WO2021184764A1 - 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车 - Google Patents

用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车 Download PDF

Info

Publication number
WO2021184764A1
WO2021184764A1 PCT/CN2020/124714 CN2020124714W WO2021184764A1 WO 2021184764 A1 WO2021184764 A1 WO 2021184764A1 CN 2020124714 W CN2020124714 W CN 2020124714W WO 2021184764 A1 WO2021184764 A1 WO 2021184764A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
rich manganese
positive electrode
calcination treatment
ion battery
Prior art date
Application number
PCT/CN2020/124714
Other languages
English (en)
French (fr)
Inventor
朱金鑫
王鹏飞
梁磊
李静
Original Assignee
蜂巢能源科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 蜂巢能源科技有限公司 filed Critical 蜂巢能源科技有限公司
Priority to EP20925911.8A priority Critical patent/EP4024526A4/en
Priority to US17/793,259 priority patent/US20230076419A1/en
Publication of WO2021184764A1 publication Critical patent/WO2021184764A1/zh

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Definitions

  • the present disclosure relates to the technical field of lithium-ion batteries, for example, to lithium-rich manganese-based cathode materials for lithium-ion batteries and preparation methods thereof, cathode sheets, lithium-ion batteries, and electric vehicles.
  • the present disclosure provides a lithium-rich manganese-based positive electrode material for lithium ion batteries.
  • the lithium-rich manganese-based positive electrode material has high structural stability during charge and discharge cycles, and is unlikely to cause grain boundaries due to expansion or contraction. The stress is unbalanced, and it is not easy to cause side reactions with the electrolyte, and is easy to realize industrialization.
  • the lithium ion battery produced by it has good cycle performance, good rate performance and good commercial prospects.
  • the lithium-rich manganese-based positive electrode material described in the present disclosure has high structural stability during charge and discharge cycles, is not prone to expansion or contraction to cause grain boundary stress imbalance, is not easy to have side reactions with electrolyte, and is easy to realize industrialization, and The lithium ion battery produced therefrom has good cycle performance, good rate performance and good commercial prospects.
  • the median diameter D50 of the lithium-rich manganese-based cathode material is 3-14 ⁇ m, for example: 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, or 14 ⁇ m Wait.
  • the median diameter D50 of the single crystal particles of the lithium-rich manganese-based cathode material is 1 to 200 nm, for example: 1 nm, 2 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 100 nm or 200nm and so on.
  • the lithium-rich manganese-based cathode material is 0.5Li 2 Mn 0.97 Ti 0.01 B 0.02 O 2.95 F 0.05 ⁇ 0.5LiNi 0.4 Co 0.4 Mn 0.22 B 0.02 O 1.95 F 0.05 or 0.5Li 2 Mn 0.98 B 0.02 At least one of O 2.95 F 0.05 ⁇ 0.5LiNi 0.4 Co 0.4 Mn 0.22 B 0.02 O 1.95 F 0.05.
  • a method for preparing the aforementioned lithium-rich manganese-based cathode material includes the following steps:
  • the precursor for preparing the lithium-rich manganese-based cathode material is subjected to a first calcination treatment to obtain a first preform
  • step (3) subjecting step (2) to the second calcination treatment of the first mixture to obtain a second preform
  • step (4) the second mixture is subjected to a third calcination treatment, so as to obtain the lithium-rich manganese-based positive electrode material.
  • the precursor in step (1) includes at least one of Ni 0.2 Co 0.2 Mn 0.595 Ti 0.005 CO 3 and Ni 0.2 Co 0.2 Mn 0.595 Ti 0.005 CO 2.95 F 0.05.
  • the temperature of the first calcination treatment in step (1) is 300-800°C, for example: 300°C, 400°C, 500°C, 600°C, 700°C, or 800°C.
  • the time of the first calcination treatment in step (1) is 4-12h, for example: 4h, 6h, 8h, 10h or 12h.
  • the first calcination treatment in step (1) is performed in an O 2 and/or N 2 atmosphere.
  • the additive containing the M and the M'in step (2) can be the same additive, containing both the M and the M', or the additive containing the M A mixture with an additive containing the M′, for example, in some embodiments of the present disclosure, the additive may be boride B 2 O 3 , boric acid H 3 BO 3 , lithium tetrafluoroborate LiBF 4, and the like.
  • the specific manner of mixing the two described above is not particularly limited, and those skilled in the art can make flexible selections according to actual needs, and will not be repeated here.
  • the temperature of the second calcination treatment in step (3) is 330-820°C, for example: 330°C, 400°C, 500°C, 600°C, 700°C, or 820°C.
  • the time of the second calcination treatment in step (3) is 6-12h, for example: 6h, 7h, 8h, 9h, 10h, 11h or 12h.
  • the second calcination treatment in step (3) is performed in an O 2 and/or N 2 atmosphere.
  • the lithium source in step (4) includes at least one of LiOH ⁇ H 2 O or Li 2 CO 3 and at least one of LiF or NH 4 F, thereby providing sufficient lithium Source, in order to more effectively prepare the aforementioned lithium-rich manganese-based cathode material.
  • the temperature of the third calcination treatment in step (5) is 700-950°C, for example: 700°C, 750°C, 800°C, 850°C, 900°C, or 950°C.
  • the time of the third calcination treatment in step (5) is 10-24h, for example: 10h, 12h, 14h, 16h, 18h, 20h, 21h, 22h, 23h or 24h.
  • the third calcination treatment in step (5) is performed in an O 2 and/or N 2 atmosphere.
  • a positive pole piece is provided, and the positive pole piece comprises the above-mentioned lithium-rich manganese-based positive electrode material.
  • a lithium ion battery is provided, and the ion battery includes the above-mentioned positive pole piece.
  • an electric vehicle in one embodiment of the present disclosure, includes the above-mentioned ion battery.
  • FIG. 1 is a schematic flow chart of a method for preparing a lithium-rich manganese-based cathode material in an embodiment of the present disclosure.
  • FIG. 2 is an XPS analysis test result of a lithium-rich manganese-based cathode material in an embodiment of the present disclosure.
  • FIG. 3 is an XPS analysis test result of a lithium-rich manganese-based cathode material in an embodiment of the present disclosure.
  • Example 4 is a test result of the cycle performance of the lithium ion battery in Example 1 and Comparative Example 1 of the present disclosure.
  • FIG. 5 is a test result of the cycle performance of the lithium ion battery in Example 2 and Comparative Example 1 of the present disclosure.
