WO2024093820A1 - 一种正极材料及其制备方法、正极和电池 - Google Patents

一种正极材料及其制备方法、正极和电池 Download PDF

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WO2024093820A1
WO2024093820A1 PCT/CN2023/127134 CN2023127134W WO2024093820A1 WO 2024093820 A1 WO2024093820 A1 WO 2024093820A1 CN 2023127134 W CN2023127134 W CN 2023127134W WO 2024093820 A1 WO2024093820 A1 WO 2024093820A1
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positive electrode
lithium
electrode material
doped
elements
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English (en)
French (fr)
Inventor
张莉
陈心怡
裴现一男
万远鑫
孔令涌
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Shenzhen Dynanonic Innovazone New Energy Technology Co Ltd
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Shenzhen Dynanonic Innovazone New Energy Technology Co Ltd
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Priority to EP23884752.9A priority Critical patent/EP4614592A4/en
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    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • C—CHEMISTRY; METALLURGY
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
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    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • 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 invention relates to the field of lithium ion batteries, in particular to a positive electrode material and a preparation method thereof, a positive electrode and a battery.
  • Lithium-ion battery cathode material is one of the key raw materials of lithium-ion batteries. Its performance directly affects the performance of lithium-ion batteries.
  • the cathode materials on the market mainly include lithium cobalt oxide, spinel lithium manganese oxide, nickel cobalt lithium manganese oxide, nickel cobalt lithium, lithium iron phosphate and other materials.
  • lithium cobalt oxide material is the most mature, but the resource reserves are limited and the cost is high; spinel lithium manganese oxide material is cheap and safe, but has low specific capacity and poor cycle performance; compared with lithium cobalt oxide, lithium nickel cobalt manganese oxide has low cost, high specific capacity, good safety and environmental friendliness, but low platform voltage and lower compaction density; although lithium iron phosphate has good electrochemical properties, it is expensive and has poor safety.
  • lithium-rich manganese-based positive electrode materials have become a research hotspot because of their advantages such as high discharge specific capacity, high discharge voltage, high energy density, low cost, high safety and long cycle life. Moreover, lithium-rich manganese-based positive electrode materials not only have the same lithium replenishing effect as other lithium replenishing materials, but can also be used as positive electrode materials themselves. Lithium replenishing materials can make up for the irreversible capacity loss caused by the formation of SEI film during the first charging process of lithium-ion batteries. Therefore, there is great market potential in the future.
  • the technical problem to be solved by the present invention is to provide a
  • the positive electrode material has at least one doped conductive layer, and the material structure is stable, and the rate performance and cycle stability are high.
  • the present invention provides a positive electrode material, comprising a lithium-rich material core and a conductive layer coated on the surface of the lithium-rich material core; at least one of the core and the conductive layer is doped with at least one of elements P and B.
  • the positive electrode material of the present invention includes a lithium-rich material core.
  • the lithium-rich material is a lithium-rich manganese-based material with a molecular formula of Li 1+x R y Mn z O s ; wherein R is selected from metal elements, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 1 ⁇ s ⁇ 4.
  • R is selected from at least one of transition metal elements such as Ni, Fe, Co, V, Cu, Mo, Al, Ti, Mg, Cr, Zr, Sn, and Zn.
  • the D50 of the lithium-rich material core of the present invention is too small, the particles will easily agglomerate, resulting in increased electronic conductivity and the internal resistance of the prepared lithium-ion battery, and poor performance; if the D50 is too large, the diffusion path of Li + will become larger, making the Li + diffusion kinetics slower, greatly reducing the reversible capacity of the material.
  • the D50 of the lithium-rich material core is 0.3 ⁇ m to 50 ⁇ m. Within this range, the particles are not easy to agglomerate and the diffusion path is moderate, which is conducive to the performance of the material's charge and discharge performance.
  • the positive electrode material of the present invention includes a conductive layer coated on the surface of the lithium-rich material core.
  • the conductive layer of the present invention is a conductive encapsulation layer coated on the surface of the lithium-rich material core, which is uniformly coated on the outer surface of the core, and the conductive layer includes at least one of a carbon layer, a conductive polymer layer or a conductive oxide layer.
  • the carbon includes at least one of amorphous carbon, carbon nanotubes, graphite, carbon black, graphene, etc.;
  • the conductive oxide may include at least one of In 2 O 3 , ZnO, SnO 2 ;
  • the conductive polymer includes at least one of an organic polymer with a structure of [C 6 H 7 O 6 Na] n , an organic polymer with a structure of [C 6 H 7 O 2 (OH) 2 OCH 2 COONa] n , an organic polymer with a structure of [C 3 H 4 O 2 ] n , an organic polymer with a structure of [C 3 H 3 O 2 Ma ] n , an organic polymer with a structure of [C 3 H 3 N] n , an organic polymer containing a -[CH 2 -CF 2 ] n - structure, etc.
  • the mass fraction of the conductive layer in the positive electrode material of the present invention is preferably 0.05wt% to 10wt%;
  • the thickness of the conductive layer is preferably 1 nm to 50 nm.
  • At least one of the core and the conductive layer of the present invention is doped with at least one of the elements P and B; wherein the element P can inhibit the structural transformation of the positive electrode material from layered to spinel, and the doping of the element B can also effectively inhibit the structural transformation of the positive electrode material, and can also inhibit the activity of side reactions on the surface of the positive electrode material, thereby improving the cycle performance of the positive electrode material.
  • only the conductive layer may be doped with at least one of the elements P and B, or only the core may be doped with at least one of the elements P and B, or both the core and the conductive layer may be doped with at least one of the elements P and B.
  • the conductive layer is a carbon layer, and only the carbon layer is doped with element P.
  • the carbon layer of the present invention improves the conductivity of the positive electrode material, and element P inhibits the structural transformation of the positive electrode material from layered to spinel.
  • the conductive layer is a carbon layer, and only the carbon layer is doped with element B.
  • the carbon layer of the present invention improves the conductivity of the positive electrode material, while element B inhibits the structural transformation of the positive electrode material from layered to spinel, and also inhibits the activity of side reactions on the surface of the positive electrode material, thereby improving the cycle performance of the positive electrode material.
  • the conductive layer is a carbon layer, and only the carbon layer is doped with elements P and B.
  • the elements P and B may be uniformly distributed in the carbon layer, or may be distributed in a gradient from the outside to the inside.
  • the conductive layer is a carbon layer, and only the carbon layer is doped with elements P and B, and the doping amounts of the elements P and B in the carbon layer increase from the outside to the inside.
  • the gradient distribution of elements P and B can form a gradient distribution of the concentration of the doping elements in the carbon layer, with a higher concentration near the surface of the lithium-rich material core, which can effectively inhibit side reactions and metal dissolution and prevent the transformation of the material structure, while the concentration far from the surface of the lithium-rich material core is lower, which means that the pure carbon layer can further improve the conductivity of the material, thereby improving the cycle stability of the positive electrode material.
  • the conductive layer is doped with elements P and B, and the mass fraction of the elements P and B in the positive electrode material is 0.01wt% to 5wt%. It should be noted that if the doping amount of elements P and B is too low, the side reaction and metal dissolution cannot be effectively suppressed, thereby causing a change in the material structure; if the doping amount of elements P and B is too high, the proportion of active substances in the positive electrode material will be reduced, thereby causing the specific capacity of the positive electrode material to decrease. Therefore, the use of an appropriate amount of element doping in the present invention is conducive to suppressing the side reaction between the electrode surface and the electrolyte during the cycle, thereby improving the positive electrode material. cycle stability.
  • the conductive layer is doped with elements P and B, and the molar ratio of the elements P and B is 1:1 to 2.5. It can be understood that compared with the doping of element P, the doping of element B can not only effectively inhibit the structural transformation of the positive electrode material, but also inhibit the activity of the side reaction on the surface of the positive electrode material. Therefore, appropriately increasing the doping of element B can further improve the cycle performance of the positive electrode material.
  • the molar ratio of the elements P and B can be 1:1, 1:1.5 or 1:2, etc.
  • the positive electrode material provided by the present invention has a lithium-rich material as the core, the surface of the core is coated with a conductive layer, and at least one of the core and the conductive layer is doped with at least one of the elements P and B, which can inhibit the side reaction of the active material with the electrolyte, thereby stabilizing the material structure; at the same time, a conductive dense layer is provided, the conductivity is improved, and the rate performance and cycle stability of the material are improved.
  • the present invention provides a method for preparing the above-mentioned positive electrode material, comprising: mixing and sintering at least one of a phosphorus source and a boron source, a conductive material and a lithium-rich material.
  • the lithium-rich material is a lithium-rich manganese - based material with a molecular formula of Li1 + xRyMnzOs ; wherein R is selected from metal elements, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 1 ⁇ s ⁇ 4.
  • R is selected from at least one of transition metal elements such as Ni, Fe, Co, V, Cu, Mo, Al, Ti, Mg, Cr, Zr, Sn, and Zn.
  • the phosphorus source is selected from at least one of an organic phosphorus source or an inorganic phosphorus source;
  • the organic phosphorus source is selected from at least one of tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, and tetraphenylphosphonium chloride;
  • the inorganic phosphorus source is selected from at least one of sodium pyrophosphate, potassium pyrophosphate, sodium acid pyrophosphate, and potassium acid pyrophosphate.
  • the boron source is selected from at least one of an organic boron source or an inorganic boron source; the organic boron source is selected from at least one of sodium tetraphenylborate, tetraphenylboron bromide, and potassium tetraphenylborate ; the inorganic boron source is selected from at least one of sodium borohydride, boric acid, B2O3 , and B2H6 .
  • the conductive material is selected from at least one of a carbon material, a conductive polymer or a conductive oxide.
