WO2023193625A1 - 正极材料及其应用 - Google Patents

正极材料及其应用 Download PDF

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Publication number
WO2023193625A1
WO2023193625A1 PCT/CN2023/084093 CN2023084093W WO2023193625A1 WO 2023193625 A1 WO2023193625 A1 WO 2023193625A1 CN 2023084093 W CN2023084093 W CN 2023084093W WO 2023193625 A1 WO2023193625 A1 WO 2023193625A1
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WIPO (PCT)
Prior art keywords
cathode material
coating layer
positive electrode
rock salt
salt phase
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
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PCT/CN2023/084093
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English (en)
French (fr)
Inventor
田业成
郝嵘
庄明昊
葛立萍
苏碧哲
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BYD Co Ltd
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BYD Co Ltd
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Publication date
Application filed by BYD Co Ltd filed Critical BYD Co Ltd
Priority to EP23784189.5A priority Critical patent/EP4507029A4/en
Priority to KR1020247036865A priority patent/KR20250004718A/ko
Priority to JP2024559224A priority patent/JP2025511764A/ja
Publication of WO2023193625A1 publication Critical patent/WO2023193625A1/zh
Priority to US18/902,094 priority patent/US20250023043A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • 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
    • C01G53/502—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 containing lithium and cobalt
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    • 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
    • C01G53/502—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 containing lithium and cobalt
    • C01G53/504—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 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
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    • 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
    • C01G53/502—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 containing lithium and cobalt
    • C01G53/504—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 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
    • C01G53/506—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 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5 with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
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Definitions

  • This application relates to the field of secondary batteries, specifically cathode materials and their applications.
  • Nickel-based electrode active materials are considered to be promising lithium-ion battery cathode materials due to their high specific capacity, high energy density, environmental friendliness and excellent safety.
  • the lithium ion diffusion coefficient of nickel-based electrode active materials is low, resulting in low charge and discharge efficiency of the material and poor battery electrochemical performance. Therefore, it is necessary to improve the structure of nickel-based electrode active materials to improve the lithium ion migration properties of nickel-based electrode active materials, thereby improving the electrochemical performance of batteries.
  • a first aspect of the present application provides a cathode material.
  • the cathode material includes secondary particles and a rock salt phase coating layer provided on the surface of the secondary particles.
  • the secondary particles are formed by stacking a plurality of primary particles; The ratio of the particle diameter of the secondary particles to the average particle diameter of the plurality of primary particles is greater than or equal to 1.5; the primary particles and the rock salt phase coating layer respectively include nickel-based active materials.
  • the nickel-based active material and the rock salt phase coating layer respectively include materials with the chemical formula Li 1-a A b (Nim M 1-m )X x O 2 Z z , wherein, -0.1 ⁇ a ⁇ 0.1, the A includes one or more of Na, K, Be, Mg, Ca, B, 0 ⁇ b ⁇ 0.1, the M includes one or more of Mn, Co, Al or Multiple, 0 ⁇ m ⁇ 1, the X includes one or more of Zr, V, Ti, Cr, Fe, Co, Ni, Zn, Nb, Mo, Os, W, Y, 0 ⁇ x ⁇ 0.1, the Z includes one or more of F, Cl, Br, I, 0 ⁇ z ⁇ 0.1.
  • the coating rate of the rock salt phase coating layer on the surface of the secondary particles is 10% to 90%.
  • the ratio r of the particle diameter of the secondary particles to the average particle diameter of the plurality of primary particles satisfies 1.5 ⁇ r ⁇ 3;
  • the ratio r of the particle diameter of the secondary particles to the average particle diameter of the plurality of primary particles satisfies 3 ⁇ r ⁇ 10;
  • the ratio r of the particle diameter of the secondary particles to the average particle diameter of the plurality of primary particles satisfies 10 ⁇ r ⁇ 50;
  • the ratio r of the particle diameter of the secondary particles to the average particle diameter of the plurality of primary particles satisfies r>50.
  • the coating rate of the rock salt phase coating layer on the surface of the secondary particles is 50% to 80%.
  • the particle size of the secondary particles is less than or equal to 15 ⁇ m.
  • the thickness of the rock salt phase coating layer is 1 nm to 20 nm.
  • the thickness of the rock salt phase coating layer is 5 nm to 15 nm.
  • the nickel-based active material has a layered hexagonal close-packed structure and belongs to the R3m space group;
  • the half-peak width of the (104) crystal plane diffraction peak of the positive electrode material is 0.1 to 0.2.
  • the half-peak width of the (104) crystal plane diffraction peak of the cathode material is 0.105 to 0.130.
  • the rock salt phase coating layer and the nickel-based active material respectively include doped or undoped lithium nickel cobalt manganate.
  • the chemical formula of the undoped lithium nickel cobalt manganate is Li( Nim Con Mn 1-mn )O 2 , 0 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 1, 0 ⁇ m +n ⁇ 1.
  • the doping elements in the doped lithium nickel cobalt manganate include Na, K, Be, Mg, Ca, B, Zr, V, Ti, Cr, Y, Fe, Co, Ni, One or more of Zn, Nb, Mo, Os, W, F, Cl, Br and I.
  • a second aspect of the present application provides a positive electrode sheet, which includes a current collector and a positive electrode material as described in the first aspect disposed on the current collector.
  • a third aspect of the present application provides a secondary battery, including a positive electrode and a negative electrode.
  • the positive electrode includes the positive electrode plate as described in the second aspect.
  • the secondary battery further includes an electrolyte and a separator located between the positive electrode and the negative electrode.
  • the secondary battery further includes a solid electrolyte or semi-solid electrolyte located between the positive electrode and the negative electrode.
  • a fourth aspect of the present application provides a vehicle including the secondary battery as described in the third aspect.
  • Figure 1 is a schematic structural diagram of a cathode material provided by an embodiment of the present application.
  • Figure 2 is an electron microscope characterization diagram of the surface of the cathode material provided in Example 4 of the present application, wherein (a) in Figure 2 is a SEM morphology characterization diagram of the cathode material in Example 4, and Figure 2 (b) is an example The HR-TEM Fourier transform diagram of the rock salt phase coating layer in the cathode material of Embodiment 4. (c) in Figure 2 is the HR-TEM Fourier transform diagram of the secondary particle core in the cathode material of Embodiment 4;
  • Figure 3 is a transmission electron microscope characterization diagram of the cross section of the cathode material provided in Example 4 of the present application, wherein (a) in Figure 3 is a morphology characterization diagram of the cross section of the cathode material in Example 4, and Figure 3 (b) is an embodiment The HR-TEM Fourier transform diagram of the rock salt phase coating layer in the cathode material of Embodiment 4. (c) in Figure 3 is the HR-TEM Fourier transform diagram of the secondary particle core in the cathode material of Embodiment 4;
  • Figure 4 is an XRD spectrum of the cathode material provided in Example 4 of the present application.
  • This application provides a cathode material that has a high lithium ion migration rate. Its application in a battery can improve the rate performance and cycle retention rate of the battery, and is conducive to the preparation of high-energy-density secondary batteries.
  • FIG. 1 is a schematic structural diagram of the cathode material provided in an embodiment of this application.
  • the cathode material 100 includes secondary particles 10 and a rock salt phase coating layer 20 provided on the surface of the secondary particles 10 , where the secondary particles 10 are formed by stacking a plurality of primary particles.
  • the ratio of the average particle diameter of the secondary particles to the primary particles is greater than or equal to 1.5.
  • the primary particles and rock salt phase coating layers respectively include nickel-based active materials.
  • the cathode material of the present application has a core-shell structure.
  • the core of the cathode material includes secondary particles
  • the shell layer of the cathode material includes a rock salt phase coating layer.
  • the nickel-based active material includes a material with the chemical formula Li 1-a A b (N m M 1-m )X x O 2 Z z , where -0.1 ⁇ a ⁇ 0.1, A includes Na, One or more of K, Be, Mg, Ca, B, 0 ⁇ b ⁇ 0.1, M includes one or more of Mn, Co, and Al, 0 ⁇ m ⁇ 1, X includes Zr, V, One or more of Ti, Cr, Fe, Co, Ni, Zn, Nb, Mo, Os, W, Y, 0 ⁇ x ⁇ 0.1, Z includes one or more of F, Cl, Br, I Species, 0 ⁇ z ⁇ 0.1.
  • the secondary particles have a layered hexagonal close-packed structure, belonging to the R3m space group, and 003, 101 and 104 crystal planes can be seen in the XRD spectrum.
  • the rock salt phase coating layer includes a material with the chemical formula Li 1-a A b ( Nim M 1-m )X x O 2 Z z , where -0.1 ⁇ a ⁇ 0.1, A includes Na , one or more of K, Be, Mg, Ca, B, 0 ⁇ b ⁇ 0.1, M includes one or more of Mn, Co, and Al, 0 ⁇ m ⁇ 1, X includes Zr, V , one or more of Ti, Cr, Fe, Co, Ni, Zn, Nb, Mo, Os, W, Y, 0 ⁇ x ⁇ 0.1, Z includes one or more of F, Cl, Br, I or Various, 0 ⁇ z ⁇ 0.1.
  • the structure of the rock salt phase coating layer belongs to the Fm3m space group, and the 111 and 200 crystal planes can be seen in the XRD spectrum.
  • the structure of the secondary particles of the nickel-based active material can enrich the diffusion path of lithium ions and effectively increase the migration rate of lithium ions in the material.
  • the rock salt phase coating layer can not only improve the liquid retention capacity of the cathode material, but also ensure the electrolysis
  • the liquid can continuously infiltrate the cathode material, enabling orderly diffusion of lithium ions, and the rock salt phase coating layer can inhibit the fragmentation of secondary particles and improve the structural stability of the cathode material.
  • lithium ions are continuously embedded and detached from the secondary particles.
  • the primary particles in the secondary particles continue to expand and contract in volume, and the gaps between the particles are constantly changing, causing the electrolysis between the primary particles.
  • the liquid is prone to bubbles, and the presence of bubbles will block the migration path of lithium ions in the electrolyte, making the lithium ion migration path unstable, reducing the lithium ion migration rate, and worsening the rate performance of the material.
  • the rock salt phase coating layer has high structural strength, which can suppress the volume change of particles, reduce the generation of bubbles, and improve the stability of lithium ion migration in the electrolyte.
  • the rock salt phase coating layer has a strong impact on the electrolyte.
