WO2019062808A1 - 氢氧化镍钴锰和正极材料及其制备方法和锂离子电池 - Google Patents

氢氧化镍钴锰和正极材料及其制备方法和锂离子电池 Download PDF

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WO2019062808A1
WO2019062808A1 PCT/CN2018/107934 CN2018107934W WO2019062808A1 WO 2019062808 A1 WO2019062808 A1 WO 2019062808A1 CN 2018107934 W CN2018107934 W CN 2018107934W WO 2019062808 A1 WO2019062808 A1 WO 2019062808A1
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nickel
cobalt
manganese
lithium
core
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PCT/CN2018/107934
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English (en)
French (fr)
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游军飞
陈靖华
徐茶清
曹文玉
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比亚迪股份有限公司
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Priority to JP2020518417A priority Critical patent/JP2020535104A/ja
Priority to KR1020207010038A priority patent/KR102429101B1/ko
Priority to EP18862886.1A priority patent/EP3675254B1/en
Priority to US16/650,835 priority patent/US11784308B2/en
Publication of WO2019062808A1 publication Critical patent/WO2019062808A1/zh
Priority to US18/452,239 priority patent/US20230395797A1/en

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    • 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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Definitions

  • the present disclosure relates to the field of lithium ion batteries, and in particular to a nickel hydroxide cobalt manganese and cathode material, a preparation method thereof and a lithium ion battery.
  • the existing methods for preparing nickel hydroxide cobalt manganese and lithium nickel cobalt manganate cathode materials and lithium ion batteries are as follows: (1) mixing sulfates containing nickel, cobalt and manganese, respectively, in deionized water to form an aqueous solution of sulfate A; (2) dissolving sodium hydroxide powder in deionized water to form aqueous solution B; (3) diluting ammonia water having a mass fraction of 25-28% to a certain concentration by deionized water to obtain diluted aqueous ammonia solution C; 4) The aqueous solution A in the step (1), the aqueous solution B in the step (2) and the aqueous ammonia solution C in the step (3) are simultaneously added dropwise under a nitrogen atmosphere, stirred and heated to 40-70 ° C.
  • the reaction is dried and washed to obtain a nickel hydroxide cobalt manganese precursor powder; (5) the lithium source compound and the nickel hydroxide cobalt manganese precursor material of the step (4) are weighed and uniformly mixed in the air. Or heating to 600-1100 ° C in an oxygen atmosphere, and continuously calcining at 600-1100 ° C for 8-20 h, and then cooling to room temperature to obtain a nickel nickel cobalt manganate finished material; (6) nickel cobalt obtained in the step (5) Lithium manganate material is made into a battery, but the nickel hydroxide obtained above is used.
  • the lithium ion battery prepared by the cobalt manganese and nickel cobalt-manganese oxide positive electrode materials has poor battery rate performance and poor high temperature storage performance of the battery.
  • the purpose of the present disclosure is to overcome the problem of poor rate performance of a lithium ion battery in the prior art, and provide a nickel hydroxide cobalt manganese and a cathode material, a preparation method thereof, and a lithium ion battery, which are prepared from the cathode material of the present disclosure.
  • Lithium-ion batteries have higher battery energy density and better battery rate performance.
  • an aspect of the present disclosure provides, in one aspect, a nickel-cobalt-cobalt manganese comprising an inner core and an outer layer coated on the outer core, the inner core including tabular particles, and the inner core
  • the flaky particles have a D 50 particle diameter of 5 to 8 ⁇ m
  • the particles in the outer layer have a D 50 particle diameter of 0.1 to 5 ⁇ m.
  • a second aspect of the present disclosure provides a method for preparing nickel hydroxide cobalt manganese, which comprises mixing an aqueous solution A containing water-soluble nickel, cobalt, and manganese ions with an aqueous solution B containing a strong alkali and ammonia water under an inert atmosphere. The complex precipitation reaction is carried out, and then metal silver powder is added for pulse current coprecipitation reaction.
  • a third aspect of the present disclosure provides a nickel cobalt manganese manganate cathode material obtained by calcining a lithium source with the above nickel cobalt cobalt manganese or the nickel nickel cobalt manganese obtained by the above method.
  • a fourth aspect of the present disclosure provides a nickel cobalt manganese manganate cathode material, the nickel cobalt cobalt manganate comprising a core and an outer layer coated outside the core, the core comprising tabular particles, and the core
  • the medium flaky particles have a D 50 particle diameter of 5 to 10 ⁇ m, and the particles in the outer layer have a D 50 particle diameter of 0.1 to 4.5 ⁇ m.
  • a fifth aspect of the present disclosure provides a method of preparing a positive electrode material, the method comprising: calcining a lithium source with the above nickel oxyhydroxide manganese or the nickel oxyhydroxide manganese obtained by the above method.
  • a sixth aspect of the present disclosure provides a lithium ion battery comprising the above positive electrode material or a positive electrode material obtained by the above method.
  • the nickel hydroxide-manganese primary particles obtained by the prior method are densely distributed, so that the subsequently prepared lithium nickel cobalt manganate finished material has a high energy density, but the rate performance is poor.
  • Ag powder is used as a conductivity inducing agent to form a porous porous nickel-cobalt-cobalt-manganese particle layer on the surface of the existing dense nickel-cobalt-manganese particles by pulse current co-precipitation, and the hydroxide prepared by the method is prepared.
  • the nickel-cobalt-manganese particles are dense inside and loose outside, and then the lithium source and nickel-nickel-cobalt-manganese are calcined, and then cooled to room temperature to obtain an internal dense, externally porous porous nickel-cobalt-manganese oxide finished material.
  • the nickel-cobalt-manganese-lithium finished material has a specific surface area of 0.1-10 m 2 /g, and the internal dense secondary particles (core flake particles) have a D 50 particle size of 5-10 ⁇ m, and the outer loose particles (outer particles) The D 50 particle size is between 0.1 and 4.5 ⁇ m.
  • the lithium ion battery prepared by using the above-mentioned lithium nickel cobalt manganate finished material as a positive electrode material has excellent battery energy density and rate performance.
  • Example 1 is an SEM image (30000 times) of nickel hydroxide cobalt manganese prepared in Example 1 of the present disclosure
  • Example 2 is an SEM image (1000 times) of nickel hydroxide cobalt manganese prepared in Example 1 of the present disclosure
  • first and second are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated.
  • features defining “first” and “second” may include at least one of the features, either explicitly or implicitly.
  • the meaning of "a plurality” is at least two, such as two, three, etc., unless specifically defined otherwise.
  • the first feature "on” or “under” the second feature may be a direct contact of the first and second features, or the first and second features may be indirectly through an intermediate medium, unless otherwise explicitly stated and defined. contact.
  • the first feature "above”, “above” and “above” the second feature may be that the first feature is directly above or above the second feature, or merely that the first feature level is higher than the second feature.
  • the first feature “below”, “below” and “below” the second feature may be that the first feature is directly below or obliquely below the second feature, or merely that the first feature level is less than the second feature.
  • the present disclosure provides a nickel hydroxide cobalt manganese comprising an inner core and an outer layer coated on the outer core, the inner core comprising tabular particles, and the flaky particles in the inner core 50 has a particle size of 5-8 ⁇ m, and the particles in the outer layer have a D 50 particle diameter of 0.1 to 5 ⁇ m.
  • the coating structure of the nickel-nickel-cobalt-manganese does not completely coat the inner core structure, but the small particles of the outer layer adhere to the surface of the large-sized particles of the inner core, and the small particles between the outer layers loosely form voids. Loose porous outer layer.
  • the inner core has a porosity of 30 to 51%
  • the outer layer has a porosity of 52 to 60%, that is, the nickel hydroxide cobalt particles of the present disclosure.
  • the inside is dense, the outside is loose and porous, and then the lithium source and nickel-nickel-cobalt-manganese are calcined, and then cooled to room temperature to obtain an internal dense, externally porous porous lithium nickel cobalt manganate finished material.
  • the porosity of the inner core refers to the porosity based on the total volume of the inner core
  • the porosity of the outer layer refers to the porosity based on the total volume of the outer layer
  • the nickel-cobalt-manganese has a chemical formula of Ni x Co y Mn 1-xy (OH) 2 , wherein 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ 1-xy ⁇ 1, so that the rate performance of the lithium ion battery obtained from the lithium nickel cobalt manganate cathode material can be remarkably improved.
  • the tabular grains in the inner core have a D 50 particle diameter of 5 to 7.5 ⁇ m, and the particles in the outer layer have a D 50 particle diameter of 0.1 to 4.5 ⁇ m.
  • the rate performance of the lithium ion battery made of the lithium nickel cobalt manganate cathode material can be remarkably improved.
