WO2017025007A1 - 锂离子二次电池的正极活性材料及其制备方法和应用 - Google Patents

锂离子二次电池的正极活性材料及其制备方法和应用 Download PDF

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WO2017025007A1
WO2017025007A1 PCT/CN2016/093952 CN2016093952W WO2017025007A1 WO 2017025007 A1 WO2017025007 A1 WO 2017025007A1 CN 2016093952 W CN2016093952 W CN 2016093952W WO 2017025007 A1 WO2017025007 A1 WO 2017025007A1
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metal oxide
positive electrode
active material
lithium
particles
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French (fr)
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王昊
林明翔
黄学杰
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Institute of Physics of CAS
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Priority to EP16834631.0A priority Critical patent/EP3336939B1/en
Priority to US15/751,519 priority patent/US20180248179A1/en
Priority to JP2018506603A priority patent/JP2018523277A/ja
Priority to KR1020187006395A priority patent/KR20180038485A/ko
Publication of WO2017025007A1 publication Critical patent/WO2017025007A1/zh
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Definitions

  • the present invention relates to a positive electrode active material of a spinel-structured lithium ion secondary battery, a preparation method and application thereof.
  • lithium ion secondary batteries Compared with other rechargeable battery systems, lithium ion secondary batteries have the advantages of high operating voltage, light weight, small size, no memory effect, low self-discharge rate, long cycle life, high energy density, etc., and have been widely used in mobile phones.
  • Mobile terminal products such as laptops and tablets.
  • electric vehicles have been rapidly developed by governments and automobile manufacturers, and lithium-ion batteries have become the ideal power source for a new generation of electric vehicles with their excellent performance.
  • the cathode material which accounts for about 30% to 40% of its cost, not only participates in the chemical reaction of the battery as an electrode material, but also is the main source of lithium ions, and has the greatest influence on improving the energy density and cost of the lithium ion battery.
  • the cathode materials for lithium ion batteries which have been studied so far, include lithium cobalt oxide (LiCoO 2 ) and lithium nickelate (LiNiO 2 ) having a layered structure, lithium manganate (LiMn 2 O 4 ) having a spinel structure, and Lithium iron phosphate (LiFePO 4 ) with an olivine structure.
  • LiCoO 2 cathode materials have been widely used in batteries for smartphones, tablets, and notebook computers, but cannot be applied to electric vehicles due to cost and safety issues.
  • the spinel-structured LiMn 2 O 4 has a low raw material cost, a simple production process, good overcharge resistance, high safety, a three-dimensional lithium ion diffusion channel, and good rate performance.
  • its main disadvantage is that the capacity is attenuated faster, especially under high temperature conditions; at the same time, during the electrochemical cycle, Mn will dissolve; its energy density is low and the cycle life is short.
  • the olivine-structured LiFePO 4 has the characteristics of low cost, environmental friendliness, high safety and long cycle life, but its disadvantage is low operating voltage (about 3.45V vs. Li/Li + ), and full battery assembled with graphite. Low energy density, low electronic conductance, and poor rate performance.
  • lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ) has a theoretical specific capacity of 146.7 mAh/g, a reversible capacity of 136 mAh/g, and an operating voltage of 4.7 V vs. Li/. Li + , the theoretical specific energy reaches 695Wh/kg.
  • LiNi 0.5 Mn 1.5 O 4 has a three-dimensional lithium ion transport channel, its rate performance is good, and it can be quickly charged and discharged, which is required for lithium ion batteries for electric vehicles.
  • the transition metal in LiNi 0.5 Mn 1.5 O 4 is mainly Mn, and the cost is low.
  • LiNi 0.5 Mn 1.5 O 4 is 4.7V vs. Li/Li + , it exceeds the electrochemical window of the common commercial electrolyte (about 4.5V vs. Li/Li + ), which causes the electrolyte to be easily oxidized.
  • a positive electrode/electrolyte interface film was formed on the surface of LiNi 0.5 Mn 1.5 O 4 . Studies have shown that the electronic conductance and Li + conductivity of the CEI film are poor, and the trace amount of the electrolyte is inevitably contained.
  • H 2 O H 2 O reacts with LiPF 6 in the electrolyte to form HF, LiNi 0.5 Mn 1.5 O 4 is attacked by HF, and at the same time, the dissolution of manganese is intensified at high voltage, resulting in an increase in impedance of the battery and attenuation of specific capacity. .
  • room temperature 25 ° C
  • the decomposition rate of the electrolyte is slow, and the specific capacity decay rate of the material is slow.
  • the high temperature of 55 ° C the decomposition of the electrolyte and the dissolution of manganese accelerate, so that the impedance of the battery increases. The capacity decays faster.
  • An object of the present invention is to provide a method for improving LiNi 0.5 Mn 1.5 O 4 which is capable of inhibiting decomposition of an electrolyte and dissolution of manganese under conditions of high charging voltage and high temperature, thereby improving capacity retention and charge and discharge coulombic efficiency.
  • the improved material can be used as a positive electrode active material of a lithium ion secondary battery, and the battery made of the material has excellent cycle performance.
  • the inventors of the present invention have found that a coated lithium transition metal oxide, such as a portion of the surface of the material covering the island with titanium dioxide, is coated with a thin layer or formed into a shallow layer in a region not covered with titanium dioxide.
  • the solid solution LiNi 0.5-x Mn 1.5-y ⁇ A ⁇ u O z has better cycle stability than the uncoated lithium transition metal oxide when used in a lithium ion secondary battery. Therefore, when the positive electrode active material of the present invention is used for a lithium ion secondary battery, it can be used as an energy source for applications such as electric tools, electric bicycles, hybrid electric vehicles, and pure electric vehicles.
  • metal oxides such as TiO 2 , ZrO 2 , SnO 2 , SiO 2 , GeO 2 , HfO 2 , Nb 2 O 5 , etc.
  • a valence of tetravalent or higher than tetravalent metals have a valence of tetravalent or higher than tetravalent metals.
  • oxides of the metal having a valence of less than tetravalent such as MgO, Al 2 O 3 , ZnO, CaO, etc., as a surface coating or a shallow gradient solid solution coating material covering the positive electrode active material A similar effect can also be produced on the surface of the material.
  • the present invention provides a positive electrode active material that a spinel structure, the positive electrode active material comprises a chemical formula LiNi 0.5-x Mn 1.5-y ⁇ A ⁇ containing a lithium compound and a particulate u O z coating the lithium-containing compound a first metal oxide and a second metal oxide on the surface of the particle, wherein the first metal oxide is at least one oxide of a metal having a valence of tetravalent or greater than tetravalent, and covers the lithium in an island shape a partial surface of the compound particle, the second metal oxide being an oxide of at least one metal having a valence of less than tetravalent, and covering a portion of the surface of the lithium-containing compound particle not covered by the first metal oxide; wherein ⁇ A ⁇ doped composition, represented by the formula I [sum] w B i, B i is the doping element, used to replace Ni and / or Mn, w i is the atomic percentage of B i ⁇ a ⁇ of the entire composition do
  • the values of x, y, z and u are capable of producing a substantially single-phase lithium metal oxide, for example 95% or more of the material, more preferably 99% or more. phase.
