Sodium-ion battery positive electrode material synthesizer
Through spray granulation and multi-layer sintering disk devices, the high consumption and bonding problems during the sintering process of sodium ion battery positive electrode materials are solved, achieving a more uniform sintering environment and higher production efficiency.
Patent Information
- Application Number
- CN202421624932.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-10
- Publication Date
- 2025-05-27
- Estimated Expiration
- 2034-07-10
AI Technical Summary
The existing sodium ion battery positive electrode materials consume a large amount of protective gas during the sintering process, and the materials are prone to bond to form agglomeration, which affects the sintering quality and equipment maintenance costs.
A device using spray granulation and multi-layer sintering disks is used to form a uniform powder by spray granulation, and multiple sintering disks are used to ensure uniform heating during the sintering process, avoiding material accumulation and bonding.
It reduces the consumption of protective gas, improves the uniformity of the sintering environment, reduces the risk of material bonding, and improves material utilization and production efficiency.
Smart Images
Figure CN222912306U_ABST
Abstract
Description
Technical Field
[0001] The utility model relates to a synthesis device for a positive electrode material of a sodium-ion battery, belonging to the technical field of battery production. Background Art
[0002] In the prior art, orbital vacuum furnaces and rotary furnaces are widely used in the preparation of positive electrode materials for sodium-ion batteries. Due to its design features, the orbital vacuum furnace has a large furnace length and space, resulting in a large consumption of protective gas during the sintering process to maintain the purity of the furnace environment. This high consumption not only increases the production cost but also poses a challenge to the effective utilization of resources. In contrast, although the rotary furnace can reduce the consumption of protective gas to a certain extent, the internal drum structure of the rotary furnace is prone to cause material agglomeration during the sintering process, especially when dealing with polyanion materials, and the bonding phenomenon is particularly serious. This not only affects the sintering quality of the material but also increases the difficulty and cost of subsequent cleaning work.
[0003] Specifically, when polyanion materials are sintered in an orbital vacuum furnace, due to the uneven temperature distribution in the furnace chamber and the influence of gas flow characteristics, the materials are easily bonded to the bottom of the crucible, forming hard agglomerates that are difficult to remove. In the rotary furnace, due to the rotation of the drum and the change of the temperature in the furnace, the materials are more likely to be bonded inside the drum, forming a continuous agglomerate layer. These agglomeration phenomena not only reduce the utilization rate of the materials but also may cause damage to the sintering equipment and an increase in maintenance costs. Summary of the Utility Model
[0004] To solve the problems in the background art, the utility model provides a synthesis device for a positive electrode material of a sodium-ion battery.
[0005] To achieve the above object, the utility model adopts the following technical solution: A synthesis device for a positive electrode material of a sodium-ion battery includes a spray granulation mechanism and a sintering mechanism; the spray granulation mechanism includes a blower, a heater, a high-speed centrifugal atomizer, a drying chamber, a cyclone separator, and a centrifugal fan; the air outlet end of the blower is communicated with the air inlet end of the heater, and the air outlet end of the heater is communicated with the drying chamber; a high-speed centrifugal atomizer is arranged at the upper end of the drying chamber, the lower end of the drying chamber is communicated with the air inlet end of the cyclone separator through a conveying pipeline, the air outlet end of the cyclone separator is communicated with the air inlet end of the centrifugal fan, and the air outlet end of the centrifugal fan is communicated with a discharge pipeline; the discharge port at the lower end of the cyclone separator is communicated with the sintering mechanism.
[0006] A dust filter screen is arranged at the air inlet end of the blower.
[0007] A circulating cooling pipeline is arranged outside the high-speed centrifugal atomizer.
[0008] An observation window is arranged on the side wall of the drying chamber.
[0009] The discharge port of the cyclone separator is provided with a bottom screen.
[0010] The discharge port of the cyclone separator is provided with a check valve.
[0011] A tail gas dust collection bag is provided between the cyclone separator and the centrifugal fan.