  • FIG. 6 is the rate performance test result of the lithium ion battery in Example 1 and Comparative Example 1 of the present disclosure.
  • FIG. 7 is the rate performance test result of the lithium ion battery in Example 2 and Comparative Example 1 of the present disclosure.
  • the lithium-rich manganese-based cathode material in the related art needs to have a high specific capacity under the condition of a high cut-off voltage (under a voltage window of 2V to 4.8V, the discharge specific capacity is ⁇ 250mAh/g). This requires very strict electrochemical stability of the electrolyte to avoid adverse side reactions between the electrolyte and the lithium-rich manganese-based cathode material. Secondly, the content of manganese in lithium-rich manganese-based cathode materials often exceeds 40%, which is much higher than the content of nickel and cobalt, while the metal conductivity of manganese is only 0.2 ⁇ 10 7 S/m, which is about cobalt metal. 1/8 of.
  • the lithium-rich manganese-based cathode material will be greatly hindered in the lithium ion insertion/de-intercalation behavior during high-current charging and discharging, which affects the rate performance.
  • the lithium-rich manganese-based cathode material consists of Li 2 MnO 3 (C2/m space group) and LiMO 2 (R3-m space group). Among them, Li 2 MnO 3 tends to phase towards LiMn 2 O 4 thermodynamically. In addition, multiple charge and discharge cycles will promote the process of this phase transition.
  • LiMn 2 O 4 When LiMn 2 O 4 accumulates to a certain content, it will greatly reduce the number of lithium ion insertion sites in the lithium-rich manganese-based cathode material, and more importantly
  • the crystals in the structure show a complex morphology due to the preferred orientation, which causes anisotropic stress at the grain boundary position between the crystal grains. In the process, these crystal grains continue to shrink and expand with the insertion and deintercalation of lithium ions, which leads to increased stress at the grain boundary, and finally microcracks appear inside the crystal grains, which in turn causes the lithium-rich manganese-based
  • the cycle performance of the lithium ion battery prepared by the cathode material is poor.
  • the M and M'described in the present disclosure introduce high-strength chemical bonds into the lithium-rich manganese-based positive electrode material to anchor the boundary area of the crystal grains, which can make the aforementioned lithium-rich manganese-based positive electrode material alleviate to a certain extent.
  • the impact of grain boundary stress improves the stability of its structure.
  • the lithium-rich manganese-based positive electrode material described in the present disclosure has high structural stability during charge and discharge cycles, and is unlikely to expand or contract to cause grain boundary stress. It is unbalanced, hard to cause side reactions with electrolyte, easy to realize industrialization, and the lithium ion battery produced by it has good cycle performance, good rate performance and good commercial prospects.
  • the lithium-rich manganese-based positive electrode material described in the present disclosure has high structural stability during charge and discharge cycles, is not prone to expansion or contraction to cause grain boundary stress imbalance, is not easy to have side reactions with electrolyte, and is easy to realize industrialization, and The lithium ion battery produced therefrom has good cycle performance, good rate performance and good commercial prospects.
  • the median diameter D50 of the lithium-rich manganese-based cathode material is 3-14 ⁇ m, for example: 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, or 14 ⁇ m Wait.
  • the median diameter D50 of lithium-rich manganese-based cathode materials is 3-14 ⁇ m, which has higher structural stability during charge and discharge cycles, and is less likely to expand or contract to cause grain boundary stress imbalance, and it is more difficult to interact with
  • the electrolyte has side reactions, which in turn makes the lithium-ion battery produced by it have better cycle performance and better rate performance
  • the median diameter D50 of the single crystal particles of the lithium-rich manganese-based cathode material is 1 to 200 nm, for example: 1 nm, 2 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 100 nm or 200nm and so on.
  • the median diameter D50 of the single crystal particles of the lithium-rich manganese-based positive electrode material described in the present disclosure is 1 to 200 nm, which has higher structural stability during charge and discharge cycles, and is less likely to expand or contract to cause grain boundary stress Imbalance, it is less likely to have side reactions with the electrolyte, which in turn makes the lithium-ion battery produced by it have better cycle performance and better rate performance
  • the lithium-rich manganese-based cathode material is 0.5Li 2 Mn 0.97 Ti 0.01 B 0.02 O 2.95 F 0.05 ⁇ 0.5LiNi 0.4 Co 0.4 Mn 0.22 B 0.02 O 1.95 F 0.05 or 0.5Li 2 Mn 0.98 B 0.02 At least one of O 2.95 F 0.05 ⁇ 0.5LiNi 0.4 Co 0.4 Mn 0.22 B 0.02 O 1.95 F 0.05.
  • the lithium-rich manganese-based positive electrode material described in the present disclosure has higher structural stability during charge and discharge cycles, and is less prone to swelling or expansion.
  • the shrinkage leads to an imbalance in the grain boundary stress, and it is more difficult to have side reactions with the electrolyte, which in turn makes the lithium ion battery produced by it have better cycle performance and better rate performance.
  • a method for preparing the aforementioned lithium-rich manganese-based cathode material includes the following steps:
  • the precursor includes at least one of Ni 0.2 Co 0.2 Mn 0.595 Ti 0.005 CO 3 and Ni 0.2 Co 0.2 Mn 0.595 Ti 0.005 CO 2.95 F 0.05.
  • the temperature of the first calcination treatment is 300-800°C, for example: 300°C, 400°C, 500°C, 600°C, 700°C, or 800°C.
  • the time of the first calcination treatment is 4-12h, for example: 4h, 6h, 8h, 10h or 12h.
  • the first calcination treatment is performed in an O 2 and/or N 2 atmosphere.
  • the first calcination process described in the present disclosure is carried out under an O 2 and/or N 2 atmosphere. It is not easy to introduce other impurities, and other side reactions are not easy to occur, and the aforementioned lithium-rich manganese-based positive electrode material can be prepared more effectively.