  • the electrolyte can penetrate into the secondary particles through the capillary effect, thereby increasing the contact area between the electrolyte and the primary particles, which is beneficial to expanding the migration path of lithium ions and improving the lithium ion migration of the nickel-cobalt-manganese ternary cathode material. performance and improve the electrochemical performance of the battery.
  • the cathode material In the cathode material provided by this application, multiple primary particles of nickel-based active material are accumulated to form secondary particles of nickel-based active material.
  • the structure of the secondary particles can not only expand the solid transmission path of lithium ions in the nickel-based active material, but also The secondary particles have a through-hole structure, which is conducive to the penetration of electrolyte, thereby enriching the transmission path of lithium ions and increasing the migration rate of ions; the rock salt phase coating layer can improve the liquid retention capacity of the cathode material and ensure that the electrolyte can continue to infiltrate the secondary sub-particles, thereby improving the lithium ion migration performance of the nickel-cobalt-manganese ternary cathode material and improving the electrochemical performance of the battery.
  • the coating rate of the rock salt phase coating layer on the surface of the secondary particles is 10% to 90%, where the coating rate refers to the coating area of the rock salt phase coating layer on the surface of the secondary particles.
  • the coating rate of the rock salt phase coating layer on the surface of the secondary particles may be, but is not limited to, 10%, 30%, 50%, 60%, 70%, 80% or 90%. Controlling the coating rate of the rock salt phase coating layer is conducive to the coating layer's favorable support for the formation of secondary particles, suppressing the volume change of secondary particles, and making the overall material have good lithium ion migration properties.
  • the coating rate of the rock salt phase coating layer on the surface of the secondary particles is 50% to 80%.
  • the thickness of the rock salt phase coating layer is 1 nm to 20 nm.
  • the thickness of the rock salt phase coating layer may be, but is not limited to, 1 nm, 3 nm, 5 nm, 10 nm, 15 nm or 20 nm. Controlling the thickness of the rock salt phase coating layer is beneficial to improving the liquid retention capacity of the cathode material, allowing the electrolyte to fully infiltrate the cathode. In some embodiments of the present application, the thickness of the rock salt phase coating layer is 5 nm to 15 nm.
  • the inventor of the present application found through research that the coating area of the rock salt phase coating layer and the secondary particle structure have a certain linkage effect, and the two can synergistically adjust the migration performance of lithium ions.
  • the ratio r of the particle size of the secondary particles to the average particle size of the primary particles is 1.5 to 3, That is, 1.5 ⁇ r ⁇ 3; when the coating rate of the rock salt phase coating layer on the surface of the secondary particles is greater than 20% and less than or equal to 50%, the ratio r of the particle size of the secondary particles to the average particle size of the primary particles is greater than 3 and less than or equal to 10, that is, 3 ⁇ r ⁇ 10; when the coating rate of the rock salt phase coating layer on the surface of the secondary particles is greater than 50% and less than or equal to 80%, the particle size of the secondary particles is the same as that of the primary particles.
  • the ratio r of the average particle diameter is greater than 10 and less than or equal to 50, that is, 10 ⁇ r ⁇ 50; when the coating rate of the rock salt phase coating layer on the surface of the secondary particles is greater than 80%, the particle size of the secondary particles is less than that of the primary particles.
  • the ratio r of the average particle diameter is greater than 50, that is, r>50. That is to say, for a single cathode material particle, when the coating rate of the rock salt phase coating layer is less than or equal to 20%, the particle size of the secondary particles is 1.5 to 3 times the average particle size of the primary particles. For example, there are n primary particles. Particles accumulate to form secondary particles.
  • the average particle size of n primary particles is x ⁇ m, and the particle size of the secondary particles is y ⁇ m.
  • y/x 1.5 ⁇ 3.
  • controlling the coating rate of the rock salt phase coating layer can make the material have good lithium ion migration properties, that is, the material has a high lithium ion migration rate, and lithium ions can migrate in an orderly manner. , the material has good cycle stability.
  • the average particle size of the secondary particles is less than or equal to 15 ⁇ m.
  • the average particle diameter of the secondary particles may specifically be, but is not limited to, 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, 11 ⁇ m, 13 ⁇ m or 15 ⁇ m.
  • primary particles are closely packed to form secondary particles.
  • the half-peak width FWHM of the 104 crystal plane diffraction peak of the cathode material is 0.1 to 0.2.
  • the 104 crystal plane diffraction peak of the cathode material The half-width FWHM of the peak may specifically be, but is not limited to, 0.1, 0.105, 0.11, 0.12, 0.13, 0.15 or 0.2.
  • the half-maximum width FWHM of the 104 crystal plane diffraction peak of the cathode material is 0.1 to 0.2, it is beneficial to prepare high-energy-density secondary batteries.
  • the half-peak width FWHM of the 104 crystal plane diffraction peak is 0.105 to 0.13.
  • the nickel-based active material includes lithium-site doping elements.
  • the lithium-site doping elements partially replace the lithium atoms in Li( NixM1 -x ) O2 .
  • the lithium-site doping elements have the chemical formula Li 1 -a A b (Ni m M 1 -m ) X
  • One or more lithium site doping elements can increase the migration rate of lithium ions in the rock salt phase coating layer and the lattice of the nickel-based active material.
  • the nickel-based active material includes transition metal doping elements, and the transition metal doping elements are X in the chemical formula Li 1-a A b ( Nim M 1-m )X x O 2 Z z , that is, x>0 in the chemical formula, transition metal doping elements include one or more of Zr, V, Ti, Cr, Y, Fe, Co, Ni, Zn, Nb, Mo, Os, W, transition metal doping Elements can improve the stability of the cathode material in the electrolyte, suppress the lithium-nickel mixing effect, and improve the conductivity of lithium ions in the solid phase.
  • the nickel-based active material includes an oxygen-site doping element
  • the oxygen-site doping element is Z in the chemical formula Li 1-a A b (Ni m M 1-m )X x O 2 Z z , that is, z in the chemical formula >0, the oxygen doping element partially replaces the oxygen atoms in Li( NixM1 -x ) O2 .
  • the oxygen doping element includes one or more of F, Cl, Br, and I.
  • the oxygen doping element Miscellaneous elements can improve the structural stability of the rock salt phase coating layer and nickel-based active materials.
  • the rock salt phase coating layer and the nickel-based active material respectively include doped or undoped lithium nickel cobalt manganate, wherein the chemical formula of undoped lithium nickel cobalt manganate is Li(Ni m Con Mn 1-mn )O 2 , 0 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 1, 0 ⁇ m+n ⁇ 1.
  • the doping elements in the doped lithium nickel cobalt manganate include Na, K, Be, Mg, Ca, B, Zr, V, Ti, Cr, Y, Fe, Co, Ni, Zn, One or more of Nb, Mo, Os, W, F, Cl, Br and I.
  • Doping elements can improve the structural stability of the rock salt phase coating layer and lithium nickel cobalt manganate and increase the lithium ion migration rate of the material.
  • the chemical formula of doped or undoped lithium nickel cobalt manganate is Li 1-a A b ( Nim Con Mn 1-mn )X x O 2 Z z , where, -0.1 ⁇ a ⁇ 0.1, A includes one or more of Na, K, Be, Mg, Ca, B, 0 ⁇ b ⁇ 0.1, X includes Zr, V, Ti, Cr, Fe, Co, Ni, Zn, Y , one or more of Nb, Mo, Os, and W, 0 ⁇ x ⁇ 0.1, Z includes one or more of F, Cl, Br, and I, 0 ⁇ z ⁇ 0.1.
  • the cathode material provided in this application effectively enriches the migration path of lithium ions and increases the migration rate of lithium ions through the secondary particles and rock salt phase coating structure.
  • the cathode material with this structure can reduce the impedance of the battery and achieve high-rate charging and discharging. Its application in secondary batteries can improve the capacity and cycle performance of secondary batteries, which is beneficial to the long-term use of batteries.
  • This application also provides a preparation method for the above-mentioned cathode material, including:
  • Nickel cobalt manganese hydroxide is mixed with a lithium source and then sintered in an oxygen-containing atmosphere to obtain a positive electrode material; wherein the oxygen content of the oxygen-containing atmosphere is 18% to 100%.
  • the preparation method of nickel cobalt manganese hydroxide includes: dispersing a nickel source, a cobalt source and a manganese source in an alkaline solution to obtain nickel cobalt manganese hydroxide, where the pH value of the alkaline solution is 9 to 14, the alkaline solution includes one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water, the nickel source includes one or more of nickel nitrate, nickel sulfate and nickel chloride, the cobalt source Including one or more of cobalt nitrate, cobalt sulfate and cobalt chloride, and the manganese source includes one or more of manganese nitrate, manganese sulfate and manganese chloride.
  • the preparation method of nickel cobalt manganese hydroxide includes: dispersing the nickel source, cobalt source and manganese source in a molar ratio of (5 to 10): (0.5 to 1.5): (0.5 to 1.5). In the alkaline solution, stir at 25°C to 45°C at a rotation speed of 5rpm to 100rpm for 360min to 1080min.
  • the lithium source includes one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate, and lithium acetate.
  • doping elements are added to the mixture, where the doping elements include lithium site doping elements. , one or more of transition metal doping elements and oxygen site doping elements.
  • the oxygen content in the oxygen-containing atmosphere will affect the structure of the rock salt phase coating layer.
  • Controlling the oxygen content in the oxygen-containing atmosphere is conducive to the formation of a rock salt phase coating layer with a stable structure, and improves the impact of the rock salt phase coating layer on secondary
  • the adhesion strength of the particles enables the cathode material to have good and stable liquid retention capabilities for the electrolyte.
  • the mass percentage of oxygen in the oxygen-containing atmosphere is 19% to 95%.
  • the mass percentage of oxygen in the oxygen-containing atmosphere can be, but is not limited to, 18%, 20%, 25%, 30%. %, 50%, 60%, 70%, 80%, 90% or 100%.
  • the sintering temperature ranges from 200°C to 980°C.
  • the sintering temperature may specifically be, but is not limited to, 200°C, 300°C, 500°C, 600°C, 700°C, 750°C, 800°C, 850°C, 900°C or 980°C.
  • the sintering time is 8h to 32h.
  • the sintering time may specifically be, but is not limited to, 8h, 10h, 15h, 20h, 25h, 30h or 32h.
  • the calcination temperature is 700°C to 1000°C, and the calcination time is 12h to 36h.
