WO2021031201A1 - 一种微通道反应器及制备锂电池正极材料和负极材料的前驱体微纳米粒子的方法 - Google Patents

一种微通道反应器及制备锂电池正极材料和负极材料的前驱体微纳米粒子的方法 Download PDF

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WO2021031201A1
WO2021031201A1 PCT/CN2019/102045 CN2019102045W WO2021031201A1 WO 2021031201 A1 WO2021031201 A1 WO 2021031201A1 CN 2019102045 W CN2019102045 W CN 2019102045W WO 2021031201 A1 WO2021031201 A1 WO 2021031201A1
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salt
lithium
nano
microchannel reactor
cathode material
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PCT/CN2019/102045
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English (en)
French (fr)
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于志远
佘玥欣
刘于航
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于志远
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Priority to PCT/CN2019/102045 priority Critical patent/WO2021031201A1/zh
Priority to CN201980009425.XA priority patent/CN112703051B/zh
Publication of WO2021031201A1 publication Critical patent/WO2021031201A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus

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  • the invention relates to the technical field of chemistry and chemical engineering, and in particular to a microchannel reactor and a method for preparing the precursor micro-nano particles of a positive electrode material and a negative electrode material of a lithium battery.
  • Lithium batteries are mainly composed of positive electrode material, negative electrode material, separator, electrolyte and battery casing.
  • the positive electrode material and the negative electrode material are the decisive factors of the electrochemical performance of lithium batteries, which directly determine the energy density and safety of the battery, and then affect the overall performance of the battery.
  • Lithium battery cathode materials mainly include ternary materials (NCM, NCA), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), and lithium manganese oxide (LMO).
  • NCM ternary materials
  • LFP lithium iron phosphate
  • LCO lithium cobalt oxide
  • LMO lithium manganese oxide
  • the precursor of the ternary cathode material directly determines the core physical and chemical properties of the ternary cathode material.
  • the ternary precursor is a key material for the production of ternary cathodes.
  • the ternary cathode is made by mixing and sintering with a lithium source. Its performance directly determines the core physical and chemical properties of the ternary cathode material.
  • the specific performance is: 1) Precursor impurities will be brought into The positive electrode material affects the content of impurities in the positive electrode; 2) The particle size and particle size distribution of the precursor directly determine the particle size and particle size distribution of the ternary positive electrode; 3) The specific surface area and morphology of the ternary precursor directly determine the specific surface area of the ternary positive electrode , Morphology; 4) The element ratio of the ternary precursor directly determines the element ratio of the ternary cathode.
  • the physical and chemical properties of the ternary cathode such as particle size, morphology, element ratio, and impurity content will affect the core electrochemical properties of lithium batteries such as energy density, rate performance, and cycle life.
  • the application and promotion of new cathode materials such as gradient and core-shell structure ternary cathodes depends on the development of corresponding precursors.
  • Ordinary ternary cathode materials have limitations.
  • the morphology of the ordinary ternary positive electrode is spherical or quasi-spherical secondary particles formed by agglomeration of primary single crystal particles, which are formed by combining multiple particles with a wide particle size distribution.
  • the main defects are: (1) Poor firmness: the secondary ball structure is poorly firm, and the compaction density is generally 3.4g/cm3 ⁇ 3.7g/cm3. Under high compaction, the secondary ball is broken, resulting in internal particles in the material.
  • silicon carbon anode As a new type of lithium-ion battery anode material, silicon carbon anode is more efficient than current graphite anode in improving battery energy density. Tesla has already applied silicon carbon anodes to power batteries for vehicles, and the application prospects of silicon carbon anode materials are getting brighter. In the future, silicon carbon anode materials are likely to become the best in anode materials.
  • the theoretical specific capacity of graphite is 372mAh/g, while the theoretical specific capacity of silicon anode is as high as 4200mAh/g.
  • graphite As a mature negative electrode material, graphite has basically fully utilized its energy density. In order to improve the energy density, combining with silicon is a better way.
  • the present invention provides a microchannel reactor, the main purpose of which is to prepare metal and metal compound particles with uniform and controllable particle size and morphology or metal and metal compound particles coated with other materials;
  • the present invention provides a method for preparing precursor micro-nano particles of lithium battery cathode materials.
  • the main purpose is to prepare precursor micro-nano particles suitable for lithium battery cathode materials, with uniform and controllable particle size and morphology, continuous process, and suitable Mass production.
  • the present invention provides a method for precursor micro/nano particles of negative electrode materials.
  • the main purpose is to prepare precursor micro/nano particles suitable for lithium battery negative materials, with uniform and controllable particle size and morphology, continuous process, and suitable for large-scale production .
  • the present invention mainly provides the following technical solutions:
  • an embodiment of the present invention provides a microchannel reactor, including: an upper sealing plate, a substrate one, a substrate two, and a lower sealing plate;
  • the upper sealing plate, the first substrate, the second substrate, and the lower sealing plate are attached and arranged in order from top to bottom;
  • the lower side of the upper sealing plate is provided with a main feeding groove and a feeding branch groove;
  • the upper side of the first substrate is provided with two main feeding grooves and two feeding branch grooves;
  • the upper sealing plate and the substrate one are sealed and fixed to each other; the first feeding main groove and the second feeding main groove correspond to each other to form the first feeding main channel; the first feeding branch groove is connected to the The two feed branch grooves correspond to each other to form a feed branch channel one; one end of the feed branch channel one communicates with the feed main channel one, and the other end is closed; the feed branch channel one is multiple One; a plurality of said feed branch channels are distributed regularly;
  • the lower side of the second substrate is provided with the third main feed groove and the third feed branch groove;
  • a through hole is provided between the second feed branch groove and the third feed branch groove; the through hole communicates the second feed branch groove and the third feed branch groove;
  • the upper side of the lower sealing plate is provided with a main feeding groove 4 and a feeding branch groove 4;
  • the lower sealing plate and the second substrate are sealed and fixed to each other; the third main feed groove and the fourth main feed groove correspond to each other to form the second main feed channel;
  • the four feeding branch grooves correspond to each other to form a feeding branch channel two; one end of the feeding branch channel two communicates with the feeding main channel two, and the other end extends toward the outer edge of the substrate two;
  • first substrate and the second substrate are integrated boards
  • the plates are bonded through high temperature.
  • multiple through holes there are multiple through holes; multiple through holes are arranged at intervals along the direction of the feed branch channel;
  • the diameter of the through hole gradually increases along the flow direction of the feed branch channel one.
  • the upper sealing plate is made of one of sapphire material, ceramic material and alloy material;
  • the first substrate, the second substrate, and the lower sealing plate are made of the same material as the upper sealing plate.
  • an embodiment of the present invention provides a method for preparing precursor micro-nano particles of a negative electrode material for a lithium battery
  • the trichlorosilane and high-purity hydrogen are respectively transported to the main feed channel 1 and the main feed channel 2 of the microchannel reactor; the microchannel reactor is at a constant temperature of 1100°C; the molar ratio of trichlorosilane to hydrogen It is 1:1 ⁇ 1:1.2;
  • Nano silicon and hydrogen chloride gas undergo rapid cooling and gas-solid separation to obtain high-purity nano silicon particles.
  • an embodiment of the present invention provides a method for preparing precursor micro-nano particles of a negative electrode material for a lithium battery
  • Precipitating agent is prepared;
  • the precipitating agent is an aqueous solution of chloride, sulfate, and nitrate, which can cause the sodium silicate solution to undergo a chemical precipitation reaction to generate silicate precipitate;
  • the precipitating agent is either hydrochloric acid, sulfuric acid, Any one of nitric acid, carbonic acid, and oxalic acid reacts chemically with sodium silicate to produce an acid solution of silica precipitation;
  • the suspension and the precipitant are respectively input into the main feed channel 1 and the main feed channel 2 of the microchannel reactor; the suspension and the precipitant meet in the microchannel reactor to cause a precipitation reaction, and the precipitation reaction uses nano-silicon as the Seed, silicate or silica is precipitated on the surface of nano-silicon; the molar ratio of sodium silicate to precipitant is 1:1;
  • the method for preparing the precursor micro-nano particles of the negative electrode material of the lithium battery uses the micro-channel reactor described in any one of the above for operation; the foregoing method prepares the nano-silicon particles.
  • an embodiment of the present invention provides a method for preparing precursor micro-nano particles of a lithium battery cathode material.
  • the lithium battery cathode material includes a ternary cathode material, a lithium-rich manganese-based cathode material, and a lithium iron phosphate cathode material.
  • the preparation method includes the following steps:
  • the metal salt is completely dissolved in water to prepare a salt solution with a metal ion concentration of 0.25-2 mol/L to obtain a mixed salt solution;
  • the metal salt is nickel salt, cobalt salt, aluminum salt, or nickel salt, cobalt salt, aluminum Salt, lithium salt, or nickel salt, cobalt salt, manganese salt, or nickel salt, cobalt salt, manganese salt, lithium salt;
  • the lithium battery micro/nano positive electrode material is a ternary positive electrode material
  • the lithium battery micro-nano cathode material is a lithium-rich manganese-based cathode material
  • the soluble alkali is completely dissolved in water to make a solution with a solubility of 1-5 mol/L to obtain an alkali solution;
  • the soluble alkali is ammonium bicarbonate, sodium hydroxide, 8-hydroxyquinoline, sodium carbonate, and ammonia One of potassium hydroxide;
  • the lithium battery micro-nano cathode material is a ternary cathode material, and when the mixed salt solution includes lithium salt, the precursor is subjected to a high-temperature curing reaction to obtain a ternary cathode material, that is, the lithium battery micro-nano cathode material ;
  • the precursor and the lithium salt are mixed uniformly, the molar ratio of the metal element in the precursor and the lithium salt is 1:1 to 1.2, and the high temperature curing reaction is performed to obtain a ternary cathode material , That is, the micro-nano cathode material for lithium batteries;
  • the lithium battery micro-nano cathode material is a lithium-rich manganese-based cathode material
  • the precursor and the lithium salt are mixed uniformly, and the molar ratio of the metal elements in the precursor except the lithium element to the metal elements in the lithium salt is 1:1. 1.2.
  • the metal salt is sulfate, nitrate, acetate, or hydrochloride
  • the soluble base is ammonium bicarbonate, sodium hydroxide, 8-hydroxyquinoline, sodium carbonate, ammonia, potassium hydroxide;
  • the lithium salt is at least one of lithium hydroxide, lithium acetate, lithium oxalate, and lithium carbonate;
  • the molar ratio of metal ions in the nickel salt, cobalt salt and manganese salt is 5-8:2-1:3-1;
  • the molar ratio of metal ions in the nickel salt, cobalt salt, and aluminum salt is 5-8:3-1.5:2-0.5.
  • the method for preparing the precursor micro-nano particles of the positive electrode material of the lithium battery uses the micro-channel reactor described in any one of the above operations.
  • the microchannel reactor and the method for preparing the precursor micro-nano particles of the positive electrode material and the negative electrode material of the lithium battery of the present invention have at least the following advantages:
  • FIG. 1 is a schematic diagram of a microchannel reactor provided by an embodiment of the present invention when substrate one and substrate two are attached;
  • FIG. 2 is a schematic diagram of a microchannel reactor provided by an embodiment of the present invention when substrate one and substrate two are separated;
  • FIG. 3 is a schematic diagram of a microchannel reactor provided by an embodiment of the present invention when substrate one and substrate two are integrated;
  • Figure 4 is a schematic diagram of a microchannel reactor provided by another embodiment of the present invention.
  • Fig. 5 is a schematic diagram of a microchannel reactor provided by still another embodiment of the present invention.
  • Fig. 6 is a schematic diagram of an upper sealing plate in a microchannel reactor provided by an embodiment of the present invention.
  • FIG. 7 is a schematic diagram of substrate one in a microchannel reactor provided by an embodiment of the present invention.
  • FIG. 8 is a schematic diagram of substrate two in a microchannel reactor provided by an embodiment of the present invention.
  • Figure 9 is a schematic diagram of a lower sealing plate in a microchannel reactor provided by an embodiment of the present invention.