  • the additive containing the M and the M' may be the same additive, and simultaneously contain the M and the M', or it may be the additive containing the M and the additive containing the M'.
  • a mixture of M'additives for example, in some embodiments of the present disclosure, the additives may be boride B 2 O 3 , boric acid H 3 BO 3 , lithium tetrafluoroborate LiBF 4, and the like.
  • the specific manner of mixing the two described above is not particularly limited, and those skilled in the art can make flexible selections according to actual needs, and will not be repeated here.
  • the temperature of the second calcination treatment is 330-820°C, for example: 330°C, 400°C, 500°C, 600°C, 700°C, or 820°C.
  • the time of the second calcination treatment in the step is 6-12h, for example: 6h, 7h, 8h, 9h, 10h, 11h or 12h.
  • the second calcination treatment in the step is performed in an O 2 and/or N 2 atmosphere.
  • the second calcination process described in the present disclosure is carried out in an O 2 and/or N 2 atmosphere, which is not easy to introduce other impurities, and other side reactions are not easy to occur, and the aforementioned lithium-rich manganese-based positive electrode material can be prepared more effectively.
  • the lithium source in step (4) includes at least one of LiOH ⁇ H 2 O or Li 2 CO 3 and at least one of LiF or NH 4 F, thereby providing sufficient lithium Source, in order to more effectively prepare the aforementioned lithium-rich manganese-based cathode material.
  • the temperature of the third calcination treatment is 700-950°C, for example: 700°C, 750°C, 800°C, 850°C, 900°C, or 950°C.
  • the time of the third calcination treatment is 10-24h, for example: 10h, 12h, 14h, 16h, 18h, 20h, 21h, 22h, 23h or 24h.
  • the third calcination treatment is performed in an O 2 and/or N 2 atmosphere.
  • the third calcination process described in the present disclosure is carried out in an O 2 and/or N 2 atmosphere that is not easy to introduce other impurities, and other side reactions are not easy to occur, and the aforementioned lithium-rich manganese-based cathode material can be more effectively prepared.
  • a positive pole piece is provided, and the positive pole piece comprises the above-mentioned lithium-rich manganese-based positive electrode material.
  • the positive electrode sheet described in the present disclosure also includes other components of a conventional positive electrode sheet, such as a substrate, a conductive agent, a binder, and a thickening agent, etc., which will not be repeated here.
  • the positive electrode sheet described in the present disclosure has strong stability, does not easily cause side reactions with the electrolyte, is easy to realize industrialization, and the lithium ion battery produced therefrom has good cycle performance, good rate performance, and good commercial prospects.
  • a lithium ion battery is provided, and the ion battery includes the above-mentioned positive pole piece.
  • the lithium ion battery described in the present disclosure has good cycle performance, good rate performance, and good commercial prospects.
  • an electric vehicle in one embodiment of the present disclosure, includes the above-mentioned ion battery.
  • the shape, structure, and manufacturing process of the electric vehicle described in the present disclosure are all the shape, structure, and manufacturing process of a conventional electric vehicle.
  • the lithium-rich manganese-based cathode material was obtained, the chemical formula is 0.5Li 2 Mn 0.97 Ti 0.006 Ce 0.004 B 0.02 O 2.95 F 0.05 ⁇ 0.5LiNi 0.4 Co 0.4 Mn 0.22 B 0.02 O 1.95 F 0.05 and the median diameter is D50 It is 11 ⁇ m, and the single crystal median diameter D50 is 120 nm.
  • the lithium-rich manganese-based cathode material was obtained, the chemical formula is 0.5Li 2 Mn 0.97 Ti 0.006 Cr 0.004 B 0.02 O 2.95 F 0.05 ⁇ 0.5LiNi 0.4 Co 0.4 Mn 0.22 B 0.02 O 1.95 F 0.05 , median diameter D50 is 11 ⁇ m, and the single crystal median diameter D50 is 120 nm.
  • Example 1 and Example 2 (1) Perform X-ray photoelectron spectroscopy (XPS) test on the lithium-rich manganese-based cathode materials obtained in Example 1 and Example 2.
  • the test process is as follows: First, place the lithium-rich manganese-based cathode material in a vacuum oven at 100°C for 4 hours, take it out, weigh a certain amount of lithium-rich manganese-based cathode material, paste it on the sample table, and put it into the sample cavity of the XPS instrument . Under certain vacuum conditions, use C 60 GCIB clusters to clean the surface of the sample for 30 minutes, and then start X-ray scanning and spectrum collection. The test results are shown in Figure 2 and Figure 3.
  • XPS X-ray photoelectron spectroscopy
  • the positive electrode sheet is composed of 92wt% active material, 4wt% Super-P conductive agent and 4wt% PVDF binder; the electrolyte is 1M LiPF 6. The same volume of ethylene carbonate, dimethyl carbonate, and additives are prepared.
  • the rate performance test was carried out at the discharge rate of 0.1C, 0.2C, 0.5C, 1C and 2C, and the potential window was 2V ⁇ 4.6V; the cycle performance test was cycled 50 times at the charge and discharge rate of 0.5C and 1C, respectively.
  • the test results are shown in Table 1 and Figure 4-7.
  • Example 1 287mAh/g 226.4mAh/g 204.4mAh/g 180.2mAh/g
  • Example 2 284.9mAh/g 226.3mAh/g 205.9mAh/g 187.9mAh/g
  • Example 3 285.6mAh/g 228.5mAh/g 209.6mAh/g 190.5mAh/g
  • Example 4 284.7mAh/g 225.1mAh/g 203.4mAh/g 184.3mAh/g
  • Example 5 289.6mAh/g 229.6mAh/g 208.1mAh/g 188.9mAh/g
  • Example 6 284.5mAh/g 223.3mAh/g 203.2mAh/g 182.3mAh/g Comparative example 1 282.8mAh/g 221.4mAh/g 199.6mAh/g 178.3mAh/g
  • Example 1 and Example 2 From the XPS spectrum analysis of Example 1 and Example 2 (refer to Figures 2 and 3), the boron element has entered the crystal lattice of the lithium-rich manganese-based cathode material and has formed chemical bonds with oxygen or transition metal elements. This shows that embodiment 1 and embodiment 2 adopt the boron element to modify the grain boundary strategy is feasible.
  • the lithium-rich manganese-based cathode material described in the present disclosure exhibits a higher specific discharge capacity under the condition of large-rate discharge.
  • 0.5C rate charge, 1C rate discharge, the discharge specific capacity of Comparative Example 1 is 197.4mAh/g, and Example 1 and Example 2 are respectively increased to 202.6mAh/g and 204.6mAh/g (1C rate increased by at least 3% ).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

