CN2423660Y - Manufacturing equipment for positive material of lithium ion battery - Google Patents

Abstract

A kind of manufacturing equipment of positive electrode material of lithium ion battery, comprises feeding tank, reaction kettle, centrifuge and pyrolysis device, feeding tank is connected with feeding pipe and leads into reaction kettle, and feeding pipe is provided with pressurizing pump; The end of the feeding pipe inside is provided with nozzles, one of which is placed in the lower part of the reaction kettle, the nozzle on it is upwards, the nozzles on the other feeding pipes are arranged in the upper part, the nozzles on it are downwards, and the material outlet of the reaction kettle is located at the bottom of the reactor. On the wall above the nozzle of the upper feeding pipe, a pipeline is provided on the material outlet leading into the centrifuge; the centrifuge is connected to the thermal decomposer. The positive electrode material produced by this equipment has remarkable characteristics such as reasonable crystal size, crystal defects, high electrochemical activity, and stable crystal form.

Description

Lithium-ion battery cathode material preparation equipment

The utility model relates to a manufacturing device of a positive electrode material of a lithium ion battery. Specifically, it is a device for manufacturing high-performance lithium-ion battery cathode materials.

Lithium ion cathode materials that have been commercialized include lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), etc., which are the positive electrode active materials of lithium ion rechargeable batteries. Its performance directly determines the capacity and performance of lithium-ion rechargeable batteries. Since the early 1990s, countries around the world have conducted a lot of research on synthesizing them and improving their performance. There are mainly two types of manufacturing methods:

One is the solid-phase thermal synthesis method, using their carbonates or their hydroxides, or their oxides, mechanically mixing according to the stoichiometric ratio, and then burning at high temperature. For example, Sony Corporation of Japan used LiOH and CoO as raw materials to burn LiCoO ₂ at 700°C. Gumman et al. used Li ₂ CO ₃ and CoCO ₃ as raw materials to synthesize LiCoO ₂ at 400°C. Shuji Yamada et al. used LiOH·H ₂ O and Ni(OH) ₂ are mechanically mixed according to Li/Ni=1:1, and then LiNiO ₂ is prepared at 500°C-900°C.

This type of method is characterized by the synthesis of positive electrode materials such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide through high-temperature thermal decomposition. The method is simple and the process is short. The disadvantage is that this kind of method uses solid raw materials, and after mechanical mixing, the product is synthesized by solid phase diffusion between particles at high temperature. Therefore, it cannot be mixed uniformly, and the synthesized product has uneven crystal form and poor particle characteristics. . Because the characteristics of the product synthesized by this method, such as particle size distribution, purity and specific gravity, etc., depend on the particle characteristics of the raw material itself, the particle size, distribution, specific gravity and purity of the raw material determine the particle size distribution, specific gravity and other characteristics of the final product. Therefore, the particle size and performance of the product cannot be stably controlled, and the randomness is large. In most cases, the particle size distribution is wide, the specific gravity is small, the electrochemical capacity is low, and the product uniformity is poor.

The other is the liquid-phase synthesis method, and R. Yazami et al. have studied a low-temperature synthesis method. Add the cobalt acetate suspension to the lithium acetate solution under vigorous stirring, and then treat it at 550°C for at least 2 hours. The obtained material has a monodisperse particle shape, a large specific surface area, good crystallization and a stoichiometric composition. .

Zhang Fuping and others mixed Li(NO ₃ ) and Co(NO ₃ ) ₂ ·6H ₂ O according to the measurement, added an appropriate amount of tartaric acid, adjusted the pH to 6-8 with ammonia water, and heated at 900°C for 27 hours to obtain hard gray-black LiCoO. ₂ .

This type of method has changed the phenomenon of uneven mixing between solid phase particles and particles at high temperature, but it still does not provide reliable equipment and methods to control the crystallization of reactants in the solution system, and still cannot produce uniform particle size and complete crystallization. positive electrode material.

The purpose of the utility model is to improve the deficiencies of the prior art, and propose a device for preparing positive electrode materials with homogeneity and crystallization, internal crystal defects, uniform particle size, high specific gravity, high purity, and large discharge specific capacity.

