CN114432994A - Continuous reactor for synthesizing high-crystallinity nano-scale solid electrolyte precursor and synthesis method - Google Patents
Continuous reactor for synthesizing high-crystallinity nano-scale solid electrolyte precursor and synthesis method Download PDFInfo
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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
- B01J19/18—Stationary reactors having moving elements inside
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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
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
- B01J2219/00063—Temperature measurement of the reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00139—Controlling the temperature using electromagnetic heating
- B01J2219/00141—Microwaves
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00177—Controlling or regulating processes controlling the pH
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Abstract
The invention relates to a continuous reactor for synthesizing a high-crystallinity nano-scale solid electrolyte precursor and a synthesis method, wherein the continuous reactor comprises a reaction kettle body, and a stirring device, a heating device and a feeding controller are arranged on the reaction kettle body; the stirring device is used for stirring reaction materials; the heating device is used for changing the temperature of the reaction; the feeding controller is used for feeding reaction materials; the reaction kettle body also comprises a temperature sensor and a pH sensor, wherein the temperature sensor is arranged in the reaction kettle body, is connected with the heating device and is used for detecting the reaction temperature and controlling the on-off of the heating device; the pH sensor is arranged in the reaction kettle body, is connected with the feeding controller and is used for detecting the pH value of the reaction and controlling the on-off of the feeding controller. The continuous reactor can monitor the temperature and pH value of the reaction system in real time, transmit signals to the heating device and the charging controller, and automatically and accurately adjust the temperature and pH value in the reaction process, so that the reaction is smoothly carried out.
Description
Technical Field
The invention belongs to the field of solid electrolytes, and particularly relates to a continuous reactor for synthesizing a high-crystallinity nano-scale solid electrolyte precursor and a synthesis method.
Background
Most of lithium ion secondary batteries in the current market adopt liquid electrolytes, so that the production process is limited to a great extent, the moisture control is very strict on the environmental requirement of assembly, and the liquid electrolytes have the safety problems of package leakage, current collector corrosion, over-high temperature explosion and the like in the application of subsequent products. In addition, the liquid electrolyte generally has a phenomenon of cycle capacity fading because of problems of protective film (SEI) generation, gas generation by side reactions, decomposition at high temperature and high pressure, and the like, which are accompanied with the liquid electrolyte in electrochemical reactions. If the solid electrolyte is adopted, the problems can be effectively improved, the solid electrolyte has the characteristics of high safety and long service life, the electrolyte is replaced in assembly, the diaphragm is also used, the structure of the battery is greatly simplified, the design with higher energy density can be achieved, the design is more flexible and convenient in profile design, the requirements on equipment and environment are reduced in production due to no need of air isolation, and most of fixed asset cost is saved.
Solid-state battery materials currently fall into two main categories: the first type is polymer type (gel type) electrolyte, including polyether (polyethylene oxide, PEO), Polyacrylonitrile (PAN), Polymethacrylate (PMMA), polyvinylidene fluoride (PVDF), etc., although the polymer electrolyte can obviously overcome some disadvantages of liquid lithium ion batteries in development and application, there are still some problems to be solved: for example, the ionic conductivity is low at normal temperature, the compatibility with electrodes is poor, and the mechanical strength is still insufficient. The second type is an inorganic solid electrolyte, which has higher thermodynamic stability and mechanical strength, can be charged and discharged with large current and has high use safety compared with gel polymer electrolytes. The inorganic type solid electrolyte is further classified into a crystalline electrolyte and an amorphous electrolyte according to its crystal structure. The main research currently developed for crystalline electrolytes is perovskite (ABO)3) Type structure, lithium ion electrolyte, NASICON type structure lithium ion electrolyte, LISICON type structure lithium ion electrolyte, etc. Of NASICON typeThe synthesis of the structural lithium ion electrolyte is particularly important, and the chemical formula of NASICON is AB2(PO4)3(A is a monovalent metal element such as Li, Na, K, Rb or Cs, B is a tetravalent element such as Ti, Zr, Ge, Si or Sn), and the structure is described as being represented by AO6Octahedron and PO4Covalent bond structure composed of regular tetrahedrons [ A ]2P3O12]-。
At present, the NASICON synthesis mode mostly adopts a hydrothermal reduction method, a solid-state sintering method and a sol-gel method. The batch quantity of the hydrothermal reduction method is too small, and the method is not suitable for industrial mass production; the material obtained by the solid state sintering method has larger grain diameter and poor uniformity, and is difficult to match with electrode materials when a battery is assembled, because the stoichiometry and the heating temperature are difficult to control; the sol-gel method has the disadvantages of long production time, severe requirements on the pH value control and the temperature control of a system, and difficulty in meeting the requirements of the existing equipment.
