WO2017096525A1 - 锂离子电池正极材料、其制备方法、锂离子电池正极以及锂离子电池 - Google Patents

锂离子电池正极材料、其制备方法、锂离子电池正极以及锂离子电池 Download PDF

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WO2017096525A1
WO2017096525A1 PCT/CN2015/096668 CN2015096668W WO2017096525A1 WO 2017096525 A1 WO2017096525 A1 WO 2017096525A1 CN 2015096668 W CN2015096668 W CN 2015096668W WO 2017096525 A1 WO2017096525 A1 WO 2017096525A1
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ion battery
lithium ion
positive electrode
core
lithium
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PCT/CN2015/096668
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English (en)
French (fr)
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陈彦彬
刘亚飞
李珊珊
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北京当升材料科技股份有限公司
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Priority to PCT/CN2015/096668 priority Critical patent/WO2017096525A1/zh
Publication of WO2017096525A1 publication Critical patent/WO2017096525A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of cathode active materials for secondary lithium and lithium ion batteries, and particularly relates to a cathode material for lithium ion batteries, a preparation method thereof, a cathode of a lithium ion battery, and a lithium ion battery.
  • Lithium-ion batteries are largely developed to meet the development needs of portable electronic products (mobile phones, notebook computers, etc.) due to their high voltage, high specific energy, light weight, small size, and good safety. Used in power tools, electric bicycles and new energy vehicles.
  • the positive active materials of lithium ion batteries are mainly lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate and lithium iron phosphate.
  • Lithium cobaltate has a high operating voltage and a long cycle life, but it is expensive and has poor overcharge resistance.
  • Lithium nickel cobalt manganese oxide has a low cost and a high capacity, but its compact density is low, and its compatibility with the electrolyte during charging and discharging is poor, and it is easy to react with the organic electrolyte to release gas, and the safety is poor.
  • Lithium nickel cobalt aluminate has high specific capacity and high power, but its synthesis is difficult, the process requirements are complex, and the hygroscopicity is strong.
  • Lithium manganate has a simple process and low cost, but its high temperature performance is not good.
  • Lithium iron phosphate has a long cycle life and good safety performance, but its voltage is low and energy density is low.
  • the positive electrode material can be overcome by coating a layer of a barrier on the surface of the positive electrode material. Stability to meet the needs of use at high voltages.
  • Many domestic and foreign literatures and patents have reported techniques for coating a positive electrode material with an oxide such as Al 2 O 3 , AlPO 4 , ZrO 2 , TiO 2 or B 2 O 3 .
  • Patent CN104752713A discloses a method for coating a positive electrode material with an oxide containing lithium, nickel, manganese and a rare earth element oxide, which can stabilize the material structure, improve the rate and low temperature performance, etc., but greatly reduces the positive electrode material. Storage performance.
  • One of the objects of the present invention is to provide a positive electrode material for a lithium battery, which can be used at a high voltage by multi-element co-coating while maintaining good high-temperature cycle performance and storage performance.
  • Another object of the present invention is to provide a method for preparing a positive electrode material for a lithium battery as described above, which provides a method for safe and stable production of the positive electrode material at a low cost.
  • the invention also provides a lithium ion battery positive electrode prepared from the above lithium ion battery positive electrode material, and a lithium ion battery including the lithium ion battery positive electrode, which has high capacity and excellent cycle performance and safety performance.
  • the present invention provides a positive electrode material for a lithium ion battery, comprising a core and a cladding layer:
  • the core is a composite metal oxide particle comprising at least one of Mn, Ni, and Co, and Li;
  • the cladding layer is a metal oxide layer disposed on at least a portion of the surface of the inner core, having an average composition represented by the formula (1):
  • M' is at least one selected from the group consisting of Mg, Ca, Mn, Sr, Fe, Cu, Ni, Zn or Co
  • M" is at least one selected from the group consisting of Al, Fe, Ti, Mn, Cr or La. ;x, y, z satisfy: 0 ⁇ x ⁇ 2, 1 ⁇ y ⁇ 3, 3 ⁇ z ⁇ 5.
  • the lithium ion battery cathode material provided by the invention comprises two parts of a composite oxide particle core and a metal oxide coating layer, and the metal oxide coating layer is disposed on at least a part of the surface of the composite oxide particle core, wherein the package
  • the coating contains the above various elements.
  • the composite coating layer can effectively improve the charge and discharge performance of the positive electrode active material, such as having higher discharge capacity, better safety performance and cycle performance, and is particularly suitable for use at high voltage.
  • the positive electrode active material having the above coating layer has better corrosion resistance and high temperature resistance, and has a stable structure and a low water absorption rate.
  • the doping element M may also be included in the core, and may have an average composition represented by the formula (2):
  • M is one or more selected from the group consisting of Cr, V, Ti, Al, Zr, Nb, Ca, B, Si, Ga, and Mg, and 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1,0 ⁇ a+b+c ⁇ 1.
  • the coating layer may contain MgAl 2 O 4 , ZnAl 2 O 4 or CoAl 2 O 4 having a spinel space group structure.
  • a magnesium-aluminum composite oxide can be formed, usually MgAl 2 O 4 having a spinel space group (Fd3m) structure.
  • the spinel space group structure of MgAl 2 O 4 , ZnAl 2 O 4 or CoAl 2 O 4 is very stable, when the cathode material is charged at a high voltage, the coating layer can stabilize the core in a high oxidation state, avoiding it
  • the side reaction of the electrolyte prevents the collapse of the core layer structure, and is more conducive to reversible insertion/extraction of Li + .
  • the lithium ion battery positive electrode material has a core-shell structure, that is, the coating layer completely coats the surface of the inner core, which is more advantageous for suppressing side reactions of the positive electrode active material and the electrolyte.
  • the coating layer in order to effectively ensure the activity of the positive electrode material while suppressing the occurrence of side reactions, generally accounts for 0.01% to 10% of the total mass of the positive electrode material of the lithium ion battery; preferably, the coating layer occupies the positive electrode material of the lithium ion battery.