  • the first metal oxide is selected from one of TiO 2 , ZrO 2 , SnO 2 , SiO 2 , GeO 2 , CeO 2 , HfO 2 , and Nb 2 O 5 . Kind or more.
  • the second metal oxide is selected from one or more of MgO, Al 2 O 3 , ZnO, Ce 2 O 3 , and CaO.
  • the LiNi 0.5-x Mn 1.5-y ⁇ A ⁇ u O z compound preferably comprises one or more doping elements, ie u>0.
  • the doping element B i is an element other than Ni and Mn, and is preferably selected from one of Al, Mg, Fe, Co, Ti, Y, Sc, Ce, Ru, Mo, W, Zr, Ca, Sr, kind or more. More preferably, the doping element B i comprises two or more doping cations.
  • the doping element B i in the LiNi 0.5-x Mn 1.5-y ⁇ A ⁇ u O z compound may contain Li + .
  • the lithium-containing compound particles have a particle diameter of 1 to 20 ⁇ m; and the first metal oxide has a particle diameter of 10 to 500 nm.
  • the first metal oxide has a coverage of 1 to 75% on the surface of the lithium-containing compound particles.
  • the second metal oxide is entirely coated on other regions of the surface of the lithium-containing compound particles which are not covered by the first metal oxide.
  • the thickness of the second metal oxide is entirely coated to 1 to 20 nm or formed.
  • a shallow gradient solid solution having a depth of less than 200 nm.
  • the positive electrode active material of the spinel structure LiNi 0.5-x Mn 1.5-y ⁇ A ⁇ u O z lithium metal oxide, a tetravalent valence of greater than or tetravalent metal oxides and less than the valence of the tetravalent metal
  • the presence of the oxide can be determined by any method known to those of ordinary skill in the art. For example, these compounds can be used to determine the relative content of each compound by measuring the area of a peak representing the above compound by an X-ray diffraction method.
  • the present invention also provides a method for preparing the above positive electrode active material, the method comprising the steps of:
  • the mixture obtained in the step (1) is sequentially fired and cooled at a temperature of 400 to 500 ° C and 800 to 1000 ° C to prepare a lithium-containing compound having a surface island covering the first metal oxide;
  • the mixing of the step (1) may preferably be dry mixing, and the mixing of the step (3) may preferably be wet mixing.
  • the source compound containing Ni, Mn, Li, and optionally ⁇ A ⁇ is sufficient to provide LiNi 0.5 between Ni, Mn, Li, and ⁇ A ⁇ as described above.
  • -x Mn 1.5-y ⁇ A ⁇ The amount of stoichiometric relationship corresponding to u O z is intimately mixed.
  • the source compound may be a pure element, but is usually a compound containing an element such as an oxide or a salt.
  • the source compound is typically a hydrated or anhydrous oxide, hydroxide, carbonate, nitrate, sulfate, chloride or fluoride, and may be any other suitable source compound as long as it does not Elemental defects in the resulting embedded compound.
  • the source compound is an oxide, acetate or carbonate because the gaseous by-products produced by these compounds during the sintering process are more environmentally friendly.
  • Each element of the lithium metal oxide may be provided by a separate source compound, or at least two elements may be provided from the same source material compound (ie, a precursor comprising two or more elements prepared by a coprecipitation method).
  • the source compounds can be intimately mixed in any desired order.
  • the term "closely bonded" as used herein means that the source compounds are thoroughly mixed together so that upon firing, the source compounds can form a single phase lithium metal oxide. According to the invention, the source compounds are often preferably tightly bound to enable the production of a substantially single phase lithium metal oxide.
  • the source compound is preferably subjected to dry mixing, for example, by mixing the source compound in a ball mill to produce an intimately mixed mixture.
  • wet processing methods such as sol-gel reaction and spray drying may be used, and the wet treatment method may be used alone or mixed with dry method. use together.
  • the present invention also provides a positive electrode of a lithium ion battery, the positive electrode comprising a current collector and a positive active material, a carbon material conductive additive and a binder supported on the current collector, wherein the positive active material is provided by the present invention A positive active material or a positive active material produced by the method of the present invention.
  • the present invention also provides a lithium ion battery comprising a battery case, an electrode group and an electrolyte, the electrode group and the electrolyte being sealed in a battery case, the electrode group comprising a positive electrode, a separator and a negative electrode, wherein The positive electrode is the positive electrode provided by the present invention.
  • the positive electrode active material provided by the present invention covers a part of the surface of the lithium transition metal oxide particle in an island shape with an oxide of a metal having a valence of tetravalent or more than tetravalent, and the valence is tetravalent or more in the uncovered region.
  • the oxide of the valence metal is coated as a thin layer or forms a shallow surface solid solution.
  • Example 1 is an XRD pattern of positive electrode active materials A2 and A18 prepared in Example 2 and Example 18 (Comparative Example).
  • Example 2 is a SEM picture of the positive electrode active material A18 prepared in Example 18.
  • Example 3 is a SEM picture of the positive electrode active material A2 prepared in Example 2.
  • Figure 4 is a graph showing the trend of discharge capacity with cycle number of batteries B2 and B18 assembled from materials A2 and A18 prepared in Example 2 and Example 18 (Comparative Example) at a high temperature test environment of 55 °C.
  • Figure 5 is a graph showing the change in discharge capacity with cycle number of batteries B2 and B18 assembled from materials A2 and A18 prepared in Example 2 and Example 18 (Comparative Example) at a room temperature test environment of 25 °C.
  • Fig. 6 is a graph showing the relationship between the discharge capacity and the number of cycles of the materials A2 and A18 prepared as positive electrode tabs, respectively, and paired with the graphite anodes, and assembled into a full-cell C2 and C18 room temperature test environment at 25 °C.
  • Li 2 CO 3 purity of 99%
  • 179.7537g of Ni 0.25 Mn 0.75 (OH) 2 and 0.7995g of TiO 2 (particle size of about 100nm) were placed in a planetary ball mill and uniformly mixed by dry method. .
  • the mixture was placed in a crucible, placed in a muffle furnace, pre-fired at 500 ° C for 5 hours, then heated to 900 ° C, sintered for 12 hours, and after natural cooling, the surface was partially covered with TiO 2 particles (coverage about A LiNi 0.5 Mn 1.5 O 4 particulate material (this material is referred to as A1) of 20%; TiO 2 particles having a particle diameter of about 100 nm).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about As for 100 nm), the remaining region was completely coated with LiO 0.5 Mn 1.5 O 4 particulate material of MgO (the thickness of the MgO cladding layer was about 3 nm) (this material was counted as A2).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered ZrO 2 particle (covering degree of about 20%; the particle size of the ZrO 2 particle was about As for 100 nm), the remaining region was completely coated with LiO 0.5 Mn 1.5 O 4 particulate material of MgO (the thickness of the MgO cladding layer was about 3 nm) (this material was counted as A3).
