WO2021121168A1 - 四元正极材料、正极、电池 - Google Patents

四元正极材料、正极、电池 Download PDF

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WO2021121168A1
WO2021121168A1 PCT/CN2020/135883 CN2020135883W WO2021121168A1 WO 2021121168 A1 WO2021121168 A1 WO 2021121168A1 CN 2020135883 W CN2020135883 W CN 2020135883W WO 2021121168 A1 WO2021121168 A1 WO 2021121168A1
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quaternary
positive electrode
cathode material
electrode material
dopant
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French (fr)
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白艳
张树涛
潘海龙
王壮
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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Priority to US17/764,572 priority Critical patent/US20220363562A1/en
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Priority to EP20901485.1A priority patent/EP4024525A4/en
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    • H—ELECTRICITY
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    • 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
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    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/50—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
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    • H—ELECTRICITY
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    • 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 invention relates to the technical field of batteries, in particular to quaternary positive electrode materials, positive electrodes, and batteries.
  • lithium-ion batteries are widely used in cameras, mobile phones, notebook computers, electric vehicles and other equipment due to their advantages of stable voltage, high specific capacity, high energy density, long cycle life, and environmental friendliness.
  • the key factor that determines its performance is the cathode material of lithium-ion batteries.
  • the positive electrode materials used include spinel structure LiMn 2 O 4 , layered structure LiCoO 2 and LiNiO 2, etc.
  • lithium-ion secondary batteries with layered LiNiO 2 as the positive electrode material have attracted much attention due to their higher charge-discharge specific capacity.
  • the LiNiO 2 cathode material has an unstable crystal structure and a low cycle life during repeated delithiation (ie repeated charge and discharge). Therefore, it is common to replace part of Ni in LiNiO 2 with Co, Al and/or Mn to obtain high nickel ternary cathode materials or quaternary cathode materials. For example , part of Ni in LiNiO 2 can be replaced by Co, Al, and Mn. The quaternary cathode material NCMA is obtained.
  • the quaternary cathode material not only maintains the characteristics of high specific capacity, but also improves the stability of the crystalline structure, so that the cycle life and thermal stability of the battery using the quaternary cathode material can be improved, and the The specific battery capacity and cycle life of the battery.
  • the main purpose of the present invention is to provide a quaternary positive electrode material, positive electrode, and battery to solve the problems of insufficient cycle stability and thermal stability in the prior art.
  • the quaternary cathode material obtained by replacing part of Ni in LiNiO 2 by Co, Al, and Mn still has poor structural stability.
  • the cycle stability, service life and use of the battery using the quaternary cathode material as the positive electrode The problem of poor security. Therefore, if a new quaternary positive electrode material can be proposed, the structural stability of the quaternary positive electrode material can be better, and it has a better layered crystal structure, which will better improve the use of the quaternary positive electrode material.
  • the cycle stability and thermal stability of the battery will be able to solve the above problems to a large extent.
  • the present invention proposes a quaternary cathode material.
  • M is a dopant, and M includes selection From one or more of Zr, Al, B, Ti, Mg, Nb, Ba, Si, P, W, Sr, F;
  • the quaternary cathode material has an ⁇ -NaFeO 2 type crystal structure, and the four
  • the space group of the X-ray diffraction pattern of the quaternary cathode material is R-3m.
  • the dopant can inhibit the mixing of cations, and can better improve the structural stability of the quaternary positive electrode material, and the c-axis unit cell parameter c of the quaternary positive electrode material and the unit cell parameter a of the a-axis can be better.
  • the quaternary positive electrode material has a better layered crystal structure and good structural stability, which can improve the cycle stability and thermal stability of the battery using the quaternary positive electrode material, and improve the battery of the battery Specific capacity and cycle life.
  • the relationship between the unit cell parameter c of the c axis and the unit cell parameter a of the a axis satisfies: 3a+5.555 ⁇ c ⁇ 3a+ 5.590. Therefore, when the above relationship is satisfied between the unit cell parameter c of the c axis and the unit cell parameter a of the a axis, the quaternary cathode material has a better layered crystal structure, and lithium ions are easier to carry out in the layered structure. Diffusion can increase the specific discharge capacity of a battery using the quaternary cathode material.
  • the numerical range of the a-axis unit cell parameter a is 2.80-2.90, preferably 2.86-2.87
  • the numerical range of the c-axis unit cell parameter c is 14.10-14.30, preferably 14.19- 14.20. Therefore, when the unit cell parameter c of the c-axis and the unit cell parameter a of the a-axis are in the above range, the specific discharge capacity and cycle life of the battery using the quaternary positive electrode material are further improved.
  • the diffraction peak intensities of the I 003 plane and the I 104 plane satisfy the following relationship: 1.921 ⁇ I 003 /I 104 ⁇ 2. Therefore, when the diffraction peak intensities of the I 003 surface and the I 104 surface meet the above relationship, the quaternary cathode material has less mixing of lithium ions and nickel ions, and the quaternary cathode material has higher structural stability.
  • the quaternary cathode material battery has better cycle stability and longer cycle life.
  • the mass fraction of the dopant is 3000-8000 ppm. Therefore, when the content of the dopant is in the above range, the structural stability of the quaternary positive electrode material can be better improved, and the specific discharge capacity of the battery using the quaternary positive electrode material will not be reduced.
  • the dopant is composed of Al and Zr, or is composed of Al, Mg and Zr. Therefore, in the quaternary cathode material co-doped with Al, Mg and Zr, the doped zirconium can enter the transition metal layer of the quaternary cathode material to stabilize its hexagonal structure; the doped aluminum can enter the quaternary cathode material. In the surface lithium layer of the cathode material matrix, the lithium layer can be better supported.
  • the doped aluminum can maintain the stability of the lattice structure of the lithium layer;
  • Doped magnesium can increase or decrease the valence state of transition metal ions in the quaternary cathode material, thereby generating holes or electrons, changing the energy band structure of the quaternary cathode material, thereby increasing its intrinsic electronic conductivity
  • the doped aluminum and magnesium can also inhibit the mixing of Li + and Ni 2+ , and can retain more reversible lithium sites, thereby increasing the reversible discharge specific capacity of the battery using the quaternary cathode material; therefore, aluminum , Magnesium and zirconium co-doping can better improve the structural stability of the quaternary cathode material, can improve the cycle stability and thermal stability of the battery using the quaternary cathode material, and improve the battery under high voltage rate.
  • the specific capacity, the battery performance using the quaternary cathode material is good.
  • the mass fraction of the dopant Al is 2500-3500 ppm
  • the mass fraction of the dopant Mg is 300-500 ppm
  • the mass fraction of the dopant Zr is 2500-3500 ppm.
  • a method for preparing any one of the above-mentioned quaternary positive electrode materials comprising: dry-mixing a nickel-cobalt-manganese-aluminum quaternary precursor with a lithium source and a dopant source , To obtain a dry mixture; calcining the dry mixture in an oxygen-containing atmosphere at 700-800°C for 10-15 hours to obtain a quaternary cathode material precursor; using aluminum and boron sources to treat the quaternary cathode material precursor in oxygen The coating and calcining process is performed in an atmosphere to obtain a quaternary positive electrode material.
  • the temperature of the coating and calcining is 250-350° C. and the time is 4-8 h.
  • the present invention provides a positive electrode.
  • the positive electrode includes the quaternary positive electrode material described in any one of the foregoing. Therefore, the positive electrode has all the features and advantages of any of the quaternary positive electrode materials described above, and will not be repeated here. In general, the positive electrode structure is stable, and has better cycle performance and rate performance.
  • the present invention provides a battery.
  • the battery includes a positive electrode, a negative electrode, a separator, and an electrolyte.
  • the separator is disposed between the positive electrode and the negative electrode; at least a part of the positive electrode, at least a part of the negative electrode, and the separator At least a part is immersed in the electrolyte. Therefore, the battery has all the features and advantages of the aforementioned positive electrode, which will not be repeated here. In general, the battery has good cycle stability and thermal stability, and the battery has a higher battery specific capacity at a high voltage rate.
  • Figure 1 shows the X-ray diffraction pattern of the quaternary cathode material prepared according to Example 1 of the present invention
  • FIG. 2 shows the X-ray diffraction pattern of the quaternary cathode material prepared according to Comparative Example 1 of the present invention.
  • the present invention proposes a quaternary cathode material.
  • M is a dopant, and M includes selection From one or more of Zr, Al, B, Ti, Mg, Nb, Ba, Si, P, W, Sr, F;
  • the quaternary cathode material has an ⁇ -NaFeO 2 type crystal structure, and the four
  • the space group of the X-ray diffraction pattern of the quaternary cathode material is R-3m.
  • the dopant can inhibit the mixing of cations, and can better improve the structural stability of the quaternary positive electrode material; and the c-axis unit cell parameter c of the quaternary positive electrode material and the unit cell parameter a of the a-axis can be better.
  • the quaternary positive electrode material has a better layered crystal structure and good structural stability, which can improve the cycle stability and thermal stability of the battery using the quaternary positive electrode material, and improve the battery of the battery Specific capacity and cycle life.
  • the quaternary cathode material obtained by substituting part of Ni in LiNiO 2 by Co, Al, and Mn still has poor structural stability, and the cycle stability of the battery using the quaternary cathode material as the positive electrode , Poor service life and poor safety in use.
