WO2024093095A1 - 碱金属离子电池正极材料修复再生方法、正极材料及应用 - Google Patents

碱金属离子电池正极材料修复再生方法、正极材料及应用 Download PDF

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WO2024093095A1
WO2024093095A1 PCT/CN2023/083148 CN2023083148W WO2024093095A1 WO 2024093095 A1 WO2024093095 A1 WO 2024093095A1 CN 2023083148 W CN2023083148 W CN 2023083148W WO 2024093095 A1 WO2024093095 A1 WO 2024093095A1
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positive electrode
alkali metal
electrode material
metal ion
repairing
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French (fr)
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吴芷菁
余海军
谢英豪
李爱霞
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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
    • H01M4/36—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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

  • the present invention relates to the technical field of alkali metal ion batteries, and in particular to a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, positive electrode materials and applications.
  • Alkali metal ion batteries include lithium ion batteries, sodium ion batteries and potassium ion batteries. Among them, lithium ion batteries are currently widely used, while sodium ion batteries and potassium ion batteries are less used and are mainly in the research stage.
  • nickel-cobalt-manganese oxide has the advantages of low pollution, low cost, high performance, and good stability.
  • CN110724818A discloses a full wet recovery process for waste lithium batteries, which has the advantages of short process and high recovery rate.
  • the traditional wet process involves acid dissolution and chemical precipitation, and a large amount of acid solution is used, which complicates the recovery process.
  • CN111410239A discloses a regeneration and recovery method for retired nickel cobalt manganese oxide battery positive electrode materials, which regenerates positive electrode materials by directly supplementing lithium calcination, and has the advantages of simple operation, low cost and high recovery rate.
  • the purpose of the present invention is to provide a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, positive electrode materials and applications.
  • the present invention is achieved in that:
  • the present invention provides a method for repairing and regenerating a positive electrode material of an alkali metal ion battery, comprising the following steps:
  • Pretreatment doping the recovered positive electrode material with halide ions, and/or reducing Ni 3+ in the positive electrode material with alkyl radicals;
  • Alkali metal supplementation analyzing the content of each element in the recovered positive electrode material, and supplementing the doped positive electrode material with alkali metal ions according to the element stoichiometric ratio of the positive electrode material;
  • Sintering Sintering the positive electrode material after supplementing the alkali metal ions to obtain a repaired positive electrode material.
  • the pretreatment is to use a plasma generator to perform plasma irradiation on the positive electrode material
  • the gas source of the plasma generating device is a halogenated hydrocarbon
  • the halogen in the alkyl halide is fluorine
  • the alkyl halide is at least one of monofluoroethane, monofluoromethane or 1-fluoropropane.
  • the fluorine doping amount is 0.5%-5% of the mass fraction of the recovered positive electrode material.
  • the power of the plasma generating device is 50-200 W, and the plasma irradiation time is 5-60 min.
  • the positive electrode material contains alkali metal and nickel
  • the positive electrode material is a lithium-ion battery positive electrode material
  • the positive electrode material is NCM positive electrode material.
  • the positive electrode material is in powder form.
  • the supplementation of alkali metal ions is to mix the pretreated positive electrode material with an alkali metal source;
  • the mixing is performed by grinding
  • the alkali metal source is one or more of alkali metal hydroxides, alkali metal carbonates, alkali metal sulfates, alkali metal nitrates, alkali metal chlorides, alkali metal oxalates, and alkali metal acetates;
  • the alkali metal is lithium.
  • the sintering temperature is 800-1000° C., and the sintering time is 2-10 h;
  • the sintering is performed in an oxygen atmosphere.
  • the positive electrode material is obtained by pyrolyzing a positive electrode sheet.
  • the present invention provides a positive electrode material obtained by the method for repairing and regenerating positive electrode materials for alkali metal ion batteries as described in any one of the aforementioned embodiments.
  • the present invention provides a use of the positive electrode material described in any one of the aforementioned embodiments in an alkali metal ion battery.
  • the present application adopts halide ions to dope the recovered positive electrode materials.
  • the incorporation of halide ions can attract alkali metal ions, reduce the migration energy of alkali metals, and stabilize the material skeleton; alkane free radicals are reducing and can reduce Ni 3+ to Ni 2+ .
  • alkane free radicals are reducing and can reduce Ni 3+ to Ni 2+ .
  • the diffusion resistance of alkali metal ions can be reduced. Both of them can make the waste positive electrode materials have a better alkali metal replenishment effect in the alkali metal replenishment process.