Therefore, the technical scheme of the invention is provided.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a continuous reactor for synthesizing a high-crystallinity nano-scale solid electrolyte precursor and a synthesis method. The continuous reactor for synthesizing the high-crystallinity nano-scale solid electrolyte precursor by microwave can monitor the temperature and the pH value of a reaction system in real time, transmit signals to the heating device and the feeding controller, automatically and accurately adjust the temperature and the pH value in the reaction process, and enable the reaction to be carried out smoothly. Compared with the traditional method, the synthesis method of the high-crystallinity nanoscale solid electrolyte precursor has the advantages that the obtained product has finer and more uniform particle size and has more excellent performance in a battery. And a protective layer is coated on the surface of the product by microwave reaction on the new synthesis path, so that Ti in the structure4+The lithium-ion battery is not easy to be reduced by metal lithium, can achieve higher energy density, is more time-saving by the synthesis method, and is expected to achieve the technical target of commercial mass production.
The scheme of the invention is to provide a continuous reactor for synthesizing a high-crystallinity nano-scale solid electrolyte precursor, which comprises a reaction kettle body;
the reaction kettle body is provided with a stirring device, a heating device and a feeding controller; wherein,
the stirring device is used for stirring reaction materials;
the heating device is used for changing the temperature in the reaction process;
the feeding controller is used for feeding reaction materials;
the reaction kettle body also comprises a temperature sensor and a pH sensor, wherein,
the temperature sensor is arranged in the reaction kettle body, is electrically connected with the heating device, and is used for detecting the reaction temperature and controlling the on-off of the heating device;
the pH sensor is arranged in the reaction kettle body, is electrically connected with the feeding controller and is used for detecting the pH value of the reaction and controlling the on-off of the feeding controller.
For the convenience of understanding the technical scheme of the present invention, the operation principle of the continuous reactor will be explained.
Firstly, in the preparation stage, reaction raw materials are respectively added into feed inlets of the continuous reactor, and the number of the feed inlets is matched with the types of the reaction raw materials.
Secondly, with the beginning of the reaction, the charging controller puts corresponding raw materials (including solvent, dispersant, acid-base modifier, monovalent element salts, trivalent element salts, tetravalent element salts and the like) into the reaction kettle body according to a parameter proportion set in advance, and at the moment, the stirring device stirs, so that the reaction system is more uniform; and meanwhile, the heating device heats to provide necessary temperature for the reaction.
In addition, the temperature sensor and the pH sensor can monitor the temperature and the pH value of the reaction system in real time while the reaction is carried out. It is emphasized that if the system pH is too low (acidity is too high) during the reaction, the pH sensor can transmit a signal of "acidity is too high, and alkaline agent needs to be added" to the feeding controller, and the feeding controller further regulates and controls the alkaline agent in the feeding port to be added to the system until the pH value meets the requirement; similarly, when the pH value of the system is too high (alkalinity is too high) in the reaction process, reverse regulation is also carried out according to the logic. And the adjustment for the temperature is: if the temperature in the reaction process is too high, the temperature sensor can transmit a signal of 'temperature is too high and temperature needs to be reduced' to the heating device, and the heating device can reduce the heating power or be directly closed, so that the reaction system is cooled until the temperature meets the requirement; similarly, when the system temperature is too low in the reaction process, reverse regulation is also carried out according to the logic.
And finally, directly discharging when the temperature of the system is balanced after the reaction is finished.
