 2019-08-05 正极材料的回收方法、得到的正极材料及其用途 WO2020206884A1 (zh)

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