  • the sintering equipment may be any one of a rotary furnace, a rotary furnace, a box furnace, a tube furnace, a roller kiln, a push plate kiln, or a fluidized bed.
  • a gradient heating method is used to sinter the nickel cobalt manganese hydroxide and the lithium source.
  • the gradient heating method includes: raising the temperature to a maximum of 720°C at a heating rate of no more than 10°C/min, and holding the temperature for 1 hour. After ⁇ 9h, the temperature is raised to a maximum of 1000°C at a heating rate of no more than 15°C/min, and the temperature is maintained for 8h to 25h to obtain the cathode material.
  • the gradient heating includes: raising the temperature to a maximum of 500°C at a heating rate of no higher than 10°C/min, and after maintaining the temperature for 2h to 9h, raising the temperature to a maximum of 850°C at a heating rate of not higher than 13.3°C/min. , keep the temperature for 8h to 25h to obtain the cathode material.
  • the present application also provides a positive electrode sheet, which includes a current collector and a positive electrode material layer disposed on the current collector, wherein the positive electrode material layer includes the battery positive electrode material of the present application.
  • the positive electrode material layer may be prepared by mixing the positive electrode material, the conductive agent, the binder and the solvent to form a positive electrode slurry, and then coating and drying the positive electrode slurry to obtain the positive electrode material layer.
  • conductive agents, binders and solvents are common choices in the battery field.
  • the binder may be selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polyimide ( One or more of PI), polyacrylic acid (PAA), polyacrylate, polyolefin, sodium carboxymethylcellulose (CMC) and sodium alginate.
  • the conductive agent may be selected from one or more types of carbon nanotubes, carbon black, and graphene.
  • the application also provides a secondary battery, which includes a positive electrode, a negative electrode, an electrolyte, and a separator between the positive electrode and the negative electrode.
  • the secondary battery includes a positive electrode, a negative electrode, and a separator between the positive electrode and the negative electrode.
  • the negative electrode of the secondary battery may be any negative electrode known in the art.
  • the negative electrode may include one or more of a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode, and a lithium negative electrode.
  • the carbon-based negative electrode can include graphite, hard carbon, soft carbon, graphene, etc.
  • the silicon-based negative electrode can include silicon-containing materials such as silicon, silicon carbon, silicon oxygen, silicon metal compounds, or this silicon-containing material and non-silicon-containing materials such as graphite.
  • tin-based negative electrodes may include tin-containing materials such as tin, tin carbon, tin oxide, tin metal compounds, or mixed materials of such tin-containing materials and non-tin-containing materials such as graphite; lithium negative electrodes may include metallic lithium or lithium alloys.
  • the lithium alloy may specifically be at least one of lithium silicon alloy, lithium sodium alloy, lithium potassium alloy, lithium aluminum alloy, lithium tin alloy and lithium indium alloy.
  • the current collector of the negative electrode is copper foil
  • the negative electrode active materials include natural graphite, artificial graphite, hard carbon, soft carbon, lithium titanate, iron oxide, lithium titanium phosphate, titanium dioxide, silicon, silicon oxide, One or more of tin and its oxides and antimony and its oxides
  • the binder includes polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), carboxymethylcellulose (CMC) and styrene-butadiene latex ( SBR)
  • the conductive agent includes one or more of acetylene black, Ketjen black, Super-P, carbon nanotubes, carbon nanofibers, activated carbon and graphene.
  • any method known in the art can be used to prepare the negative electrode.
  • the separator of the secondary battery can be any separator known to those skilled in the art.
  • the separator can be a polyolefin microporous membrane, polyethylene terephthalate, polyethylene felt, glass fiber mat or ultrafine One or more types of fiberglass paper.
  • the electrolyte of the secondary battery includes a solution of electrolyte lithium salt in a non-aqueous solvent.
  • the electrolyte lithium salt includes lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluorosilicate ( Li 2 SiF 6 ), lithium tetraphenylborate (LiB(C 6 H5) 4 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium chloroaluminate (LiAlCl 4 ), lithium fluoroalkyl sulfonate (LiC( One or more of SO 2 CF 3 ) 3 ), LiCH 3 SO 3 , LiN(SO 2 CF 3 ) 2 and LiN(SO 2 C 2 F 5 )
  • the non-aqueous solvent includes one or more of chain acid esters and cyclic acid esters.
  • chain acid esters include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC) and dipropyl carbonate (DPC). ) one or more.
  • chain acid esters include chain organic esters containing fluorine, sulfur, or unsaturated bonds.
  • cyclic acid esters include ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), One or more of ⁇ -butyrolactone ( ⁇ -BL) and sultone.
  • the cyclic acid ester includes fluorine-containing, sulfur-containing or unsaturated bond-containing cyclic organic ester.
  • the non-aqueous solvent includes one or more of chain ether and cyclic ether solutions.
  • the cyclic ethers include tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,3-dioxopentane (DOL) and 4-methyl-1,3-dioxo One or more of cyclopentane (4-MeDOL).
  • the cyclic ether includes fluorine-containing, sulfur-containing or unsaturated bond-containing cyclic organic ether.
  • chain ethers include dimethoxymethane (DMM), 1,2-dimethoxyethane (DME), 1,2-dimethoxypropane (DMP) and diethylene glycol One or more of dimethyl ether (DG).
  • chain ethers include fluorine-containing, sulfur-containing or unsaturated bond-containing chain organic ethers.
  • concentration of the electrolyte lithium salt in the electrolyte is 0.1 mol/L-15 mol/L. In some embodiments of the present application, the concentration of the electrolyte lithium salt is 1 mol/L-10 mol/L.
  • the secondary battery can be prepared using either a lamination process or a winding process. In some embodiments of the present application, a lamination process is used to prepare the battery.
  • This application also provides a vehicle, which includes the secondary battery provided by this application, and the secondary battery supplies power to the vehicle.
  • a preparation method of cathode material including:
  • Nickel nitrate, cobalt nitrate and manganese sulfate to a sodium hydroxide aqueous solution with a pH of 11 at a molar ratio of 6:2:2, stir at 30°C at a rate of 50 rpm, filter to obtain nickel cobalt manganese hydroxide, and Nickel cobalt manganese hydroxide is mixed with lithium hydroxide and yttrium oxide and then sintered in an oxygen-containing atmosphere with an oxygen mass percentage of 22%. The temperature is raised to 500°C at a heating rate of 10°C/min.
  • the cathode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is LiNi 0.60 Co 0.20 Mn 0.20 Y 0.02 O 2 .
  • the prepared battery positive electrode material, conductive agent, and binder were dispersed in N-methylpyrrolidone in a mass ratio of 95:3:2 to obtain a positive electrode slurry, in which the conductive agent was conductive carbon black and the binder was PVDF. , coat the positive electrode slurry on the surface of the aluminum foil with a thickness of 20um, dry it and roll it.
  • the compacted density of the positive active material layer formed is 3.4g/cm 3 to obtain the positive electrode; combine graphite and carboxymethyl fiber
  • the anode and conductive carbon black are dispersed in N-methylpyrrolidone according to a mass ratio of 95:3:2 to obtain a negative electrode slurry.
  • the negative electrode slurry is coated on the surface of the copper foil.
  • the negative electrode active material layer becomes The compacted density is 1.4g/cm 3 to obtain the electrode negative electrode; the battery positive electrode, battery negative electrode and polyolefin microporous membrane separator prepared above are rolled to form a battery core, and after packaging, 1mol/L lithium hexafluorophosphate electrolyte (solvent: 1:1 EC:EMC) to obtain a battery, the battery of Example 1 was named S1.
  • the preparation method of the cathode material in Example 2 includes:
  • the cathode material included a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer was LiNi 0.50 Co 0.20 Mn 0.30 O 2 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 2 was named S2.
  • the preparation method of the cathode material in Example 3 includes:
  • nickel sulfate, cobalt sulfate and manganese sulfate to an aqueous sodium hydroxide solution with a pH of 12 at a molar ratio of 8:1:1, stir at 30°C at a rate of 50 rpm, filter to obtain nickel cobalt manganese hydroxide, and Nickel cobalt manganese hydroxide and lithium hydroxide
  • the yttrium oxide is sintered in an oxygen-containing atmosphere with an oxygen mass percentage of 35%.
  • the temperature is raised to 480°C at a heating rate of 10°C/min. After being kept for 3 hours, the temperature is raised to 700°C at a heating rate of 13.3°C/min.
  • the cathode material was obtained after being incubated for 22 hours.
  • the cathode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is LiNi 0.8 Co 0.1 Mn 0.1 Y 0.02 O 2 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 3 was named S3.
  • the preparation method of the cathode material in Example 4 includes:
  • the cathode material included a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer was LiNi 0.60 Co 0.20 Mn 0.20 O 2 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 4 was named S4.
  • the preparation method of the cathode material in Example 5 includes:
  • the cathode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is Li 0.99 Na 0.01 Ni 0.8 Co 0.1 Mn 0.1 O 2 Cl 0.1 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 5 was named S5.
  • the preparation method of the cathode material in Example 6 includes:
  • Nickel sulfate, cobalt sulfate and manganese sulfate to an aqueous sodium hydroxide solution with a pH of 12 at a molar ratio of 8:1:1, stir at 30°C at a rate of 50 rpm, filter to obtain nickel cobalt manganese hydroxide, and Nickel cobalt manganese hydroxide is mixed with lithium hydroxide and iodine elements and then sintered in an oxygen-containing atmosphere with an oxygen mass percentage of 60%. The temperature is raised to 650°C at a heating rate of 11°C/min.
  • the cathode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is LiNi 0.8 Co 0.1 Mn 0.1 O 2 I 0.1 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 6 was named S6.
  • the preparation method of the cathode material in Example 7 includes:
  • the cathode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is LiB 0.02 Ni 0.8 Co. 0.1 Mn 0.1 O 2 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 7 was named S7.
  • the preparation method of the cathode material in Example 8 includes:
  • the cathode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is LiNi 0.80 Co 0.10 Mn. 0.10 O 2 F 0.05 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 8 was named S8.
  • the preparation method of the cathode material in Example 9 includes:
  • the cathode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is Li 0.99 Na 0.01 Ni 0.8 Co 0.1 Mn 0.1 O 2 F 0.1 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 9 was named S9.
  • the preparation method of the cathode material in Example 10 includes:
  • the cathode material included a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer was LiNi 0.40 Co 0.30 Mn 0.30 O 2 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 10 was named S10.
