WO2023155930A1 - 锂离子电池正极材料及其制备方法 - Google Patents

锂离子电池正极材料及其制备方法 Download PDF

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WO2023155930A1
WO2023155930A1 PCT/CN2023/078661 CN2023078661W WO2023155930A1 WO 2023155930 A1 WO2023155930 A1 WO 2023155930A1 CN 2023078661 W CN2023078661 W CN 2023078661W WO 2023155930 A1 WO2023155930 A1 WO 2023155930A1
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positive electrode
electrode material
sintering
nickel
cobalt
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PCT/CN2023/078661
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English (en)
French (fr)
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佟俊凡
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北京当升材料科技股份有限公司
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Priority to KR1020237037755A priority Critical patent/KR102665768B1/ko
Priority to JP2023572644A priority patent/JP2024520207A/ja
Publication of WO2023155930A1 publication Critical patent/WO2023155930A1/zh
Priority to US18/383,715 priority patent/US11996560B1/en

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    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of lithium ion batteries, and in particular relates to a lithium ion battery cathode material and a preparation method thereof.
  • lithium-ion batteries As a secondary battery, lithium-ion batteries have the advantages of large specific energy, high cell voltage, and long cycle life, and have been widely used in mobile phones, notebook computers and other fields.
  • the various components of lithium-ion batteries have a clear division of labor, mainly including positive electrode materials, separators, electrolytes, and negative electrode materials.
  • the electrode material is the core component of the battery, which determines the generation of electric energy.
  • the positive electrode material is the most important factor affecting the performance of the battery, which directly determines the capacity and cycle performance of the lithium-ion battery.
  • ternary materials As battery cathode materials.
  • the structural formula of the ternary material is LiNix Co y M 1-xy O 2 (M is Mn or Al), and it is divided into NCM and NCA according to the difference of metal M. It has become one of the mainstream choices of current battery cathode materials and has been widely developed and applied.
  • ternary materials also have some potential problems, including poor cycle performance and more serious gas production.
  • multiple primary particles of ternary materials are composed of secondary particles, which are used in batteries as positive electrode materials.
  • the positive electrode material containing the ternary material will be in contact with the electrolyte.
  • the ternary material in the positive electrode material and the electrolyte will have side reactions, such as the dissolution of metal ions.
  • the side reaction will indirectly lead to the reduction of the particle strength of the positive electrode material, the gradual increase and expansion of cracks in the primary particles or at the interface, and even the particle breakage of the positive electrode material. And this will make the surface of the positive electrode material more exposed to the electrolyte, causing more side reactions, forming a vicious circle. Accordingly, battery performance, especially cycle performance is adversely affected.
  • the main improvement methods currently used include controlling particle size and structure morphology, coating, doping, and single crystallization.
  • doping can enhance the strength of the ternary material particles themselves.
  • Coating can limit the contact of the electrolyte with the ternary material.
  • the present invention provides a positive electrode material, which has an intrinsic specific surface area and intrinsic pore size within the protection range.
  • the cathode material of the invention has excellent particle strength, excellent Li ion migration ability and good ability to resist electrolyte erosion. When it is used in a lithium battery, it endows the battery with excellent rate performance and cycle performance.
  • the invention also relates to a preparation method of the cathode material.
  • the present invention provides a positive electrode material, the intrinsic specific surface area of which is 5-13m 2 /g.
  • the "intrinsic specific surface area" used in the present invention refers to the BET specific surface area measured after the tested material undergoes extreme water washing treatment. Specifically, the particles of the material to be tested were added into deionized water at a solid-to-liquid weight ratio of 1:40 at room temperature, and washed with water for 30 min at a stirring rate of 500 rpm/min. The BET specific surface area test is carried out on the particles of the tested material after washing to obtain the BET specific surface area, which is regarded as the "specific surface area after washing".
  • the present invention provides a method for preparing the above positive electrode material, comprising:
  • the cathode material precursor is subjected to lithiation treatment, which is carried out as follows:
  • the programmed sintering is carried out under an oxygen atmosphere, and the programmed sintering includes:
  • the sintering temperature T and the Ni content in the nickel-cobalt-manganese active material conform to the following formula:
  • the present invention provides an application of the above positive electrode material in a lithium battery.
  • the present invention provides a positive electrode for a lithium battery, which contains the above-mentioned positive electrode material.
  • the present invention provides a lithium battery, which includes a positive electrode, a negative electrode and a A separator between the negative electrodes, wherein the positive electrode contains the above-mentioned positive electrode material.
  • the intrinsic specific surface area and intrinsic pore size of the above-mentioned positive electrode material are measured by extreme water washing to remove free substances on the surface of the tested material and even some substances inside the tested material. Due to the intrinsic specific surface area and intrinsic pore size within the claimed range, it means that even after a long battery cycle, the positive electrode material of the present invention still has controlled pore characteristics. This means that even after long-term operation, the positive electrode material of the present invention can still provide a migration path with a suitable length for the transmission of lithium ions, avoiding the capacity loss and rate performance loss caused by the migration path being too long; at the same time, it has a certain resistance to electrolyte The ability to erode and avoid a large number of side reactions.
  • the lithium battery using this cathode material has a discharge capacity of up to 223.8mAh/g at a rate of 0.1C; and a capacity retention rate of 93.6% after 80 cycles at a rate of 1C.
  • Fig. 1 schematically shows the SEM images of positive electrode material P1 obtained in embodiment 1-1 before and after extreme water washing
  • FIG. 2 schematically shows the XRD images of the positive electrode material p1 obtained in Example 1-1 before and after extreme water washing.
  • the present invention provides a positive electrode material, wherein the intrinsic specific surface area of the doped nickel-cobalt-manganese active material is 5-13m 2 /g;
  • the intrinsic pore size of the positive electrode material conforms to the following formula:
  • the cathode material of the present invention is in the form of particles.
  • the properties of particles can be characterized by BET specific surface area test.
  • the BET specific surface area test can be used to measure the specific surface area (BET specific surface area), pore volume, pore size distribution and nitrogen adsorption-desorption curve of particles.
  • the BET specific surface area refers to the total area of a unit mass of material.
  • the "intrinsic specific surface area" used in the present invention refers to the BET specific surface area measured after the tested material undergoes extreme water washing treatment. Specifically, the particles of the material to be tested were added into deionized water at a solid-to-liquid weight ratio of 1:40 at room temperature, and washed with water for 30 min at a stirring rate of 500 rpm/min. The BET specific surface area test is carried out on the particles of the tested material after washing to obtain the BET specific surface area, which is regarded as the "specific surface area after washing".
  • the "intrinsic pore size" used in the present invention refers to the measured data of the pore size of each pore in the particle after the positive electrode material undergoes extreme water washing treatment.
  • the pore sizes in the pore size data are arranged from small to large, and the pore sizes corresponding to the pores located at the 10th, 50th, and 90th percentile positions are R 10 , R 50 , and R 50 , respectively. 90 .
  • the intrinsic specific surface area and intrinsic pore size are measured after removing free substances on the surface of the tested material and even some substances inside the tested material by extreme water washing. While in the battery, the material to be tested (the positive electrode material) may come into contact with the electrolyte, so that similar substances are also eluted. Therefore, the above extreme water washing can be regarded as a simulation of the long-term operation of the cathode material. Therefore, the intrinsic specific surface area and intrinsic pore size can truly reflect the properties of the tested material after a long cycle, especially the particle strength and the binding strength of Li ions in it.
  • the positive electrode material of the present invention has an intrinsic specific surface area and an intrinsic pore size within the claimed range, which means that even after a long battery cycle, the positive electrode material of the present invention still has controlled pore characteristics. This means that even after long-term operation, the positive electrode material of the present invention can still provide a migration path with a suitable length for the transmission of lithium ions, avoiding the capacity loss and rate performance loss caused by the migration path being too long; at the same time, it has a certain resistance to electrolyte The ability to erode and avoid a large number of side reactions.
  • the D 50 of the positive electrode material is 7.8-14.2nm
  • the positive electrode material has a compacted density of 2.0-3.8 g/cm 3 .
  • the compacted specific surface area of the cathode material is measured. Specifically, the positive electrode material was compacted with pressure i, and then ground and sieved to test the specific surface area of the positive electrode material under the sieve.
  • SSA i is the specific surface area of the positive electrode material after compaction
  • SSA 0 is the specific surface area of the positive electrode material before compaction.
  • the specific surface area increase rate ⁇ SSA 1.5 of the positive electrode material after compaction does not exceed 15%;
  • the specific surface area increase rate ⁇ SSA 2.5 of the positive electrode material after compaction is not more than 40%;
  • the specific surface area increase rate ⁇ SSA 3.5 of the positive electrode material after compaction is not more than 60%;
  • the specific surface area increase rate ⁇ SSA 4.5 of the positive electrode material after compaction does not exceed 100%.
  • the positive electrode material comprises a doped nickel-cobalt-manganese active material and optionally a coating layer on at least part of its surface.
  • the general formula of the nickel-cobalt-manganese active material in the doped nickel-cobalt-manganese active material is LiNi x Co y Mn z O 2 , where 0.3 ⁇ x ⁇ 0.99, 0.01 ⁇ y ⁇ 0.5, 0.01 ⁇ z ⁇ 0.5, and the values of x, y, z make the algebraic sum of the valences of all elements in the chemical formula be zero, wherein the doped nickel-cobalt-manganese active material dopant includes the first doping element M, which is selected from Al and Zr at least one of; the second doping element G, which is selected from at least one of Y, Ti, Nb, Cr, Er and Mg; and the third doping element T, which is selected from Ba, V, Sr, At least one of Ta, Mo,
  • the positive electrode material is obtained by performing doping and lithiation treatment on the nickel-cobalt-manganese active material including programmed sintering steps, so as to obtain higher particle strength.
  • the dopant element will partly enter into the framework of the particulate material, stabilizing the lattice structure, thereby increasing the strength of the particulate material.
  • the coating layer can inhibit or alleviate the interface reaction between the positive electrode material and the electrolyte, thereby inhibiting or alleviating the corrosion of the positive electrode material by the electrolyte.
  • the doped NiCoMn active material forms the skeleton of the cathode material. This enables the positive electrode material of the present invention to have an intrinsic specific surface area and intrinsic pore size within the claimed range, so that a controlled pore structure can still be maintained even after multiple battery cycles.
  • the cathode material has good rate performance and cycle Good ring stability.