  • a dopant is added to the conventional nickel-cobalt-manganese-aluminum quaternary cathode material.
  • the dopant may be selected from Zr, Al, B, Ti, Mg, One or more of Nb, Ba, Si, P, W, Sr, F, the dopant can improve the structural stability of the quaternary cathode material, for example, doped Zr can enter the transition of the quaternary cathode material The metal layer stabilizes its hexagonal structure; the doped aluminum can enter the surface lithium layer of the quaternary cathode material matrix, which can then better support the lithium layer.
  • the doped aluminum can maintain the stability of the lattice structure of the lithium layer; the doped magnesium can increase or decrease the valence of the transition metal ions in the quaternary cathode material, thereby generating holes or electrons and changing the The energy band structure of the quaternary cathode material improves its intrinsic electronic conductivity; and the doped aluminum and magnesium can also inhibit the mixing of Li + and Ni 2+ , and can retain more reversible lithium sites, thereby increasing The reversible discharge specific capacity of the battery using the quaternary cathode material; therefore, the above-mentioned dopants can better improve the structural stability of the quaternary cathode material, and can improve the cycle stability and thermal stability of the battery using the quaternary cathode material.
  • the unit cell parameter c of the c axis and the unit cell parameter a of the a axis satisfy the relationship of c/a>4.943. It is found that when the above relationship is satisfied between the unit cell parameter c of the c-axis and the unit cell parameter a of the a-axis, the quaternary cathode material has a better layered crystal structure, and lithium ions are easier to carry out in the layered structure.
  • Diffusion can further increase the specific discharge capacity of the battery using the quaternary positive electrode material; specifically, by controlling the type of dopant added and the amount of dopant, etc., the c in the quaternary positive electrode material can be easily adjusted.
  • the relationship between the unit cell parameter c of the axis and the unit cell parameter a of the a axis can easily make the unit cell parameter c of the c axis of the quaternary cathode material and the unit cell parameter a of the a axis satisfy c/a
  • the relationship of >4.943 can further improve the cycle stability and thermal stability of the battery using the quaternary positive electrode material, and increase the battery specific capacity of the battery at a high voltage rate.
  • the battery using the quaternary positive electrode material has good performance.
  • the molar content of Li in the quaternary cathode material that is, the value of x in the general structural formula above satisfies 1 ⁇ x ⁇ 1.05.
  • x can satisfy 1.01 ⁇ x ⁇ 1.035, for example, x can be equal to 1.02, 1.025, 1.03, etc. Therefore, when the molar content of Li in the quaternary positive electrode material is within the above range, the battery using the quaternary positive electrode material has a higher charge-discharge specific capacity and better performance.
  • the Li content in the quaternary cathode material is too small, for example, when x ⁇ 1.0, Ni easily enters the Li layer, resulting in an increase in the occupancy rate of transition metal elements at the lithium position, and the charge-discharge specific capacity of the quaternary cathode material is lower;
  • the content of Li in the quaternary cathode material is too large, for example, when x>1.05, the mixing amount of Li at the transition metal site is large, so there is more Ni driven out of the transition metal site by Li, and Ni is easily mixed into the Li layer. It will also lead to a larger occupancy rate of transition metal elements in the lithium position, which will affect the specific charge and discharge capacity of the quaternary cathode material.
  • the molar content of Co in the quaternary cathode material that is, the value of b in the general structural formula above satisfies 0.03 ⁇ b ⁇ 0.1, specifically, b can satisfy 0.05 ⁇ b ⁇ 0.06, for example, b can be equal to 0.055, etc. .
  • Co can improve the structural stability of the quaternary positive electrode material, and will not significantly affect the specific charge and discharge capacity of the quaternary positive electrode material.
  • the molar content of Mn in the quaternary cathode material that is, the value of c in the general structural formula above satisfies 0.01 ⁇ c' ⁇ 0.05, specifically, c'may satisfy 0.02 ⁇ c' ⁇ 0.03, for example, c' Can be equal to 0.025 and so on.
  • the molar content of Al in the quaternary cathode material that is, the value of d in the general structural formula above satisfies 0.01 ⁇ d ⁇ 0.05, specifically, d can satisfy 0.02 ⁇ d ⁇ 0.03, for example, d can be equal to 0.025, etc. .
  • the structural stability of the quaternary positive electrode material can be improved, and the specific charge and discharge capacity of the quaternary positive electrode material will not be significantly affected.
  • M is a dopant
  • M includes one or more selected from Zr, Al, B, Ti, Mg, Nb, Ba, Si, P, W, Sr, and F
  • the molar content of M in the quaternary cathode material that is, the value of y in the general structural formula above satisfies 0 ⁇ y ⁇ 0.0250, specifically, y can satisfy 0.003 ⁇ y ⁇ 0.0220, for example, y can be equal to 0.005, 0.01 , 0.015, 0.02, etc.
  • the mass fraction of the dopant in the quaternary cathode material may be 3000-8000 ppm, for example, it may be 3500 ppm, it may be 4000 ppm, it may be 4500 ppm, it may be 5000 ppm, it may be 5500 ppm, it may be 6000 ppm, It can be 6500ppm, it can be 7000ppm, it can be 7500ppm and so on. Therefore, when the content of the dopant is in the above range, the structural stability of the quaternary positive electrode material can be better improved, and the specific discharge capacity of the battery using the quaternary positive electrode material will not be reduced.
  • the content of the dopant in the quaternary cathode material is too small, for example, the mass fraction of the dopant in the quaternary cathode material is less than 3000 ppm, the effect of improving the stability of the crystal structure of the quaternary cathode material is not very prominent;
  • the content of the dopant in the quaternary positive electrode material is too large, for example, the mass fraction of the dopant in the quaternary positive electrode material is greater than 8000 ppm, which will affect the specific discharge capacity of the battery using the quaternary positive electrode material.
  • the mass fraction of the dopant in the quaternary cathode material mentioned above refers to the total mass fraction of all the dopants in the quaternary cathode material.
  • the dopant includes co-doping of multiple elements.
  • the mass fraction of the dopant is the mass fraction of all doping elements.
  • the dopant may be one, two, three, or four of the aforementioned, for example, the dopant may be Al and Zr co-doped, or Al, Mg, and Zr may be co-doped. Doping can be Al, Mg, Zr and Ti co-doping. According to specific embodiments of the present invention, the dopant may be composed of Al, Mg, and Zr. Therefore, in the quaternary cathode material co-doped with Al, Mg and Zr, the dopants Al, Mg and Zr have a synergistic effect: the doped zirconium can enter the transition metal layer of the quaternary cathode material to stabilize it.
  • doped aluminum can enter the surface lithium layer of the quaternary cathode material matrix, which can then better support the lithium layer.
  • the doped aluminum The stability of the lattice structure of the lithium layer can be maintained; the doped magnesium can increase or decrease the valence state of the transition metal ions in the quaternary cathode material, thereby generating holes or electrons, and changing the quaternary cathode material Band structure, thereby improving its intrinsic electronic conductivity; and doped aluminum and magnesium can also inhibit the mixing of Li + and Ni 2+ , and can retain more reversible lithium sites, thereby increasing the use of the quaternary anode The reversible discharge specific capacity of the battery of the material; therefore, the co-doping of aluminum, magnesium and zirconium can better improve the structural stability of the quaternary cathode material, and can improve the cycle stability and thermal stability of the battery
  • the mass fraction of the dopant Al can be 2500-3500 ppm, for example, 3000 ppm, etc.
  • the mass fraction of the dopant Mg is 300-500 ppm
  • the mass fraction of dopant Zr is 2500-3500 ppm, for example, it can be 3000 ppm.
  • the structural stability of the quaternary cathode material can be improved, and the specific discharge capacity of the battery using the quaternary cathode material will not be reduced. It is beneficial to improve the overall performance of the battery using the quaternary cathode material.
  • the quaternary positive electrode material has an ⁇ -NaFeO 2 type crystal structure, and the space group of the X-ray diffraction pattern of the quaternary positive electrode material is R-3m.
  • the crystalline structure characteristics of the quaternary cathode material can be expressed by the unit cell parameters of the a-axis and the c-axis.
  • the crystalline structure of R-3m is a layered structure formed by a transition metal-oxygen octahedral layer with a transition metal as the center and a lithium layer.
  • the unit cell parameter a of the a-axis is determined by the distance between transition metal-transition metal, the distance between lithium-lithium and the distance between oxygen and oxygen, and the lattice parameter c of the c-axis is determined by the transition metal-oxygen- Determined by the role of lithium-oxygen.
  • the content of each transition metal, the content of lithium, the ion radius of each element and the valence state of the transition metal will all affect the transition metal-transition metal and transition metal
  • the distance between the metal and the oxygen ultimately changes the various lattice parameters.
  • the quaternary positive electrode material has a better layered crystal structure, and lithium ions are relatively easy to diffuse in the layered structure, and the specific discharge capacity of the battery using the quaternary positive electrode material can be improved.
  • the crystalline structure of R-3m varies with the ratio of transition metal (Me) and Li element, and the type and content of dopant elements. Therefore, by adjusting the ratio of transition metal (Me) and Li (Li/Me ), the type and content of dopant elements, the relationship between the unit cell parameter c of the c axis and the unit cell parameter a of the a axis can be adjusted, so that the unit cell parameter c of the c axis and the unit cell parameter a of the a axis can meet the above Conditions, the formation of a better layered crystal structure.