Preferably, the outer side of the reaction kettle body is wrapped with a cooling liquid interlayer, and the cooling liquid interlayer can be filled with cooling liquid; the cooling liquid interlayer is communicated with a cooling inlet and a cooling outlet, the cooling inlet is located at the bottom of the cooling liquid interlayer, and the cooling outlet is located at the top of the cooling liquid interlayer.
Preferably, the stirring device comprises a stirring driving device and a stirring execution device; the stirring driving device is arranged at the top of the reaction kettle body, and the stirring executing device is arranged in the reaction kettle body; the output end of the stirring driving device is connected with the stirring execution device through a stirring rod; the bottom of the stirring driving device is provided with a driving cooling liquid inlet, and the top of the stirring driving device is provided with a driving cooling liquid outlet; the driving cooling liquid inlet and the driving cooling liquid outlet are used for respectively introducing and discharging cooling liquid, and the cooling liquid is used for cooling the stirring driving device; the stirring executing device comprises a plurality of groups of stirring paddles which are arranged from top to bottom in sequence, and the stirring executing device is adjacent to the stirring paddles and is vertically arranged along the direction of the stirring rod.
Preferably, the heating device is a microwave generator; the microwave generator comprises a plurality of groups of microwave generating units, wherein the microwave generating units are arranged on the inner side of the reaction kettle body and are uniformly arranged along the circumferential direction of the reaction kettle body.
Preferably, the continuous reactor further comprises a display; the display is connected with the temperature sensor and the pH sensor and is used for displaying the reaction temperature and the pH value.
Preferably, the continuous reactor further comprises a discharge filtering device and a lifting foot rest, wherein,
the discharging filtering device is arranged at the bottom outlet of the reaction kettle body and is used for filtering feed liquid impurities during discharging;
the lifting foot rest is arranged at the bottom of the reaction kettle body and is used for adjusting the height of the reaction kettle body.
Based on the same technical concept, the invention provides a synthesis method of a high-crystallinity nanoscale solid electrolyte precursor, which comprises the following steps:
(S1) solvent preheating: in order to make the reaction raw material fully absorb microwave energy, the solvent is mainly selected from polar solvents such as water, alcohols, carboxylic acids and the like, wherein, the solvent is preferably one or the combination of a plurality of water, ethanol or glycol; more preferably, the combination of water and glycol is selected, wherein the weight ratio of the water to the glycol is 1: 3-3: 1. After the solvent is selected, putting the solvent into the reaction kettle body, starting a stirring device and preheating to the temperature of more than 50 ℃ to obtain a mixture a;
(S2) dispersant dissolution: the purpose of adding the dispersing agent is to reduce the interfacial tension between solid and liquid, to make the surface of the material easier to wet, and to increase the suspension performance, so that the received microwave energy can be more uniform; the used dispersing agent is a high molecular dispersing agent, can be a homopolymer, an oxidized homopolymer, an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate copolymer, a low molecular ionomer and the like, is preferably one or a combination of more of polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol, and the addition amount of the dispersing agent is 0.1-0.3% of the weight of the solvent; the specific operation is as follows: adding a dispersing agent into the mixture a, and uniformly stirring to obtain a mixture b;
(S3)AO6octahedral pre-nucleation: after the dispersant is dissolved, adding metal salt into the mixture b, wherein the metal salt is one or two of tetravalent element salts or pre-doped trivalent element salts, and the tetravalent element saltsIs Ti, Zr, Ge, Si or Sn, the pre-doped trivalent element salt is Al, Cr, Ga, Fe, Sc, In, Lu, Y or La, wherein the acid radical of the salt can be OH-、 Cl-、CO3 2-、HCO3 -、PO4 3-、CH3COO-Or SO4 2-Preferably Cl-、HCO3 -And CH3COO-(ii) a Wherein the concentration of dissolved tetravalent element salt is preferably 15000-25000 ppm, more preferably 18000-20000 ppm, the molar ratio of the pre-doped trivalent element salt to the tetravalent element salt is not more than 0.4, at the moment, low-speed stirring is used, and a microwave generator is started in the feeding process in the following mode: and (3) turning on the microwave generating units a, c and e for 30s, then turning off, switching on the microwave generating units b, d and f for the same time, and sequentially circulating until the system temperature reaches 75 ℃. At the moment, after the material absorbs microwave energy, suspended matters are gradually generated, the output power of a microwave reaction generator is set to be 1000-2500W, and the preferred power is 1000-1500W, so that a mixture c is obtained after the microwave reaction generator finishes the microwave reaction;