  • FIG. 10 is a process flow diagram of preparing nano-silicon particles in a method for preparing precursor micro-nano particles of a lithium battery negative electrode material according to an embodiment of the present invention
  • 11 is an embodiment of the present invention provides a method for preparing precursor micro-nano particles of a lithium battery negative electrode material. Highly dispersed nano-silicon particles or silica and oxide coated with silicate and silicon oxide are prepared. Process flow chart of highly dispersed silicon nanoparticles coated with sub-silicon;
  • FIG. 12 is a process flow diagram of preparing a ternary cathode material and preparing a lithium-rich manganese-based cathode material when no lithium salt is added in the preparation of a mixed salt solution according to the present invention
  • FIG. 13 is a process flow diagram of adding lithium salt when preparing a mixed salt solution to prepare a ternary cathode material in the present invention
  • Figure 14 shows the microchannel reactor, the aging tube reactor and the aging tank.
  • 1 is the upper sealing plate
  • 1-1 is the main feeding trough one
  • 1-2 is the feeding branch one
  • 2 is the substrate one
  • 2-1 is the main feeding trough two
  • 2-2 is the feeding branch two
  • 2-3 is the through hole
  • 3 is the substrate two
  • 3-1 is the main feed slot three
  • 3-2 is the feed branch three
  • 3-3 is the connecting hole
  • 4 is the lower sealing plate
  • 4-1 is the Feeding main trough four
  • 4-2 is feeding branch trough four
  • an embodiment of the present invention provides a microchannel reactor, including: an upper sealing plate 1, a substrate one 2, a substrate two 3, and a lower sealing plate 4;
  • the upper sealing plate 1, the base plate 1, the base plate 2 3 and the lower sealing plate 4 are arranged in order from top to bottom; the lower side of the upper sealing plate 1 is provided with a main feed slot 1-1 and a feed branch slot 1 -2;
  • the upper side of the substrate one 2 is provided with the main feed slot two 2-2 and the feed branch two 2-2; the upper sealing plate 1 and the substrate one 2 are sealed and fixed to each other;
  • the main feed slot one 1- 1 Corresponding to the main feeding trough two 2-2 to form the main feeding channel one;
  • the feeding branch trough one 1-2 and the feeding branch trough two 2-2 correspond to each other, forming the feeding branch channel one;
  • One end of the first channel is connected with the main feed channel, and the other end is closed;
  • one feed branch channel is multiple; multiple feed branch channels are regularly distributed;
  • the lower side of the substrate two 3 is provided with a main feed groove three 3-1 and a feed branch groove three 3-2; a through hole 2 is provided between the feed branch groove two 2-2 and the feed branch groove three 3-2 -3;
  • the through hole 2-3 connects the feeding branch groove 2-2 and the feeding branch groove 3-3-2; the through hole 2-3 is punched through by laser drilling; the upper side of the lower sealing plate 4 is provided with The main feed slot 44-1 and the feed branch slot 4 4-2; the feed branch slot 3 3-2 can penetrate the thickness direction of the substrate 2 3, and the through hole 2-3 communicates with the feed branch slot 3 3-2
  • the feed support three may not penetrate the thickness direction of the substrate two 3. It is necessary to provide a connecting hole 3-3 on the substrate two 3.
  • the connecting hole 3-3 and the through hole 2-3 are arranged correspondingly; preferably the connecting hole 3- 3 has the same diameter as the through hole 2-3 and is arranged coaxially.
  • the bottom sealing plate 4 and the base plate two 3 are sealed and fixed to each other; the main feed slot three 3-1 and the feed main slot four 4-1 correspond to each other to form the feed main channel two; the feed branch slot three 3-2 and Feeding branch grooves four 4-2 correspond to each other to form feed branch channel two; one end of the feed branch channel two communicates with the main feed channel two, and the other end extends to the outer edge of the substrate two 3; the feed branch channel two is Multiple; the feeding branch channel two corresponds to the feeding branch channel one.
  • the upper sealing plate 1 and the lower sealing plate 4 are preferably double-sided polished plates; in the processing of the main feeding slot 1-1, the feeding main slot 2 2-2, the feeding main slot 3 3-1, and the feeding main slot 4 4-1.
  • feeding branch groove 1 1-2, feeding branch groove 2 2-2, feeding branch groove 3 3-2 and feeding branch groove 4 4-2 when the width is less than 2 mm, the grooves are etched and combined by laser Supplemented by wet etching, grooves with a width greater than 2mm are processed by a CNC machine tool diamond grinding head, supplemented by wet etching.
  • the depth of the feeding trough two 2-2 of the substrate one 2 is 100um-1000um, the width is 100um-1000um, and the aspect ratio is 1:1-1.5:1; the thickness of the substrate one 2 is preferably the thickness of the feed trough two 2-2 2-5 times the depth; preferably, the feeding branch groove 2 2-2 is a groove with a semicircular cross section;
  • the depth of the feeding trough three 3-2 of the substrate two 3 is 100um-1000um, the width is 100um-1000um, and the aspect ratio is 1:1-1.5:1; the thickness of the substrate two 3 is preferably the depth of the feed trough three 3-2 2-5 times of;
  • the feed branch 3-2 is a trough with a semicircular cross section;
  • the upper sealing plate 1, the base plate 1, the base plate 2 3 and the lower sealing plate 4 are sealed and bonded, and the sealing bonding method is 1500°C-2000°C high temperature bonding.
  • the edges of the upper sealing plate 1, the substrate one 2, the substrate two 3, and the lower sealing plate 4 are welded by laser or hydrogen-oxygen flame cladding at about 2050°C, supplemented by nano high-purity alumina as the solder, ensuring high temperature, strong acid and alkali
  • the environment does not cause secondary pollution to the reactants.
  • the microchannel reactor provided by the embodiment of the present invention has obvious advantages in material synthesis: the reaction fluid can be mixed quickly, the mixing time is shorter than the reaction time, a stable and uniform reaction environment is formed, and there is no backmixing, and the resulting micro-nano particle size distribution Narrow, so that the material can reach the stoichiometric ratio of molecular or atomic lines to mix, and the product can be removed in time, thereby reducing agglomeration.
  • the base plate one 2 and the base plate two 3 are integrated plates; that is, the main feed slot two 2-2 and the feed branch two 2-2 are processed on the upper side of the plate;
  • the main feeding slot 33-1 and the feeding support slot 3 3-2 are processed on the side; the upper side of the plate is attached to the upper sealing plate 1; the lower side of the plate is attached to the lower sealing plate 4.
  • the substrate one 2 and the substrate two 3 can also be arranged independently, and the substrate one 2 and the substrate two 3 are bonded through high temperature bonding.
  • the multiple through holes 2-3 are arranged at intervals along the direction of the feed branch channel one; in order to make the flow of the multiple through holes 2-3 equal to that of the branch channel one
  • the flow rate, the area of the multiple through holes 2-3 and the cross-sectional area of the branch channel one are the same.
  • the number of through holes 2-3 is preferably 2-20.
  • the diameter of the through hole 2-3 gradually increases along the flow direction of the feed branch channel 1, so that the flow of each through hole 2-3 is uniform, and the fluid gradient in the branch channel 1 is mixed and reacted with the fluid in the branch channel 2.
  • the fluid in the branch channel 1 reacts with the fluid in the branch channel 2 through the through holes 2-3, and is arranged in multiple channels at intervals, and the fluid is injected into the branch channel 2 at intervals, so that the seed crystal can pass through the multiple through holes 2- At 3 o'clock, it reacts with the fluid flowing in through hole 2-3 and gradually grows into crystals.
  • the upper sealing plate 1 is made of one of sapphire material, ceramic material and alloy material; the material of the substrate one 2, the substrate two 3 and the lower sealing plate 4 are the same as the upper sealing plate 1.
  • Substrate one 2, substrate two 3, lower sealing plate 4 and upper sealing plate 1 are preferably made of sapphire; the sapphire material is resistant to high temperature and corrosion, does not need anti-corrosion treatment, does not produce secondary pollution to the product, and is very suitable for the production of lithium batteries. , Electronic materials, nano materials, nano whisker materials, electromagnetic, advanced ceramics and other high-purity materials.
  • the microchannel reactor provided in the embodiments of the present invention can achieve precise control under microscopic conditions, and precise control package
  • the thickness of the coating, and the coating material has a high degree of consistency, high dispersion and no agglomeration.
  • the front end of the lithium calcination stage is added in the later stage, and the precursor and nano silicon coated by the lithium battery are not ground and classified to avoid damage to the coating.
  • the structure of the precursor and nano-silicon affects the performance of lithium battery cathode materials and silicon-carbon composite materials.
  • Lithium batteries have very high requirements on materials.
  • the positive electrode and negative electrode materials have very high requirements on the content of impurities that affect battery performance.
  • the microchannel reactor provided by the embodiment of the present invention is made of sapphire material resistant to strong acid and alkali, which can completely avoid the pollution of production equipment in a strong acid and alkali environment, especially the pollution of magnetic impurities.
  • microchannel reactor technology process provided by the embodiment of the present invention has huge technical and cost advantages in the preparation, doping, and coating of precursors of single crystal, high nickel, lithium-rich manganese-based cathode materials, and silicon-carbon composite anode materials.
  • the thickness of the upper sealing plate 1 and the lower sealing plate 4 are the same; the thickness of the substrate one 2 and the substrate two 3 are the same to facilitate processing and manufacturing; the thickness of the upper sealing plate 1 or the lower sealing plate 4 is that of the substrate one 2 or the substrate two 3. 2 to 5 times the thickness to ensure the overall strength and stability of the microchannel reactor.
  • an embodiment of the present invention provides a method for preparing precursor micro-nano particles of a negative electrode material for a lithium battery. Refer to FIG. 10 for the process flow.
  • the trichlorosilane and high-purity hydrogen are respectively transported to the main feed channel 1 and the main feed channel 2 of the microchannel reactor; the microchannel reactor is at a constant temperature of 1100°C; the molar ratio of trichlorosilane to hydrogen It is 1:1 ⁇ 1:1.2;
  • the gas reacts at high temperature in the microchannel reactor to generate nano-silicon and hydrogen chloride gas; by selecting the pore diameters of different feed branch channels 1 and 2 to obtain nano silicon particles of different sizes.
  • Nano silicon and hydrogen chloride gas undergo rapid cooling and gas-solid separation to obtain high-purity nano silicon particles.
  • the embodiment of the present invention provides a method for preparing precursor micro-nano particles of lithium battery negative electrode materials.
  • the produced high-purity nano-silicon particles have uniform morphology, precise control in size, no secondary pollution, and are truly nano-sized. Nanostructured particles.
  • a method for preparing precursor micro-nano particles of a negative electrode material of a lithium battery uses the above-mentioned microchannel reactor for operation.
  • the embodiment of the present invention provides a method for preparing the precursor micro-nano particles of the negative electrode material of the lithium battery.
  • the number of the through holes 2-3 through the microchannel reactor and the pore diameter of the through holes 2-3 are controlled in a gradient from small to large. Furthermore, the formation of seed crystals and the growth of crystals are controlled; in order to avoid the blockage of the feeding branch channel 1 and the feeding branch channel 2, the crystal grows to a certain size, and the reactant flows out of the feeding branch channel 2 to quickly cool down and separate gas and solid to obtain high Pure nano-silicon particles.
  • an embodiment of the present invention provides a method for preparing precursor micro-nano particles of a negative electrode material for a lithium battery. Refer to FIG. 11 for the process flow.
  • Precipitating agent is prepared;
  • the precipitating agent is an aqueous solution of chloride, sulfate, and nitrate, which can cause the sodium silicate solution to undergo a chemical precipitation reaction to generate silicate precipitate;
  • the precipitating agent is either hydrochloric acid, sulfuric acid, Any one of nitric acid, carbonic acid, and oxalic acid reacts chemically with sodium silicate to form an acid solution of silica precipitation;
  • the suspension and the precipitant are respectively input into the main feed channel 1 and the main feed channel 2 of the microchannel reactor; the suspension and the precipitant meet in the microchannel reactor to cause a precipitation reaction, and the precipitation reaction uses nano-silicon as the Seed, silicate or silica is precipitated on the surface of nano-silicon; the molar ratio of sodium silicate to precipitant is 1:1;
  • a method for preparing precursor micro-nano particles of a negative electrode material of a lithium battery uses the above-mentioned microchannel reactor for operation.
  • the embodiment of the present invention provides a method for preparing the precursor micro-nano particles of the negative electrode material of the lithium battery.
  • the number of the through holes 2-3 through the microchannel reactor and the pore diameter of the through holes 2-3 are controlled in a gradient from small to large. Then control the formation of seed crystals and the growth of crystals; in order to avoid blockage of the feeding branch channel 1 and feeding branch channel 2, the crystal grows to a certain size, and the reactant flows out of the feeding branch channel 2 to quickly cool down and separate gas and solid to obtain sub-channels.