  • the total mass is 0.03% to 5%.
  • the lithium ion battery cathode material provided by the present invention may have a median diameter D 50 of generally 3 to 30 ⁇ m.
  • the median diameter D 50 refers to a particle diameter value corresponding to a particle size distribution volume percentage of 50%, which can be adjusted according to actual needs.
  • the D 50 range for the lithium cobaltate positive electrode material is 3 to 25 ⁇ m
  • the D 50 range for other lithium battery positive electrode materials such as lithium nickel cobalt manganate is 5 to 16 ⁇ m.
  • the range of D 50 can be adjusted by selecting precursors of different median diameters, adjusting the temperature and time of heat treatment, and the composition of the coating.
  • a compound containing at least one element selected from the group consisting of Mn, Ni, and Co, and a compound containing Li as a source material of the element are mixed, and then heat-treated in an oxygen-containing atmosphere to obtain a core, which will contain M' and After the compound of M" is mixed with the inner core, heat treatment is performed in an oxygen-containing atmosphere to obtain the above-mentioned lithium ion battery positive electrode material.
  • the invention also provides a preparation method of the above lithium ion battery cathode material, comprising:
  • the mixture obtained in the step (1) is heat-treated at 700 to 1400 ° C in an atmosphere having an oxygen partial pressure of 15 kPa or more, and is cooled to obtain an inner core;
  • the coating material is heat-treated at 300 to 1000 ° C in an atmosphere having an oxygen partial pressure of 15 kPa or more, and is cooled to be crushed to obtain the lithium ion battery positive electrode material.
  • the first heat treatment is a reaction between a compound containing at least one element of Mn, Ni or Co, and a compound containing Li, thereby forming a core;
  • the second heat treatment is between the cladding layer and the core and
  • the reaction between the different cladding elements forms a coating on at least a portion of the surface of the core.
  • the preparation method can uniformly coat the coating layer on the surface of the inner core, effectively blocking the side reaction between the positive electrode active material and the electrolyte, and suppressing the reaction between the positive electrode active material and the HF in the electrolyte, and the conventional oxide. Compared with discontinuous coating, the performance of the positive electrode material can be improved.
  • the doping element M may also be contained in the core.
  • the step (1) is to uniformly mix the compound containing M with at least one element containing Mn, Ni or Co, and a compound containing Li, which is selected from Cr, One or more of V, Ti, Al, Zr, Nb, Ca, B, Si, Ga, and Mg.
  • the above M-containing compound may be selected from one or more of the M-containing oxides, oxyhydroxides, hydroxides, phosphates, fluorides, borates, oxalates or carbonates.
  • the coating layer may be formed by uniformly mixing the compound containing M′ and M′′ with the core, and coating the core with a liquid phase chemical method or a solid phase mixing method.
  • the cladding is obtained on at least a portion of the surface.
  • the Li-containing compound is a lithium source commonly used for preparing a positive electrode of a lithium ion battery, and may be, for example, one or two of lithium hydroxide, lithium acetate or lithium carbonate.
  • the compound containing M' and M" may be one of anhydrous oxides, oxyhydroxides, hydroxides, nitrates, carbonates, fluorides, acetates and citrates containing M' and M".
  • the present invention also provides a lithium ion battery positive electrode comprising a conductive agent, a binder, and the above lithium ion battery positive electrode material.
  • the conductive agent and the binder are common raw materials for preparing the positive electrode of the lithium ion battery in the prior art, for example, the conductive agent may be one or more of carbon black, graphite, acetylene black, graphene, carbon nanotube or carbon fiber.
  • the binder may, for example, be one or more of polyvinylidene fluoride, polytetrafluoroethylene and styrene-butadiene rubber.
  • the present invention also provides a lithium ion battery comprising a negative electrode, a separator, an electrolyte, and the above positive electrode of the lithium ion battery.
  • the lithium ion battery cathode material provided by the invention has a composite coating layer and has stable structure, and Moreover, the structure of the positive electrode material can be maintained at a high voltage, so that the structural change during charging and discharging is small, thereby improving the safety performance and cycle performance of the positive electrode active material.
  • the preparation method of the lithium ion battery cathode material provided by the invention is simple and easy, low in cost, and is favorable for large-scale production.
  • FIG. 1A and FIG. 1B are X-ray diffraction patterns of a coating material for a positive electrode material of a lithium ion battery obtained in Example 1;
  • Example 2 is a scanning electron micrograph of the surface of a positive electrode material of a lithium ion battery obtained in Example 5;
  • 3A is a scanning electron micrograph of a surface of a positive electrode material of a lithium ion battery obtained in Example 5;
  • 3B is a distribution diagram of magnesium elements in a coating layer of a positive electrode material for a lithium ion battery obtained in Example 5;
  • 3C is a distribution diagram of aluminum elements in a coating layer of a positive electrode material for a lithium ion battery obtained in Example 5;
  • Example 4 is a cycle curve of a battery prepared by using a positive electrode material of a lithium ion battery in Example 1, Comparative Example 1 and Example 2 at a normal temperature of 25 ° C;
  • FIG. 5 is a cycle curve of a battery prepared by using a positive electrode material of a lithium ion battery in Example 1, Comparative Example 1 and Example 2 at a high temperature of 45 ° C.
  • FIG. 5 is a cycle curve of a battery prepared by using a positive electrode material of a lithium ion battery in Example 1, Comparative Example 1 and Example 2 at a high temperature of 45 ° C.
  • Lithium carbonate, cobalt tetraoxide, antimony pentoxide and calcium oxide were thoroughly mixed, wherein the molar ratio of Li:(Co+Nb+Ca) was 1.03:1, and the obtained mixture was sintered in an air atmosphere at 1000 ° C for 10 h, and cooled to At room temperature, after crushing and sieving, a nearly spherical core having a median diameter of about 14.1 ⁇ m was obtained.