  • the present invention provides a method for preparing the above positive electrode material, comprising:
  • the cathode material precursor is subjected to lithiation treatment, which is carried out as follows:
  • the programmed sintering is carried out under an oxygen atmosphere, and the programmed sintering includes:
  • the sintering temperature T and the Ni content in the nickel-cobalt-manganese active material conform to the following formula:
  • the method for preparing the above positive electrode material includes:
  • Co-deposit nickel salt, cobalt salt and manganese salt to form the precursor of nickel-cobalt-manganese active material
  • the programmed sintering is carried out under an oxygen atmosphere, and the programmed sintering includes:
  • the sintering temperature T and the Ni content in the nickel-cobalt-manganese active material conform to the following formula:
  • the nickel salt, cobalt salt and manganese salt may be the nickel salt, cobalt salt and manganese salt conventionally used in the art for the preparation of lithium battery positive electrode materials or positive electrode material precursors.
  • the nickel salt, cobalt salt, and manganese salt are selected from at least one of sulfate, nitrate, acetate, hydrochloride, and oxalate of nickel, cobalt, and manganese, respectively.
  • nickel salt can be selected from at least one of nickel sulfate, nickel nitrate, nickel acetate, nickel oxalate and nickel chloride;
  • cobalt salt can be selected from at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate and the manganese salt may be selected from at least one of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.
  • the salts of nickel, cobalt and manganese are used in solution.
  • the concentration of the solution is 0.01-5mol/L, preferably 0.5-3mol/L, more preferably 1-2mol/L; for example, it can be 0.01mol/L, 0.1mol/L, 0.5 mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L.
  • Co-deposition can be performed in the presence of a precipitant solution and a complexing agent solution.
  • the co-deposition is carried out in a continuous manner.
  • the precipitating agent may be selected from at least one of NaOH, KOH and LiOH.
  • the concentration of the precipitant solution may be 0.02-10 mol/L, such as 0.05 mol/L, 0.1 mol/L, 0.5 mol/L, about 1 mol/L, 5 mol/L or 10 mol/L.
  • the complexing agent is any compound capable of forming complexes with Ni, Co and Mn from the nickel, cobalt and manganese salts in aqueous solution.
  • the complexing agent is selected from at least one of an ammonium ion donor, an ethanolamine-based complexing agent, and a carboxylate-based complexing agent.
  • the complexing agent is the ammonium ion donor, preferably at least one selected from ammonia water, ammonium oxalate, ammonium carbonate and ammonium hydroxide, more preferably ammonia water.
  • the concentration of the complexing agent solution is 0.01-15mol/L, for example, it can be 0.01mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 5mol/L, 10mol/L or 15mol/L.
  • nickel salt, cobalt salt and manganese salt solution, precipitant solution and complexing agent solution are respectively fed into the reaction system in a continuous manner, wherein the molar ratio of nickel salt, cobalt salt and manganese salt is x:y : z, x, y and z are as defined above.
  • the reaction conditions for co-deposition include, for example: a temperature of 50-90° C., preferably 60-80° C.; a pH of 9-13, preferably 10-12, and a complexing agent solution concentration of 2-8 g/L.
  • the feed rate of nickel salt, cobalt salt and manganese salt solution and precipitant solution and complexing agent solution can be selected in a wider range, as long as the feed rate can satisfy the pH value of the reaction system to remain in the set range within.
  • the co-deposition is carried out under stirring conditions.
  • the preferred stirring speed is about 100-1000r/min, preferably about 400-800r/min; for example, it can be 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min or 800r/min.
  • the co-deposited product can be aged, separated, washed and dried to obtain the precursor of the nickel-cobalt-manganese active material.
  • Relevant operations can be performed in any conventional manner in the art.
  • Doping and lithiation treatment of the precursor of the nickel-cobalt-manganese active material obtained in the co-deposition step including: mixing the precursor of the nickel-cobalt-manganese active material with a lithium source, the first dopant containing the first doping element, the first dopant containing a second dopant of a second dopant element and a third dopant comprising a third dopant element; and performing programmed sintering.
  • the lithium source is at least one selected from lithium nitrate, lithium hydrochloride, lithium carbonate, lithium hydroxide and lithium acetate.
  • the first dopant containing the first dopant element is an oxide of the first dopant element or a salt of the first dopant element capable of being converted into an oxide of the first dopant element under the second sintering condition, said The salt of the first doping element is selected from at least one of sulfate, nitrate, acetate, hydrochloride and oxalate of the first doping element;
  • the second dopant containing the second doping element is an oxide of a second doping element or a salt of a second doping element capable of being converted into an oxide of a second doping element under a second sintering condition, and the salt of the second doping element is selected from the group consisting of the second doping element At least one of sulfate, nitrate, acetate, hydrochloride, and oxalate of
  • the mixing is carried out by means of ball milling, shearing, grinding, mixing and the like.
  • the mixing time is 1-4h.
  • the blended mixture is subjected to programmed sintering.
  • Programmed sintering is carried out under an oxygen atmosphere.
  • the oxygen atmosphere is realized by feeding oxygen, wherein the oxygen flow rate Q can be 1-2m 3 /kg ⁇ h.
  • the programmed sintering includes: performing a first sintering treatment at 300-500° C. to obtain a first sintered product; and performing a second sintering treatment at a sintering temperature T to obtain a second sintered product.
  • the conditions for the first sintering include: sintering at a temperature of 300-500°C, preferably 350-450°C, for example, 300°C, 350°C, 400°C, 450°C or 500°C for 1-10 hours, preferably 4- 8h, eg 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h.
  • the sintering temperature T of the second sintering is: 670+(1-x)*500 to 780+(1-x)*500°C, preferably 690+(1-x)*500 to 770+(1-x)*500 to 770+(1-x)*500°C.
  • x)*500°C for example 700+(1-x)*500°C, 710+(1-x)*500°C, 720+(1-x)*500°C, 730+(1-x)*500°C, 740+(1-x )*500°C, 750+(1-x)*500°C or 760+(1-x)*500°C.
  • x is the Ni content in the nickel-cobalt-manganese active material. As mentioned above, 0.3 ⁇ x ⁇ 0.99.
  • the relationship between the oxygen flow Q (m 3 /kg ⁇ h) and the second sintering time t(h) satisfies -13.17ln(Q)+14.54 ⁇ t ⁇ -13.17ln(Q)+16.54.
  • the oxidation of divalent nickel mainly occurs in the second sintering process. Therefore, if the sintering time is too short, the oxidation reaction will be insufficient, which will lead to too much divalent nickel, so that the mixed lithium and nickel will occupy a lot of space, and the performance of the obtained positive electrode material will be reduced; The cycle performance of the material will deteriorate, and the cost will rise at the same time. Therefore, the proper sintering time is determined according to the oxygen flow rate in the sintering process. Correspondingly, this can control the oxidation process of divalent nickel, reduce the content of divalent nickel in the Li layer, suppress lithium-nickel mixing, and avoid excessive crystallization of the positive electrode material. Finally, the charge-discharge capacity, rate performance and cycle performance of the lithium-ion battery containing the positive electrode material can be improved.
  • the first sintering may be a constant temperature treatment or a variable temperature treatment.
  • the first sintering includes keeping at a temperature selected from 300-500° C. for 1-10 hours, preferably 4-8 hours.
  • the first sintering includes heating and cooling between two or more temperatures selected from 300-500° C. (for example, heating and cooling at a uniform rate, preferably at a rate of 1-10° C./min, such as 1° C./min. min, 2°C/min, 4°C/min, 5°C/min, 7°C/min or 10°C/min), the total time is 1-10h, preferably 4-8h.
  • a holding step may be further included between the temperature rise and the temperature drop.
  • the second sintering may be a constant temperature treatment or a variable temperature treatment.
  • the second sintering includes performing the second sintering at a sintering temperature T selected from 670+(1-x)*500 to 780+(1-x)*500° C. under an oxygen flow rate of Q, for a time t(h) is -13.17ln(Q)+14.54 to -13.17ln(Q)+16.54.
  • the second sintering includes heating and cooling between two or more temperatures selected from 670+(1-x)*500 to 780+(1-x)*500° C.
  • Cooling preferably at a rate of 1-10°C/min, such as 1°C/min, 2°C/min, 4°C/min, 5°C/min, 7°C/min or 10°C/min), total time t(h) It is -13.17ln(Q)+14.54 to -13.17ln(Q)+16.54.
  • a holding step may be further included between the temperature rise and the temperature drop.
  • the temperature rise process to the temperature required for the first sintering and the second sintering The heating rate is not particularly limited, and the preferred rate is 1-10°C/min, such as 1°C/min, 2°C/min, 4°C/min, 5°C/min, 7°C/min or 10°C/min.
  • the second sintered product is the doped nickel cobalt manganese active material described above.
  • a cladding layer is provided on at least part of the surface of the second sintered product.
  • the cladding layer contains at least one oxide selected from B 2 O 3 , Al 2 O 3 , SiO 2 and W 2 O 5 .
  • Setting the cladding layer includes: mixing the second sintered product and the cladding agent, and performing the third sintering treatment at 250-500°C.
  • the mixing is carried out by means of ball milling, shearing, grinding, mixing and the like.
  • the mixing ratio of the second sintered product and the coating agent is, for example, a molar ratio of 1:0.01-0.1.
  • the mixing time is 1-4h.
  • the coating agent is a material that can be converted into a coating layer under the third sintering condition, which includes, for example, boric acid, aluminum hydroxide, pseudoboehmite, boehmite, gibbsite, bayerite, silicic acid, ortho Silicic acid or ammonium paratungstate.
  • the third sintering may be a constant temperature treatment or a variable temperature treatment.
  • the third sintering includes keeping at a temperature selected from 250-500°C for 1-24h, preferably 6-12h.
  • the third sintering includes heating and cooling between two or more temperatures selected from 300-500° C. (for example, heating and cooling at a uniform rate, preferably at a rate of 1-10° C./min, such as 1° C./min. min, 2°C/min, 4°C/min, 5°C/min, 7°C/min or 10°C/min), the total time is 1-24h, preferably 6-12h.
  • a holding step may be further included between the temperature rise and the temperature drop.
  • the heating rate during the heating process is 1-10°C/min, such as 1°C/min, 2°C/min, 4°C/min, 5°C /min, 7°C/min or 10°C/min.
  • the third sintered product is the cathode material of the present invention.
  • the third sintered product is cooled, screened and iron impurities are removed.
  • the inventors of the present application unexpectedly discovered during the research process that in the process of preparing the positive electrode material, by introducing a variety of doping elements and performing programmed sintering, the prepared positive electrode material has a stable lattice structure and improved particle strength .