  • FIG1 is a flow chart of the repair and regeneration of positive electrode materials for alkali metal ion batteries in the present application.
  • This embodiment provides a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, as shown in FIG1 , comprising the following steps:
  • Pretreatment doping the recovered positive electrode material with halide ions, and/or reducing Ni 3+ in the positive electrode material with alkyl radicals;
  • Sintering Sintering the positive electrode material after supplementing the alkali metal ions to obtain a repaired positive electrode material.
  • the present application adopts halide ions to dope the recovered positive electrode material.
  • the incorporation of halide ions can attract alkali metal ions, reduce the migration energy of alkali metals, and stabilize the material skeleton; alkane free radicals are reducing and can reduce Ni 3+ to Ni 2+ .
  • alkane free radicals are reducing and can reduce Ni 3+ to Ni 2+ .
  • the diffusion resistance of alkali metal ions can be reduced. Both of them can make the waste positive electrode powder have a better alkali metal replenishment effect in the alkali metal replenishment process.
  • the prior art has fluorine doping in the process of synthesizing positive electrode materials, but the technical problem solved by this application is different from that solved by this application.
  • the purpose of doping with halogen ions such as fluorine is to make the replenishment process of alkali metal ions more efficient and effective.
  • doping with fluorine during the synthesis process will replace the position of other anions (such as oxygen) instead of increasing the anion content, and cannot increase the anion ratio and adjust the charge balance.
  • the pretreatment is to use a plasma generator to perform plasma irradiation on the positive electrode material
  • the gas source of the plasma generating device is a halogenated hydrocarbon
  • the halogen in the alkyl halide is fluorine
  • the alkyl halide is at least one of monofluoroethane, monofluoromethane or 1-fluoropropane.
  • the fluorine doping amount is 0.5%-5% of the mass fraction of the recovered positive electrode material.
  • the plasma in this embodiment can be generated by electrostatic coupling, inductive coupling, and electromagnetic wave coupling.
  • plasma doping on the one hand, will not cause the introduction of a large amount of carbon elements while doping fluorine ions, and will not reduce the initial discharge gram capacity of the material; on the other hand, alkyl radicals and halide ions can react more fully with the positive electrode material, and the doping effect is better.
  • the plasma doping method adopted does not need to introduce other impurities.
  • the doping effect can be controlled by controlling the flow rate of the doping material and the power of the plasma generator.
  • the doping method is more environmentally friendly and controllable.
  • the power of the plasma generating device is any value between 50-200 W, for example, 50 W, 100 W, 150 W, 200 W, etc. can be selected; the plasma irradiation time is any value between 5-60 min, for example, 5 min, 15 min, 30 min, 45 min, 60 min, etc. can be selected.
  • the optimal parameters of power, irradiation time and doping material flow rate can be adjusted according to the doping amount.
  • the positive electrode material contains alkali metal and nickel
  • the positive electrode material is a lithium-ion battery positive electrode material
  • the positive electrode material is NCM positive electrode material.
  • the positive electrode material is in powder form, and the particle size is related to the recycled positive electrode material.
  • the powder form is beneficial to improving the uniformity of doping.
  • the supplementary alkali metal ions are added by mixing the pretreated positive electrode material and the alkali metal source. mix;
  • the mixing is performed by grinding
  • the alkali metal source is one or more of alkali metal hydroxides, alkali metal carbonates, alkali metal sulfates, alkali metal nitrates, alkali metal chlorides, alkali metal oxalates, and alkali metal acetates;
  • the alkali metal is lithium.
  • the sintering temperature can be any value between 800-1000°C, for example, 800°C, 850°C, 900°C, 950°C, 100°C, etc. can be selected, and the sintering time can be any value between 2-10h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc. can be selected;
  • the sintering is performed in an oxygen atmosphere.
  • the positive electrode material is obtained by pyrolysis of the positive electrode sheet. Pyrolysis is only to separate the positive electrode material in the positive electrode sheet. In order to improve the doping effect, the positive electrode material can be crushed after separation to make the positive electrode material into powder.
  • the present invention provides a positive electrode material obtained by the method for repairing and regenerating positive electrode materials for alkali metal ion batteries as described in any one of the aforementioned embodiments.
  • the present invention provides a use of the positive electrode material described in any one of the aforementioned embodiments in an alkali metal ion battery.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, comprising the following steps:
  • Step 1 After discharging, disassemble and sort the used NCM523 batteries to obtain the positive electrode sheets.
  • Step 2 Pyrolysis the positive electrode sheet to peel off the positive electrode powder.