本公开提供了用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车。所述富锂锰基正极材料在充放电循环中具有较高的结构稳定性，不易发生膨胀或者收缩而导致晶界应力失衡，不易与电解液发生副反应，易于实现产业化，且由其制作得到的锂离子电池的循环性能好、倍率性能好、商业前景好。

Description

用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车 技术领域
本公开涉及锂离子电池技术领域，例如涉及用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车。
背景技术
目前，得益于电池技术的快速发展，汽车行业正进行着一场巨大的变革。纯电动汽车以及混合动力汽车获得了前所未有的关注，各大主流汽车制造商正投入大量的资金和人力以加快相关技术开发与积累，以避免在新能源赛道上失去先机、甚至被淘汰。然而，尽管以电力为动力源的纯电动汽车具有环境友好的优点，但是当前的电池技术仍不能完全满足市场的需求，例如电池成本、性能衰减、续航里程、安全问题等，都或多或少地影响消费者的购买欲望。为解决里程焦虑问题，科研人员们一直试图开发高能量密度的用于锂离子电池正极材料，以获得具有高能量密度的锂离子电池。其中，富锂锰基正极材料xLi 2MnO 3·(1-x)LiMO 2(M＝Ni，Co，Mn etc.)正是一款具有高放电比容量的高能量密度正极材料，并受到了学术界以及工业界广泛的关注。此外，该材料具有良好的热稳定性，DSC分解温度可达240℃，相较于高镍三元正极材料镍钴锰酸锂以及镍钴铝酸锂表现出明显的优势。然而，富锂锰基正极材料也存在诸多问题，其中较为突出一个问题是其在充放电循环过程中容量衰减严重，这个缺陷直接影响着富锂锰基正极材料的商业化应用前景。
因而，现有的富锂锰基正极材料的相关技术仍有待改进。
发明内容
本公开提供一种用于锂离子电池的富锂锰基正极材料，所述的富锂锰基正极材料在充放电循环中具有较高的结构稳定性，不易发生因膨胀或者收缩而导致晶界应力失衡且不易与电解液发生副反应、易于实现产业化，由其制作得到的锂离子电池的循环性能好、倍率性能好且商业前景好。
本公开在一实施例中提供一用于锂离子电池的富锂锰基正极材料，所述富锂锰基正极材料包括：由xLi 2+αMn (1-μ-λ)Ti μM λO 3-νM’ ν·(1-x)Li 1+α’Ni aCo bMn cM λ’O 2-ν’M’ ν’形成的晶体，其中，0.4<x<0.6，0≤α<0.1，0<μ≤0.2，0<λ≤0.05，0.005≤ν≤0.02；0≤α’≤0.04，0<a<0.3，0<b<0.3，0<c<0.5，0<λ’<0.1，0<ν’≤0.01，且α’+a+b+c+λ’＝1，所述M 包括Al 3+、Mg 2+、Ti 4+、Zr 4+、Zn 2+、Ca 2+、B 3+、Cr 3+、Cr 6+或者Ce 3+、Ce 4+中的至少一种，所述M’包括F -、Cl -、Br -、C 4-、N 3-、S 2-、P 3-或者Se 2-中的至少一种。
本公开所述的富锂锰基正极材料在充放电循环中具有较高的结构稳定性，不易发生膨胀或者收缩而导致晶界应力失衡，不易与电解液发生副反应，易于实现产业化，且由其制作得到的锂离子电池的循环性能好、倍率性能好、商业前景好。
在一实施例中，所述富锂锰基正极材料的中值粒径D50为3～14μm，例如：3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm或14μm等。
在一实施例中，所述的富锂锰基正极材料的单晶颗粒的中值粒径D50为1～200nm，例如：1nm、2nm、5nm、10nm、20nm、30nm、40nm、50nm、100nm或200nm等。
在一实施例中，所述富锂锰基正极材料为0.5Li 2Mn 0.97Ti 0.01B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05或者0.5Li 2Mn 0.98B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05中的至少一种。
本公开在一实施例中，提供了一种制备前面所述的富锂锰基正极材料的方法，包括以下步骤：
(1)将制备所述富锂锰基正极材料的前驱体进行第一煅烧处理，得到第一预制物；
(2)将步骤(1)所述第一预制物与含有所述M和所述M’的添加剂混合，得到第一混合物；
(3)将步骤(2)将所述第一混合物进行第二煅烧处理，得到第二预制物；
(4)将步骤(3)将所述第二预制物与锂源混合，得到第二混合物；
(5)将步骤(4)将所述第二混合物进行第三煅烧处理，以便得到所述富锂锰基正极材料。
在一实施例中，步骤(1)所述前驱体包括Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 3者Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 2.95F 0.05中的至少一种。
在一实施例中，步骤(1)所述第一煅烧处理的温度为300～800℃，例如： 300℃、400℃、500℃、600℃、700℃或800℃等。
在一实施例中，步骤(1)所述第一煅烧处理的时间为4～12h，例如：4h、6h、8h、10h或12h等。
在一实施例中，步骤(1)所述第一煅烧处理是在O 2和/或N 2气氛下进行的。
在一实施例中，步骤(2)所述含有所述M和所述M’的添加剂既可以是同一种添加剂，同时含有所述M和所述M’，也可以是含有所述M的添加剂与含有所述M’的添加剂的混合物，例如，在本公开的一些实施例中，所述添加剂可以是硼化物B 2O 3、硼酸H 3BO 3、四氟硼酸锂LiBF 4等。将前面所述的两者混合的具体方式不受特别限制，本领域技术人员可以根据实际需要进行灵活选择，在此不再过多赘述。
在一实施例中，步骤(3)所述第二煅烧处理的温度为330～820℃，例如：330℃、400℃、500℃、600℃、700℃或820℃等。
在一实施例中，步骤(3)所述第二煅烧处理的时间为6～12h，例如：6h、7h、8h、9h、10h、11h或12h等。
在一实施例中，步骤(3)所述第二煅烧处理是在O 2和/或N 2气氛下进行的。
在一实施例中，步骤(4)所述锂源包括LiOH·H 2O或Li 2CO 3中的至少一种和LiF或NH 4F中的至少一种，由此，可以提供足够的锂源，以较为有效地制备前面所述的富锂锰基正极材料。
在一实施例中，步骤(5)所述第三煅烧处理的温度为700～950℃，例如：700℃、750℃、800℃、850℃、900℃或950℃等。
在一实施例中，步骤(5)所述第三煅烧处理的时间为10～24h，例如：10h、12h、14h、16h、18h、20h、21h、22h、23h或24h等。
在一实施例中，步骤(5)所述第三煅烧处理是在O 2和/或N 2气氛下进行的。
本公开在一实施例中提供一种正极极片，所述的正极极片包含上述富锂锰基正极材料。
本公开在一实施例中提供一种锂离子电池，所述的离子电池包含上述正极极片。
本公开在一实施例中提供一种电动汽车，所述的电动汽车包含上述离子电池。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1是本公开一实施例中制备富锂锰基正极材料的方法的流程示意图。
图2是本公开一实施例中富锂锰基正极材料的XPS分析测试结果。
图3是本公开一实施例中富锂锰基正极材料的XPS分析测试结果。
图4是本公开实施例1和对比例1中的锂离子电池的循环性能测试结果。
图5是本公开实施例2和对比例1中的锂离子电池的循环性能测试结果。
图6是本公开实施例1和对比例1中的锂离子电池的倍率性能测试结果。
图7是本公开实施例2和对比例1中的锂离子电池的倍率性能测试结果。
具体实施方式
相关技术中的富锂锰基正极材料需要在高截止电压条件下才能发挥出高比容量(在2V～4.8V的电压窗口下，放电比容量≥250mAh/g)。这对电解液的电化学稳定性要求非常苛刻，以避免电解液与富锂锰基正极材料发生不利的副反应。其次，锰元素在富锂锰基正极材料中的含量往往超过40％、远高于镍和钴元素含量，而锰金属元素的金属电导率仅为0.2×10 7S/m，约为钴金属的1/8。这样便会导致富锂锰基正极材料在大电流充放电时锂离子嵌入/脱嵌行为受到很大的阻力，影响了倍率性能的发挥。再次，富锂锰基正极材料包括Li 2MnO 3(C2/m空间群)和LiMO 2(R3-m空间群)组成，其中，Li 2MnO 3在热力学上倾向于向LiMn 2O 4发生相转变，并且，多次充放电循环会促进这种相转变的进程，当LiMn 2O 4积累到一定含量后，会大幅减少锂离子在富锂锰基正极材料中嵌入位点的数量，更重要的是，对于富锂锰基正极材料，在结构中的晶体因择优取向而表现出复杂的存在形态，这使得晶粒之间的晶界位置处存在着各向异性的应力，在充放电循环过程中这些晶粒随着锂离子的嵌入和脱嵌而不断出现收缩和膨胀的行为，导致晶粒边界处的应力加剧，最终在晶粒的内部出现微裂纹，进而导致由该富锂锰基正极材料制备得到的锂离子电池的循环性能较差。