  • the magnesium-aluminum composite oxide is coated on the surface of the core by a solid phase mixing method.
  • the specific steps are as follows: mixing the above-mentioned core, nano-magnesium carbonate and nano-alumina with a molar ratio of 1:0.003:0.003 for 3 hours, and the resulting mixture is In an air atmosphere, sintering at 700 ° C for 8 h, cooling to room temperature, crushing and sieving to obtain a coated lithium ion battery cathode material, wherein the position diameter is about 14.3 ⁇ m.
  • the lithium carbonate, the cobalt trioxide, the silica, the aluminum oxide and the zinc dioxide are thoroughly mixed, wherein the molar ratio of Li:(Co+Si+Al+Zn) is 1.03:1, and the obtained mixture is in an air atmosphere, 1000 After sintering at ° C for 10 h, it was cooled to room temperature, and after crushing and sieving, a nearly spherical core was obtained, and the inner diameter of the core was about 14.7 ⁇ m.
  • the magnesium-aluminum composite oxide is coated on the surface of the core by liquid phase chemical method.
  • the specific steps are: adding a core with a molar ratio of 1:0.005:0.01, magnesium nitrate and aluminum nitrate to the coating kettle containing a certain amount of deionized water.
  • the stirring speed is 600r/min and the mixing is uniform.
  • the heating was turned on, and the heating temperature was controlled at 100 ⁇ 5 ° C until the water was evaporated to obtain a coating material.
  • the coated powder is placed in a box furnace and heated at a rate of 5 ° C / min to 500 ° C for 10 hours, and after cooling to room temperature after passing through a 300 mesh sieve, the coated lithium ion battery cathode material is obtained. , wherein the position diameter is about 14.7 ⁇ m.
  • the compound containing Mn, Ni and Co was thoroughly mixed with lithium hydroxide in a molar ratio of 1:1.04, wherein the molar ratio of Mn, Ni and Co was 2:6:2, and the obtained mixture was sintered at 820 ° C in an air atmosphere. After 12 h, it was cooled to room temperature, and after crushing and sieving, a nearly spherical core was obtained.
  • the magnesium-aluminum composite oxide is coated on the surface of the inner core by liquid phase chemical method.
  • the specific steps are: adding a core, a nano-magnesia and a nano-alumina having a molar ratio of 1:0.006:0.006 to a package containing a certain amount of deionized water.
  • the stirring speed was 800 r/min, and the mixture was evenly stirred.
  • the heating was turned on, and the heating temperature was controlled at 100 ⁇ 5 ° C, and dried while stirring to obtain a coating material.
  • the coated powder is placed in a box furnace and heated at a rate of 10 ° C/min to 500 ° C for 3 hours. After cooling to room temperature and passing through a 300 mesh sieve, the cathode material of the lithium ion battery is obtained. It is about 11.5 ⁇ m.
  • the compound containing Mn, Ni and Co was thoroughly mixed with lithium hydroxide in a molar ratio of 1:1.04, wherein the molar ratio of Mn, Ni and Co was 2:6:2, and the obtained mixture was sintered at 820 ° C in an air atmosphere. After 12 h, it was cooled to room temperature, and after crushing and sieving, a nearly spherical core was obtained.
  • the zinc-aluminum composite oxide is coated on the surface of the inner core by a solid phase mixing method.
  • the specific steps are as follows: mixing the above-mentioned inner core, nano zinc oxide and nano aluminum oxide with a molar ratio of 1:0.003:0.003 for 3 hours, and the resulting mixture is In an air atmosphere, sintering at 600 ° C for 5 h, cooling to room temperature, crushing and sieving to obtain a coated lithium ion battery cathode material, wherein the position diameter is about 11.5 ⁇ m.
  • the compound containing Mn, Ni and Co was thoroughly mixed with lithium hydroxide in a molar ratio of 1:1.02, wherein the molar ratio of Mn, Ni and Co was 3:5:2, and the obtained mixture was sintered at 900 ° C in an air atmosphere. After 11 h, it was cooled to room temperature, and after crushing and sieving, a nearly spherical core was obtained.
  • the magnesium-aluminum composite oxide is coated on the surface of the core by a solid phase mixing method.
  • the specific steps are: mixing the core, the nanometer magnesium oxide powder and the nano aluminum hydroxide powder in a molar ratio of 1:0.01:0.02 for 3 hours, and the obtained mixture is Under the air atmosphere, sintering at 750 ° C for 5 h, cooling to room temperature, crushing and sieving to obtain a lithium ion battery cathode material, wherein the position diameter is about 12 ⁇ m.
  • the compound containing Mn, Ni and Co was thoroughly mixed with lithium hydroxide in a molar ratio of 1:1.04, wherein the molar ratio of Mn, Ni and Co was 1:8:1, and the obtained mixture was sintered at 750 ° C under an oxygen atmosphere. After 12 h, it was cooled to room temperature, and after crushing and sieving, a nearly spherical core was obtained.
  • Cobalt-aluminum composite oxide (cobalt blue, molecular formula Al 2 Co 2 H 6 O 5 ) was coated on the surface of the core by solid phase mixing. The specific steps were: core and nano cobalt blue powder with a molar ratio of 1:0.01. After mixing for 4 h, the resulting mixture was sintered at 350 ° C for 5 h under an oxygen atmosphere, cooled to room temperature, and sieved to obtain a lithium ion battery positive electrode material having a pore diameter of about 8 ⁇ m.
  • a positive electrode material for a lithium ion battery wherein the position diameter is about 14.1 ⁇ m.
  • 1A and 1B are X-ray diffraction patterns of a coating material for a positive electrode material of a lithium ion battery obtained in Example 1.
  • Example 1 MgAl 2 O 4 in which a spinel space group structure (Fd3m) was formed in a coating layer of a positive electrode material of a lithium ion battery was obtained.
  • the composite coating layer with spinel space group structure has stable performance, no chemical activity, and is resistant to electrolyte corrosion under high voltage.