  • the carbon material includes at least one of amorphous carbon, carbon nanotubes, graphite, carbon black, graphene, sucrose, glucose, citric acid, fructose, stearic acid, lauric acid, etc.
  • the conductive oxide may include at least one of In 2 O 3 , ZnO, SnO 2
  • the conductive polymer includes an organic polymer with a structure of [C 6 H 7 O 6 Na] n , an organic polymer with a structure of [C 6 H 7 O 2 (OH) 2 OCH 2 COONa] n , an organic polymer with a structure of [C 3 H 4 O 2 ] n , an organic polymer with a structure of [C 3 H 3 O 2 Ma ] n, an organic polymer with a structure of [C 3 H 3 N] n , or
  • the sintering temperature is 300° C. to 500° C.
  • the sintering time is 2 h to 6 h.
  • the preparation method provided by the present invention can prepare three positive electrode materials with different structures.
  • the prepared positive electrode material has the lithium-rich material as the core, and the surface of the core is coated with a conductive layer doped with at least one of the elements P and B; or, the lithium-rich material is the core, the surface of the core is coated with a conductive layer, and at least one of the elements P and B is doped in the core; or, the prepared positive electrode material has the lithium-rich material as the core, the surface of the core is coated with a conductive layer, and the core and the conductive layer are independently doped with at least one of the elements P and B.
  • the present invention can firstly mix at least one of the phosphorus source and the boron source with a conductive material to obtain a conductive material doped with at least one of the elements P and B, and then mix the conductive material with a lithium-rich material and sinter them.
  • the obtained positive electrode material has the lithium-rich material as the core, and the surface of the core is coated with a conductive layer doped with at least one of the elements P and B.
  • the phosphorus source, boron source and conductive material are mixed and reacted in a solution to obtain a conductive material doped with elements P and B; the conductive material doped with elements P and B and the lithium-rich material are mixed and sintered to obtain the above-mentioned positive electrode material.
  • the phosphorus source, boron source and conductive material are dissolved in anhydrous ethanol, mixed and reacted, and dried to obtain a conductive material doped with elements P and B; the conductive material doped with elements P and B and the lithium-rich material are mixed, stirred in anhydrous ethanol, dried and sintered in a protective gas atmosphere to obtain the above-mentioned positive electrode material.
  • the protective gas of the present invention is selected from at least one of nitrogen, helium or argon; the phosphorus source, boron source, conductive material and lithium-rich material are the same as those described above and will not be described in detail.
  • the mass ratio of the phosphorus source to the boron source is 1:0.5-8; the mass fraction of the carbon material doped with elements P and B in the total amount after mixing with the lithium-rich material is 0.05wt%-20wt%.
  • the reaction temperature is 150°C-180°C, and the reaction time is 5h-12h.
  • the sintering temperature of the present invention is the same as that described above and will not be described in detail.
  • the phosphorus source and boron source of the present invention are preferably selected from organic phosphorus sources and organic boron sources.
  • Organic matter is used as the phosphorus source and boron source, and a conductive layer can be formed without adding additional conductive materials, which is simpler to operate and has lower costs.
  • the organic phosphorus source and the organic boron source are mixed and reacted to obtain a carbon material doped with elements P and B, and then the carbon material is mixed and sintered with a lithium-rich material to obtain a positive electrode material with the lithium-rich material as the core and a carbon layer doped with elements P and B on the surface of the core.
  • the organic phosphorus source and the organic boron source are mixed and reacted to obtain a carbon material doped with elements P and B.
  • the organic phosphorus source and the organic boron source are mixed and reacted in a solution to obtain a carbon material doped with elements P and B; the carbon material doped with elements P and B and the lithium-rich material are mixed and sintered to obtain the above-mentioned positive electrode material.
  • the organic phosphorus source and the organic boron source are dissolved in anhydrous ethanol and mixed and reacted, and the carbon material doped with elements P and B is obtained after drying; the carbon material doped with elements P and B and the lithium-rich material are mixed, stirred in anhydrous ethanol, dried and sintered under a protective gas atmosphere to obtain the above-mentioned positive electrode material.
  • the protective gas, organic phosphorus source, organic boron source, lithium-rich material, the temperature and time of the reaction, the temperature and time of the sintering, the mass ratio of the phosphorus source and the boron source, and the mass fraction of the carbon material doped with elements P and B in the total amount after mixing with the lithium-rich manganese-based material are the same as above and will not be repeated.
  • the present invention can use a spraying method to make the elements P and B gradiently doped in the conductive layer from the outside to the inside.
  • the present invention sprays a solution containing a phosphorus source, a boron source and a conductive material on the surface of the heated lithium-rich material, and presses it; then repeats the steps of spraying and pressing on the sprayed and pressed lithium-rich material, that is, pressing once for each spraying.
  • Such an operation can make the inner layer more pressed, and the doping amount of elements B and P is also greater.
  • it includes: A) spraying a solution containing a phosphorus source, a boron source and a conductive material on the surface of the heated lithium-rich material, and pressing; B) after repeating the step A), calcining the obtained product, and the obtained positive electrode material has the lithium-rich material as the core, and the surface of the core is coated with a conductive layer doped with elements P and B, and the elements P and B are gradiently doped in the conductive layer from the outside to the inside.
  • the method comprises: A) spraying a mixed solution of a phosphorus source, a boron source and a conductive material on the surface of a lithium-rich material at a temperature of 200°C to 300°C, and then pressing the obtained product into a cake shape; B) repeating step A), calcining the obtained product under an inert gas atmosphere to obtain the above-mentioned positive electrode material.
  • the number of repetitions is 10 to 50 times.
  • the concentration of the mixed solution is 1 mol/L to 3 mol/L, preferably 2 mol/L; the mass ratio of the phosphorus source, boron source and carbon source in the mixed solution is 0.5 to 1.5:0.5 to 4:10 to 15, preferably 1:3.5:12.
  • the calcination temperature is 300°C to 500°C, preferably 400°C; the calcination time is 5h to 10h.
  • the inert gas is selected from at least one of helium and argon.
  • the phosphorus source, boron source, conductive material and lithium-rich material of the present invention are the same as those described above and will not be repeated.
  • the present invention can firstly mix and sinter at least one of the phosphorus source and the boron source with a lithium-rich material to obtain a lithium-rich material doped with at least one of the elements P and B, and then mix and sinter the lithium-rich material doped with at least one of the elements P and B with a conductive material to obtain a positive electrode material with the lithium-rich
  • the material is a core, the surface of the core is coated with a conductive layer, and at least one of the elements P and B is doped in the core.
  • the phosphorus source, boron source, conductive material, lithium-rich material, sintering temperature and time, and the mass ratio of the phosphorus source and the boron source of the present invention are the same as those described above and are not repeated here.
  • the present invention can also directly mix and sinter at least one of the phosphorus source and the boron source, the conductive material and the lithium-rich material together, and the obtained positive electrode material has the lithium-rich material as the core, the surface of the core is coated with a conductive layer, and the core and the conductive layer are independently doped with at least one of the elements P and B.
  • the phosphorus source, boron source, conductive material and lithium-rich material, the sintering temperature and time, and the mass ratio of the phosphorus source and the boron source of the present invention are the same as those described above and will not be repeated.
  • the lithium-rich material is selected from the lithium-rich manganese -based material with the molecular formula Li1 + xRyMnzOs , and the preparation method thereof comprises the following steps: mixing a manganese source, an R source, a precipitant and a complexing agent, and reacting in a solution to obtain a precursor; mixing the precursor with a lithium source, and calcining to obtain a lithium-rich manganese-based material.
  • a solution containing a manganese source and an R source is mixed with a solution containing a precipitant and a complexing agent under a nitrogen or argon atmosphere and the mixing conditions are controlled to perform co-precipitation to obtain a precursor; the precursor is mixed with a lithium source, and calcined at high temperature to obtain a lithium-rich manganese-based material.
  • a solution containing a manganese source and a N source is mixed with a solution containing a precipitant and a complexing agent at a temperature of 50°C to 60°C under a nitrogen or argon atmosphere, and stirred at a speed of 600rpm to 800rpm, and the pH value is adjusted to 9.5 to 10.5, and co-precipitation is performed for 20h to 30h to obtain a precursor; the precursor is mixed with a lithium source, and calcined at high temperature, and naturally cooled to obtain a lithium-rich manganese-based material.
  • the calcination of the present invention is a three-stage calcination, that is, the temperature is increased to 300°C to 500°C at a heating rate of 2°C/min to 5°C/min, and the temperature is kept for 2h to 6h, and then the temperature is increased to 750°C to 900°C at a heating rate of 2°C/min to 5°C/min, and the temperature is kept for 8h to 15h, and the temperature is reduced to 500°C to 700°C at a rate of 2°C/min to 5°C/min, and the temperature is kept for 10h to 15h.
  • the manganese source of the present invention is selected from at least one of MnSO 4 , Mn(NO 3 ) 2 or MnCO 3 ;
  • the R source is selected from salts of Ni, Fe, Co, V, Cu, Mo, Al, Ti, Mg, Cr, Zr, Sn or Zn, and the salt is at least one of sulfate, nitrate or carbonate;
  • the precipitant is selected from at least one of hydroxide, carbonate or oxalate;
  • the complexing agent is selected from at least one of ammonia, citric acid or ethylenediamine;
  • the lithium source is selected from at least one of LiOH ⁇ H 2 O, LiNO 3 , Li 2 CO 3 , LiF or Li 2 O.
  • the molar ratio of the lithium source to the precursor is 1 to 1.5:1.
  • the present invention provides a positive electrode, comprising the positive electrode material or the positive electrode material obtained by the above preparation method.