  • the nickel oxyhydroxide manganese of the present disclosure preferably, contains Ag, preferably, the content of Ag is less than 20 ppm (preferably less than 10 ppm), thereby being able to avoid excessive Ag content on subsequent lithium The impact of ion battery performance.
  • the form of Ag in the nickel-cobalt-cobalt manganese is not particularly limited, and may be in the form of a simple substance or a compound.
  • the nickel-nickel-cobalt manganese has a specific surface area of 0.1 to 10 m 2 /g, more preferably 5 to 8 m 2 /g, so that the lithium ion finally obtained can be obtained.
  • the performance of the battery performance is superior.
  • a second aspect of the present disclosure provides a method for preparing nickel hydroxide cobalt manganese, which comprises mixing an aqueous solution A containing water-soluble nickel, cobalt, and manganese ions with an aqueous solution B containing a strong alkali and ammonia water under an inert atmosphere. The complex precipitation reaction is carried out, and then metal silver powder is added for pulse current coprecipitation reaction.
  • the pulse current coprecipitation reaction refers to a coprecipitation reaction carried out under pulse current conditions.
  • a method of preparing an aqueous solution A of water-soluble nickel, cobalt, and manganese ions may include dissolving a water-soluble nickel salt, a water-soluble cobalt salt, and a water-soluble manganese salt in water.
  • the water-soluble nickel salt may be various water-soluble nickel salts in the art, and may be, for example, at least one of nickel sulfate, nickel nitrate, and nickel chloride, preferably nickel sulfate.
  • the water-soluble cobalt salt may be various water-soluble cobalt salts in the art, and may be, for example, at least one of cobalt sulfate, cobalt nitrate and cobalt chloride, preferably cobalt sulfate.
  • the water-soluble manganese salt may be various water-soluble manganese salts in the art, and may be, for example, at least one of manganese sulfate, manganese nitrate, and manganese chloride, and is preferably manganese sulfate.
  • the concentration of the water-soluble nickel, cobalt, and manganese ions in the aqueous solution A is from 0.1 to 3 mol/L, preferably from 0.1 to 2 mol/L.
  • the concentration of water-soluble nickel, cobalt, and manganese ions refers to the total concentration of three elements of nickel, cobalt, and manganese in the salt.
  • the concentration of the aqueous ammonia may be from 0.1 to 1.6 mol/L, preferably from 0.1 to 1.2 mol/L.
  • Ammonia water of the desired concentration of the present disclosure can be obtained by diluting with a concentration of 25-28% aqueous ammonia.
  • the strong base may be various strong bases in the art, such as sodium hydroxide and/or potassium hydroxide.
  • concentration of the strong base in the aqueous solution B may be from 0.1 to 16 mol/L, preferably from 0.1 to 10 mol/L.
  • the strong base of the present disclosure is a precipitating agent for the complex precipitation reaction
  • the ammonia water is a complexing agent for the complex precipitation reaction. Therefore, in the present disclosure, the amount of the strong base and the ammonia water can be such that the nickel ions, the cobalt ions and the manganese ions in the aqueous solution A are completely complexed and precipitated to form nickel hydroxide cobalt manganese, that is, the amount of the strong base and the ammonia water is only dissolved relative to the water.
  • the nickel, cobalt and manganese salts can be used in excess.
  • the method further preferably comprises formulating a nickel sulfate, cobalt, manganese solution (aqueous solution A) with CoSO 4 .7H 2 O, NiSO 4 .6H 2 O, and MnSO 4 .H 2 O.
  • a nickel sulfate, cobalt, manganese solution aqueous solution A
  • CoSO 4 .7H 2 O, NiSO 4 .6H 2 O, and MnSO 4 .H 2 O a nickel sulfate, cobalt, manganese solution.
  • the amount of ammonia water of 0.1-1.2 mol L -1 is compared with 40 L of nickel sulfate, cobalt and manganese solution of 0.1-2 mol/L concentration.
  • 0.1-40 L 0.1-10 mol L -1 concentration of aqueous NaOH solution (aqueous solution B) is used in an amount of 0.1-40 L.
  • the method in order to more uniformly produce nickel hydroxide, manganese, preferably further comprises simultaneously dropping the aqueous solution A, the aqueous ammonia and the aqueous solution B into the reactor under stirring.
  • the drop acceleration can be 0.2-2L/h
  • the stirring speed can be 4-10ms -1 .
  • the conditions of the complexation precipitation reaction may be various complex precipitation reaction conditions in the art, and may include, for example, a temperature of 40-70 ° C, preferably 40-60 ° C; a time of 0.1- 80h, preferably 0.1-60h (more preferably 0.1-20h), so that the overall particle size distribution of nickel oxyhydroxide manganese can be controlled.
  • the manner of performing the pulse current coprecipitation reaction comprises: inserting a metal electrode in the reactor, forming an electrolytic cell with the metal reactor, then adding metallic silver powder to the reactor, and then introducing Pulse power supply.
  • the metal electrode may be at least one of a Pt electrode, an Au electrode, and an Ag electrode, and is preferably a Pt electrode.
  • the reactor can be a variety of conventional reactors in the art.
  • the conditions of the pulse current coprecipitation reaction include a pulse ratio of 1:1 to 10, more preferably 1:1 to 5, and a reaction time of 0.1 to 40 h, more preferably 0.1-30h, thereby further controlling the porosity and particle size distribution of the obtained nickel-cobalt-manganese core and outer layer, thereby significantly improving the rate performance of the lithium ion battery obtained from the lithium nickel cobalt manganate cathode material.
  • the preferred pulse ratios described above can be provided in the present disclosure using a pulsed power supply of 0-32V.
  • the metal silver powder is preferably used in an amount of 0.36-1 g, more preferably 0.36-0.6 g, relative to 1566 g of the nickel element, which can further control the porosity of the obtained nickel-nickel-cobalt-manganese core and outer layer. And the particle size distribution and the like, thereby significantly improving the rate performance of the lithium ion battery obtained from the lithium nickel cobalt manganate cathode material.
  • the method may further include: washing and drying the slurry obtained by the pulse current coprecipitation reaction to obtain nickel hydroxide cobalt manganese.
  • the washing time may be 3-7 times, and the drying temperature may be 100-120 °C.
  • the inert atmosphere may be provided by nitrogen and/or an inert gas.
  • the inert gas may be helium (He), neon (Ne), argon (Ar), krypton (Kr), or xenon (Xe).
  • a third aspect of the present disclosure provides a lithium nickel cobalt manganate cathode material obtained by calcining a lithium source with the above nickel nickel cobalt manganese or the nickel nickel cobalt manganese obtained by the above method.
  • a fourth aspect of the present disclosure provides a lithium nickel cobalt manganate cathode material, wherein the lithium nickel cobalt manganese oxide material comprises a core and an outer layer coated on the outer core, the core comprising a sheet a particle, and the flaky particles in the core have a D 50 particle diameter of 5 to 10 ⁇ m, and the particles in the outer layer have a D 50 particle diameter of 0.1 to 4.5 ⁇ m, thereby being improved by a lithium nickel cobalt manganate cathode material.
  • the rate performance of lithium-ion batteries comprises a core and an outer layer coated on the outer core, the core comprising a sheet a particle, and the flaky particles in the core have a D 50 particle diameter of 5 to 10 ⁇ m, and the particles in the outer layer have a D 50 particle diameter of 0.1 to 4.5 ⁇ m, thereby being improved by a lithium nickel cobalt manganate cathode material.
  • the core has a porosity of 8-15%
  • the outer layer has a porosity of 20-40%, that is, the nickel cobalt manganese acid of the present disclosure.
  • the interior of lithium is dense and the outside is porous and porous.
  • the flaky particles in the core have a D 50 particle diameter of 7 to 10 ⁇ m, and the particles in the outer layer have a D 50 particle diameter of 0.9 to 2.5 ⁇ m. , thereby significantly improving the rate performance of the lithium ion battery produced by the lithium nickel cobalt manganate cathode material.
  • the chemical formula of the lithium nickel cobalt manganese oxide is LiNi x Co y Mn 1-xy O 2 , wherein 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ 1-xy ⁇ 1, so that the rate performance of the lithium ion battery obtained from the lithium nickel cobalt manganate cathode material can be remarkably improved.
  • the content of Ag in the cathode material is less than 20 ppm (preferably less than 10 ppm), so that the influence of excessive Ag content on the performance of the subsequent lithium ion battery can be avoided.
  • the cathode material preferably has a specific surface area of 0.1 to 10 m 2 /g, more preferably 0.5 to 1.5 m 2 /g, thereby enabling the lithium ion battery performance to be finally obtained.