  • FIG. 3A is a scanning electron micrograph of the surface of the positive electrode material of the lithium ion battery obtained in Example 5 at a different magnification from FIG. 2.
  • FIG. 3B is a distribution diagram of magnesium element in a coating layer of a positive electrode material for a lithium ion battery obtained in Example 5.
  • FIG. 3C is a distribution diagram of aluminum elements in a coating layer of a positive electrode material for a lithium ion battery obtained in Example 5.
  • FIG. 3B and 3C, the magnesium element and the aluminum element are uniformly coated on the surface of the core to form a uniformly distributed coating layer.
  • the lithium ion battery positive electrode materials prepared in the above Example 1, Example 2 and Comparative Example 1 were made into a soft pack battery having a thickness of 5 mm, a width of 30 mm, and a length of 48 mm, and the battery had a capacity of about 600 mAh.
  • the battery making steps are as follows:
  • the positive and negative plates are soldered to the ears and the tabs are secured with high temperature tape.
  • the separator was added, wound, compacted, and placed in a soft aluminum-clad plastic film. After sealing, the electrolyte is injected, and then allowed to stand, pre-fill, seal, and divide.
  • the battery performance is tested after the volume is divided.
  • Constant current constant voltage charging 0.2 CmA (terminal voltage 4.4 V, termination current 0.02 CmA);
  • Steps (4) to (6) were repeated 300 times to obtain a normal temperature cycle test result.
  • the battery was placed in an oven at 45 ° C for testing.
  • the working procedure was as follows.
  • Constant current constant voltage charging 1.0 CmA (terminal voltage 4.4 V, termination current 0.02 CmA);
  • Steps (4) to (6) were repeated 300 times to obtain a high temperature cycle test result.
  • Constant current constant voltage charging 1.0 CmA (terminal voltage 4.4 V, termination current 0.02 CmA);
  • Constant current discharge 1.0 CmA (termination voltage 3.0 V), the discharge capacity before storage of the battery is obtained, and the thickness of the battery is tested with a micrometer;
  • FIG. 4 is a cycle diagram of a battery prepared by using a positive electrode material of a lithium ion battery in Example 1, Comparative Example 1 and Example 2, at 3.0 to 4.4 V, 1 C charge and discharge, and 25 ° C normal temperature. It can be seen from FIG. 4 that the battery prepared by the positive electrode material of the lithium ion battery in Comparative Example 1 has a capacity retention rate of 82.4% at a normal temperature of 25 ° C, and the positive electrode material preparation of the lithium ion battery in Examples 1 and 2. The battery maintains a capacity retention rate of 89.7% or more at a normal temperature of 25 ° C for 300 cycles, and is excellent in cycle performance at normal temperature.