  • Nb 2 O 5 particles coverage of about 20%; Nb 2 O 5 particles having a particle diameter of about 100 nm
  • LiNi 0.5 Mn 1.5 O 4 particulate material and 2.145 g of Mg (CH 3 ).
  • COO) 2 ⁇ 4H 2 O purity 99.997% was placed in a beaker containing 500 mL of deionized water, and the beaker was placed in a magnetic stirrer and stirred evenly for 12 hours (500 rpm), followed by complete deionized water. evaporation.
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered Nb 2 O 5 particle (covering degree of about 20%; Nb 2 O 5 particles).
  • the particle size is about 100 nm), and the remaining region is completely coated with LiO 0.5 Mn 1.5 O 4 particulate material (this material is referred to as A4) of MgO (the thickness of the MgO cladding layer is about 3 nm).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 40%; the particle size of the TiO 2 particles was about As for 100 nm), the remaining region was completely coated with a LiNi 0.5 Mn 1.5 O 4 particulate material of MgO (the thickness of the MgO cladding layer was about 3 nm) (this material was counted as A5).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (coverage of about 60%; the particle size of the TiO 2 particles was about As for 100 nm), the remaining region was completely coated with a LiNi 0.5 Mn 1.5 O 4 particulate material of MgO (the thickness of the MgO cladding layer was about 3 nm) (this material was counted as A6).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about The remaining region is completely covered with a LiNi 0.5 Mn 1.5 O 4 particulate material (this material is referred to as A7) of MgO (the thickness of the MgO cladding layer is about 3 nm).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about The area is 150 nm), and the remaining region is completely coated with LiO 0.5 Mn 1.5 O 4 particulate material (this material is referred to as A8) of MgO (the thickness of the MgO cladding layer is about 3 nm).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about The remaining area is completely covered with MgO (the thickness of the MgO cladding layer is about 3 nm) of LiNi 0.5 Mn 1.5 O 4 particulate material (this material is counted as A9).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about As for 100 nm), the remaining region was completely coated with a LiNi 0.5 Mn 1.5 O 4 particulate material of MgO (the thickness of the MgO cladding layer was about 6 nm) (this material was counted as A10).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about The remaining area is completely covered with a LiNi 0.5 Mn 1.5 O 4 particulate material (this material is referred to as A11) of MgO (the thickness of the MgO cladding layer is about 9 nm).
  • A11 LiNi 0.5 Mn 1.5 O 4 particulate material
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about The remaining region is completely covered with LiNi 0.5 Mn 1.5 O 4 particulate material (this material is referred to as A12) of ZnO (the thickness of the ZnO cladding layer is about 3 nm).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about The remaining region is completely covered with a LiNi 0.5 Mn 1.5 O 4 particulate material of Al 2 O 3 (the thickness of the Al 2 O 3 cladding layer is about 3 nm) (this material is counted as A13).
  • the mixture was placed in a crucible, placed in a muffle furnace, pre-fired at 500 ° C for 5 hours, then heated to 900 ° C, sintered for 12 h, and naturally cooled to obtain a surface partially covered with TiO 2 particles (coverage is about 20%; LiNi 0.4 Mn 1.5 Mg 0.1 O 4 particulate material having a particle size of about 100 nm of TiO 2 particles (this material is counted as A14).
  • Example 14 183 g of the A14 material prepared in Example 14 and 2.145 g of Mg(CH 3 COO) 2 ⁇ 4H 2 O (purity of 99.997%) were placed in a beaker containing 500 mL of deionized water, and the beaker was placed in a magnetic stirrer and uniformly stirred. 12 hours (500 rpm for stirring), then the deionized water was completely evaporated.
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 500 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (covering degree of about 20%; the particle size of the TiO 2 particles was about It is 100 nm), and the remaining region is completely coated with a LiNi 0.4 Mn 1.5 Mg 0.1 O 4 particulate material (this material is referred to as A15) of MgO (the thickness of the MgO cladding layer is about 3 nm).
  • Li 2 CO 3 purity of 99%
  • Ni 0.225 Mn 0.725 Al 0.05 (OH) 2 0.7995 g of TiO 2 (purchased from Alfa Aesar, purity 99.9%, particle size of about 100 nm) ) placed in a planetary ball mill and mixed evenly by dry method.
  • the mixture was placed in a crucible, placed in a muffle furnace, pre-fired at 500 ° C for 5 hours, then heated to 900 ° C, sintered for 12 h, and naturally cooled to obtain a surface partially covered with TiO 2 particles (coverage is about 20%; LiNi 0.45 Mn 1.45 Al 0.1 O 4 particulate material having a particle size of about 100 nm of TiO 2 particles (this material is counted as A16).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 600 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (coverage of about 20%; the particle size of the TiO 2 particles was about As for 100 nm), the remaining region forms a LiNi 0.5 Mn 1.5 O 4 particulate material of LiNi 0.5-x Mn 1.5 Mg x O 4 shallow solid solution having a depth of about 20 nm (this material is counted as A19).
  • the resulting mixture was then placed in a muffle furnace (under an air atmosphere), sintered at 60 ° C for 5 hours, and naturally cooled to obtain a surface-covered TiO 2 particle (coverage of about 20%; the particle size of the TiO 2 particles was about As for 100 nm), the remaining region forms a LiNi 0.5 Mn 1.5 O 4 particulate material of LiNi 0.5-x Mn 1.5-y Al x+y O 4 shallow solid solution having a depth of about 20 nm (this material is counted as A20).
  • Figure 1 is an XRD pattern of materials A2 and A18 (comparative material), the XRD of which is almost the same, both are cubic spinel structures, indicating LiNi 0.5 Mn 1.5 O 4 material after coating with TiO 2 and MgO (A2 The structure of the material did not change.
  • Figure 2 and Figure 3 are SEM photographs of A18 (comparative material) and A2, respectively.
  • the shape of A18 (comparative material) is a regular truncated octahedron with a smooth surface and a surface of A2 material partially covering TiO 2 particles. The other areas are coated with MgO material.
  • the LiNi 0.5 Mn 1.5 O 4 particles have a particle diameter of 1 to 20 ⁇ m
  • the TiO 2 particles have a particle diameter of 50 to 200 nm.
  • the materials A1 to A20 prepared in Examples 1 to 20 were assembled into a button battery in accordance with the following procedure.
  • the materials A1 to A20 prepared in Examples 1 to 20 were respectively used as a positive electrode active material, carbon black was used as a conductive additive, and polyvinylidene fluoride (PVDF) was used as a binder, and the ratio was 90:5:5 by weight.