  • Step 3 Plasma doping of the waste positive electrode powder.
  • the plasma power is 100W
  • the treatment time is 5min
  • the doping raw material is fluoroethane.
  • the fluorine doping amount is 1% of the mass fraction of the failed positive electrode material. If the fluorine doping amount obtained by elemental analysis is insufficient, the treatment is performed again until the fluorine doping amount is 1% of the mass fraction of the failed positive electrode material.
  • Step 4 Weigh the lithium source to be supplemented according to the element stoichiometric ratio of the positive electrode material. Grind and mix the waste positive electrode powder after doping with lithium carbonate.
  • Step 5 After grinding, the powder is sintered at 850°C for 4 hours in an oxygen atmosphere to obtain the repaired positive electrode material.
  • the repaired positive electrode material was tested in the following way: the repaired positive electrode was The material, acetylene black and PVDF were homogenized and then coated on aluminum foil. After drying, the electrode pieces were cut, weighed, rolled and vacuum dried to obtain the positive electrode pieces.
  • the metal lithium sheet was used as the negative electrode, Celgard 2500 was used as the separator, the electrolyte lithium salt was 1.0M LiPF 6 , and the electrolyte solvent was EC:DMC with a mass ratio of 3:7.
  • CR2032 button batteries were assembled in a glove box.
  • the test temperature was 25°C
  • the test cutoff voltage was 2.8-4.3V
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, comprising the following steps:
  • Step 1 After discharging, disassemble and sort the used NCM523 batteries to obtain the positive electrode sheets.
  • Step 2 Pyrolysis the positive electrode sheet to peel off the positive electrode powder.
  • Step 3 Plasma doping of the waste positive electrode powder.
  • the plasma power is 100W
  • the treatment time is 3min
  • the doping raw material is fluoromethane.
  • the fluorine doping amount is 0.5% of the mass fraction of the failed positive electrode material. If the fluorine doping amount obtained by elemental analysis is insufficient, the treatment is performed again until the fluorine doping amount is 0.5% of the mass fraction of the failed positive electrode material.
  • Step 4 Analyze the content of each element, and grind and mix the waste positive electrode powder after doping with lithium carbonate according to the element stoichiometric ratio of the positive electrode material.
  • Step 5 After grinding, the powder is sintered at 850°C for 4 hours in an oxygen atmosphere to obtain the repaired positive electrode material.
  • Example 2 Under the same method and conditions as in Example 1, it was measured that the initial discharge capacity of the repaired and regenerated material could reach 151.8 mAh/g. After 100 cycles, the discharge capacity was 141 mAh/g, and the capacity retention rate was 92.9%.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • This embodiment provides a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, comprising the following steps:
  • Step 1 After discharging, disassemble and sort the used NCM523 batteries to obtain the positive electrode sheets.
  • Step 2 Pyrolysis the positive electrode sheet to peel off the positive electrode powder.
  • Step 3 Plasma doping of the waste positive electrode powder.
  • the plasma power is 100W
  • the treatment time is 8min
  • the doping raw material is fluoromethane.
  • the fluorine doping amount is 2% of the mass fraction of the failed positive electrode material. If the fluorine doping amount obtained by elemental analysis is insufficient, the treatment is performed again until the fluorine doping amount is 2% of the mass fraction of the failed positive electrode material.
  • Step 4 Analyze the content of each element, and grind and mix the waste positive electrode powder after doping with lithium carbonate according to the element stoichiometric ratio of the positive electrode material.
  • Step 5 After grinding, the powder is sintered at 850°C for 4 hours in an oxygen atmosphere to obtain the repaired positive electrode material.
  • Example 2 Under the same method and conditions as in Example 1, it was measured that the initial discharge capacity of the repaired and regenerated material could reach 150.9 mAh/g. After 100 cycles, the discharge capacity was 140.9 mAh/g, and the capacity retention rate was 93.4%.
  • This embodiment provides a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, comprising the following steps:
  • Step 1 After discharging, disassemble and sort the used NCM523 batteries to obtain the positive electrode sheets.
  • Step 2 Pyrolysis the positive electrode sheet to peel off the positive electrode powder.
  • Step 3 Plasma doping of the waste positive electrode powder.
  • the plasma power is 100W
  • the treatment time is 2min
  • the doping raw material is fluorine gas.
  • the fluorine doping amount is 1% of the mass fraction of the failed positive electrode material. If the fluorine doping amount obtained by elemental analysis is insufficient, the treatment is performed again until the fluorine doping amount is 1% of the mass fraction of the failed positive electrode material.