(S4)PO4nucleation of regular tetrahedrons: after the temperature rises to 75 ℃, slowly adding a phosphoric acid compound (NH)4)H2PO4、(NH4)2HPO4Or H3PO4The weight ratio of the phosphoric acid compound to the tetravalent element salt is 0.98-1.02, the pH value of the system needs to be adjusted at the stage, oxalic acid or ammonia water is used as an acid-base adjusting agent, the preferable pH range is 6-8, and the more preferable pH is 7. Use low-speed stirring this moment, microwave generator is opened in the charging process, and the mode is: and (3) switching off the microwave generating units a, c and e after being switched on for 30s, switching on the microwave generating units b, d and f for the same time, and circulating in sequence. The output power of the microwave generator is 1000-2500W, and the preferable power is 1400-1800W. Gradually increasing crystallization and solvent viscosity along with the reaction, and properly opening a high-speed dispersion disc to obtain a mixture d;
(S5) covalent bond Structure [ A2P3O12]-Molding: after the reaction is finished, adding monovalent element salt, wherein the monovalent element salt is Li, Na, K, Rb or Cs and the like, and the acid radical of the salt is OH-、Cl-、 CO3 2-、HCO3 -、PO4 3-、CH3COO-Or SO4 2-Preferably OH-、Cl-Or CH3COO-At the moment, the output power of the microwave generator is 1500-2500W, preferably 1800-2200W, the reaction time is determined according to the particle size of the material, and a mixture e is obtained after the reaction is finished;
(S6) drying and sintering the material: drying the mixture e, wherein the drying adopts one of spray granulation drying or freeze drying, and if the finished product material is used as a positive electrode conduction or isolation material, the spray granulation drying is selected, so that the secondary forming size can be freely controlled; if the finished material is used as a negative electrode conducting material, freeze drying is selected, so that a more compact coating effect can be obtained; and (3) after drying, using a continuous atmosphere control track furnace for sintering the material, wherein the temperature is controlled to be 500-1200 ℃, preferably 700-1100 ℃, and the atmosphere is controlled by using gases such as nitrogen, argon, air and the like.
For the convenience of subsequent use, the finished material is crushed and sieved, and mainly comprises continuous airflow crushing and grid sieving. When the finished product material is used as an isolation material, ball milling is preferred, wherein the pressure of jet milling is preferably 0.6-0.9 MPa, more preferably 0.7-0.85 MPa, and the materials of the milling balls and the milling tank of the ball milling are preferably stainless steel, aluminum oxide, zirconium oxide or agate; the ball-milling material ball ratio is preferably 1: 6-10; the ball milling rotating speed is preferably 450-550 rpm; the ball milling time is preferably 30min to 120 min.
The invention has the beneficial effects that:
the continuous reactor for synthesizing the high-crystallinity nanoscale solid electrolyte precursor by microwaves can monitor the temperature and the pH value of a reaction system in real time, transmit signals to the heating device and the feeding controller, automatically and accurately adjust the temperature and the pH value in the reaction process, and ensure that the reaction is smoothly carried out.
Compared with the traditional method, the synthesis method of the high-crystallinity nanoscale solid electrolyte precursor provided by the invention has the advantages that the particle size of the obtained product is finer and more uniform, and the product has more excellent performance in a battery. And a protective layer is coated on the surface of the product by microwave reaction on the new synthesis path, so that Ti in the structure4+The lithium-ion battery is not easy to be reduced by metal lithium, can achieve higher energy density, is more time-saving by the synthesis method, and is expected to achieve the technical target of commercial mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of the structure of a continuous reactor according to the present invention;
FIG. 2 is a schematic top view of a reactor body according to the present invention;
FIG. 3 is a schematic structural view of a stirring paddle according to the present invention;
FIG. 4 is a schematic view of the discharge filter apparatus of the present invention;
FIG. 5 is an SEM photograph of the product obtained in example 3;
FIG. 6 is a graph showing the results of electrochemical impedance measurements of the products of example 3 and control.