  • the positive electrode is a positive electrode of a lithium ion battery.
  • the present invention also provides a battery, comprising the positive electrode, the negative electrode and a
  • the negative electrode and the separator of the present invention are independently common negative electrodes and separators for those skilled in the art.
  • the battery is a lithium-ion battery, comprising the lithium-ion battery positive electrode, the negative electrode and the separator stacked between the positive electrode and the negative electrode.
  • the present invention provides a positive electrode material, comprising a lithium-rich material core and a conductive layer coated on the surface of the lithium-rich material core; at least one of the core and the conductive layer is doped with at least one of elements P and B; wherein the element P can inhibit the structural transformation of the positive electrode material from layered to spinel, and the doping of the element B can also effectively inhibit the structural transformation of the positive electrode material, and can also inhibit the activity of side reactions on the surface of the positive electrode material, thereby improving the cycle performance of the positive electrode material.
  • the positive electrode material provided by the present invention has a conductive layer doped with at least one of elements P and B, and the material structure is stable, and the rate performance and cycle stability are high.
  • the present invention discloses a positive electrode material and a preparation method thereof, a positive electrode and a battery.
  • Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve it. It is particularly important to point out that all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention.
  • the method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.
  • the present embodiment provides a B, P co-doped carbon-coated manganese-rich positive electrode material (B,P@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ), which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, and a conductive layer is coated on the surface of the core, and the conductive layer is a carbon layer co-doped with B and P, wherein the mass fraction of the carbon layer in the positive electrode material is 0.05wt%, the thickness of the carbon layer is 1nm, the molar ratio of the elements P and B is 1:1, and the mass fraction of the elements P and B in the positive electrode material is 0.01wt%.
  • Step 2 uniformly mix Ni 0.35 Mn 0.65 (OH) 2 and LiOH ⁇ H 2 O at a molar ratio of 1:1.3, put it into a tubular furnace in an air atmosphere, first increase the temperature from room temperature to 500°C at a heating rate of 5°C/min and keep it for 5 hours, then increase the temperature to 850°C at the same heating rate and calcine for 12 hours, and then cool it to 600°C at the same cooling rate and keep it for 10 hours, finally obtaining the lithium-rich manganese-based material Li 1.3 Ni 0.35 Mn 0.65 O 2 .
  • Step 3 tetraphenylphosphonium bromide and sodium tetraphenylborate in a mass ratio of 1:0.82 are dissolved in anhydrous ethanol, and the mixture is placed in a water bath at 180° C. for 5 hours and then dried to obtain B and P co-doped carbon (B,P@C).
  • Step 4 1w% B,P@C, Li 1.3 Ni 0.35 Mn 0.65 O 2 and anhydrous ethanol are mixed and stirred for 4 hours, and then dried and heat treated at 400°C for 2 hours in a nitrogen atmosphere to finally obtain a B,P co-doped carbon-coated manganese-rich positive electrode material (B,P@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ).
  • the present embodiment provides a B, P co-doped carbon-coated manganese-rich positive electrode material (B,P@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ), which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, and a conductive layer is coated on the surface of the core, and the conductive layer is a carbon layer co-doped with B and P, wherein the mass fraction of the carbon layer in the positive electrode material is 1.5wt%, the thickness of the carbon layer is 2nm, the molar ratio of the elements P and B is 1:1.22, and the mass fraction of the elements P and B in the positive electrode material is 0.05wt%.
  • the preparation method of the product in this embodiment is different from that in Example 1 in that the 1w% B,P@C in step 4 is changed to 3w% B,P@C, and the other steps remain the same.
  • the present embodiment provides a B, P co-doped carbon-coated manganese-rich positive electrode material (B,P@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ), which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, and a conductive layer is coated on the surface of the core, and the conductive layer is a carbon layer co-doped with B and P, wherein the mass fraction of the carbon layer in the positive electrode material is 10wt%, the thickness of the carbon layer is 50nm, the molar ratio of the elements P and B is 1:2.5, and the mass fraction of the elements P and B in the positive electrode material is 5wt%.
  • the preparation method of the product in this embodiment is different from that in embodiment 1 in that the 1w% B,P@C in step 4 is changed to 20w% B,P@C, and the other steps remain the same.
  • This embodiment provides a B, P co-doped carbon-coated manganese-rich positive electrode material (B, P@C@Li 1.2 Fe 0.2 Mn 0.6 O 2 ), which has Li 1.2 Fe 0.2 Mn 0.6 O 2 as a core, and a conductive layer is coated on the surface of the core, and the conductive layer is a carbon layer co-doped with B and P, wherein the mass fraction of the carbon layer in the positive electrode material is 2.1wt%, the thickness of the carbon layer is 2.8nm, the molar ratio of the elements P and B is 1:1.24, and the molar ratio of the elements P and B is 1:1.24.
  • the mass fraction of the positive electrode material is 0.08wt%.
  • Step 2 Fe 0.2 Mn 0.6 (OH) 2 and LiOH ⁇ H 2 O are uniformly mixed at a molar ratio of 1:1.25, and placed in an air atmosphere of a tubular furnace.
  • the temperature is increased from room temperature to 450°C at a heating rate of 3°C/min and kept for 4 hours, then the temperature is increased to 800°C at the same heating rate and calcined for 12 hours, and then the temperature is reduced to 650°C at the same cooling rate and kept for 12 hours, finally obtaining a lithium-rich manganese-based positive electrode material Li 1.2 Fe 0.2 Mn 0.6 O 2 .
  • Step 3 tetraphenylphosphonium bromide and sodium tetraphenylborate in a mass ratio of 1:1.01 are dissolved in anhydrous ethanol, and the mixture is placed in a water bath at 160° C. for 8 hours and then dried to obtain B and P co-doped carbon (B,P@C).
  • Step 4 4w% B,P@C , Li1.2Fe0.2Mn0.6O2 and anhydrous ethanol are mixed and stirred for 5h, and then dried and heat treated at 450°C for 4h in a nitrogen atmosphere to finally obtain a B,P co - doped carbon-coated manganese - rich positive electrode material (B,P@C@ Li1.2Fe0.2Mn0.6O2 ).
  • This embodiment provides a positive electrode material, which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, the core is a B and P co-doped core, the core surface is coated with a carbon layer, wherein the carbon layer accounts for 1.8wt% of the positive electrode material, the thickness of the carbon layer is 2.4nm, the molar ratio of the elements P and B is 1:1.23, and the mass fraction of the elements P and B in the positive electrode material is 0.065wt%.
  • Step 2 Ni 0.35 Mn 0.65 (OH) 2 , LiOH ⁇ H 2 O, B 2 O 3 and Na 4 P 2 O 7 were uniformly mixed in a molar ratio of 1:1.3:0.0246:0.02, and placed in a tubular furnace in an air atmosphere.
  • the mixture was first heated from room temperature to 500°C at a heating rate of 5°C/min and kept at that temperature for 5 h. Then, the mixture was heated to 800°C at the same heating rate and calcined. 15h, and then cooled to 550°C at the same cooling rate and kept for 15h, finally obtaining B, P co-doped manganese-rich positive electrode material B,P@Li 1.3 Ni 0.35 Mn 0.65 O 2 .
  • Step 3 after ball milling B,P@Li 1.3 Ni 0.35 Mn 0.65 O 2 and 3wt% C 8 H 11 NO 2 at 25 Hz for 60 min, put it into a tubular furnace in an argon atmosphere, and heat it from room temperature to 550°C at a heating rate of 2°C/min for 3 h, finally obtaining a B, P co-doped manganese-rich positive electrode material and carbon coating it (B,P@Li 1.3 Ni 0.35 Mn 0.65 O 2 @C).
  • the present embodiment provides a positive electrode material, which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, the core is a B and P co-doped core, the surface of the core is coated with a B and P co-doped carbon layer, wherein the mass fraction of the carbon layer in the positive electrode material is 2.3wt%, the thickness of the carbon layer is 2.9nm, the molar ratio of the elements P and B is 1:1.27, and the mass fraction of the elements P and B in the positive electrode material is 0.11wt%.
  • the preparation of lithium-rich manganese-based positive electrode materials with element co-doping in both the core and the carbon layer is carried out according to the following steps:
  • Step 2 Ni 0.35 Mn 0.65 (OH) 2 , LiOH ⁇ H 2 O, B 2 O 3 , Na 4 P 2 O 7 and C 6 H 12 O 6 are uniformly mixed by ball milling at a molar ratio of 1:1.3:0.0254:0.02:0.05, and placed in a tubular furnace in an air atmosphere, firstly, the temperature is increased from room temperature to 450°C at a heating rate of 3°C/min and kept for 5 hours, then the temperature is increased to 780°C at the same heating rate and calcined for 10 hours, and then the temperature is reduced to 650°C at the same cooling rate and kept for 12 hours, finally obtaining B and P co-doped carbon-coated manganese-rich positive electrode material B,P-Li 1.3 Ni 0.35 Mn 0.65 O 2 @C.
  • the present embodiment provides a B-doped carbon-coated manganese-rich positive electrode material (B@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ), which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, and a conductive layer is coated on the surface of the core, and the conductive layer is a B-doped carbon layer, wherein the mass fraction of the carbon layer in the positive electrode material is 1.83wt%, the thickness of the carbon layer is 2.4nm, and the mass fraction of element B in the positive electrode material is 0.062wt%.