本公开在一实施例中提供一用于锂离子电池的富锂锰基正极材料，所述富锂锰基正极材料包括：由xLi 2+αMn (1-μ-λ)Ti μM λO 3-νM’ ν·(1-x)Li 1+α’Ni aCo bMn cM λ’O 2-ν’M’ ν’形成的晶体，其中，0.4<x<0.6，0≤α<0.1，0<μ≤0.2，0<λ≤0.05，0.005≤ν≤0.02；0≤α’≤0.04， 0<a<0.3，0<b<0.3，0<c<0.5，0<λ’<0.1，0<ν’≤0.01，且α’+a+b+c+λ’＝1，所述M包括Al 3+、Mg 2+、Ti 4+、Zr 4+、Zn 2+、Ca 2+、B 3+、Cr 3+、Cr 6+或者Ce 3+、Ce 4+中的至少一种，所述M’包括F -、Cl -、Br -、C 4-、N 3-、S 2-、P 3-或者Se 2-中的至少一种。
本公开所述的M和M’在富锂锰基正极材料中引入了高强度的化学键来锚定晶粒的边界区域，可以使得前面所述的富锂锰基正极材料在一定程度上能够缓解晶界应力的冲击，从而改善其结构的稳定性，进而，本公开所述的富锂锰基正极材料在充放电循环中具有较高的结构稳定性，不易发生膨胀或者收缩而导致晶界应力失衡，不易与电解液发生副反应，易于实现产业化，且由其制作得到的锂离子电池的循环性能好、倍率性能好、商业前景好。本公开所述的富锂锰基正极材料在充放电循环中具有较高的结构稳定性，不易发生膨胀或者收缩而导致晶界应力失衡，不易与电解液发生副反应，易于实现产业化，且由其制作得到的锂离子电池的循环性能好、倍率性能好、商业前景好。
在一实施例中，所述富锂锰基正极材料的中值粒径D50为3～14μm，例如：3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm或14μm等。
相关技术中，富锂锰基正极材料的中值粒径D50为3～14μm，在充放电循环中具有更高的结构稳定性，更加不易发生膨胀或者收缩而导致晶界应力失衡，更加不易与电解液发生副反应，进而使得由其制作得到的锂离子电池的循环性能更好、倍率性能更好
在一实施例中，所述的富锂锰基正极材料的单晶颗粒的中值粒径D50为1～200nm，例如：1nm、2nm、5nm、10nm、20nm、30nm、40nm、50nm、100nm或200nm等。
本公开所述的富锂锰基正极材料的单晶颗粒的中值粒径D50为1～200nm，在充放电循环中具有更高的结构稳定性，更加不易发生膨胀或者收缩而导致晶界应力失衡，更加不易与电解液发生副反应，进而使得由其制作得到的锂离子电池的循环性能更好、倍率性能更好
在一实施例中，所述富锂锰基正极材料为0.5Li 2Mn 0.97Ti 0.01B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05或者0.5Li 2Mn 0.98B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05中的至少一种。
本公开所述的富锂锰基正极材料相较于其他具体种类的富锂锰基正极材料，该富锂锰基正极材料在充放电循环中具有更高的结构稳定性，更加不易发生膨胀或者收缩而导致晶界应力失衡，更加不易与电解液发生副反应，进而使得由其制作得到的锂离子电池的循环性能更好、倍率性能更好。
本公开一实施例中，提供了一种制备前面所述的富锂锰基正极材料的方法，参照图1，包括以下步骤：
S100：将制备所述富锂锰基正极材料的前驱体进行第一煅烧处理，得到第一预制物。
在一实施例中，所述前驱体包括Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 3者Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 2.95F 0.05中的至少一种。
在一实施例中，所述第一煅烧处理的温度为300～800℃，例如：300℃、400℃、500℃、600℃、700℃或800℃等。
在一实施例中，所述第一煅烧处理的时间为4～12h，例如：4h、6h、8h、10h或12h等。
在一实施例中，所述第一煅烧处理是在O 2和/或N 2气氛下进行的。
本公开所述的第一煅烧处理是在O 2和/或N 2气氛下进行不易引入其他杂质，不易发生其他副反应，可以较为有效地制备前面所述的富锂锰基正极材料。
S200：将所述第一预制物与含有所述M和所述M’的添加剂混合，得到第一混合物。
在一实施例中，所述含有所述M和所述M’的添加剂既可以是同一种添加剂，同时含有所述M和所述M’，也可以是含有所述M的添加剂与含有所述M’的添加剂的混合物，例如，在本公开的一些实施例中，所述添加剂可以是硼化物B 2O 3、硼酸H 3BO 3、四氟硼酸锂LiBF 4等。将前面所述的两者混合的具体方式不受特别限制，本领域技术人员可以根据实际需要进行灵活选择，在此不再过多赘述。
S300：将所述第一混合物进行第二煅烧处理，得到第二预制物。
在一实施例中，所述第二煅烧处理的温度为330～820℃，例如：330℃、400℃、500℃、600℃、700℃或820℃等。
在一实施例中，步骤所述第二煅烧处理的时间为6～12h，例如：6h、7h、8h、9h、10h、11h或12h等。
在一实施例中，步骤所述第二煅烧处理是在O 2和/或N 2气氛下进行的。
本公开所述的第二煅烧处理是在O 2和/或N 2气氛下进行不易引入其他杂质，不易发生其他副反应，可以较为有效地制备前面所述的富锂锰基正极材料。
S400：将所述第二预制物与锂源混合，得到第二混合物。
在一实施例中，步骤(4)所述锂源包括LiOH·H 2O或Li 2CO 3中的至少一种和LiF或NH 4F中的至少一种，由此，可以提供足够的锂源，以较为有效地制备前面所述的富锂锰基正极材料。
S500：将所述第二混合物进行第三煅烧处理，以便得到所述富锂锰基正极材料。
在一实施例中，所述第三煅烧处理的温度为700～950℃，例如：700℃、750℃、800℃、850℃、900℃或950℃等。
在一实施例中，所述第三煅烧处理的时间为10～24h，例如：10h、12h、14h、16h、18h、20h、21h、22h、23h或24h等。
在一实施例中，所述第三煅烧处理是在O 2和/或N 2气氛下进行的。
本公开所述的第三煅烧处理是在O 2和/或N 2气氛下进行不易引入其他杂质，不易发生其他副反应，可以较为有效地制备前面所述的富锂锰基正极材料。
本公开在一实施例中提供一种正极极片，所述的正极极片包含上述富锂锰基正极材料。
本公开所述的正极片还包括常规正极片的其他成分，例如基片、导电剂、粘结剂以及增稠剂等，在此不再过多赘述。
本公开所述的正极片稳定性强，不易与电解液发生副反应，易于实现产业化，且由其制作得到的锂离子电池的循环性能好、倍率性能好、商业前景好。
本公开在一实施例中提供一种锂离子电池，所述的离子电池包含上述正极极片。
本公开所述的该锂离子电池的循环性能好、倍率性能好、商业前景好。
本公开在一实施例中提供一种电动汽车，所述的电动汽车包含上述离子电池。
本公开所述的电动汽车的形状、构造、制造工艺等均为常规电动汽车的形状、构造、制造工艺。
实施例1
将1mol的Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 3置于600℃的煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第一煅烧处理4h，然后与0.01mol的B 2O 3置于研磨中充分研磨混合，随后置于630℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第二煅烧处理6h，然后将第二煅烧处理后的粉末样品与1.45mol的LiOH·H 2O、0.05mol的LiF置于研钵中充分研磨混合，随后置于820℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第三煅烧处理12h，得到富锂锰基正极材料，化学式为0.5Li 2Mn 0.97Ti 0.01B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05，中值粒径D50为11μm，单晶中值粒径D50为120nm。
实施例2