[0012] The sintering mechanism includes a central transmission shaft, a heat preservation housing, a collection hopper and sintering units; an inlet is provided at the upper end of the heat preservation housing, and the inlet is communicated with the discharge port; the lower end of the heat preservation housing is communicated with the collection hopper, and an air inlet and an air outlet are provided on the side wall of the heat preservation housing; a vertically arranged central transmission shaft is rotatably arranged in the heat preservation housing, and multiple groups of sintering units are arranged on the outer side of the central transmission shaft from top to bottom in a matching manner. The feeding end of the sintering unit at the uppermost end is matched with the inlet, and the discharging end of the sintering unit at the lowermost end is matched with the collection hopper.
[0013] Each group of sintering units includes an upper sintering disc, a lower sintering disc, an upper rolling brush and a lower rolling brush. The upper sintering disc and the lower sintering disc are coaxially and rotatably sleeved on the outer side of the central transmission shaft in parallel. The upper sintering disc and the lower sintering disc are both fixedly connected to the heat preservation housing. The diameter of the upper sintering disc is smaller than that of the lower sintering disc. The upper sintering disc is a disc structure with a convex middle part. The upper end of the upper sintering disc is in rolling fit connection with multiple upper rolling brushes. Each upper rolling brush is a spiral structure with the length decreasing from inside to outside in diameter; the lower sintering disc is a disc structure with a concave middle part. The lower sintering disc is in rolling fit connection with multiple lower rolling brushes. Each lower rolling brush is a spiral structure with the length decreasing from outside to inside in diameter; a plurality of material discharging holes are provided in the middle of the lower sintering disc; the inner ends of each upper rolling brush and each lower rolling brush are rotatably connected to the central transmission shaft.
[0014] Compared with the prior art, the beneficial effects of the present utility model are as follows:
[0015] 1. The present utility model first atomizes and then sinters, and uses multiple sintering discs arranged in sequence during the sintering process, ensuring a more uniform sintering environment, and solving the problems of large differences in internal and external atmospheres caused by material accumulation during the traditional sintering process, and thus poor consistency of sintered products.
[0016] 2. The present utility model enables the precursor after spray granulation to be seamlessly docked into the sintering mechanism, realizes a continuous operation mode, omits the cumbersome transfer process, shortens the production cycle, improves the production efficiency, and reduces the production cost. Description of the Drawings
[0017] Figure 1 It is a schematic structural diagram of the synthesis device of the present utility model;
[0018] Figure 2 It is a schematic structural diagram of the sintering mechanism of the synthesis device of the present utility model;
[0019] Figure 3 It is the charge-discharge curve of sodium iron pyrophosphate prepared in Example 1;
[0020] Figure 4 It is the cycle curve of sodium iron pyrophosphate prepared in Example 1;
[0021] Figure 5 It is the charge-discharge curve of sodium vanadium phosphate prepared in Example 2. Specific embodiments
[0022] Next, the technical solutions in the embodiments of the present utility model will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present utility model. Obviously, the described embodiments are only a part of the embodiments of the utility model, rather than all the embodiments. Based on the embodiments in the present utility model, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present utility model.
[0023] A sodium ion battery cathode material synthesis device includes a spray granulation mechanism 100 and a sintering mechanism 200; the spray granulation mechanism 100 includes a blower 102, a heater 103, a high-speed centrifugal atomizer 108, a drying chamber 109, a cyclone separator 111, and a centrifugal fan 113; the air outlet end of the blower 102 is communicated with the air inlet end of the heater 103 of the resistance wire, and the air outlet end of the heater 103 is communicated with the drying chamber 109 through an air supply pipeline 104; the upper end of the drying chamber 109 is provided with a high-speed centrifugal atomizer 108, and the upper end of the high-speed centrifugal atomizer 108 is provided with a feed inlet 107; the lower end of the drying chamber 109 is communicated with the air inlet end of the cyclone separator 111 through a conveying pipeline, the air outlet end of the cyclone separator 111 is communicated with the air inlet end of the centrifugal fan 113, and the air outlet end of the centrifugal fan 113 is communicated with a discharge pipeline 114; the discharge port 117 at the lower end of the cyclone separator 111 is communicated with the sintering mechanism 200.