  • B element doped carbon coated lithium-rich manganese-based positive electrode material is carried out according to the following steps:
  • Step 2 uniformly mix Ni 0.35 Mn 0.65 (OH) 2 and LiOH ⁇ H 2 O at a molar ratio of 1:1.3, put it into a tubular furnace in an air atmosphere, first increase the temperature from room temperature to 500°C at a heating rate of 5°C/min and keep it for 5 hours, then increase the temperature to 850°C at the same heating rate and calcine for 12 hours, and then cool it to 600°C at the same cooling rate and keep it for 10 hours, finally obtaining the lithium-rich manganese-based material Li 1.3 Ni 0.35 Mn 0.65 O 2 .
  • Step 3 dissolving sodium tetraphenylborate in anhydrous ethanol at a mass percentage of 9.2 wt%, and drying in a water bath at 170° C. for 5 h to obtain B-doped carbon (B@C).
  • Step 4 1.2w% B@C, Li1.3Ni0.35Mn0.65O2 and anhydrous ethanol are mixed and stirred for 4h, dried and then heat treated at 500°C for 2h in a nitrogen atmosphere to finally obtain a B-doped carbon-coated manganese - rich positive electrode material (B@C @ Li1.3Ni0.35Mn0.65O2 ).
  • the present embodiment provides a P-doped carbon-coated manganese-rich positive electrode material (P@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ), which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, and a conductive layer is coated on the surface of the core, and the conductive layer is a P-doped carbon layer, wherein the mass fraction of the carbon layer in the positive electrode material is 1.58wt%, the thickness of the carbon layer is 2.1nm, and the mass fraction of the element P in the positive electrode material is 0.054wt%.
  • P@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 a P-doped carbon layer
  • the preparation of P-doped carbon-coated lithium-rich manganese-based positive electrode material is carried out according to the following steps:
  • Step 2 uniformly mix Ni 0.35 Mn 0.65 (OH) 2 and LiOH ⁇ H 2 O at a molar ratio of 1:1.3, put it into a tubular furnace in an air atmosphere, first increase the temperature from room temperature to 500°C at a heating rate of 5°C/min and keep it for 5 hours, then increase the temperature to 850°C at the same heating rate and calcine for 12 hours, and then cool it to 600°C at the same cooling rate and keep it for 10 hours, finally obtaining the lithium-rich manganese-based material Li 1.3 Ni 0.35 Mn 0.65 O 2 .
  • Step 3 dissolving tetraphenylphosphonium bromide in anhydrous ethanol at a mass percentage of 7.9 wt%, and drying in a water bath at 150° C. for 10 h to obtain P-doped carbon (P@C).
  • Step 4 1.05w% P@C, Li1.3Ni0.35Mn0.65O2 and anhydrous ethanol are mixed and stirred for 4h, dried and then heat treated at 300°C for 6h in a nitrogen atmosphere to finally obtain a P-doped carbon-coated manganese - rich positive electrode material (P@C @ Li1.3Ni0.35Mn0.65O2 ).
  • the present embodiment provides a B, P co-doped carbon-coated manganese-rich positive electrode material (B,P-gradient@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ), which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, and a conductive layer is coated on the surface of the core, and the conductive layer is a B and P co-doped carbon layer, wherein the doping amounts of B and P in the carbon layer increase gradiently from the outside to the inside; the mass fraction of the carbon layer in the positive electrode material is 1.68wt%, the thickness of the carbon layer is 2.2nm, the molar ratio of the elements P and B is 1:1.23, and the mass fraction of the elements P and B in the positive electrode material is 0.058wt%.
  • Step 2 uniformly mix Ni 0.35 Mn 0.65 (OH) 2 and LiOH ⁇ H 2 O at a molar ratio of 1:1.3, put it into a tubular furnace in an air atmosphere, first increase the temperature from room temperature to 500°C at a heating rate of 5°C/min and keep it for 5 hours, then increase the temperature to 850°C at the same heating rate and calcine for 12 hours, and then cool it to 600°C at the same cooling rate and keep it for 10 hours, finally obtaining the lithium-rich manganese-based material Li 1.3 Ni 0.35 Mn 0.65 O 2 .
  • Step 3 heating Li 1.3 Ni 0.35 Mn 0.65 O 2 to 200°C, spraying a mixed solution of B 2 O 3 , Na 4 P 2 O 7 and C 8 H 11 NO 2 with a mass ratio of 1:3.5:12 and a concentration of 2 mol/L onto the surface of the Li 1.3 Ni 0.35 Mn 0.65 O 2 , and pressing the mixture into a cake-shaped product with a diameter of 2 cm and a thickness of 0.5 cm by external pressure, and repeatedly spraying the pressed product with the mixed solution and then pressing the pressed product, the number of repetitions being 22 times; heating the product after repeated spraying and pressing to 400°C for heat treatment for 8 hours under an argon atmosphere at a heating rate of 2°C/min, and finally obtaining a B, P gradient co-doped carbon-coated manganese-rich positive electrode material (B, P-gradient@C@Li 1.3 Ni 0.35 Mn 0.65 O 2 ).
  • This embodiment provides a carbon-coated manganese-rich positive electrode material (Li 1.3 Ni 0.35 Mn 0.65 O 2 @C), which has Li 1.3 Ni 0.35 Mn 0.65 O 2 as a core, and the surface of the core is coated with a conductive layer, and the conductive layer is a carbon layer.
  • the mass fraction of the carbon layer in the positive electrode material is 1.57wt%, and the thickness of the carbon layer is 2nm.
  • Positive electrode sheet The positive electrode materials of Examples 1 to 9 and Comparative Example 1 were respectively used as active materials, and the active materials were mixed with polyvinylidene fluoride and SP-Li in a mass ratio of 95:3:2 by ball milling to obtain positive electrode slurry, and the positive electrode slurry was coated on the surface of aluminum foil, and dried at 120° C. for 30 min to obtain positive electrode sheets;
  • Negative electrode lithium metal sheet
  • Electrolyte Ethylene carbonate and ethyl methyl carbonate were mixed in a volume ratio of 3:7, and LiPF 6 with a concentration of 1 mol/L was added to form an electrolyte;
  • 4Separator polypropylene microporous separator
  • Lithium-ion battery assembly Lithium-ion batteries are assembled in an inert atmosphere glove box in the order of negative electrode-diaphragm-electrolyte-positive electrode plate; wherein, the lithium-ion batteries corresponding to the positive electrode materials of Examples 1 to 9 are batteries A1 to A9, respectively, and the lithium-ion batteries corresponding to the positive electrode materials of Comparative Example 1 are battery B1, respectively.
  • the electrochemical performance of batteries A1-A9 and battery B1 was tested.
  • the test conditions were as follows: the assembled batteries were placed at room temperature for 6 hours before charge and discharge tests.
  • the charge and discharge voltage was 2.0-4.6V and the rate was 0.1C.
  • batteries A1 to A6 compared with batteries A1 and A3, battery A5 (elements are doped in the core and then coated with a carbon layer on the surface of the core), battery A6 (elements are doped in both the core and the carbon layer), battery A2 and battery A4 (using a liquid phase one-step synthesis method to form a P and B co-doped carbon layer) are more conducive to inhibiting the side reactions between the active material and the electrolyte, thereby stabilizing the material structure; at the same time, a conductive dense layer is provided, which improves the conductivity and the cycle stability of the material; it also has a better charge and discharge specific capacity and coulomb efficiency.
  • the core material changes, and the theoretical capacity is different.
  • the theoretical capacity of Li 1.3 Ni 0.35 Mn 0.65 O 2 is 358mAh/g
  • the theoretical capacity of Li 1.2 Fe 0.2 Mn 0.6 O 2 is 381mAh/g, so the performance of battery A4 will be slightly higher than other batteries.
  • batteries A7 and A8 the performance results in Table 2 show that their performance is slightly worse than that of batteries A2, A4, A5 and A6, which shows that the effect of doping only with element B or element P is slightly inferior to the effect of co-doping with element P and B, but the performance of batteries A7 and A8 is still much higher than that of battery B1.
  • the performance of battery A9 is slightly better than that of batteries A2, A4, A5 and A6, indicating that the gradient doping of doping elements can better suppress the side reactions between active materials and electrolytes and stabilize the material structure.