Reference numbers in the figures:
1-a continuous reactor; 11-a reaction kettle body; 111-coolant interlayer; 112-cooling inlet; 113-a cooling outlet; 12-a stirring device; 121-stirring driving means; 1211 — drive coolant inlet; 1212-driving coolant outlet; 122-a stirring paddle; 13-a temperature sensor; 14-a pH sensor; 15-a heating device; 151-a microwave generating unit; 16-a feed controller; 17-a display; 18-a discharge filtration unit; 19-lifting foot stool.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
Referring to fig. 1, the present embodiment provides a continuous reactor for synthesizing a highly-crystalline nanoscale solid electrolyte precursor, where the continuous reactor 1 includes a reactor body 11;
the reaction kettle body 11 is provided with a stirring device 12, a heating device 15 and a feeding controller 16; wherein,
the stirring device 12 is used for stirring reaction materials;
the heating device 15 is used for changing the temperature in the reaction process;
the feed controller 16 is used for adding reaction materials;
the reaction kettle body 11 also comprises a temperature sensor 13 and a pH sensor 14, wherein,
the temperature sensor 13 is arranged inside the reaction kettle body 11, is electrically connected with the heating device 15, and is used for detecting the reaction temperature and controlling the on-off of the heating device 15;
the pH sensor 14 is disposed inside the reaction kettle body 11, and is electrically connected to the charging controller 16, for detecting a reaction pH value and controlling the charging controller 16 to open and close.
Example 2
On the basis of example 1, as an alternative embodiment, referring to fig. 2, a cooling liquid interlayer 111 is wrapped on the outer side of the reaction kettle body 11, and the cooling liquid interlayer 111 can be filled with cooling liquid; the cooling liquid interlayer 111 is provided with a cooling inlet 112 and a cooling outlet 113 in a communicating manner, the cooling inlet 112 is located at the bottom of the cooling liquid interlayer 111, and the cooling outlet 113 is located at the top of the cooling liquid interlayer 111. In practical operation, the size of the reaction vessel 11 will vary with the reaction requirements. When the reaction kettle body 11 is large and the reaction temperature is too high and needs rapid cooling, the effect is limited only by the method of closing the heating device. Therefore, the cooling liquid interlayer 111, the cooling inlet 112 and the cooling outlet 113 are arranged on the outer side of the reaction kettle body 11, and the effect of rapid cooling is achieved by introducing external cooling liquid.
As an alternative embodiment, referring to fig. 1, the stirring device 12 includes a stirring driving device 121 and a stirring execution device; the stirring driving device 121 is arranged at the top of the reaction kettle body 11, and the stirring executing device is arranged inside the reaction kettle body 11; the output end of the stirring driving device 121 is connected to the stirring executing device through a stirring rod. The stirring driving device 121 may be a motor, and the motor generates a driving force to drive the stirring executing device to stir through the stirring rod.
As an alternative embodiment, referring to fig. 1, the stirring driving device 121 is provided with a driving cooling liquid inlet 1211 at the bottom and a driving cooling liquid outlet 1212 at the top; the driving cooling liquid inlet 1211 and the driving cooling liquid outlet 1212 respectively introduce and flow out cooling liquid, and the cooling liquid is used for cooling the stirring driving device 121. In the actual operation process, the whole chemical reaction process needs to be in a stirring environment, and long-time work can make the stirring driving device 121 be in a high-temperature state, and if the temperature is not lowered in time, mechanical parts can be damaged. Therefore, the stirring driving device 121 is provided with a driving cooling liquid inlet 1211 and a driving cooling liquid outlet 1212, and the stirring driving device 121 can be in a better working environment by adding cooling liquid, so that the service life is prolonged.