  • the preparation method of the cathode material in Example 11 includes:
  • Nickel sulfate, cobalt sulfate and manganese sulfate to an aqueous sodium hydroxide solution with a pH of 10 at a molar ratio of 1:1:1, stir at 30°C at a rate of 50 rpm, filter to obtain nickel cobalt manganese hydroxide, and Nickel cobalt manganese hydroxide is mixed with lithium hydroxide, beryllium fluoride and lithium fluoride and then sintered in an oxygen-containing atmosphere with an oxygen mass percentage of 19%.
  • the temperature is raised to 550°C at a heating rate of 10°C/min and kept warm.
  • the cathode material included a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is Li 0.99 Be 0.01 Ni 1/3 Co 1/3 Mn 1/3 O 2 F 0.05 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 11 was named S11.
  • the preparation method of the cathode material in Example 12 includes:
  • Nickel sulfate, cobalt sulfate and manganese sulfate to an aqueous sodium hydroxide solution with a pH of 10 at a molar ratio of 8:1:1, stir at 30°C at a rate of 50 rpm, filter to obtain nickel cobalt manganese hydroxide, and Nickel cobalt manganese hydroxide is mixed with lithium hydroxide and yttrium fluoride and then sintered in an oxygen-containing atmosphere with an oxygen mass percentage of 85%.
  • the temperature is raised to 550°C at a heating rate of 10°C/min. After 8 hours of heat preservation, Raise the temperature to 800°C at a heating rate of 13.3°C/min and keep it warm for 20 hours to obtain the positive electrode material.
  • the material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is Li 1.01 Ni 0.8 Co 0.1 Mn 0.1 Y 0.01 O 2 F 0.05 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Example 12 was named S12.
  • the preparation method of the cathode material in Comparative Example 1 includes:
  • Nickel sulfate, cobalt sulfate and manganese sulfate to an aqueous sodium hydroxide solution with a pH of 10 at a molar ratio of 8:1:1, stir at 30°C at a rate of 50 rpm, filter to obtain nickel cobalt manganese hydroxide, and Nickel cobalt manganese hydroxide is mixed with lithium hydroxide and lithium fluoride and then sintered in an oxygen-containing atmosphere with an oxygen mass percentage of 5%.
  • the temperature is raised to 550°C at a heating rate of 10°C/min. After 8 hours of heat preservation, Raise the temperature to 950°C at a heating rate of 13.3°C/min and keep it for 18 hours to obtain the cathode material.
  • the cathode material includes a nickel-based active material and does not have a rock salt phase coating on its surface.
  • the chemical formula of the nickel-based active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 F 0.1 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Comparative Example 1 was named D1.
  • the preparation method of the cathode material in Comparative Example 2 includes:
  • Nickel sulfate, cobalt sulfate and manganese sulfate to an aqueous sodium hydroxide solution with a pH of 10 at a molar ratio of 8:1:1, stir at 30°C at a rate of 50 rpm, filter to obtain nickel cobalt manganese hydroxide, and Nickel cobalt manganese hydroxide is mixed with lithium hydroxide and sodium fluoride and then sintered in an oxygen-containing atmosphere with an oxygen mass percentage of 10%.
  • the temperature is raised to 550°C at a heating rate of 10°C/min. After 4 hours of heat preservation, Raise the temperature to 900°C at a heating rate of 13.3°C/min and maintain the temperature for 14 hours to obtain the cathode material.
  • the cathode material includes a nickel-based active material and does not have a rock salt phase coating on its surface.
  • the chemical formula of the nickel-based active material is Li 0.99 Na 0.01 Ni 0.8 Co 0.1 Mn 0.1 O 2 F
  • a secondary battery was prepared using the same method as Example 1, and the battery of Comparative Example 2 was named D2.
  • the preparation method of the cathode material in Comparative Example 3 includes:
  • the positive electrode material includes a secondary particle core and a rock salt phase coating layer.
  • the chemical formula of the secondary particle core and rock salt phase coating layer is Li 0.99 Na 0.01 Ni 0.8 Co 0.1 Mn 0.1 Zr 0.02 O 2 .
  • a secondary battery was prepared using the same method as Example 1, and the battery of Comparative Example 3 was named D2.
  • this application also provides effect examples.
  • Figure 2 is a scanning electron microscope characterization diagram of the cathode material provided in Example 4 of the present application.
  • (a) in Figure 2 is a morphology characterization diagram of the cathode material in Example 4.
  • Figure 2 (a) is a morphology characterization diagram of the cathode material in Example 4.
  • b) is the HR-TEM Fourier transform diagram of the rock salt phase coating layer in the cathode material of Example 4
  • (c) in Figure 2 is the HR-TEM Fourier transform diagram of the secondary particle core in the cathode material of Example 4. Conversion diagram.
  • Figure 2 can reflect the morphological information of the cathode material surface.
  • the coating rate of the rock salt phase coating layer is about 37%
  • the average particle size of the primary particles is 1.89 ⁇ m
  • the particle size of the secondary particles is 8.12 ⁇ m
  • the secondary particle size is 8.12 ⁇ m.
  • the diameter ratio of secondary particles to primary particles is 4.3. From the crystal plane analysis, it can be seen that the space group of the rock salt phase coating layer is Fm3m, and the space group of the secondary particles is R3m. Please refer to Figure 3.
  • Figure 3 is a transmission electron microscope characterization diagram of the cross-section of the cathode material provided in Example 4 of the present application, wherein (a) in Figure 3 is a morphology characterization diagram of the cross-section of the cathode material in Example 4, and (a) in Figure 3 b) is the HR-TEM Fourier transform diagram of the rock salt phase coating layer in the cathode material of Example 4, and (c) in Figure 3 is the HR-TEM Fourier transform diagram of the secondary particle core in the cathode material of Example 4. Conversion diagram, as can be seen from Figure 3, the positive electrode of Embodiment 4 In the material, the thickness of the rock salt phase coating layer is 15nm. The same method was used to characterize the cathode materials of each embodiment and comparative example, and the corresponding characterization results are shown in Table 1.
  • FIG. 4 is the XRD spectrum of the cathode material provided in Example 4 of the present application. It can be seen from the spectrum that, The cathode material of Example 4 has a high degree of crystallization, good material stability, and the half-maximum width FWHM of the (104) crystal plane diffraction peak of the cathode material is 0.117. The same method is used to measure the results of each embodiment and comparative example. The cathode materials were characterized, and the corresponding characterization results are shown in Table 2.
  • the rate discharge test conditions are: discharge the battery to 2.5V at 5C at 100% SOC and 25°C, and record the ratio of the discharge capacity to the nominal capacity. Get the discharge rate of the battery.
  • the conditions for the cycle test are: cycle the battery at 100% depth of discharge (DOD) at 1C for 2000 cycles and then calculate the cycle retention rate of the battery. Please refer to Table 3 for the test results.
  • the coating rate of the rock salt phase coating layer of the cathode materials of Examples 1 and 2 is less than 20%.
  • the particle size of the secondary particles and primary particles in the cathode material of Example 1 is relatively moderate, and more It is conducive to the diffusion of lithium ions, and the rock salt phase coating layer and the secondary particle structure can cooperate well, so that the cathode material has good structural stability, and the battery has good cycle performance and rate performance;
  • the coating rate of the rock salt phase coating layer is 20% to 50%.
  • the particle size ratio of the secondary particles and primary particles of the cathode material in Example 3 is too small, and the coating layer is too thick, which reduces the lithium ions.
  • the migration performance, rate performance and cycle performance of the battery are poor; in the cathode material of Example 5, the coating layer and the secondary particle structure have a good coordination, and the resulting battery not only has a high discharge rate, but also has poor cycle performance. Good; in the cathode material of Example 8, the thickness of the coating layer is relatively large, which reduces the rate performance of the material.
  • the coating rate of the rock salt phase coating layer of the cathode materials of Examples 9 and 10 is 50% to 80%.
  • the particle size of the secondary particles and primary particles in the cathode material of Example 10 is moderate, which is beneficial to lithium ions. diffusion, and the coating layer and the structure of the secondary particles can cooperate well, so that the cathode material has good structural stability, and the battery has good cycle performance and rate performance; the rock salt phase coating of the cathode material in Examples 11 and 12
  • the coating rate of the coating layer is greater than 80%.
  • the particle size of the secondary particles and primary particles in the cathode material of Example 12 is relatively moderate, which is conducive to the diffusion of lithium ions, and the structure of the coating layer and secondary particles can The good coordination makes the cathode material have good structural stability, and the battery has good cycle performance and rate performance.
  • the cathode material of Comparative Example 1 has no coating layer and has a primary particle structure, and the resulting battery has poor cycle performance and rate performance; although the cathode material of Comparative Example 2 has a secondary particle structure, the lithium ion migration efficiency is improved, but due to no The coating layer and particles have poor liquid retention ability, the contact area between the positive electrode material and the electrolyte is limited, the lithium ion migration is relatively disordered, and the structural stability of the electrode material is poor, and the battery has poor cycle performance and rate performance; Comparative Example 3 The coating rate and coating thickness of the positive electrode material are too large, and the particle size ratio of secondary particles to primary particles is very low, making it difficult for lithium ions to migrate, and the discharge rate of the battery is very poor.
  • the cathode material provided by this application can effectively improve the rate performance and cycle performance of the battery, which is beneficial to its application in batteries.