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Abstract

一种正极材料及其制备方法、正极和电池。正极材料包括富锂材料内核和包覆在富锂材料内核表面的导电层；富锂材料内核和导电层中的至少一种掺杂有元素P和B中的至少一种。正极材料具有元素P和B中的至少一种掺杂的导电层，能够稳定材料结构，进而提高材料的倍率性能和循环稳定性。

Description

一种正极材料及其制备方法、正极和电池
本申请要求于2022年11月01日提交中国国家知识产权局、申请号为202211356094.7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
本发明涉及锂离子电池领域，具体是一种正极材料及其制备方法、正极和电池。
背景技术
锂离子电池正极材料是锂离子电池的关键原材料之一，其性能的优劣直接影响锂离子电池的性能，目前市场上的正极材料主要有钴酸锂，尖晶石锰酸锂、镍钴锰酸锂、镍钴酸锂、磷酸亚铁锂等材料。其中，钴酸锂材料应用最为成熟，但资源储量有限且成本高；尖晶石锰酸锂材料价格低廉且安全性好，但比容量低、循环性能差；镍钴锰酸锂与钴酸锂相比成本低、比容量高、安全性好、环境友好，但平台电压低，压实密度也要更低；磷酸亚铁锂虽然电化学性能好，但价格高、安全性差。
目前，富锂锰基正极材料因为具有放电比容量高、放电电压高、能量密度高、成本低、安全性高、循环寿命长等优点而成为研究热点，而且富锂锰基正极材料不仅与其它补锂材料一样具有补锂效果，同时自身可以作为正极材料，补锂材料可以弥补锂离子电池在首次充电过程中因形成SEI膜而引起的不可逆容量的损失，因此未来市场潜力大，但其在循环过程中，材料的结构转变(从层状到尖晶石)造成电压的下降；尖晶石结构中Mn3+的Jahn-Teller效应也会使尖晶石结构逐渐被破坏造成容量的衰减；同时Mn3+与电解液中微量的HF发生歧化反应造成Mn溶解到电解液中，从而导致循环稳定性较差。
发明内容
有鉴于此，本发明所要解决的技术问题在于提供具有元素P和B中的至 少一种掺杂的导电层的正极材料，材料结构稳定，倍率性能和循环稳定性高。
本发明提供了一种正极材料，包括富锂材料内核和包覆在所述富锂材料内核表面的导电层；所述内核和所述导电层中的至少一种具有元素P和B中的至少一种掺杂。
本发明所述正极材料包括富锂材料内核。在本发明的某些实施例中，所述富锂材料为分子式为Li1+xRyMnzOs的富锂锰基材料；其中，R选自金属元素，0＜x≤1，0≤y＜1，0＜z≤1，1≤s≤4。在本发明的某些实施例中，所述R选自过渡金属元素如Ni、Fe、Co、V、Cu、Mo、Al、Ti、Mg、Cr、Zr、Sn、Zn中的至少一种。
本发明所述富锂材料内核的D50若过小，则颗粒会很容易团聚，从而导致电子传导性及所制备的锂离子电池的内阻增加，性能变差；若D50过大则会导致Li+的扩散路径变大，使得Li+扩散动力学较为缓慢，大大降低了材料的可逆容量。在本发明的某些实施例中，所述富锂材料内核的D50为0.3μm～50μm，在该范围内颗粒不容易发生团聚且扩散路径适中，有利于材料充放电性能的发挥。
本发明所述正极材料包括包覆在所述富锂材料内核表面的导电层。本发明所述导电层为包覆在所述富锂材料内核表面的导电封装层，其均匀包覆在所述内核的外表面，所述导电层包括碳层、导电聚合物层或导电氧化物层中的至少一种。在本发明的某些实施例中，所述碳包括无定形碳、碳纳米管、石墨、炭黑、石墨烯等中的至少一种；所述导电氧化物可以包括In2O3、ZnO、SnO2中的至少一种；所述导电聚合物包括以[C6H7O6Na]n为结构的有机聚合物、以[C6H7O2(OH)2OCH2COONa]n为结构的有机聚合物、以[C3H4O2]n为结构的有机聚合物、以[C3H3O2Ma]n为结构的有机聚合物、以[C3H3N]n为结构的有机聚合物、含有-[CH2-CF2]n-结构的有机聚合物等中的至少一种。
本发明所述导电层占所述正极材料的质量分数若过低，会导致导电层包覆的不连续，从而导致材料与电解液发生副反应；若导电层占所述正极材料的质量分数过高，会阻碍锂在脱嵌过程中的扩散并增加电极/电解液界面的电阻，阻碍电子运动，从而导致容量衰退；而在优选范围内则会形成均匀且薄的包覆层，锂离子和电子的正常传输得以保持，从而提高材料的性能。在本发明的某些实施例中，所述导电层占所述正极材料的质量分数优选为0.05wt％～10wt％； 所述导电层的厚度优选为1nm～50nm。
本发明所述内核和所述导电层中的至少一种具有元素P和B中的至少一种掺杂；其中，元素P能够抑制正极材料从层状到尖晶石的结构转变，元素B的掺杂同样能够有效抑制正极材料的结构转变，还能抑制正极材料表面副反应的活性，提高正极材料的循环性能。在本发明的某些实施例中，可以是仅所述导电层具有元素P和B中的至少一种掺杂，也可以是仅所述内核具有元素P和B中的至少一种掺杂，还可以是所述内核和所述导电层均具有元素P和B中的至少一种掺杂。
在本发明的某些实施例中，所述导电层为碳层，仅所述碳层具有元素P掺杂。本发明所述碳层提高了正极材料的导电性，同时元素P抑制了正极材料从层状到尖晶石的结构转变。
在本发明的某些实施例中，所述导电层为碳层，仅所述碳层具有元素B掺杂。本发明所述碳层提高了正极材料的导电性，同时元素B抑制了正极材料从层状到尖晶石的结构转变，还抑制了正极材料表面副反应的活性，提高正极材料的循环性能。
在本发明的某些实施例中，所述导电层为碳层，仅所述碳层具有元素P和B掺杂，所述元素P和B可以均匀分布在所述碳层中，也可以由外至内分呈梯度分布。
在一些实施例中，所述导电层为碳层，仅所述碳层具有元素P和B掺杂，碳层中所述元素P和B的掺杂量由外至内梯度增加。元素P和B的梯度分布可以使掺杂元素的浓度在碳层中形成一个梯度分布，在靠近富锂材料内核表面的浓度较高，可以有效抑制副反应和金属的溶出，防止材料结构的转变，而远离富锂材料内核表面的浓度较低，意味着纯碳层可以进一步改善材料的导电性，从而提高正极材料的循环稳定性。
在本发明的某些实施例中，所述导电层具有元素P和B掺杂，所述元素P和B占所述正极材料的质量分数为0.01wt％～5wt％，需要说明的是，如果元素P和B掺杂量过低，则不能有效抑制副反应和金属的溶出，从而导致材料结构的转变；如果元素P和B掺杂量过高，则会导致正极材料中活性物质占比减小，从而造成正极材料的比容量降低。因此，本发明采用适量的元素掺杂有利于抑制材料在循环过程中电极表面与电解液的副反应，从而提高正极材料 的循环稳定性。
在本发明的某些实施例中，所述导电层具有元素P和B掺杂，所述元素P和B的摩尔比1：1～2.5。可以理解的是，由于相较于元素P的掺杂，元素B的掺杂不仅能够有效抑制正极材料的结构转变，还能抑制正极材料表面副反应的活性，因此，适当提高元素B的掺杂能够进一步提高正极材料的循环性能。在一些实施例中，所述元素P和B的摩尔比可以为1：1、1：1.5或1：2等。
本发明提供的正极材料，以富锂材料为内核，所述内核表面包覆有导电层，并且所述内核和所述导电层中的至少一种具有元素P和B中的至少一种掺杂，可以抑制活性材料与电解液的副反应，从而稳定材料结构；同时提供了导电致密层，改善了导电性，提高了材料的倍率性能和循环稳定性。
本发明提供了上述正极材料的制备方法，包括：将磷源和硼源中的至少一种、导电材料和富锂材料混合烧结。在本发明的某些实施例中，所述富锂材料为分子式为Li1+xRyMnzOs的富锂锰基材料；其中，R选自金属元素，0＜x≤1，0≤y＜1，0＜z≤1，1≤s≤4。在本发明的某些实施例中，所述R选自过渡金属元素如Ni、Fe、Co、V、Cu、Mo、Al、Ti、Mg、Cr、Zr、Sn、Zn中的至少一种。
在本发明的某些实施例中，所述磷源选自有机磷源或无机磷源中的至少一种；所述有机磷源选自四苯基溴化磷中、四苯基碘化磷、四苯基氯化磷中的至少一种；所述无机磷源选自焦磷酸钠、焦磷酸钾、酸式焦磷酸钠、酸式焦磷酸钾中的至少一种。
在本发明的某些实施例中，所述硼源选自有机硼源或无机硼源中的至少一种；所述有机硼源选自四苯基硼酸钠、四苯基溴化硼、四苯基硼酸钾中的至少一种；所述无机硼源选自硼氢化钠、硼酸、B2O3、B2H6中的至少一种。
在本发明的某些实施例中，所述导电材料选自碳材料、导电聚合物或导电氧化物中的至少一种。在本发明的某些实施例中，所述碳材料包括无定形碳、碳纳米管、石墨、炭黑、石墨烯、蔗糖、葡萄糖、柠檬酸、果糖、硬脂酸、月桂酸等中的至少一种；所述导电氧化物可以包括In2O3、ZnO、SnO2中的至少一种；所述导电聚合物包括以[C6H7O6Na]n为结构的有机聚合物、以[C6H7O2(OH)2OCH2COONa]n为结构的有机聚合物、以[C3H4O2]n为结构的有机聚合物、以[C3H3O2Ma]n为结构的有机聚合物、以[C3H3N]n为结构的有机聚合 物、含有-[CH2-CF2]n-结构的有机聚合物等中的至少一种。在本发明的某些实施例中，所述烧结的温度为300℃～500℃，所述烧结的时间为2h～6h。
本发明提供的制备方法可以制备得到三种不同结构的正极材料，例如，制备得到的正极材料以所述富锂材料为内核，所述内核表面包覆有元素P和B中的至少一种掺杂的导电层；或者，以所述富锂材料为内核，所述内核表面包覆有导电层，所述元素P和B中的至少一种掺杂在所述内核中；或者，制备得到的正极材料以所述富锂材料为内核，所述内核表面包覆有导电层，所述内核和所述导电层独立地具有元素P和B中的至少一种掺杂。