将1mol的Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 3置于600℃的煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第一煅烧处理4h，然后与0.02mol的H 3BO 3置于研磨中充分研磨混合，随后置于650℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第二煅烧处理5h，然后将第二煅烧处理后的粉末样品与1.45mol的LiOH·H 2O、0.05mol的LiF置于研钵中充分研磨混合，随后置于820℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第三煅烧处理12h，得到富锂锰基正极材料，化学式为0.5Li 2Mn 0.97Ti 0.01B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05，中值粒径D50为11μm，单晶中值粒径D50为120nm。
实施例3
将1mol的Ni 0.2Co 0.2Mn 0.595Ti 0.003Ce 0.002CO 3置于600℃的煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第一煅烧处理4h，然后与0.02mol的H 3BO 3置于研磨中充分研磨混合，随后置于650℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第二煅烧处理5h，然后将第二煅烧处理后的粉末样品与1.45mol的LiOH·H 2O、0.05mol的LiF置于研钵中充分研磨混合，随后置于 820℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第三煅烧处理12h，得到富锂锰基正极材料，化学式为0.5Li 2Mn 0.97Ti 0.006Ce 0.004B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05，中值粒径D50为11μm，单晶中值粒径D50为120nm。
实施例4
将1mol的Ni 0.2Co 0.2Mn 0.595Ti 0.003Al 0.002CO 3置于600℃的煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第一煅烧处理4h，然后与0.02mol的H 3BO 3置于研磨中充分研磨混合，随后置于650℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第二煅烧处理5h，然后将第二煅烧处理后的粉末样品与1.45mol的LiOH·H 2O、0.05mol的LiF置于研钵中充分研磨混合，随后置于820℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第三煅烧处理12h，得到富锂锰基正极材料，化学式为0.5Li 2Mn 0.97Ti 0.006Al 0.004B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05，中值粒径D50为11μm，单晶中值粒径D50为120nm。
实施例5
将1mol的Ni 0.2Co 0.2Mn 0.595Ti 0.003Zr 0.002CO 3置于600℃的煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第一煅烧处理4h，然后与0.02mol的H 3BO 3置于研磨中充分研磨混合，随后置于650℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第二煅烧处理5h，然后将第二煅烧处理后的粉末样品与1.45mol的LiOH·H 2O、0.05mol的LiF置于研钵中充分研磨混合，随后置于820℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第三煅烧处理12h，得到富锂锰基正极材料，化学式为0.5Li 2Mn 0.97Ti 0.006Zr 0.004B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05，中值粒径D50为11μm，单晶中值粒径D50为120nm。
实施例6
将1mol的Ni 0.2Co 0.2Mn 0.595Ti 0.003Cr 0.002CO 3置于600℃的煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第一煅烧处理4h，然后与0.02mol的H 3BO 3置于研磨中充分研磨混合，随后置于650℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第二煅烧处理5h，然后将第二煅烧处理后的粉末样品与1.45mol的LiOH·H 2O、0.05mol的LiF置于研钵中充分研磨混合，随后置于820℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第三煅烧处理12 h，得到富锂锰基正极材料，化学式为0.5Li 2Mn 0.97Ti 0.006Cr 0.004B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05，中值粒径D50为11μm，单晶中值粒径D50为120nm。
对比例1
将1mol的Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 3置于600℃的煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第一煅烧处理4h，然后与1.5mol的LiOH·H 2O置于研钵中充分研磨混合，随后置于820℃煅烧炉、氧气体积分数为2％O 2和N 2的混合气体中进行第三煅烧处理12h，得到富锂锰基正极材料，化学式为0.5Li 2Mn 0.99Ti 0.01O 3·0.5LiNi 0.4Co 0.4Mn 0.2O 2，中值粒径D50为11μm，单晶中值粒径D50为120nm。
材料测试：
(1)对实施例1和实施例2得到的富锂锰基正极材料进行X射线光电子能谱(XPS)测试。测试过程如下：首先将富锂锰基正极材料置于100℃真空烘箱干燥4h，取出后称量一定量的富锂锰基正极材料粘贴在样品台上，并放入到XPS仪器的样品腔中。在一定的真空度条件下，使用C 60GCIB团簇对样品表面进行清洁处理30min后，然后启动X射线扫描采谱。测试结果如图2和图3所示。
(2)对实施例1-6和对比例1进行扣式半电池的电性能评测
在充满氩气的手套箱中用锂金属片组装扣式电池：正极片由92wt％的活性物质、4wt％的Super-P导电剂和4wt％的PVDF粘结剂组成；电解液由1M的LiPF 6、相同体积的碳酸亚乙酯和碳酸二甲酯、以及助剂配制而成。
倍率性能测试分别在0.1C、0.2C、0.5C、1C和2C的放电倍率下进行测试，电位窗口为2V～4.6V；循环性能测试分别在0.5C和1C的充放电倍率下循环50次，测试结果如表1和图4-7所示。
表1
  0.1C放电倍率 0.5C放电倍率 1C放电倍率 2C放电倍率
实施例1 287mAh/g 226.4mAh/g 204.4mAh/g 180.2mAh/g
实施例2 284.9mAh/g 226.3mAh/g 205.9mAh/g 187.9mAh/g
实施例3 285.6mAh/g 228.5mAh/g 209.6mAh/g 190.5mAh/g
实施例4 284.7mAh/g 225.1mAh/g 203.4mAh/g 184.3mAh/g
实施例5 289.6mAh/g 229.6mAh/g 208.1mAh/g 188.9mAh/g
实施例6 284.5mAh/g 223.3mAh/g 203.2mAh/g 182.3mAh/g
对比例1 282.8mAh/g 221.4mAh/g 199.6mAh/g 178.3mAh/g
从实施例1和实施例2的XPS图谱分析(参照图2和图3)，硼元素已经进入到富锂锰基正极材料的晶体晶格中，且与氧元素或者过渡金属元素形成了化学键，这说明实施例1和实施例2采用硼元素对晶界的改性策略是可行的。
由图4和图5可以看出，在充电倍率是0.5C，放电倍率是1C的条件下，经过50个充放电循环，实施例1所述的正极材料制备的电池循环容量保持率87.4％；实施例2所述的正极材料制备的电池循环容量保持率达到87.7％；对比例1所述的正极材料制备的电池循环容量保持率为83.2％。可以得出，本公开对富锂锰基正极材料的晶粒的晶界进行改性后，富锂锰基正极材料的循环性能得到了改善(容量保持率提高至少4％)。
由图6和图7可以看出，在大倍率放电条件下，本公开所述的富锂锰基正极材料表现出了较高的放电比容量。例如0.5C倍率充电、1C倍率放电，对比例1的放电比容量为197.4mAh/g、实施例1和实施例2则分别提高到202.6mAh/g和204.6mAh/g(1C倍率提高至少3％)。
由表1可以看出，由实施例1-6对比可知，本公开提供的富锂锰基正极材料的循环性能和倍率性能均较对比例1有了明显的提高。