  • the rate performance is superior.
  • a fifth aspect of the present disclosure provides a method of preparing a positive electrode material, the method comprising: calcining a lithium source with the above nickel oxyhydroxide manganese or the nickel oxyhydroxide manganese obtained by the above method.
  • the method may further include: mixing the lithium source and the obtained nickel, cobalt, and manganese to be uniformly calcined.
  • the lithium source may be various lithium-containing compounds that may be used in lithium ion batteries in the art, such as lithium carbonate and/or lithium hydroxide.
  • the molar ratio of the lithium element to the nickel hydroxide to manganese in the lithium source is from 1.0 to 1.1:1, more preferably from 1.0 to 1.08:1, thereby enabling the preparation
  • the chemical formula of lithium nickel cobalt manganese oxide is LiNi x Co y Mn 1-xy O 2 , where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ 1-xy ⁇ 1.
  • the calcination conditions may be various calcination conditions in the art, and may include, for example, a temperature of 600 to 1100 ° C, preferably 750 to 950 ° C, and a time of 8 to 20 h, preferably 10 to 15 h.
  • the calcined oxidizing environment can be provided for air and/or oxygen, for example by introducing air and/or oxygen into the muffle furnace.
  • a sixth aspect of the present disclosure provides a lithium ion battery comprising the above positive electrode material or a positive electrode material obtained by the above method.
  • the preparation method of the lithium ion battery of the present disclosure may be various conventional lithium ion battery preparation methods in the art, for example, may include: i. inserting two layers of foamed nickel in the negative electrode case, and placing the negative electrode case and the positive electrode case in an oven. Baking for 30-40 minutes; ii. transferring the positive electrode sheet (including the prepared positive electrode material) and the positive electrode case and the negative electrode case taken out from the oven into the glove box, starting from the negative electrode; iii. placing the negative electrode case on the filter paper The lithium piece is taken out, the lithium piece is placed on the foamed nickel in the negative electrode case, and the lithium piece is clamped flat with a pair of pliers; iv.
  • the positive electrode case is placed on the filter paper, the pressed positive electrode piece is placed, and the positive electrode piece is placed in the The positive center of the positive electrode shell, gently put it when placed, do not let the positive electrode material drop, inject a proper amount of electrolyte; v. Add a layer of ⁇ 16 diaphragm paper, add the diaphragm paper so that the end of the diaphragm paper first wet the electrolyte, then Slowly lower the other end, so that the diaphragm paper is completely immersed in the electrolyte, there is no air bubble in the middle; vi. Inject an appropriate amount of electrolyte, cover the negative electrode shell, put a little pressure after flattening, press the negative electrode shell and fit inside the positive electrode shell. ;vii. remove the seal, seal as much as possible to keep each Hydrostatic pressure consistent with the time, after sealing, wipe the surface of the battery electrolyte.
  • the lithium ion battery of the present disclosure has an energy density as high as 1.5-2.5 Wh/cm 3 and a magnification of 5 C/0.2 C as high as 90-99%.
  • the scanning electron microscope (SEM) was a S4800 scanning electron microscope manufactured by Hitachi, Japan, and the test voltage was 5 kV.
  • the preparation method of the lithium ion battery i. inserting two layers of foamed nickel in the negative electrode case, baking the negative electrode case and the positive electrode case in an oven for 30 minutes; ii. placing the positive electrode piece (including the prepared positive electrode material) and the oven from the oven The positive and negative shells taken out are transferred to the glove box and assembled from the negative electrode; iii. The negative electrode case is placed on the filter paper, the lithium piece is taken out, the lithium piece is placed on the foamed nickel in the negative electrode case, and the lithium is pliers The chip clamp is flat; iv.
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • the stirring paddle was started at a speed of 5 ms -1 ; then the nickel sulfate, cobalt, manganese solution, sodium hydroxide solution and aqueous ammonia solution were simultaneously dropped into a reaction vessel (droplet acceleration of 0.2 L/h) in a nitrogen atmosphere for complex precipitation. The reaction was continued for 40 hours. Then, a Pt electrode was inserted into the reaction vessel, and an electrolytic cell was formed with the stainless steel of the reactor. 0.3 g of Ag powder was added into the reaction vessel, and a 32 V pulse power source was applied thereto. The pulse ratio was 1:1, and the pulse current was co-deposited.
  • FIG. 1 is a nickel cobalt manganese hydroxide powder A1 SEM pictures (30,000 times)
  • FIG. 2 is Nickel-cobalt-manganese oxide powder A1 SEM picture (1000);
  • step (2) Weigh 0.37kg of lithium carbonate, 0.915kg of nickel hydroxide cobalt powder prepared in step (1), using a high-speed mixer according to the molar ratio of lithium source (as lithium element) and nickel cobalt cobalt manganese powder. The ratio of 1:1 is evenly mixed.
  • the air is heated to 950 ° C in a muffle furnace, sintered at a constant temperature for 12 h, and then cooled to room temperature to obtain a nickel-cobalt-manganese hydride finished material having an inner core and an outer layer coated on the outer core.
  • B1 the chemical formula is LiNi 1/3 Co 1/3 Mn 1/3 O 2 ;
  • a lithium ion battery C1 is prepared by using the nickel nickel cobalt manganate finished material B1 obtained in the step (2).
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • the stirring paddle was turned on at a speed of -1 ; then, a nickel sulfate, a cobalt, a manganese solution, a sodium hydroxide solution, and an aqueous ammonia solution were simultaneously dropped into a reaction vessel at a dropping rate of 2 L/h in a nitrogen atmosphere to carry out a complex precipitation reaction.
  • the reaction was carried out for 40 h; then, a Pt electrode was inserted into the reaction vessel, and an electrolytic cell was formed with the stainless steel of the reactor.
  • 0.5 g of Ag powder was added into the reaction vessel, and a pulse power of 32 V was applied. The pulse ratio was 1:3, and the pulse current co-deposition continued to react for 5 hours.
  • the prepared slurry was washed 5 times and dried at 110 ° C to obtain nickel hydroxide cobalt manganese powder A2 having a core and an outer layer coated on the outer core of the core, and its chemical formula was Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 ;
  • step (2) Weigh 0.37kg of lithium carbonate, 0.915kg of nickel hydroxide cobalt powder prepared in step (1), using a high-speed mixer according to the molar ratio of lithium source (as lithium element) and nickel cobalt cobalt manganese powder. The ratio of 1:1 is evenly mixed.
  • the air is heated to 750 ° C in a muffle furnace, sintered at a constant temperature for 20 h, and then cooled to room temperature to obtain a nickel-cobalt-manganese hydride finished material having an inner core and an outer layer coated on the outer core.
  • B2 the chemical formula is LiNi 1/3 Co 1/3 Mn 1/3 O 2 ;
  • a lithium ion battery C2 is prepared by using the nickel nickel cobalt manganese oxide finished material B2 obtained in the step (2).
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • the stirring paddle was started at a speed of 3 ms -1 ; then the nickel sulfate, cobalt, manganese solution, sodium hydroxide solution and aqueous ammonia solution were simultaneously dropped into a reaction vessel (dropping acceleration of 1 L/h) in a nitrogen atmosphere for complex precipitation reaction. The reaction was continued for 40 hours; then the Pt electrode was inserted into the reactor, and an electrolytic cell was formed with the stainless steel of the reactor. 0.6 g of Ag powder was added into the reactor, and a pulse power of 32 V was applied. The pulse ratio was 1:5, and the pulse current co-deposition continued.
  • the reaction was washed for 5 hours; the prepared slurry was washed 5 times, and dried at 120 ° C to obtain nickel hydroxide cobalt manganese powder A3 having a core and an outer layer coated on the outer core of the core, the chemical formula of which is Ni 1/3 Co 1 /3 Mn 1/3 (OH) 2 ;
  • step (2) Weigh 0.37kg of lithium carbonate, 0.915kg of nickel hydroxide cobalt powder prepared in step (1), using a high-speed mixer according to the molar ratio of lithium source (as lithium element) and nickel cobalt cobalt manganese powder. The ratio of 1:1 is evenly mixed.
  • the air is heated to 800 ° C in a muffle furnace, sintered at a constant temperature for 20 h, and then cooled to room temperature to obtain a nickel-cobalt-manganese-manganese finished material having an inner core and an outer layer coated on the outer core.
  • B3 the chemical formula is LiNi 1/3 Co 1/3 Mn 1/3 O 2 ;
  • a lithium ion battery C3 is prepared by using the nickel nickel cobalt manganese oxide finished material B3 obtained in the step (2).