  • Step 4 Analyze the content of each element, and grind and mix the waste positive electrode powder after doping with lithium carbonate according to the element stoichiometric ratio of the positive electrode material.
  • Step 5 After grinding, the powder is sintered at 850°C for 4 hours in an oxygen atmosphere to obtain the repaired positive electrode material.
  • Example 2 Under the same method and conditions as in Example 1, it was measured that the initial discharge capacity of the repaired and regenerated material could reach 142.3 mAh/g. After 100 cycles, the discharge capacity was 125.4 mAh/g, and the capacity retention rate was 88.1%.
  • This embodiment provides a method for repairing and regenerating positive electrode materials of alkali metal ion batteries, comprising the following steps:
  • Step 1 After discharging, disassemble and sort the used NCM523 batteries to obtain the positive electrode sheets.
  • Step 2 Pyrolysis the positive electrode sheet to peel off the positive electrode powder.
  • Step 3 Plasma doping of waste cathode powder.
  • Plasma power is 100 W
  • treatment time is 5 min
  • doping raw material is methane.
  • Step 4 Analyze the content of each element, and grind and mix the waste positive electrode powder after doping with lithium carbonate according to the element stoichiometric ratio of the positive electrode material.
  • Step 5 After grinding, the powder is sintered at 850°C for 4 hours in an oxygen atmosphere to obtain the repaired positive electrode material.
  • Example 2 Under the same method and conditions as in Example 1, it was measured that the initial discharge capacity of the repaired and regenerated material could reach 147.2 mAh/g. After 100 cycles, the discharge capacity was 119.4 mAh/g, and the capacity retention rate was 81.1%.
  • This comparative example provides a method for repairing and regenerating a positive electrode material of an alkali metal ion battery, comprising the following steps:
  • Step 1 After discharging, disassemble and sort the used NCM523 batteries to obtain the positive electrode sheets.