  • NMP N-methylpyrrolidone
  • a uniform positive electrode slurry was uniformly coated on an aluminum foil current collector having a thickness of 15 ⁇ m, and dried at 55 ° C to form a 100 ⁇ m thick pole piece, which was placed under a roll press and pressed at a pressure of about 1 MPa ⁇ 1.5 cm 2 . ), cut the pole piece to a diameter of
  • the wafer was baked in a vacuum oven at 120 ° C for 6 h, naturally cooled, and taken out in a glove box for use as a positive electrode tab.
  • Graphite is used as a negative electrode active material
  • carbon black is used as a conductive additive
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • metal lithium is used as the negative electrode of the battery, and a three-layer film of PP/PE/PP coated with alumina on both sides is placed as a separator between the positive electrode and the negative electrode, and 1 M LiPF 6 is added dropwise thereto.
  • the positive electrode tab prepared in the step (1) was used as a positive electrode, and a button battery of the molding number CR2032 (counted as B1 to B20) was assembled.
  • the graphite negative electrode sheet prepared in the step (1) is used as a negative electrode of the battery, and a three-layer film of PP/PE/PP coated with alumina on both sides is used as a separator between the positive electrode and the negative electrode.
  • 1M LiPF 6 was added dropwise to the EC/DMC (1:1, volume ratio) non-aqueous electrolyte solution, and the positive electrode tab prepared in the step (1) was used as the positive electrode, and the button battery of the molding number CR2032 was assembled. C1 ⁇ C20).
  • the button battery prepared above was subjected to a charge and discharge cycle test using a blue electric battery charge and discharge tester. First, it was cycled at room temperature (25 ° C) at a rate of 0.1 C for 1 week, and then continued at a rate of 0.2 C for 4 weeks, wherein the charge and discharge voltage of the control battery was in the range of 3.5 V to 4.9 V. Then, the button battery was transferred to a high temperature environment of 55 ° C, and the cycle was continued for 200 weeks at a rate of 0.2 C, while the charge and discharge voltage range of the control battery was still 3.5 V - 4.9 V.
  • the capacity retention ratios of the button batteries B1 to B20 after circulating for 200 weeks in a high temperature environment of 55 ° C were counted as D1 to D20, respectively.
  • the button battery prepared above was subjected to a charge and discharge cycle test using a blue electric battery charge and discharge tester. First, it was cycled at room temperature (25 ° C) for 1 week at a rate of 0.1 C, and then continued for 199 cycles at a rate of 0.2 C, wherein the charge and discharge voltage of the control battery was in the range of 3.5 V to 4.9 V.
  • the capacity retention ratios of the button cells B1 to B20 after circulating for 200 weeks in a room temperature environment of 25 ° C were counted as E1 to E20, respectively.
  • the above-prepared button type was prepared by using a blue electric battery charge and discharge tester (purchased from Wuhan Landian Electronics Co., Ltd.). The battery is tested for charge and discharge cycles. First, it was cycled at room temperature (25 ° C) for 1 week at a rate of 0.1 C, and then continued for 199 cycles at a rate of 0.2 C, wherein the charge and discharge voltage of the control battery was in the range of 3.4 V to 4.8 V. Button battery C1 ⁇ C20 at room temperature of 25 ° C The capacity retention ratio after 200 cycles was counted as F1 to F18, respectively. Table 1 shows the test results (D1 to D20 and E1 to E20 and F1 to F20) of Test Examples 1 to 18.
  • Figure 4 is a graph showing the trend of discharge capacity as a function of cycle number for batteries B2 and B18 assembled from materials A2 and A18 prepared in Example 2 and Example 18 (Comparative Example) at a high temperature test environment of 55 °C.
  • the results show that the uncovered A18 (comparative material) assembled battery B18 in the high temperature test environment of 55 ° C, after 200 weeks, the capacity retention rate is about 60%, the capacity attenuation is faster, because of the high temperature test Under the environment, electrolyte decomposition and Mn dissolution are intensified, resulting in faster material capacity decay; battery B2 assembled from A2 material in a high temperature test environment of 55 ° C, after 200 weeks, the capacity retention rate is about 88%, because after After coating of TiO 2 and MgO, direct contact between the LiNi 0.5 Mn 1.5 O 4 material and the electrolyte is inhibited, and decomposition of the electrolyte and dissolution of Mn are suppressed, thereby improving the cycle stability of the battery.
  • Figure 5 is a graph showing the change in discharge capacity with cycle number of batteries B2 and B18 assembled from materials A2 and A18 prepared in Example 2 and Example 18 (Comparative Example) at a room temperature test environment of 25 °C.
  • the results show that the B2 battery assembled from A2 material has a capacity retention rate of about 95% after 200 cycles in a room temperature test environment of 25 ° C, and the B18 battery assembled from A18 (comparative material) material has a room temperature test environment at 25 ° C.
  • the capacity retention rate after 200 weeks of the lower cycle was about 88%.
  • the capacity retention (88% and 95%) of the A18 material and the A2 material in the room temperature test environment at 25 ° C is higher than the capacity retention rate (60% and 88%) in the high temperature test environment at 55 ° C because The decomposition of the electrolyte and the amount of dissolution of Mn are less in a room temperature environment than in a high temperature environment, so that the capacity at a room temperature environment is kept high and high.
  • Fig. 6 is a graph showing the relationship between the discharge capacity and the number of cycles of the material A2 and A18 prepared as positive electrode tabs, respectively, and paired with the graphite negative electrode, and assembled into a full-cell C2 and C18 at room temperature test environment of 25 ° C, respectively.
  • the results show that the capacity retention rate of the full battery C2 after cycling for 200 weeks in a room temperature test environment of 25 ° C is about 68%, while the capacity retention rate of the full battery C18 after cycling for 200 weeks in a room temperature test environment of 25 ° C is about 62.