  • This cathode material endows lithium batteries with better electrochemical performance, such as improved rate capability and cycle stability.
  • the cathode material of the present invention can be used in secondary batteries, such as lithium ion batteries.
  • a lithium-ion battery includes a negative electrode, a positive electrode, a separator, and an electrolyte.
  • the positive electrode includes a positive electrode material layer on a positive electrode current collector, the positive electrode material layer comprising the positive electrode material of the present invention.
  • the cathode material layer may further include a binder and a conductive agent.
  • the binder can be selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) and other resin materials.
  • the conductive agent may include carbon-based materials or conductive polymers. Carbon-based materials may include, for example, graphite, acetylene black, carbon fibers, nanotubes, graphene, carbon black.
  • the conductive polymer may include polyaniline, polythiophene, polyacetylene, polypyrrole, and the like.
  • the current collector may comprise at least one of stainless steel, aluminum, nickel, iron, titanium, copper, tin, or any other conductive material known to those skilled in the art. In some variations, the current collector can be pre-coated, such as carbon-coated aluminum foil.
  • the specific composition of the negative electrode is not particularly limited, and it may be a negative electrode conventionally used in the field, such as a lithium metal sheet.
  • the separator is a porous membrane made of polyolefin such as polytetrafluoroethylene, polypropylene, or polyethylene.
  • the electrolyte can be various conventional electrolytes, such as non-aqueous electrolytes.
  • the non-aqueous electrolytic solution is a solution formed of an electrolyte lithium salt in a non-aqueous solvent, and conventional non-aqueous electrolytic solutions known to those skilled in the art can be used.
  • the electrolyte can be selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ) and lithium hexafluorosilicate (LiSiF 6 ). at least one.
  • the non-aqueous solvent may be selected from chain acid esters, cyclic acid esters or mixtures thereof.
  • Chain ester can be at least one in dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC) and dipropyl carbonate (DPC) .
  • the cyclic acid ester may be at least one of ethylene carbonate (EC), propylene carbonate (PC), and vinylene carbonate (VC).
  • BET specific surface area measurements were performed using a Tristar II 3020 instrument from Micromeritics Instruments Ltd. Sample pretreatment conditions include: vacuum degassing at 300 °C for 1 h. The BET specific surface area and pore size of the samples were calculated using the BET equation.
  • the prepared positive electrode material, conductive carbon black and polyvinylidene fluoride (PVDF) were weighed and mixed according to the mass ratio of 95%: 2.5%: 2.5%, and N-methylpyrrolidone (NMP) was added and stirred to form a uniform mixture.
  • the coin cell assembly process was carried out in an Ar gas-protected glove box, where the water content and oxygen content were both less than 5 ppm.
  • Use the pole piece obtained above as the positive electrode use a Li metal sheet with a diameter of 17mm and a thickness of 1mm as the negative electrode; use a polyethylene porous membrane with a thickness of 25 ⁇ m as the separator, and use 1mol/L LiPF6 Ethylene carbonate (EC ) and divinyl carbonate (DEC) with a volume ratio of 1:1 was used as the electrolyte, and a 2025 button battery case was used as the battery case.
  • EC Ethylene carbonate
  • DEC divinyl carbonate
  • the assembled lithium-ion battery samples were tested to obtain the charge specific capacity and discharge specific capacity data for the first cycle of the cycle.
  • the first-week efficiency was calculated by the ratio of the first-week discharge specific capacity to the charge specific capacity.
  • the activated battery sample at a temperature of 45° C., with a current density of 1 C and a voltage range of 3.0-4.3 V, perform a specified number of charge and discharge cycles, for example, 80 times.
  • the lithium ion transfer coefficient was tested by EIS test method. Specifically, the unactivated battery samples were left to stand for 2 hours, charged at a constant current density of 0.1C to a cut-off voltage of 4.3V, then charged at a constant voltage for 30 minutes, and then discharged at a constant current density of 0.1C to The cut-off voltage is 3.0V; then, constant current charging is performed at a current density of 0.1C to a cut-off voltage of 4.3V to obtain a fully charged battery sample. It is tested by EIS within the frequency range of 100kHz ⁇ 0.01Hz, and the amplitude is 10mV. According to the following formula, the slope of the fitted line between Zre and ⁇ -1/2, that is, ⁇ :
  • Zre is the real part of the measured impedance spectrum
  • Rs is the solution resistance
  • Rct is the charge transfer resistance
  • ⁇ is the angular frequency
  • f is the test frequency
  • ⁇ is the Warburg factor
  • R is the ideal gas constant
  • T is the absolute temperature
  • A is the cross-sectional area of the electrode
  • n is the electron transfer number
  • F is the Faraday constant
  • C is the concentration of lithium ions in the electrode.
  • the mixed salt solution, precipitating agent solution and complexing agent solution were respectively fed into the reactor, wherein the feeding rate was controlled so that the reaction temperature was 60°C, the pH was 11.3, and the ammonia concentration was 6g/L.
  • Co-deposition was performed at a stirring speed of 600 rpm. After 80 hours, the reaction was completed, and the precursor of the nickel-cobalt-manganese active material was obtained. The precursor of the nickel-cobalt-manganese active material is aged, separated, washed and dried before use.
  • the precursor of the above-mentioned nickel-cobalt-manganese active material, lithium hydroxide as a lithium source, aluminum oxide as a first dopant, tungsten oxide as a second dopant, and strontium carbonate as a third dopant are prepared in moles Mix in a mixer at a ratio of 0.99:1.03:0.007:0.002:0.001.
  • Programmed sintering is carried out in a sintering furnace. Among them, oxygen is introduced at a flow rate of 1.33m 3 /kg ⁇ h, and the mixture The temperature was raised from room temperature to 300° C. at a constant speed for 3 hours, and kept at a constant temperature of 300° C. for 2 hours to perform the first sintering treatment.
  • the temperature was raised to 780° C. at a constant speed for 6 hours, and kept at 780° C. for 12 hours to carry out the second sintering treatment. Finally, the temperature was naturally lowered to room temperature to obtain a doped nickel-cobalt-manganese active material.
  • the doped nickel-cobalt-manganese active material is cooled, crushed and sieved for standby use.
  • the doped nickel-cobalt-manganese active material and boric acid as a coating agent were mixed in a high-speed mixer at a molar ratio of 1:0.01.
  • a third sintering treatment was performed in a sintering furnace, in which sintering was performed at 350 °C for 10 h to obtain the positive electrode material P1, which had the structural formula Li 1.03 (Ni 0.896 Co 0.057 Mn 0.037 Al 0.007 Zr 0.002 Sr 0.001 )O 2 /B 2 O 3 .
  • the positive electrode material P1 is ready for use after cooling, sieving and removing iron impurities.
  • the obtained positive electrode material P1 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • the obtained positive electrode material P1 was washed with extreme water, and it was measured by SEM and XRD, and the results are shown in Figures 1 and 2, respectively.
  • FIG. 1 schematically shows the SEM images of the positive electrode material P1 of Example 1-1 before and after extreme water washing, wherein A is its SEM image before extreme water washing, and B is its SEM image after extreme water washing.
  • Figure 1 shows that the SEM images of the positive electrode material P1 in Example 1-1 are not significantly different before and after extreme water washing, which means that extreme water washing has no significant impact on the structure of the positive electrode material P1 in Example 1-1.
  • FIG. 2 schematically shows the XRD images of the positive electrode material P1 of Example 1-1 before and after extreme water washing, wherein A is the XRD image before extreme water washing, and B is the XRD image after extreme water washing.
  • Figure 2 shows that the XRD images of the positive electrode material P1 in Example 1-1 are basically the same before and after extreme water washing, which means that extreme water washing has no significant impact on the structure of the positive electrode material P1 in Example 1-1. This is consistent with the results obtained by SEM images.
  • Example 1-1 was repeated, except that the materials and process conditions listed in Table 1-1 were used instead of the corresponding materials and process conditions in Example 1-1 to obtain positive electrode material P2.
  • the positive electrode material P2 has the structural formula Li 1.03 (Ni 0.896 Co 0.057 Mn 0.037 Al 0.006 Nb 0.003 W 0.001 )O 2 /B 2 O 3 .
  • the obtained positive electrode material P2 was subjected to limit water washing, and its intrinsic water washing specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 1-1 was repeated, except that the materials and process conditions listed in Table 1-1 were used instead of the corresponding materials and process conditions in Example 1-1 to obtain positive electrode material P3.
  • the positive electrode material P3 has the structural formula Li 1.03 (Ni 0.896 Co 0.057 Mn 0.037 Zr 0.005 La 0.004 W 0.001 )O 2 /B 2 O 3 .
  • the obtained positive electrode material P3 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 1-1 was repeated, except that the materials and process conditions listed in Table 1-1 were used instead of the corresponding materials and process conditions in Example 1-1 to obtain positive electrode material P4.
  • the positive electrode material P4 has the structural formula Li 1.03 (Ni 0.896 Co 0.057 Mn 0.037 Al 0.007 Zr 0.002 Sr 0.001 )O 2 /B 2 O 3 .
  • the obtained positive electrode material P4 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 1-1 was repeated, except that the materials and process conditions listed in Table 1-1 were used instead of the corresponding materials and process conditions in Example 1-1 to obtain positive electrode material P5.
  • the positive electrode material P5 has the structural formula Li 1.03 (Ni 0.896 Co 0.057 Mn 0.037 Al 0.007 Zr 0.002 Sr 0.001 )O 2 /B 2 O 3 .
  • the obtained positive electrode material P5 was subjected to extreme water washing, and its intrinsic ratio was measured Surface area and intrinsic pore size.
  • the test results are listed in Table 1-2.
  • the mixed salt solution, precipitant solution and complexing agent solution are fed into the reactor respectively, wherein the control The feed rate was such that the reaction temperature was 40 °C, the pH was 11.6, and the ammonia concentration was 6 g/L.
  • Co-deposition was performed at a stirring speed of 600 rpm. After 80 hours, the reaction was completed, and the precursor of the nickel-cobalt-manganese active material was obtained. The precursor of the nickel-cobalt-manganese active material is aged, separated, washed and dried before use.
  • the precursor of the above-mentioned nickel-cobalt-manganese active material, lithium hydroxide as a lithium source, zirconia as a first dopant, yttrium oxide as a second dopant, and tungsten carbonate as a third dopant are prepared in moles Mix in a mixer at a ratio of 1.05:0.99:0.006:0.002:0.002.