  • the method for preparing the precursor micro-nano particles of the negative electrode material of lithium battery according to the present invention has simple process and continuous process, and prepares a high-capacity, high-rate, high-consistency negative electrode material precursor, and the particle size of the negative electrode material precursor , Good morphology consistency, no agglomeration, high particle yield, good batch product consistency, and stable results.
  • the method of the present invention for preparing precursor micro-nano particles of negative electrode materials for lithium batteries can be achieved by changing the flow rate, injection pressure, inner diameter and length of the microchannel reaction channel and other parameters of the liquid flowing into each inlet of the microchannel reactor. Production of micron and nano particles of different sizes.
  • the precipitating agent is composed of aqueous solutions of magnesium chloride, sulfate and nitrate, or aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid and carbonic acid;
  • the suspension and the precipitant are respectively input into the main feed channel 1 and the main feed channel 2 of the microchannel reactor; the suspension and the precipitant meet in the microchannel reactor to cause a precipitation reaction, and the precipitation reaction uses nano-silicon as the Seed, silicate or silica is precipitated on the surface of nano-silicon; the molar ratio of sodium silicate to precipitant is 1:1;
  • an embodiment of the present invention provides a method for preparing precursor micro-nano particles of a lithium battery cathode material.
  • the lithium battery anode material includes a ternary cathode material, a lithium-rich manganese-based cathode material, and a lithium iron phosphate cathode material.
  • the preparation method includes the following steps:
  • the metal salt is completely dissolved in water to make a salt solution with a metal ion concentration of 0.25-2mol/L to obtain a mixed salt solution;
  • the metal salt is nickel salt, cobalt salt, aluminum salt, or nickel salt, cobalt salt, aluminum salt, Lithium salt, or nickel salt, cobalt salt, manganese salt, or nickel salt, cobalt salt, manganese salt, lithium salt;
  • the lithium battery micro-nano cathode material is a ternary cathode material
  • the molar ratio of metal ions in Li: Ni+Co+Al or Mn 1-1.2:1;
  • the lithium battery micro-nano cathode material is a lithium-rich manganese-based cathode material
  • the soluble alkali is completely dissolved in water to make a solution with a solubility of 1-5mol/L to obtain an alkali solution;
  • the soluble alkali is ammonium bicarbonate, sodium hydroxide, 8-hydroxyquinoline, sodium carbonate, ammonia, hydrogen One of potassium oxide;
  • the lithium battery micro-nano cathode material is a ternary cathode material, and when the mixed salt solution includes lithium salt, the precursor is subjected to a high-temperature curing reaction to obtain a ternary cathode material, that is, a lithium battery micro-nano cathode material;
  • the lithium salt When the lithium salt is not included in the mixed salt solution: mix the precursor and the lithium salt uniformly, the molar ratio of the metal element in the precursor to the lithium salt is 1:1 to 1.2, and the high temperature curing reaction is carried out to obtain the ternary cathode material, namely Lithium battery micro-nano cathode material;
  • the lithium battery micro-nano cathode material is a lithium-rich manganese-based cathode material
  • the precursor and the lithium salt are mixed uniformly, and the molar ratio of the metal elements in the precursor except the lithium element to the metal elements in the lithium salt is 1:1-1.2
  • the high-temperature curing reaction is carried out to obtain lithium-rich manganese-based cathode materials, namely, lithium battery micro-nano cathode materials.
  • the method of the present invention for preparing precursor micro-nano particles of lithium battery cathode material does not require pre-synthesis of seed crystals, the reaction conditions are mild, the water phase system is adopted, the process is simple, the process is continuous, and the preparation is high-capacity, high-rate, Highly consistent cathode material precursor.
  • the particle size and morphology of the cathode material precursor are consistent.
  • the material reaches the molecular or atomic linearity stoichiometric ratio mixing, no agglomeration, high particle yield, and good batch product consistency. Repeat and stabilize.
  • the method of the present invention for preparing the precursor micro-nano particles of the positive electrode material of the lithium battery can be achieved by changing the flow rate, injection pressure, the inner diameter and length of the microchannel reaction channel and other parameters of the liquid flowing into each inlet of the microchannel reactor. Production of micron and nano particles of different sizes.
  • the prepared cathode material precursors can be classified into micro-particles and nano-silicon particles, and the micron particle size ranges from 0.1um to 500um.
  • the particle size range is 10nm-1000nm.
  • the metal salt is sulfate, nitrate, acetate, or hydrochloride
  • the soluble base is ammonium bicarbonate, sodium hydroxide, 8-hydroxyquinoline, sodium carbonate, ammonia, potassium hydroxide;
  • the lithium salt is at least one of lithium hydroxide, lithium acetate, lithium oxalate, and lithium carbonate;
  • the molar ratio of metal ions in nickel salt, cobalt salt and manganese salt is 5-8:2-1:3-1;
  • the molar ratio of metal ions in nickel salt, cobalt salt and aluminum salt is 5-8:3-1.5:2-0.5.
  • the method for preparing the precursor micro-nano particles of the positive electrode material of the lithium battery provided by the embodiment of the present invention uses a micro-channel reactor for operation.
  • the metal salt is a soluble metal salt
  • the manganese salt can be one of manganese sulfate, manganese nitrate, manganese chloride, and manganese acetate or a mixed salt thereof
  • the nickel salt can be nickel sulfate, nickel nitrate One of nickel chloride and nickel acetate or a mixed salt thereof
  • the cobalt salt is one of cobalt sulfate, cobalt nitrate, and cobalt chloride or a mixed salt thereof.
  • lithium salt is added when the salt solution is prepared, then the high temperature curing reaction is directly carried out after the precursor is prepared; 2 The lithium salt is added after the precursor is prepared.
  • the lithium battery micro-nano cathode material in the present invention is a lithium-rich manganese-based cathode material
  • a lithium salt must be added when preparing the salt solution, and the molar ratio of Li:Mn+Ni+Co in the metal salt is 3:2,
  • the Mn element accounts for 50%-90% of the (Mn+Ni+Co) element; after the precursor is prepared, a lithium salt is added to perform a high-temperature curing reaction.
  • Figure 14 shows the microchannel reactor, aging tube reactor and aging tank of the application.
  • A is the liquid inlet channel I
  • B is the liquid inlet channel II
  • C is the reaction channel
  • D is the aging tubular reactor
  • E is the aging tank
  • F is the microchannel reactor unit.
  • the substrate of the microchannel reactor of the present invention is corrosion-resistant sapphire , Ceramics, alloys, glass, preferably sapphire.
  • the substrate of this embodiment is sapphire.
  • the microchannel reactor includes two sealing plates and 1-100 microchannel plates. The microchannel plates are equipped with 2-1000 microchannels.
  • the microchannel reactor is a T-shaped microchannel reactor (as shown in FIG. 14), which includes a liquid inlet channel I, a liquid inlet channel II and a reaction channel, and the outlet end of the reaction channel is in communication with the aged tube reactor; liquid The diameter of the inlet channel is 1mm; the inner diameter of the reaction channel is 1mm and the length is 10mm; the length of the aged tubular reactor is 50mm.
  • the present invention selects the T-type microchannel reactor and restricts the size of the liquid inlet channel, the reaction channel and the aged tubular reactor, which can effectively avoid the reaction liquid back-mixing, avoid pipeline blockage, and ensure complete reaction.
  • the physical and chemical properties of the ternary cathode material precursor are improved, and the bulk density and cycle performance of the nickel, cobalt and aluminum ternary cathode material can be improved.
  • the products prepared in this embodiment are micron particles, and the yield of micron particles with a particle size of 10 um is 91%.
  • the yield of micron particles with a particle size of 10 um is 32%, and further grinding and sieving are required.
  • the method for preparing lithium battery micron cathode material according to the embodiment of the present invention can continuously prepare lithium battery cathode material precursor micro/nano particles, under mild conditions, water phase system, simple process, and lithium battery cathode material precursor morphology Controllable, high particle yield, good batch product consistency, continuous process, suitable for large-scale production.
  • NiSO4 nickel sulfate
  • CoSO4 cobalt sulfate
  • MnSO4 manganese sulfate
  • the base material of the microchannel reactor is corrosion-resistant ceramics, including two sealing plates and 5-20 microchannel plates.
  • the microchannel plates are provided with 20-100 microchannels.
  • the microchannel reactor is a T-shaped microchannel reactor (as shown in FIG. 14), which includes a liquid inlet channel I, a liquid inlet channel II and a reaction channel.
  • the outlet end of the reaction channel is connected to the aged tube reactor.
  • the diameter of the reaction channel in the microchannel reactor is the same as the diameter of the inlet channel, the diameter of the liquid inlet channel is 0.01-1mm; the inner diameter of the reaction channel is 0.01-1.5mm, and the length is 10-200mm; the length of the aged tubular reactor is 50 -5000mm, select the appropriate micro-channel design according to the particle size and morphology of the required product.
  • the present invention selects the T-type microchannel reactor and restricts the size of the liquid inlet channel, the reaction channel and the aged tubular reactor, which can effectively avoid the reaction liquid back-mixing, avoid pipeline blockage, and ensure complete reaction.
  • the product prepared in this embodiment is micron particles, and the yield of micron particles with a diameter of 5um is 92%.
  • the yield of micron particles with a diameter of 5 um is 31%, and further grinding, crushing, and sieving are required.
  • the method for preparing lithium battery micron cathode material according to the embodiment of the present invention can continuously prepare lithium battery cathode material precursor micro/nano particles, under mild conditions, water phase system, simple process, and lithium battery cathode material precursor morphology Controllable, high particle yield, good batch product consistency, continuous process, suitable for large-scale production.
  • NiSO4 nickel sulfate
  • CoSO4 cobalt sulfate
  • MnSO4 manganese sulfate
  • the potassium hydroxide is completely dissolved in water to make a 5mol/L alkali solution.
  • the substrate of the microchannel reactor is corrosion-resistant glass, including two sealing plates and 1-100 microchannel plates.
  • the microchannel plates are equipped with 2-1000 microchannels; preferably, the microchannel reactor includes 5-20 A microchannel plate is provided with 20-100 microchannels on the microchannel plate.
  • the microchannel reactor is a T-shaped microchannel reactor (as shown in FIG. 14), which includes a liquid inlet channel I, a liquid inlet channel II and a reaction channel, and the outlet end of the reaction channel is in communication with the aged tubular reactor.
  • the diameter of the reaction channel in the microchannel reactor is the same or different from the diameter of the inlet channel, the diameter of the liquid inlet channel is 0.01-1mm; the inner diameter of the reaction channel is 0.01-1.5mm, and the length is 10-200mm; the length of the aged tubular reactor It is 50-5000mm.
  • the products prepared in this embodiment are nanoparticles, and the yield of nanoparticles with a diameter of 400 nm is 94%.
  • the yield of the nanoparticles with a diameter of 400 nm is 35%, which requires further grinding, crushing, and sieving.
  • the method for preparing lithium battery nano-positive electrode material according to the embodiment of the present invention can continuously prepare lithium battery positive electrode material precursor micro-nano particles, under mild conditions, water phase system, simple process, and lithium battery positive electrode material precursor morphology Controllable, high particle yield, good batch product consistency, continuous process, suitable for large-scale production.
  • Battery-grade iron sulfate is completely dissolved in water and prepared into a mixed solution with a metal ion concentration of 2mol/L.
  • the molar ratio of iron phosphate to phosphoric acid is 1:2;
  • the mixed salt solution and alkali solution are injected into the microchannel reactor for reaction, and then flowed into the aging tank for 5 hours under normal pressure stirring to obtain the co-precipitation reaction mixture.
  • the solid material was washed 4 times with deionized water, and then placed in an oven, and vacuum dried at 120° C. for 12 hours to obtain a nano-lithium iron phosphate cathode material precursor iron phosphate.
  • the products prepared in this embodiment are nanoparticles, and the yield of micron particles with a diameter of 50 nm is 90%.
  • the yield of micron particles with a diameter of 50 nm is 40%, which requires further grinding, crushing, and sieving.
  • the method for preparing lithium battery nano-positive electrode material can continuously prepare lithium-ion battery lithium iron phosphate positive electrode material precursor iron phosphate nano-particles, under mild conditions, water phase system, simple process, and lithium battery positive electrode material Controllable precursor morphology, high particle yield, good batch product consistency, continuous process, suitable for large-scale production.