本发明可以先将所述磷源和硼源中的至少一种与导电材料混合反应得到具有元素P和B中的至少一种掺杂的导电材料，再将所述导电材料与富锂材料混合烧结，得到的正极材料以所述富锂材料为内核，所述内核表面包覆有元素P和B中的至少一种掺杂的导电层。
在本发明的某些实施例中，将所述磷源、硼源和导电材料混合，在溶液中反应，得到具有元素P和B掺杂的导电材料；将所述具有元素P和B掺杂的导电材料和所述富锂材料混合烧结，得到上述正极材料。在本发明的某些实施例中，将所述磷源、硼源和导电材料溶解在无水乙醇中混合反应，烘干后得到具有元素P和B掺杂的导电材料；将所述具有元素P和B掺杂的导电材料和所述富锂材料混合，在无水乙醇中搅拌，烘干后在保护气体气氛下进行烧结，得到上述正极材料。
本发明所述保护气体选自氮气、氦气或氩气中的至少一种；所述磷源、硼源、导电材料和富锂材料与上述一样，不再赘述。在本发明的某些实施例中，所述磷源和硼源的质量比为1：0.5～8；所述具有元素P和B掺杂的碳材料占其与所述富锂材料混合后的总量的质量分数为0.05wt％～20wt％。在一些实施例中，所述反应的温度为150℃～180℃，所述反应的时间为5h～12h。本发明所述烧结的温度和上述一样，不再赘述。
本发明所述磷源和硼源优选选用有机磷源和有机硼源，以有机物作为磷源和硼源，不必额外添加导电材料便可形成导电层，操作更加简便，成本更低；将所述有机磷源和有机硼源混合反应能得到具有元素P和B掺杂的碳材料，再将所述碳材料与富锂材料混合烧结，得到以所述富锂材料为内核且所述内核表面包覆有元素P和B掺杂的碳层的正极材料。具体而言，将有机磷源和有 机硼源混合，在溶液中反应，得到具有元素P和B掺杂的碳材料；将所述具有元素P和B掺杂的碳材料和所述富锂材料混合烧结，得到上述正极材料。在本发明的某些实施例中，将有机磷源和有机硼源溶解在无水乙醇中混合反应，烘干后得到具有元素P和B掺杂的碳材料；将所述具有元素P和B掺杂的碳材料和所述富锂材料混合，在无水乙醇中搅拌，烘干后在保护气体气氛下进行烧结，得到上述正极材料。本发明所述保护气体、有机磷源、有机硼源、富锂材料、所述反应的温度和时间、所述烧结的温度和时间、所述磷源和硼源的质量比，以及所述具有元素P和B掺杂的碳材料占其与所述富锂锰基材料混合后的总量的质量分数，均和上述一样，不再赘述。
本发明在制备上述结构的正极材料时，可以通过喷涂的方法使得元素P和B由外至内梯度掺杂在所述导电层中。本发明将含有磷源、硼源和导电材料的溶液喷涂在加热的富锂材料表面，压制；然后对所述喷涂和压制后的富锂材料重复进行喷涂后压制的步骤，即每喷涂一次就压制一次，这样的操作能使越往内层被压制的次数越多，元素B和P的掺杂量也越多。具体而言，包括：A)将含有磷源、硼源和导电材料的溶液喷涂在加热的富锂材料表面，压制；B)重复进行所述步骤A)后，对所得产物进行煅烧，得到的正极材料以所述富锂材料为内核，所述内核表面包覆有元素P和B掺杂的导电层，所述元素P和B由外至内梯度掺杂在所述导电层中。在本发明的某些实施例中，包括：A)将磷源、硼源和导电材料的混合溶液喷涂在温度为200℃～300℃的富锂材料表面，然后将所得产物压制成饼状；B)重复进行所述步骤A)后，将所得产物在惰性气体氛围下煅烧，得到上述正极材料。在一些实施例中，所述重复的次数为10次～50次。在一些实施例中，所述混合溶液的浓度为1mol/L～3mol/L，优选为2mol/L；所述混合溶液中的磷源、硼源和碳源的质量比为0.5～1.5:0.5～4:10～15，优选为1:3.5:12。在一些实施例中，所述煅烧的温度为300℃～500℃，优选为400℃；所述煅烧的时间为5h～10h。在一些实施例中，所述惰性气体选自氦气、氩气中的至少一种。本发明所述磷源、硼源、导电材料和富锂材料与上述一样，不再赘述。
本发明可以先将所述磷源和硼源中的至少一种和富锂材料混合烧结得到具有元素P和B中的至少一种掺杂的富锂材料，再将所述具有元素P和B中的至少一种掺杂的富锂材料与导电材料混合烧结，得到的正极材料以所述富锂 材料为内核，所述内核表面包覆有导电层，所述元素P和B中的至少一种掺杂在所述内核中。本发明所述磷源、硼源、导电材料、富锂材料、所述烧结的温度和时间，以及所述磷源和硼源的质量比，均和上述一样，不在赘述。
本发明还可以直接将所述磷源和硼源中的至少一种、导电材料和富锂材料一同混合烧结，得到的正极材料以所述富锂材料为内核，所述内核表面包覆有导电层，所述内核和所述导电层独立地具有元素P和B中的至少一种掺杂。本发明所述磷源、硼源、导电材料和富锂材料，以及所述烧结的温度和时间，所述磷源和硼源的质量比，均和上述一样，不在赘述。
在本发明的某些实施例中，所述富锂材料选自上述分子式为Li1+xRyMnzOs的富锂锰基材料，其制备方法包括以下步骤：将锰源、R源、沉淀剂和络合剂混合，在溶液中反应得到前驱体；将所述前驱体与锂源混合，煅烧，得到富锂锰基材料。在一些实施例中，在氮气或氩气的气氛下将含锰源和R源的溶液与含沉淀剂和络合剂的溶液混合并控制混合条件进行共沉淀，得到前驱体；将所述前驱体与锂源混合，并高温煅烧，得到富锂锰基材料。在一些实施例中，在氮气或氩气的气氛下将含锰源和N源的溶液与含沉淀剂和络合剂的溶液在温度为50℃～60℃下混合，并以600rpm～800rpm的速度搅拌，调节pH值为9.5～10.5，进行共沉淀20h～30h，得到前驱体；将所述前驱体与锂源混合，并高温煅烧，自然冷却，得到富锂锰基材料。本发明所述煅烧为三段式煅烧，即以2℃/min～5℃/min的升温速率升温至300℃～500℃保温2h～6h，再以2℃/min～5℃/min的升温速率升温至750℃～900℃保温8h～15h，以2℃/min～5℃/min的速率降温至500℃～700℃保温10h～15h。
本发明所述锰源选自MnSO4、Mn(NO3)2或MnCO3中的至少一种；所述R源选自Ni、Fe、Co、V、Cu、Mo、Al、Ti、Mg、Cr、Zr、Sn或Zn的盐，所述盐为硫酸盐、硝酸盐或碳酸盐中的至少一种；所述沉淀剂选自氢氧化物、碳酸盐或草酸盐中的至少一种；所述络合剂选自氨水、柠檬酸或乙二胺中的至少一种；所述锂源选自LiOH·H2O、LiNO3、Li2CO3、LiF或Li2O中的至少一种。在本发明的某些实施例中，所述锂源和前驱体的摩尔比为1～1.5:1。
本发明提供了一种正极，包括上述正极材料或上述制备方法得到的正极材料。在本发明的某些实施例中，所述正极为锂离子电池正极。
本发明还提供了一种电池，包括上述提供的正极、负极和设置在所述正极 和负极之间的隔膜。本发明所述负极和隔膜独立地为本领域技术人员常见的负极和隔膜。在本发明的某些实施例中，所述电池为锂离子电池，包括上述提供的锂离子电池正极、负极和叠设于所述正极与负极之间的隔膜。
本发明提供了一种正极材料，包括富锂材料内核和包覆在所述富锂材料内核表面的导电层；所述内核和所述导电层中的至少一种具有元素P和B中的至少一种掺杂；其中，元素P能够抑制正极材料从层状到尖晶石的结构转变，元素B的掺杂同样能够有效抑制正极材料的结构转变，还能抑制正极材料表面副反应的活性，提高正极材料的循环性能。本发明提供的正极材料具有元素P和B中的至少一种掺杂的导电层，材料结构稳定，倍率性能和循环稳定性高。
具体实施方式
本发明公开了一种正极材料及其制备方法、正极和电池。本领域技术人员可以借鉴本文内容，适当改进工艺参数实现。特别需要指出的是，所有类似的替换和改动对本领域技术人员来说是显而易见的，它们都被视为包括在本发明。本发明的方法及应用已经通过较佳实施例进行了描述，相关人员明显能在不脱离本发明内容、精神和范围内对本文的方法和应用进行改动或适当变更与组合，来实现和应用本发明技术。
以下结合实施例对本发明进行进一步阐述：
实施例1
本实施例提供一种B、P共掺杂碳包覆富锰正极材料(B,P@C@Li1.3Ni0.35Mn0.65O2)，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核表面包覆有导电层，所述导电层为B和P共掺杂的碳层，其中碳层占所述正极材料的质量分数为0.05wt％，碳层的厚度为1nm，元素P和B的摩尔比为1：1，元素P和B占所述正极材料的质量分数为0.01wt％。
按照以下步骤进行元素共掺杂碳包覆富锂锰基正极材料的制备：
步骤1，在氮气气氛中，将浓度为1.6mol/L的硫酸镍和硫酸锰的水溶液(Ni/Mn＝0.35:0.65)泵入连续搅拌的反应器中，同时，将浓度为1.6mol/L的NaOH和一定浓度的NH4OH作为沉淀剂和络合剂分别泵入反应器中，在55℃、PH＝10.5、搅拌速度800rpm、反应时间20h，得到前驱体，所述前驱体的分子式为Ni0.35Mn0.65(OH)2。
步骤2，按摩尔比1：1.3，将Ni0.35Mn0.65(OH)2与LiOH·H2O均匀混合，将其放入管式炉空气气氛中，首先以5℃/min的升温速率从室温升至500℃保温5h，其次以相同的升温速率升温至850℃煅烧12h，再以相同的降温速率降温至600℃保温10h，最终得到富锂锰基材料Li1.3Ni0.35Mn0.65O2。