  • Programmed sintering is carried out in a sintering furnace. Among them, oxygen was introduced at a flow rate of 1.33m 3 /kg ⁇ h, the temperature of the mixture was raised from room temperature to 300°C at a constant speed for 3h, and the temperature was kept at 300°C for 2h to perform the first sintering treatment.
  • the temperature was raised to 780° C. at a constant speed for 6 hours, and kept at 780° C. for 12 hours to carry out the second sintering treatment. Finally, the temperature was naturally lowered to room temperature to obtain a doped nickel-cobalt-manganese active material.
  • the doped nickel-cobalt-manganese active material is cooled, crushed and sieved for standby use.
  • the doped nickel-cobalt-manganese active material was mixed with boric acid and aluminum hydroxide as coating agents in a high-speed mixer at a molar ratio of 1/0.01/0.01.
  • a third sintering treatment was carried out in a sintering furnace, in which sintering was carried out at 450°C for 10 h to obtain the positive electrode material P6, which had the structural formula Li 1.03 (Ni 0.648 Co 0.152 Mn 0.200 Zr 0.006 Y 0.002 W 0.002 )O 2 /B 2 O 3 + Al2O 3 .
  • the positive electrode material P6 is ready for use after cooling, sieving and removing iron impurities.
  • the obtained positive electrode material P6 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 2-1 was repeated, except that the materials and process conditions listed in Table 2-1 were used instead of the corresponding materials and process conditions in Example 2-1 to obtain positive electrode material P7.
  • the positive electrode material P7 has the structural formula Li 1.03 (Ni 0.648 Co 0.152 Mn 0.200 Nb 0.003 Sr 0.002 )O 2 /B 2 O 3 +Al2O 3 .
  • the obtained positive electrode material P7 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 2-1 was repeated, except that the materials and process conditions listed in Table 2-1 were used instead of the corresponding materials and process conditions in Example 2-1 to obtain positive electrode material P8.
  • the positive electrode material P8 has the structural formula Li 1.03 (Ni 0.648 Co 0.152 Mn 0.200 Ti 0.005 Y 0.004 Sr 0.001 )O 2 /B 2 O 3 +Al2O 3 .
  • the obtained positive electrode material P8 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 2-1 was repeated, except that the materials and process conditions listed in Table 2-1 were used instead of the corresponding materials and process conditions in Example 2-1 to obtain positive electrode material P9.
  • the positive electrode material P9 has the structural formula Li 1.03 (Ni 0.648 Co 0.152 Mn 0.200 Zr 0.006 Y 0.002 W 0.002 )O 2 /B 2 O 3 +Al2O 3 .
  • the obtained positive electrode material P9 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 2-1 was repeated, except that the materials and process conditions listed in Table 2-1 were used instead of the corresponding materials and process conditions in Example 2-1 to obtain positive electrode material P10.
  • the positive electrode material P10 has the structural formula Li 1.03 (Ni 0.648 Co 0.152 Mn 0.200 Zr 0.006 Y 0.002 W 0.002 )O 2 /B 2 O 3 +Al2O 3 .
  • the obtained positive electrode material P10 was subjected to limit water washing, and its intrinsic specific surface area and intrinsic pore size were measured.
  • the test results are listed in Table 1-2.
  • Example 1-1 and Example 1-2 show that, compared with Example 1-1 and Example 1-2, the doping elements used in Comparative Example 1-1 are changed.
  • the intrinsic specific surface area and intrinsic pore distribution (R10, R50 and R90) of the positive electrode material obtained in Comparative Example 1-1 are larger than those of the positive electrode materials in Example 1-1 and Example 1-2.
  • its cycle retention decreased, and the capacity retention after 80 cycles was only 88.6%.
  • the positive electrode material obtained in Comparative Example 1-1 did not have a sufficiently good ion-stabilized layered structure, which resulted in cracks being more likely to occur at the grain boundaries, resulting in a significant drop in the compression resistance.
  • Comparative Example 1-2 Although it has a relatively excellent first-cycle capacity, the performance of cycling under high current can get worse.
  • the doping system of Comparative Example 1-2 is the same as that of Example 1-1 and Example 1-2, the sintering temperature is too low. This leads to imperfect crystal phase formation, poor Li+ migration channel construction, low Li+ migration number, and capacity performance not reaching the desired level.
  • Comparative examples 1-3 use reduced oxygen flow rate, resulting in longer sintering time and slower oxidation reaction. As a result, the lithium-nickel mixture occupies a serious phenomenon, intragranular cracks are easier to form, and the compressive capacity is reduced.