  • Aluminum hydroxide is added to a sodium hydroxide solution at 50°C-90°C, and the molar ratio of sodium hydroxide to aluminum hydroxide is 1:1 to prepare a sodium aluminate solution with a concentration of 2mol/L.
  • the cathode material precursor nano nickel cobalt manganese powder is added to the sodium aluminate solution and stirred to form a homogeneous suspension.
  • Ammonium bicarbonate was completely dissolved in water to make a 2mol/L alkaline solution.
  • the substrate of the microchannel reactor is corrosion-resistant sapphire, and the rest is the same as the microchannel reactor of Example 3.
  • the products prepared in this embodiment are micron particles, and the yield of micron particles with a particle size of 100 nm is 95%.
  • the yield of micron particles with a diameter of 100 nm is 36%, and further grinding and sieving are required.
  • the method for preparing alumina-coated nano-anode material for lithium battery can continuously prepare alumina-coated nano-particles, the precursor of lithium battery cathode material, with mild conditions, water-phase system and simple process ,
  • the morphology of the precursor coated with the cathode material of the lithium battery is controllable, the particle yield is high, the batch product consistency is good, the process is continuous, and it is suitable for large-scale production.
  • the substrate of the microchannel reactor is corrosion-resistant sapphire, and the rest is the same as the microchannel reactor of Example 3.
  • the ternary cathode material precursor is pre-fired at 500°C for 8 hours in an oxygen atmosphere, and then calcined at 700°C for 20 hours to obtain the ternary cathode material, that is, the lithium battery micron cathode material.
  • the product prepared in this embodiment is micron particles, and the yield of the micron particles with a diameter of 3um is 94%.
  • the yield of micron particles with a particle size of 3um is 38%, which requires further grinding and sieving.
  • the method for preparing lithium battery micron cathode material according to the embodiment of the present invention can continuously prepare lithium battery cathode material precursor micro/nano particles, under mild conditions, water phase system, simple process, and lithium battery cathode material precursor morphology Controllable, high particle yield, good batch product consistency, continuous process, suitable for large-scale production.
  • the substrate of the microchannel reactor is corrosion-resistant sapphire, and the rest is the same as the microchannel reactor of Example 3.
  • the molar ratio of the metal elements in the precursor except lithium to the metal elements in the lithium salt is 1:1.2, and then calcined in an oxygen atmosphere at 500°C for 8 hours , Calcined at 800° C. for 20 hours to obtain lithium-rich manganese-based cathode material, that is, the lithium battery nano anode material.
  • the products prepared in this embodiment are nanoparticles, and the yield of nanoparticles with a diameter of 800 nm is 93%.
  • the yield of 800 nm nanoparticles is 34%, which requires further grinding and sieving.
  • the method for preparing lithium battery nano-positive electrode material according to the embodiment of the present invention can continuously prepare lithium battery positive electrode material precursor micro-nano particles, under mild conditions, water phase system, simple process, and lithium battery positive electrode material precursor morphology Controllable, high particle yield, good batch product consistency, continuous process, suitable for large-scale production.
  • the substrate of the microchannel reactor is corrosion-resistant sapphire, and the rest is the same as the microchannel reactor of Example 3.
  • the molar ratio of the metal elements in the precursor except lithium to the metal elements in the lithium salt is 1:1, and then calcined in an oxygen atmosphere at 400°C for 8 hours , Calcined at 800° C. for 20 hours to obtain lithium-rich manganese-based cathode material, that is, the lithium battery micron cathode material.
  • the product prepared in this embodiment is micron particles, and the yield of the micron particles with a diameter of 4um is 92%.
  • the yield of 4um micron particles is 32%, which requires further grinding and sieving.
  • the titanyl sulfate solution and the precipitant ammonia solution are injected into the microchannel reactor for precipitation reaction, and the reaction speed is controlled to make the precipitate crystals form a specific size and morphology.
  • the reaction mixture flows out of the microchannel reactor and enters the aging tank for aging for 4 hours.
  • the solid matter was washed with deionized water three times, and then placed in an oven and vacuum dried at 140° C. for 6 hours to obtain nano titanium oxide particles.
  • the substrate of the microchannel reactor is corrosion-resistant sapphire, and the rest is the same as the microchannel reactor of Example 3.
  • the method for preparing lithium battery micron cathode material according to the embodiment of the present invention can continuously prepare lithium battery cathode material precursor micro/nano particles, under mild conditions, water phase system, simple process, and lithium battery cathode material precursor morphology Controllable, high particle yield, good batch product consistency, continuous process, suitable for large-scale production.
  • first, second, etc. may be used herein to describe various elements, these terms should not limit these elements. These terms are only used to distinguish one element from another element. For example, a first element may be referred to as a second element, and, similarly, a second element may be referred to as a first element, and these terms are only used to distinguish one element from another element. This does not depart from the scope of the exemplary embodiment. Similarly, element one and element two do not represent the order of elements, and these terms are only used to distinguish one element from another element. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