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Abstract

一种正极材料及其应用，正极材料包括二次颗粒和设置在二次颗粒表面的岩盐相包覆层，二次颗粒由多个一次颗粒堆积形成；二次颗粒的粒径与多个一次颗粒的平均粒径之比大于或等于1.5；一次颗粒和岩盐相包覆层分别包括镍基活性材料。

Description

正极材料及其应用
本申请要求于2022年4月6日提交中国专利局、申请号为202210353912.1、发明名称为“一种正极材料及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及二次电池领域，具体涉及正极材料及其应用。
背景技术
镍基电极活性材料由于具有比容量高、能量密度高、环境友好和安全性优良等优点，因此被认为是极具应用前景的锂离子电池正极材料。然而，镍基电极活性材料的锂离子扩散系数较低，导致材料的充放电效率低、电池电化学性能差。因此，需要对镍基电极活性材料的结构进行改进，以改善镍基电极活性材料的锂离子迁移性能，从而提高电池的电化学性能。
发明内容
本申请第一方面提供了一种正极材料，所述正极材料包括二次颗粒和设置在所述二次颗粒表面的岩盐相包覆层，所述二次颗粒由多个一次颗粒堆积形成；所述二次颗粒的粒径与所述多个一次颗粒的平均粒径之比大于或等于1.5；所述一次颗粒和所述岩盐相包覆层分别包括镍基活性材料。
本申请一些实施方式中，所述镍基活性材料和所述岩盐相包覆层分别包括化学式为Li1-aAb(NimM1-m)XxO2Zz的材料，其中，-0.1≤a≤0.1，所述A包括Na、K、Be、Mg、Ca、B中的一种或多种，0≤b≤0.1，所述M包括Mn、Co、Al中的一种或多种，0＜m≤1，所述X包括Zr、V、Ti、Cr、Fe、Co、Ni、Zn、Nb、Mo、Os、W、Y中的一种或多种，0≤x≤0.1，所述Z包括F、Cl、Br、I中的一种或多种，0≤z≤0.1。
本申请一些实施方式中，所述岩盐相包覆层在所述二次颗粒表面的包覆率为10％～90％。
本申请一些实施方式中，当所述包覆率小于或等于20％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足1.5≤r≤3；
当所述包覆率大于20％且小于或等于50％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足3＜r≤10；
当所述包覆率大于50％且小于或等于80％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足10＜r≤50；
当所述包覆率大于80％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足r＞50。
本申请一些实施方式中，所述岩盐相包覆层在所述二次颗粒表面的包覆率为50％～80％。
本申请一些实施方式中，所述二次颗粒的粒径小于或等于15μm。
本申请一些实施方式中，所述岩盐相包覆层的厚度为1nm～20nm。
本申请一些实施方式中，所述岩盐相包覆层的厚度为5nm～15nm。
本申请一些实施方式中，所述镍基活性材料为层状六方密堆积结构，属于R3m空间群； 所述正极材料的X射线衍射图谱中，所述正极材料的(104)晶面衍射峰的半峰宽为0.1～0.2。
本申请一些实施方式中，所述正极材料的(104)晶面衍射峰的半峰宽为0.105～0.130。
本申请一些实施方式中，所述岩盐相包覆层和所述镍基活性材料分别包括掺杂或未掺杂的镍钴锰酸锂。
本申请一些实施方式中，所述未掺杂的镍钴锰酸锂的化学式为Li(NimConMn1-m-n)O2，0＜m＜1，0＜n＜1，0＜m+n＜1。
本申请一些实施方式中，所述掺杂的镍钴锰酸锂中掺杂元素包括Na、K、Be、Mg、Ca、B、Zr、V、Ti、Cr、Y、Fe、Co、Ni、Zn、Nb、Mo、Os、W、F、Cl、Br和I中的一种或多种。
本申请一些实施方式中，所述掺杂或未掺杂的镍钴锰酸锂的化学式为Li1-aAb(NimConMn1-m-n)XxO2Zz，其中，-0.1≤a≤0.1，所述A包括Na、K、Be、Mg、Ca、B中的一种或多种，0≤b≤0.1，所述X包括Zr、V、Ti、Cr、Fe、Co、Ni、Zn、Y、Nb、Mo、Os、W中的一种或多种，0≤x≤0.1，所述Z包括F、Cl、Br、I中的一种或多种，0≤z≤0.1。
本申请第二方面提供了一种正极极片，所述正极极片包括集流体和设置在所述集流体上的如第一方面所述的正极材料。
本申请第三方面提供了一种二次电池，包括正极和负极，所述正极包括如第二方面所述的正极极片。
本申请一些实施方式中，所述二次电池还包括电解液以及位于所述正极与所述负极之间的隔膜。
本申请一些实施方式中，所述二次电池还包括位于所述正极与所述负极之间的固态电解质或半固态电解质。
本申请第四方面提供了一种车辆，所述车辆包括如第三方面所述的二次电池。
附图说明
图1为本申请的实施方式提供的正极材料的结构示意图；
图2为本申请实施例4提供的正极材料表面的电镜表征图，其中，图2中(a)为实施例4的正极材料的扫描电镜形貌表征图，图2中(b)为实施例4的正极材料中岩盐相包覆层的HR-TEM傅里叶转换图，图2中(c)为实施例4的正极材料中二次颗粒内核的HR-TEM傅里叶转换图；
图3为本申请实施例4提供的正极材料截面的透射电镜表征图，其中，图3中(a)为实施例4的正极材料截面的形貌表征图，图3中(b)为实施例4的正极材料中岩盐相包覆层的HR-TEM傅里叶转换图，图3中(c)为实施例4的正极材料中二次颗粒内核的HR-TEM傅里叶转换图；
图4为本申请实施例4提供的正极材料的XRD谱图。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请提供了一种正极材料，该正极材料具有较高的锂离子迁移速率，将其应用在电池中能够提高电池的倍率性能和循环保持率，有利于制备高能量密度的二次电池。
镍基电极活性材料由于具有较高的比容量被认为是极具应用前景的锂离子电池正极材料，但镍基电极活性材料的锂离子扩散系数较低，材料的充放电效率低，电池电化学性能差。为改善镍基电极活性材料的锂离子迁移性能，提高电池的电化学性能，本申请提供了一种正极材料，请参阅图1，图1为本申请的实施方式提供的正极材料的结构示意图，图1中，正极材料100包括二次颗粒10和设置在二次颗粒10表面的岩盐相包覆层20，其中，二次颗粒10由多个一次颗粒堆积形成。本申请实施方式中，二次颗粒与一次颗粒的平均粒径之比大于或等于1.5。一次颗粒和岩盐相包覆层分别包括镍基活性材料。
本申请的正极材料为核壳结构，在一些实施方式中，正极材料的内核包括二次颗粒，正极材料的壳层包括岩盐相包覆层。本申请一些实施方式中，镍基活性材料包括化学式为Li1-aAb(NimM1-m)XxO2Zz的材料，其中，-0.1≤a≤0.1，A包括Na、K、Be、Mg、Ca、B中的一种或多种，0≤b≤0.1，M包括Mn、Co、Al中的一种或多种，0＜m≤1，X包括Zr、V、Ti、Cr、Fe、Co、Ni、Zn、Nb、Mo、Os、W、Y中的一种或多种，0≤x≤0.1，Z包括F、Cl、Br、I中的一种或多种，0≤z≤0.1。本申请中，二次颗粒为层状六方密堆积结构，属于R3m空间群，在XRD谱图中可以看到003、101和104晶面。本申请一些实施方式中，岩盐相包覆层包括化学式为Li1-aAb(NimM1-m)XxO2Zz的材料，其中，-0.1≤a≤0.1，A包括Na、K、Be、Mg、Ca、B中的一种或多种，0≤b≤0.1，M包括Mn、Co、Al中的一种或多种，0＜m≤1，X包括Zr、V、Ti、Cr、Fe、Co、Ni、Zn、Nb、Mo、Os、W、Y中的一种或多种，0≤x≤0.1，Z包括F、Cl、Br、I中的一种或多种，0≤z≤0.1。本申请中，岩盐相包覆层的结构属于Fm3m空间群，在XRD谱图中可以看到111和200晶面。
本申请中，镍基活性材料二次颗粒的结构可以丰富锂离子的扩散路径，有效地提高锂离子在材料中的迁移速率，岩盐相包覆层不仅能够提高正极材料的保液能力，保证电解液能够持续浸润正极材料，使锂离子实现有序的扩散，而且岩盐相包覆层能够抑制二次颗粒的破碎，提高正极材料的结构稳定性。具体的，二次颗粒在电池充放电过程中，锂离子不断嵌入和脱出，二次颗粒中的一次颗粒持续地出现体积膨胀和收缩，颗粒之间的空隙不断变化，使得一次颗粒之间的电解液易产生气泡，气泡的存在会阻断锂离子在电解液中的迁移路径，使得锂离子迁移路径不稳定、锂离子迁移速率降低，材料的倍率性能变差。岩盐相包覆层一方面具有较高的结构强度，能够抑制颗粒的体积变化，减少气泡的产生，提高锂离子在电解液迁移的稳定性，另一方面，岩盐相包覆层对电解液具有良好的浸润性能，电解液可通过毛细效应渗入到二次颗粒中，从而提高电解液与一次颗粒的接触面积，有利于扩展锂离子的迁移路径，改善镍钴锰三元正极材料的锂离子迁移性能，提高电池的电化学性能。
本申请提供的正极材料中，多个镍基活性材料一次颗粒堆积形成镍基活性材料二次颗粒，二次颗粒的结构不仅能够拓展锂离子在镍基活性材料中的固固传输路径，并且二次颗粒中具有贯通的孔道结构，有利于电解液渗入，从而丰富锂离子的传输路径，提高离子的迁移速率；岩盐相包覆层可提高正极材料的保液能力，保证电解液能够持续浸润二次颗粒，从而改善镍钴锰三元正极材料的锂离子迁移性能，提高电池的电化学性能。
本申请一些实施方式中，岩盐相包覆层在二次颗粒表面的包覆率为10％～90％，其中，包覆率指的是岩盐相包覆层在二次颗粒表面的包覆面积与二次颗粒表面积的比值。岩盐相包覆层在二次颗粒表面的包覆率具体可以但不限于为10％、30％、50％、60％、70％、80％或90％。 控制岩盐相包覆层的包覆率有利于包覆层对二次颗粒形成有利的支持，抑制二次颗粒的体积变化，并使材料整体具有良好的锂离子迁移性能。本申请一些实施方式中，岩盐相包覆层在二次颗粒表面的包覆率为50％～80％。
本申请一些实施方式中，岩盐相包覆层的厚度为1nm～20nm。岩盐相包覆层的厚度具体可以但不限于为1nm、3nm、5nm、10nm、15nm或20nm。控制岩盐相包覆层的厚度有利于提高正极材料的保液能力，使电解液能够充分浸润正极。本申请一些实施方式中，岩盐相包覆层的厚度为5nm～15nm。