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Abstract

本公开涉及锂离子电池正极材料及其制备方法。本公开的正极材料的本征比表面积为5-13m2/g。本公开的正极材料具有处于保护范围内的本征比表面积和本征孔隙尺寸，因此本发明的正极材料具有优异的颗粒强度，优异的Li离子迁移能力以及良好的抵抗电解液侵蚀的能力。在将其用于锂电池时，赋予电池优异的倍率性能和循环性能。本公开还涉及该正极材料的制备方法。

Description

锂离子电池正极材料及其制备方法 技术领域
本发明属于锂离子电池领域，具体涉及锂离子电池正极材料及其制备方法。
背景技术
锂离子电池作为一种二次电池，具有比能量大、单体电压高、循环寿命长等优势，已被广泛应用于手机、笔记本电脑等领域。锂离子电池的各个组成部分分工明确，主要包括正极材料、隔膜、电解液以及负极材料。其中电极材料是电池的核心组成部分，决定了电能的产生。相较于负极材料而言，正极材料更是影响电池性能的最主要因素，它直接决定着锂离子电池的容量大小和循环性能。要想电池的安全性能和比能量都进一步提升，就要开发更优化的正极材料与之匹配。
人们已经提出使用三元材料作为电池正极材料。三元材料的结构式为LiNixCoyM1-x-yO2(M为Mn或Al)，根据金属M的不同分为NCM和NCA。它已经成为当下电池正极材料的主流选择之一，被广泛开发与应用。
但是，三元材料也存在一些潜在问题，包括循环性能变差及产气更严重等。一般将多个三元材料的一次颗粒组成二次颗粒，作为正极材料用于电池中。含有三元材料的正极材料将与电解液接触。在电池充电时，正极材料中的三元材料与电解液会发生副反应，例如金属离子的溶出。副反应会间接导致正极材料的颗粒强度的下降，在一次颗粒中或界面处的裂纹逐渐增多和扩大，甚至是正极材料的颗粒破碎。而这又会使正极材料的表面更多地暴露在电解液中，引起更多副反应，形成恶性循环。相应地，电池性能，特别是循环性能受到不利影响。
为解决这些问题，目前主要采用的改善手段包括控制颗粒尺寸和结构形貌、包覆、掺杂以及单晶化等。例如，掺杂可以增强三元材料颗粒本身的强度。包覆可以限制电解液与三元材料的接触。
新能源电动汽车以及大容量储能系统的发展推动着性能进一步改善的二次电池的开发。因此，仍然需要开发进一步改善的正极材料，以提升电池循环性能。
发明内容
为了提升电池的循环性能，本发明提供一种正极材料，其具有处于保护范围内的本征比表面积和本征孔隙尺寸。本发明的正极材料具有优异的颗粒强度，优异的Li离子迁移能力以及良好的抵抗电解液侵蚀的能力。在将其用于锂电池时，赋予电池优异的倍率性能和循环性能。本发明还涉及该正极材料的制备方法。
第一方面，本发明提供了一种正极材料，其本征比表面积为5-13m2/g。
本发明中所用的“本征比表面积”是指被测材料在经历极限水洗处理后，测得的BET比表面积。具体地说，在室温下将被测材料的颗粒以固液重量比为1∶40加入去离子水中，在500rpm/min的搅拌速率下进行水洗30min。对水洗后的被测材料的颗粒进行BET比表面积测试，获得其BET比表面积，视为“水洗后的比表面积”。重复上述水洗和BET比表面积测试，直至相邻两个“水洗后的比表面积”基本上不再发生变化(例如两者之差不超过5％，优选不超过2％，更优选不超过1％，更加优选不超过0.5％，最优选不超过0.1％)时，最后一次测得的“水洗后的比表面积”即为该正极材料的“本征比表面积”。
第二方面，本发明提供了一种制备上述正极材料的方法，包括：
将正极材料前驱体进行锂化处理，其通过如下进行：
混合前驱体与锂源；和
在氧气气氛下进行程序化烧结，所述程序化烧结包括：
在300-500℃进行第一烧结处理，得到第一烧结产物；和
进行第二烧结处理，得到第二烧结产物，
其中在第二烧结处理过程中，烧结温度T与镍钴锰活性材料中的Ni含量符合下式：
670+(1-x)*500≤T≤780+(1-x)*500，
其中0.3≤x≤0.99。
第三方面，本发明提供上述正极材料在锂电池中的应用。
第四方面，本发明提供一种用于锂电池的正极，其含有上述正极材料。
第五方面，本发明提供一种锂电池，其包括正极，负极和位于正 极负极之间的隔膜，其中所述正极含有上述正极材料。
上述正极材料的本征比表面积和本征孔隙尺寸通过极限水洗去除了被测材料表面的游离物质甚至被测材料内部的部分物质后测量得到。由于具有处于请求保护范围内的本征比表面积和本征孔隙尺寸，意味着即使经历长久电池循环，本发明的正极材料仍然具有受控的孔隙特征。这意味着，即使经历长久运行，本发明的正极材料仍然可以为锂离子的传输提供长度合适的迁移路径，避免伴随迁移路径过长引起的容量损失以及倍率性能损失；同时具有一定的抵抗电解液侵蚀的能力，避免副反应的大量发生。
采用该正极材料的锂电池，在0.1C倍率下，放电容量可高达223.8mAh/g；在1C倍率下，循环80圈后的容量保持率可高达93.6％。
附图说明
本文中描述的附图仅用于说明所选实施方案而非所有可能的实施方式的目的，并且无意限制本公开的范围。
图1示意显示实施例1-1获得的正极材料P1在进行极限水洗前后的SEM图像；和
图2示意显示实施例1-1获得的正极材料p1在进行极限水洗前后的XRD图像。
具体实施方式
除了在实施例外，在本文中，参数的所有数值都应理解为在所有情况下均由术语“约”修饰，无论“约”是否实际上出现在该数值之前。
除非另有说明，本文所用的术语具有与本领域技术人员通常所理解的相同的含义，如果术语在本文中有定义，且其定义与本领域的通常理解不同，则以本文的定义为准。
一方面，本发明提供了一种正极材料，并且其中所述掺杂的镍钴锰活性材料的本征比表面积为5-13m2/g；
在一个优选的实施例方式中，所述正极材料的本征孔隙孔径尺寸符合下式：
2.1nm≤R10≤2.5nm，23.0nm≤R50≤27.0nm并且100.0nm≤R90≤160.0nm。
本发明的正极材料为颗粒形式。颗粒的性质可以通过BET比表面积测试进行表征。BET比表面积测试可用于测颗粒的比表面积(BET比表面积)、孔容、孔径分布以及氮气吸附脱附曲线。BET比表面积是指单位质量物料所具有的总面积。
本发明中所用的“本征比表面积”是指被测材料在经历极限水洗处理后，测得的BET比表面积。具体地说，在室温下将被测材料的颗粒以固液重量比为1∶40加入去离子水中，在500rpm/min的搅拌速率下进行水洗30min。对水洗后的被测材料的颗粒进行BET比表面积测试，获得其BET比表面积，视为“水洗后的比表面积”。重复上述水洗和BET比表面积测试，直至相邻两个“水洗后的比表面积”基本上不再发生变化(例如两者之差不超过5％，优选不超过2％，更优选不超过1％，更加优选不超过0.5％，最优选不超过0.1％)时，最后一次测得的“水洗后的比表面积”即为该正极材料的“本征比表面积”。
相应地，本发明中所用的“本征孔隙尺寸”是指正极材料在经历极限水洗处理后，测得颗粒内的各孔隙的孔径大小的数据。使用该孔径大小的数据中对应的R10、R50和R90来表征正极材料的“本征孔隙尺寸”。其中，将所述孔径大小的数据中孔径大小由小到大排列，相对于所有孔隙位于第10％、50％和90％位置的孔隙所对应的孔径大小则分别为R10、R50和R90。
本征比表面积和本征孔隙尺寸通过极限水洗去除了被测材料表面的游离物质甚至被测材料内部的部分物质后测量得到。在电池中时，被测材料(所述正极材料)可能接触电解液，从而同样也会出现类似的物质被洗脱的情况。因此，上述极限水洗可以看作正极材料进行长久运行的模拟。因此，本征比表面积和本征孔隙尺寸可以真实反映出被测材料的在长久循环后的性质，特别是颗粒强度及其中Li离子的结合强度。本发明的正极材料具有处于请求保护范围内的本征比表面积和本征孔隙尺寸，这意味着即使经历长久电池循环，本发明的正极材料仍然具有受控的孔隙特征。这意味着，即使经历长久运行，本发明的正极材料仍然可以为锂离子的传输提供长度合适的迁移路径，避免伴随迁移路径过长引起的容量损失以及倍率性能损失；同时具有一定的抵抗电解液侵蚀的能力，避免副反应的大量发生。
在优选方案中，所述正极材料的D50为7.8-14.2nm；
在优选的方案中，所述正极材料的压实密度为：2.0-3.8g/cm3。
在一个方案中，测量正极材料的压实后的比表面积。具体地说，采用压力i对正极材料进行压实，然后研磨过筛，测试筛下的正极材料的比表面积。SSAi为压实后所述正极材料的比表面积，SSA0为压实前正极材料的比表面积。通过以下公式计算比表面积增加率ΔSSAi＝(SSAi-SSA0)/SSA0。
在优选的方案中，在压实压力i为1.5吨时，压实后所述正极材料的比表面积增加率ΔSSA1.5不超过15％；
或者，在压实压力i为2.5吨时，压实后所述正极材料的比表面积增加率ΔSSA2.5不超过40％；
或者，在压实压力i为3.5吨时，压实后所述正极材料的比表面积增加率ΔSSA3.5不超过60％；
或者，在压实压力i为4.5吨时，压实后所述正极材料的比表面积增加率ΔSSA4.5不超过100％。
在优选的方案中，所述正极材料包含掺杂的镍钴锰活性材料和任选的在其至少部分表面上的包覆层。在一个方案中，掺杂的镍钴锰活性材料中的镍钴锰活性材料的通式为LiNixCoyMnzO2，其中0.3≤x≤0.99，0.01≤y≤0.5，0.01≤z≤0.5，并且x、y、z的取值使得化学式中所有元素的化合价的代数和为零，其中掺杂的镍钴锰活性材料掺杂剂包括第一掺杂元素M，其选自Al和Zr中的至少一种；第二掺杂元素G，其选自Y、Ti、Nb、Cr、Er和Mg中的至少一种；和第三掺杂元素T，其选自Ba、V、Sr、Ta、Mo、W和Ce中的至少一种。在一个方案中，包覆层包含选自B2O3、Al2O3、SiO2和W2O5中的至少一种氧化物。
本发明中正极材料通过对镍钴锰活性材料进行包含程序化烧结步骤的掺杂和锂化处理而获得，从而获得更高的颗粒强度。不希望束缚于任何理论，发明人认为，掺杂元素将部分进入颗粒材料的骨架中，稳定了晶格结构，从而增加颗粒材料的强度。同时，如果存在包覆层，包覆层能够抑制或缓解正极材料与电解液之间的界面反应，从而抑制或缓解了电解液对正极材料的腐蚀。更重要的是，掺杂的镍钴锰活性材料形成正极材料的骨架。这使得本发明的正极材料具有处于请求保护范围内的本征比表面积和本征孔隙尺寸，因此即使经历多次电池循环，仍然能够保持受控的孔隙结构。该正极材料具有倍率性能好和循 环稳定性好的特点。
在优选方案中，在镍钴锰活性材料的通式中，0.6≤x≤0.94，0.03≤y≤0.2，0.03≤z≤0.2。
在一个方案中，掺杂的镍钴锰活性材料通式为Li1+a(NixCoyMnzMdGeTf)O2，其中0≤a≤0.1，0.3≤x≤0.99，0.01≤y≤0.5，0.01≤z≤0.5，0＜d≤0.08，0＜e≤0.05，0＜f≤0.03，1＜e/f＜5且x+y+z+d+e+f＝1。
另一方面，本发明提供了一种制备上述正极材料的方法，包括：
将正极材料前驱体进行锂化处理，其通过如下进行：
混合前驱体与锂源；和