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Abstract

一种微通道反应器，包括：上封板（1）、基板一（2）、基板二（3）和下封板（4）从上至下依次贴合设置；上封板（1）与基板一（2）之间形成进料主通道一和进料支通道一；进料支通道一的一端与进料主通道一连通，另一端为封闭状；基板二（3）与下封板（4）之间形成进料主通道二和进料支通道二；通孔（2-3）连通进料支通道一和进料支通道二；进料支通道二的一端与进料主通道二连通，另一端延伸向基板二（3）的外缘。通过上述微通道反应器能够制备粒径、形貌均匀可控的金属及金属化合物粒子或被其它材料包覆的金属及金属化合物粒子。

Description

一种微通道反应器及制备锂电池正极材料和负极材料的前驱体微纳米粒子的方法 技术领域
本发明涉及化学化工技术领域，尤其涉及一种微通道反应器及制备锂电池正极材料和负极材料的前驱体微纳米粒子的方法。
背景技术
近年来，全球能源与环境保护意识高涨，许多国家极力推广电动车，带动全球电动车的市场蓬勃发展。锂电池主要由正极材料、负极材料、隔膜、电解质和电池外壳几个部分组成。正极材料和负极材料是锂电池电化学性能的决定性因素，直接决定电池的能量密度及安全性，进而影响电池的综合性能。
锂电池正极材料主要包括三元材料(NCM、NCA)、磷酸铁锂(LFP)、钴酸锂(LCO)以及锰酸锂(LMO)，四大材料因各自的特性差异应用于不同市场。受到车用动力电池、电动工具用电池、电动自行车用电池等快速增长，以及3C电池的低钴化影响，2017年NCM三元正极材料已替代磷酸铁锂，成为国内占比最大的锂电池正极材料。
三元正极材料前驱体直接决定三元正极材料核心理化性能。三元前驱体是生产三元正极的关键性材料，通过与锂源混合烧结制成三元正极，其性能直接决定三元正极材料核心理化性能，具体表现为：1)前驱体杂质会带入正极材料，影响正极杂质含量；2)前驱体粒径大小、粒径分布直接决定三元正极粒径大小、粒径分布；3)三元前驱体比表面积、形貌直接决定三元正极比表面积、形貌；4)三元前驱体元素配比直接决定三元正极元素配比等。三元正极的粒径、形貌、元素配比、杂质含量等理化性能将影响锂电池能量密度、倍率性能、循环寿命等核心电化学性能。此外，新型正极材料如梯度、核壳结构三元正极的应用推广，取决于相应前驱体的研发突破。
普通三元正极材料存在局限性。普通三元正极形貌为一次单晶颗粒聚集成的球形或类球形二次颗粒，由多个微粒结合而成，粒度分布较宽。其主要缺陷有：(1)牢固性差：二次球结构牢固性差，压实密度一般为3.4g/cm3～3.7g/cm3，在 较高的压实下，二次球破碎，导致材料内部颗粒裸露，副反应增加和金属离子溶出加剧，导致电学性能下降；(2)结构缺陷多：二次球内部、外部一次粒径小且结构缺陷多，在高电压充放电条件下易发生结构坍塌；(3)包覆性差：二次球颗粒内部难以被包覆，高电压充放电过程中界面副反应难以抑制，造成材料结构破坏；(4)易胀气：二次球颗粒容易导致气胀等问题。目前大部分厂商采用连续法制备常规颗粒尺寸(10μm～15μm)的三元前驱体材料，此方法不仅产量高，而且批次稳定性好。但在制备小颗粒尺寸(3μm～5μm)的三元前驱体材料时，采用连续法生产粒径分布难以控制，造成粒径误差较大。
硅碳负极作为新型锂离子电池负极材料，在提升电池能量密度方面比当前石墨负极更高效。特斯拉已经将硅碳负极应用于车用动力电池，硅碳负极材料应用前景越来越光明，未来硅碳负极材料很可能成为负极材料中的佼佼者。
石墨的理论比容量是372mAh/g，而硅负极的理论比容量高达4200mAh/g。石墨作为成熟的负极材料，其能量密度已经基本被充分发挥，要想在能量密度上有所提升，与硅结合是一种较好的方式。
在硅系负极方面，研究界认为氧化亚硅-碳复合材料的实际应用效果好于纯硅-碳复合材料，特别是在电池循环性和稳定性方面，这同时也是业界在高能量负极材料方面的另一个研究重点。
发明内容
有鉴于此，本发明提供一种微通道反应器，主要目的在于，制备粒径、形貌均匀可控的金属及金属化合物粒子或被其它材料包覆的金属及金属化合物粒子；
本发明提供一种制备锂电池正极材料的前驱体微纳米粒子的方法，主要目的在于，制备适用于锂电池正极材料的前驱体微纳米粒子，粒径、形貌均匀可控，过程连续，适宜大规模生产。
本发明提供一种负极材料的前驱体微纳米粒子的方法，主要目的在于，制备适用于锂电池负极材料的前驱体微纳米粒子，粒径、形貌均匀可控，过程连续， 适宜大规模生产。
为达到上述目的，本发明主要提供如下技术方案：
一方面，本发明的实施例提供一种微通道反应器，包括：上封板、基板一、基板二和下封板；
所述上封板、所述基板一、所述基板二和所述下封板从上至下依次贴合设置；
所述上封板的下侧面设置有进料主槽一和进料支槽一；
所述基板一的上侧面设置有进料主槽二和进料支槽二；
所述上封板与所述基板一相互密封贴合固定；所述进料主槽一与所述进料主槽二相互对应，形成进料主通道一；所述进料支槽一与所述进料支槽二相互对应，形成进料支通道一；所述进料支通道一的一端与所述进料主通道一连通，另一端为封闭状；所述进料支通道一为多个；多个所述进料支通道一规则分布；
所述基板二的下侧面设置有进料主槽三和进料支槽三；
所述进料支槽二与所述进料支槽三之间设置有通孔；所述通孔连通所述进料支槽二与所述进料支槽三；
所述下封板的上侧面设置有进料主槽四和进料支槽四；
所述下封板与所述基板二相互密封贴合固定；所述进料主槽三与所述进料主槽四相互对应，形成进料主通道二；所述进料支槽三与所述进料支槽四相互对应，形成进料支通道二；所述进料支通道二的一端与所述进料主通道二连通，另一端延伸向所述基板二的外缘；所述进料支通道二为多个；所述进料支通道二与所述进料支通道一对应分布。
进一步地，所述基板一与所述基板二为一体化板件；
所述板件为多个；多个所述板件上下叠加密封贴合；
所述板件之间通过高温键合。
进一步地，所述通孔为多个；多个所述通孔沿所述进料支通道一的方向间隔设置；
所述通孔的直径沿所述进料支通道一的流通方向逐渐变大。
进一步地，所述上封板为蓝宝石材质、陶瓷材质和合金材质中的一种；
所述基板一、所述基板二和所述下封板与所述上封板的材质相同。
另一方面，本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒 子的方法，
(1)将高纯四氯化硅或三氯氢硅加温至1000℃；
(2)将高纯氢气加温至1000℃；
(3)将高纯四氯化硅与高纯氢气或三氯氢硅与高纯氢气分别输送到微通道反应器的进料主通道一和进料主通道二；微通道反应器处于1380℃的恒温中；四氯化硅与氢气的摩尔比为1：2～1：2.5；
或将三氯氢硅与高纯氢气分别输送到微通道反应器的进料主通道一和进料主通道二；微通道反应器处于1100℃的恒温中；三氯氢硅与氢气的摩尔比为1：1～1：1.2；
(4)气体在微通道反应器中高温反应，生成纳米硅和氯化氢气体；
(5)纳米硅和氯化氢气体经过快速降温、气固分离，得到高纯纳米硅颗粒。
再一方面，本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法，
(1)制备纳米硅与硅酸钠溶液的悬浮液；
(2)制备沉淀剂；沉淀剂为氯化盐、硫酸盐和硝酸盐的水溶液，所述水溶液能够使硅酸钠溶液发生化学沉淀反应生成硅酸盐沉淀物；沉淀剂或是盐酸、硫酸、硝酸、碳酸、草酸中任一种与硅酸钠发生化学沉淀反应生成二氧化硅沉淀的酸溶液；
(3)将悬浮液和沉淀剂分别输入微通道反应器的进料主通道一和进料主通道二；悬浮液和沉淀剂在微通道反应器中交汇发生沉淀反应，沉淀反应以纳米硅为晶种，纳米硅表面沉淀硅酸盐或二氧化硅；硅酸钠与沉淀剂摩尔比为1：1；
(4)反应物经固液分离、清洗、烘干；
(5)在500℃～1200℃之间缓慢升温煅烧，得到有亚硅酸盐和氧化亚硅包覆的高分散的纳米硅颗粒或二氧化硅和氧化亚硅包覆的高分散的纳米硅颗粒。
进一步地，所述的一种制备锂电池负极材料的前驱体微纳米粒子的方法，采用上述任一项所述的微通道反应器进行作业；上述方法制备纳米硅颗粒。
另一方面，本发明的实施例提供一种制备锂电池正极材料的前驱体微纳米粒子的方法，所述锂电池正极材料有三元正极材料、富锂锰基正极材料、磷酸铁锂 正极材料，其制备方法包括以下步骤：
(1)制备混合盐溶液：
将金属盐完全溶解于水中，制成金属离子浓度为0.25-2mol/L的盐溶液，得混合盐溶液；所述金属盐为镍盐、钴盐、铝盐，或镍盐、钴盐、铝盐、锂盐，或镍盐、钴盐、锰盐，或镍盐、钴盐、锰盐、锂盐；
其中，所述锂电池微纳米正极材料为三元正极材料时，所述镍盐、钴盐、铝盐或锰盐中的金属离子的摩尔比为Ni：Co：Al或Mn＝5-9：0.05-3：0.05-3；或Ni:Co:Mn＝5-9：0.05-3：0.05-3；其中Ni+Co+Al＝10或Ni+Co+Mn＝10；所述锂盐与除锂盐外的金属盐中的金属离子的摩尔比为Li：Ni+Co+Al或Mn＝1-1.2:1；
所述锂电池微纳米正极材料为富锂锰基正极材料时，所述金属盐中金属离子的摩尔比为Li：Mn+Ni+Co＝3:2，Mn：Ni+Co＝5-9:1-5；
(2)制备碱溶液：
将可溶性碱完全溶解于水中，制成可溶性碱溶度为1-5mol/L的溶液，得碱溶液；所述可溶性碱为碳酸氢铵、氢氧化钠、8-羟基喹啉、碳酸钠、氨水、氢氧化钾中的一种；
(3)在10-80℃下，将混合盐溶液和碱溶液注入微通道反应器的进料主通道一和进料主通道二；混合盐溶液和碱溶液在微通道反应器中交汇发生沉淀反应，经历晶种生成到晶体生长过程，在晶体生长到一定程度时，混合反应的流体及时流出微通道反应器，流入管式反应器继续加温加速反应，晶体生长到设计要求时，流入陈化罐常压搅拌陈化2-10h，得共沉淀反应混合物；
(4)将沉淀反应混合物固液分离后，将固体物质洗涤3-4次，再干燥，得前驱体；
(5)所述锂电池微纳米正极材料为三元正极材料，混合盐溶液中包括锂盐时，将前驱体进行高温固化反应，得三元正极材料，即所述的锂电池微纳米正极材料；
所述混合盐溶液中不包括锂盐时：将前驱体与锂盐混合均匀，前驱体与锂盐中的金属元素的摩尔比为1:1-1.2，进行高温固化反应，得三元正极材料，即所述的锂电池微纳米正极材料；
所述锂电池微纳米正极材料为富锂锰基正极材料时，将前驱体与锂盐混合均匀，前驱体中除锂元素外的金属元素与锂盐中金属元素的摩尔比为1:1-1.2，进行 高温固化反应，得富锂锰基正极材料，即所述的锂电池微纳米正极材料。
进一步地，所述步骤(1)中，所述金属盐为硫酸盐、硝酸盐、乙酸盐、或盐酸盐；
所述步骤(2)中，所述可溶性碱为碳酸氢铵、氢氧化钠、8-羟基喹啉、碳酸钠、氨水、氢氧化钾；；
所述步骤(5)中，所述锂盐为氢氧化锂、乙酸锂、草酸锂、碳酸锂中的至少一种；
所述镍盐、钴盐、锰盐中的金属离子的摩尔比5-8:2-1:3-1；
所述镍盐、钴盐、铝盐中的金属离子的摩尔比5-8:3-1.5:2-0.5。
进一步地，所述的制备锂电池正极材料的前驱体微纳米粒子的方法，采用上述任一项所述的微通道反应器进行作业。
借由上述技术方案，本发明微通道反应器及制备锂电池正极材料和负极材料的前驱体微纳米粒子的方法，至少具有下列优点：
能够制备适用于锂电池正极材料和负极材料的前驱体微纳米粒子，粒径、形貌均匀可控，过程连续，适宜大规模生产。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1为本发明实施例提供的一种微通道反应器在基板一和基板二贴合时的示意图；
图2为本发明实施例提供的一种微通道反应器在基板一和基板二分离时的示意图；
图3为本发明实施例提供的一种微通道反应器在基板一和基板二一体化设置时的示意图；
图4为本发明另一实施例提供的一种微通道反应器的示意图；
图5为本发明再一实施例提供的一种微通道反应器的示意图；
图6为本发明实施例提供的一种微通道反应器中上封板的示意图；
图7为本发明实施例提供的一种微通道反应器中基板一的示意图；；
图8为本发明实施例提供的一种微通道反应器中基板二的示意图；
图9为本发明实施例提供的一种微通道反应器中下封板的示意图；
图10为本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法中制备纳米硅颗粒的工艺流程图；
图11为本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法中制备有亚硅酸盐和氧化亚硅包覆的高分散的纳米硅颗粒或二氧化硅和氧化亚硅包覆的高分散的纳米硅颗粒的工艺流程图；
图12为本发明在制备混合盐溶液中不加入锂盐时制备三元正极材料，和制备富锂锰基正极材料的工艺流程图；
图13为本发明中在制备混合盐溶液时加入锂盐，制备三元正极材料的工艺流程图；
图14为微通道反应器、陈化管式反应器和陈化罐。
图中所示：
1为上封板，1-1为进料主槽一，1-2为进料支槽一，2为基板一，2-1为进料主槽二，2-2为进料支槽二，2-3为通孔，3为基板二，3-1为进料主槽三，3-2为进料支槽三，3-3为连接孔，4为下封板，4-1为进料主槽四，4-2为进料支槽四
具体实施方式
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,以下结合附图及较佳实施例，对依据本发明申请的具体实施方式、结构、特征及其功效，详细说明如后。在下述说明中，不同的“一实施例”或“实施例”指的不一定是同一实施例。此外，一或多个实施例中的特定特征、结构、或特点可由任何 合适形式组合。
如图1至图9所示，一方面，本发明的实施例提供一种微通道反应器，包括：上封板1、基板一2、基板二3和下封板4；
上封板1、基板一2、基板二3和下封板4从上至下依次贴合设置；上封板1的下侧面设置有进料主槽一1-1和进料支槽一1-2；基板一2的上侧面设置有进料主槽二2-2和进料支槽二2-2；上封板1与基板一2相互密封贴合固定；进料主槽一1-1与进料主槽二2-2相互对应，形成进料主通道一；进料支槽一1-2与进料支槽二2-2相互对应，形成进料支通道一；进料支通道一的一端与进料主通道一连通，另一端为封闭状；进料支通道一为多个；多个进料支通道一规则分布；