Claims (18)

  1. 一种用于锂离子电池的富锂锰基正极材料，包括：由xLi 2+αMn (1-μ-λ)Ti μM λO 3-νM’ ν·(1-x)Li 1+α’Ni aCo bMn cM λ’O 2-ν’M’ ν’形成的晶体，其中，0.4<x<0.6，0≤α<0.1，0<μ≤0.2，0<λ≤0.05，0.005≤ν≤0.02；
    0≤α’≤0.04，0<a<0.3，0<b<0.3，0<c<0.5，0<λ’<0.1，0<ν’≤0.01，且α’+a+b+c+λ’＝1。
  2. 根据权利要求1所述的富锂锰基正极材料，其中，M包括Al 3+、Mg 2+、Ti 4+、Zr 4+、Zn 2+、Ca 2+、B 3+、Cr 3+、Cr 6+、Ce 3+或者Ce 4+中的至少一种。
  3. 根据权利要求1或2所述的富锂锰基正极材料，其中，M’包括F -、Cl -、Br -、C 4-、N 3-、S 2-、P 3-或者Se 2-中的至少一种。
  4. 根据权利要求1-3任一项所述的富锂锰基正极材料，其中，所述富锂锰基正极材料的中值粒径D50为3μm～14μm。
  5. 根据权利要求1-4任一项所述的富锂锰基正极材料，其中，所述富锂锰基正极材料为0.5Li 2Mn 0.97Ti 0.01B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05或0.5Li 2Mn 0.98B 0.02O 2.95F 0.05·0.5LiNi 0.4Co 0.4Mn 0.22B 0.02O 1.95F 0.05中的至少一种。
  6. 根据权利要求1-5任一项所述富锂锰基正极材料的制备方法，包括以下步骤：
    (1)将制备所述富锂锰基正极材料的前驱体进行第一煅烧处理，得到第一预制物；
    (2)将步骤(1)所述第一预制物与含有所述M和所述M’的添加剂混合，得到第一混合物；
    (3)将步骤(2)将所述第一混合物进行第二煅烧处理，得到第二预制物；
    (4)将步骤(3)将所述第二预制物与锂源混合，得到第二混合物；
    (5)将步骤(4)将所述第二混合物进行第三煅烧处理，以便得到所述富锂锰基正极材料。
  7. 根据权利要求6所述的制备方法，其中，所述前驱体包括Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 3或者Ni 0.2Co 0.2Mn 0.595Ti 0.005CO 2.95F 0.05中的至少一种。
  8. 根据权利要求6或7所述的制备方法，其中，所述第一煅烧处理的温度为300～800℃；
  9. 根据权利要求6-8任一项所述的制备方法，其中,所述第一煅烧处理的时间为4～12h。
  10. 根据权利要求6-9任一项所述的制备方法，其中，所述第二煅烧处理的温度为330～820℃；
  11. 根据权利要求6-10任一项所述的制备方法，其中，所述第二煅烧处理的时间为6～12h。
  12. 根据权利要求6-11任一项所述的制备方法，其中，所述第三煅烧处理的温度为700～950℃；
  13. 根据权利要求6-12任一项所述的制备方法，其中所述第三煅烧处理的时间为10～24h。
  14. 根据权利要求6-13任一项所述的制备方法，其中，所述第一煅烧处理、所述第二煅烧处理或者所述第三煅烧处理中的至少一种是在O 2和/或N 2气氛下进行的。
  15. 根据权利要求6-14任一项所述的制备方法，其中，所述锂源包括LiOH·H 2O或者Li 2CO 3中的至少一种和LiF或者NH 4F中的至少一种。
  16. 一种正极极片，所述正极极片包括权利要求1-5任意一项所述的富锂锰 基正极材料。
  17. 一种锂离子电池，所述锂离子电池包含如权利要求16所述的正极极片。
  18. 一种电动汽车，所述的电动汽车包含如权利要求17所述的锂离子电池。
PCT/CN2020/124714 2020-03-18 2020-10-29 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车 WO2021184764A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20925911.8A EP4024526A4 (en) 2020-03-18 2020-10-29 LITHIUM-RICH MANGANESE-BASED POSITIVE ELECTRODE MATERIAL FOR USE IN LITHIUM-ION BATTERY, METHOD FOR PREPARING THE MATERIAL, POSITIVE ELECTRODE TAB, LITHIUM-ION BATTERY AND ELECTRIC VEHICLE
US17/793,259 US20230076419A1 (en) 2020-03-18 2020-10-29 Lithium-rich manganese-based positive electrode material for use in lithium-ion battery, preparation method for the material, positive electrode tab, lithium-ion battery, and electric vehicle

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010190732.7 2020-03-18
CN202010190732.7A CN111430703B (zh) 2020-03-18 2020-03-18 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车

Publications (1)

Publication Number Publication Date
WO2021184764A1 true WO2021184764A1 (zh) 2021-09-23