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Abstract

一种尖晶石结构的正极活性材料，包括化学式为LiNi 0.5-xMn 1.5-y{A} uO z的含锂化合物颗粒以及包覆在该含锂化合物颗粒表面的第一金属氧化物和第二金属氧化物，其中所述第一金属氧化物为化合价为四价或大于四价的金属的氧化物，作为包覆材料局部覆盖在含锂化合物颗粒表面；所述第二金属氧化物为化合价小于四价的金属的氧化物，在含锂化合物颗粒表面未被第一金属氧化物覆盖的其他区域包覆所述的第二金属氧化物的厚度为1～20nm或者形成深度小于200nm的浅层梯度固溶体。将该正极活性材料用于锂离子二次电池时，比未包覆的锂过渡金属氧化物具有更好的循环稳定性。

Description

锂离子二次电池的正极活性材料及其制备方法和应用 技术领域
本发明涉及一种尖晶石结构的锂离子二次电池的正极活性材料及其制备方法和应用。
背景技术
相比于其他可充电电池体系，锂离子二次电池具有工作电压高、重量轻、体积小、无记忆效应、自放电率低、循环寿命长、能量密度高等优点，目前已广泛应用于手机、笔记本电脑、平板电脑等移动终端产品。近年来，出于对环境保护方面的考虑，电动汽车在各国政府和汽车制造商的推动下得到了迅速的发展，而锂离子电池凭借其优良的性能成为新一代电动汽车的理想动力源。
在锂离子电池中，占其成本约30％～40％的正极材料不仅作为电极材料参与电池的化学反应，而且是锂离子的主要来源，对提高锂离子电池的能量密度和降低成本影响最大。目前研究较多的锂离子电池正极材料包括具有层状结构的钴酸锂(LiCoO2)和镍酸锂(LiNiO2)，具有尖晶石结构的锰酸锂(LiMn2O4)，以及具有橄榄石结构的磷酸铁锂(LiFePO4)。LiCoO2正极材料已经广泛应用于智能手机、平板电脑以及笔记本电脑的电池，但由于成本和安全性问题而不能应用于电动汽车。尖晶石结构的LiMn2O4的原料成本较低、生产工艺简单、耐过充性能好、安全性高，具有三维的锂离子扩散通道，倍率性能好。但其主要的缺点是容量衰减较快，特别是在高温条件下；同时在电化学循环的过程中，Mn会溶解；其能量密度低，循环寿命短。橄榄石结构的LiFePO4具有低成本、环境友好、高安全性和长循环寿命的特点，但其缺点是工作电压低(约3.45V vs.Li/Li+)，与石墨装配成的全电池的能量密度低，电子电导低，倍率性能较差等。
相比于这些传统的锂离子电池正极材料，镍锰酸锂(LiNi0.5Mn1.5O4)的理论比容量为146.7mAh/g，可逆容量达到136mAh/g，工作电压为4.7V vs.Li/Li+，理论比能量达到695Wh/kg。此外，由于LiNi0.5Mn1.5O4具有三维的锂离子传输通道，其倍率性能较好，可快速充放电，这正是电动汽车用锂离子电池所需要的。另外，LiNi0.5Mn1.5O4中的过渡金属以Mn为主，成本较低。 但由于LiNi0.5Mn1.5O4的工作电压为4.7V vs.Li/Li+，超过了普通商用电解液的电化学窗口(约为4.5V vs.Li/Li+)，导致电解液容易被氧化，在LiNi0.5Mn1.5O4表面形成正极/电解质界面膜(CEI膜)，研究表明CEI膜的电子电导和Li+导电性较差，还由于所使用的电解液中不可避免的含有痕量的H2O，H2O和电解液中的LiPF6反应生成HF，LiNi0.5Mn1.5O4会受到HF的侵蚀，同时在高电压下锰的溶解加剧，导致电池的阻抗增大和比容量的衰减。在室温(25℃)下，电解液的分解速度缓慢，材料的比容量衰减速度较慢；而在55℃的高温条件下，电解液的分解和锰的溶解加速，使得电池的阻抗不断增大，容量衰减更快。
发明内容
本发明的目的是提供一种改进LiNi0.5Mn1.5O4的方法，使之在高充电电压和高温条件下电解液分解和锰的溶解得到抑制，从而提高其容量保持率和充放电库伦效率。改进后的材料可用作锂离子二次电池的正极活性材料，该材料做成的电池具有优异的循环性能。
本发明的发明人发现，包覆的锂过渡金属氧化物，如用二氧化钛以岛状覆盖材料的部分表面，在未被二氧化钛覆盖的区域，用氧化镁等作为薄层包覆或形成浅层梯度固溶体的LiNi0.5-xMn1.5-y{A}uOz用于锂离子二次电池时，比未包覆的锂过渡金属氧化物具有更好的循环稳定性。因此，当本发明的正极活性材料用于锂离子二次电池时，可用作电动工具、电动自行车、混合动力电动交通工具和纯电动交通工具等应用的能量源。除TiO2和MgO外，其他的金属氧化物，如TiO2、ZrO2、SnO2、SiO2、GeO2、HfO2、Nb2O5等化合价为四价或高于四价的金属的氧化物作为岛状覆盖材料以及MgO、Al2O3、ZnO、CaO等化合价小于四价的金属的氧化物中的一种或多种作为表层包覆或浅层梯度固溶体包覆材料覆盖在正极活性材料的表面时，也能产生类似的效果。
本发明提供了一种尖晶石结构的正极活性材料，所述正极活性材料包括化学式为LiNi0.5-xMn1.5-y{A}uOz的含锂化合物颗粒以及包覆在该含锂化合物颗粒表面的第一金属氧化物和第二金属氧化物，其中所述第一金属氧化物为至少一种化合价为四价或大于四价的金属的氧化物，并且呈岛状覆盖所述含锂化合物颗粒的部分表面，所述第二金属氧化物为至少一种化合价小于四价的金属的氧化物，并且覆盖所述含锂化合物颗粒未被第一金属 氧化物覆盖的部分表面；其中{A}是掺杂组合物，由式∑wiBi表示，Bi是掺杂元素，用于置换Ni和/或Mn，wi是Bi在整个掺杂组合物{A}中的原子百分数，∑wi＝1；其中u＝x+y；0≤x≤0.2；0≤y≤0.2；0≤u≤0.4；3.8≤z≤4.2。
根据本发明提供的正极活性材料，其中，x、y、z和u的值能够生产基本为单相的锂金属氧化物，例如材料的95％或更多，更优选99％或更多为单相。根据本发明，对应于式LiNi0.5-xMn1.5-y{A}uOz的合适的锂金属氧化物包括掺杂的(其中u＞0)和未掺杂的(其中u＝0)化学式为LiNi0.4Mn1.5Mg0.1O4、LiNi0.5Mn1.5O4、LiNi0.4Mn1.6O4等的锂金属氧化物。
根据本发明提供的正极活性材料，优选地，所述第一金属氧化物选自TiO2、ZrO2、SnO2、SiO2、GeO2、CeO2、HfO2、和Nb2O5中的一种或多种。
根据本发明提供的正极活性材料，优选地，所述第二金属氧化物选自MgO、Al2O3、ZnO、Ce2O3、和CaO中的一种或多种。
在本发明的一种实施方案中，所述LiNi0.5-xMn1.5-y{A}uOz化合物优选包含一种或多种掺杂元素，即u＞0。掺杂元素Bi是除Ni和Mn之外的元素，优选地选自Al、Mg、Fe、Co、Ti、Y、Sc、Ce、Ru、Mo、W、Zr、Ca、Sr、中的一种或多种。更优选地，掺杂元素Bi包含两种或多种掺杂阳离子。
根据本发明，掺杂元素Bi置换的是LiNi0.5-xMn1.5-y{A}uOz化合物中的过渡金属Ni和Mn而不是Li，从而最大化锂金属氧化物的放电比容量。即在掺杂的嵌入化合物(u＞0)中Li和O的比例不小于未掺杂的嵌入化合物(u＝0)中Li和O的比例。LiNi0.5-xMn1.5-y{A}uOz化合物中的掺杂元素Bi可以包含Li+。
根据本发明提供的正极活性材料，其中，所述含锂化合物颗粒的粒径为1～20μm；所述第一金属氧化物的粒径为10～500nm。根据本发明提供的正极活性材料，其中所述第一金属氧化物在含锂化合物颗粒表面的覆盖度为1～75％。在含锂化合物颗粒表面而未被第一金属氧化物覆盖的其他区域，全部包覆所述的第二金属氧化物。
根据本发明提供的正极活性材料，其中，在所述含锂化合物颗粒表面而未被第一金属氧化物覆盖的其他区域，全部包覆所述第二金属氧化物的厚度为1～20nm或者形成深度小于200nm的浅层梯度固溶体。
该尖晶石结构的正极活性材料中LiNi0.5-xMn1.5-y{A}uOz锂金属氧化物、化合价为四价或大于四价的金属的氧化物和化合价小于四价的金属的氧化 物的存在可以用本领域普通技术人员已知的任何方法测定。例如，这些化合物可以用X射线衍射方法通过测量代表上述化合物的峰的面积来测定每种化合物的相对含量。
本发明还提供了上述正极活性材料的制备方法，该方法包括以下步骤：
(1)按照化学计量比将含有Li、Ni、Mn和任选的{A}以及第一金属氧化物的源化合物混合均匀；
(2)将步骤(1)得到的混合物依次在400～500℃和800～1000℃的温度下烧制并冷却以制备表面岛状覆盖第一金属氧化物的含锂化合物；
(3)将步骤(2)制得的表面岛状覆盖第一金属氧化物的含锂化合物与所述第二金属氧化物的源化合物混合；
(4)将步骤(3)得到的混合物在400～800℃的温度下烧制并冷却以制备所述正极活性材料。
根据本发明提供的制备方法，其中，所述的步骤(1)的混合可以优选为干法混合，所述步骤(3)的混合可以优选为湿法混合。