  • Step 2 Pyrolysis the positive electrode sheet to peel off the positive electrode powder.
  • Step 3 Analyze the content of each element, grind and mix the waste positive electrode powder and the lithium source according to the element stoichiometric ratio of the positive electrode material.
  • the lithium source is lithium hydroxide.
  • Step 4 After grinding, the powder is sintered at 850°C for 4 hours in an oxygen atmosphere to obtain the repaired positive electrode material.
  • Example 2 Under the same method and conditions as in Example 1, it was measured that the initial discharge capacity of the repaired and regenerated material could reach 140.3 mAh/g. After 100 cycles, the discharge capacity was 116.7 mAh/g, and the capacity retention rate was 83.2%.

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Abstract

本发明公开了碱金属离子电池正极材料修复再生方法、正极材料及应用，其中修复再生方法包括：预处理，采用卤离子对回收的正极材料进行掺杂，和/或采用烷基自由基对正极材料中的Ni3+进行还原；补碱金属，向预处理后的正极材料中补充碱金属离子；烧结，对补充碱金属离子后的正极材料进行烧结。本申请采用卤离子对回收的正极材料进行掺杂，卤离子的掺入能够起到吸引碱金属离子的作用，降低碱金属的迁移能，并且还能够稳定材料骨架；烷烃自由基具有还原性，能够将Ni3+还原成Ni2+，根据电荷守恒的原理，能够降低碱金属离子的扩散阻力，二者均能够使得废旧正极粉末在补碱金属过程中能具有更好的补碱金属效果。

Description

碱金属离子电池正极材料修复再生方法、正极材料及应用 技术领域
本发明涉及碱金属离子电池技术领域，具体而言，涉及碱金属离子电池正极材料修复再生方法、正极材料及应用。
背景技术
碱金属离子电池包括锂离子电池、钠离子电池和钾离子电池等，其中锂离子电池目前已广泛使用，钠离子电池和钾离子电池使用较少，主要处于研究阶段。
对于锂离子电池而言，镍钴锰酸锂具有低污染、低成本、高性能、稳定好等优点，作为目前使用最广泛的锂电池正极材料之一，其具有极好的发展前景。随着三元电池的用量逐年增加，产生了大量废旧电池，其含有的大量有价组分具有极大的回收价值和意义。面对如此巨大的回收市场，急需开发高效低成本的回收技术以避免资源的浪费。
传统工艺一般是通过回收有价金属元素，将其制备成有价金属盐后再制备正极材料。如CN110724818A公开了一种废旧锂电池的全湿法回收工艺，具有流程简短且回收率高的优势。但是传统湿法工艺涉及酸溶解和化学沉淀，会大量使用酸液，使回收过程复杂化。此外存在部分再生方法，通过直接通过补充锂元素的方式再生修复正极材料。如CN111410239A公开了一种退役镍钴锰酸锂电池正极材料的再生回收方法，采用直接补锂煅烧的方式再生正极材料，具有操作简单、成本低廉、回收率高的优点。但是废旧正极材料中Ni3+的存在给与补锂过程中Li+离子很大的排斥力，使得Li+离子难以补充回废旧正极材料的缺陷位中，导致补锂效率难以满足期待。
根据目前锂离子电池的发展情况，我们可以推测钠离子电池和钾离子电池等可能也会面临与锂离子电池相似的情况，因此开发一种补碱金属效率高的废旧碱金属离子电池正极修复再生方法十分有必要。
鉴于此，特提出本发明。
发明内容
本发明的目的在于提供碱金属离子电池正极材料修复再生方法、正极材料及应用。
本发明是这样实现的：
第一方面，本发明提供一种碱金属离子电池正极材料修复再生方法，包括以下步骤：
预处理，采用卤离子对回收的正极材料进行掺杂，和/或采用烷基自由基对正极材料中的Ni3+进行还原；
补碱金属，分析回收的正极材料中各元素的含量，依据正极材料的元素计量比，向掺杂后的正极材料中补充碱金属离子；
烧结，对补充碱金属离子后的正极材料进行烧结，得到修复后的正极材料。
在可选的实施方式中，所述预处理是采用等离子体发生装置对正极材料进行等离子体照射；
优选地，所述等离子体发生装置的气源为卤代烷；