  • FIG. 5 is a cycle curve of a battery prepared by using a positive electrode material of a lithium ion battery in Example 1, Comparative Example 1 and Example 2 at a temperature of 3.0 to 4.4 V, 1 C charge and discharge, and 45 ° C high temperature. It can be seen from FIG. 5 that the battery prepared by the positive electrode material of the lithium ion battery in Comparative Example 1 has a capacity retention rate of about 700.6% after circulating at a high temperature of 45 ° C, and the positive electrode material of the lithium ion battery in Examples 1 and 2. The prepared battery maintained a capacity retention rate of more than 88% at a high temperature of 45 ° C for 300 cycles, and showed excellent cycle performance at high temperatures.
  • Table 1 is the 1.0C discharge capacity of the lithium ion battery cathode material and the 4.4V-3.0V battery 60 ° C * 7D Store data at high temperatures. It can be seen from Table 1 that the battery prepared by the positive electrode material of the lithium ion battery provided by the present invention can maintain a low inflation rate and has excellent high-temperature storage performance under high pressure and high temperature.

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Abstract

本发明提供一种锂离子电池正极材料、其制备方法、锂离子电池正极以及锂离子电池。本发明提供的锂离子电池正极材料包括内核和包覆层，所述内核为包括Ni、Co和Mn中至少一种元素、以及Li的复合金属氧化物颗粒；所述包覆层为设置于所述内核表面的至少一部分上的金属氧化物层，具有由式(1)表示的平均组成：M'xM"yOz式(1)，其中，M'选自Mg、Ca、Mn、Sr、Fe、Cu、Ni、Zn或Co元素中的至少一种，M"选自Al、Fe、Ti、Mn、Cr或La中的至少一种；x、y、z满足0＜x≤2，1≤y≤3且3<z≤5。本发明提供的锂离子电池正极材料能在高电压下使用，同时保持较好的高温循环性能和存储性能。

Description

锂离子电池正极材料、其制备方法、锂离子电池正极以及锂离子电池 技术领域
本发明属二次锂和锂离子电池的正极活性材料技术领域，具体涉及一种锂离子电池正极材料、其制备方法、锂离子电池正极以及锂离子电池。
背景技术
锂离子电池以其电压高、比能量高、重量轻、体积小、安全性好等优点，在很大程度上满足了便携式电子产品(移动电话、笔记本电脑等)的发展需求，并逐步被开发运用于电动工具、电动自行车及新能源汽车等领域。目前常用的锂离子电池正极活性材料主要有钴酸锂，镍钴锰酸锂、镍钴铝酸锂、锰酸锂和磷酸铁锂等。钴酸锂工作电压高，循环寿命长，但是其价格昂贵，耐过充性差。镍钴锰酸锂成本较低，容量高，但是其压实密度较低，且其在充放电过程中与电解液的兼容性较差，容易与有机电解质反应放出气体，安全性差。镍钴铝酸锂比容量高，功率高，但是其合成难度大，工艺要求复杂，且吸湿性强。锰酸锂工艺简单，成本低，但是其高温性能不佳。磷酸铁锂循环寿命长，安全性能好，但是其电压低，能量密度低。
随着手机、平板电脑等智能终端电子设备和电动交通工具的不断发展，十分有必要对现有正极活性材料进行改良，提升其能量密度等性能指标，来满足设备对锂离子正极活性材料越来越高的要求。而提高锂离子正极活性材料的能量密度，最简单直接的方法就是提高正极材料的充电电压，使其在较高的充电电压下发挥出更多的容量。但是在高电压下，锂离子的过度脱嵌会导致正极材料结构不稳定，安全性能下降。因此，为了锂离子正极材料在较高电压下仍保持结构稳定，安全性好，同时还具有较好的循环寿命和存储性能，可以通过在正极材料表面包覆一层阻隔物来克服提高正极材料的稳定性，以满足在高电压下的使用需求。国内外很多文献和专利报道了采用Al2O3、AlPO4、ZrO2、TiO2或B2O3等氧化物包覆正极材料的技术。例如，Jaephil Cho等提出使用磷酸盐和金属氧化物包覆改善材料的循环性能，但同时该技术降低了材料的放电容量和倍率性能(Journal of The Electrochemical Society，2005； 152(6),A1142-A1148)。专利CN104752713A公开了一种用含有锂、镍、锰的氧化物和稀土元素氧化物包覆正极材料的方法，该方法可稳定材料结构，改善其倍率和低温性能等，但大大降低了正极材料的存储性能。
发明内容
本发明的目的之一是提供一种锂电池正极材料，通过多元素共包覆使正极材料能在高电压下使用，同时保持较好的高温循环性能和存储性能。
本发明的另一目的是提供一种上述锂电池正极材料的制备方法，本发明所提供的方法使所述正极材料能够安全稳定的生产，且成本较低。