  • the relationship between the c-axis unit cell parameter c and the a-axis unit cell parameter a may further satisfy: 3a+5.555 ⁇ c ⁇ 3a+5.590. Therefore, when the above relationship is satisfied between the unit cell parameter c of the c axis and the unit cell parameter a of the a axis, the quaternary cathode material has a better layered crystal structure, and lithium ions are easier to carry out in the layered structure. Diffusion can increase the specific discharge capacity of a battery using the quaternary cathode material.
  • the value range of the unit cell parameter a of the a-axis can be 2.80-2.90, preferably 2.86-2.87, for example, it can be 2.85, it can be 2.86, it can be 2.87, etc.;
  • the value range of the c-axis unit cell parameter c can be It is 14.10-14.30, preferably 14.19-14.20, for example, it can be 14.19, it can be 14.2, it can be 14.25, etc. Therefore, when the unit cell parameter c of the c axis and the unit cell parameter a of the a axis are in the above range, the quaternary cathode material has a better layered crystal structure, and lithium ions are easier to diffuse in the layered structure. The specific discharge capacity of the battery using the quaternary cathode material can be improved.
  • the diffraction peak intensities of the I 003 plane and the I 104 plane may satisfy the following relationship: 1.921 ⁇ I 003 /I 104 ⁇ 2.
  • the diffraction peak of the I 003 plane reflects the hexagonal structure
  • the diffraction peak of the I 104 plane reflects the hexagonal structure and the cubic structure.
  • the dopant can inhibit the mixing of cations, and can better improve the structural stability of the quaternary positive electrode material; and the c-axis of the quaternary positive electrode material
  • the quaternary cathode material has a better layered crystal structure and good structural stability, which can improve the use of the quaternary
  • the cycle stability and thermal stability of the battery of the positive electrode material improve the battery specific capacity and cycle life of the battery.
  • the preparation method includes: combining a nickel-cobalt-manganese-aluminum quaternary precursor with a lithium source and a dopant.
  • the source is dry mixed to obtain a dry mixture; the dry mixture is calcined in an oxygen-containing atmosphere at 700-800°C for 10-15 hours to obtain a quaternary cathode material precursor; the aluminum source and boron source are used for the quaternary cathode material.
  • the body is coated and calcined in an oxygen-containing atmosphere to obtain a quaternary positive electrode material.
  • the temperature of the coating and calcining is 250-350°C and the time is 4-8h.
  • the dopant is mixed into the quaternary positive electrode material to obtain the quaternary positive electrode material of the present application.
  • the preparation method is simple and is beneficial to industrial implementation.
  • the last step of the coating treatment is not to form a coating layer with a clear coating structure on the surface of the quaternary positive electrode material precursor, but to dope the aluminum source and boron source on the surface of the quaternary positive electrode material precursor.
  • the treatment can inhibit the side reaction between the surface of the particles and the electrolyte, reduce the amount of oxygen released, and then improve the conductivity of the particles and the diffusion rate of lithium ions at the interface, and improve the electrical performance.
  • the present invention provides a positive electrode.
  • the positive electrode includes the quaternary positive electrode material described in any one of the foregoing. Therefore, the positive electrode has all the features and advantages of any of the quaternary positive electrode materials described above, and will not be repeated here. In general, the positive electrode structure is stable, and has better cycle performance and rate performance.
  • the present invention provides a battery.
  • the battery includes the aforementioned positive electrode, negative electrode and separator, the separator is arranged between the positive electrode and the negative electrode, and at least a part of the positive electrode, at least part of the negative electrode, and at least part of the separator are immersed in the electrolyte. Therefore, the battery has all the features and advantages of the aforementioned positive electrode, which will not be repeated here. In general, the battery has good cycle stability and thermal stability, and the battery has a higher battery specific capacity at a high voltage rate.
  • the high-nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , the Li source (LiOH) and the Zr source (Zr(OH) 4 ) were dry mixed, and the high-nickel precursor Ni 0.88 Co 0.06
  • the molar ratio of Mn 0.03 Al 0.03 (OH) 2 , Zr source (Zr(OH) 4 ) and Li source (LiOH) is 1:0.003:1.025 to form a mixture; calcined, cooled, crushed, and sieved to obtain Zr Doped quaternary cathode material matrix, in which calcination is carried out at 700°C for 8 hours in an oxygen atmosphere; in the Zr-doped quaternary cathode material matrix, the mass fraction of Zr is 3000 ppm;
  • the Zr-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ), and the quaternary cathode material matrix and Al source
  • Al source Al 2 O 3
  • boron source H 3 BO 3
  • the mass ratio of (Al 2 O 3 ) and boron source (H 3 BO 3 ) is 100:0.01:0.01, and after calcination treatment, the final quaternary cathode material A is obtained.
  • the calcination treatment is continued under an oxygen atmosphere at 300°C. After 6h.
  • the high-nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH) and Al source (Al 2 O 3 ) are mixed, and the high-nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al
  • the molar ratio of 0.03 (OH) 2 , Al source (Al 2 O 3 ) and Li source (LiOH) is 1:0.003:1.025 to form a mixture; and calcined, cooled, pulverized, and sieved to obtain Al-doped four Elementary cathode material matrix; wherein the calcination is carried out at 700°C for 8 hours in an oxygen atmosphere, and the Al-doped quaternary cathode material matrix has an Al mass fraction of 3000 ppm;
  • the Al-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ), and the quaternary cathode material matrix and Al source ( The mass ratio of Al 2 O 3 ) and boron source (H 3 BO 3 ) is 100:0.01:0.01, and after calcination treatment, the final quaternary cathode material B is obtained. The calcination treatment lasts for 6 hours under an oxygen atmosphere at 300°C. Rear
  • the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH), Al source (Al 2 O 3 ) and Zr source (Zr(OH) 4 ) are mixed, where the high The molar ratio of nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 and Li source (LiOH) is 1:1.025 to form a mixture; calcined, cooled, crushed, and sieved to obtain Al and Zr co-doped A quaternary cathode material matrix; wherein the calcination is carried out at 700°C in an oxygen atmosphere for 8 hours, the Al and Zr co-doped quaternary cathode material matrix has an Al mass fraction of 3000 ppm, and a Zr mass fraction of 1500 ppm;
  • the Al and Zr co-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ).
  • the quaternary cathode material matrix The mass ratio with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ) is 100:0.01:0.01, and after calcination treatment, the final quaternary cathode material C is obtained.
  • the calcination treatment is performed at 300°C in oxygen The atmosphere lasted 6h later.
  • the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH), Al source (Al 2 O 3 ) and Zr source (Zr(OH) 4 ) are mixed, where the high Nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH) molar ratio of 1:1.025 to form a mixture; and calcined, cooled, crushed, sieved, Al and Zr co-doped four Elementary cathode material matrix; wherein the calcination lasts for 8 hours in an oxygen atmosphere at 700°C.
  • the mass fraction of Al is 3000 ppm
  • the mass fraction of Zr is 3000 ppm;
  • the Al and Zr co-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ).
  • the quaternary cathode material matrix The mass ratio with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ) is 100:0.01:0.01, and after calcination treatment, the final quaternary cathode material D is obtained.
  • the calcination treatment is performed at 300°C in oxygen The atmosphere lasted 6h later.
  • the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH), Al source (Al 2 O 3 ), Mg source (Mg(OH) 2 ), Zr source (Zr (OH) 4 ) is mixed, wherein the molar ratio of the high-nickel precursor Ni0.88Co0.06Mn0.03Al0.03(OH)2, Li source (LiOH), is 1:1.025; and is calcined, cooled, pulverized, and passed.
  • the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH), Al source (Al 2 O 3 ), Mg source (Mg(OH) 2 ), Zr source (Zr (OH) 4 ) is mixed, wherein the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 and the molar ratio of Li source (LiOH) are 1:1.025 to form a mixture; and the mixture is calcined, cooled, crushed, and processed.
  • step (1) The Al, Mg, and Zr co-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ), quaternary anode
  • Al source Al 2 O 3
  • boron source H 3 BO 3
  • the mass ratio of the material matrix to the Al source (Al 2 O 3 ) and the boron source (H 3 BO 3 ) is 100:0.01:0.01, and after calcination treatment, the final quaternary cathode material F is obtained.
  • the calcination treatment is performed at 300 After 6h under oxygen atmosphere.
  • the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH), Al source (Al 2 O 3 ), Mg source (Mg(OH) 2 ), Zr source (Zr (OH) 4 ) is mixed, wherein the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 and the molar ratio of Li source (LiOH) are 1:1.025 to form a mixture; and the mixture is calcined, cooled, crushed, and processed.
  • step (1) The Al, Mg, and Zr co-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ), quaternary anode
  • Al source Al 2 O 3
  • boron source H 3 BO 3
  • the mass ratio of the material matrix to the Al source (Al 2 O 3 ) and the boron source (H 3 BO 3 ) is 100:0.01:0.01, and after calcination treatment, the final quaternary cathode material G is obtained.
  • the calcination treatment is performed at 300 After 6h under oxygen atmosphere.