优选地，所述卤代烷中的卤素为氟；
优选地，所述卤代烷为一氟乙烷、一氟甲烷或1-氟丙烷1-氟丙烷中的至少一种。
优选地，所述氟元素掺杂量为所述回收的正极材料质量分数的0.5％-5％。
在可选的实施方式中，所述等离子体发生装置的功率为50-200W，所述等离子体照射的时间5-60min。
在可选的实施方式中，所述正极材料中含有碱金属和镍；
优选地，所述正极材料为锂离子电池正极材料；
优选地，所述正极材料为NCM正极材料。
在可选的实施方式中，所述正极材料为粉末状。
在可选的实施方式中，所述补充碱金属离子是将预处理后的正极材料和碱金属源混合；
优选地，所述混合采用研磨的方式进行；
优选地，所述碱金属源为碱金属的氢氧化物、碱金属的碳酸盐、碱金属的硫酸盐、碱金属的硝酸盐、碱金属的氯盐、碱金属的草酸盐、碱金属的醋酸盐中的一种或多种；
优选地，所述碱金属为锂。
在可选的实施方式中，所述烧结温度为800-1000℃，烧结时间为2-10h；
优选地，所述烧结在氧气气氛下进行。
在可选的实施方式中，所述正极材料是对正极片进行热解得到。
第二方面，本发明提供一种前述实施方式任意一项所述碱金属离子电池正极材料修复再生方法得到的正极材料。
第三方面，本发明提供一种前述实施方式任意一项所述正极材料在碱金属离子电池中的应用。
本发明具有以下有益效果：
本申请采用卤离子对回收的正极材料进行掺杂，卤离子的掺入能够起到吸引碱金属离子的作用，降低碱金属的迁移能，并且还能够稳定材料骨架；烷烃自由基具有还原性，能够将Ni3+还原成Ni2+，根据电荷守恒的原理，能够降低碱金属离子的扩散阻力，二者均能够使得废旧正极材料在补碱金属过程中能具有更好的补碱金属效果。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本申请中碱金属离子电池正极材料修复再生的流程图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本实施例提供一种碱金属离子电池正极材料修复再生方法，如图1所示，包括以下步骤：
预处理，采用卤离子对回收的正极材料进行掺杂，和/或采用烷基自由基对正极材料中的Ni3+进行还原；
补碱金属，分析各元素的含量，依据回收的正极材料的元素计量比，向掺杂后的正极材料中补充碱金属离子；
烧结，对补充碱金属离子后的正极材料进行烧结，得到修复后的正极材料。
本申请采用卤离子对回收的正极材料进行掺杂，卤离子的掺入能够起到吸引碱金属离子的作用，降低碱金属的迁移能，并且还能够稳定材料骨架；烷烃自由基具有还原性，能够将Ni3+还原成Ni2+，根据电荷守恒的原理，能够降低碱金属离子的扩散阻力，二者均能够使得废旧正极粉末在补碱金属过程中能具有更好的补碱金属效果。
当采用卤离子对正极材料进行掺杂，同时采用烷基自由基对正极材料中的Ni3+进行还原，二者协同使得这一方式处理后的废旧正极粉末在补碱金属过程中，相对单独掺杂卤离子、或单独采用烷基自由基对正极材料中的Ni3+进行还原，补碱金属效果具有更加明显的提升。
现有技术有在合成正极材料的过程中掺氟，但本申请与其解决的技术问题不同，本申请进 行掺氟等卤离子是为了使得碱金属离子的补充过程效率更高、效果更好。而且合成过程中掺氟，会取代其它阴离子(比如氧)的位置，而不是增加阴离子含量，并不能起到提高阴离子比例，调节电荷平衡的作用。
本申请的其他可选实施方式中，所述预处理是采用等离子体发生装置对正极材料进行等离子体照射；
优选地，所述等离子体发生装置的气源为卤代烷；
优选地，所述卤代烷中的卤素为氟；
优选地，所述卤代烷为一氟乙烷、一氟甲烷或1-氟丙烷1-氟丙烷中的至少一种。
优选地，所述氟元素掺杂量为所述回收的正极材料质量分数的0.5％-5％。
本实施例中的等离子体可以采用静电耦合、感应耦合、电磁波耦合的方式产生，等离子体掺杂相比于普通的混合掺杂方式，一方面，采用等离子体掺杂在掺杂氟离子的同时不会造成碳元素的大量引入，不会降低材料的初始放电克容量；另一方面，烷基自由基和卤离子能够更充分的与正极材料进行作用，掺杂效果更好。
失效的三元正极材料中存在氧空位，氟的电负性比氧强，氟进入氧空位后不易被夺取，氟进入氧空位增加负离子的含量，而由于正极材料中并没有能够容纳烷基自由基的空位，因此，烷基自由基使三价镍还原成二价镍后，并未掺杂在正极材料内，返二者可共同减小补锂过程中锂进入的阻力。
以卤代烷作为掺杂原料，采用的等离子掺杂方式无需引入其他杂质，通过控制掺杂原料流速以及等离子体发生装置功率可以控制掺杂效果，掺杂方式更为环保可控。
本申请的其他可选实施方式中，所述等离子体发生装置的功率为50-200W之间的任意数值，例如可以选择50W、100W、150W、200W等；所述等离子体照射的时间5-60min之间的任意数值，例如可以选择5min、15min、30min、45min、60min等。
功率、照射时间以及掺杂原料流速的最优参数可以根据掺杂量进行调整。
本申请的其他可选实施方式中，所述正极材料中含有碱金属和镍；