基板二3的下侧面设置有进料主槽三3-1和进料支槽三3-2；进料支槽二2-2与进料支槽三3-2之间设置有通孔2-3；通孔2-3连通进料支槽二2-2与进料支槽三3-2；通孔2-3以激光打孔的方式打穿；下封板4的上侧面设置有进料主槽四4-1和进料支槽四4-2；进料支槽三3-2可以贯穿基板二3的厚度方向，通孔2-3与进料支槽三3-2连通；进料支撑三也可以不贯穿基板二3的厚度方向，增需要在基板二3上设置有连接孔3-3，连接孔3-3与通孔2-3对应设置；优选连接孔3-3与通孔2-3直径相同，同轴设置。
下封板4与基板二3相互密封贴合固定；进料主槽三3-1与进料主槽四4-1相互对应，形成进料主通道二；进料支槽三3-2与进料支槽四4-2相互对应，形成进料支通道二；进料支通道二的一端与进料主通道二连通，另一端延伸向基板二3的外缘；进料支通道二为多个；进料支通道二与进料支通道一对应分布。上封板1和下封板4优选为双面抛光板；在加工进料主槽一1-1、进料主槽二2-2、进料主槽三3-1、进料主槽四4-1、进料支槽一1-2、进料支槽二2-2、进料支槽三3-2和进料支槽四4-2时，宽度小于2mm槽利用激光刻蚀并辅以湿法刻蚀，宽度大于2mm槽利用数控机床金刚石磨头加工后，辅以湿法刻蚀。
基板一2的进料支槽二2-2的深度100um-1000um，宽度100um-1000um，宽深比1：1-1.5：1；基板一2的厚度优选为进料支槽二2-2的深度的2-5倍；优选进料支槽二2-2为截面为半圆形的槽；
基板二3的进料支槽三3-2深度100um-1000um，宽度100um-1000um，宽深比 1：1-1.5：1；基板二3的厚度优选为进料支槽三3-2的深度的2-5倍；优选进料支槽三3-2为截面为半圆形的槽；
上封板1、基板一2、基板二3和下封板4之间密封贴合，密封贴合方法为1500℃-2000℃高温键合。上封板1、基板一2、基板二3和下封板4的边缘使用2050℃左右的激光或氢氧焰覆熔焊接并辅以纳米高纯氧化铝作为焊料，保证在高温、强酸碱环境中不对反应物造成二次污染。
本发明实施例提供的微通道反应器在材料合成方面优势明显：反应流体可以快速混合，混合时间短于反应时间，形成稳定均一的反应环境，而且没有返混，得到的微纳米粒子粒径分布窄，使材料达到分子或原子线度化学计量比混合，产物可以及时移出，从而减少团聚。
作为上述实施例的优选，基板一2与基板二3为一体化板件；即在板件的上侧面加工进料主槽二2-2和进料支槽二2-2；板件的下侧面加工进料主槽三3-1和进料支槽三3-2；板件的上侧面与上封板1贴合；板件的下侧面与下封板4贴合。
板件为多个；多个板件上下叠加密封贴合；以形成多个通道，同时进行作业，提高作业效率。板件之间通过高温键合，以使结构可靠，实现密封。
当然，基板一2和基板二3也可以独立设置，将基板一2和基板二3通过高温键合。
作为上述实施例的优选，通孔2-3为多个；多个通孔2-3沿进料支通道一的方向间隔设置；为了使多个通孔2-3的流量等于支通道一的流量，多个通孔2-3的面积和与支通道一的截面积相同。通孔2-3优选为2～20个。通孔2-3的直径沿进料支通道一的流通方向逐渐变大，以使各个通孔2-3能够流量均匀，使支通道一中的流体分梯度与支通道二中的流体混合反应，达到晶种生成—晶体生长—晶体成型的目的。
支通道一内的流体，通过通孔2-3与支通道二内的流体反应，在多个通道间隔设置，间隔地向支通道二内融入流体，可以使晶种通过多个通孔2-3时，与通孔2-3流入的流体反应，逐步生长成晶体。
作为上述实施例的优选，上封板1为蓝宝石材质、陶瓷材质和合金材质中的一种；基板一2、基板二3和下封板4与上封板1的材质相同。基板一2、基板二3和下封板4与上封板1优选为蓝宝石材质；蓝宝石材料耐高温、耐腐蚀，不需要做防腐处理，对产物不产生二次污染，非常适合生产满足锂电池、电子材料、纳米材料、纳米晶须材料、电磁、先进陶瓷等高纯材料的要求。在锂电池正极材料前驱体和锂电池负极材料纳米硅包覆氧化物或碳材料以提高材料性能方面，本发明实施例提供的微通道反应器可以做到微观条件下的精准控制，精准控制包覆物的厚度，并使包覆材料具有高度一致性、高度分散性无团聚，后期加锂煅烧阶段的前端，不用对锂电池包覆的前驱体和纳米硅进行研磨分级，避免破坏包覆的前驱体和纳米硅的机构，影响锂电池正极材料和硅碳复合材料的性能。
锂电池对材料的要求非常高，正极材料和负极材料对影响电池性能的杂质含量有非常高的要求，杂质来源主要有两个途径，原材料带入和生产设备的二次污染。本发明实施例提供的微通道反应器由耐强酸碱的蓝宝石材料加工而成，完全可以避免强酸碱环境下的生产装备的污染，特别是磁性杂质的污染。
本发明实施例提供的微通道反应器技术工艺在单晶、高镍、富锂锰基正极材料、硅碳复合负极材料的前驱体制备、参杂、包覆具有巨大的技术和成本优势。
进一步优选上封板1与下封板4厚度相同；基板一2与基板二3的厚度相同，以便于加工制造；上封板1或下封板4的厚度是基板一2或基板二3的厚度的2～5倍，以保证微通道反应器的整体强度和稳定性。
另一方面，本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法，工艺流程参考图10，
(1)将高纯四氯化硅或三氯氢硅加温至1000℃；
(2)将高纯氢气加温至1000℃；
(3)将高纯四氯化硅与高纯氢气或三氯氢硅与高纯氢气分别输送到微通道反应器的进料主通道一和进料主通道二；微通道反应器处于1380℃的恒温中；四氯化硅与氢气的摩尔比为1：2～1：2.5；
或将三氯氢硅与高纯氢气分别输送到微通道反应器的进料主通道一和进料主通道二；微通道反应器处于1100℃的恒温中；三氯氢硅与氢气的摩尔比为1：1～1：1.2；
(4)气体在微通道反应器中高温反应，生成纳米硅和氯化氢气体；通过选择不同进料支通道一和进料支通道二的孔径，得到不同尺寸的纳米硅颗粒。
(5)纳米硅和氯化氢气体经过快速降温、气固分离，得到高纯纳米硅颗粒。
本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法，生产的高纯纳米硅颗粒，形貌均匀、大小可以精准控制，无二次污染，是真正具有纳米特性的纳米结构颗粒。
作为上述实施例的优选，本发明实施例提供的一种制备锂电池负极材料的前驱体微纳米粒子的方法，采用上述的微通道反应器进行作业。
本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法中微通道反应器通过通孔2-3的数量和通孔2-3的孔径由小到大的梯度控制，进而控制晶种的形成和晶体的生长；为避免进料支通道一和进料支通道二堵塞，晶体生长到一定大小，反应物流出进料支通道二，快速降温、气固分离，得到高纯纳米硅颗粒。
再一方面，本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法，工艺流程参考图11，
(1)制备纳米硅与硅酸钠溶液的悬浮液；纳米硅的制备可采用上述方法制备。
(2)制备沉淀剂；沉淀剂为氯化盐、硫酸盐和硝酸盐的水溶液，所述水溶液能够使硅酸钠溶液发生化学沉淀反应生成硅酸盐沉淀物；沉淀剂或是盐酸、硫酸、硝酸、碳酸、草酸中任一种与硅酸钠发生化学沉淀反应生成二氧化硅沉淀的酸溶液；
(3)将悬浮液和沉淀剂分别输入微通道反应器的进料主通道一和进料主通道二；悬浮液和沉淀剂在微通道反应器中交汇发生沉淀反应，沉淀反应以纳米硅为晶种，纳米硅表面沉淀硅酸盐或二氧化硅；硅酸钠与沉淀剂摩尔比为1：1；
(4)反应物经固液分离、清洗、烘干；
(5)在500℃～1200℃之间缓慢升温煅烧，得到有亚硅酸盐和氧化亚硅包覆的高分散的纳米硅颗粒或二氧化硅和氧化亚硅包覆的高分散的纳米硅颗粒。
作为上述实施例的优选，本发明实施例提供的一种制备锂电池负极材料的前驱体微纳米粒子的方法，采用上述的微通道反应器进行作业。
本发明的实施例提供一种制备锂电池负极材料的前驱体微纳米粒子的方法中微通道反应器通过通孔2-3的数量和通孔2-3的孔径由小到大的梯度控制，进而控制晶种的形成和晶体的生长；为避免进料支通道一和进料支通道二堵塞，晶体生长到一定大小，反应物流出进料支通道二，快速降温、气固分离，得到亚硅酸盐和氧化亚硅包覆的高分散的纳米硅颗粒或二氧化硅和氧化亚硅包覆的高分散的纳米硅颗粒。
本发明所述的一种制备锂电池负极材料的前驱体微纳米粒子的方法，工艺简单、过程连续，制备得到高容量、高倍率、高一致性的负极材料前驱体，负极材料前驱体粒径、形貌一致性好，无团聚，粒子产率高、批次产品一致性好，结果重复稳定。
本发明所述的一种制备锂电池负极材料的前驱体微纳米粒子的方法，通过改变流入微通道反应器各个入口处液体的流量、注入压力、微通道反应通道的内径、长度等参数，可生产不同粒径的微米、纳米粒子。
实施例1.
(1)将纳米硅改性后与硅酸钠溶液制备浆料，保持一定的搅拌速度使纳米硅均匀分布在硅酸钠溶液中，形成纳米硅与硅酸钠溶液的悬浮液；
(2)制备沉淀剂；沉淀剂由镁的氯化盐、硫酸盐和硝酸盐的水溶液组成，或由盐酸、硫酸、硝酸和碳酸等水溶液组成；
(3)将悬浮液和沉淀剂分别输入微通道反应器的进料主通道一和进料主通道二；悬浮液和沉淀剂在微通道反应器中交汇发生沉淀反应，沉淀反应以纳米硅为晶种，纳米硅表面沉淀硅酸盐或二氧化硅；硅酸钠与沉淀剂摩尔比为1：1；
(4)反应物经固液分离、清洗、烘干；
(5)在500℃～1200℃之间缓慢升温煅烧，得到有亚硅酸盐和氧化亚硅包覆 的高分散的纳米硅颗粒或二氧化硅和氧化亚硅包覆的高分散的纳米硅颗粒。包覆的纳米硅材料与碳材料复合，形成硅碳复合锂电池负极材料。
另一方面，本发明的实施例提供的一种制备锂电池正极材料的前驱体微纳米粒子的方法，锂电池正极材料有三元正极材料、富锂锰基正极材料、磷酸铁锂正极材料，其制备方法包括以下步骤：
(1)制备混合盐溶液：
将金属盐完全溶解于水中，制成金属离子浓度为0.25-2mol/L的盐溶液，得混合盐溶液；金属盐为镍盐、钴盐、铝盐，或镍盐、钴盐、铝盐、锂盐，或镍盐、钴盐、锰盐，或镍盐、钴盐、锰盐、锂盐；
其中，锂电池微纳米正极材料为三元正极材料时，镍盐、钴盐、铝盐或锰盐中的金属离子的摩尔比为Ni：Co：Al或Mn＝5-9：0.05-3：0.05-3；或Ni:Co:Mn＝5-9：0.05-3：0.05-3；其中Ni+Co+Al＝10或Ni+Co+Mn＝10；锂盐与除锂盐外的金属盐中的金属离子的摩尔比为Li：Ni+Co+Al或Mn＝1-1.2:1；
锂电池微纳米正极材料为富锂锰基正极材料时，金属盐中金属离子的摩尔比为Li：Mn+Ni+Co＝3:2，Mn：Ni+Co＝5-9:1-5；
(2)制备碱溶液：
将可溶性碱完全溶解于水中，制成可溶性碱溶度为1-5mol/L的溶液，得碱溶液；可溶性碱为碳酸氢铵、氢氧化钠、8-羟基喹啉、碳酸钠、氨水、氢氧化钾中的一种；
(3)在10-80℃下，将混合盐溶液和碱溶液注入微通道反应器的进料主通道一和进料主通道二；混合盐溶液和碱溶液在微通道反应器中交汇发生沉淀反应，经历晶种生成到晶体生长过程，在晶体生长到一定程度时，混合反应的流体及时流出微通道反应器，流入管式反应器继续加温加速反应，晶体生长到设计要求时，流入陈化罐常压搅拌陈化2-10h，得共沉淀反应混合物；
(4)将沉淀反应混合物固液分离后，将固体物质洗涤3-4次，再干燥，得前驱体；
(5)锂电池微纳米正极材料为三元正极材料，混合盐溶液中包括锂盐时，将前驱体进行高温固化反应，得三元正极材料，即的锂电池微纳米正极材料；
混合盐溶液中不包括锂盐时：将前驱体与锂盐混合均匀，前驱体与锂盐中的金属元素的摩尔比为1:1-1.2，进行高温固化反应，得三元正极材料，即的锂电池微纳米正极材料；
锂电池微纳米正极材料为富锂锰基正极材料时，将前驱体与锂盐混合均匀，前驱体中除锂元素外的金属元素与锂盐中金属元素的摩尔比为1:1-1.2，进行高温固化反应，得富锂锰基正极材料，即的锂电池微纳米正极材料。
本发明所述的一种制备锂电池正极材料的前驱体微纳米粒子的方法，无需预先合成晶种，反应条件温和、采用水相体系、工艺简单、过程连续，制备得到高容量、高倍率、高一致性的正极材料前驱体，正极材料前驱体粒径、形貌一致性好，材料达到分子或原子线度化学计量比混合，无团聚，粒子产率高、批次产品一致性好，结果重复稳定。
本发明所述的一种制备锂电池正极材料的前驱体微纳米粒子的方法，通过改变流入微通道反应器各个入口处液体的流量、注入压力、微通道反应通道的内径、长度等参数，可生产不同粒径的微米、纳米粒子。
本发明所述的一种制备锂电池正极材料的前驱体微纳米粒子的方法，制得的正极材料前驱体可以分类为微米颗粒和纳米硅颗粒，微米粒径范围0.1um-500um，纳米硅颗粒粒径范围10nm-1000nm。
作为上述实施例的优选，步骤(1)中，金属盐为硫酸盐、硝酸盐、乙酸盐、或盐酸盐；
步骤(2)中，可溶性碱为碳酸氢铵、氢氧化钠、8-羟基喹啉、碳酸钠、氨水、氢氧化钾；；
步骤(5)中，锂盐为氢氧化锂、乙酸锂、草酸锂、碳酸锂中的至少一种；
镍盐、钴盐、锰盐中的金属离子的摩尔比5-8:2-1:3-1；
镍盐、钴盐、铝盐中的金属离子的摩尔比5-8:3-1.5:2-0.5。
作为上述实施例的优选，本发明的实施例提供的制备锂电池正极材料的前驱体微纳米粒子的方法，采用微通道反应器进行作业。
制备混合盐溶液中，所述的金属盐为可溶性金属盐，锰盐可以是硫酸锰、硝酸锰、氯化锰、乙酸锰中的一种或其混合盐；镍盐可以是硫酸镍、硝酸镍、氯化 镍、乙酸镍中的一种或其混合盐；钴盐为硫酸钴，硝酸钴、氯化钴中的一种或其混合盐。
本发明中所述的锂电池微纳米正极材料为三元正极材料时，锂盐有两种加入方式：①锂盐在制备盐溶液时加入，那么制备出前驱体后直接进行高温固化反应；②锂盐在制备出前驱体后再加入。
本发明中所述的锂电池微纳米正极材料为富锂锰基正极材料时，在制备盐溶液时就要加入锂盐，金属盐中Li：Mn+Ni+Co的摩尔比为3:2，Mn元素占(Mn+Ni+Co)元素的50％-90％；制备出前驱体后，还要加入锂盐，进行高温固化反应。
图14为本申请的微通道反应器、陈化管式反应器和陈化罐。图中，A为液体进口通道Ⅰ，B为液体进口通道Ⅱ，C为反应通道，D为陈化管式反应器，E为陈化罐，F为微通道反应器单元。
在了解了上述方法等之后，下面将结合具体实施例和图12、图14对本发明一种锂电池微纳米正极材料的制备方法做进一步的详细介绍：
实施例1.