在本发明的优选的方法实施方案中，含有Ni、Mn、Li以及任选的{A}的源化合物以足以能够在Ni、Mn、Li和{A}之间提供与如上所述的LiNi0.5-xMn1.5-y{A}uOz对应的化学计量关系的量紧密混合。源化合物可以是纯元素，但通常是含有氧化物或盐等元素的化合物。例如，源化合物通常是水合的或无水的氧化物、氢氧化物、碳酸盐、硝酸盐、硫酸盐、氯化物或氟化物，也可以是任何其它合适的源化合物，只要其不会导致所得的嵌入化合物中的元素缺陷。优选地，该源化合物是氧化物、醋酸盐或碳酸盐，因为这些化合物在烧结过程中产生的气态副产品更加环保。锂金属氧化物的每种元素可以由单独的源化合物提供，或至少两种元素可以从相同的源材料化合物(即利用共沉淀方法制备的包含两种或两种以上元素的前驱体)提供。该源化合物可以以任何所需的顺序紧密混合。
这里使用的术语“紧密结合”是指将源化合物一起充分混合，从而一旦被烧成，这些源化合物就可以形成单相的锂金属氧化物。根据本发明，源化合物常常优选被紧密结合从而使其能够生产一种基本单相的锂金属氧化物。所述源化合物优选进行干法混合，例如，通过在球磨机中混合该源化合物从而生产紧密混合的混合物。但作为另一种可选择的方式，也可以通过溶胶-凝胶反应和喷雾干燥等湿处理方法，湿处理方法可以单独使用或与干法混合 一起使用。
本发明还提供了一种锂离子电池的正极，该正极包括集流体以及负载在该集流体上的正极活性材料、碳材料导电添加剂和粘结剂，其中所述正极活性材料为本发明提供的正极活性材料或者按照本发明方法制得的正极活性材料。
本发明还提供了一种锂离子电池，该电池包括电池壳体、电极组和电解液，所述电极组和电解液密封在电池壳体内，所述电极组包括正极、隔膜和负极，其中所述正极为本发明提供的正极。
本发明提供的正极活性材料用化合价为四价或大于四价的金属的氧化物以岛状覆盖锂过渡金属氧化物颗粒的部分表面，在未被覆盖的区域，用化合价为四价或大于四价的金属的氧化物作为薄层包覆或形成浅层表面固溶体。将该正极活性材料用于锂离子二次电池时，比未包覆的锂过渡金属氧化物具有更好的循环稳定性。因此，当本发明的正极活性材料用于锂离子二次电池时，可用作电动工具、电动自行车、混合动力电动交通工具和纯电动交通工具等应用的能量源。
附图说明
以下，结合附图来详细说明本发明的实施方案，其中：
图1为实施例2和实施例18(对比例)制备的正极活性材料A2和A18的XRD图谱。
图2为实施例18制备的正极活性材料A18的SEM图片。
图3为实施例2制备的正极活性材料A2的SEM图片。
图4为由实施例2和实施例18(对比例)制备的材料A2和A18装配成的电池B2和B18在55℃的高温测试环境下的放电容量随循环次数的变化趋势图。
图5为由实施例2和实施例18(对比例)制备的材料A2和A18装配成的电池B2和B18在25℃的室温测试环境下的放电容量随循环次数的变化趋势图。
图6为由材料A2和A18分别制备成正极极片，并与石墨负极配对，并分别装配成全电池C2和C18在25℃的室温测试环境下的放电容量随循环次数的变化趋势图。
具体实施方式
下面结合具体实施方式对本发明进行进一步的详细描述，给出的实施例仅为了阐明本发明，而不是为了限制本发明的范围。
实施例1
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12小时，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A1)。
实施例2
取183g实施例1制得的A1材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.97％)置于盛有500mL去离子水的烧杯中，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A2)。
实施例3
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、1.245g ZrO2(纯度为99％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有ZrO2颗粒(覆盖度约为20％；ZrO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取184g上述制备的表面局部覆盖有ZrO2颗粒(覆盖度约为20％；ZrO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)， 接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖ZrO2颗粒(覆盖度约为20％；ZrO2颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A3)。
实施例4
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、2.66g Nb2O5(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有Nb2O5颗粒(覆盖度约为20％；Nb2O5颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取185g上述制备的表面局部覆盖有Nb2O5颗粒(覆盖度约为20％；Nb2O5颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖Nb2O5颗粒(覆盖度约为20％；Nb2O5颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A4)。
实施例5
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、1.599g TiO2(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为40％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取184g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为40％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和2.145g  Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为40％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A5)。
实施例6
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、2.4g TiO2(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为60％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取184g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为60％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为60％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A6)。
实施例7
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为50nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为50nm)的LiNi0.5Mn1.5O4颗粒材料。
取183g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为50nm)的LiNi0.5Mn1.5O4颗粒材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为50nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A7)。
实施例8
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为150nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为150nm)的LiNi0.5Mn1.5O4颗粒材料。