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • the stirring paddle was started at a speed of 3 ms -1 ; then the nickel sulfate, cobalt, manganese solution, potassium hydroxide solution and aqueous ammonia solution were simultaneously dropped into a reaction vessel (droplet acceleration of 0.2 L/h) in a nitrogen atmosphere for complex precipitation. The reaction was continued for 40 hours. Then, a Pt electrode was inserted into the reaction vessel, and an electrolytic cell was formed with the stainless steel of the reactor. 0.3 g of Ag powder was added into the reaction vessel, and a 32 V pulse power source was applied thereto. The pulse ratio was 1:1, and the pulse current was co-deposited.
  • the reaction was continued for 15 hours; the prepared slurry was washed 5 times, and dried at 100 ° C to obtain a nickel hydroxide cobalt manganese powder A4 having a core and an outer layer coated outside the core, the chemical formula of which is Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 ;
  • a lithium ion battery C4 was prepared by using the nickel nickel cobalt manganese oxide finished material B4 obtained in the step (2).
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • Nickel hydroxide cobalt manganese A5 and positive electrode material B5 and lithium ion battery C5 were prepared in the same manner as in Example 1, except that the amount of metallic silver powder was 1.0 g with respect to 1566.0 g of the nickel element.
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • Nickel hydroxide cobalt manganese A6 and positive electrode material B6 and lithium ion battery C6 were prepared in the same manner as in Example 1, except that the amount of metallic silver powder was 0.8 g with respect to 1566.0 g of the nickel element.
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • Nickel hydroxide cobalt A7 and cathode material B7 and lithium ion battery C7 were prepared in the same manner as in Example 1, except that the pulse current coprecipitation reaction had a pulse ratio of 6:1 and a reaction time of 10 hours.
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • Nickel hydroxide cobalt manganese A8 and cathode material B8 and lithium ion battery C8 were prepared in the same manner as in Example 1, except that the pulse current coprecipitation reaction had a pulse ratio of 1:20 and a reaction time of 10 hours.
  • This embodiment is for explaining the nickel hydroxide cobalt manganese and cathode materials of the present disclosure, a method for preparing the same, and a lithium ion battery.
  • Nickel hydroxide cobalt A10 and cathode material B10 and lithium ion battery C10 were prepared in the same manner as in Example 1, except that the temperature of the complexation precipitation reaction was 90 ° C for 40 hours.
  • Nickel hydroxide cobalt manganese D1 and cathode material DS1 and lithium ion battery DSS1 were prepared according to the method of Example 1, except that the nickel hydroxide cobalt manganese obtained by the complex precipitation reaction was directly washed and dried without pulse current.
  • Co-deposition reaction Fig. 3 is an SEM image (20000 times) of nickel hydroxide cobalt manganese D1 powder, and Fig. 4 is an SEM image (1000 times) of nickel hydroxide cobalt manganese D1 powder.
  • the nickel-nickel-cobalt-manganese produced by the method of the present disclosure has an inner core and an outer layer coated on the outer core, the inner core being tabular particles, and the core has a porosity of 30-51%.
  • the flaky particles in the core have a D 50 particle diameter of 5 to 8 ⁇ m
  • the outer layer has a porosity of 52 to 60%
  • the particles in the outer layer have a D 50 particle diameter of 0.1 to 5 ⁇ m
  • the specific surface area is from 5.0 to 8.0 m 2 /g.
  • the nickel-cobalt-manganese hydride prepared therefrom also has an inner core and an outer layer coated on the outer core of the core, the inner core being tabular particles, the inner core having a porosity of 8-15%, and the flaky particles in the inner core
  • the D 50 particle size is 7-10 ⁇ m
  • the outer layer has a porosity of 20-40%