本发明还提供一种由上述锂离子电池正极材料制备的锂离子电池正极，以及包括该锂离子电池正极的锂离子电池，其兼具较高的容量以及优异的循环性能和安全性能。
为实现上述目的，本发明提供一种锂离子电池正极材料，包括内核和包覆层：
所述内核为包括Mn、Ni和Co中至少一种元素、以及Li的复合金属氧化物颗粒；
所述包覆层为设置于所述内核表面的至少一部分上的金属氧化物层，具有由式(1)表示的平均组成：
M’xM”yOz  式(1)
其中，M’选自Mg、Ca、Mn、Sr、Fe、Cu、Ni、Zn或Co元素中的至少一种，M”选自Al、Fe、Ti、Mn、Cr或La中的至少一种；x、y、z满足：0＜x≤2，1≤y≤3，3<z≤5。
本发明提供的锂离子电池正极材料，包括复合氧化物颗粒内核和金属氧化物包覆层两个部分，金属氧化物包覆层被设置于复合氧化物颗粒内核的表面的至少一部分上，其中包覆层中含有上述多种元素。这种复合包覆层能够有效提高正极活性材料的充放电性能，如具有更高的放电容量，更好的安全性能和循环性能，尤其适用于在高电压下使用。而且，具有上述包覆层的正极活性材料具有更好的抗腐蚀性和耐高温性能，且其结构稳定，吸水率低。
进一步地，内核中还可包含掺杂元素M，同时可具有由式(2)表示的平均组成：
LiMnaNibCocM1-a-b-cO2  式(2)
其中，M选自Cr、V、Ti、Al、Zr、Nb、Ca、B、Si、Ga和Mg中的一种或几种，0≤a≤1，0≤b≤1，0≤c≤1，0<a+b+c<1。
本发明中，所述包覆层中可含有具有尖晶石空间群结构的MgAl2O4、ZnAl2O4或CoAl2O4。例如当包覆层采用含镁的化合物和含铝的化合物同时包覆内核时，能形成镁铝复合氧化物，通常为具有尖晶石空间群(Fd3m)结构的MgAl2O4。尖晶石空间群结构的MgAl2O4、ZnAl2O4或CoAl2O4很稳定，当该正极材料在高电压充电时，该包覆层能够稳定处于高氧化态的内核，避免其与电解液的副反应，防止内核层状结构坍塌，更有利于可逆地嵌入/脱出Li+。
优选地，所述锂离子电池正极材料具有核壳结构，即包覆层将内核表面完全包覆，更有利于抑制正极活性材料与电解液的副反应。
本发明中，为了有效保证正极材料的活性同时抑制副反应的发生，上述包覆层一般占锂离子电池正极材料总质量0.01％～10％；优选的，上述包覆层占锂离子电池正极材料总质量0.03％～5％。
进一步地，本发明提供的锂离子电池正极材料的中位径D50一般可以为3～30μm。所述中位径D50是指粒径分布体积百分数达到50％时所对应的粒径值，具体可依据实际需求调节。一般来讲，对于钴酸锂正极材料的D50范围为3～25μm，对于镍钴锰酸锂等其他锂电池正极材料的D50范围为5～16μm。可通过选择不同中位径的前驱体，调节热处理的温度、时间以及包覆层的组成等手段来调整D50的范围。
本发明中，将含有Mn、Ni和Co中至少一种元素的化合物、以及含有Li的化合物作为元素的源物质混匀后，在含氧气氛中进行热处理后获得内核，再将含有M’和M”的化合物与内核混匀后，在含氧气氛中进行热处理，从而得到上述锂离子电池正极材料。
本发明还提供一种上述锂离子电池正极材料的制备方法，包括：
(1)将含有Mn、Ni或Co中至少一种元素的化合物、以及含有Li的化合物混合均匀；
(2)将步骤(1)获得的混合物在氧气分压为15kPa以上的气氛中，在700～1400℃下热处理，冷却后破碎得到内核；
(3)将含有M’和M”的化合物与所述内核混合均匀，并将其包覆在所述内核表面的至少一部分上，得到包覆物；
(4)将所述包覆物在氧气分压为15kPa以上的气氛中，在300～1000℃下热处理，冷却后破碎得到所述锂离子电池正极材料。
上述制备方法中，第一次热处理是含有Mn、Ni或Co中至少一种元素的化合物、以及含有Li的化合物之间反应，从而形成内核；第二次热处理是包覆层与内核之间以及不同包覆元素之间的反应，从而在内核表面的至少一部分形成包覆层。该制备方法能够使包覆层均匀地包覆在内核表面，有效的阻断了正极活性材料与电解液的副反应，而且抑制了正极活性材料与电解液中HF的反应，与传统的氧化物不连续包覆相比，更能提高正极材料的性能。
内核中还可包含掺杂元素M，此时步骤(1)为将含有M的化合物与含有Mn、Ni或Co中至少一种元素、以及含有Li的化合物混合均匀，所述M选自Cr、V、Ti、Al、Zr、Nb、Ca、B、Si、Ga和Mg中的一种或几种。
通常，上述含M的化合物可选自含M的氧化物、羟基氧化物、氢氧化物、磷酸盐、氟化物、硼酸盐、草酸盐或碳酸盐中的一种或几种。
步骤(2)中，包覆层的形成过程具体可为，将含有M’和M”的化合物与所述内核混合均匀，采用液相化学法或固相混合法将其包覆在所述内核表面的至少一部分上，得到所述包覆物。
上述制备方法中，含有Li的化合物为制备锂离子电池正极常用的锂源，例如可为氢氧化锂、醋酸锂或碳酸锂中的一种或两种。
含有M’和M”的化合物可为含有M’和M”的无水氧化物，羟基氧化物，氢氧化物，硝酸盐，碳酸盐，氟化物、醋酸盐和柠檬酸盐中的一种或几种，优选无水氧化物，羟基氧化物以及氢氧化物。
本发明还提供一种锂离子电池正极，其包括导电剂、粘合剂、以及上述锂离子电池正极材料。其中，导电剂和粘合剂为现有技术中制备锂离子电池正极的常用原料，例如导电剂可为碳黑、石墨、乙炔黑、石墨烯、碳纳米管或碳纤维中的一种或几种，粘合剂可列举聚偏二氟乙烯、聚四氟乙烯和丁苯橡胶中的一种或几种。
本发明还提供一种锂离子电池，其中包括负极、隔膜、电解液和上述锂离子电池正极。
本发明方案的实施，至少具有以下优势：
1、本发明提供的锂离子电池正极材料，具有复合包覆层，结构稳定，并 且在高电压下能够维持正极材料的结构，使其在充放电过程中，结构变化较小，从而提高正极活性材料的安全性能和循环性能。
2、本发明提供的锂离子电池正极材料的制备方法简单易行，成本低廉，有利于大规模生产。
附图说明
图1A和图1B是实施例1得到锂离子电池正极材料包覆层的X-射线衍射图；
图2是实施例5中得到的锂离子电池正极材料表面的扫描电镜图；
图3A为实施例5得到的锂离子电池正极材料表面的扫描电镜图；
图3B是实施例5中得到的锂离子电池正极材料的包覆层中镁元素分布图；
图3C是实施例5中得到的锂离子电池正极材料的包覆层中铝元素分布图；
图4是实施例1、对比例1和实施例2中锂离子电池正极材料制备的电池常温25℃下的循环曲线；
图5是实施例1、对比例1和实施例2中锂离子电池正极材料制备的电池高温45℃下的循环曲线。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将碳酸锂、四氧化三钴、五氧化二铌和氧化钙充分混合，其中Li:(Co+Nb+Ca)的摩尔比为1.03:1，将所得混合物于空气气氛中、1000℃下烧结10h，冷却至室温，破碎过筛后得到近球形的内核，该内核的中位径约为14.1μm。