取183g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为150nm)的LiNi0.5Mn1.5O4颗粒材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为150nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A8)。
实施例9
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为200nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为200nm)的 LiNi0.5Mn1.5O4颗粒材料。
取183g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为200nm)的LiNi0.5Mn1.5O4颗粒材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为200nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A9)。
实施例10
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取183g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和4.29g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为6nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A10)。
实施例11
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧 5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取183g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和6.435g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为9nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A11)。
实施例12
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取183g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和2.263g Zn(CH3COO)2·2H2O(纯度为97％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆ZnO(ZnO包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A12)。
实施例13
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用 干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料。
取183g上述制备的表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.5Mn1.5O4颗粒材料和4.13g异丙醇铝(纯度为99％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆Al2O3(Al2O3包覆层的厚度约为3nm)的LiNi0.5Mn1.5O4颗粒材料(此材料计作A13)。
实施例14
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.2Mn0.75Mg0.05(OH)2、0.7995g TiO2(纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.4Mn1.5Mg0.1O4颗粒材料(此材料计作A14)。
实施例15
取183g实施例14制备的A14材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.4Mn1.5Mg0.1O4颗粒材料(此材料计作A15)。
实施例16
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.225Mn0.725Al0.05(OH)2、 0.7995g TiO2(购自Alfa Aesar公司，纯度为99.9％，颗粒的粒径约为100nm)置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到表面局部覆盖有TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)的LiNi0.45Mn1.45Al0.1O4颗粒材料(此材料计作A16)。
实施例17
取183g实施例16制备的A16材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.997％)置于盛有500mL去离子水中的烧杯，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在500℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％)，其余区域完全包覆MgO(MgO包覆层的厚度约为3nm)的LiNi0.45Mn1.45Al0.1O4颗粒材料(此材料计作A17)。
实施例18(对比例)
取37.323g Li2CO3(纯度为99％)、179.7537g Ni0.25Mn0.75(OH)2置于行星式球磨机中，用干法混合均匀。将混合物置于坩埚中，放在马弗炉中，在500℃下先预烧5小时，然后再升温到900℃，烧结12h，自然冷却之后得到LiNi0.5Mn1.5O4颗粒材料(此材料计作A18)。
实施例19
取183g实施例1制得的A1材料和2.145g Mg(CH3COO)2·4H2O(纯度为99.97％)置于盛有500mL去离子水的烧杯中，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在600℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域形成深度约为20nm的LiNi0.5-xMn1.5MgxO4浅层固溶体的LiNi0.5Mn1.5O4颗粒材料(此材料计作A19)。
实施例20
取183g实施例1制得的A1材料和4.13g异丙醇铝(纯度为99％)置 于盛有500mL去离子水的烧杯中，将烧杯置于磁力搅拌器中均匀搅拌12小时(搅拌的转速为500rpm)，接着将去离子水完全蒸发。然后将得到的混合物置于马弗炉(空气气氛下)中，在60℃下烧结5个小时，自然冷却得到表面局部覆盖TiO2颗粒(覆盖度约为20％；TiO2颗粒的粒径约为100nm)，其余区域形成深度约为20nm的LiNi0.5-xMn1.5-yAlx+yO4浅层固溶体的LiNi0.5Mn1.5O4颗粒材料(此材料计作A20)。
形貌表征
图1是材料A2和A18(对比材料)的XRD图谱，二者的XRD几乎没有差别，都是立方尖晶石结构，说明用TiO2和MgO包覆之后的LiNi0.5Mn1.5O4材料(A2材料)的结构没有发生变化。
图2和图3分别是A18(对比材料)和A2的扫描电镜照片，A18(对比材料)的形貌是规则的截角八面体，其表面很光滑，A2材料的表面局部覆盖TiO2颗粒，在其他区域包覆有MgO材料。在图3中，LiNi0.5Mn1.5O4颗粒的粒径为1～20μm，TiO2颗粒的粒径为50～200nm。
性能测试
将实施例1至20制备的材料A1至A20按照如下的步骤装配成扣式电池。
(1)制备正极极片和负极极片
将实施例1至20中制备的材料A1至A20分别作为正极活性材料，炭黑作为导电添加剂，聚偏二氟乙烯(PVDF)作为粘结剂，并按照重量比为90∶5∶5的比例分散于N-甲基吡咯烷酮(NMP)中，混合均匀，制备成均匀的正极浆料。将均匀的正极浆料均匀涂覆在厚度为15μm的铝箔集流体上，在55℃下烘干，形成100μm厚的极片，置于辊压机下辊压(压力约为1MPa×1.5cm2)，将极片裁剪成直径为
Figure PCTCN2016093952-appb-000001