在氧气气氛下进行程序化烧结，所述程序化烧结包括：
在300-500℃进行第一烧结处理，得到第一烧结产物；和
进行第二烧结处理，得到第二烧结产物，
其中在第二烧结处理过程中，烧结温度T与镍钴锰活性材料中的Ni含量符合下式：
670+(1-x)*500≤T≤780+(1-x)*500，
其中0.3≤x≤0.99。
在一个方案中，制备上述正极材料的方法，包括：
(1)使镍盐、钴盐和锰盐共沉积，形成镍钴锰活性材料的前驱体；
(2)对镍钴锰活性材料的前驱体进行掺杂和锂化处理，其通过如下进行：
混合镍钴锰活性材料的前驱体与锂源、含有第一掺杂元素的第一掺杂剂、含有第二掺杂元素的第二掺杂剂和含有第三掺杂元素的第三掺杂剂；和
在氧气气氛下进行程序化烧结，所述程序化烧结包括：
在300-500℃进行第一烧结处理，得到第一烧结产物；和
进行第二烧结处理，得到第二烧结产物；
其中，在第二烧结处理过程中，烧结温度T与镍钴锰活性材料中的Ni含量符合下式：
670+(1-x)*500≤T≤780+(1-x)*500，
其中0.3≤x≤0.99；和
(3)在第二烧结产物的至少部分表面上设置包覆层。
所述镍盐、钴盐和锰盐可以为本领域常规用于锂电池正极材料或正极材料前驱体制备的镍盐、钴盐和锰盐。作为非限制实例，所述镍盐、钴盐和锰盐分别选自镍、钴和锰的硫酸盐、硝酸盐、乙酸盐、盐酸盐和草酸盐中的至少一种。例如，镍盐可以选自硫酸镍、硝酸镍、乙酸镍、草酸镍和氯化镍中的至少一种；钴盐可以选自硝酸钴、氯化钴、乙酸钴和硫酸钴中的至少一种；并且锰盐可以选自硫酸锰、硝酸锰、乙酸锰和氯化锰中的至少一种。
在一个方案中，所述镍盐、钴盐和锰盐以溶液形式使用。以相应的金属元素计，所述溶液的浓度为0.01-5mol/L，优选为0.5-3mol/L，更优选为1-2mol/L；例如可以为0.01mol/L、0.1mol/L、0.5mol/L、1mol/L、2mol/L、3mol/L、4mol/L、5mol/L。
共沉积可以在沉淀剂溶液和络合剂溶液存在下进行。优选共沉积以连续方式进行。
在一个方案中，所述沉淀剂可以选自NaOH、KOH和LiOH中的至少一种。优选地，所述沉淀剂溶液的浓度可以为0.02-10mol/L，例如可以为0.05mol/L、0.1mol/L、0.5mol/L、约1mol/L、5mol/L或10mol/L。
所述络合剂是任何能够在水溶液中与来自所述镍盐、钴盐和锰盐的Ni、Co和Mn形成络合物的化合物。在一个方案中，所述络合剂选自铵离子供体、乙醇胺基络合剂、和羧酸盐基络合剂中的至少一种。优选，所述络合剂为所述铵离子供体，优选选自氨水、草酸铵、碳酸铵和氢氧化铵中的至少一种，更优选为氨水。在一个变型中，所述络合剂溶液的浓度为0.01-15mol/L，例如可以为0.01mol/L、0.1mol/L、0.5mol/L、1mol/L、5mol/L、10mol/L或15mol/L。
在一个方案中，将镍盐、钴盐和锰盐溶液与沉淀剂溶液和络合剂溶液分别以连续方式进料到反应体系中，其中镍盐、钴盐和锰盐的摩尔比x∶y∶z，x、y和z如上文定义。共沉积的反应条件例如包括：温度为50-90℃，优选60-80℃；pH为9-13，优选10-12，并且络合剂溶液浓度为2-8g/L。镍盐、钴盐和锰盐溶液与沉淀剂溶液和络合剂溶液的进料速率可以在较宽范围内进行选择，只要所述进料速率能够满足使反应体系的pH值保持在设定范围内即可。优选共沉积在搅拌条件下进行。优选搅拌速度为约100-1000r/min，优选为约400-800r/min；例如可以为100r/min、200r/min、300r/min、400r/min、500r/min、600r/min、 700r/min或者800r/min。
共沉积的产物可以进行陈化、分离、洗涤和干燥，得到镍钴锰活性材料的前驱体。相关操作可以采用任何本领域常规的方式进行。
对共沉积步骤得到镍钴锰活性材料的前驱体进行掺杂和锂化处理，包括：混合镍钴锰活性材料的前驱体与锂源、含有第一掺杂元素的第一掺杂剂、含有第二掺杂元素的第二掺杂剂和含有第三掺杂元素的第三掺杂剂；和进行程序化烧结。
锂源选自硝酸锂、盐酸锂、碳酸锂、氢氧化锂和乙酸锂中的至少一种。含有第一掺杂元素的第一掺杂剂为第一掺杂元素的氧化物或在第二烧结条件下能够转化为第一掺杂元素的氧化物的第一掺杂元素的盐，所述第一掺杂元素的盐选自第一掺杂元素的硫酸盐、硝酸盐、乙酸盐、盐酸盐和草酸盐中的至少一种；含有第二掺杂元素的第二掺杂剂为第二掺杂元素的氧化物或在第二烧结条件下能够转化为第二掺杂元素的氧化物的第二掺杂元素的盐，所述第二掺杂元素的盐选自第二掺杂元素的硫酸盐、硝酸盐、乙酸盐、盐酸盐和草酸盐中的至少一种；并且含有第三掺杂元素的第三掺杂剂为第三掺杂元素的氧化物或在第二烧结条件下能够转化为第三掺杂元素的氧化物的第一掺杂元素的盐，所述第三掺杂元素的盐选自第三掺杂元素的硫酸盐、硝酸盐、乙酸盐、盐酸盐和草酸盐中的至少一种。锂源、第一掺杂剂、第二掺杂剂和第三掺杂剂的用量符合摩尔比(1+a)∶d∶e∶f，其中a、d、e和f如上文定义。
在所述掺杂和锂化处理步骤中，所述混合通过球磨、剪切、研磨、混料等方式进行。优选，所述混合的时间为1-4h。
然后，混合后的混合物进行程序化烧结。程序化烧结在氧气气氛下进行。氧气气氛通过通入氧气实现，其中氧气流量Q可以为1-2m3/kg·h。
在一个方案中，所述程序化烧结包括：在300-500℃进行第一烧结处理，得到第一烧结产物；和在烧结温度T下进行第二烧结处理，得到第二烧结产物。优选，所述第一烧结的条件包括：在300-500℃，优选350-450℃，例如在300℃、350℃、400℃、450℃或500℃的温度下烧结1-10h，优选4-8h，例如1h、2h、3h、4h、5h、6h、7h或8h。
优选，所述第二烧结的烧结温度T为：670+(1-x)*500至780+(1-x)*500℃，优选690+(1-x)*500至770+(1-x)*500℃，例如 700+(1-x)*500℃、710+(1-x)*500℃、720+(1-x)*500℃、730+(1-x)*500℃、740+(1-x)*500℃、750+(1-x)*500℃或760+(1-x)*500℃。其中，x为镍钴锰活性材料中的Ni含量。如上所述，0.3≤x≤0.99。
在一个方案中，氧气流量Q(m3/kg·h)与第二烧结时间t(h)的关系满足-13.17ln(Q)+14.54≤t≤-13.17ln(Q)+16.54。优选-13.17ln(Q)+14.54≤t≤-13.17ln(Q)+16.54，例如t＝-13.17ln(Q)+15、t＝-13.17ln(Q)+15.5、t＝-13.17ln(Q)+16、或t＝-13.17ln(Q)+16.5。
第二烧结过程主要发生二价镍的氧化。因此，烧结时间过短会导致氧化反应不充分，相应导致二价镍过多，从而锂镍混占位严重，使所得正极材料的性能下降；烧结时间过长会导致结晶程度大，使所得正极材料的循环性能变差，同时成本也会上涨。因此，依据烧结过程的氧气流量来确定适宜的烧结时间。相应地，这可以控制二价镍的氧化过程，减少Li层中的二价镍含量，抑制锂镍混排，同时可避免正极材料的过度结晶化。最终，包含该正极材料的锂离子电池的充放电容量、倍率性能以及循环性能可以得到改善。
所述第一烧结可以是恒温处理或变温处理。例如，所述第一烧结包括在选自300-500℃的温度下保持1-10h，优选4-8h。或者，所述第一烧结包括在选自300-500℃的两个或更多个温度之间进行升温和降温(例如匀速升温和降温，优选速率为1-10℃/min，例如1℃/min、2℃/min、4℃/min、5℃/min、7℃/min或10℃/min)，总时间为1-10h，优选4-8h。在一个变型中，在升温和降温之间可以进一步包括保温步骤。
所述第二烧结可以是恒温处理或变温处理。例如，所述第二烧结包括在选自670+(1-x)*500至780+(1-x)*500℃的烧结温度T下，在氧气流量为Q下，进行第二烧结，时间t(h)为-13.17ln(Q)+14.54至-13.17ln(Q)+16.54。或者，所述第二烧结包括在选自670+(1-x)*500至780+(1-x)*500℃的两个或更多个温度之间进行升温和降温(例如匀速升温和降温，优选速率为1-10℃/min，例如1℃/min、2℃/min、4℃/min、5℃/min、7℃/min或10℃/min)，总时间t(h)为-13.17ln(Q)+14.54至-13.17ln(Q)+16.54。在一个变型中，在升温和降温之间可以进一步包括保温步骤。
本文对于升温至所述第一烧结和第二烧结所需温度的升温过程的 升温速率没有特别的限制，优选速率为1-10℃/min，例如1℃/min、2℃/min、4℃/min、5℃/min、7℃/min或10℃/min。
所述第二烧结后进行降温，例如自然冷却降到室温。第二烧结产物为上文所述的掺杂的镍钴锰活性材料。
在一个实施方式中，在第二烧结产物的至少部分表面上设置包覆层。包覆层包含选自B2O3、Al2O3、SiO2和W2O5中的至少一种氧化物。设置包覆层包括：混合第二烧结产物和包覆剂，和在250-500℃进行第三烧结处理。在设置包覆层步骤中，所述混合通过球磨、剪切、研磨、混料等方式进行。第二烧结产物和包覆剂的混合比例为，例如摩尔比1∶0.01-0.1。优选，所述混合的时间为1-4h。包覆剂为可以在第三烧结条件下转化为包覆层的材料，其包括例如硼酸、氢氧化铝、拟薄水铝石、勃姆石、三水铝石、拜耳石、硅酸、原硅酸或仲钨酸铵。
所述第三烧结可以是恒温处理或变温处理。例如，所述第三烧结包括在选自250-500℃的温度下保持1-24h，优选6-12h。或者，所述第三烧结包括在选自300-500℃的两个或更多个温度之间进行升温和降温(例如匀速升温和降温，优选速率为1-10℃/min，例如1℃/min、2℃/min、4℃/min、5℃/min、7℃/min或10℃/min)，总时间为1-24h，优选6-12h。在一个变型中，在升温和降温之间可以进一步包括保温步骤。对于升温至所述第三烧结所需温度的升温过程的升温速率没有特别的限制，优选速率为1-10℃/min，例如1℃/min、2℃/min、4℃/min、5℃/min、7℃/min或10℃/min。
所述第三烧结的产物为本发明的正极材料。任选地，对所述第三烧结的产物进行冷却、过筛和除铁杂质处理。
本申请的发明人在研究过程中意外发现，在制备正极材料的过程中，通过引入多种掺杂元素并进行程序化烧结，所制备的正极材料具有稳定的晶格结构，具有改善的颗粒强度。这种正极材料赋予锂电池更好的电化学性能，例如改善的倍率性能和循环稳定性。
本发明的正极材料可用于二次电池，如锂离子电池中。锂离子电池包括负极、正极、隔膜和电解液。
所述正极包括在正极集电器上的正极材料层，所述正极材料层包含本发明的正极材料。所述正极材料层还可以包含粘合剂和导电剂。粘结剂可以选自聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚丙烯腈 (PAN)、丁苯橡胶(SBR)和羧甲基纤维素(CMC)等树脂材料。导电剂可以包括碳基材料或导电聚合物。碳基材料可以包括，例如石墨、乙炔黑、碳纤维、纳米管、石墨烯、炭黑。导电聚合物可以包括聚苯胺、聚噻吩、聚乙炔、聚吡咯等。集电器可包括不锈钢、铝、镍、铁、钛、铜、锡或本领域技术人员已知的任何其它导电材料中的至少一种。在某些变体中，集电器可以是预涂覆的，如碳涂覆的铝箔。