  • the particles in the outer layer have a D 50 particle diameter of 0.9-2.5 ⁇ m and a specific surface area of 0.5-1.5 m 2 . /g.
  • the lithium ion battery produced by the lithium nickel cobalt manganate of the present disclosure has an energy density as high as 1.5-2.5 Wh/cm 3 and a magnification of 5 C/0.2 C as high as 90-99%.
  • a porous porous nickel-cobalt-cobalt-manganese particle is formed on the surface of the original dense nickel-nickel-cobalt-manganese particles by means of pulse current deposition, and the nickel hydroxide-manganese internal particles obtained by the method are dense and externally loose. It is porous and has high tap density and good crystallinity.
  • the nickel-nickel-cobalt-manganese-manufactured material obtained by the same has a structure having a high internal density and an outer porous structure, and has excellent crystallinity and conductivity, and the lithium nickel cobalt manganate cathode material obtained above is prepared into a battery.
  • the battery has high energy density and good rate performance.

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Abstract

公开了氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。该氢氧化镍钴锰包括内核和包覆在内核外的外层，所述内核包括片状颗粒，且所述内核中片状颗粒的D50粒径为5-8μm，且所述外层中颗粒的D50粒径为0.1-5μm。

Description

氢氧化镍钴锰和正极材料及其制备方法和锂离子电池 技术领域
本公开涉及锂离子电池领域，具体涉及一种氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
背景技术
现有制备氢氧化镍钴锰和镍钴锰酸锂正极材料以及锂离子电池的方法为：(1)将分别含有镍、钴、锰的硫酸盐混合在一起溶解于去离子水中形成硫酸盐水溶液A；(2)将氢氧化钠粉末溶解于去离子水中形成水溶液B；(3)将质量分数为25-28％的氨水通过去离子水稀释至一定浓度后得到稀释后的氨水溶液C；(4)将步骤(1)中的水溶液A、步骤(2)中的水溶液B和步骤(3)中的氨水溶液C在氮气保护下、搅拌并加热至40-70℃的条件下同时滴加进入反应釜当中，反应一定时间后，洗涤干燥，得到氢氧化镍钴锰前躯体粉末；(5)称取锂源化合物和步骤(4)的氢氧化镍钴锰前躯体材料并混合均匀，在空气或者氧气气氛中加热至600-1100℃，并在600-1100℃下持续煅烧8-20h，然后冷却至室温，得到镍钴锰酸锂成品材料；(6)将步骤(5)得到的镍钴锰酸锂材料做成电池，但是，采用上述制得的氢氧化镍钴锰和镍钴-锰酸锂正极材料制备的锂离子电池的电池倍率性能差且电池的高温存储性能差。
因此，现在急需一种能够显著提高电池倍率性能和高温存储性能的氢氧化镍钴锰和镍钴锰酸锂正极材料。
公开内容
本公开的目的是为了克服现有技术中锂离子电池的倍率性能较差的问题，提供一种氢氧化镍钴锰和正极材料及其制备方法和锂离子电池，由本公开的正极材料制得的锂离子电池具有较高的电池能量密度和较好的电池倍率性能。
为了实现上述目的，本公开一方面提供了一种氢氧化镍钴锰，该氢氧化镍钴锰包括内核和包覆在内核外的外层，所述内核包括片状颗粒，且所述内核中片状颗粒的D 50粒径为5-8μm，且所述外层中颗粒的D 50粒径为0.1-5μm。
本公开第二方面提供了一种制备氢氧化镍钴锰的方法，该方法包括：在惰性气氛下，将含有水溶性镍、钴、锰离子的水溶液A与含有强碱的水溶液B以及氨水混合进行络合沉淀反应，然后加入金属银粉进行脉冲电流共沉淀反应。
本公开第三方面提供了一种镍钴锰酸锂正极材料，该镍钴锰酸锂由将锂源与上述氢氧 化镍钴锰或者上述方法制得的氢氧化镍钴锰进行煅烧制得。
本公开第四方面提供了一种镍钴锰酸锂正极材料，所述镍钴锰酸锂包括内核和包覆在所述内核外的外层，所述内核包括片状颗粒，且所述内核中片状颗粒的D 50粒径为5-10μm，且所述外层中颗粒的D 50粒径为0.1-4.5μm。
本公开第五方面提供了一种制备正极材料的方法，该方法包括：将锂源与上述氢氧化镍钴锰或者上述方法制得的氢氧化镍钴锰进行煅烧。
本公开第六方面提供了一种锂离子电池，该锂离子电池包括上述正极材料或者上述方法制得的正极材料。
现有方法制得的氢氧化镍钴锰一次颗粒之间致密分布，使得后续制备出的镍钴锰酸锂成品材料虽然能量密度较高，但是倍率性能很差。而本公开中以Ag粉作为导电诱导剂，通过脉冲电流共沉淀方式在现有致密的氢氧化镍钴锰颗粒表面形成疏松多孔的氢氧化镍钴锰颗粒层，采用此方法制备出的氢氧化镍钴锰颗粒内部致密，外部疏松多孔，然后将锂源和氢氧化镍钴锰进行煅烧，再冷却至室温，得到内部致密、外部疏松多孔的镍钴锰酸锂成品材料。此种镍钴锰酸锂成品材料比表面积介于0.1-10m 2/g，内部致密二次颗粒(内核片状颗粒)D 50粒径介于5-10μm之间，外部疏松颗粒(外层颗粒)D 50粒径为0.1-4.5μm之间。采用上述镍钴锰酸锂成品材料作为正极材料制得的锂离子电池的同时具有较优异的电池能量密度和倍率性能。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
附图是用来提供对本公开的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本公开，但并不构成对本公开的限制。在附图中：
图1是本公开实施例1制得的氢氧化镍钴锰的SEM图(30000倍)；
图2是本公开实施例1制得的氢氧化镍钴锰的SEM图(1000倍)；
图3是本公开对比例1制得的氢氧化镍钴锰的SEM图(20000倍)；
图4是本公开对比例1制得的氢氧化镍钴锰的SEM图(1000倍)。
公开详细描述
下面详细描述本公开的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本公开，而不能理解为对本公开的限制。
在本公开的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本公开和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本公开的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本公开的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。
在本公开中，除非另有明确的规定和限定，第一特征在第二特征“上”或“下”可以是第一和第二特征直接接触，或第一和第二特征通过中间媒介间接接触。而且，第一特征在第二特征“之上”、“上方”和“上面”可是第一特征在第二特征正上方或斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”可以是第一特征在第二特征正下方或斜下方，或仅仅表示第一特征水平高度小于第二特征。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本公开一方面提供了一种氢氧化镍钴锰，该氢氧化镍钴锰包括内核和包覆在内核外的外层，所述内核包括片状颗粒，且所述内核中片状颗粒的D 50粒径为5-8μm，且所述外层中颗粒的D 50粒径为0.1-5μm。需要说明的是，该氢氧化镍钴锰的包覆结构并非外层完全包覆内核结构，而是外层的小颗粒附着在内核片状大颗粒表面，外层小颗粒间疏松形成空隙，形成了疏松多孔的外层。
根据本公开所述的氢氧化镍钴锰，优选地，所述内核的孔隙率为30-51％，所述外层的孔隙率为52-60％，即本公开的氢氧化镍钴锰颗粒内部致密，外部疏松多孔，然后将锂源和氢氧化镍钴锰进行煅烧，再冷却至室温，得到内部致密、外部疏松多孔的镍钴锰酸锂成品材料。
本公开中，内核的孔隙率是指以内核的总体积为基准的孔隙率，外层的孔隙率是指以外层的总体积为基准的孔隙率。
根据本公开所述的氢氧化镍钴锰，优选地，所述氢氧化镍钴锰的化学式为Ni xCo yMn 1-x-y(OH) 2，其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1，从而能够显著提高由镍钴锰酸锂正极材料制得的锂离子电池的倍率性能。