  • the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH), Al source (Al 2 O 3 ), Mg source (Mg(OH) 2 ), Zr source (Zr (OH) 4 ) is mixed, wherein the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 and the molar ratio of Li source (LiOH) are 1:1.025 to form a mixture; and the mixture is calcined, cooled, crushed, and processed.
  • step (1) The Al, Mg, and Zr co-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ), quaternary anode
  • Al source Al 2 O 3
  • boron source H 3 BO 3
  • the mass ratio of the material matrix to the Al source (Al 2 O 3 ) and the boron source (H 3 BO 3 ) is 100:0.01:0.01, and after calcination treatment, the final quaternary cathode material H is obtained.
  • the calcination treatment is performed at 300 After 6h under oxygen atmosphere.
  • the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 , Li source (LiOH), Al source (Al 2 O 3 ), Mg source (Mg(OH) 2 ), Zr source (Zr (OH) 4 ) and Ti source (TiO 2 ) are mixed, wherein the high nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 and the Li source (LiOH) molar ratio are 1:1.025 to form a mixture; and Calcined, cooled, pulverized, and sieved to obtain a quaternary cathode material matrix co-doped with Al, Mg, Zr, and Ti; the calcination lasts for 8 hours in an oxygen atmosphere at 700°C, and the Al, Mg, Zr, and Ti co-doped In the quaternary cathode material matrix, the mass fraction of Al is 3000 ppm, the mass fraction of Mg is 400 ppm, the mass fraction of Zr is 1500
  • step (1) The Al, Mg, Zr, and Ti co-doped quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ).
  • the mass ratio of the primary cathode material matrix to the Al source (Al 2 O 3 ) and the boron source (H 3 BO 3 ) is 100:0.01:0.01, and the final quaternary cathode material I is obtained after calcination treatment, etc., the calcination treatment After 6h at 300°C under oxygen atmosphere.
  • the high-nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 (OH) 2 and Li source (LiOH) are calcined, cooled, crushed and sieved, and the high-nickel precursor Ni 0.88 Co 0.06 Mn 0.03 Al 0.03 ( The molar ratio of OH) 2 and Li source (LiOH) is 1:1.025, wherein calcination is carried out at 700°C for 8 hours in an oxygen atmosphere to obtain a quaternary cathode material matrix;
  • step (1) The quaternary cathode material matrix formed in step (1) is sequentially coated with Al source (Al 2 O 3 ) and boron source (H 3 BO 3 ), and the quaternary cathode material matrix and Al source (Al 2 The mass ratio of O 3 ) and the boron source (H 3 BO 3 ) is 100:0.01:0.01, and the final quaternary cathode material J is obtained after calcination treatment.
  • Table 1 X-ray diffraction pattern data table of the quaternary cathode materials prepared in Examples 1-9 and Comparative Example 1
  • the value of c/a in the X-ray diffraction pattern of the quaternary cathode material in Examples 1-9 is greater than the value of c/a in the X-ray diffraction pattern of the quaternary cathode material in Comparative Example 1.
  • the quaternary cathode material in Examples 1-9 is The charge and discharge specific capacity, the first efficiency, and the 50-week cycle retention rate are all higher than those of the quaternary cathode material in Comparative Example 1.
  • the quaternary cathode material of the embodiment of the present invention by adding dopants to the matrix of the traditional nickel-cobalt-manganese-aluminum quaternary cathode material, and making the X-ray diffraction pattern of the quaternary cathode material, c
  • the relationship between the unit cell parameter c of the axis and the unit cell parameter a of the a axis satisfies c/a>4.943.
  • the quaternary cathode material has a better layered crystal structure and good structural stability, which can improve the use of the four
  • the cycle stability and thermal stability of the battery of the meta-positive electrode material improve the battery specific capacity of the battery.
  • the value of I 003 /I 104 in the X diffraction pattern that is, the diffraction peak intensities of the I 003 plane and the I 104 plane in the X diffraction patterns of the quaternary cathode materials in Examples 1 and 2, 4-9 satisfy the following relationship : 1.921 ⁇ I 003 /I 104 ⁇ 2, the structural stability of the quaternary cathode material is higher, and the battery using the quaternary cathode material has better cycle stability and longer cycle life.
  • the quaternary positive electrode materials prepared in the foregoing Examples 1-9 and Comparative Example 1 were prepared into a slurry with a conductive agent and a binder in a certain proportion, coated on aluminum foil, and vacuum dried and rolled to form a positive electrode.
  • the pole piece, the lithium metal piece is used as the negative electrode
  • the electrolyte includes a lithium hexafluorophosphate (LiPF 6 ) solution with a concentration of 1.15M
  • the solvent is a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC), and the volume of EC and DMC The ratio is 1:1, and button batteries are assembled.
  • the electrochemical performance test of the foregoing battery was performed.
  • the electrochemical performance test uses the blue battery test system to test at 25°C, and the test voltage ranges from 3V to 4.3V.
  • the quaternary positive electrode material according to the embodiment of the present invention adds a dopant to the matrix of the traditional nickel-cobalt-manganese-aluminum quaternary positive electrode material, and makes the X-ray diffraction pattern of the quaternary positive electrode material, the c-axis
  • the relationship between the unit cell parameter c of the a axis and the unit cell parameter a of the a axis satisfies c/a>4.943.
  • the dopant can inhibit the mixing of cations and can better improve the structural stability of the quaternary cathode material.
  • the quaternary positive electrode material has a better layered crystal structure and good structural stability, which can improve the cycle stability and thermal stability of the battery using the quaternary positive electrode material, and increase the battery specific capacity and cycle life of the battery.
  • electrochemical performance test data generally refer to charge specific capacity, discharge specific capacity, first efficiency, and 50-week cycle Retention rate, the same below. It can be seen that the electrochemical performance of the quaternary cathode material dopant containing two or more elements is better than that of the quaternary cathode material doped with only one element; Examples 5-8 The quaternary cathode materials in the quaternary cathode materials are all doped with Al, Mg, and Zr, and their electrochemical performance is better than that of the single-doped and double-doped quaternary cathode materials in other embodiments; The electrochemical performance test data of the quaternary cathode material is significantly better than the other examples, which proves that the mass fraction of the dopant Al in the quaternary cathode material co-doped with Al, Mg and Zr is 2500-3500 ppm When
  • the exothermic peak peak temperature value in the above table is the exothermic peak temperature of the reaction between the quaternary cathode material and the electrolyte. The higher the value, the better the thermal stability of the quaternary cathode material. It can be seen from the test data in the above table that the thermal stability of the quaternary cathode material in Examples 1 and 2, 4, 5, and 7-9 is higher than that of the quaternary cathode material in Comparative Example 1.
  • the quaternary positive electrode material according to the embodiment of the present invention adds a dopant to the matrix of the traditional nickel-cobalt-manganese-aluminum quaternary positive electrode material, and makes the X-ray diffraction pattern of the quaternary positive electrode material, the c-axis
  • the relationship between the unit cell parameter c and the unit cell parameter a of the a axis satisfies c/a>4.943, and the quaternary cathode material has good structural stability.
  • the quaternary cathode material doped with three elements of Al, Mg and Zr in a specific ratio in Example 5 has better thermal stability than other examples.
  • the mass fraction of dopant Al is 2500-3500 ppm
  • the mass fraction of dopant Mg is 300-500 ppm
  • the mass fraction of dopant Zr When the mass fraction is 2500-3500 ppm, the structural stability of the quaternary cathode material can be improved.