本申请发明人研究发现，岩盐相包覆层的包覆面积和二次颗粒结构具有一定的联动效果，二者能够协同地调节锂离子的迁移性能。本申请一些实施方式中，当岩盐相包覆层在二次颗粒表面的包覆率小于或等于20％时，二次颗粒的粒径与一次颗粒的平均粒径的比值r为1.5～3，即1.5≤r≤3；当岩盐相包覆层在二次颗粒表面的包覆率大于20％且小于或等于50％时，二次颗粒的粒径与一次颗粒的平均粒径的比值r大于3且小于或等于10，即3＜r≤10；当岩盐相包覆层在二次颗粒表面的包覆率大于50％且小于或等于80％时，二次颗粒的粒径与一次颗粒的平均粒径的比值r大于10且小于或等于50，即10＜r≤50；当岩盐相包覆层在二次颗粒表面的包覆率大于80％时，二次颗粒的粒径与一次颗粒的平均粒径的比值r大于50,即r＞50。也就是说，对于单个正极材料颗粒，当岩盐相包覆层的包覆率小于或等于20％时，二次颗粒的粒径是一次颗粒平均粒径的1.5～3倍，例如有n个一次颗粒堆积形成二次颗粒，n个一次颗粒的平均粒径为xμm，二次颗粒的粒径为yμm，当岩盐相包覆层的包覆率小于或等于20％时，y/x＝1.5～3。本申请研究发现，二次颗粒与一次颗粒的粒径相差较大时，可以有效地提高锂离子迁移速率，但二次颗粒的体积变化也更显著，一次颗粒之间容易产生气泡，而岩盐相包覆层可以有效地抑制气泡的产生，保证电解液与一次颗粒能够充分地接触，使得锂离子能够有序迁移并具有较高的传输速率。但是过大的包覆率会影响电极材料的倍率性能。因此对于一定结构的二次颗粒，控制岩盐相包覆层的包覆率可以使材料具有良好的锂离子的迁移性能，即材料既具有较高的锂离子迁移速率，并且锂离子能够有序迁移，材料具有良好的循环稳定性。
本申请一些实施方式中，二次颗粒的平均粒径小于或等于15μm。二次颗粒的平均粒径具体可以但不限于为0.1μm、0.5μm、1μm、2μm、5μm、10μm、11μm、13μm或15μm。
本申请一些实施方式中，一次颗粒紧密堆积形成二次颗粒，正极材料的X射线衍射图谱中，正极材料的104晶面衍射峰的半峰宽FWHM为0.1～0.2，正极材料的104晶面衍射峰的半峰宽FWHM具体可以但不限于为0.1、0.105、0.11、0.12、0.13、0.15或0.2。正极材料的104晶面衍射峰的半峰宽FWHM为0.1～0.2时，有利于制备高能量密度的二次电池。本申请一些实施例中，正极材料的X射线衍射图谱中，104晶面衍射峰的半峰宽FWHM为0.105～0.13。
本申请一些实施方式中，当a＝0、b＝0、x＝0、z＝0时，镍基活性材料包括化学式为Li(NimM1-m)O2的材料。本申请一些实施方式中，镍基活性材料包括锂位掺杂元素，锂位掺杂元素部分取代Li(NixM1-x)O2中的锂原子，锂位掺杂元素为化学式Li1-aAb(NimM1-m)XxO2Zz中的A，即化学式中的b＞0，锂位掺杂元素包括Na、K、Be、Mg、Ca、B中的一种或多种，锂位掺杂元素能够提高锂离子在岩盐相包覆层和镍基活性材料晶格中的迁移速率。本申请一些实施方式中，镍基活性材料包括过渡金属掺杂元素，过渡金属掺杂元素为化学式Li1-aAb(NimM1-m)XxO2Zz中的X，即化学式中的x＞0，过渡金属掺杂元素包括Zr、V、Ti、Cr、Y、Fe、Co、Ni、Zn、Nb、Mo、Os、W中的一种或多种，过渡金属掺杂元素能够提高正极材料的在电解液中的稳定性，抑制锂镍混排效应，并提升锂离子在固相中的传导性能。本申请一些实施方 式中，镍基活性材料包括氧位掺杂元素，氧位掺杂元素为化学式Li1-aAb(NimM1-m)XxO2Zz中的Z，即化学式中的z＞0，氧位掺杂元素部分取代Li(NixM1-x)O2中的氧原子，氧位掺杂元素包括F、Cl、Br、I中的一种或多种，氧位掺杂元素可以提高岩盐相包覆层和镍基活性材料的结构稳定性。
本申请一些实施方式中，岩盐相包覆层和镍基活性材料分别包括掺杂或未掺杂的镍钴锰酸锂，其中，未掺杂的镍钴锰酸锂的化学式为Li(NimConMn1-m-n)O2，0＜m＜1，0＜n＜1，0＜m+n＜1。本申请一些实施方式中，掺杂的镍钴锰酸锂中掺杂元素包括Na、K、Be、Mg、Ca、B、Zr、V、Ti、Cr、Y、Fe、Co、Ni、Zn、Nb、Mo、Os、W、F、Cl、Br和I中的一种或多种。掺杂元素能够改善岩盐相包覆层和镍钴锰酸锂的结构稳定性并提高材料的锂离子迁移速率。本申请一些实施方式中，掺杂或未掺杂的镍钴锰酸锂的化学式为Li1-aAb(NimConMn1-m-n)XxO2Zz，其中，-0.1≤a≤0.1，A包括Na、K、Be、Mg、Ca、B中的一种或多种，0≤b≤0.1，X包括Zr、V、Ti、Cr、Fe、Co、Ni、Zn、Y、Nb、Mo、Os、W中的一种或多种，0≤x≤0.1，Z包括F、Cl、Br、I中的一种或多种，0≤z≤0.1。
本申请提供的正极材料通过二次颗粒和岩盐相包覆结构有效地丰富了锂离子的迁移路径并提高锂离子的迁移速率，该结构的正极材料能够降低电池的阻抗实现高倍率的充放电，将其应用在二次电池中能够提高二次电池的容量和循环性能，有利于电池的长期使用。
本申请还提供了上述正极材料的制备方法，包括：
将镍钴锰氢氧化物与锂源混合后在含氧气氛下进行烧结，得到正极材料；其中，含氧气氛的氧含量为18％～100％。
本申请一些实施方式中，镍钴锰氢氧化物的制备方法包括：将镍源、钴源和锰源分散在碱性溶液中，得到镍钴锰氢氧化物，其中，碱性溶液的pH值为9～14，碱性溶液包括氢氧化钠溶液、氢氧化钾溶液和氨水中的一种或多种，镍源包括硝酸镍、硫酸镍和氯化镍中的一种或多种，钴源包括硝酸钴、硫酸钴和氯化钴中的一种或多种，锰源包括硝酸锰、硫酸锰和氯化锰中的一种或多种。本申请一些实施方式中，镍钴锰氢氧化物的制备方法包括：将镍源、钴源和锰源按照(5～10):(0.5～1.5):(0.5～1.5)的摩尔比分散在碱性溶液中，在25℃～45℃下以5rpm～100rpm的转速搅拌360min～1080min。
本申请一些实施方式中，锂源包括碳酸锂、氢氧化锂、硝酸锂、草酸锂、醋酸锂中的一种或多种。本申请一些实施方式中，将镍钴锰氢氧化物与锂源按照1：(0.9～1.2)的摩尔比混合后，向混合物中加入掺杂元素，其中，掺杂元素包括锂位掺杂元素、过渡金属掺杂元素和氧位掺杂元素中的一种或多种。本申请中，含氧气氛中氧的含量会影响岩盐相包覆层的结构，控制含氧气氛中氧的含量有利于形成结构稳定的岩盐相包覆层，提高岩盐相包覆层对二次颗粒的附着强度，使正极材料对电解液具有良好且稳定的保液能力。本申请一些实施方式中，含氧气氛中氧的质量百分含量为19％～95％，含氧气氛中氧的质量百分含量具体可以但不限于为18％、20％、25％、30％、50％、60％、70％、80％、90％或100％。
本申请一些实施方式中，烧结的温度为200℃～980℃。烧结的温度具体可以但不限于为200℃、300℃、500℃、600℃、700℃、750℃、800℃、850℃、900℃或980℃。本申请一些实施方式中，烧结的时间为8h～32h。烧结的时间具体可以但不限于为8h、10h、15h、20h、25h、30h或32h。本申请一些实施方式中，煅烧的温度为700℃～1000℃，煅烧的时间为12h～36h。控制煅烧的时间和温度有利于形成紧密堆积的二次颗粒结构和稳定包覆在二次颗粒表面的岩盐相包覆层。本申请一些实施方式中，烧结的设备可以是旋转炉、回转炉、箱式炉、管式炉、辊道窑、推板窑或流化床中的任意一种。
本申请一些实施方式中，将镍钴锰氢氧化物与锂源烧结是采用梯度升温的方法，其中，梯度升温包括：以不高于10℃/min的升温速度升温至最高720℃，保温1h～9h后，以不高于15℃/min的升温速度升温至最高1000℃，保温8h～25h得到正极材料。本申请一些实施方式中，梯度升温包括：以不高于10℃/min的升温速度升温至最高500℃，保温2h～9h后，以不高于13.3℃/min的升温速度升温至最高850℃，保温8h～25h得到正极材料。
本申请还提供了一种正极极片，该正极极片包括集流体和设置在集流体上的正极材料层，其中，正极材料层包括本申请的电池正极材料。本申请中，正极材料层的制备可以是将正极材料、导电剂、粘结剂和溶剂混合形成正极浆料，将正极浆料经涂覆、干燥后得到正极材料层。在配制正极浆料时，可以先将粘结剂与溶剂混合，充分搅拌后，再加入导电剂，经搅拌后再加入电池正极材料，搅拌后过筛得到正极浆料。其中，导电剂、粘结剂和溶剂为电池领域的常规选择。例如，粘结剂可以选自聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚乙烯醇(PVA)、丁苯橡胶(SBR)、聚丙烯腈(PAN)、聚酰亚胺(PI)、聚丙烯酸(PAA)、聚丙烯酸酯、聚烯烃、羧甲基纤维素钠(CMC)和海藻酸钠中的一种或多种。导电剂可以选自碳纳米管、炭黑以及石墨烯中的一种或多种。
本申请还提供了一种二次电池，该二次电池包括正极、负极、电解液以及位于正极与负极之间的隔膜，或者，该二次电池包括正极、负极以及位于正极与负极之间的固态电解质或半固态电解质；其中，正极包括本申请提供的正极极片。
本申请中，二次电池的负极可以是本领域公知的任意负极。本申请实施方式中，负极可包括碳基负极、硅基负极、锡基负极和锂负极中的一种或多种。其中碳基负极可包括石墨、硬碳、软碳、石墨烯等；硅基负极可包括硅、硅碳、硅氧、硅金属化合物等含硅材料或者此含硅材料与非含硅材料如石墨的混合材料；锡基负极可包括锡、锡碳、锡氧、锡金属化合物等含锡材料或者此含锡材料与非含锡材料如石墨的混合材料；锂负极可包括金属锂或锂合金。锂合金具体可以是锂硅合金、锂钠合金、锂钾合金、锂铝合金、锂锡合金和锂铟合金中的至少一种。本申请一些实施例中，负极的集流体为铜箔，负极活性材料包括天然石墨、人造石墨、硬碳、软碳、钛酸锂、氧化铁、磷酸钛锂、二氧化钛、硅、氧化亚硅、锡及其氧化物和锑及其氧化物中的一种或多种；粘结剂包含聚丙烯酸(PAA)、聚偏氟乙烯(PVDF)、羧甲基纤维素(CMC)和丁苯乳胶(SBR)中的一种或多种；导电剂包括乙炔黑、科琴碳黑、Super-P、碳纳米管、碳纳米纤维、活性炭和石墨烯中的一种或多种。本申请中，负极的制备方法可以采用本领域公知的任意方法。
本申请中，二次电池的隔膜可以是本领域技术人员公知的任意隔膜，例如隔膜可以是聚烯烃微多孔膜、聚对苯二甲酸乙二醇酯、聚乙烯毡、玻璃纤维毡或超细玻璃纤维纸中的一种或多种。
本申请中，二次电池的电解液包括电解质锂盐在非水溶剂中形成的溶液。本申请实施方式中，电解质锂盐包括六氟磷酸锂(LiPF6)、高氯酸锂(LiClO4)、四氟硼酸锂(LiBF4)、六氟砷酸锂(LiAsF6)、六氟硅酸锂(Li2SiF6)、四苯基硼酸锂(LiB(C6H5)4)、氯化锂(LiCl)、溴化锂(LiBr)、氯铝酸锂(LiAlCl4)、氟烃基磺酸锂(LiC(SO2CF3)3)、LiCH3SO3、LiN(SO2CF3)2和LiN(SO2C2F5)2中的一种或多种。本申请一些实施方式中，非水溶剂包括链状酸酯和环状酸酯中的一种或多种。本申请一些实施方式中，链状酸酯包括碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)和碳酸二丙酯(DPC)中的一种或多种。本申请一些实施方式中，链状酸酯包括含氟、含硫或含不饱和键的链状有机酯类。本申请一些实施方式中，环状酸酯包括碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸亚乙烯酯(VC)、 γ-丁内酯(γ-BL)和磺内酯中的一种或多种。本申请一些实施方式中，环状酸酯包括含氟、含硫或含不饱和键的环状有机酯。本申请一些实施方式中，非水溶剂包括链状醚和环状醚溶液中的一种或多种。本申请一些实施方式中，环状醚包括四氢呋喃(THF)、2-甲基四氢呋喃(2-MeTHF)、1,3-二氧戊烷(DOL)和4-甲基-1,3-二氧环戊烷(4-MeDOL)中的一种或多种。本申请一些实施方式中，环状醚包括含氟、含硫或含不饱和键的环状有机醚。本申请一些实施方式中，链状醚包括二甲氧基甲烷(DMM)、1,2-二甲氧基乙烷(DME)、1,2-二甲氧基丙烷(DMP)和二甘醇二甲醚(DG)中的一种或多种。本申请一些实施方式中，链状醚包括含氟、含硫或含不饱和键的链状有机醚。本申请实施方式中，电解液中电解质锂盐的浓度为0.1mol/L-15mol/L。本申请一些实施方式中，电解质锂盐的浓度为1mol/L-10mol/L。