步骤3，将质量比为1：0.82的四苯基溴化磷、四苯基硼酸钠溶解在无水乙醇中，180℃水浴5h后烘干，得到B、P共掺杂的碳(B,P@C)。
步骤4，将1w％的B,P@C、Li1.3Ni0.35Mn0.65O2和无水乙醇混合搅拌4h，烘干后将其在氮气的气氛下，400℃热处理2h，最终得到一种B、P共掺杂碳包覆富锰正极材料(B,P@C@Li1.3Ni0.35Mn0.65O2)。
实施例2
本实施例提供一种B、P共掺杂碳包覆富锰正极材料(B,P@C@Li1.3Ni0.35Mn0.65O2)，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核表面包覆有导电层，所述导电层为B和P共掺杂的碳层，其中碳层占所述正极材料的质量分数为1.5wt％，碳层的厚度为2nm，元素P和B的摩尔比为1：1.22，元素P和B占所述正极材料的质量分数为0.05wt％。
本实施例产品的制备方法与实施例1的区别在于：步骤4中所述1w％的B,P@C更改为3w％的B,P@C，其他步骤保持一致。
实施例3
本实施例提供一种B、P共掺杂碳包覆富锰正极材料(B,P@C@Li1.3Ni0.35Mn0.65O2)，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核表面包覆有导电层，所述导电层为B和P共掺杂的碳层，其中碳层占所述正极材料的质量分数为10wt％，碳层的厚度为50nm，元素P和B的摩尔比为1：2.5，元素P和B占所述正极材料的质量分数为5wt％。
本实施例产品的制备方法与实施例1的区别在于：步骤4中所述1w％的B,P@C更改为20w％的B,P@C，其他步骤保持一致。
实施例4
本实施例提供一种B、P共掺杂碳包覆富锰正极材料(B,P@C@Li1.2Fe0.2Mn0.6O2)，其以Li1.2Fe0.2Mn0.6O2为内核，所述内核表面包覆有导电层，所述导电层为B和P共掺杂的碳层，其中碳层占所述正极材料的质量分数为2.1wt％，碳层的厚度为2.8nm，元素P和B的摩尔比为1：1.24，元素P和B 占所述正极材料的质量分数为0.08wt％。
按照以下步骤进行元素共掺杂碳包覆富锂锰基正极材料的制备：
步骤1，在氮气气氛中，将浓度为1.6mol/L的硫酸镍和硫酸锰的水溶液(Fe/Mn＝0.2:0.6)泵入连续搅拌的反应器中，同时，将浓度为1.6mol/L的NaOH和一定浓度的NH4OH作为沉淀剂和络合剂分别泵入反应器中，在50℃、PH＝10.2、搅拌速度600rpm、反应时间15h，得到前驱体，所述前驱体的分子式为Fe0.2Mn0.6(OH)2。
步骤2，按摩尔比1：1.25，将Fe0.2Mn0.6(OH)2与LiOH·H2O均匀混合，将其放入管式炉空气气氛中，首先以3℃/min的升温速率从室温升至450℃保温4h，其次以相同的升温速率升温至800℃煅烧12h，再以相同的降温速率降温至650℃保温12h，最终得到富锂锰基正极材料Li1.2Fe0.2Mn0.6O2。
步骤3，将质量比为1:1.01的四苯基溴化磷、四苯基硼酸钠溶解在无水乙醇中，160℃水浴8h后烘干，得到B、P共掺杂的碳(B,P@C)。
步骤4，将4w％的B,P@C、Li1.2Fe0.2Mn0.6O2和无水乙醇混合搅拌5h，烘干后将其在氮气的气氛下，450℃热处理4h，最终得到一种B、P共掺杂碳包覆富锰正极材料(B,P@C@Li1.2Fe0.2Mn0.6O2)。
实施例5
本实施例提供一种正极材料，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核为B和P共掺杂的内核，所述内核表面包覆有碳层，其中碳层占所述正极材料的质量分数为1.8wt％，碳层的厚度为2.4nm，元素P和B的摩尔比为1：1.23，元素P和B占所述正极材料的质量分数为0.065wt％。
按照以下步骤进行仅内核具有元素共掺杂的富锂锰基正极材料的制备：
步骤1，在氮气气氛中，将浓度为1.6mol/L的硫酸镍和硫酸锰的水溶液(Ni/Mn＝0.35:0.65)泵入连续搅拌的反应器中，同时，将浓度为1.6mol/L的NaOH和一定浓度的NH4OH作为沉淀剂和络合剂分别泵入反应器中，在55℃、PH＝10.5、搅拌速度800rpm、反应时间20h，得到前驱体，所述前驱体的分子式为Ni0.35Mn0.65(OH)2。
步骤2，按摩尔比1：1.3：0.0246：0.02，将Ni0.35Mn0.65(OH)2、LiOH·H2O、B2O3和Na4P2O7均匀混合，将其放入管式炉空气气氛中，首先以5℃/min的升温速率从室温升至500℃保温5h，其次以相同的升温速率升温至800℃煅烧 15h，再以相同的降温速率降温至550℃保温15h，最终得到B、P共掺杂富锰正极材料B,P@Li1.3Ni0.35Mn0.65O2。
步骤3，将B,P@Li1.3Ni0.35Mn0.65O2和3wt％C8H11NO2，在25Hz下球磨60min后，将其放入管式炉氩气气氛中，以2℃/min的升温速率从室温升至550℃保温3h，最终得到一种B、P共掺杂富锰正极材料并进行碳包覆(B,P@Li1.3Ni0.35Mn0.65O2@C)。
实施例6
本实施例提供一种正极材料，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核为B和P共掺杂的内核，所述内核表面包覆有B和P共掺杂的碳层，其中碳层占所述正极材料的质量分数为2.3wt％，碳层的厚度为2.9nm，元素P和B的摩尔比为1：1.27，元素P和B占所述正极材料的质量分数为0.11wt％。
按照以下步骤进行内核和碳层均具有元素共掺杂的富锂锰基正极材料的制备：
步骤1，在氮气气氛中，将浓度为1.6mol/L的硫酸镍和硫酸锰的水溶液(Ni/Mn＝0.35:0.65)泵入连续搅拌的反应器中，同时，将浓度为1.6mol/L的NaOH和一定浓度的NH4OH作为沉淀剂和络合剂分别泵入反应器中，在55℃、PH＝10.5、搅拌速度800rpm、反应时间20h，得到前驱体，所述前驱体的分子式为Ni0.35Mn0.65(OH)2。
步骤2，按摩尔比1：1.3：0.0254：0.02：0.05，将Ni0.35Mn0.65(OH)2、LiOH·H2O、B2O3、Na4P2O7和C6H12O6通过球磨均匀混合，将其放入管式炉空气气氛中，首先以3℃/min的升温速率从室温升至450℃保温5h，其次以相同的升温速率升温至780℃煅烧10h，再以相同的降温速率降温至650℃保温12h，最终得到B、P共掺杂于碳包覆的富锰正极材料B,P-Li1.3Ni0.35Mn0.65O2@C。
实施例7
本实施例提供一种B掺杂碳包覆富锰正极材料(B@C@Li1.3Ni0.35Mn0.65O2)，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核表面包覆有导电层，所述导电层为B掺杂的碳层，其中碳层占所述正极材料的质量分数为1.83wt％，碳层的厚度为2.4nm，元素B占所述正极材料的质量分数为0.062wt％。
按照以下步骤进行B元素掺杂碳包覆富锂锰基正极材料的制备：
步骤1，在氮气气氛中，将浓度为1.6mol/L的硫酸镍和硫酸锰的水溶液 (Ni/Mn＝0.35:0.65)泵入连续搅拌的反应器中，同时，将浓度为1.6mol/L的NaOH和一定浓度的NH4OH作为沉淀剂和络合剂分别泵入反应器中，在55℃、PH＝10.5、搅拌速度800rpm、反应时间20h，得到前驱体，所述前驱体的分子式为Ni0.35Mn0.65(OH)2。
步骤2，按摩尔比1：1.3，将Ni0.35Mn0.65(OH)2与LiOH·H2O均匀混合，将其放入管式炉空气气氛中，首先以5℃/min的升温速率从室温升至500℃保温5h，其次以相同的升温速率升温至850℃煅烧12h，再以相同的降温速率降温至600℃保温10h，最终得到富锂锰基材料Li1.3Ni0.35Mn0.65O2。
步骤3，将四苯基硼酸钠按9.2wt％的质量百分比溶解在无水乙醇中，170℃水浴5h后烘干，得到B掺杂的碳(B@C)。
步骤4，将1.2w％的B@C、Li1.3Ni0.35Mn0.65O2和无水乙醇混合搅拌4h，烘干后将其在氮气的气氛下，500℃热处理2h，最终得到一种B掺杂碳包覆富锰正极材料(B@C@Li1.3Ni0.35Mn0.65O2)。
实施例8
本实施例提供一种P掺杂碳包覆富锰正极材料(P@C@Li1.3Ni0.35Mn0.65O2)，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核表面包覆有导电层，所述导电层为P掺杂的碳层，其中碳层占所述正极材料的质量分数为1.58wt％，碳层的厚度为2.1nm，元素P占所述正极材料的质量分数为0.054wt％。
按照以下步骤进行P元素掺杂碳包覆富锂锰基正极材料的制备：
步骤1，在氮气气氛中，将浓度为1.6mol/L的硫酸镍和硫酸锰的水溶液(Ni/Mn＝0.35:0.65)泵入连续搅拌的反应器中，同时，将浓度为1.6mol/L的NaOH和一定浓度的NH4OH作为沉淀剂和络合剂分别泵入反应器中，在55℃、PH＝10.5、搅拌速度800rpm、反应时间20h，得到前驱体，所述前驱体的分子式为Ni0.35Mn0.65(OH)2。