[0024] The air inlet end of the blower 102 is provided with a dust filter net 101.
[0025] A circulating cooling pipeline is arranged outside the high-speed centrifugal atomizer 108. Cooling water is pumped into the cooling pipeline through a cold water inlet 105, and the cooling water is pumped out through a cold water outlet 106 to cool the high-speed centrifugal atomizer 108 and prevent the electrode from being burned due to excessive temperature.
[0026] The side wall of the drying chamber 109 is provided with an observation window 110. The observation window 110 is convenient for real-time monitoring of the drying process.
[0027] A bottom screen 116 is provided at the discharge port 117 of the cyclone separator 111.
[0028] A check valve 115 is provided at the discharge port 117 of the cyclone separator 111.
[0029] A tail gas dust collection bag 112 is provided between the cyclone separator 111 and the centrifugal fan 113. The tail gas dust collection bag 112 can collect fine dust in the dried tail gas to prevent dust pollution. The tail gas after dust removal is discharged through the discharge pipe 114 by the centrifugal fan 113.
[0030] The sintering mechanism 200 includes a central drive shaft 205, a heat preservation housing 207, a collection hopper 208 and a sintering unit; an inlet 209 is provided at the upper end of the heat preservation housing 207, and the inlet 209 is communicated with the discharge port 117; the lower end of the heat preservation housing 207 is communicated with the collection hopper 208, and an air inlet 201 and an air outlet 202 are provided on the side wall of the heat preservation housing 207; the air inlet 201 is a protective gas inlet channel, and the air outlet 202 is a sintering tail gas discharge channel. The heat preservation housing 207 ensures the stability of the temperature in the sintering mechanism 200; a vertically arranged central drive shaft 205 is rotatably provided in the heat preservation housing 207, and the central drive shaft 205 is driven to rotate by a motor. This is prior art and will not be described in detail here. The motor is fixed on the heat preservation housing 207; a plurality of groups of sintering units are evenly arranged on the outer side of the central drive shaft 205 from top to bottom. The feeding end of the sintering unit at the uppermost end is matched with the inlet 209, and the discharging end of the sintering unit at the lowermost end is matched with the collection hopper 208.
[0031] Each of the sintering units includes an upper sintering plate 203, a lower sintering plate 210, an upper rolling brush 206, and a lower rolling brush 211. The upper sintering plate 203 and the lower sintering plate 210 are coaxially arranged side by side and rotatably sleeved outside the central transmission shaft 205 through bearings. The gap between the upper sintering plate 203 and the lower sintering plate 210 needs to be small enough to ensure that all the powder materials can fall into the lower sintering plate 210. Both the upper sintering plate 203 and the lower sintering plate 210 are fixedly connected to the heat preservation housing 207. The diameter of the upper sintering plate 203 is smaller than that of the lower sintering plate 210. The upper sintering plate 203 has a disc structure with a convex middle part. The upper end of the upper sintering plate 203 is in rolling contact connection with a plurality of upper rolling brushes 206 evenly distributed along its circumference. Each of the upper rolling brushes 206 has a spiral structure with the length decreasing gradually from the inside to the outside; the lower sintering plate 210 has a disc structure with a concave middle part. The lower sintering plate 210 is in rolling contact connection with a plurality of lower rolling brushes 211 evenly distributed along its circumference. Each of the lower rolling brushes 211 has a spiral structure with the length decreasing gradually from the outside to the inside; a plurality of material discharging holes 204 penetrating through its thickness direction are evenly arranged along the circumference of the middle part of the lower sintering plate 210; the inner ends of each upper rolling brush 206 and each lower rolling brush 211 are rotatably connected to the central transmission shaft 205 through bearings.
[0032] The heating temperature range of the heater 103 is 50 - 400 °C.
[0033] The rotation frequency range of the high - speed centrifugal atomizer 108 is 50 Hz - 450 Hz.