根据本公开所述的氢氧化镍钴锰，优选地，所述内核中片状颗粒的D 50粒径为5-7.5μm，所述外层中颗粒的D 50粒径为0.1-4.5μm，从而能够显著提高由镍钴锰酸锂正极材料制得的锂离子电池的倍率性能。
根据本公开所述的氢氧化镍钴锰，优选地，该氢氧化镍钴锰含有Ag，优选地，Ag的含量低于20ppm(优选低于10ppm)，从而能够避免Ag含量过高对后续锂离子电池性能的影响。需要说明的是，氢氧化镍钴锰中Ag的存在形式并不受特别限制，可以是单质形式存在，也可以是以化合物形式存在。
根据本公开所述的氢氧化镍钴锰，优选地，该氢氧化镍钴锰的比表面积为0.1-10m 2/g，更优选为5-8m 2/g，从而能够最终制得的锂离子电池性能的倍率性能较优异。
本公开第二方面提供了一种制备氢氧化镍钴锰的方法，该方法包括：在惰性气氛下，将含有水溶性镍、钴、锰离子的水溶液A与含有强碱的水溶液B以及氨水混合进行络合沉淀反应，然后加入金属银粉进行脉冲电流共沉淀反应。
本公开中，脉冲电流共沉淀反应是指在脉冲电流条件下进行的共沉淀反应。
根据本公开所述的方法，制备水溶性镍、钴、锰离子的水溶液A的方法可以包括：将水溶性镍盐、水溶性钴盐和水溶性锰盐溶于水。本公开中，水溶性镍盐可以为本领域各种水溶性镍盐，例如可以为硫酸镍、硝酸镍和氯化镍中的至少一种，优选为硫酸镍。水溶性钴盐可以为本领域各种水溶性钴盐，例如可以为硫酸钴、硝酸钴和氯化钴中的至少一种，优选为硫酸钴。水溶性锰盐可以为本领域各种水溶性锰盐，例如可以为硫酸锰、硝酸锰和氯化锰中的至少一种，优选为硫酸锰。
根据本公开所述的方法，优选地，水溶液A中元素镍、钴、锰的摩尔比为：Ni:Co:Mn＝x:y:1-x-y，其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1，从而使得制得的氢氧化镍钴锰化学式为Ni xCo yMn 1-x-y(OH) 2，其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1，进而显著提高由镍钴锰酸锂正极材料制得的锂离子电池的倍率性能。
根据本公开所述的方法，水溶液A中水溶性镍、钴、锰离子的浓度为0.1-3mol/L，优选为0.1-2mol/L。在此，水溶性镍、钴、锰离子的浓度是指该盐中镍、钴、锰三种元素的浓度总和。
根据本公开所述的方法，所述氨水的浓度可以为0.1-1.6mol/L，优选为0.1-1.2mol/L。本公开所需浓度的氨水可以由浓度为25-28％的氨水稀释得到。
根据本公开所述的方法，所述强碱可以本领域各种强碱，例如可以为氢氧化钠和/或氢氧化钾。本公开中，水溶液B中强碱的浓度可以为0.1-16mol/L，优选为0.1-10mol/L。
本公开的强碱为络合沉淀反应的沉淀剂，氨水为络合沉淀反应的络合剂。因此，本公开中强碱和氨水的用量只要能够使得水溶液A中的镍离子、钴离子和锰离子完全络合沉淀 形成氢氧化镍钴锰即可，即强碱和氨水的用量只要相对于水溶性镍钴锰盐过量即可。
根据本公开所述的方法，该方法还优选包括：用CoSO 4.7H 2O、NiSO 4.6H 2O和MnSO 4.H 2O配制硫酸镍、钴、锰溶液(水溶液A)。其中，为了使得其中的钴、镍和锰离子均形成氢氧化镍钴锰，相对于40L 0.1-2mol/L浓度的硫酸镍、钴、锰溶液，0.1-1.2molL -1浓度的氨水的用量为0.1-40L，0.1-10molL -1浓度的NaOH水溶液(水溶液B)的用量为0.1-40L。
根据本公开所述的方法，为了更均匀地制得氢氧化镍钴锰，该方法还优选包括：在搅拌条件下，将水溶液A、氨水和水溶液B同时滴加到反应器中。其中，滴加速度可以为0.2-2L/h，搅拌速度可以为4-10ms -1。
根据本公开所述的方法，所述络合沉淀反应的条件可以为本领域各种络合沉淀反应条件，例如可以包括：温度为40-70℃，优选为40-60℃；时间为0.1-80h，优选为0.1-60h(更优选为0.1-20h)，从而能够控制氢氧化镍钴锰的整体粒径分布。
根据本公开所述的方法，进行脉冲电流共沉淀反应的方式包括：在反应器中插入金属电极，其与金属反应器之间形成电解池，然后在该反应器中加入金属银粉，然后通入脉冲电源。其中，金属电极可以为Pt电极、Au电极和Ag电极中的至少一种，优选为Pt电极。反应器可以为本领域各种常规的反应釜。
根据本公开所述的方法，优选地，所述脉冲电流共沉淀反应的条件包括：脉冲比为1:1-10，更优选为1:1-5，反应时间为0.1-40h，更优选为0.1-30h，从而能够进一步控制制得的氢氧化镍钴锰内核和外层的孔隙率以及粒径分布等，进而显著提高由镍钴锰酸锂正极材料制得的锂离子电池的倍率性能。本公开中可以采用0-32V的脉冲电源提供上述优选的脉冲比。
根据本公开所述的方法，相对于1566g镍元素，金属银粉的用量优选为0.36-1g，更优选为0.36-0.6g，能够进一步控制制得的氢氧化镍钴锰内核和外层的孔隙率以及粒径分布等，进而显著提高由镍钴锰酸锂正极材料制得的锂离子电池的倍率性能。
根据本公开所述的方法，该方法还可以包括：将脉冲电流共沉淀反应得到的浆料洗涤、烘干，即可得到氢氧化镍钴锰。其中，洗涤的次数可以为3-7次，烘干的温度可以为100-120℃。
本公开中，惰性气氛可以由氮气和/或惰性气体提供。其中，惰性气体可以为氦(He)、氖(Ne)、氩(Ar)、氪(Kr)、氙(Xe)。
本公开第三方面提供了一种镍钴锰酸锂正极材料，该镍钴锰酸锂由将锂源与上述氢氧化镍钴锰或者上述方法制得的氢氧化镍钴锰进行煅烧制得。
本公开第四方面提供了一种镍钴锰酸锂正极材料，所述镍钴锰酸锂正极材料中镍钴锰酸锂包括内核和包覆在内核外的外层，所述内核包括片状颗粒，且所述内核中片状颗粒的D 50粒径为5-10μm，且所述外层中颗粒的D 50粒径为0.1-4.5μm，从而提高由镍钴锰酸锂正 极材料制得的锂离子电池的倍率性能。
根据本公开所述的镍钴锰酸锂正极材料，优选地，所述内核的孔隙率为8-15％，所述外层的孔隙率为20-40％，即本公开的镍钴锰酸锂内部致密、外部疏松多孔。
根据本公开所述的镍钴锰酸锂正极材料，优选地，所述内核中片状颗粒的D 50粒径为7-10μm，所述外层中颗粒的D 50粒径为0.9-2.5μm，从而显著提高由镍钴锰酸锂正极材料制得的锂离子电池的倍率性能。
根据本公开所述的镍钴锰酸锂正极材料，优选地，所述镍钴锰酸锂的化学式为LiNi xCo yMn 1-x-yO 2，其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1，从而能够显著提高由镍钴锰酸锂正极材料制得的锂离子电池的倍率性能。
根据本公开所述的镍钴锰酸锂正极材料，优选地，该正极材料中Ag的含量低于20ppm(优选低于10ppm)，从而能够避免Ag含量过高对后续锂离子电池性能的影响。
根据本公开所述的镍钴锰酸锂正极材料，该正极材料的比表面积优选为0.1-10m 2/g，更优选为0.5-1.5m 2/g，从而能够最终制得的锂离子电池性能的倍率性能较优异。
本公开第五方面提供了一种制备正极材料的方法，该方法包括：将锂源与上述氢氧化镍钴锰或者上述方法制得的氢氧化镍钴锰进行煅烧。
根据本公开所述的方法，该方法还可以包括：将锂源和制得的氢氧化镍钴锰混合均匀后再进行煅烧。
根据本公开所述的方法，所述锂源可以为本领域各种可以用于锂离子电池的含锂化合物，例如可以为碳酸锂和/或氢氧化锂。
根据本公开所述的方法，优选地，所述锂源中的锂元素与氢氧化镍钴锰的摩尔比为1.0-1.1：1，更优选为1.0-1.08：1，从而能够使得制得的镍钴锰酸锂的化学式为LiNi xCo yMn 1-x-yO 2，其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1。
根据本公开所述的方法，煅烧的条件可以为本领域各种煅烧条件，例如可以包括：温度为600-1100℃，优选为750-950℃，时间为8-20h，优选为10-15h。本公开中，煅烧的氧化环境可以为空气和/或氧气提供，例如可以通过向马弗炉中通入空气和/或氧气实现。
本公开第六方面提供了一种锂离子电池，该锂离子电池包括上述正极材料或者上述方法制得的正极材料。
本公开的锂离子电池的制备方法可以为本领域各种常规的锂离子电池制备方法，例如可以包括：i.在负极壳中塞上两层发泡镍，把负极壳、正极壳放烘箱中烘30-40分钟；ii.将正极片(包括制得的正极材料)以及从烘箱中取出的正极壳、负极壳转移到手套箱中，从负极开始装配；iii.将负极壳放在滤纸上，取出锂片，将锂片放入负极壳中的泡沫镍上，用钳子将锂片钳平；iv.将正极壳放在滤纸上，放入压好的的正极片，将正极片放置在正极壳 的正中心位置，放入时轻拿轻放，勿使正极片掉料，注入适量电解液；v.加入一层Φ16隔膜纸，加隔膜纸时使隔膜纸一端先浸润电解液，然后将另一端慢慢放下，使隔膜纸完全浸润电解液，中间不能有气泡；vi.注入适量电解液，盖上负极壳，放平后稍加压力，将负极壳压下，套于正极壳内；vii.取出封口，封口尽量保持每个的压力与静压时间一致，封口后，擦净电池表面的电解液。
本公开的锂离子电池的能量密度高达1.5-2.5Wh/cm 3、倍率5C/0.2C高达90-99％。
以下将通过实施例对本公开进行详细描述。
扫描电子显微镜(SEM)为日本日立公司(Hitachi)生产的S4800型扫描电子显微镜，测试电压为5KV。
锂离子电池的制备方法：i.在负极壳中塞上两层发泡镍，把负极壳、正极壳放烘箱中烘30分钟；ii.将正极片(包括制得的正极材料)以及从烘箱中取出的正极壳、负极壳转移到手套箱中，从负极开始装配；iii.将负极壳放在滤纸上，取出锂片，将锂片放入负极壳中的泡沫镍上，用钳子将锂片钳平；iv.将正极壳放在滤纸上，放入压好的的正极片，将正极片放置在正极壳的正中心位置，放入时轻拿轻放，勿使正极片掉料，注入适量电解液；v.加入一层Φ16隔膜纸，加隔膜纸时使隔膜纸一端先浸润电解液，然后将另一端慢慢放下，使隔膜纸完全浸润电解液，中间不能有气泡；vi.注入适量电解液，盖上负极壳，放平后稍加压力，将负极壳压下，套于正极壳内；vii.取出封口，封口尽量保持每个的压力与静压时间一致，封口后，擦净电池表面的电解液。