工艺流程如图12所示，具体操作步骤如下：
(1)制备混合盐溶液：
将硝酸镍、硝酸钴、硫酸铝(Al2(SO4)3)按照镍:钴：铝＝8:1.5:0.05的摩尔比混合，并完全溶解于水中，制备成金属离子浓度为0.25mol/L的混合盐溶液；
(2)制备碱溶液：
将碳酸氢铵完全溶解于水中，制成1mol/L的碱溶液；
(3)在25℃下，将混合盐溶液和碱溶液分别注入微通道反应器进行反应，再通过陈化管式反应器继续反应后，流入陈化罐常压搅拌陈化2h，得共沉淀反应混合物。
由于锂电池正极材料生产中的原材料锂盐、镍盐、钴盐等，以及沉淀剂、络合剂、氧化剂是强酸和强碱，因此，本发明微通道反应器的基材为耐腐蚀的蓝宝石、陶瓷、合金、玻璃，优选为蓝宝石。本实施例的基材为蓝宝石。微通道反应器包括两块封板和1-100片微通道板，微通道板上设置2-1000条微通道。
所述微通道反应器为T型微通道反应器(如图14所示)，包括液体进口通道Ⅰ，液体进口通道Ⅱ和反应通道，反应通道的出口端与陈化管式反应器连通；液 体进口通道的直径为1mm；反应通道内径为1mm，长度为10mm；陈化管式反应器的长度为50mm。本发明选择T型微通道反应器，并对液体进口通道、反应通道和陈化管式反应器的尺寸进行限制，可以有效避免反应液体反混，避免管道堵塞，同时保证反应完全。
通过釆用微通道反应器共沉淀法制备三元正极材料前驱体，改善了三元正极材料前驱体的物化性能，可以提高镍钴铝三元正极材料的堆积密度和循环性能。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤4次，再置于烘箱中，在80℃-200℃下真空干燥24h，得三元正极材料前驱体；
(5)将三元正极材料前驱体与氢氧化锂混合均匀，Li:(Ni+Co+Al)的摩尔比为1.2:1，再在氧气气氛中，500℃预烧5h后，在900℃煅烧24h，得到正极材料LiNi0.8Co0.15Al0.05O2，简称NCA811，即所述的锂电池微米正极材料。
本实施例制备的产品为微米颗粒，10um粒径的微米颗粒产率为91％。
常规制备方法制备的产品中，10um粒径的微米颗粒产率为32％，需要进一步的打磨粉碎，筛分。
本发明实施例所述的一种锂电池微米正极材料的制备方法，可连续制备锂电池正极材料前驱体微纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
实施例2.
具体操作步骤如下：
(1)制备混合盐溶液：
将硫酸镍(NiSO4)、硫酸钴(CoSO4)、硫酸锰(MnSO4)按Ni:Co:Mn＝8:1:1的摩尔比混合，并完全溶解于水中，制备成金属离子浓度为1mol/L的混合盐溶液。
(2)制备碱溶液：
将氢氧化钠完全溶解于水中，制成2mol/L的碱溶液。
(3)在50℃下，将混合盐溶液和碱溶液注入微通道反应器进行反应，再通过陈化管式反应器继续反应后，流入陈化罐常压搅拌陈化3h，得共沉淀反应混合物。
微通道反应器的基材为耐腐蚀的陶瓷，包括两块封板和5-20片微通道板，微通道板上设置20-100条微通道。
微通道反应器为T型微通道反应器(如图14所示)，包括液体进口通道Ⅰ，液体进口通道Ⅱ和反应通道，反应通道的出口端与陈化管式反应器连通。微通道反应器中反应通道的直径与进口通道直径相同，液体进口通道的直径为0.01-1mm；反应通道内径为0.01-1.5mm，长度为10-200mm；陈化管式反应器的长度为50-5000mm，根据所需求产品的粒径和形貌选择合适的微通道设计。本发明选择T型微通道反应器，并对液体进口通道、反应通道和陈化管式反应器的尺寸进行限制，可以有效避免反应液体反混，避免管道堵塞，同时保证反应完全。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤3次，再置于烘箱中，在200℃下真空干燥12h，得三元正极材料前驱体。
(5)将三元正极材料前驱体与氢氧化锂(LiOH)混合均匀，Li:(Ni+Co+Mn)的摩尔比为1.1:1，再在氧气气氛中，300℃预烧20h后，在700℃煅烧40h，得到未包覆的正极材料LiNi0.8Co0.1Mn0.1，简称NCM811，即所述的锂电池微米正极材料。
本实施例制备的产品为微米颗粒，5um粒径的微米颗粒产率为92％。
常规制备方法制备的产品中，5um粒径的微米颗粒产率为31％，需要进一步的打磨粉碎，筛分。
本发明实施例所述的一种锂电池微米正极材料的制备方法，可连续制备锂电池正极材料前驱体微纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
实施例3.
具体操作步骤如下：
(1)制备混合盐溶液：
将硫酸镍(NiSO4)、硫酸钴(CoSO4)、硫酸锰(MnSO4)按Ni:Co:Mn＝6:2:2的摩尔比混合，并完全溶解于水中，制备成金属离子浓度为2mol/L的混合盐溶液。
(2)制备碱溶液：
将氢氧化钾完全溶解于水中，制成5mol/L的碱溶液。
(3)在80℃下，将混合盐溶液和碱溶液注入微通道反应器进行反应，再通过陈化管式反应器继续反应后，流入陈化罐常压搅拌陈化10h，得共沉淀反应混合物。
微通道反应器的基材为耐腐蚀的玻璃，包括两块封板和1-100片微通道板，微通道板上设置2-1000条微通道；优选的，微通道反应器包括5-20片微通道板，微通道板上设置20-100条微通道。
所述微通道反应器为T型微通道反应器(如图14所示)，包括液体进口通道Ⅰ，液体进口通道Ⅱ和反应通道，反应通道的出口端与陈化管式反应器连通。微通道反应器中反应通道的直径与进口通道直径相同或不同，液体进口通道的直径为0.01-1mm；反应通道内径为0.01-1.5mm，长度为10-200mm；陈化管式反应器的长度为50-5000mm。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤4次，再置于烘箱中，在150℃下真空干燥18h，得三元正极材料前驱体。
(5)将三元正极材料前驱体与乙酸锂混合均匀，Li:(Ni+Co+Mn)的摩尔比为1.1:1，再在氧气气氛中，500℃预烧5h后，在900℃煅烧24h，得到未包覆的正极材料LiNi0.6Co0.2Mn0.2O2，简称NCM622，即所述的锂电池纳米正极材料。
本实施例制备的产品为纳米颗粒，400nm粒径的纳米颗粒产率为94％。
常规制备方法制备的产品中，400nm粒径的纳米颗粒产率为35％，需要进一步的打磨粉碎，筛分。
本发明实施例所述的一种锂电池纳米正极材料的制备方法，可连续制备锂电池正极材料前驱体微纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
实施例4.磷酸铁锂正极材料
具体操作步骤如下：
(1)制备硫酸铁溶液与磷酸混合溶液：
电池级硫酸铁完全溶解于水中，制备成金属离子浓度为2mol/L的混合溶液。磷酸铁与磷酸的摩尔比为1：2；
(2)制备沉淀溶液：
将氢氧化钠完全溶解于水中，制成3mol/L的碱溶液。
(3)在50℃下，将混合盐溶液和碱溶液注入微通道反应器进行反应后，流入陈化罐常压搅拌陈化5h，得共沉淀反应混合物。
本实施例的微通道反应器的基材蓝宝石基材
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤4次，再置于烘箱中，在120℃下真空干燥12h，得纳米磷酸铁锂正极材料前驱体磷酸铁。
(5)将纳米磷酸铁锂正极材料前驱体与碳酸锂混合均匀，Li:Fe的摩尔比为1:1，在600℃预烧2h后，在900℃煅烧2h，得到纳米磷酸铁锂正极材料，即所述的锂电池纳米正极材料。
本实施例制备的产品为纳米颗粒，50nm粒径的微米颗粒产率为90％。
常规制备方法制备的产品中，50nm粒径的微米颗粒产率为40％，需要进一步的打磨粉碎，筛分。
本发明实施例所述的一种锂电池纳米正极材料的制备方法，可连续制备锂电池磷酸铁锂正极材料前驱体磷酸铁纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
实施例5.氧化铝包覆的NCM811
具体操作步骤如下：
(1)制备铝酸钠溶液：
将氢氧化铝加入50℃-90℃的氢氧化钠溶液，氢氧化钠与氢氧化铝摩尔比为1：1，制备成浓度为2mol/L的铝酸钠溶液。
(2)制备悬浮溶液：
将正极材料前驱体纳米镍钴锰粉体加入铝酸钠溶液经搅拌形成均质的悬浮液。
(3)沉淀液制备
将碳酸氢铵完全溶解于水中，制成2mol/L的碱溶液。
(4)在60℃下，将混合悬浮液溶液过滤后和碱溶液注入微通道反应器进行反应，镍钴锰纳米颗粒为晶种，在表面沉淀一层氢氧化铝沉淀，流入陈化罐常压搅拌陈化8h，得氢氧化铝包覆的镍钴锰前驱体混合物。
微通道反应器的基材为耐腐蚀的蓝宝石，其余与实施例3的微通道反应器相同。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤4次，再置 于烘箱中，在200℃下真空干燥18h，得氧化铝包覆镍钴锰三元正极材料前驱体；
(5)将氧化铝包覆的镍钴锰三元正极材料前驱体与碳酸锂混合均匀，Li:(Ni+Co+Mn)的摩尔比为1.2:1，再在氧气气氛中，在500℃预烧8h后，在800℃煅烧20h，得所述的锂电池氧化铝包覆的镍钴锰纳米正极材料。
本实施例制备的产品为微米颗粒，100nm粒径的微米颗粒产率为95％。
常规制备方法制备的产品中，100nm粒径的微米颗粒产率为36％，需要进一步的打磨粉碎，筛分。
本发明实施例所述的一种锂电池氧化铝包覆的纳米正极材料的制备方法，可连续制备锂电池正极材料前驱体氧化铝包覆的纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料包覆的前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
实施例6.
工艺流程如图13所示，具体操作步骤如下：
(1)制备混合盐溶液：
将乙酸锂、氯化镍、氯化钴、氯化铝按Li:Ni：Co：Al＝12：8.5:1.45:0.05的摩尔比混合，并完全溶解于水中，制备成金属离子浓度为1mol/L的混合盐溶液。
(2)制备碱溶液：
将碳酸钠完全溶解于水中，制成2mol/L的碱溶液。
(3)在50℃下，将混合盐溶液和碱溶液注入微通道反应器进行反应，再通过陈化管式反应器继续反应后，流入陈化罐常压搅拌陈化8h，得共沉淀反应混合物。
微通道反应器的基材为耐腐蚀的蓝宝石，其余与实施例3的微通道反应器相同。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤4次，再置于烘箱中，在110℃下真空干燥18h，得三元正极材料前驱体；
(5)将三元正极材料前驱体在氧气气氛中，在500℃预烧8h后，在700℃煅烧20h，得三元正极材料，即所述的锂电池微米正极材料。
本实施例制备的产品为微米颗粒，3um粒径的微米颗粒产率为94％。
常规制备方法制备的产品中，3um粒径的微米颗粒产率为38％，需要进一步的 打磨粉碎，筛分。
本发明实施例所述的一种锂电池微米正极材料的制备方法，可连续制备锂电池正极材料前驱体微纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
实施例7.
工艺流程如图14所示，具体操作步骤如下：
(1)制备混合盐溶液：
将乙酸锂、乙酸钴、乙酸镍、乙酸锰按Li：Ni：Co：Mn＝1.20:0.13:0.13:0.54的摩尔比混合，并完全溶解于水中，制备成金属离子浓度为1mol/L的混合盐溶液。
(2)制备碱溶液：
将碳酸钠完全溶解于水中，制成2mol/L的碱溶液。
(3)在60℃下，将混合盐溶液和碱溶液注入微通道反应器进行反应，再通过陈化管式反应器继续反应后，流入陈化罐常压搅拌陈化7h，得共沉淀反应混合物。
微通道反应器的基材为耐腐蚀的蓝宝石，其余与实施例3的微通道反应器相同。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤3次，再置于烘箱中，在140℃下真空干燥16h，得前驱体；
(5)将前驱体与碳酸锂混合均匀后，前驱体中除锂元素外的金属元素与锂盐中金属元素的摩尔比为1:1.2，再在氧气气氛中，在500℃预烧8h后，在800℃煅烧20h，得富锂锰基正极材料，即所述的锂电池纳米正极材料。
本实施例制备的产品为纳米颗粒，800nm粒径的纳米颗粒产率为93％。
常规制备方法制备的产品中，800nm粒径的纳米颗粒产率为34％，需要进一步的打磨粉碎，筛分。
本发明实施例所述的一种锂电池纳米正极材料的制备方法，可连续制备锂电池正极材料前驱体微纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
实施例8.