Carbonate and or hydroxide composite crystals of lithium or doped lithium and cobalt or nickel or manganese deposited by atomization hydrolysis, followed by gradient thermal decomposition into _LiCoO2 or LiNiO at stable multi-stage temperatures under an oxygen atmosphere ₂ or LiMn ₂ O ₄ or doped LiCoO ₂ or LiNiO ₂ or LiMn ₂ O ₄ can produce positive electrode materials with the above characteristics.

The equipment used to prepare the above-mentioned lithium-ion battery cathode material includes a feeding tank, a reaction kettle, a centrifuge and a thermal decomposer, the feeding tank is connected with a feeding pipe, and the feeding pipe is passed into the reaction kettle. The feeding pipe is provided with a pressurizing pump; the reactor is a jacketed container, and the end of each feeding pipe located in the reactor is provided with a shower nozzle, and one of the nozzles on the feeding pipe (i.e. spraying lye) nozzle) is placed in the bottom of the reaction kettle, the nozzle on it is upward, the nozzle on the other feeding pipe is arranged on the top of the reaction kettle, the nozzle on it is downward, and the material outlet of the reaction kettle is arranged on the upper feeding pipe On the wall above the nozzle, a stirrer is set in the reaction kettle, and a pipeline is set on the material outlet to lead to the centrifuge; the centrifuge is provided with a discharge port, which is connected to the transmission path and the thermal decomposer. .

The spray head is a conical spray head or a multi-pipe spray head or a porous coil. The agitator is composed of an agitator rod and a stirring blade fixed thereon. Two kinds of agitating blades are fixed on the upper and lower parts of the agitator. Be framed or anchored. The propeller-type stirring blade is preferably fixed on the upper part of the stirrer rod, and the anchor-type stirring blade is fixed on the lower part. The thermal decomposer is a horizontal multi-stage timing and temperature-controlled continuous boat-pushing furnace.

In the device used for the reaction, the lithium salt, lye nickel salt or cobalt salt or manganese salt feeding ports are respectively placed in the reactor, and the best configuration is that the lye feeding nozzle is below the reactor, and the other feeding nozzles are at the bottom of the reactor. above. When spraying the reaction liquid in the reaction kettle, the lye is sprayed from bottom to top, and other reaction liquids are sprayed from top to bottom, and the crystallized crystals are discharged from the outlet on the wall of the reaction kettle higher than the upper spray port; The stirring in the reactor, the liquid in the upper part of the reactor is in the form of axial flow, and the liquid in the lower part is in the form of radial flow.

When producing high-performance lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide and other positive electrode materials, the raw materials lithium salt, cobalt salt or nickel salt or manganese salt and lye are respectively loaded into the feeding tank, and then fed into a jacketed The reaction is carried out in a heated reactor, and the reaction product is separated and washed by a centrifuge, and then the product is thermally decomposed in a horizontal boat pusher furnace, and finally the product lithium cobalt oxide or lithium nickel oxide or lithium manganese oxide is obtained.

The spray feeding device provided by the utility model adopts the atomization hydrolysis method, and the reaction raw materials are evenly added into the reactor by spraying, and the alkali spray nozzle sprays the alkali liquid mist upward, and other raw materials are sprayed downward, which makes the crystallization process more efficient. All kinds of raw materials are evenly distributed in the tank, and the design of the stirrer with different types of stirring blades on the top and bottom makes the solution in the reactor mix more evenly, and at the same time, by adjusting the reaction parameters, such as PH value, reaction temperature, reaction time, etc., the crystallization can be guaranteed. The particle size distribution is uniform and the specific gravity is large. The third is that when the composite crystal is decomposed under a gradient temperature at a high temperature in the thermal decomposition equipment, due to the different decomposition characteristics of carbonate and hydroxide, the decomposition product has lattice defects and a huge internal pore volume, so it has a larger specific surface area and higher capacitance.

Below by embodiment and accompanying drawing, the utility model will be further described.