[0034] The material of the sintering plate is graphite, alumina, ceramic or other high - temperature - resistant materials. Each sintering plate can independently control the heating temperature, and the heating range is 200 - 1200 °C.
[0035] The protective gas entering the sintering mechanism through the air inlet 201 can be nitrogen, argon, helium, hydrogen - argon mixture, or other inert gases.
[0036] The bottom screen 116 can be replaced with different mesh screens to prevent impurity particles from entering the sintering mechanism.
[0037] A working method of a device for synthesizing a cathode material of a sodium - ion battery according to the present utility model is characterized in that the method includes the following steps:
[0038] S1: Air is inhaled into the heater 103 by the blower 102 to heat the air, prepare the raw material solution, and introduce the protective gas into the heat preservation housing 207;
[0039] S2: The air passes through the heater 103 and enters the drying chamber 109 through the air supply pipeline 104;
[0040] S3: The raw material solution enters the high - speed centrifugal atomizer 108 from the feed inlet 107 for atomization;
[0041] Disperse sodium sources, phosphorus sources, iron sources or vanadium sources, carbon sources, dopants, etc. required for synthesizing the cathode material of the sodium-ion battery in a solvent, and use a peristaltic pump to pump the dispersed solution into the spray granulation mechanism 100 that has been heated to a preset temperature through the feed port 107;
[0042] The sodium source is an inorganic salt or organic sodium salt containing sodium such as sodium carbonate, sodium hydroxide, sodium pyrophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, etc.
[0043] The phosphorus source is a phosphate such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, or phosphoric acid.
[0044] The iron source is an iron-containing oxide or salt such as iron phosphate, iron nitrate, iron powder, ferrous oxalate, iron rust, etc.; the vanadium source is a vanadium-containing oxide or salt such as vanadium pentoxide, ammonium metavanadate, etc.
[0045] The carbon source is one or more of organic substances such as graphene oxide, carbon nanotubes, carbon quantum dots, citric acid, glucose, starch, oleic acid, ethylene glycol, n-propanol, etc.
[0046] The dopant includes one or more of manganese-containing oxides and their salts, aluminum-containing oxides and their salts, magnesium-containing oxides and their salts, sodium fluoride, etc.
[0047] S4: The atomized raw materials are dried into powder in the drying chamber 109 by hot air;
[0048] S5: The dried powder is sucked into the cyclone separator 111 through the conveying pipeline under the action of the centrifugal fan 113, and the completely dried powder settles on the bottom screen 116. The powder collected on the bottom screen 116 is the precursor powder;
[0049] S6: After opening the check valve 115, the dried powder falls through the discharge port 117 and the feed port 209 to the middle of the upper sintering plate 203 of the uppermost sintering unit, and the precursor powder is heated and sintered using the sintering plate under a protective atmosphere;
[0050] S7: The central drive shaft 205 rotates to drive the upper brush 206 and the lower brush 211 to revolve. At the same time, since the upper brush 206 is in contact with the upper sintering plate 203, the upper brush 206 rotates while revolving on the upper sintering plate 203, driving the powder to move outward on the upper sintering plate 203 until the powder falls onto the lower sintering plate 210;
[0051] S8: Since the lower rolling brush 211 is in contact with the lower sintering plate 210, the lower rolling brush 211 rotates around its own axis while revolving on the lower sintering plate 210, driving the powder to move inward. After the powder reaches the feeding hole 204, it falls onto the middle part of the upper sintering plate 203 of the next sintering unit. Control the rotation speed of the central transmission shaft 205 to make the precursor powder flow through the sintering plates at different temperatures at a certain rate in sequence.
[0052] The atomization frequency of the spray drying of the sodium-ion battery cathode material of the polyanion compound is 50 Hz - 400 Hz, and the temperature of the inlet is 80 - 200 °C; the sintering temperature is 200 - 950 °C, the heating rate is 1 - 5 °C / min, and the sintering time is 2 h - 20 h. The sintering time is controlled according to the number of sintering plates and the rotation speed of the rolling brush.
[0053] The dosage of the dopant is 0 wt% - 10 wt%.