本申请实施方式中，二次电池的制备可以采用叠片工艺或卷绕工艺中的任意一种。本申请一些实施例中，采用叠片工艺制备电池。
本申请还提供了一种车辆，该车辆包括本申请提供的二次电池，二次电池为车辆供电。
下面分多个实施例对本申请技术方案进行进一步的说明。
实施例1
一种正极材料的制备方法，包括：
将硝酸镍、硝酸钴和硫酸锰按照6:2:2的摩尔比加入pH为11的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氧化钇混合后在氧质量百分含量为22％的含氧气氛中烧结，以10℃/min的升温速度升温至500℃，保温4h后，以13.3℃/min的升温速度升温至850℃，保温16h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiNi0.60Co0.20Mn0.20Y0.02O2。
将制备得到的电池正极材料与导电剂、粘结剂按照95：3：2的质量比分散于N-甲基吡咯烷酮中得到正极浆料，其中，导电剂为导电碳黑，粘结剂为PVDF，将正极浆料涂覆在厚度为20um的铝箔表面，烘干后进行辊压，形成的正极活性材料层的压实密度为3.4g/cm3，得到电极正极；将石墨与羧甲基纤维素和导电炭黑按照95：3：2的质量比分散于N-甲基吡咯烷酮中得到负极浆料，将负极浆料涂覆在铜箔表面，经烘干和辊压后负极活性材料层的压实密度为1.4g/cm3，得到电极负极；将上述制备得到的电池正极、电池负极和聚烯烃微多孔膜隔膜卷绕制成电芯，包装后注入1mol/L六氟磷酸锂电解液(溶剂为1:1的EC：EMC)得到电池，实施例1的电池命名为S1。
实施例2
实施例2中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照5:2:3的摩尔比加入pH为10的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂混合后在氧质量百分含量为21％的含氧气氛中烧结，以10℃/min的升温速度升温至550℃，保温4h后，以13.3℃/min的升温速度升温至900℃，保温14h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiNi0.50Co0.20Mn0.30O2。
采用与实施例1相同的方法制备得到二次电池，实施例2的电池命名为S2。
实施例3
实施例3中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为12的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和 氧化钇混合后在氧质量百分含量为35％的含氧气氛中烧结，以10℃/min的升温速度升温至480℃，保温3h后，以13.3℃/min的升温速度升温至700℃，保温22h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiNi0.8Co0.1Mn0.1Y0.02O2。
采用与实施例1相同的方法制备得到二次电池，实施例3的电池命名为S3。
实施例4
实施例4中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照6:2:2的摩尔比加入pH为11的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂混合后在氧质量百分含量为30％的含氧气氛中烧结，以10℃/min的升温速度升温至700℃，保温6h后，以13.3℃/min的升温速度升温至850℃，保温13h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiNi0.60Co0.20Mn0.20O2。
采用与实施例1相同的方法制备得到二次电池，实施例4的电池命名为S4。
实施例5
实施例5中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为12的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氯化钠混合后在氧质量百分含量为50％的含氧气氛中烧结，以10.2℃/min的升温速度升温至550℃，保温6h后，以13.8℃/min的升温速度升温至850℃，保温14h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为Li0.99Na0.01Ni0.8Co0.1Mn0.1O2Cl0.1。
采用与实施例1相同的方法制备得到二次电池，实施例5的电池命名为S5。
实施例6
实施例6中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为12的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和碘单质混合后在氧质量百分含量为60％的含氧气氛中烧结，以11℃/min的升温速度升温至650℃，保温3h后，以13.8℃/min的升温速度升温至930℃，保温15h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiNi0.8Co0.1Mn0.1O2I0.1。
采用与实施例1相同的方法制备得到二次电池，实施例6的电池命名为S6。
实施例7
实施例7中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为12的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和纳米氧化硼混合后在氧质量百分含量为90％的含氧气氛中烧结，以13.3℃/min的升温速度升温至700℃，保温6h后，以13.3℃/min的升温速度升温至880℃，保温19h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiB0.02Ni0.8Co0.1Mn0.1O2。
采用与实施例1相同的方法制备得到二次电池，实施例7的电池命名为S7。
实施例8
实施例8中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为12的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氟化锂混合后在氧质量百分含量为90％的含氧气氛中烧结，以10.3℃/min的升温速度升温至550℃，保温4h后，以13.3℃/min的升温速度升温至960℃，保温15h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiNi0.80Co0.10Mn0.10O2F0.05。
采用与实施例1相同的方法制备得到二次电池，实施例8的电池命名为S8。
实施例9
实施例9中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为12的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氟化钠混合后在氧质量百分含量为90％的含氧气氛中烧结，以11.2℃/min的升温速度升温至440℃，保温8h后，以13.3℃/min的升温速度升温至860℃，保温20h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为Li0.99Na0.01Ni0.8Co0.1Mn0.1O2F0.1。
采用与实施例1相同的方法制备得到二次电池，实施例9的电池命名为S9。
实施例10
实施例10中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照4:3:3的摩尔比加入pH为10的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂混合后在氧质量百分含量为19％的含氧气氛中烧结，以10.8℃/min的升温速度升温至580℃，保温2h后，以13.3℃/min的升温速度升温至990℃，保温17h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为LiNi0.40Co0.30Mn0.30O2。
采用与实施例1相同的方法制备得到二次电池，实施例10的电池命名为S10。
实施例11
实施例11中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照1:1:1的摩尔比加入pH为10的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氟化铍、氟化锂混合后在氧质量百分含量为19％的含氧气氛中烧结，以10℃/min的升温速度升温至550℃，保温4h后，以14.1℃/min的升温速度升温至980℃，保温16h得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为Li0.99Be0.01Ni1/3Co1/3Mn1/3O2F0.05。
采用与实施例1相同的方法制备得到二次电池，实施例11的电池命名为S11。
实施例12
实施例12中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为10的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氟化钇混合后在氧质量百分含量为85％的含氧气氛中烧结，以10℃/min的升温速度升温至550℃，保温8h后，以13.3℃/min的升温速度升温至800℃，保温20h得到正极材料，正极 材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为Li1.01Ni0.8Co0.1Mn0.1Y0.01O2F0.05。
采用与实施例1相同的方法制备得到二次电池，实施例12的电池命名为S12。
对比例1