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Abstract

一种四元正极材料、正极、电池，四元正极材料的化学结构通式为：Li xNi aCo bMn cAl dM yO 2，其中，1≤x≤1.05，0＜y≤0.025，0.3≤a≤0.95，0.03≤b≤0.1，0.01≤c≤0.05，0.01≤d≤0.05，且a+b+c+d＝1；M为掺杂剂，M包括选自Zr、Al、B、Ti、Mg、Nb、Ba、Si、P、W、Sr、F中的一种或多种；四元正极材料具有α-NaFeO 2型晶体结构，四元正极材料的X-射线衍射图案的空间群为R-3m，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足：c/a＞4.943。由此，掺杂剂可以较好地提高该四元正极材料的结构稳定性，且该四元正极材料具有较好的层状晶体结构，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池的电池比容量和循环寿命。

Description

四元正极材料、正极、电池 技术领域
本发明涉及电池技术领域，具体地，涉及四元正极材料、正极、电池。
背景技术
目前，锂离子电池因其电压稳定、比容量高、能量密度大、循环寿命长、环境友好等优势，被广泛应用于摄像机、移动电话、笔记本电脑、电动交通工具等设备上。其中，决定其性能的关键因素是锂离子电池的正极材料。在高能量型锂离子二次电池中，所使用的正极材料包括尖晶石结构的LiMn 2O 4、层状结构的LiCoO 2和LiNiO 2等。其中，层状结构的LiNiO 2作为正极材料的锂离子二次电池因其较高的充放电比容量备受关注。但是，LiNiO 2正极材料在反复脱锂(即反复充放电)过程中，结晶结构不稳定，循环寿命低。因此，目前通常将LiNiO 2中的部分Ni用Co、Al和/或Mn取代，得到高镍三元正极材料或四元正极材料，例如LiNiO 2中的部分Ni被Co、Al、Mn共同取代可以得到四元正极材料NCMA，该四元正极材料既保持了高比容量特性，还能提高结晶结构的稳定性，从而可以提高采用该四元正极材料的电池的循环寿命和热稳定性，提高该电池的电池比容量和循环寿命。
然而，目前的四元正极材料、正极、电池仍有待改进。
发明内容
本发明的主要目的在于提供一种四元正极材料、正极、电池，以解决现有技术中的循环稳定性、热稳定性不足的问题。
本申请是基于发明人对以下事实和问题的发现和认识作出的：
目前，LiNiO 2中的部分Ni被Co、Al、Mn共同取代得到的四元正极材料，仍然存在结构稳定性较差、使用该四元正极材料作为正极的电池的循环稳定性、使用寿命和使用安全性较差的问题。因此，如果能提出一种新的四元正极材料，该四元正极材料的结构稳定性可以更好，并且具有较好的层状晶体结构，将能较好地提高使用该四元正极材料的电池的循环稳定性、热稳定性，将能在很大程度上解决上述问题。
在本发明的一个方面，本发明提出了一种四元正极材料。根据本发明的实施例，该四元正极材料的化学结构通式为：Li xNi a’Co bMn c’Al dM yO 2，其中，1≤x≤1.05，0＜y≤0.025，0.3≤a’≤0.95，0.03≤b≤0.1，0.01≤c’≤0.05，0.01≤d≤0.05，且a’+b+c’+d＝1；M为掺杂剂，所述M包括选自Zr、Al、B、Ti、Mg、Nb、Ba、Si、P、W、Sr、F中的一种或多种；所述四元正极材料具有α-NaFeO 2型晶体结构，所述四元正极材料的X-射线衍射图案的空间群为R-3m，所述四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足：c/a＞4.943。
由此，掺杂剂可以抑制阳离子混排，可以较好地提高该四元正极材料的结构稳定性，并且该四元正极材料的c轴的晶胞参数c和a轴的晶胞参数a之间满足上述关系时，该四元正极材料具有较好的层状晶体结构，结构稳定性较好，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池的电池比容量和循环寿命。
根据本发明的实施例，所述四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足：3a+5.555≤c≤3a+5.590。由此，c轴的晶胞参数c和a轴的晶胞参数a之间满足上述关系时，该四元正极材料具有较好的层状晶体结构，锂离子比较容易在该层状结构中进行扩散，可以提高使用该四元正极材料的电池的放电比容量。
根据本发明的实施例，所述a轴的晶胞参数a的数值范围为2.80-2.90，优选为2.86-2.87，所述c轴晶胞参数c的数值范围为14.10-14.30，优选为14.19-14.20。由此，c轴的晶胞参数c和a轴的晶胞参数a在上述范围时，进一步提高了使用该四元正极材料的电池的放电比容量和循环寿命。
根据本发明的实施例，所述四元正极材料的X-射线衍射图案中，I 102面、I 006面和I 101面的衍射峰强度满足下列关系：R＝(I 102+I 006)/I 101，且0.4≤R≤0.44。由此，R值在上述范围时，该四元正极材料的六方晶体结构的有序性较高，不仅有利于锂离子在该晶体结构中的脱嵌，也能提高该四元正极材料的结构稳定性和热稳定性，从而提高使用该四元正极材料的电池的放电比容量和循环寿命。
根据本发明的实施例，所述四元正极材料的X-射线衍射图案中，I 003面和I 104面的衍射峰强度满足下列关系：1.921＜I 003/I 104≤2。由此，I 003面和I 104面的衍射峰强度满足上述关系时，该四元正极材料中锂离子和镍离子的混排较少，该四元正极材料的结构稳定性较高，使用该四元正极材料的电池的循环稳定性较好，循环寿命较长。
根据本发明的实施例，所述四元正极材料中，所述掺杂剂的质量分数为3000-8000ppm。由此，掺杂剂的含量在上述范围时，可以较好地提高四元正极材料的结构稳定性，并且不会降低使用该四元正极材料的电池的放电比容量。
根据本发明的实施例，所述掺杂剂由Al和Zr组成，或者由Al、Mg和Zr组成。由此，由Al、Mg和Zr共掺杂形成的四元正极材料中，掺杂的锆可以进入该四元正极材料的过渡金属层，稳定其六方结构；掺杂的铝可以进入该四元正极材料基体的表层锂层中，进而可以较好地支撑锂层，在高电压充放电过程中，锂离子大量嵌出时，该掺杂的铝可以保持锂层晶格结构的稳定性；掺杂的镁可以使该四元正极材料中的过渡金属离子的价态升高或降低，进而可以产生空穴或电子，改变该四元正极材料的能带结构，从而提高其本征电子导电率；并且掺杂的铝和镁还能抑制Li +和Ni 2+的混排，可以保留更多可逆的锂位置，从而提高了使用该四元正极材料的电池的可逆放电比容量；因此，铝、镁和锆共掺杂可以较好地提高四元正极材料的结构稳定性，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池在高电压倍率下的电池比容量，使用该四元正极材料的电池性能良好。
根据本发明的实施例，所述四元正极材料中，掺杂剂Al的质量分数为2500-3500ppm，掺杂剂Mg的质量分数为300-500ppm，掺杂剂Zr的质量分数为2500-3500ppm。由此，掺杂剂的含量在上述范围时，可以较好地提高四元正极材料的结构稳定性，并且不会降低使用该四元正极材料的电池的放电比容量，有利于提高使用该四元正极材料的电池的综合性能。
根据本申请的另一方面，还提供了一种上述任一种四元正极材料的制备方法，该制备方法包括：将镍钴锰铝四元前驱体与锂源、掺杂剂源进行干混，得到干混物；将干混物在含氧气氛中、700～800℃下煅烧10～15h，得到四元正极材料前体；采用铝源和硼源对四元正极材料前体在含氧气氛中进行包覆煅烧处理，得到四元正极材料，述包覆煅烧的温度为250～350℃、时间为4～8h。
在本发明的另一方面，本发明提出了一种正极。根据本发明的实施例，所述正极包括前面任一项所述的四元正极材料。由此，该正极具有前面任一项所述的四元正极材料所具有的全部特征以及优点，在此不再赘述。总的来说，该正极结构稳定，且具有较佳的循环性能以及倍率性能。
在本发明的又一方面，本发明提出了一种电池。根据本发明的实施例，该电池包括正极、负极、隔膜和电解液，隔膜设置在所述正极与所述负极之间；所述正极的至少一部分、所述负极的至少一部分以及所述隔膜的至少一部分浸没在所述电解液中。由此，该电池具有前面所述的正极所具有的全部特征以及优点，在此不再赘述。总的来说，该电池具有良好的循环稳定性和热稳定性，该电池在高电压倍率下具有较高的电池比容量。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1示出了根据本发明实施例1所制备的四元正极材料的X-射线衍射图谱，以及
图2示出了根据本发明对比例1所制备的四元正极材料的X-射线衍射图谱。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
在本发明的一个方面，本发明提出了一种四元正极材料。根据本发明的实施例，该四元正极材料的化学结构通式为：Li xNi a’Co bMn c’Al dM yO 2，其中，1≤x≤1.05，0＜y≤0.025，0.3≤a’≤0.95，0.03≤b≤0.1，0.01≤c’≤0.05，0.01≤d≤0.05，且a’+b+c’+d＝1；M为掺杂剂，所述M包括选自Zr、Al、B、Ti、Mg、Nb、Ba、Si、P、W、Sr、F中的一种或多种；所述四元正极材料具有α-NaFeO 2型晶体结构，所述四元正极材料的X-射线衍射图案的空间群为 R-3m，所述四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足：c/a＞4.943。
由此，掺杂剂可以抑制阳离子混排，可以较好地提高该四元正极材料的结构稳定性；并且该四元正极材料的c轴的晶胞参数c和a轴的晶胞参数a之间满足上述关系时，该四元正极材料具有较好的层状晶体结构，结构稳定性较好，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池的电池比容量和循环寿命。
为了便于理解，下面对根据本发明实施例的四元正极材料能够实现上述有益效果的原理进行简单描述：