工艺流程如图14所示，具体操作步骤如下：
(1)制备混合盐溶液：
将乙酸锂、乙酸钴、乙酸镍、氯化锰按Li：Ni：Co：Al＝15：1:1:8的摩尔比混合，并完全溶解于水中，制备成金属离子浓度为1mol/L的混合盐溶液。
(2)制备碱溶液：
将碳酸钠完全溶解于水中，制成2mol/L的碱溶液。
(3)在60℃下，将混合盐溶液和碱溶液注入微通道反应器进行反应，再通过陈化管式反应器继续反应后，流入陈化罐常压搅拌陈化7h，得共沉淀反应混合物。
微通道反应器的基材为耐腐蚀的蓝宝石，其余与实施例3的微通道反应器相同。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤3次，再置于烘箱中，在140℃下真空干燥16h，得前驱体；
(5)将前驱体与碳酸锂混合均匀后，前驱体中除锂元素外的金属元素与锂盐中金属元素的摩尔比为1:1，再在氧气气氛中，在400℃预烧8h后，在800℃煅烧20h，得富锂锰基正极材料，即所述的锂电池微米正极材料。
本实施例制备的产品为微米颗粒，4um粒径的微米颗粒产率为92％。
常规制备方法制备的产品中，4um粒径的微米颗粒产率为32％，需要进一步的打磨粉碎，筛分。
实施例9：纳米氧化钛
(1)制备硫酸氧钛溶液，氧化钛加入稀硫酸溶液中，制备成钛离子浓度2mol/L的硫酸氧钛溶液。
(2)制备沉淀剂，制备4mol/L的氨水溶液。
(3)在常温下，将硫酸氧钛溶液与沉淀剂氨水溶液注入微通道反应器进行沉淀反应，控制反应速度，使沉淀物晶体形成特定的大小和形貌。反应混合物流出微通道反应器进入陈化罐陈化4小时。
将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤3次，再置于烘箱中，在140℃下真空干燥6h，得到纳米氧化钛粒子。
实施例10：纳米铁氧体制备
(1)制备盐溶液，将硫酸铁、硫酸锰、硫酸锌或硫酸铁、硫酸镍、硫酸锌等组合的铁氧体成分配比，按照一定的摩尔比溶于去离子水中，配比为金属离子液浓度2mol/L的混合溶液。
(2)制备沉淀液，将可溶性碱溶液如氢氧化钠、碳酸氢铵等溶于去离子水中，碱离子浓度2mol/L的溶液。
(3)在10℃至80℃下，将混合盐溶液和沉淀液注入微通道反应器进行反应，再通过陈化管式反应器继续反应后，流入陈化罐常压搅拌陈化2h，得共沉淀反应混合物。
微通道反应器的基材为耐腐蚀的蓝宝石，其余与实施例3的微通道反应器相同。
(4)将沉淀反应混合物固液分离后，将固体物质用去离子水洗涤3次，再置于烘箱中，在140℃下真空干燥16h，得到高分散、高一致性的微纳米铁氧体粉体颗粒。
本发明实施例所述的一种锂电池微米正极材料的制备方法，可连续制备锂电池正极材料前驱体微纳米粒子，条件温和、采用水相体系、工艺简单、锂电池正极材料前驱体形貌可控、粒子产率高、批次产品一致性好、过程连续，适宜大规模生产。
进一步说明，虽然术语第一、第二等在本文中可以用于描述各种元件，但是这些术语不应该限制这些元件。这些术语仅用于区别一个元件与另一元件。例如，第一元件可以被称为第二元件，并且，类似地，第二元件可以被称为第一元件，这些术语仅用于区别一个元件与另一元件。这没有脱离示例性实施例的范围。类似地，元件一、元件二也不代表元件的顺序，这些术语仅用于区别一个元件与另一元件。如本文所用，术语“和/或”包括一个或多个相关联的列出项目的任意结合和所有结合。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限 制，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (10)

  1. 一种微通道反应器，其特征在于，包括：上封板、基板一、基板二和下封板；
    所述上封板、所述基板一、所述基板二和所述下封板从上至下依次贴合设置；
    所述上封板的下侧面设置有进料主槽一和进料支槽一；
    所述基板一的上侧面设置有进料主槽二和进料支槽二；
    所述上封板与所述基板一相互密封贴合固定；所述进料主槽一与所述进料主槽二相互对应，形成进料主通道一；所述进料支槽一与所述进料支槽二相互对应，形成进料支通道一；所述进料支通道一的一端与所述进料主通道一连通，另一端为封闭状；所述进料支通道一为多个；多个所述进料支通道一规则分布；
    所述基板二的下侧面设置有进料主槽三和进料支槽三；
    所述进料支槽二与所述进料支槽三之间设置有通孔；所述通孔连通所述进料支槽二与所述进料支槽三；
    所述下封板的上侧面设置有进料主槽四和进料支槽四；
    所述下封板与所述基板二相互密封贴合固定；所述进料主槽三与所述进料主槽四相互对应，形成进料主通道二；所述进料支槽三与所述进料支槽四相互对应，形成进料支通道二；所述进料支通道二的一端与所述进料主通道二连通，另一端延伸向所述基板二的外缘；所述进料支通道二为多个；所述进料支通道二与所述进料支通道一对应分布。
  2. 根据权利要求1所述的微通道反应器，其特征在于，
    所述基板一与所述基板二为一体化板件；
    所述板件为多个；多个所述板件上下叠加密封贴合；
    所述板件之间通过高温键合。
  3. 根据权利要求1所述的微通道反应器，其特征在于，
    所述通孔为多个；多个所述通孔沿所述进料支通道一的方向间隔设置；
    所述通孔的直径沿所述进料支通道一的流通方向逐渐变大。
  4. 根据权利要求1所述的微通道反应器，其特征在于，
    所述上封板为蓝宝石材质、陶瓷材质和合金材质中的一种；
    所述基板一、所述基板二和所述下封板与所述上封板的材质相同。
  5. 一种制备锂电池负极材料的前驱体微纳米粒子的方法，其特征在于，
    (1)将高纯四氯化硅或三氯氢硅加温至1000℃；
    (2)将高纯氢气加温至1000℃；
    (3)将高纯四氯化硅与高纯氢气或三氯氢硅与高纯氢气分别输送到微通道反应器的进料主通道一和进料主通道二；微通道反应器处于1380℃的恒温中；四氯化硅与氢气的摩尔比为1：2～1：2.5；
    或将三氯氢硅与高纯氢气分别输送到微通道反应器的进料主通道一和进料主通道二；微通道反应器处于1100℃的恒温中；三氯氢硅与氢气的摩尔比为1：1～1：1.2；
    (4)气体在微通道反应器中高温反应，生成纳米硅和氯化氢气体；
    (5)纳米硅和氯化氢气体经过快速降温、气固分离，得到纳米硅颗粒。
  6. 一种制备锂电池负极材料的前驱体微纳米粒子的方法，其特征在于，
    (1)制备纳米硅与硅酸钠溶液的悬浮液；
    (2)制备沉淀剂；沉淀剂为氯化盐、硫酸盐和硝酸盐的水溶液，所述水溶液能够使硅酸钠溶液发生化学沉淀反应生成硅酸盐沉淀物；沉淀剂或是盐酸、硫酸、硝酸、碳酸、草酸中任一种与硅酸钠发生化学沉淀反应生成二氧化硅沉淀的酸溶液；
    (3)将悬浮液和沉淀剂分别输入微通道反应器的进料主通道一和进料主通道二；悬浮液和沉淀剂在微通道反应器中交汇发生沉淀反应，沉淀反应以纳米硅为晶种，纳米硅表面沉淀硅酸盐或二氧化硅；硅酸钠与沉淀剂摩尔比为1：1；
    (4)反应物经固液分离、清洗、烘干；
    (5)在500℃～1200℃之间缓慢升温煅烧，得到有亚硅酸盐和氧化亚硅包覆的高分散的纳米硅颗粒或二氧化硅和氧化亚硅包覆的高分散的纳米硅颗粒。
  7. 根据权利要求6所述的一种制备锂电池负极材料的前驱体微纳米粒子的方法，其特征在于，
    采用权利要求1-4任一项所述的微通道反应器进行作业；
    采用权利要求5所述的方法制备纳米硅颗粒。
  8. 一种制备锂电池正极材料的前驱体微纳米粒子的方法，其特征在于，所述 锂电池正极材料有三元正极材料、富锂锰基正极材料、磷酸铁锂正极材料，其制备方法包括以下步骤：
    (1)制备混合盐溶液：
    将金属盐完全溶解于水中，制成金属离子浓度为0.25-2mol/L的盐溶液，得混合盐溶液；所述金属盐为镍盐、钴盐、铝盐，或镍盐、钴盐、铝盐、锂盐，或镍盐、钴盐、锰盐，或镍盐、钴盐、锰盐、锂盐；
    其中，所述锂电池微纳米正极材料为三元正极材料时，所述镍盐、钴盐、铝盐或锰盐中的金属离子的摩尔比为Ni：Co：Al或Mn＝5-9：0.05-3：0.05-3；或Ni:Co:Mn＝5-9：0.05-3：0.05-3；其中Ni+Co+Al＝10或Ni+Co+Mn＝10；所述锂盐与除锂盐外的金属盐中的金属离子的摩尔比为Li：Ni+Co+Al或Mn＝1-1.2:1；
    所述锂电池微纳米正极材料为富锂锰基正极材料时，所述金属盐中金属离子的摩尔比为Li：Mn+Ni+Co＝3:2，Mn：Ni+Co＝5-9:1-5；
    (2)制备碱溶液：
    将可溶性碱完全溶解于水中，制成可溶性碱溶度为1-5mol/L的溶液，得碱溶液；所述可溶性碱为碳酸氢铵、氢氧化钠、8-羟基喹啉、碳酸钠、氨水、氢氧化钾中的一种；
    (3)在10-80℃下，将混合盐溶液和碱溶液注入微通道反应器的进料主通道一和进料主通道二；混合盐溶液和碱溶液在微通道反应器中交汇发生沉淀反应，经历晶种生成到晶体生长过程，在晶体生长到一定程度时，混合反应的流体及时流出微通道反应器，流入管式反应器继续加温加速反应，晶体生长到设计要求时，流入陈化罐常压搅拌陈化2-10h，得共沉淀反应混合物；
    (4)将沉淀反应混合物固液分离后，将固体物质洗涤3-4次，再干燥，得前驱体；
    (5)所述锂电池微纳米正极材料为三元正极材料，混合盐溶液中包括锂盐时，将前驱体进行高温固化反应，得三元正极材料，即所述的锂电池微纳米正极材料；
    所述混合盐溶液中不包括锂盐时：将前驱体与锂盐混合均匀，前驱体与锂盐中的金属元素的摩尔比为1:1-1.2，进行高温固化反应，得三元正极材料，即所述的锂电池微纳米正极材料；
    所述锂电池微纳米正极材料为富锂锰基正极材料时，将前驱体与锂盐混合均 匀，前驱体中除锂元素外的金属元素与锂盐中金属元素的摩尔比为1:1-1.2，进行高温固化反应，得富锂锰基正极材料，即所述的锂电池微纳米正极材料。
  9. 根据权利要求7所述的制备锂电池正极材料的前驱体微纳米粒子的方法，其特征在于，
    所述步骤(1)中，所述金属盐为硫酸盐、硝酸盐、乙酸盐、或盐酸盐；
    所述步骤(2)中，所述可溶性碱为碳酸氢铵、氢氧化钠、8-羟基喹啉、碳酸钠、氨水、氢氧化钾；
    所述步骤(5)中，所述锂盐为氢氧化锂、乙酸锂、草酸锂、碳酸锂中的至少一种；
    所述镍盐、钴盐、锰盐中的金属离子的摩尔比为5-8:2-1:3-1；
    所述镍盐、钴盐、铝盐中的金属离子的摩尔比为5-8:3-1.5:2-0.5。
  10. 根据权利要求8-9任一项所述的制备锂电池正极材料的前驱体微纳米粒子的方法，其特征在于，采用权利要求1-4任一项所述的微通道反应器进行作业。
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