下面通过实施例对本公开做进一步说明，但并不因此而限制本公开的内容。
实施例1
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
(1)将7.495kg CoSO 4.7H 2O、7.009kg NiSO 4.6H 2O、4.507kg MnSO 4.H 2O溶解于去离子水中配成40L 2.0mol L -1的硫酸镍、钴、锰溶液；将6.4kg NaOH溶解于去离子水中配成40L 4.0molL -1的氢氧化钠溶液；将1.632kg质量分数为25％的氨水溶解于去离子水中配制成40L 0.6molL -1的氨水溶液，以5ms -1的速度开启搅拌桨；随后在氮气气氛中将硫酸镍、钴、锰溶液、氢氧化钠溶液以及氨水溶液同时滴入(滴加速度为0.2L/h)反应釜中进行络合沉淀反应，持续反应40h；然后在反应釜内插入Pt电极，与反应釜不锈钢形成电解池，在反应釜内加入0.3g Ag粉，通入32V脉冲电源，脉冲比为1：1，脉冲电流共沉积持续反应30h；将制备出的浆料洗涤5次，在100℃下烘干，得到具有内核和包覆在内核外的外层的氢氧化 镍钴锰粉末A1，其化学式为Ni 1/3Co 1/3Mn 1/3(OH) 2，图1是氢氧化镍钴锰粉末A1的SEM图(30000倍)，图2是氢氧化镍钴锰粉末A1的SEM图(1000倍)；
(2)称取0.37kg碳酸锂、0.915kg步骤(1)制得的氢氧化镍钴锰粉末，采用高速混料机按照锂源(以锂元素计)和氢氧化镍钴锰粉末摩尔比为1：1的比例混合均匀，在马弗炉中通入空气加热至950℃，恒温烧结12h，然后冷却至室温，得到具有内核和包覆在内核外的外层的镍钴锰酸锂成品材料B1，其化学式为LiNi 1/3Co 1/3Mn 1/3O 2；
(3)采用步骤(2)制得的镍钴锰酸锂成品材料B1制备锂离子电池C1。
实施例2
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
(1)将7.495kg CoSO 4.7H 2O、7.009kg NiSO 4.6H 2O、4.507kg MnSO 4.H 2O溶解于去离子水中配成40L 2.0mol L -1的硫酸镍、钴、锰溶液；将16kg NaOH溶解于去离子水中配成40L 10molL -1的氢氧化钠溶液；将3.264kg质量分数为25％的氨水溶解于去离子水中配制成40L 1.2molL -1的氨水溶液，以4ms -1的速度开启搅拌桨；随后在氮气气氛中将硫酸镍、钴、锰溶液、氢氧化钠溶液以及氨水溶液同时滴入(滴加速度为2L/h)反应釜中进行络合沉淀反应，持续反应40h；然后在反应釜内插入Pt电极，与反应釜不锈钢形成电解池，在反应釜内加入0.5g Ag粉，通入32V脉冲电源，脉冲比为1：3，脉冲电流共沉积持续反应5h；将制备出的浆料洗涤5次，在110℃下烘干，得到具有内核和包覆在内核外的外层的氢氧化镍钴锰粉末A2，其化学式为Ni 1/3Co 1/3Mn 1/3(OH) 2；
(2)称取0.37kg碳酸锂、0.915kg步骤(1)制得的氢氧化镍钴锰粉末，采用高速混料机按照锂源(以锂元素计)和氢氧化镍钴锰粉末摩尔比为1：1的比例混合均匀，在马弗炉中通入空气加热至750℃，恒温烧结20h，然后冷却至室温，得到具有内核和包覆在内核外的外层的镍钴锰酸锂成品材料B2，其化学式为LiNi 1/3Co 1/3Mn 1/3O 2；
(3)采用步骤(2)制得的镍钴锰酸锂成品材料B2制备锂离子电池C2。
实施例3
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
(1)将7.495kg CoSO 4.7H 2O、7.009kg NiSO 4.6H 2O、4.507kg MnSO 4.H 2O溶解于去离子水中配成40L 2.0mol L -1的硫酸镍、钴、锰溶液；将6.4kg NaOH溶解于去离子水中配成40L 4.0molL -1的氢氧化钠溶液；将1.632kg质量分数为25％的氨水溶解于去离子水中配制成40L 0.6molL -1的氨水溶液，以3ms -1的速度开启搅拌桨；随后在氮气气氛中将硫酸镍、钴、锰溶液、氢氧化钠溶液以及氨水溶液同时滴入(滴加速度为1L/h)反应釜中进行络合沉淀 反应，持续反应40h；然后在反应釜内插入Pt电极，与反应釜不锈钢形成电解池，在反应釜内加入0.6g Ag粉，通入32V脉冲电源，脉冲比为1:5，脉冲电流共沉积持续反应1h；将制备出的浆料洗涤5次，在120℃下烘干，得到具有内核和包覆在内核外的外层的氢氧化镍钴锰粉末A3，其化学式为Ni 1/3Co 1/3Mn 1/3(OH) 2；
(2)称取0.37kg碳酸锂、0.915kg步骤(1)制得的氢氧化镍钴锰粉末，采用高速混料机按照锂源(以锂元素计)和氢氧化镍钴锰粉末摩尔比为1：1的比例混合均匀，在马弗炉中通入空气加热至800℃，恒温烧结20h，然后冷却至室温，得到具有内核和包覆在内核外的外层的镍钴锰酸锂成品材料B3，其化学式为LiNi 1/3Co 1/3Mn 1/3O 2；
(3)采用步骤(2)制得的镍钴锰酸锂成品材料B3制备锂离子电池C3。
实施例4
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
(1)将7.495kg CoSO 4.7H 2O、7.009kg NiSO 4.6H 2O、4.507kg MnSO 4.H 2O溶解于去离子水中配成40L 2.0mol L -1的硫酸镍、钴、锰溶液；将8.98kg KOH溶解于去离子水中配成40L 4.0molL -1的氢氧化钾溶液；将1.632kg质量分数为25％的氨水溶解于去离子水中配制成40L 0.6molL -1的氨水溶液，以3ms -1的速度开启搅拌桨；随后在氮气气氛中将硫酸镍、钴、锰溶液、氢氧化钾溶液以及氨水溶液同时滴入(滴加速度为0.2L/h)反应釜中进行络合沉淀反应，持续反应40h；然后在反应釜内插入Pt电极，与反应釜不锈钢形成电解池，在反应釜内加入0.3g Ag粉，通入32V脉冲电源，脉冲比为1：1，脉冲电流共沉积持续反应15h；将制备出的浆料洗涤5次，在100℃下烘干，得到具有内核和包覆在内核外的外层的氢氧化镍钴锰粉末A4，其化学式为Ni 1/3Co 1/3Mn 1/3(OH) 2；
(2)称取0.026kg氢氧化锂、0.915kg步骤(1)制得的氢氧化镍钴锰粉末，采用高速混料机按照锂源(以锂元素计)和氢氧化镍钴锰粉末摩尔比为1.08：1的比例混合均匀，在马弗炉中通入空气加热至950℃，恒温烧结12h，然后冷却至室温，得到具有内核和包覆在内核外的外层的镍钴锰酸锂成品材料B4，其化学式为LiNi 1/3Co 1/3Mn 1/3O 2；
(3)采用步骤(2)制得的镍钴锰酸锂成品材料B4制备锂离子电池C4。
实施例5
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
按照实施例1的方法制备氢氧化镍钴锰A5和正极材料B5和锂离子电池C5，不同的是，相对于1566.0g镍元素，金属银粉的用量为1.0g。
实施例6
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
按照实施例1的方法制备氢氧化镍钴锰A6和正极材料B6和锂离子电池C6，不同的是，相对于1566.0g镍元素，金属银粉的用量为0.8g。
实施例7
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
按照实施例1的方法制备氢氧化镍钴锰A7和正极材料B7和锂离子电池C7，不同的是，所述脉冲电流共沉淀反应的脉冲比为6：1，反应时间为10h。
实施例8
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
按照实施例1的方法制备氢氧化镍钴锰A8和正极材料B8和锂离子电池C8，不同的是，所述脉冲电流共沉淀反应的脉冲比为1：20，反应时间为10h。
实施例9
本实施例用于说明本公开的氢氧化镍钴锰和正极材料及其制备方法和锂离子电池。
按照实施例1的方法制备氢氧化镍钴锰A10和正极材料B10和锂离子电池C10，不同的是，络合沉淀反应的温度为90℃，时间为40h。
对比例1
按照实施例1的方法制备氢氧化镍钴锰D1和正极材料DS1和锂离子电池DSS1，不同的是，将络合沉淀反应得到的氢氧化镍钴锰直接进行洗涤烘干，而不进行脉冲电流共沉积反应，图3是氢氧化镍钴锰D1粉末SEM图(20000倍)，图4是氢氧化镍钴锰D1粉末SEM图(1000倍)。
测试例
1、采用扫描电子显微镜观察氢氧化镍钴锰粉末A1-A9和D1以及镍钴锰酸锂正极材料B1-B9和DS1，得到SEM图。然后通过SEM软件得到氢氧化镍钴锰粉末内核中片状颗粒的粒径分布以及外层中颗粒的粒径分布(测试方法：用离子研磨仪对粉末进行离子研磨，得到粉末截面。再使用扫描电镜对粉末截面进行观察，得到截面SEM图并对截面SEM图进行测量，统计测量内核片状颗粒区域的直径平均值即为内核片状颗粒的D 50，统计测量外层颗粒区域的厚度平均值即为外层颗粒D 50)，具体结果参见表1。
2、测定氢氧化镍钴锰粉末A1-A9和D1以及镍钴锰酸锂正极材料B1-B9和DS1内核和外层的孔隙率(测试方法：用离子研磨仪对粉末进行离子研磨，得到粉末截面。再使用扫描电镜对粉末截面进行观察，得到截面SEM图并对截面SEM图进行测量，统计测量内核片状颗粒区域的孔隙面积/内核总面积比值即为内核孔隙率，统计测量外层颗粒区域孔隙面积/外层总面积比值即为外层孔隙率)，测定结果见表1。