[0054] S9: After the powder is sintered by multiple groups of sintering units, it falls into the collection hopper 208. After cooling, the sodium-ion battery cathode material of the polyanion compound is obtained.
[0055] S10: The collection hopper 208 discharges the powder.
[0056] Example 1:
[0057] S1: Weigh ferrous oxalate, sodium pyrophosphate, ammonium dihydrogen phosphate, and citric acid according to the stoichiometric ratio, add them to water, stir, mix, and disperse to prepare a raw material mixed solution.
[0058] S2: Turn on the blower 102, the heater 103, and the centrifugal fan 113.
[0059] S3: Pass in cooling water and adjust the rotation speed of the high-speed centrifugal atomizer 108 to 380 Hz.
[0060] S4: At an inlet air temperature of 150 °C, while stirring, pump the raw material mixed solution into the spray granulation mechanism 100 through a peristaltic pump.
[0061] S5: A total of 11 groups of sintering units are installed in the sintering mechanism 200. Adjust the temperatures of the first and second sintering plates to 150 °C, and adjust the temperatures of the third to sixth sintering plates to increase by 50 °C compared with the previous sintering plate in sequence, that is, the temperature of the sixth sintering plate is 350 °C. The temperatures of the seventh to ninth sintering plates are all 350 °C. The temperatures of the tenth to twelfth sintering plates increase by 50 °C compared with the previous sintering plate in sequence, that is, the temperature of the twelfth sintering plate is 500 °C. The thirteenth to eighteenth sintering plates are all 500 °C. The nineteenth to twenty-second sintering plates are all turned off for heating and are used for cooling.
[0062] S6: Pass in nitrogen.
[0063] S7: Adjust the rotation speed of the central transmission shaft 205 so that the time for the powder to flow through a single sintering plate is 20 minutes. Then, the powder obtained from the collection hopper 208 after 7 hours is sodium iron pyrophosphate phosphate coated with carbon.
[0064] Example 2:
[0065] S1: Weigh vanadium pentoxide, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, and citric acid according to the stoichiometric ratio, add 30% ethanol aqueous solution, stir and dissolve them to prepare a raw material mixed solution.
[0066] S2: Turn on the blower 102, the heater 103, and the centrifugal fan 113.
[0067] S3: Pass in cooling water and adjust the rotation speed of the high-speed centrifugal atomizer 108 to 300 Hz.
[0068] S4: At an inlet air temperature of 130 °C, while stirring, pump the raw material mixed solution into the spray granulation mechanism 100 through a peristaltic pump.
[0069] S5: A total of 15 sintering units are loaded into the sintering mechanism 200. Adjust the temperatures of the first and second sintering plates to 150 °C, and the temperatures of the third to the thirteenth sintering plates increase by 50 °C successively compared with the previous sintering plate, that is, the temperature of the thirteenth sintering plate is 700 °C, the temperatures of the fourteenth to the twenty-fifth sintering plates are all 700 °C, and the twenty-sixth to the thirtieth sintering plates are all turned off for heating and are used for cooling.
[0070] S6: Pass in helium.
[0071] S7: Adjust the rotation speed of the central transmission shaft 205 so that the time for the powder to flow through a single sintering plate is 20 minutes. Then, the powder obtained from the collection hopper 208 after 10 hours is sodium vanadium phosphate coated with carbon.
[0072] For those skilled in the art, it is obvious that the present utility model is not limited to the details of the above exemplary embodiments, and the present utility model can be implemented in other forms without departing from the spirit or basic characteristics of the present utility model. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present utility model is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent conditions of the claims are intended to be included in the present utility model. Any reference signs in the claims should not be regarded as limiting the claimed rights.