对比例1中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为10的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氟化锂混合后在氧质量百分含量为5％的含氧气氛中烧结，以10℃/min的升温速度升温至550℃，保温8h后，以13.3℃/min的升温速度升温至950℃，保温18h得到正极材料，正极材料包括镍基活性材料，其表面不具有岩盐相包覆层，镍基活性材料的化学式为LiNi0.8Co0.1Mn0.1O2F0.1。
采用与实施例1相同的方法制备得到二次电池，对比例1的电池命名为D1。
对比例2
对比例2中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为10的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂和氟化钠混合后在氧质量百分含量为10％的含氧气氛中烧结，以10℃/min的升温速度升温至550℃，保温4h后，以13.3℃/min的升温速度升温至900℃，保温14h得到正极材料，正极材料包括镍基活性材料，其表面不具有岩盐相包覆层，镍基活性材料的化学式为Li0.99Na0.01Ni0.8Co0.1Mn0.1O2F0.1。
采用与实施例1相同的方法制备得到二次电池，对比例2的电池命名为D2。
对比例3
对比例3中正极材料的制备方法包括：
将硫酸镍、硫酸钴和硫酸锰按照8:1:1的摩尔比加入pH为10的氢氧化钠水溶液中，在30℃下以50rpm的速率搅拌，过滤后得到镍钴锰氢氧化物，将镍钴锰氢氧化物与氢氧化锂、氧化锆和碳酸钠混合后在氧质量百分含量为70％的含氧气氛中烧结，烧结的温度为840℃，烧结时间为22h，得到正极材料，正极材料包括二次颗粒内核和岩盐相包覆层，二次颗粒内核和岩盐相包覆层的化学式为Li0.99Na0.01Ni0.8Co0.1Mn0.1Zr0.02O2。
采用与实施例1相同的方法制备得到二次电池，对比例3的电池命名为D2。
效果实施例
为验证本申请制得的正极材料和电池性能，本申请还提供了效果实施例。
1)请参阅图2，图2为本申请实施例4提供的正极材料的扫描电镜表征图，其中，图2中(a)为实施例4的正极材料的形貌表征图，图2中(b)为实施例4的正极材料中岩盐相包覆层的HR-TEM傅里叶转换图，图2中(c)为实施例4的正极材料中二次颗粒内核的HR-TEM傅里叶转换图。图2可以体现出正极材料表面的形貌信息。由图2可以看出，实施例4的正极材料中，岩盐相包覆层的包覆率约为37％，一次颗粒的平均粒径为1.89μm，二次颗粒的粒径为8.12μm，二次颗粒与一次颗粒的直径比为4.3，由晶面分析可以看出，岩盐相包覆层的空间群为Fm3m，二次颗粒的空间群为R3m。请参阅图3，图3为本申请实施例4提供的正极材料截面的透射电镜表征图，其中，图3中(a)为实施例4的正极材料截面的形貌表征图，图3中(b)为实施例4的正极材料中岩盐相包覆层的HR-TEM傅里叶转换图，图3中(c)为实施例4的正极材料中二次颗粒内核的HR-TEM傅里叶转换图，由图3可以看出，实施例4的正极 材料中，岩盐相包覆层的厚度为15nm。采用相同的方法对各实施例和对比例的正极材料进行表征，相应的表征结果如表1所示。
表1实施例1-12和对比例1-3正极材料的结构参数表
2)对实施例4的正极材料进行X射线衍射表征，并分析其衍射图谱，请参阅图4，图4为本申请实施例4提供的正极材料的XRD谱图，由谱图可以看出，实施例4的正极材料具有较高的结晶程度，材料的稳定性好，并且正极材料的(104)晶面衍射峰的半峰宽FWHM为0.117，采用相同的方法对各实施例和对比例的正极材料进行表征，相应的表征结果如表2所示。
表2实施例1-12和对比例1-3正极材料的结构参数表

3)对各实施例和对比例的电池进行充放电循环测试，倍率放电测试条件为：将电池在100％SOC、25℃下以5C放电至2.5V，记录放电容量与标称容量的比值，得到电池的放电倍率。循环测试的条件为：将电池在100％放电深度(DOD)以1C循环2000周后测算电池的循环保持率，测试结果请参阅表3。
表3实施例1-12和对比例1-3的电池性能表
表3中，实施例1和实施例2正极材料的岩盐相包覆层的包覆率小于20％，其中，实施例1正极材料中二次颗粒与一次颗粒的粒径比较为适中，更有利于锂离子的扩散，且岩盐相包覆层与二次颗粒结构能够很好的配合，使得正极材料具有良好的结构稳定性，电池具有良好的循环性能和倍率性能；实施例3-8正极材料的岩盐相包覆层的包覆率在20％～50％，其中，实施例3的正极材料二次颗粒与一次颗粒的粒径比偏小，且包覆层过厚，降低了锂离子的迁移性能，电池的倍率性能和循环性能较差；实施例5的正极材料中，包覆层和二次颗粒结构具有良好的配合，所得的电池不仅具有较高的放电倍率，其循环性能也很好；实施例8的正极材料中，包覆层厚度较大，降低了材料的倍率性能。
实施例9和10正极材料的岩盐相包覆层的包覆率在50％～80％，其中，实施例10的正极材料中二次颗粒与一次颗粒的粒径比较为适中，有利于锂离子的扩散，且包覆层与二次颗粒的结构能够很好的配合，使得正极材料具有良好的结构稳定性，电池具有良好的循环性能和倍率性能；实施例11和12正极材料的岩盐相包覆层的包覆率大于80％，其中，实施例12的正极材料中二次颗粒与一次颗粒的粒径比较为适中，有利于锂离子的扩散，且包覆层与二次颗粒的结构能够很好的配合，使得正极材料具有良好的结构稳定性，电池具有良好的循环性能和倍率性能。
对比例1的正极材料没有包覆层且为一次颗粒结构，所得电池的循环性能和倍率性能差；对比例2的正极材料尽管为二次颗粒结构，锂离子迁移效率有所提升，但由于没有包覆层，颗粒的保液能力较差，正极材料与电解液接触面积有限，锂离子迁移较为无序，且电极材料的结构稳定性较差，电池的循环性能和倍率性能差；对比例3的正极材料包覆率和包覆厚度过大，而二次颗粒与一次颗粒的粒径比很低，锂离子迁移较为困难，电池的放电倍率很差。
由此可以看出，本申请提供的正极材料可以有效地提高电池的倍率性能和循环性能，有利于其在电池中的应用。
以上所述是本申请的一些实施方式，但并不能因此而理解为对本申请范围的限制。应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本申请的保护范围。

Claims (19)

  1. 一种正极材料，其特征在于，所述正极材料包括：
    二次颗粒，所述二次颗粒由多个一次颗粒堆积形成；以及
    设置在所述二次颗粒表面的岩盐相包覆层；所述二次颗粒的粒径与所述多个一次颗粒的平均粒径之比大于或等于1.5；所述一次颗粒和所述岩盐相包覆层分别包括镍基活性材料。
  2. 如权利要求1所述的正极材料，其特征在于，所述镍基活性材料包括化学式为Li1-aAb(NimM1-m)XxO2Zz的材料，其中，-0.1≤a≤0.1，所述A包括Na、K、Be、Mg、Ca、B中的一种或多种，0≤b≤0.1，所述M包括Mn、Co、Al中的一种或多种，0＜m≤1，所述X包括Zr、V、Ti、Cr、Fe、Co、Ni、Zn、Nb、Mo、Os、W、Y中的一种或多种，0≤x≤0.1，所述Z包括F、Cl、Br、I中的一种或多种，0≤z≤0.1。
  3. 如权利要求1所述的正极材料，其特征在于，所述岩盐相包覆层在所述二次颗粒表面的包覆率为10％～90％。
  4. 如权利要求3所述的正极材料，其特征在于，
    当所述包覆率小于或等于20％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足1.5≤r≤3；
    当所述包覆率大于20％且小于或等于50％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足3＜r≤10；
    当所述包覆率大于50％且小于或等于80％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足10＜r≤50；
    当所述包覆率大于80％时，所述二次颗粒的粒径与所述多个一次颗粒的平均粒径的比值r满足r＞50。
  5. 如权利要求1-4中任一项所述的正极材料，其特征在于，所述岩盐相包覆层在所述二次颗粒表面的包覆率为50％～80％。
  6. 如权利要求1-5中任一项所述的正极材料，其特征在于，所述二次颗粒的粒径小于或等于15μm。
  7. 如权利要求1-6中任一项所述的正极材料，其特征在于，所述岩盐相包覆层的厚度为1nm～20nm。
  8. 如权利要求1-7中任一项所述的正极材料，其特征在于，所述岩盐相包覆层的厚度为5nm～15nm。
  9. 如权利要求1-8中任一项所述的正极材料，其特征在于，所述二次颗粒为层状六方密堆积结构，属于R3m空间群；所述正极材料的X射线衍射图谱中，所述正极材料的(104)晶面衍射峰的半峰宽为0.1～0.2。
  10. 如权利要求9所述的正极材料，其特征在于，所述正极材料的(104)晶面衍射峰的半峰宽为0.105～0.130。
  11. 如权利要求1-10中任一项所述的正极材料，其特征在于，所述岩盐相包覆层和所述镍基活性材料分别包括掺杂或未掺杂的镍钴锰酸锂。
  12. 如权利要求11所述的正极材料，其特征在于，所述未掺杂的镍钴锰酸锂的化学式为Li(NimConMn1-m-n)O2，0＜m＜1，0＜n＜1，0＜m+n＜1。
  13. 如权利要求11或12所述的正极材料，其特征在于，所述掺杂的镍钴锰酸锂中掺杂元素包括Na、K、Be、Mg、Ca、B、Zr、V、Ti、Cr、Y、Fe、Co、Ni、Zn、Nb、Mo、Os、W、F、Cl、Br和I中的一种或多种。
  14. 如权利要求11-13中任一项所述的正极材料，其特征在于，所述掺杂或未掺杂的镍钴锰酸锂的化学式为Li1-aAb(NimConMn1-m-n)XxO2Zz，其中，-0.1≤a≤0.1，所述A包括Na、K、Be、Mg、Ca、B中的一种或多种，0≤b≤0.1，所述X包括Zr、V、Ti、Cr、Fe、Co、Ni、Zn、Y、Nb、Mo、Os、W中的一种或多种，0≤x≤0.1，所述Z包括F、Cl、Br、I中的一种或多种，0≤z≤0.1。
  15. 一种正极极片，其特征在于，所述正极极片包括集流体和设置在所述集流体上的如权利要求1-14中任一项所述的正极材料。
  16. 一种二次电池，其特征在于，包括：
    正极，所述正极包括如权利要求15所述的正极极片；以及
    负极。
  17. 如权利要求16所述的二次电池，其特征在于，所述二次电池还包括电解液以及位于所述正极与所述负极之间的隔膜。
  18. 如权利要求16所述的二次电池，其特征在于，所述二次电池还包括位于所述正极与所述负极之间的固态电解质或半固态电解质。
  19. 一种车辆，其特征在于，所述车辆包括如权利要求16-18中任一项所述的二次电池。
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