Family

ID=71549533

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/124714 WO2021184764A1 (zh) 2020-03-18 2020-10-29 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车

Country Status (4)

Country Link
US (1) US20230076419A1 (zh)
EP (1) EP4024526A4 (zh)
CN (1) CN111430703B (zh)
WO (1) WO2021184764A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115411250A (zh) * 2022-09-15 2022-11-29 山东大学 一种锂离子电池改性富锂锰基正极的制备方法与应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430703B (zh) * 2020-03-18 2023-09-22 蜂巢能源科技有限公司 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103069622A (zh) * 2010-08-06 2013-04-24 Tdk株式会社 活性物质、活性物质的制造方法以及锂离子二次电池
CN104282879A (zh) * 2013-07-03 2015-01-14 三星Sdi株式会社 正极活性物质、其制备方法、及正极和可再充电锂电池
CN105164834A (zh) * 2013-07-29 2015-12-16 株式会社Lg化学 能量密度提高的电极活性材料和包含其的锂二次电池
CN106910887A (zh) * 2015-12-22 2017-06-30 国联汽车动力电池研究院有限责任公司 一种富锂锰基正极材料、其制备方法及包含该正极材料的锂离子电池
US20170207500A1 (en) * 2016-01-20 2017-07-20 Uchicago Argonne, Llc Electroactive materials for rechargeable batteries
CN109565046A (zh) * 2016-12-02 2019-04-02 松下知识产权经营株式会社 正极活性物质和使用正极活性物质的电池
CN111430703A (zh) * 2020-03-18 2020-07-17 蜂巢能源科技有限公司 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8026003B2 (en) * 2003-08-21 2011-09-27 Samsung Sdi Co., Ltd. Negative active material for a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery comprising the same
CN102484249A (zh) * 2009-08-27 2012-05-30 安维亚系统公司 具有高比容量和优异循环的层层富含锂的复合金属氧化物
CN102610806B (zh) * 2012-02-27 2014-11-12 宁德新能源科技有限公司 一种锂离子电池及其正极活性材料
KR101835586B1 (ko) * 2012-08-23 2018-03-07 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극 및 리튬 전지
CN102916169B (zh) * 2012-10-26 2015-05-13 中国科学院宁波材料技术与工程研究所 一种富锂锰基正极材料及其制备方法
JP7241287B2 (ja) * 2017-07-27 2023-03-17 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
CN109411735A (zh) * 2018-11-30 2019-03-01 厦门大学 一种正极材料及其制备方法和锂离子电池
CN109860569B (zh) * 2019-02-28 2021-06-18 蜂巢能源科技有限公司 锂离子电池的正极材料及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103069622A (zh) * 2010-08-06 2013-04-24 Tdk株式会社 活性物质、活性物质的制造方法以及锂离子二次电池
CN104282879A (zh) * 2013-07-03 2015-01-14 三星Sdi株式会社 正极活性物质、其制备方法、及正极和可再充电锂电池
CN105164834A (zh) * 2013-07-29 2015-12-16 株式会社Lg化学 能量密度提高的电极活性材料和包含其的锂二次电池
CN106910887A (zh) * 2015-12-22 2017-06-30 国联汽车动力电池研究院有限责任公司 一种富锂锰基正极材料、其制备方法及包含该正极材料的锂离子电池
US20170207500A1 (en) * 2016-01-20 2017-07-20 Uchicago Argonne, Llc Electroactive materials for rechargeable batteries
CN109565046A (zh) * 2016-12-02 2019-04-02 松下知识产权经营株式会社 正极活性物质和使用正极活性物质的电池
CN111430703A (zh) * 2020-03-18 2020-07-17 蜂巢能源科技有限公司 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115411250A (zh) * 2022-09-15 2022-11-29 山东大学 一种锂离子电池改性富锂锰基正极的制备方法与应用

Also Published As

Publication number Publication date
US20230076419A1 (en) 2023-03-09
CN111430703A (zh) 2020-07-17
EP4024526A4 (en) 2023-10-25
CN111430703B (zh) 2023-09-22
EP4024526A1 (en) 2022-07-06

Similar Documents

Publication Publication Date Title
WO2021196732A1 (zh) 正极材料及其制备方法、锂离子电池和电动汽车
Tang et al. Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2
CN109390563B (zh) 改性磷酸铁锂正极材料及其制备方法、正极片、锂二次电池
Liu et al. Fluorine doping and Al2O3 coating Co-modified Li [Li0. 20Ni0. 133Co0. 133Mn0. 534] O2 as high performance cathode material for lithium-ion batteries
CN103094550A (zh) 一种富锂正极材料的制备方法
CN110459764B (zh) 一种锂离子电池正极材料及其制备方法与应用
WO2021184764A1 (zh) 用于锂离子电池的富锂锰基正极材料及其制备方法、正极片、锂离子电池和电动汽车
CN106099066B (zh) 一种二氧化锗/石墨烯复合材料及其制备方法
Kong et al. Synthesis of lithium rich layered oxides with controllable structures through a MnO2 template strategy as advanced cathode materials for lithium ion batteries
US6972134B2 (en) Method of preparing positive active material for rechargeable lithium batteries
CN113611839A (zh) 一种新型混合体系富锂锰基正极片及其制备方法，锂离子电池
CN114229921B (zh) Al2O3-ZrO2包覆的富锂锰基正极材料及其制备方法
CN106025182A (zh) 一种钛铬掺杂氟化铁-碳纳米复合正极材料及其制备方法和应用
Wang et al. Preparation and performance of Mg-doped spinel-structured LiMn2O4 cathode materials
CN113066988B (zh) 一种负极极片及其制备方法和用途
CN112777611B (zh) 一种菱形相普鲁士蓝衍生物及其制备方法和应用
JP2003308880A (ja) リチウム二次電池の製造方法
CN111900473B (zh) 一种用于提高正极材料性能的锂离子电池电解液及锂离子电池
Li et al. Effect of Nb 5+ doping on LiNi 0.5 Co 0.25 Mn 0.25 O 2 cathode material
CN113871737A (zh) 一种含有富锂锰基材料的锂离子电池活化方法及得到的锂离子电池
CN112186166A (zh) 一种钼/钴氧化物-碳复合材料及其制备方法、锂离子电池负极极片和锂离子电池
CN109860592B (zh) 一种含硼分子修饰的镍钴锰酸锂正极材料及其制备方法
CN108183216B (zh) 一种碳包覆富锂锰基正极材料及其制备方法和锂离子电池
KR20050049746A (ko) 리튬 2차전지용 양극 활물질, 그 제조 방법 및 그를포함하는 리튬 2차전지
CN115312754A (zh) 一种片层状无钴富锂锰基正极材料及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20925911

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020925911

Country of ref document: EP

Effective date: 20220328

NENP Non-entry into the national phase

Ref country code: DE