步骤2，按摩尔比1：1.3，将Ni0.35Mn0.65(OH)2与LiOH·H2O均匀混合，将其放入管式炉空气气氛中，首先以5℃/min的升温速率从室温升至500℃保温5h，其次以相同的升温速率升温至850℃煅烧12h，再以相同的降温速率降温至600℃保温10h，最终得到富锂锰基材料Li1.3Ni0.35Mn0.65O2。
步骤3，将四苯基溴化磷按7.9wt％的质量百分比溶解在无水乙醇中，150℃水浴10h后烘干，得到P掺杂的碳(P@C)。
步骤4，将1.05w％的P@C、Li1.3Ni0.35Mn0.65O2和无水乙醇混合搅拌4h，烘干后将其在氮气的气氛下，300℃热处理6h，最终得到一种P掺杂碳包覆富锰正极材料(P@C@Li1.3Ni0.35Mn0.65O2)。
实施例9
本实施例提供一种B、P共掺杂碳包覆富锰正极材料(B,P-gradient@C@Li1.3Ni0.35Mn0.65O2)，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核表面包覆有导电层，所述导电层为B和P共掺杂的碳层，其中所述B和P的掺杂量在所述碳层中由外向内梯度增加；所述碳层占所述正极材料的质量分数为1.68wt％，碳层的厚度为2.2nm，元素P和B的摩尔比为1：1.23，元素P和B占所述正极材料的质量分数为0.058wt％。
按照以下步骤进行元素梯度共掺杂碳包覆富锂锰基正极材料的制备：
步骤1，在氮气气氛中，将浓度为1.6mol/L的硫酸镍和硫酸锰的水溶液(Ni/Mn＝0.35:0.65)泵入连续搅拌的反应器中，同时，将浓度为1.6mol/L的NaOH和一定浓度的NH4OH作为沉淀剂和络合剂分别泵入反应器中，在55℃、PH＝10.5、搅拌速度800rpm、反应时间20h，得到前驱体，所述前驱体的分子式为Ni0.35Mn0.65(OH)2。
步骤2，按摩尔比1：1.3，将Ni0.35Mn0.65(OH)2与LiOH·H2O均匀混合，将其放入管式炉空气气氛中，首先以5℃/min的升温速率从室温升至500℃保温5h，其次以相同的升温速率升温至850℃煅烧12h，再以相同的降温速率降温至600℃保温10h，最终得到富锂锰基材料Li1.3Ni0.35Mn0.65O2。
步骤3，将Li1.3Ni0.35Mn0.65O2加热至200℃，将浓度为2mol/L的质量比为1：3.5：12的B2O3、Na4P2O7和C8H11NO2的混合溶液喷涂至所述Li1.3Ni0.35Mn0.65O2表面，并通过外界压力压制成直径为2cm、厚度为0.5cm的饼状产物，重复对压制后所得产物用上述混合溶液进行喷涂后压制的步骤，所述重复的次数为22次；将重复喷涂和压制后所得产物在氩气的气氛下，升温速率在2℃/min的情况下，升温至400℃热处理8h，最终得到一种B、P梯度共掺杂碳包覆富锰正极材料(B,P-gradient@C@Li1.3Ni0.35Mn0.65O2)。
对比例1
本实施例提供一种碳包覆富锰正极材料(Li1.3Ni0.35Mn0.65O2@C)，其以Li1.3Ni0.35Mn0.65O2为内核，所述内核表面包覆有导电层，所述导电层为碳层， 其中碳层占所述正极材料的质量分数为1.57wt％，碳层的厚度为2nm。
性能测试
进一步的，为了验证本申请实施例的进步性，对实施例1～9和对比例1的富锂材料进行如下性能测试：
1、扣电评估方法：
A)电池组装：
①正极极片：分别以实施例1至实施例9和对比例1的正极材料作为活性物质，将所述活性物质与聚偏氟乙烯和SP-Li以95：3：2的质量比混合球磨搅拌得到正极浆料，将正极浆料涂覆在铝箔表面，120℃下干燥30min，分别得到正极极片；
②负极：锂金属片；
③电解液：将碳酸乙烯酯和碳酸甲乙酯以3:7的体积比混合，并加入浓度为1mol/L的LiPF6，形成电解液；
④隔膜：聚丙烯微孔隔；
⑤锂离子电池组装：按照负极-隔膜-电解液-正极极片的组装顺序在惰性气氛手套箱内组装得到锂离子电池；其中，实施例1～9正极材料对应的锂离子电池依次为电池A1～A9，对比例1正极材料对应的锂离子电池依次为电池B1。
B)性能测试：
对电池A1～A9和电池B1的电化学性能进行测试，测试条件为：将装配好的电池在室温下放置6h后进行充放电测试，充放电电压为2.0～4.6V，倍率为0.1C。
测试结果如下表2所示：
表2

从表2的电池B1的测试结果可以看出，单纯进行碳包覆，远不能达到稳定材料结构和提高性能的效果，从充放电比容量、库伦效率和0.1C循环50cycles的容量保持率的结果来看都不如电池A1～A9的测试结果。而从电池A1～A3的测试结果可以看出，将具有P和B共掺杂碳层的正极材料组装为电池，当所述碳层的厚度为2nm时，可以在富锂材料表面包覆一层薄且均匀的膜，使得材料达到性能最优。
在电池A1～A6中，与电池A1和A3相比，电池A5(元素掺杂于内核，再于内核表面包覆碳层)、电池A6(元素同时掺杂于内核和碳层中)、电池A2和电池A4(使用液相一步合成法形成P、B共掺杂的碳层)更有利抑制活性材料与电解液的副反应，从而稳定材料结构；同时提供了导电致密层，改善了导电性，提高了材料的循环稳定性；同样也具有更优异的充放电比容量和库伦效率。另外，内核材料改变，理论容量不一样，Li1.3Ni0.35Mn0.65O2的理论容量为358mAh/g，Li1.2Fe0.2Mn0.6O2的理论容量为381mAh/g，所以电池A4的性能会略高于其他电池。
对于电池A7和A8，由表2的性能结果可知，其性能稍差于电池A2、A4、A5和A6，由此可见仅掺杂了元素B或元素P的效果要稍逊于元素P和B共掺杂的效果，但电池A7和A8的性能仍然远高于电池B1的性能。而电池A9的性能则稍微优于电池A2、A4、A5和A6的性能，表明掺杂元素的梯度掺杂更能抑制活性材料与电解液的副反应，并稳定材料结构。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (18)

  1. 一种正极材料，其特征在于，包括富锂材料内核和包覆在所述富锂材料内核表面的导电层；
    所述内核和所述导电层中的至少一种具有元素P和B中的至少一种掺杂。
  2. 根据权利要求1所述的正极材料，其特征在于，所述富锂材料为分子式为Li1+xRyMnzOs的富锂锰基材料；
    其中，所述R选自金属元素中的至少一种，0＜x≤1，0≤y＜1，0＜z≤1，1≤s≤4。
  3. 根据权利要求1或2所述的正极材料，其特征在于，所述导电层包括碳层、导电聚合物层或导电氧化物层中的至少一种。
  4. 根据权利要求3所述的正极材料，其特征在于，所述导电层为碳层，所述碳层具有元素P掺杂。
  5. 根据权利要求3所述的正极材料，其特征在于，所述导电层为碳层，所述碳层具有元素B掺杂。
  6. 根据权利要求3所述的正极材料，其特征在于，所述导电层为碳层，所述碳层具有元素P和B掺杂。
  7. 根据权利要求6所述的正极材料，其特征在于，碳层中，所述元素P和B的掺杂量由外至内梯度增加。
  8. 根据权利要求1所述的正极材料，其特征在于，所述导电层占所述正极材料的质量分数为0.05wt％～10wt％；
    所述导电层的厚度为1nm～50nm。
  9. 根据权利要求6所述的正极材料，其特征在于，所述元素P和B的摩尔比为1：1～2.5。
  10. 根据权利要求6所述的正极材料，其特征在于，所述元素P和B占所述正极材料的质量分数为0.01wt％～5wt％。
  11. 根据权利要求1所述的正极材料，其特征在于，所述富锂材料内核的D50为0.3μm～50μm。
  12. 一种正极材料的制备方法，其特征在于，包括：将磷源和硼源中的至少一种、导电材料和富锂材料混合烧结，得到正极材料。
  13. 根据权利要求12所述的制备方法，其特征在于，具体包括：
    A)将含有磷源、硼源和导电材料的溶液喷涂在加热的富锂材料表面，压制；
    B)重复进行所述步骤A)后，对所得产物进行煅烧。
  14. 根据权利要求12所述的制备方法，其特征在于，具体包括：将所述磷源、硼源和导电材料混合，在溶液中反应，得到具有元素P和B掺杂的导电材料；
    将所述具有元素P和B掺杂的导电材料和富锂锰基材料混合烧结，得到正极材料。
  15. 根据权利要求14所述的制备方法，其特征在于，具体包括：将有机磷源和有机硼源混合，在溶液中反应，得到具有元素P和B掺杂的碳材料；
    将所述具有元素P和B掺杂的碳材料和富锂锰基材料混合烧结，得到正极材料。
  16. 根据权利要求14所述的制备方法，其特征在于，所述磷源和硼源的质量比为1：0.5～8；
    所述具有元素P和B掺杂的导电材料占其与所述富锂锰基材料混合后的总量的质量分数为0.05wt％～20wt％。
  17. 一种正极，其特征在于，包括权利要求1～11中任一所述的正极材料或权利要求12～16中任一所述的制备方法得到的正极材料。
  18. 一种电池，包括正极、负极和设置在所述正极和负极之间的隔膜，其特征在于，所述正极为权利要求17所述的正极。
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