3、采用电感耦合等离子体光谱仪测定氢氧化镍钴锰粉末A1-A9和D1以及镍钴锰酸锂正极材料B1-B9和DS1的Ag含量，测定结果见表1。
4、采用比表面测试仪测定氢氧化镍钴锰粉末A1-A9和D1以及镍钴锰酸锂正极材料B1-B9和DS1的比表面积，测定结果见表1。
5、按照下述公式1计算锂离子电池C1-C9和DSS1的电池能量密度，按照下述公式2计算锂离子电池C1-C9和DSS1的电池倍率5C/0.2C，测定结果见表2。
公式1为：电池能量密度＝UIt/g*粉体压实密度(其中U为材料充电平均电压，I为充放电电流、t为充放电时间、粉体压实密度的单位为g/cm 3)，电池能量密度单位为Wh/cm 3。
公式2为：电池倍率5C/0.2C＝5*材料额定容量/0.2*材料额定容量(其中，材料额定容量是指材料本身具有的理论容量)。
表1
Figure PCTCN2018107934-appb-000001
Figure PCTCN2018107934-appb-000002
表2
Figure PCTCN2018107934-appb-000003
通过表1的结果可以看出，采用本公开方法制得的氢氧化镍钴锰具有内核和包覆在内核外的外层，内核为片状颗粒，所述内核的孔隙率为30-51％，且所述内核中片状颗粒的D 50粒径为5-8μm，所述外层的孔隙率为52-60％，且所述外层中颗粒的D 50粒径为0.1-5μm，且比表面积为5.0-8.0m 2/g。而由其制得的镍钴锰酸锂也具有内核和包覆在内核外的外层，内核为片状颗粒，所述内核的孔隙率为8-15％，且所述内核中片状颗粒的D 50粒径为7-10μm，所述外层的孔隙率为20-40％，且所述外层中颗粒的D 50粒径为0.9-2.5μm，且比表面积为0.5-1.5m 2/g。因此，由本公开的镍钴锰酸锂制得的锂离子电池的能量密度高达1.5-2.5Wh/cm 3、倍率5C/0.2C高达90-99％。具体地，通过脉冲电流沉积的方式在原有的致密氢氧化镍钴锰颗粒表面形成一层疏松多孔的氢氧化镍钴锰颗粒，采用该方法制得的氢氧化镍钴锰内部颗粒致密、外部疏松多孔，且振实密度高、结晶度好。进而由其制得的镍钴 锰酸锂成品材料也具有内部致密度高且外部疏松多孔的结构，具有优异的结晶度和导电性，将上述得的镍钴锰酸锂正极材料制备成电池，其电池能量密度高、倍率性能也较好。
以上详细描述了本公开的优选实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本公开的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本公开的限制，本领域的普通技术人员在本公开的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (40)

  1. 一种氢氧化镍钴锰，其中，所述氢氧化镍钴锰包括内核和包覆在所述内核外的外层，所述内核包括片状颗粒，且所述内核中片状颗粒的D 50粒径为5-8μm，且所述外层中颗粒的D 50粒径为0.1-5μm。
  2. 根据权利要求1所述的氢氧化镍钴锰，其中，所述氢氧化镍钴锰的化学式为Ni xCo yMn 1-x-y(OH) 2，其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1。
  3. 根据权利要求1或2所述的氢氧化镍钴锰，其中，所述内核的孔隙率为30-51％，所述外层的孔隙率为52-60％。
  4. 根据权利要求1-3中任一项所述的氢氧化镍钴锰，其中，所述内核中片状颗粒的D 50粒径为5-7.5μm，所述外层中颗粒的D 50粒径为0.1-4.5μm。
  5. 根据权利要求1-4中任一项所述的氢氧化镍钴锰，其中，所述氢氧化镍钴锰含有Ag。
  6. 根据权利要求1-5中任一项所述的氢氧化镍钴锰，其中，所述Ag的含量低于20ppm。
  7. 根据权利要求1-6中任一项所述的氢氧化镍钴锰，其中，所述氢氧化镍钴锰的比表面积为0.1-10m 2/g。
  8. 根据权利要求1-7中任一项所述的氢氧化镍钴锰，其中，所述氢氧化镍钴锰的比表面积为5-8m 2/g。
  9. 一种制备氢氧化镍钴锰的方法，其中，所述方法包括：在惰性气氛下，将含有水溶性镍、钴、锰离子的水溶液A与含有强碱的水溶液B以及氨水混合进行沉淀反应，然后加入金属银粉进行脉冲电流共沉淀反应。
  10. 根据权利要求9所述的方法，其中，所述脉冲电流共沉淀反应的条件包括：脉冲比为1：1-10，反应时间为0.1-40h。
  11. 根据权利要求9或10所述的方法，其中，所述脉冲电流共沉淀反应的条件包括：所述脉冲比为为1：1-5，所述反应时间为0.1-30h。
  12. 根据权利要求9-11所述的方法，其中，所述络合沉淀反应的条件包括：温度为40-70℃，时间为0.1-80h。
  13. 根据权利要求9-12所述的方法，其中，所述络合沉淀反应的条件包括：所述温度为40-60℃，所述时间为0.1-60h。
  14. 根据权利要求9-13中任一项所述的方法，其中，制备所述含有水溶性镍、钴、锰离子的水溶液A的方法包括：将水溶性镍盐、水溶性钴盐和水溶性锰盐溶于水。
  15. 根据权利要求9-14中任一项所述的方法，其中，所述水溶性镍盐为硫酸镍、硝酸镍和氯化镍中的至少一种。
  16. 根据权利要求9-15中任一项所述的方法，其中，所述水溶性钴盐为硫酸钴、硝酸钴和氯化钴中的至少一种。
  17. 根据权利要求9-16中任一项所述的方法，其中，所述水溶性锰盐为硫酸锰、硝酸锰和氯化锰中的至少一种。
  18. 根据权利要求9-17中任一项所述的方法，其中，所述水溶液A中元素镍、钴、锰的摩尔比为：Ni:Co:Mn＝x:y:1-x-y；其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1，所述水溶液A中水溶性镍、钴、锰离子的总浓度为0.1-3mol/L。
  19. 根据权利要求9-18中任一项所述的方法，其中，所述水溶液A中水溶性镍、钴、锰离子的总浓度为0.1-2mol/L。
  20. 根据权利要求9-19中任一项所述的方法，其中，所述氨水的浓度为0.1-1.6mol/L。
  21. 根据权利要求9-20中任一项所述的方法，其中，所述氨水的浓度为0.1-1.2mol/L。
  22. 根据权利要求9-21中任一项所述的方法，其中，所述强碱为氢氧化钠和/或氢氧化钾。
  23. 根据权利要求9-22中任一项所述的方法，其中，所述水溶液B中强碱的浓度为0.1-16mol/L。
  24. 根据权利要求9-23中任一项所述的方法，其中，所述水溶液B中强碱的浓度为0.1-10mol/L。
  25. 根据权利要求9-24中任一项所述的方法，其中，相对于1566g所述镍元素，所述金属银粉的用量为0.36-1g。
  26. 根据权利要求9-25中任一项所述的方法，其中，相对于1566g所述镍元素，所述金属银粉的用量为0.36-0.6g。
  27. 一种镍钴锰酸锂正极材料，其中，所述镍钴锰酸锂是将锂源与权利要求1-8中任一项所述的氢氧化镍钴锰或者权利要求9-26中任一项所述的方法制得的氢氧化镍钴锰进行煅烧制得。
  28. 一种镍钴锰酸锂正极材料，其中，所述镍钴锰酸锂正极材料中镍钴锰酸锂包括内核和包覆在所述内核外的外层，所述内核包括片状颗粒，且所述内核中片状颗粒的D 50粒径为5-10μm，且所述外层中颗粒的D 50粒径为0.1-4.5μm。
  29. 根据权利要求28所述的镍钴锰酸锂正极材料，其中，所述内核的孔隙率为8-15％，所述外层的孔隙率为20-40％。
  30. 根据权利要求28或29所述的镍钴锰酸锂正极材料，其中，所述内核中片状颗粒的D 50粒径为7-10μm，所述外层中颗粒的D 50粒径为0.9-2.5μm。
  31. 根据权利要求28-30中任一项所述的镍钴锰酸锂正极材料，其中，所述正极材料中Ag的含量低于20ppm。
  32. 根据权利要求28-31中任一项所述的镍钴锰酸锂正极材料，其中，所述正极材料的比表面积为0.1-10m 2/g。
  33. 根据权利要求28-32中任一项所述的镍钴锰酸锂正极材料，其中，所述正极材料的比表面积为0.5-1.5m 2/g。
  34. 根据权利要求28-33中任一项所述的镍钴锰酸锂正极材料，其中，所述镍钴锰酸锂的化学式为LiNi xCo yMn 1-x-yO 2，其中，0＜x＜1，0＜y＜1，0＜1-x-y＜1。
  35. 一种制备正极材料的方法，其中，所述方法包括：将锂源与权利要求1-8中任一项所述的氢氧化镍钴锰或者权利要求9-26中任一项所述的方法制得的氢氧化镍钴锰进行煅烧。
  36. 根据权利要求35所述的方法，其中，所述锂源中的锂元素与所述氢氧化镍钴锰的摩尔比为1.0-1.1：1。
  37. 根据权利要求35或36所述的方法，其中，所述锂源中的锂元素与所述氢氧化镍钴锰的摩尔比为1.0-1.08：1。
  38. 根据权利要求35-37中任一项所述的方法，其中，所述煅烧的条件包括：温度为600-1100℃，时间为8-20h。
  39. 根据权利要求35-38中任一项所述的方法，其中，所述煅烧的条件包括：所述温度为750-950℃，所述时间为10-15h。
  40. 一种锂离子电池，其中，所述锂离子电池包括权利要求27-34中任一项所述的正极材料或者权利要求35-39中任一项所述方法制得的正极材料。
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