本发明对负极的具体组成没有特别的限定，可以为本领域常规使用的负极，例如锂金属片。
本发明对隔膜的具体组成没有特别的限定，可以为本领域常规使用的隔膜。例如，隔膜为聚四氟乙烯、聚丙烯或聚乙烯等聚烯烃制成的多孔膜。
所述电解液可为各种常规的电解液，例如非水电解液。所述非水电解液为电解质锂盐在非水溶剂中形成的溶液，可以使用本领域技术人员已知的常规的非水电解液。比如电解质可以选自六氟磷酸锂(LiPF6)、高氯酸锂(LiClO4)、四氟硼酸锂(LiBF4)、六氟砷酸锂(LiAsF6)和六氟硅酸锂(LiSiF6)中的至少一种。非水溶剂可以选自链状酸酯、环状酸酯或其混合物。链状酸酯可以为碳酸二甲酯(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)中的至少一种。环状酸酯可以为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)和碳酸亚乙烯酯(VC)中的至少一种。
实施例
通过以下实施例使明本发明的特点和优点显而易见。实施例旨在描述而非以任何方式限制本发明。
测试方法
1.BET比表面积和孔隙尺寸测试
使用来自麦克莫瑞提克仪器有限公司的Tristar II 3020仪器进行BET比表面积测试。样品预处理条件包括：300℃真空脱气1h。采用BET方程计算样品的BET比表面积和孔隙尺寸。
2.比表面积随压力的变化
取3g样品，分别施加0吨、1.5吨、2.5吨、3.5吨及4.5吨压力，获得受压后的样品。用该受压后的样品进行BET比表面积测试，获得 不同压力下的比表面积数据，以表征比表面积随压力的变化。
3.电池性能
3.1电池样品的制备：
将制备的正极材料、导电炭黑及聚偏二氟乙烯(PVDF)按照质量比95％∶2.5％∶2.5％分别称量后混合，加N-甲基吡咯烷酮(NMP)并搅拌使混合物形成均匀浆料，涂覆于铝箔上，刮平，烘干处理后辊压平整，以100MPa的压力冲压成直径12mm、厚120μm的正极极片，然后置于真空烘箱中120℃烘干12h。
扣式电池组装过程在Ar气保护的手套箱中进行，其中水含量和氧含量均小于5ppm。使用上述获得的极片作为正极，使用直径为17mm，厚度为1mm的Li金属片作为负极；使用厚度为25μm的聚乙烯多孔膜作为隔膜，使用溶解有1mol/L的LiPF6的碳酸乙烯酯(EC)和碳酸二乙烯酯(DEC)体积比1∶1的混合液作为电解液，使用型号为2025的扣式电池壳作为电池壳。组装完成后，获得未活化的半电池。
3.2电池样品的性能评价：
(1)首周效率：
在室温(25℃)，电流密度为0.1C(1C＝200mA/g)下，对组装的锂离子电池样品进行测试，获得其循环首周充电比容量及放电比容量数据。通过首周放电比容量与充电比容量的比值计算出首周效率。
(2)循环性能：
电池的活化：
扣式电池样品组装完成后，静置2h，待其开路电压稳定后，以电流密度为0.1C进行恒流充电至截止电压4.3V，然后保持恒压充电30min，随后以0.1C电流恒流放电至截止电压3.0V；随后再以同样的方式进行充放电循环一次，使电池活化。
使用活化后的电池样品，在45℃温度下，以1C的电流密度在3.0-4.3V的电压区间，进行指定次充放电循环，例如80次。获得每次充放电循环的放电比容量，用于计算容量保持率，其中所述容量保持率＝在指定次循环时的放电比容量/首周放电比容量*100％。
(3)倍率性能测试
使用上述已活化后的电池样品，在室温下，在3.0-4.3V电压区间，分别以0.1C、0.2C、0.33C、0.5C、1C的电流密度进行充放电循环，以 获得在不同倍率下的放电比容量值。
(4)锂离子迁移系数
采用EIS测试方法测试锂离子迁移系数。具体地说，将未活化的电池样品，静置2h，在0.1C的电流密度下进行恒流充电至截止电压4.3V，然后保持恒压充电30min，随后以0.1C的电流密度恒流放电至截止电压3.0V；随后再在0.1C的电流密度下进行恒流充电至截止电压4.3V，得到满电态的电池样品。在100kHz～0.01Hz频率范围内对其进行EIS测试，其中振幅为10mV。根据以下公式得到Zre与ω-1/2拟合直线斜率，即σ：
Zre＝Rs+Rct+σω-1/2，以及
ω＝2πf，
其中，Zre为测试所得阻抗谱的实部，Rs为溶液电阻，Rct为电荷转移电阻，ω为角频率，f为测试频率，σ为Warburg因子；
再根据锂离子扩散系数计算公式计算得到材料体相Li+扩散系数：
DLi +＝R2T2/(2A2n4F4C2σ2)
其中R为理想气体常数，T为绝对温度，A为电极横截面积，n为电子转移数，F为法拉第常数，C为电极中锂离子浓度。
实施例1-1
(1)制备镍钴锰活性材料的前驱体
将摩尔比为90∶6∶4的硫酸镍、硫酸钴和硫酸锰溶于水中，形成浓度为2mol/L的混合盐溶液。配制浓度为8mol/L的氢氧化钠溶液作为沉淀剂溶液。配制浓度为6mol/L的氨水作为络合剂溶液。将混合盐溶液、沉淀剂溶液和络合剂溶液分别进料到反应釜中，其中控制进料速率，使得反应温度为60℃，pH为11.3，氨浓度为6g/L。在搅拌转速为600rpm下进行共沉积。80小时后，反应完成，得到镍钴锰活性材料的前驱体。镍钴锰活性材料的前驱体经陈化、分离、洗涤和烘干后备用。
(2)制备掺杂的镍钴锰活性材料
将上述镍钴锰活性材料的前驱体、作为锂源的氢氧化锂、作为第一掺杂剂的氧化铝、作为第二掺杂剂的氧化钨、作为第三掺杂剂的碳酸锶以摩尔比0.99∶1.03∶0.007∶0.002∶0.001在混料机中混合。在烧结炉中进行程序化烧结。其中，在流量1.33m3/kg·h下通入氧气，将混合物 从室温下匀速升温3h升温至300℃，并在300℃恒温2h，进行第一烧结处理。然后匀速升温6h升温至780℃，并在780℃恒温12h，进行第二烧结处理。最后，自然降温到室温，得到掺杂的镍钴锰活性材料。掺杂的镍钴锰活性材料经冷却、破碎、过筛后备用。
(3)制备正极材料
将掺杂的镍钴锰活性材料与作为包覆剂的硼酸以摩尔比为1∶0.01在高速混料机中混合。在烧结炉中进行第三烧结处理，其中在350℃下烧结10h，得到正极材料P1，其具有结构式Li1.03(Ni0.896Co0.057Mn0.037Al0.007Zr0.002Sr0.001)O2/B2O3。正极材料P1经冷却、过筛并除去铁杂质后备用。
如上所述，对得到的正极材料P1进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
同时，对得到的正极材料P1进行极限水洗，并对其就行SEM和XRD测量，结果分别显示在图1和2中。
图1示意显示实施例1-1的正极材料P1在进行极限水洗前后的SEM图像，其中A为其在极限水洗前的SEM图像，而B为其在极限水洗后的SEM图像。图1显示，实施例1-1的正极材料P1在进行极限水洗前后的SEM图像差别不大，这意味着极限水洗并未对实施例1-1的正极材料P1的结构产生重大影响。
图2示意显示实施例1-1的正极材料P1在进行极限水洗前后的XRD图像，其中A为其在极限水洗前的XRD图像，而B为其在极限水洗后的XRD图像。图2显示，实施例1-1的正极材料P1在进行极限水洗前后的XRD图像基本上相同，这意味着极限水洗并未对实施例1-1的正极材料P1的结构产生重大影响。这与通过SEM图像获得的结果相一致。
同时，如上所述，使用正极材料P1制备锂离子电池样品，并进行性能测试。测试结果列在表1-3中。
实施例1-2
重复实施例1-1，不同之处在于，采用表1-1中所列的材料和工艺条件替换实施例1-1中的相应材料和工艺条件，得到正极材料P2。
正极材料P2具有结构式 Li1.03(Ni0.896Co0.057Mn0.037Al0.006Nb0.003W0.001)O2/B2O3。
如上所述，对得到的正极材料P2进行极限水洗，并测量其本征水洗比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P2制备锂离子电池样品，并进行性能测试。测试结果列在表1-3中。
对比例1-1
重复实施例1-1，不同之处在于，采用表1-1中所列的材料和工艺条件替换实施例1-1中的相应材料和工艺条件，得到正极材料P3。
正极材料P3具有结构式Li1.03(Ni0.896Co0.057Mn0.037Zr0.005La0.004W0.001)O2/B2O3。
如上所述，对得到的正极材料P3进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P3制备锂离子电池样品，并进行性能测试。测试结果列在表1-3中。
对比例1-2
重复实施例1-1，不同之处在于，采用表1-1中所列的材料和工艺条件替换实施例1-1中的相应材料和工艺条件，得到正极材料P4。
正极材料P4具有结构式Li1.03(Ni0.896Co0.057Mn0.037Al0.007Zr0.002Sr0.001)O2/B2O3。
如上所述，对得到的正极材料P4进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P4制备锂离子电池样品，并进行性能测试。测试结果列在表1-3中。
对比例1-3
重复实施例1-1，不同之处在于，采用表1-1中所列的材料和工艺条件替换实施例1-1中的相应材料和工艺条件，得到正极材料P5。
正极材料P5具有结构式Li1.03(Ni0.896Co0.057Mn0.037Al0.007Zr0.002Sr0.001)O2/B2O3。
如上所述，对得到的正极材料P5进行极限水洗，并测量其本征比 表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P5制备锂离子电池样品，并进行性能测试。测试结果列在表1-3中。
表1-1实施例和对比例所用材料和工艺条件汇总
表1-2正极材料的参数
表1-3正极材料的性能
实施例2-1
(1)制备镍钴锰活性材料的前驱体
将摩尔比为65∶15∶20的硫酸镍、硫酸钴和硫酸锰溶于水中，形成浓度为1.7mol/L的混合盐溶液。配制浓度为8mol/L的氢氧化钠溶液作为沉淀剂溶液。配制浓度为13mol/L的氨水作为络合剂溶液。将混合盐溶液、沉淀剂溶液和络合剂溶液分别进料到反应釜中，其中控制 进料速率，使得反应温度为40℃，pH为11.6，氨浓度为6g/L。在搅拌转速为600rpm下进行共沉积。80小时后，反应完成，得到镍钴锰活性材料的前驱体。镍钴锰活性材料的前驱体经陈化、分离、洗涤和烘干后备用。
(2)制备掺杂的镍钴锰活性材料
将上述镍钴锰活性材料的前驱体、作为锂源的氢氧化锂、作为第一掺杂剂的氧化锆、作为第二掺杂剂的氧化钇、作为第三掺杂剂的碳酸钨以摩尔比1.05∶0.99∶0.006∶0.002∶0.002在混料机中混合。在烧结炉中进行程序化烧结。其中，在流量1.33m3/kg·h下通入氧气，将混合物从室温下匀速升温3h升温至300℃，并在300℃恒温2h，进行第一烧结处理。然后匀速升温6h升温至780℃，并在780℃恒温12h，进行第二烧结处理。最后，自然降温到室温，得到掺杂的镍钴锰活性材料。掺杂的镍钴锰活性材料经冷却、破碎、过筛后备用。