的圆片，置于真空烘箱中于120℃下烘6h，自然冷却后，取出置于手套箱中用作正极极片。
将石墨作为负极活性材料，炭黑作为导电添加剂，聚偏二氟乙烯(PVDF)作为粘结剂，并按照重量比为90∶5∶5的比例分散于N-甲基吡咯烷酮(NMP)中，混合均匀，制备成均匀的负极浆料，将均匀的负极浆料均匀涂覆在厚度为8μm的铝箔集流体上，在55℃下烘干，形成100μm厚的极片，置于辊压机下辊压(压力约为1MPa×1.5cm2)，将极片裁剪成直 径为
Figure PCTCN2016093952-appb-000002
的圆片，置于真空烘箱中于120℃下烘6h，自然冷却后，取出置于手套箱中用作负极极片。
(2)装配锂离子二次电池
在充满惰性气氛的手套箱中，以金属锂作为电池的负极，双面涂覆氧化铝的PP/PE/PP的三层膜作为隔膜放在正极和负极之间，滴加1M LiPF6溶解在EC/DMC(1∶1，体积比)的非水系电解液，以步骤(1)制备的正极极片为正极，装配成型号为CR2032的扣式电池(计作B1～B20)。
在充满惰性气氛的手套箱中，以步骤(1)制备的石墨负极极片作为电池的负极，双面涂覆氧化铝的PP/PE/PP的三层膜作为隔膜放在正极和负极之间，滴加1M LiPF6溶解在EC/DMC(1∶1，体积比)的非水系电解液，以步骤(1)制备的正极极片为正极，装配成型号为CR2032的扣式电池(计作C1～C20)。
试验例1～20
将制备的扣式电池B1～B20在室温(25℃)条件下静置10个小时后，采用蓝电电池充放电测试仪对上述制备的扣式电池进行充放电循环测试。首先在室温条件下(25℃)，以0.1C的倍率循环1周，然后以0.2C的倍率继续循环4周，其中，控制电池的充放电电压范围为3.5V-4.9V。然后，将扣式电池转移至55℃的高温环境中，以0.2C的倍率继续循环200周，同时控制电池的充放电电压范围仍为3.5V-4.9V。扣式电池B1～B20在55℃的高温环境下循环200周之后的容量保持率分别计作D1～D20。
将制备的扣式电池B1～B20在室温(25℃)条件下静置10个小时后，采用蓝电电池充放电测试仪对上述制备的扣式电池进行充放电循环测试。首先在室温条件下(25℃)，以0.1C的倍率循环1周，然后以0.2C的倍率继续循环199周，其中，控制电池的充放电电压范围为3.5V-4.9V。扣式电池B1～B20在25℃的室温环境下循环200周之后的容量保持率分别计作E1～E20。
将制备的扣式电池C1～C20在室温(25℃)条件下静置10个小时后，采用蓝电电池充放电测试仪(购自武汉市蓝电电子股份有限公司)对上述制备的扣式电池进行充放电循环测试。首先在室温条件下(25℃)，以0.1C的倍率循环1周，然后以0.2C的倍率继续循环199周，其中，控制电池的充放电电压范围为3.4V-4.8V。扣式电池C1～C20在25℃的室温环境下 循环200周之后的容量保持率分别计作F1～F18。表1给出了试验例1～18的测试结果(D1～D20和E1～E20以及F1～F20)。
表1
Figure PCTCN2016093952-appb-000003
图4是由实施例2和实施例18(对比例)制备的材料A2和A18装配成的电池B2和B18在55℃的高温测试环境下的放电容量随循环次数的变化趋势图。结果显示：未包覆的A18(对比材料)装配成的电池B18在55℃的高温测试环境下，经过200周之后的容量保持率约为60％，容量衰减较 快，这是由于在高温测试环境下，电解液分解和Mn溶解加剧，导致材料的容量衰减较快；A2材料装配成的电池B2在55℃的高温测试环境下，经过200周之后的容量保持率约为88％，因为经过TiO2和MgO包覆之后，阻碍LiNi0.5Mn1.5O4材料与电解液之间的直接接触，电解液分解和Mn的溶解得到抑制，从而使电池的循环稳定性提高。
图5是由实施例2和实施例18(对比例)制备的材料A2和A18装配成的电池B2和B18在25℃的室温测试环境下的放电容量随循环次数的变化趋势图。结果显示：A2材料装配得到的B2电池在25℃的室温测试环境下循环200周之后的容量保持率约为95％，而A18(对比材料)材料装配得到的B18电池在25℃的室温测试环境下循环200周之后的容量保持率约为88％。A18材料和A2材料在25℃的室温测试环境下的容量保持率(88％和95％)均比在55℃的高温测试环境下的容量保持率(60％和88％)高，这是因为相比于在高温环境下，在室温环境下电解液的分解和Mn的溶解的量较少，从而使得在室温环境下的容量保持高较高。
图6是由材料A2和A18分别制备成正极极片，并与石墨负极配对，并分别装配成全电池C2和C18在25℃的室温测试环境下的放电容量随循环次数的变化趋势图。结果显示：全电池C2在25℃的室温测试环境下循环200周之后的容量保持率约为68％，而全电池C18在25℃的室温测试环境下循环200周之后的容量保持率约为62％，由于全电池在循环的过程中，会在石墨负极的表面形成SEI膜，消耗来自正极材料的可循环的锂离子，同时电解液发生分解，Mn溶解，导致未包覆的材料A18在室温下的循环稳定性较差，而经过TiO2和MgO包覆的A2材料装配形成的全电池的循环稳定性提高，经过200周的容量保持率约为68％。
最后应说明的是，以上各实施例仅用于说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (12)

  1. 一种尖晶石结构的正极活性材料，其特征在于，所述正极活性材料包括化学式为LiNi0.5-xMn1.5-y{A}uOz的含锂化合物颗粒以及包覆在该含锂化合物颗粒表面的第一金属氧化物和第二金属氧化物，其中所述第一金属氧化物为至少一种化合价为四价或大于四价的金属的氧化物，并且呈岛状覆盖所述含锂化合物颗粒的部分表面，所述第二金属氧化物为至少一种化合价小于四价的金属的氧化物，并且覆盖所述含锂化合物颗粒未被第一金属氧化物覆盖的部分表面；其中{A}是掺杂组合物，由式∑wiBi表示，Bi是掺杂元素，用于置换Ni和/或Mn，wi是Bi在整个掺杂组合物{A}中的原子百分数，∑wi＝1；其中u＝x+y；0≤x≤0.2；0≤y≤0.2；0≤u≤0.4；3.8≤z≤4.2。
  2. 根据权利要求1所述的正极活性材料，其中，所述第一金属氧化物选自TiO2、ZrO2、SnO2、SiO2、GeO2、CeO2、HfO2、和Nb2O5中的一种或多种。
  3. 根据权利要求1或2所述的正极活性材料，其中，所述第二金属氧化物选自Al2O3、MgO、ZnO、Ce2O3和CaO中的一种或多种。
  4. 根据权利要求1至3中任一项所述的正极活性材料，其中，u＞0。
  5. 根据权利要求1至4中任一项所述的正极活性材料，其中，Bi选自Al、Mg、Fe、Co、Ti、Y、Sc、Ru、Cu、Mo、Ce、W、Zr、Ca、Sr中的一种或多种。
  6. 根据权利要求1至5中任一项所述的正极活性材料，其中，所述含锂化合物颗粒的粒径为1～20μm；所述第一金属氧化物的粒径为10～500nm。
  7. 根据权利要求1至6中任一项所述的正极活性材料，其中，所述第一金属氧化物在所述含锂化合物颗粒表面的覆盖度为1～75％。
  8. 根据权利要求1至7中任一项所述的正极活性材料，其中在所述含锂化合物颗粒表面而未被第一金属氧化物覆盖的其他区域，全部包覆所述第二金属氧化物的厚度为1～20nm或者形成深度小于200nm的浅层梯度固溶体。
  9. 权利要求1至8中任一项所述的正极活性材料的制备方法，所述方 法包括以下步骤：
    (1)按照化学计量比将含有Li、Ni、Mn和任选的{A}以及第一金属氧化物的源化合物混合均匀；
    (2)将步骤(1)得到的混合物依次在400～500℃和800～1000℃的温度下烧制并冷却以制备表面岛状覆盖第一金属氧化物的含锂化合物；
    (3)将步骤(2)制得的表面岛状覆盖第一金属氧化物的含锂化合物与所述第二金属氧化物的源化合物混合；
    (4)将步骤(3)得到的混合物在400～800℃的温度下烧制并冷却以制备所述正极活性材料。
  10. 根据权利要求9所述的制备方法，其中，所述的步骤(1)的混合为干法混合，所述步骤(3)的混合为湿法混合。
  11. 一种锂离子电池的正极，该正极包括集流体以及负载在该集流体上的正极活性材料、碳材料导电添加剂和粘结剂，其特征在于，所述正极活性材料为权利要求1至8中任一项所述的正极活性材料或者按照权利要求9至10中任一项所述方法制得的正极活性材料。
  12. 一种锂离子电池，该电池包括电池壳体、电极组和电解液，所述电极组和电解液密封在电池壳体内，所述电极组包括正极、隔膜和负极，其特征在于，所述正极为权利要求11所述的正极。
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