The drawings of the accompanying drawings of the utility model are described as follows:

Fig. 1 is the utility model reaction device schematic diagram;

Example:

As shown in Figure 1, the device used to prepare the positive electrode material of lithium-ion batteries consists of a feeding tank 1, a reaction kettle 3, a centrifuge 9 and a horizontal push boat furnace 10, and the raw materials lithium salt, cobalt salt or nickel salt or manganese salt and lye are respectively loaded into the feeding tank 1, the feeding tank can be selected as a 1.5 cubic meter tank, and after being pressurized by the booster pump 2, it is sent into the reactor 3 for reaction. The reactor 3 can be 2.5 cubic meters, and the reactor 3 peripherals Jacket 4 is used to control the reaction temperature with water or steam, and is equipped with a pH value inspection port. The lye feeding nozzle 5 is placed below the reactor 3, and the lithium sulfate and dopant solution and the cobalt sulfate solution feeding nozzle 6 are arranged above the reactor. Cone nozzle is used for the feeding port, and the material is ejected by pressure. Other types of nozzles or porous tubes or porous coils can also be used to make small holes instead of cone nozzles to eject materials. A discharge port 7 is arranged above the raw material inlet, from which the reaction product overflows. In order to control the residence time of the reactants, multiple discharge ports 7 may also be provided. The material is stirred and mixed, and the reaction will be more uniform. There is a stirrer in the center of the reaction kettle 3, and a propeller 8' is installed on the upper part to make the material move up and down in the axial direction, and the anchor stirrer 8 is installed on the lower part to make the material move radially. The crystallized crystals are discharged from the reaction kettle 3 through the upper outlet 7, and the product is separated, washed and dried by a centrifuge 9 to obtain wet lithium cobalt oxygen or lithium nickel oxygen or lithium manganese oxygen. After that, the product enters the horizontal Multi-stage timing temperature control continuous boat pushing furnace 10 thermally decomposes and packs to obtain products. Agitator 6, centrifuge 9, pressurizing pump 2 and horizontal multi-stage timing temperature control continuous boat pushing furnace 10 etc. all have ready-made technology in this cover device, can learn from, do not do detailed description.

Lithium sulfate solution mixed with dopant, cobalt sulfate solution and lye are respectively placed in the feeding tank and sprayed into the reaction kettle at a certain speed through a booster pump, wherein the nozzle of lye is sprayed from bottom to top , the nozzles of other materials are on the upper part, spray from top to bottom, and the agitator rotates during the reaction process. The crystallized crystals overflow through the upper discharge port, enter the centrifuge for separation, and then enter the pusher boat furnace, where they move continuously on the conveyor belt, thermally decompose at 400°C in the first stage control room for 24 hours, and then go to the second stage Thermal decomposition at 800°C in the second-stage control room for 15 hours, the dissolved oxygen amount is 2M ³ /hour.

Claims (5)

1, a kind of used equipment of anode material for lithium-ion batteries for preparing, it is characterized in that: include charging spout (1), reactor (3), centrifuge (9) and thermal decomposer (10), described charging spout (1) connects charge pipe, described charge pipe feeds in the described reactor (3), be provided with force (forcing) pump (2) on described charge pipe: described reactor (3) is a jacketed vessel, the termination of each charge pipe in being located at reactor (3) is provided with shower nozzle (5), one of them places the bottom of reactor shower nozzle on the described charge pipe, shower nozzle on it upwards, shower nozzle on other charge pipe is located at the top of reactor, shower nozzle on it is downward, the material outlet of described reactor is located on the wall of top of described top charge pipe shower nozzle, establishes pipeline on the described material outlet (7) and leads in the described centrifuge (9); Establish blender in the described reactor, described centrifuge is established discharging opening, connects drive access and is connected with described thermal decomposer (10).

2, equipment according to claim 1 is characterized in that: described shower nozzle (5) is circular cone shower nozzle or multitube shower nozzle or porous coil pipe.

3, equipment according to claim 1, it is characterized in that: described blender is made up of blender bar and solid paddle thereon, the upper and lower of described blender sets firmly two kinds of paddles, the paddle (8 ') on described top is oar formula or propeller type, and the paddle of bottom (8) is frame or anchor formula.

4, equipment according to claim 3 is characterized in that: described blender bar top sets firmly propeller type paddle (8 '), and the bottom sets firmly anchor formula paddle (8).

5, equipment according to claim 1 is characterized in that: described thermal decomposer is that horizontal multistage timing temperature control pushes away boat stove (10) continuously.

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