优选地，所述正极材料为锂离子电池正极材料；
优选地，所述正极材料为NCM正极材料。
本申请的其他可选实施方式中，所述正极材料为粉末状，粒径与回收的正极材料有关，粉末状有利于提高掺杂的均匀性。
本申请的其他可选实施方式中，所述补充碱金属离子是将预处理后的正极材料和碱金属源 混合；
优选地，所述混合采用研磨的方式进行；
优选地，所述碱金属源为碱金属的氢氧化物、碱金属的碳酸盐、碱金属的硫酸盐、碱金属的硝酸盐、碱金属的氯盐、碱金属的草酸盐、碱金属的醋酸盐中的一种或多种；
优选地，所述碱金属为锂。
本申请的其他可选实施方式中，所述烧结温度可以为800-1000℃之间的任意数值，例如可以选择800℃、850℃、900℃、950℃、100℃0等，烧结时间可以为2-10h之间的任意数值，例如可以选择2h、3h、4h、5h、6h、7h、8h、9h、10h等；
优选地，所述烧结在氧气气氛下进行。
本申请的其他可选实施方式中，所述正极材料是对正极片进行热解得到，热解仅仅是对正极片中的正极材料进行分离，为了提高掺杂效果，正极材料分离后可以进行破碎操作，使得正极材料成粉末状。
第二方面，本发明提供一种前述实施方式任意一项所述碱金属离子电池正极材料修复再生方法得到的正极材料。
第三方面，本发明提供一种前述实施方式任意一项所述正极材料在碱金属离子电池中的应用。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
实施例1：
本实施例提供一种碱金属离子电池正极材料修复再生方法，包括以下步骤：
步骤1：将废旧NCM523电池放电后进行拆解分选，得到正极片。
步骤2：对正极片进行热解处理，剥离正极粉末。
步骤3：对废旧正极粉末进行等离子体掺杂。等离子体功率100W，处理时间5min，掺杂原料为氟乙烷。根据元素分析得到，所述氟元素掺杂量为失效正极材料质量分数的1％。若元素分析得到的氟掺杂量不足，则再次进行处理，直至氟元素掺杂量为失效正极材料质量分数的1％。
步骤4：依据正极材料的元素计量比，称取需要补充的锂源。将掺杂完成后的废旧正极粉末和碳酸锂研磨混合。
步骤5：研磨完成后，在氧气气氛下，850℃对粉末烧结4h，得到修复后的正极材料。
对修复后的正极材料进行容量测试，具体方式为：按照8:1:1的质量比将修复再生后的正极 材料、乙炔黑和PVDF进行匀浆，然后将其涂布在铝箔上，干燥后进行裁极片，称重，辊压，真空干燥后得到正极极片；以金属锂片为负极，以Celgard 2500为隔膜，电解液锂盐为1.0M LiPF6，电解液溶剂为EC：DMC的质量比为3:7。在手套箱中组装成CR2032扣式电池。
测试温度为25℃，测试截止电压为2.8-4.3V，测试过程以1C(1C＝150mAh/g)倍率下进行充放电，测得修复再生后材料的初始放电克容量可达到151.5mAh/g，100周循环后，放电克容量为141.2mAh/g，容量保持率93.2％。
实施例2：
本实施例提供一种碱金属离子电池正极材料修复再生方法，包括以下步骤：
步骤1：将废旧NCM523电池放电后进行拆解分选，得到正极片。
步骤2：对正极片进行热解处理，剥离正极粉末。
步骤3：对废旧正极粉末进行等离子体掺杂。等离子体功率100W，处理时间3min，掺杂原料为氟甲烷。根据元素分析得到，所述氟元素掺杂量为失效正极材料质量分数的0.5％。若元素分析得到的氟掺杂量不足，则再次进行处理，直至氟元素掺杂量为失效正极材料质量分数的0.5％。
步骤4：分析各元素的含量，依据正极材料的元素计量比，将掺杂完成后的废旧正极粉末和碳酸锂研磨混合。
步骤5：研磨完成后，在氧气气氛下，850℃对粉末烧结4h，得到修复后的正极材料。
在与实施例1相同的方法和条件下，测得修复再生后材料的初始放电克容量可达到151.8mAh/g，100周循环后，放电克容量为141mAh/g，容量保持率92.9％。
实施例3：
本实施例提供一种碱金属离子电池正极材料修复再生方法，包括以下步骤：
步骤1：将废旧NCM523电池放电后进行拆解分选，得到正极片。
步骤2：对正极片进行热解处理，剥离正极粉末。
步骤3：对废旧正极粉末进行等离子体掺杂。等离子体功率100W，处理时间8min，掺杂原料为氟甲烷。根据元素分析得到，所述氟元素掺杂量为失效正极材料质量分数的2％。若元素分析得到的氟掺杂量不足，则再次进行处理，直至氟元素掺杂量为失效正极材料质量分数的2％。
步骤4：分析各元素的含量，依据正极材料的元素计量比，将掺杂完成后的废旧正极粉末和碳酸锂研磨混合。
步骤5：研磨完成后，在氧气气氛下，850℃对粉末烧结4h，得到修复后的正极材料。
在与实施例1相同的方法和条件下，测得修复再生后材料的初始放电克容量可达到150.9mAh/g，100周循环后，放电克容量为140.9mAh/g，容量保持率93.4％。
对比例1：
本实施例提供一种碱金属离子电池正极材料修复再生方法，包括以下步骤：
步骤1：将废旧NCM523电池放电后进行拆解分选，得到正极片。