采用固相混合法将镁铝复合氧化物包覆于内核表面，具体步骤为：将摩尔比为1:0.003:0.003的上述内核、纳米碳酸镁、纳米三氧化二铝混合3h，将所得混合物于空气气氛中、700℃下烧结8h，冷却至室温，破碎过筛即得包覆后的锂离子电池正极材料，其中位径约为14.3μm。
实施例2
将碳酸锂、四氧化三钴、二氧化硅、三氧化二铝和二氧化锌充分混合，其中Li:(Co+Si+Al+Zn)的摩尔比为1.03:1，将所得混合物于空气气氛中、1000℃下烧结10h，冷却至室温，破碎过筛后得到近球形的内核，该内核的中位径约为14.7μm。
采用液相化学法将镁铝复合氧化物包覆于内核表面，具体步骤为：将摩尔比为1:0.005:0.01的内核、硝酸镁、硝酸铝加入到含有一定量去离子水的包覆釜，搅拌转速为600r/min，搅拌均匀。开启加热，加热温度控制在100±5℃，直至水分蒸发完毕，得到包覆材料。
将包覆后的粉末置于箱式炉内以5℃/min的速度升温至500℃后保持10小时，随炉冷却至室温后过300目筛，即得包覆后的锂离子电池正极材料，其中位径约为14.7μm。
实施例3
将含有Mn、Ni和Co的化合物与氢氧化锂以1:1.04摩尔比充分混合，其中Mn、Ni和Co的摩尔比为2:6:2，将所得混合物在空气气氛下，于820℃烧结12h，冷却至室温，破碎过筛后，即得到近球形的内核。
采用液相化学法将镁铝复合氧化物包覆于内核表面，具体步骤为：将摩尔比为1:0.006:0.006的内核、纳米氧化镁和纳米氧化铝加入到含有一定量去离子水的包覆釜中，搅拌转速为800r/min，搅拌均匀。开启加热，加热温度控制在100±5℃，边搅拌边烘干，得到包覆材料。
将包覆后的粉末置于箱式炉内以10℃/min的速度升温至500℃后保持3小时，随炉冷却至室温后过300目筛，即得锂离子电池正极材料，其中位径约为11.5μm。
实施例4
将含有Mn、Ni和Co的化合物与氢氧化锂以1:1.04摩尔比充分混合，其中Mn、Ni和Co的摩尔比为2:6:2，将所得混合物在空气气氛下，于820℃烧结12h，冷却至室温，破碎过筛后，即得到近球形的内核。
采用固相混合法将锌铝复合氧化物包覆于内核表面，具体步骤为：将摩尔比为1:0.003:0.003的上述内核、纳米氧化锌、纳米三氧化二铝混合3h，将所得混合物于空气气氛中、600℃下烧结5h，冷却至室温，破碎过筛即得包覆后的锂离子电池正极材料，其中位径约为11.5μm。
实施例5
将含有Mn、Ni和Co的化合物与氢氧化锂以1:1.02摩尔比充分混合，其中Mn、Ni和Co的摩尔比为3:5:2，将所得混合物在空气气氛下，于900℃烧结11h，冷却至室温，破碎过筛后，即得到近球形的内核。
采用固相混合法将镁铝复合氧化物包覆于内核表面，具体步骤为：将摩尔比为1:0.01:0.02的内核、纳米氧化镁粉末、纳米氢氧化铝粉末混合3h，将所得混合物在空气气氛下、于750℃烧结5h，冷却至室温，破碎过筛即得锂离子电池正极材料，其中位径约为12μm。
实施例6
将含有Mn、Ni和Co的化合物与氢氧化锂以1:1.04摩尔比充分混合，其中Mn、Ni和Co的摩尔比为1:8:1，将所得混合物在氧气气氛下，于750℃烧结12h，冷却至室温，破碎过筛后，即得到近球形的内核。
采用固相混合法将钴铝复合氧化物(钴蓝，分子式为Al2Co2H6O5)包覆于内核表面，具体步骤为：将摩尔比为1:0.01的内核和纳米钴蓝粉末混合4h，将所得混合物在氧气气氛下、于350℃烧结5h，冷却至室温，破碎过筛即得锂离子电池正极材料，其中位径约为8μm。
对比例1
将碳酸锂、四氧化三钴、五氧化二铌混合，其中Li:(Co+Nb)的摩尔比为1.03:1，将所得混合物于空气气氛中、1000℃烧结10h，冷却至室温，破碎过筛即得锂离子电池正极材料，其中位径约为14.1μm。
锂离子电池正极材料结构表征
用X-射线衍射仪对包覆层进行测定。图1A和图1B是实施例1得到锂离子电池正极材料包覆层的X-射线衍射图。其中图1A中较高的峰代表包覆的正极材料的(101)峰(2θ＝37.3°)，而在(101)峰底部的代表MgAl2O4的峰(2θ＝36.9°)。图1B中较高的峰代表包覆的正极材料的(104)峰(2θ＝45.2°)，而在(104)峰底部的代表MgAl2O4的峰(2θ＝44.8°)。由图1A和图1B可知，实施例1得到锂离子电池正极材料包覆层中形成了尖晶石 空间群结构(Fd3m)的MgAl2O4。具有尖晶石空间群结构的复合包覆层，性能稳定，无化学活性，在高电压下耐电解液腐蚀。
用扫描电子显微镜对锂离子电池正极材料表面进行测定。图2是实施例5得到的锂离子电池正极材料表面的扫描电镜图，可以看出包覆层在内核表面形成了均匀包覆。图3A为实施例5得到的锂离子电池正极材料表面与图2不同倍率下的的扫描电镜图。图3B是实施例5中得到的锂离子电池正极材料的包覆层中镁元素分布图。图3C是实施例5中得到的锂离子电池正极材料的包覆层中铝元素分布图。由图3B和图3C可知，镁元素和铝元素均匀包覆在内核表面，形成均匀分布的包覆层。
锂离子电池正极电性能测试
将上述实施例1、实施例2和对比例1中制备的锂离子电池正极材料做成软包电池，厚度为5mm，宽度为30mm，长度为48mm，该电池具有约600mAh的容量。电池制作步骤如下：
1)正极的制作
将970g包覆后的正极材料粉末，15g Super-P，15g PVDF和380g NMP混合均匀，调制成正极浆料。将该浆料涂布到铝箔上，干燥。将得到的正极极板裁切、压延。
2)负极的制作
将950g人造石墨，13g Super-P，14g CMC，46g SBR溶液和1200g去离子水混合均匀，调制成负极浆料。将该浆料涂布到铜箔上，干燥。将得到的负极极板裁切、压延。
3)电池的组装
正极极板和负极极板焊接极耳，并用高温胶带固定极耳。加入隔膜，卷绕、压实，放入软包铝塑膜中。封口后，注入电解液，再静置、预充、二次封口和分容。
4)电池的测试
分容后对电池性能进行检测。
放电容量和常温循环测试：
(1)恒流恒压充电：0.2CmA(终止电压4.4V，终止电流0.02CmA)；
(2)恒流放电：0.2CmA(终止电压3.0V)，得到放电容量测试结果；
(3)静置：10分钟；
(4)恒流恒压充电：1.0CmA(终止电压4.4V，终止电流0.02CmA)；
(5)恒流放电：1.0CmA(终止电压3.0V)；
(6)静置：10分钟；