如前所述，目前，LiNiO 2中的部分Ni被Co、Al、Mn共同取代得到的四元正极材料，仍然存在结构稳定性较差、使用该四元正极材料作为正极的电池的循环稳定性、使用寿命和使用安全性较差的问题。而根据本发明实施例的四元正极材料，一方面，在常规的镍钴锰铝四元正极材料中加入了掺杂剂，例如掺杂剂可以选自Zr、Al、B、Ti、Mg、Nb、Ba、Si、P、W、Sr、F中的一种或多种，该掺杂剂可以提高四元正极材料的结构稳定性，例如掺杂的Zr可以进入该四元正极材料的过渡金属层，稳定其六方结构；掺杂的铝可以进入该四元正极材料基体的表层锂层中，进而可以较好地支撑锂层，在高电压充放电过程中，锂离子大量嵌出时，该掺杂的铝可以保持锂层晶格结构的稳定性；掺杂的镁可以使该四元正极材料中的过渡金属离子的价态升高或降低，进而可以产生空穴或电子，改变该四元正极材料的能带结构，从而提高其本征电子导电率；并且掺杂的铝和镁还能抑制Li +和Ni 2+的混排，可以保留更多可逆的锂位置，从而提高了使用该四元正极材料的电池的可逆放电比容量；因此，上述掺杂剂可以较好地提高四元正极材料的结构稳定性，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性。另一方面，根据本发明实施例的四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间满足c/a＞4.943的关系，发明人发现，当c轴的晶胞参数c和a轴的晶胞参数a之间满足上述关系时，该四元正极材料具有较好的层状晶体结构，锂离子比较容易在该层状结构中进行扩散，进而可以提高使用该四元正极材料的电池的放电比容量；具体的，通过控制加入的掺杂剂的种类和掺杂剂的量等，可以简便地调节该四元正极材料中的c轴的晶胞参数c和a轴的晶胞参数a之间的关系，可以简便地使该四元正极材料的c轴的晶胞参数c和a轴的晶胞参数a之间满足c/a＞4.943的关系，可以进一步提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池在高电压倍率下的电池比容量，使用该四元正极材料的电池性能良好。
根据本发明的实施例，该四元正极材料的化学结构通式为：Li xNi a‘Co bMn c’Al dM yO 2，其中，1≤x≤1.05，0＜y≤0.025，0.3≤a’≤0.95，0.03≤b≤0.1，0.01≤c’≤0.05，0.01≤d≤0.05，且a’+b+c’+d＝1。
具体的，该四元正极材料中的Li的摩尔含量，即上述结构通式中的x的值满足1≤x≤1.05，具体的，x可以满足1.01≤x≤1.035，例如x可以等于1.02、1.025、1.03等。由此，当四元正极材料中的Li的摩尔含量在上述范围时，使用该四元正极材料的电池具有较高的充放电比容量，使用性能较佳。当四元正极材料中的Li含量过小，例如x＜1.0时，Ni容易进入Li层， 导致锂位置的过渡金属元素占有率增大，该四元正极材料的充放电比容量较低；当四元正极材料中的Li含量过大，例如x＞1.05时，过渡金属位置上的Li的混入量较大，因而被Li从过渡金属位置赶出的Ni也较多，Ni容易混入Li层，也会导致锂位置的过渡金属元素占有率较大，影响该四元正极材料的充放电比容量。
具体的，该四元正极材料中的Co的摩尔含量，即上述结构通式中的b的值满足0.03≤b≤0.1，具体的，b可以满足0.05≤b≤0.06，例如b可以等于0.055等。由此，当四元正极材料中的Co的摩尔含量在上述范围时，Co可以提高四元正极材料的结构稳定性，并且不会显著影响四元正极材料的充放电比容量。当Co的含量过小，例如b＜0.03时，Co容易发生极化导致四元正极材料的充放电比容量较低，并且首次放电效率较低；当Co含量过大时，该四元正极材料的成本较高，不利于大规模生产。
具体的，该四元正极材料中的Mn的摩尔含量，即上述结构通式中的c的值满足0.01≤c’≤0.05，具体的，c’可以满足0.02≤c’≤0.03，例如c’可以等于0.025等。具体的，该四元正极材料中的Al的摩尔含量，即上述结构通式中的d的值满足0.01≤d≤0.05，具体的，d可以满足0.02≤d≤0.03，例如d可以等于0.025等。由此，当四元正极材料中的Mn和Al的摩尔含量在上述范围时，可以提高四元正极材料的结构稳定性，并且不会显著影响四元正极材料的充放电比容量。
具体的，该四元正极材料中的Ni的摩尔含量，即上述结构通式中的a’的值满足0.3≤a’≤0.95，具体的，a’可以满足0.8≤a’≤0.92，例如a’可以等于0.85、0.9等，且a’+b+c’+d＝1。
具体的，该四元正极材料中，M为掺杂剂，M包括选自Zr、Al、B、Ti、Mg、Nb、Ba、Si、P、W、Sr、F中的一种或多种，且该四元正极材料中的M的摩尔含量，即上述结构通式中的y的值满足0＜y≤0.0250，具体的，y可以满足0.003≤y≤0.0220，例如y可以等于0.005，0.01，0.015，0.02等。根据本发明的实施例，该四元正极材料中掺杂剂的质量分数可以为3000-8000ppm，例如可以为3500ppm，可以为4000ppm，可以为4500ppm，可以为5000ppm，可以为5500ppm，可以为6000ppm，可以为6500ppm，可以为7000ppm，可以为7500ppm等。由此，掺杂剂的含量在上述范围时，可以较好地提高四元正极材料的结构稳定性，并且不会降低使用该四元正极材料的电池的放电比容量。当该四元正极材料中的掺杂剂含量过小，例如该四元正极材料中掺杂剂的质量分数小于3000ppm，对于四元正极材料的结晶结构稳定性的提高效果不是很突出；当该四元正极材料中的掺杂剂含量过大，例如该四元正极材料中掺杂剂的质量分数大于8000ppm，会影响使用该四元正极材料的电池的放电比容量。需要说明的是，前面所述的四元正极材料中的掺杂剂的质量分数，是指四元正极材料中的所有掺杂剂的总的质量分数，例如掺杂剂包括多种元素共掺杂时，掺杂剂的质量分数即为所有掺杂元素的质量分数。
根据本发明的实施例，掺杂剂可以为前面所述的一种、两种、三种或四种等，例如掺杂剂可以为Al和Zr共掺杂，可以为Al、Mg和Zr共掺杂，可以为Al、Mg、Zr和Ti共掺杂等。根据本发明的具体实施例，掺杂剂可以由Al、Mg和Zr组成。由此，由Al、Mg和Zr共掺杂形成的四元正极材料中，掺杂剂Al、Mg和Zr具有协同作用：掺杂的锆可以进入该四元正极 材料的过渡金属层，稳定其六方结构；掺杂的铝可以进入该四元正极材料基体的表层锂层中，进而可以较好地支撑锂层，在高电压充放电过程中，锂离子大量嵌出时，该掺杂的铝可以保持锂层晶格结构的稳定性；掺杂的镁可以使该四元正极材料中的过渡金属离子的价态升高或降低，进而可以产生空穴或电子，改变该四元正极材料的能带结构，从而提高其本征电子导电率；并且掺杂的铝和镁还能抑制Li +和Ni 2+的混排，可以保留更多可逆的锂位置，从而提高了使用该四元正极材料的电池的可逆放电比容量；因此，铝、镁和锆共掺杂可以较好地提高四元正极材料的结构稳定性，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池在高电压倍率下的电池比容量，使用该四元正极材料的电池性能良好。具体的，由Al、Mg和Zr共掺杂形成的四元正极材料中，掺杂剂Al的质量分数可以为2500-3500ppm，例如可以为3000ppm等；掺杂剂Mg的质量分数为300-500ppm，例如可以为350ppm，可以为400ppm，可以为450ppm等；掺杂剂Zr的质量分数为2500-3500ppm，例如可以为3000ppm等。由此，掺杂剂Al、Mg和Zr的含量分别在上述范围时，可以较好地提高四元正极材料的结构稳定性，并且不会降低使用该四元正极材料的电池的放电比容量，有利于提高使用该四元正极材料的电池的综合性能。
根据本发明的实施例，该四元正极材料具有α-NaFeO 2型晶体结构，该四元正极材料的X-射线衍射图案的空间群为R-3m。需要说明的是，该四元正极材料的结晶结构特征可以用a轴和c轴的晶胞参数来表示。R-3m的结晶结构是以过渡金属为中心的过渡金属-氧八面体层和锂层共同形成的层状结构。a轴的晶胞参数a是由过渡金属-过渡金属间的距离、锂-锂之间的距离和氧-氧间的距离作用决定的，c轴的晶格参数c是由过渡金属-氧-锂-氧的作用决定的。当结晶结构中各过渡金属或过量的锂存在于过渡金属位置时，各过渡金属的含量、锂的含量、各元素离子半径和过渡金属的价态，均会影响过渡金属-过渡金属间以及过渡金属-氧间的距离，最终改变各个晶格参数。具体的，该四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足：c/a＞4.943。由此，该四元正极材料具有较好的层状晶体结构，锂离子比较容易在该层状结构中进行扩散，可以提高使用该四元正极材料的电池的放电比容量。
此外，R-3m的结晶结构随过渡金属(Me)和Li元素的比例、掺杂剂元素的种类和含量的变化而变化，因此，通过调整过渡金属(Me)和Li的比例(Li/Me)、掺杂剂元素的种类和含量，可以调整c轴的晶胞参数c和a轴的晶胞参数a的关系，可以使c轴的晶胞参数c和a轴的晶胞参数a满足上述条件，形成较好的层状晶体结构。
具体的，该四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系可以进一步满足：3a+5.555≤c≤3a+5.590。由此，c轴的晶胞参数c和a轴的晶胞参数a之间满足上述关系时，该四元正极材料具有较好的层状晶体结构，锂离子比较容易在该层状结构中进行扩散，可以提高使用该四元正极材料的电池的放电比容量。更具体地，a轴的晶胞参数a的数值范围可以为2.80-2.90，优选为2.86-2.87，例如可以为2.85，可以为2.86，可以为2.87等；c轴晶胞参数c的数值范围可以为14.10-14.30，优选为14.19-14.20，例如可以为14.19，可以为14.2，可以为14.25等。由此，c轴的晶胞参数c和a轴的晶胞参数a在上 述范围时，该四元正极材料具有较好的层状晶体结构，锂离子比较容易在该层状结构中进行扩散，可以提高使用该四元正极材料的电池的放电比容量。
根据本发明的实施例，该四元正极材料的X-射线衍射图案中，I 102面、I 006面和I 101面的衍射峰强度可以满足下列关系：R＝(I 102+I 006)/I 101，且0.4≤R≤0.44。由此，R值在上述范围时，该四元正极材料的六方晶体结构的有序性较高，不仅有利于锂离子在该晶体结构中的脱嵌，也能提高该四元正极材料的结构稳定性和热稳定性，从而提高使用该四元正极材料的电池的放电比容量和循环寿命。