步骤2：对正极片进行热解处理，剥离正极粉末。
步骤3：对废旧正极粉末进行等离子体掺杂。等离子体功率100W，处理时间2min，掺杂原料为氟气。根据元素分析得到，所述氟元素掺杂量为失效正极材料质量分数的1％。若元素分析得到的氟掺杂量不足，则再次进行处理，直至氟元素掺杂量为失效正极材料质量分数的1％。
步骤4：分析各元素的含量，依据正极材料的元素计量比，将掺杂完成后的废旧正极粉末和碳酸锂研磨混合。
步骤5：研磨完成后，在氧气气氛下，850℃对粉末烧结4h，得到修复后的正极材料。
在与实施例1相同的方法和条件下，测得修复再生后材料的初始放电克容量可达到142.3mAh/g，100周循环后，放电克容量为125.4mAh/g，容量保持率88.1％。
对比例2：
本实施例提供一种碱金属离子电池正极材料修复再生方法，包括以下步骤：
步骤1：将废旧NCM523电池放电后进行拆解分选，得到正极片。
步骤2：对正极片进行热解处理，剥离正极粉末。
步骤3：对废旧正极粉末进行等离子体掺杂。等离子体功率100W，处理时间5min，掺杂原料为甲烷。
步骤4：分析各元素的含量，依据正极材料的元素计量比，将掺杂完成后的废旧正极粉末和碳酸锂研磨混合。
步骤5：研磨完成后，在氧气气氛下，850℃对粉末烧结4h，得到修复后的正极材料。
在与实施例1相同的方法和条件下，测得修复再生后材料的初始放电克容量可达到147.2mAh/g，100周循环后，放电克容量为119.4mAh/g，容量保持率81.1％。
对比例3：
本对比例提供一种碱金属离子电池正极材料修复再生方法，包括以下步骤：
步骤1：将废旧NCM523电池放电后进行拆解分选，得到正极片。
步骤2：对正极片进行热解处理，剥离正极粉末。
步骤3：分析各元素的含量，依据正极材料的元素计量比，将废旧正极粉末和锂源研磨混合。锂源为氢氧化锂。
步骤4：研磨完成后，在氧气气氛下，850℃对粉末烧结4h，得到修复后的正极材料。
在与实施例1相同的方法和条件下，测得修复再生后材料的初始放电克容量可达到140.3mAh/g，100周循环后，放电克容量为116.7mAh/g，容量保持率83.2％。
表1各实施例和对比例的效果
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种碱金属离子电池正极材料修复再生方法，其特征在于，包括以下步骤：
    预处理，采用卤离子对回收的正极材料进行掺杂，和/或采用烷基自由基对正极材料中的Ni3+进行还原；
    补碱金属，向预处理后的正极材料中补充碱金属离子；
    烧结，对补充碱金属离子后的正极材料进行烧结，得到修复后的正极材料。
  2. 根据权利要求1所述的碱金属离子电池正极材料修复再生方法，其特征在于，所述预处理是采用等离子体发生装置对正极材料进行等离子体照射；
    优选地，所述等离子体发生装置的气源为卤代烷；
    优选地，所述卤代烷中的卤素为氟；
    优选地，所述卤代烷为一氟乙烷、一氟甲烷或1-氟丙烷1-氟丙烷中的至少一种；
    优选地，所述氟元素掺杂量为所述回收的正极材料质量分数的0.5％-5％。
  3. 根据权利要求1所述的碱金属离子电池正极材料修复再生方法，其特征在于，所述等离子体发生装置的功率为50-200W，所述等离子体照射的时间5-60min。
  4. 根据权利要求1所述的碱金属离子电池正极材料修复再生方法，其特征在于，所述正极材料中含有碱金属和镍；
    优选地，所述正极材料为锂离子电池正极材料；
    优选地，所述正极材料为NCM正极材料。
  5. 根据权利要求1所述的碱金属离子电池正极材料修复再生方法，其特征在于，所述正极材料为粉末状。
  6. 根据权利要求1所述的碱金属离子电池正极材料修复再生方法，其特征在于，所述补充碱金属离子是将预处理后的正极材料和碱金属源混合；
    优选地，所述混合采用研磨的方式进行；
    优选地，所述碱金属源为碱金属的氢氧化物、碱金属的碳酸盐、碱金属的硫酸盐、碱金属的硝酸盐、碱金属的氯盐、碱金属的草酸盐、碱金属的醋酸盐中的一种或多种；
    优选地，所述碱金属为锂。
  7. 根据权利要求1所述的碱金属离子电池正极材料修复再生方法，其特征在于，所述烧结温度为800-1000℃，烧结时间为2-10h；
    优选地，所述烧结在氧气气氛下进行。
  8. 根据权利要求1所述的碱金属离子电池正极材料修复再生方法，其特征在于，所述正极材料是对正极片进行热解得到。
  9. 一种权利要求1-8任意一项所述碱金属离子电池正极材料修复再生方法得到的正极材料。
  10. 一种权利要求9所述正极材料在碱金属离子电池中的应用。
PCT/CN2023/083148 2022-11-04 2023-03-22 碱金属离子电池正极材料修复再生方法、正极材料及应用 Ceased WO2024093095A1 (zh)

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