[0073] In addition, it should be understood that although this specification is described in terms of embodiments, not every embodiment contains only an independent technical solution. This narrative style of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A sodium ion battery positive electrode material synthesis device, characterized in that: The invention comprises a spray granulation mechanism (100) and a sintering mechanism (200); the spray granulation mechanism (100) comprises a blower (102), a heater (103), a high-speed centrifugal atomizer (108), a drying chamber (109), a cyclone separator (111) and a centrifugal fan (113); the air outlet end of the blower (102) is connected to the air inlet end of the heater (103), and the air outlet end of the heater (103) is connected to the drying chamber (109); A high-speed centrifugal atomizer (108) is provided at the upper end of the drying chamber (109); the lower end of the drying chamber (109) is connected to the air inlet end of a cyclone separator (111) through a conveying pipeline; the air outlet end of the cyclone separator (111) is connected to the air inlet end of a centrifugal fan (113); the air outlet end of the centrifugal fan (113) is connected to a discharge pipeline (114); and the discharge port (117) at the lower end of the cyclone separator (111) is connected to the sintering mechanism (200).
2. A sodium ion battery positive electrode material synthesis device according to claim 1, characterized in that: The air inlet end of the blower (102) is provided with a dust filter (101).
3. A sodium ion battery positive electrode material synthesis device according to claim 1, characterized in that: A circulating cooling pipeline is provided on the outer side of the high-speed centrifugal atomizer (108).
4. A sodium ion battery positive electrode material synthesis device according to claim 1, characterized in that: The side wall of the drying chamber (109) is provided with an observation window (110).
5. A sodium ion battery positive electrode material synthesis device according to claim 1 or 4, characterized in that: The discharge port (117) of the cyclone separator (111) is provided with a bottom screen (116).
6. A sodium ion battery positive electrode material synthesis device according to claim 5, characterized in that: The discharge port (117) of the cyclone separator (111) is provided with a check valve (115).
7. A sodium ion battery positive electrode material synthesis device according to claim 6, characterized in that: An exhaust dust collecting bag (112) is provided between the cyclone separator (111) and the centrifugal fan (113).
8. A sodium ion battery positive electrode material synthesis device according to claim 6 or 7, characterized in that: The sintering mechanism (200) comprises a central transmission shaft (205), a heat-insulating shell (207), a collecting hopper (208) and a sintering unit; the upper end of the heat-insulating shell (207) is provided with a material inlet (209), and the material inlet (209) is connected to a material outlet (117); the lower end of the heat-insulating shell (207) is connected to a collecting hopper (208), and the side wall of the heat-insulating shell (207) is provided with an air inlet (201) and an air outlet (202); a vertically arranged central transmission shaft (205) is rotatably arranged inside the heat-insulating shell (207), and multiple groups of sintering units are arranged from top to bottom on the outer side of the central transmission shaft (205), the material inlet end of the sintering unit located at the uppermost end is arranged in cooperation with the material inlet (209), and the material outlet end of the sintering unit located at the lowermost end is arranged in cooperation with the collecting hopper (208).
9. A sodium ion battery positive electrode material synthesis device according to claim 8, characterized in that: Each group of the sintering units comprises an upper sintering disk (203), a lower sintering disk (210), an upper roller brush (206) and a lower roller brush (211); the upper sintering disk (203) and the lower sintering disk (210) are coaxially rotated in parallel and are sleeved on the outside of the central transmission shaft (205); the upper sintering disk (203) and the lower sintering disk (210) are both fixedly connected to the heat-insulating shell (207); the diameter of the upper sintering disk (203) is smaller than the diameter of the lower sintering disk (210); the upper sintering disk (203) is a convex disc structure in the middle; the upper end of the upper sintering disk (203) is connected to a plurality of The upper roller brushes (206) are all connected by rolling fit, and each of the upper roller brushes (206) is a spiral structure with a diameter decreasing from the inside to the outside; the lower sintering disk (210) is a concave disc structure in the middle, and the lower sintering disk (210) and the plurality of lower roller brushes (211) are all connected by rolling fit, and each of the lower roller brushes (211) is a spiral structure with a diameter decreasing from the outside to the inside; a plurality of material discharge holes (204) are provided in the middle of the lower sintering disk (210); the inner ends of each upper roller brush (206) and each lower roller brush (211) are rotatably connected to the central transmission shaft (205).