根据本发明的实施例，该四元正极材料的X-射线衍射图案中，I 003面和I 104面的衍射峰强度可以满足下列关系：1.921＜I 003/I 104≤2。具体的，I 003面的衍射峰反映六方结构，I 104面的衍射峰反映六方结构和立方结构，当1.921＜I 003/I 104≤2时，该四元正极材料中锂离子和镍离子的混排较少，该四元正极材料的结构稳定性较高，使用该四元正极材料的电池的循环稳定性较好，循环寿命较长。
综上可知，根据本发明实施例的四元正极材料中，掺杂剂可以抑制阳离子混排，可以较好地提高该四元正极材料的结构稳定性；并且该四元正极材料的c轴的晶胞参数c和a轴的晶胞参数a之间满足c/a＞4.943等关系时，该四元正极材料具有较好的层状晶体结构，结构稳定性较好，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池的电池比容量和循环寿命。
在本申请另一种典型的实施方式中，还提供了一种上述任一种四元正极材料的制备方法，该制备方法包括：将镍钴锰铝四元前驱体与锂源、掺杂剂源进行干混，得到干混物；将干混物在含氧气氛中、700～800℃下煅烧10～15h，得到四元正极材料前体；采用铝源和硼源对四元正极材料前体在含氧气氛中进行包覆煅烧处理，得到四元正极材料，述包覆煅烧的温度为250～350℃、时间为4～8h。采用上述传统流程即可见掺杂剂掺入四元正极材料中，得到本申请的四元正极材料，制备方法简单，有利于工业实施。且最后一步的包覆处理并不是在四元正极材料前体的表面形成具有明确包覆结构的包覆层，而是将铝源和硼源在四元正极材料前体表面进行掺杂，该处理可以以抑制颗粒表面与电解液的副反应，减少释氧量，进而改善颗粒导电性及界面锂离子扩散速率，改善电性能。
在本发明的另一方面，本发明提出了一种正极。根据本发明的实施例，该正极包括前面任一项所述的四元正极材料。由此，该正极具有前面任一项所述的四元正极材料所具有的全部特征以及优点，在此不再赘述。总的来说，该正极结构稳定，且具有较佳的循环性能以及倍率性能。
在本发明的又一方面，本发明提出了一种电池。根据本发明的实施例，该电池包括：前面所述的正极、负极以及隔膜，隔膜设置在正极与负极之间，正极的至少一部分、负极的至少一部分以及隔膜的至少一部分浸没在电解液中。由此，该电池具有前面所述的正极所具有的全部特征以及优点，在此不再赘述。总的来说，该电池具有良好的循环稳定性和热稳定性，该电池在高电压倍率下具有较高的电池比容量。
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市面购买获得的常规产品。
实施例1、制备四元正极材料A
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)和Zr源(Zr(OH) 4)进行干法混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Zr源(Zr(OH) 4)和Li源(LiOH)的摩尔比为1:0.003:1.025，形成混合物；并进行煅烧、冷却、粉碎、过筛，得到Zr掺杂的四元正极材料基体，其中煅烧在700℃氧气气氛下持续8h；该Zr掺杂的四元正极材料基体中，Zr的质量分数为3000ppm；
(2)对步骤(1)形成的Zr掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料A，该煅烧处理在300℃氧气气氛下持续6h后。
实施例2、制备四元正极材料B
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)和Al源(Al 2O 3)进行混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Al源(Al 2O 3)和Li源(LiOH)的摩尔比为1:0.003:1.025，形成混合物；并进行煅烧、冷却、粉碎、过筛，得到Al掺杂的四元正极材料基体；其中煅烧在700℃氧气气氛下持续8h，该Al掺杂的四元正极材料基体中，Al的质量分数为3000ppm；
2)对步骤(1)形成的Al掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料B，该煅烧处理在300℃氧气气氛下持续6h后
实施例3、制备四元正极材料C
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)、Al源(Al 2O 3)和Zr源(Zr(OH) 4)进行混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)的摩尔比为1:1.025形成混合物；并进行煅烧、冷却、粉碎、过筛，得到Al和Zr共掺杂的四元正极材料基体；其中煅烧在700℃氧气气氛下持续8h，该Al和Zr共掺杂的四元正极材料基体中，Al的质量分数为3000ppm，Zr的质量分数为1500ppm；
(2)对步骤(1)形成的Al和Zr共掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料C，该煅烧处理在300℃氧气气氛下持续6h后。
实施例4、制备四元正极材料D
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)、Al源(Al 2O 3)和Zr源(Zr(OH) 4)进行混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)摩尔比为1:1.025形成混合物；并进行煅烧、冷却、粉碎、过筛，得到Al和Zr共掺杂的四元正极材料基体；其中煅烧在700℃氧气气氛下持续8h，该Al和Zr共掺杂的四元正极材料基体中，Al的质量分数为3000ppm，Zr的质量分数为3000ppm；
(2)对步骤(1)形成的Al和Zr共掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料D，该煅烧处理在300℃氧气气氛下持续6h后。
实施例5、制备四元正极材料E
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)、Al源(Al 2O 3)、Mg源(Mg(OH) 2)、Zr源(Zr(OH) 4)进行混合，其中高镍前驱体Ni0.88Co0.06Mn0.03Al0.03(OH)2、Li源(LiOH)、的摩尔比为1:1.025；并进行煅烧、冷却、粉碎、过筛，其中煅烧在700℃氧气气氛下持续8h得到Al、Mg和Zr共掺杂的四元正极材料基体；该Al、Mg和Zr共掺杂的四元正极材料基体中，Al的质量分数为3000ppm，Mg的质量分数为400ppm，Zr的质量分数为3000ppm；
(2)对步骤(1)形成的Al、Mg和Zr共掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料E，该煅烧处理在300℃氧气气氛下持续6h后。实施例6、制备四元正极材料F
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)、Al源(Al 2O 3)、Mg源(Mg(OH) 2)、Zr源(Zr(OH) 4)进行混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)摩尔比为1:1.025形成混合物；；并进行煅烧、冷却、粉碎、过筛，得到Al、Mg和Zr共掺杂的四元正极材料基体；其中煅烧在700℃氧气气氛下持续8h，该Al、Mg和Zr共掺杂的四元正极材料基体中，Al的质量分数为3000ppm，Mg的质量分数为900ppm，Zr的质量分数为3000ppm；
(2)对步骤(1)形成的Al、Mg和Zr共掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料F，该煅烧处理在300℃氧气气氛下持续6h后。
实施例7、制备四元正极材料G
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)、Al源(Al 2O 3)、Mg源(Mg(OH) 2)、Zr源(Zr(OH) 4)进行混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)摩尔比为1:1.025形成混合物；；并进行煅烧、冷却、粉碎、过筛，得到Al、Mg和 Zr共掺杂的四元正极材料基体；其中煅烧在700℃氧气气氛下持续8h，该Al、Mg和Zr共掺杂的四元正极材料基体中，Al的质量分数为2000ppm，Mg的质量分数为400ppm，Zr的质量分数为3000ppm；
(2)对步骤(1)形成的Al、Mg和Zr共掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料G，该煅烧处理在300℃氧气气氛下持续6h后。
实施例8、制备四元正极材料H
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)、Al源(Al 2O 3)、Mg源(Mg(OH) 2)、Zr源(Zr(OH) 4)进行混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)摩尔比为1:1.025形成混合物；；并进行煅烧、冷却、粉碎、过筛，得到Al、Mg和Zr共掺杂的四元正极材料基体；其中煅烧在700℃氧气气氛下持续8h，该Al、Mg和Zr共掺杂的四元正极材料基体中，Al的质量分数为4500ppm，Mg的质量分数为400ppm，Zr的质量分数为3000ppm；
(2)对步骤(1)形成的Al、Mg和Zr共掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料H，该煅烧处理在300℃氧气气氛下持续6h后。
实施例9、制备四元正极材料I
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)、Al源(Al 2O 3)、Mg源(Mg(OH) 2)、Zr源(Zr(OH) 4)、Ti源(TiO 2)进行混合，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)摩尔比为1:1.025形成混合物；；并进行煅烧、冷却、粉碎、过筛，得到Al、Mg、Zr和Ti共掺杂的四元正极材料基体；其中煅烧在700℃氧气气氛下持续8h，该Al、Mg、Zr和Ti共掺杂的四元正极材料基体中，Al的质量分数为3000ppm，Mg的质量分数为400ppm，Zr的质量分数为1500ppm，Ti的质量分数为1500ppm；