(3)制备正极材料
将掺杂的镍钴锰活性材料与作为包覆剂的硼酸和氢氧化铝以摩尔比为1/0.01/0.01在高速混料机中混合。在烧结炉中进行第三烧结处理，其中在450℃下烧结10h，得到正极材料P6，其具有结构式Li1.03(Ni0.648Co0.152Mn0.200Zr0.006Y0.002W0.002)O2/B2O3+Al2O3。正极材料P6经冷却、过筛并除去铁杂质后备用。
如上所述，对得到的正极材料P6进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P6制备锂离子电池样品，并进行性能测试。测试结果列在表2-3中。
实施例2-2
重复实施例2-1，不同之处在于，采用表2-1中所列的材料和工艺条件替换实施例2-1中的相应材料和工艺条件，得到正极材料P7。
正极材料P7具有结构式Li1.03(Ni0.648Co0.152Mn0.200Nb0.003Sr0.002)O2/B2O3+Al2O3。
如上所述，对得到的正极材料P7进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P7制备锂离子电池样品，并进行性能测 试。测试结果列在表2-3中。
对比例2-1
重复实施例2-1，不同之处在于，采用表2-1中所列的材料和工艺条件替换实施例2-1中的相应材料和工艺条件，得到正极材料P8。
正极材料P8具有结构式Li1.03(Ni0.648Co0.152Mn0.200Ti0.005Y0.004Sr0.001)O2/B2O3+Al2O3。
如上所述，对得到的正极材料P8进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P8制备锂离子电池样品，并进行性能测试。测试结果列在表2-3中。
对比例2-2
重复实施例2-1，不同之处在于，采用表2-1中所列的材料和工艺条件替换实施例2-1中的相应材料和工艺条件，得到正极材料P9。
正极材料P9具有结构式Li1.03(Ni0.648Co0.152Mn0.200Zr0.006Y0.002W0.002)O2/B2O3+Al2O3。
如上所述，对得到的正极材料P9进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P9制备锂离子电池样品，并进行性能测试。测试结果列在表2-3中。
对比例2-3
重复实施例2-1，不同之处在于，采用表2-1中所列的材料和工艺条件替换实施例2-1中的相应材料和工艺条件，得到正极材料P10。
正极材料P10具有结构式Li1.03(Ni0.648Co0.152Mn0.200Zr0.006Y0.002W0.002)O2/B2O3+Al2O3。
如上所述，对得到的正极材料P10进行极限水洗，并测量其本征比表面积和本征孔隙尺寸。测试结果列在表1-2中。
如上所述，使用正极材料P10制备锂离子电池样品，并进行性能测试。测试结果列在表2-3中。
表2-1实施例和对比例所用材料和工艺条件汇总
表2-2正极材料的参数
表2-3正极材料的性能
以上实施例显示，相较于实施例1-1及实施例1-2，对比例1-1所用掺杂元素发生改变。相应地，对比例1-1获得的正极材料的本征比表面积以及本征孔隙分布(R10、R50及R90)均大于实施例1-1及实施例1-2的正极材料。相应地，其循环保持率下降，80次循环后的容量保持率仅为88.6％。同时，对比例1-1获得的正极材料不具有足够好的离子稳定层状结构，导致晶界处更容易产生裂纹，使其抗压能力下降明显。因此，其虽有相对出色的首圈容量，但是在大电流下循环的性 能变差。对比例1-2虽然掺杂体系与实施例1-1及实施例1-2相同但是烧结温度过低。这导致晶体成相不完善，Li+迁移通道构建较差，Li+迁移数较低，容量发挥没有达到应有水平。对比例1-3采用减小的氧气流量，从而导致烧结时间变长，氧化反应缓慢进行。结果是，锂镍混占位现象严重，晶内裂纹较易生成，抗压能力下降，同时Li+迁移受阻，初始容量发挥正常但是Li+不能有效回到原有位置，倍率性能及循环保持率都有所降低。在比较实施例2-1和2-2与对比例2-1至2-3时，结果与上述一致。

Claims (17)

  1. 一种正极材料，其本征比表面积为5-13m2/g。
  2. 根据权利要求1所述的正极材料，其中，所述正极材料的本征孔隙尺寸符合2.1nm≤R10≤2.5nm，23.0nm≤R50≤27.0nm并且100.0nm≤R90≤160.0nm。
  3. 根据权利要求1所述的正极材料，其中正极材料的平均粒径为7.8-14.2nm；或者
    正极材料的压实密度为2.0-3.8g/cm3。
  4. 根据权利要求1所述的正极材料，其中在以1.5吨压力压实所述正极材料时，压实后所述正极材料的比表面积增加率ΔSSA1.5不超过15％；或者
    以2.5吨压力压实所述正极材料时，压实后所述正极材料的比表面积增加率ΔSSA2.5不超过40％；或者
    在以3.5吨压力压实所述正极材料时，压实后所述正极材料的比表面积增加率ΔSSA3.5不超过60％；或者
    在以4.5吨压力压实所述正极材料时，压实后所述正极材料的比表面积增加率ΔSSA4.5不超过100％。
  5. 根据权利要求1所述的正极材料，其包含掺杂的镍钴锰活性材料和任选的在其至少部分表面上的包覆层，其中掺杂的镍钴锰活性材料中的镍钴锰活性材料的通式为LiNixCoyMnzO2，其中0.3≤x≤0.99，0.01≤y≤0.5，0.01≤z≤0.5，其中掺杂的镍钴锰活性材料中的掺杂剂包括第一掺杂元素M，其选自Al和Zr中的至少一种；第二掺杂元素G，其选自Y、Ti、Nb、Cr、Er和Mg中的至少一种；和第三掺杂元素T，其选自Ba、V、Sr、Ta、Mo、W和Ce中的至少一种，其中包覆层包含选自B2O3、Al2O3、SiO2和W2O5中的至少一种氧化物。
  6. 根据权利要求1所述的正极材料，其中掺杂的镍钴锰活性材料通式为Li1+a(NixCoyMnzMdGeTf)O2，其中0≤a≤0.1，0.3≤x≤0.99，0.01≤y≤0.5，0.01≤z≤0.5，0＜d≤0.08，0＜e≤0.05，0＜f≤0.03，1＜e/f＜5且x+y+z+d+e+f＝1。
  7. 一种制备根据权利要求1-4任一所述的正极材料的方法，包括：
    将正极材料前驱体进行锂化处理，其通过如下进行：
    混合前驱体与锂源；和
    在氧气气氛下进行程序化烧结，所述程序化烧结包括：
    在300-500℃进行第一烧结处理，得到第一烧结产物；和
    进行第二烧结处理，得到第二烧结产物，
    其中在第二烧结处理过程中，烧结温度T与镍钴锰活性材料中的Ni含量符合下式：
    670+(1-x)*500≤T≤780+(1-x)*500，
    其中0.3≤x≤0.99。
  8. 根据权利要求7所述的方法，其中氧气气氛通过通入氧气实现，优选氧气流量Q为1-2m3/kg·h。
  9. 根据权利要求8所述的方法，其中在350-450℃的温度下进行第一烧结处理1-10h，并且
    所述第二烧结的烧结温度T为：690+(1-x)*500至770+(1-x)*500℃，其中0.3≤x≤0.99，并且氧气流量Q(m3/kg·h)与第二烧结时间t(h)的关系满足-13.17ln(Q)+14.54≤t≤-13.17ln(Q)+16.54，其中氧气流量Q为1-2m3/kg·h。
  10. 根据权利要求7所述的方法，包括：
    (1)使镍盐、钴盐和锰盐共沉积，形成镍钴锰活性材料的前驱体；
    (2)对镍钴锰活性材料的前驱体进行掺杂和锂化处理，其通过如下进行：
    混合镍钴锰活性材料的前驱体与锂源、含有第一掺杂元素的第一掺杂剂、含有第二掺杂元素的第二掺杂剂和含有第三掺杂元素的第三掺杂剂；和
    在氧气气氛下进行程序化烧结，所述程序化烧结包括：
    在300-500℃进行第一烧结处理，得到第一烧结产物；和
    进行第二烧结处理，得到第二烧结产物，
    其中在第二烧结处理过程中，烧结温度T与镍钴锰活性材料中的Ni含量符合下式：
    670+(1-x)*500≤T≤780+(1-x)*500，
    其中0.3≤x≤0.99；和
    (3)在第二烧结产物的至少部分表面上设置包覆层。
  11. 根据权利要求10所述的方法，其中镍盐选自硫酸镍、硝酸镍、 乙酸镍、草酸镍和氯化镍中的至少一种；
    钴盐选自硝酸钴、氯化钴、乙酸钴和硫酸钴中的至少一种；
    锰盐选自硫酸锰、硝酸锰、乙酸锰和氯化锰中的至少一种；
    锂源选自硝酸锂、盐酸锂、碳酸锂、氢氧化锂和乙酸锂中的至少一种；含有第一掺杂元素的第一掺杂剂为第一掺杂元素的氧化物或在第二烧结条件下能够转化为第一掺杂元素的氧化物的第一掺杂元素的盐，所述第一掺杂元素的盐选自第一掺杂元素的硫酸盐、硝酸盐、乙酸盐、盐酸盐和草酸盐中的至少一种；
    含有第二掺杂元素的第二掺杂剂为第二掺杂元素的氧化物或在第二烧结条件下能够转化为第二掺杂元素的氧化物的第二掺杂元素的盐，所述第二掺杂元素的盐选自第二掺杂元素的硫酸盐、硝酸盐、乙酸盐、盐酸盐和草酸盐中的至少一种；
    含有第三掺杂元素的第三掺杂剂为第三掺杂元素的氧化物或在第二烧结条件下能够转化为第三掺杂元素的氧化物的第一掺杂元素的盐，所述第三掺杂元素的盐选自第三掺杂元素的硫酸盐、硝酸盐、乙酸盐、盐酸盐和草酸盐中的至少一种。
  12. 根据权利要求10所述的方法，其中共沉积在沉淀剂溶液和络合剂溶液存在下进行；
    优选，所述沉淀剂选自NaOH、KOH和LiOH中的至少一种，并且所述络合剂选自氨水、草酸铵、碳酸铵和氢氧化铵中的至少一种。
  13. 根据权利要求10所述的方法，其中设置包覆层包括：混合第二烧结产物和包覆剂，和在250-500℃进行第三烧结处理，
    优选，包覆剂包括硼酸，氢氧化铝、拟薄水铝石、勃姆石，三水铝石、拜耳石、硅酸、原硅酸或仲钨酸铵。
  14. 根据权利要求10所述的方法，其中所述第一烧结是恒温处理，所述第二烧结是恒温处理，并且所述第三烧结是恒温处理。
  15. 一种如权利要求1-6所述正极材料在锂电池中的应用。
  16. 一种用于锂电池的正极，其含有如权利要求1-6所述正极材料。
  17. 一种锂电池，其包括正极，负极和位于正极负极之间的隔膜，其中所述正极含有如权利要求1-6所述正极材料。
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CN117458021A (zh) * 2023-10-19 2024-01-26 常州大学 一种基于硫酸钠电解的废旧三元锂离子电池正极材料回收方法
CN117550656A (zh) * 2024-01-09 2024-02-13 阜阳海钠科技有限责任公司 一种正极材料及其制备方法和钠电池
CN117550656B (zh) * 2024-01-09 2024-04-23 阜阳海钠科技有限责任公司 一种正极材料及其制备方法和钠电池

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