(7)步骤(4)～(6)重复300次，得到常温循环测试结果。
高温循环测试：
将电池置于45℃的烘箱中进行测试，工作步骤如下。
(1)恒流恒压充电：1.0CmA(终止电压4.4V，终止电流0.02CmA)；
(2)恒流放电：1.0CmA(终止电压3.0V)；
(3)静置：10分钟；
(4)步骤(4)～(6)重复300次，得到高温循环测试结果。
高温存储测试：
(1)恒流恒压充电：1.0CmA(终止电压4.4V，终止电流0.02CmA)；
(2)恒流放电：1.0CmA(终止电压3.0V)，得到电池存储前的放电容量，并用千分尺测试电池的厚度；
(3)将电池置于60℃的烘箱中静置7天；
(4)取出电池再用千分尺测试电池的厚度，得到鼓胀率的测试结果；
(5)将取出的电池按照步骤(1)～(2)进行测试，得到电池存储后的放电容量。
图4是实施例1、对比例1和实施例2中锂离子电池正极材料制备的电池，在3.0～4.4V，1C充放电，25℃常温条件下的循环曲线。由图4可知，对比例1中锂离子电池正极材料制备的电池，在25℃常温下，循环300次容量保持率下降至82.4％，而实施例1和实施例2中锂离子电池正极材料制备的电池，在25℃常温下，循环300次容量保持率仍保持在89.7％以上，常温下的循环性能优异。
图5是实施例1、对比例1和实施例2中锂离子电池正极材料制备的电池在3.0～4.4V，1C充放电，45℃高温条件下的循环曲线。由图5可知，对比例1中锂离子电池正极材料制备的电池，在45℃高温下，循环300次容量保持率下降至78.6％左右，而实施例1和实施例2中锂离子电池正极材料制备的电池，在45℃高温下，循环300次容量保持率仍保持在88％以上，高温下仍显示出优异的循环性能。
表1是锂离子电池正极材料的1.0C放电容量和4.4V-3.0V电池60℃*7D 高温存储数据。由表1可知，在高压高温下，本发明提供的锂离子电池正极材料制备的电池能够保持较低的鼓胀率，高温存储性能优异。
表1
  放电容量 鼓胀率％ 容量保持率％
实施例1 177.8 0.63 86.4
实施例2 177.3 0.78 85.0
对比例1 176.9 11.0 54.2
最后应说明的是：以上各实施例仅用以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 (17)

  1. 一种锂离子电池正极材料，其特征在于，包括内核和包覆层，
    所述内核为包括Ni、Co和Mn中至少一种元素、以及Li的复合金属氧化物颗粒；
    所述包覆层为设置于所述内核表面的至少一部分上的金属氧化物层，具有由式(1)表示的平均组成：
    M’xM”yOz  式(1)，
    其中，M’选自Mg、Ca、Mn、Sr、Fe、Cu、Ni、Zn或Co元素中的至少一种，M”选自Al、Fe、Ti、Mn、Cr或La中的至少一种；x、y、z满足0＜x≤2，1≤y≤3且3<z≤5。
  2. 根据权利要求1所述的锂离子电池正极材料，其特征在于，所述内核具有由式(2)表示的平均组成：
    LiMnaNibCocM1-a-b-cO2  式(2)
    其中，M选自Cr、V、Ti、Al、Zr、Nb、Ca、B、Si、Ga和Mg中的一种或几种，0≤a≤1，0≤b≤1，0≤c≤1且0<a+b+c<1。
  3. 根据权利要求1或2所述的锂离子电池正极材料，其特征在于，所述包覆层含有具有尖晶石空间群结构的MgAl2O4、ZnAl2O4或CoAl2O4。
  4. 根据权利要求1或2所述的锂离子电池正极材料，其特征在于，所述锂离子电池正极材料具有核壳结构。
  5. 根据权利要求1或2所述的锂离子电池正极材料，其特征在于，所述包覆层占所述锂离子电池正极材料总质量的0.01～10％。
  6. 根据权利要求1或2所述的锂离子电池正极材料，其特征在于，所述锂离子电池正极材料的中位径为3～30μm。
  7. 根据权利要求1或2所述的锂离子电池正极材料，其特征在于，其是将含有Mn、Ni和Co中至少一种元素、以及含有Li的化合物在氧气存在下进行热处理后获得内核，再将含有M’和M”的化合物与内核混匀后，在氧气存在下进行热处理而获得的。
  8. 根据权利要求1-7任一项所述的锂离子电池正极材料的制备方法，其特征在于，包括：
    (1)将含有Mn、Ni和Co中至少一种元素、以及含有Li的化合物在氧 气分压为15kPa以上的气氛中，在700～1400℃下热处理至少一次，冷却后破碎得到所述内核；
    (2)将含有M’和M”的化合物与所述内核混合均匀，并将其包覆在所述内核表面的至少一部分上，得到前驱体；
    (3)将所述前驱体在氧气分压为15kPa以上的气氛中，在300～1000℃下热处理至少一次，冷却后破碎得到所述锂离子电池正极材料。
  9. 根据权利要求8所述的制备方法，其特征在于，所述步骤(1)为将含有M的化合物与含有Ni、Co和Mn中至少一种元素、以及含有Li的化合物混合均匀，所述M选自Cr、V、Ti、Al、Zr、Nb、Ca、B、Si、Ga和Mg中的一种或几种。
  10. 根据权利要求9所述的制备方法，其特征在于，所述含M的化合物为含M的氧化物、羟基氧化物、氢氧化物、磷酸盐、氟化物、硼酸盐、草酸盐或碳酸盐中的一种或几种。
  11. 根据权利要求8所述的制备方法，其特征在于，所述步骤(2)为将含有M’和M”的化合物与所述内核混合均匀，采用液相化学法或固相混合法将其包覆在所述内核表面的至少一部分上，得到所述前驱体。
  12. 根据权利要求8所述的制备方法，其特征在于，所述含有Li的化合物为氢氧化锂或碳酸锂中的一种或两种。
  13. 根据权利要求8所述的制备方法，其特征在于，所述含有M’和M”的化合物为含有M’和M”的无水氧化物，羟基氧化物，氢氧化物，硝酸盐，碳酸盐，氟化物，醋酸盐和柠檬酸盐中的一种或几种，优选无水氧化物，羟基氧化物以及氢氧化物。
  14. 一种锂离子电池正极，其特征在于，包括导电剂、粘合剂、以及如权利要求1-7任一项所述的锂离子电池正极材料。
  15. 根据权利要求14所述的锂离子电池正极，其特征在于，所述导电剂为碳黑、石墨、乙炔黑、石墨烯、碳纳米管或碳纤维中的一种或几种。
  16. 根据权利要求14所述的锂离子电池正极，其特征在于，所述粘合剂为聚偏二氟乙烯、聚四氟乙烯和丁苯橡胶中的一种或几种。
  17. 一种锂离子电池，其特征在于，包括负极、隔膜、电解液和如权利要求14-16任一项所述的锂离子电池正极。
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