(2)对步骤(1)形成的Al、Mg、Zr和Ti共掺杂四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料I，该煅烧处理在300℃氧气气氛下持续6h后。
对比例1、制备四元正极材料J
(1)将高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2和Li源(LiOH)进行煅烧、冷却、粉碎、过筛，其中高镍前驱体Ni 0.88Co 0.06Mn 0.03Al 0.03(OH) 2、Li源(LiOH)的摩尔比为1:1.025，；其中煅烧在700℃氧气气氛下持续8h得到四元正极材料基体；
(2)对步骤(1)形成的四元正极材料基体依次进行Al源(Al 2O 3)包覆和硼源(H 3BO 3)包覆，四元正极材料基体和Al源(Al 2O 3)、硼源(H 3BO 3)的质量比为100:0.01:0.01，并经过煅烧处理等，得到最终的四元正极材料J。
X-射线衍射测试：
分别对上述实施例1-9以及对比例1中所制备的四元正极材料的X-射线衍射图案进行测试，图1示出了实施例1所制备的四元正极材料的X-射线衍射图谱，图2示出了对比例1所制备的四元正极材料的X-射线衍射图谱，测得的X-射线衍射谱图中的特征衍射峰及其强度数据参见表1：
表1：实施例1-9以及对比例1中所制备的四元正极材料的X-射线衍射图谱数据表
Figure PCTCN2020135883-appb-000001
由上表的测试数据可知，实施例1-9中的四元正极材料的X衍射图案中的c/a的值均大于对比例1中的四元正极材料的X衍射图案中的c/a的值，即实施例1-9中的四元正极材料的X衍射图案中的c/a＞4.943，通过后面的电化学性能测试结果可知，即实施例1-9中的四元正极材料的充、放电比容量、首次效率、50周循环保持率均高于对比例1中的四元正极材料。由此可以证明，根据本发明实施例的四元正极材料，通过在传统的镍钴锰铝四元正极材料基体中添加掺杂剂，并且令四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足c/a＞4.943，该四元正极材料具有较好的层状晶体结构，结构稳定性较好，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池的电池比容量。
同样地，由上表的测试数据可知，实施例1和2、4-9中的四元正极材料的X衍射图案中的I 003/I 104的值均大于对比例1中的四元正极材料的X衍射图案中的I 003/I 104的值，即实施例1和2、4-9中的四元正极材料的X衍射图案中的I 003面和I 104面的衍射峰强度满足下列关系：1.921＜I 003/I 104≤2时，该四元正极材料的结构稳定性较高，使用该四元正极材料的电池的循环稳定性较好，循环寿命较长。
电化学性能测试
分别将上述实施例1-9以及对比例1中所制备的四元正极材料与导电剂、粘结剂按一定比例制成浆料，涂布在铝箔上，经过真空干燥和辊压做成正极极片，以锂金属片为负极，电解 液包括浓度为1.15M的六氟磷酸锂(LiPF 6)溶液，溶剂为碳酸乙烯酯(EC)和碳酸二甲酯(DMC)的混合溶剂，EC和DMC的体积比为1：1，并组装扣式电池。对前述电池进行电化学性能测试。电化学性能测试采用蓝电电池测试系统在25℃下进行测试，测试电压范围为3V～4.3V。
分别对利用实施例1-9以及对比例1中所制备的四元正极材料制作的电池的充电比容量、放电比容量、电池在不同倍率下的循环性能等进行测试，并计算利用实施例1-9以及对比例1中所制备的四元正极材料制作的电池的首次效率以及50周的循环保持率，测试结果见表2：
表2：利用实施例1-9和对比例1中所制备的四元正极材料的电池的电化学性能数据表
Figure PCTCN2020135883-appb-000002
由上表的测试数据可知，实施例1-9中的四元正极材料的X衍射图案中的充电比容量、放电比容量、首次效率以及50周的循环保持率均大于对比例1中的四元正极材料。由此证明了根据本发明实施例的四元正极材料，通过在传统的镍钴锰铝四元正极材料基体中添加掺杂剂，并且令四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足c/a＞4.943，掺杂剂可以抑制阳离子混排，可以较好地提高该四元正极材料的结构稳定性，该四元正极材料具有较好的层状晶体结构，结构稳定性较好，可以提高使用该四元正极材料的电池的循环稳定性和热稳定性，提高该电池的电池比容量和循环寿命。
将实施例1和2的电化学性能测试数据，和实施例3-9的电化学性能测试数据(“电化学性能测试数据”泛指充电比容量、放电比容量、首次效率以及50周的循环保持率，下同)相比较可知，掺杂剂包含两种或两种以上元素的四元正极材料的电化学性能优于只有一种元素进行掺杂的四元正极材料；实施例5-8中的四元正极材料均采用Al、Mg和Zr三种元素进行掺杂，其电化学性能优于其他实施例中单掺杂和双掺杂的四元正极材料；并且，实施例6中的四元正极材料的电化学性能测试数据明显优于其他实施例，由此，证明了由Al、Mg和Zr共掺杂形成的四元正极材料中，掺杂剂Al的质量分数为2500-3500ppm，掺杂剂Mg的质量分数为300-500ppm，掺杂剂Zr的质量分数为2500-3500ppm时，可以较好地提高四元正极材料的结构稳定性，并且不会降低使用该四元正极材料的电池的放电比容量，有利于提高使用该 四元正极材料的电池的综合性能。掺杂剂的质量分数相对于上述范围过大或过小，均不利于提高电池的综合性能。
热稳定性测试
利用差示扫描量热法分别对实施例1和2、4和5、7-9以及对比例1中的四元正极材料进行热稳定性测试，测试结果见表3：
Figure PCTCN2020135883-appb-000003
上表中的放热峰峰值温度数值是四元正极材料与电解液反应的放热峰温度，该值越高，表示四元正极材料的热稳定性越好。由上表的测试数据可知，实施例1和2、4和5、7-9中的四元正极材料的热稳定性高于对比例1中的四元正极材料。由此证明了根据本发明实施例的四元正极材料，通过在传统的镍钴锰铝四元正极材料基体中添加掺杂剂，并且令四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足c/a＞4.943，该四元正极材料具有较好的结构稳定性。并且，实施例5中的采用Al、Mg和Zr三种元素按特定比例进行掺杂的四元正极材料，其热稳定性优于其他实施例。由此，证明了由Al、Mg和Zr共掺杂形成的四元正极材料中，掺杂剂Al的质量分数为2500-3500ppm，掺杂剂Mg的质量分数为300-500ppm，掺杂剂Zr的质量分数为2500-3500ppm时，可以较好地提高四元正极材料的结构稳定性。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
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. 一种四元正极材料，其特征在于，所述四元正极材料的化学结构通式为：Li xNi a’Co bMn c’Al dM yO 2，其中，1≤x≤1.05，0＜y≤0.025，0.3≤a’≤0.95，0.03≤b≤0.1，0.01≤c’≤0.05，0.01≤d≤0.05，且a’+b+c’+d＝1；
    M为掺杂剂，所述M包括选自Zr、Al、B、Ti、Mg、Nb、Ba、Si、P、W、Sr、F中的一种或多种；
    所述四元正极材料具有α-NaFeO 2型晶体结构，所述四元正极材料的X-射线衍射图案的空间群为R-3m，所述四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足：c/a＞4.943。
  2. 根据权利要求1所述的四元正极材料，其特征在于，所述四元正极材料的X-射线衍射图案中，c轴的晶胞参数c和a轴的晶胞参数a之间的关系满足：3a+5.555≤c≤3a+5.590。
  3. 根据权利要求2所述的四元正极材料，其特征在于，所述a轴的晶胞参数a的数值范围为2.80-2.90，优选为2.86-2.87，所述c轴晶胞参数c的数值范围为14.10-14.30，优选为14.19-14.20。
  4. 根据权利要求1所述的四元正极材料，其特征在于，所述四元正极材料的X-射线衍射图案中，I 003面和I 104面的衍射峰强度满足下列关系：1.921＜I 003/I 104≤2。
  5. 根据权利要求1所述的四元正极材料，其特征在于，所述四元正极材料中，所述掺杂剂的质量分数为3000-8000ppm。
  6. 根据权利要求1所述的四元正极材料，其特征在于，所述掺杂剂由Al和Zr组成，或者由Al、Mg和Zr组成。
  7. 根据权利要求5或6所述的四元正极材料，其特征在于，所述四元正极材料中，掺杂剂Al的质量分数为2500-3500ppm，掺杂剂Mg的质量分数为300-500ppm，掺杂剂Zr的质量分数为2500-3500ppm。
  8. 一种权利要求1至7中任一项所述四元正极材料的制备方法，其特征在于，所述制备方法包括：
    将镍钴锰铝四元前驱体与锂源、掺杂剂源进行干混，得到干混物；
    将所述干混物在含氧气氛中、700～800℃下煅烧10～15h，得到所述四元正极材料前体；
    采用铝源和硼源对所述四元正极材料前体在含氧气氛中进行包覆煅烧处理，得到所述四元正极材料，所述包覆煅烧的温度为250～350℃、时间为4～8h。
  9. 一种正极，所述正极包括四元正极材料，其特征在于，所述四元正极材料为权利要求1至7中任一项所述的四元正极材料。
  10. 一种电池，包括：正极、负极、隔膜和电解液，所述隔膜设置在所述正极与所述负极之间；所述正极的至少一部分、所述负极的至少一部分以及所述隔膜的至少一部分浸没在所述电解液中，其特征在于，所述正极为权利要求9所述的正极。
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