As an optional implementation manner, referring to fig. 3, the stirring executing device includes a plurality of groups of stirring paddles 122 sequentially arranged from top to bottom, and the adjacent stirring paddles 122 are vertically arranged along the direction of the stirring rod. So set up, can make the stirring process more even to increase the lifting surface area of reaction system, be favorable to going on of reaction.
As an alternative embodiment, the heating device 15 is a microwave generator. As the name implies, a microwave generator is capable of generating microwaves, which are electromagnetic waves propagating in a straight line and having a frequency of 300MHz to 300 GHz. The microwave absorbing capacity of a substance is mainly determined by the dielectric loss factor of the substance, the substance with large dielectric loss factor has strong microwave absorbing capacity, for example, water molecules belong to polar molecules, the dielectric constant is large, the dielectric loss factor is also large, and the substance has strong microwave absorbing capacity; while some solid substances, e.g. NiO, CuO, Fe3O4Or carbon black, etc., which can absorb microwave energy strongly and be heated rapidly, and some substances, such as CaO, Fe2O3Or TiO2And so on, the microwave energy is hardly absorbed, and the temperature rise range is small. When the microwave penetrates through an object, a directional electromagnetic field is attached, so that polar molecules are always arranged in the direction of the electromagnetic field under the action of the electric field, the molecules are called to be polarized, and because the microwave is an electromagnetic field oscillating for hundreds of millions of times per second, the arrangement direction of the molecules is changed for hundreds of millions of times per second when the microwave is placed in the electromagnetic field, so that a large number of molecules absorb the energy of the microwave and rotate violently at high frequency, a large amount of internal energy is generated, and the temperature of the object is increased. According to the principle, the NASICON precursor can be quickly and regularly arranged and uniformly reacted under the microwave heating, the average grain diameter of the obtained product is smaller, and Li in the crystal+The conduction path is more unobstructed.
As an alternative embodiment, referring to fig. 2, the microwave generator includes multiple sets of microwave generating units 151, where the microwave generating units 151 are disposed inside the reaction kettle body 11 and are uniformly arranged along the circumferential direction of the reaction kettle body 11. In actual operation, in order to prevent the interference of microwave to communication, the microwave generation frequency is 915MHz and 2450MHz, wherein the 2450MHz is mainly used for household cooking utensils, and the 915MHz is used for industries such as drying, disinfection and the like, medical industries and the like. The frequency emitted by the microwave generating unit 151 is 915MHz, so that the microwave generating unit has better penetration distance and output power of 1000-2500W. In order to make the heating more uniform, the microwave generating units 151 are circumferentially and uniformly disposed inside the reaction kettle body 11. For example, 6 groups of the microwave generating units 151 are selected, and the microwave generating units are sequentially numbered as a, b, c, d, e, and f according to the clockwise number, so that the microwave generating units are arranged according to a regular six-sided layout, when heating is required, the microwave generating units numbered as a, c, and e or the microwave generating units numbered as b, d, and f are simultaneously turned on (turned on at intervals), if a, c, and e are turned on first, then turned off after heating for 20s, and then turned on b, d, and f, and the process is repeated until the temperature reaches a set value. The intermittent heating at different angles can also increase the uniformity of the energy received by the material.
As an alternative embodiment, with reference to fig. 1, the continuous reactor 1 further comprises a display 17; the display 17 is connected with the temperature sensor 13 and the pH sensor 14 and is used for displaying the reaction temperature and the pH value. The display 17 is arranged to observe the reaction state of the system in real time, so that the emergency situation can be handled in the first time.
As an alternative embodiment, with reference to fig. 4, the outlet at the bottom of the continuous reactor 1 further comprises an outlet filtering device 18 for filtering feed liquid impurities during outlet. When the reaction is finished and the material is discharged, the discharging and filtering device 18 can filter impurities and purify the material liquid.
As an optional implementation manner, referring to fig. 1, the continuous reactor 1 further includes a liftable foot rest 19, and the liftable foot rest 19 is disposed at the bottom of the reaction kettle body 11 and is used for adjusting the height of the reaction kettle body 11. The foot rests enable the continuous reactor 1 to be more stable; in addition, when the reaction is finished and the material is discharged, the foot rest can be lifted, and the material outlet is higher than the collecting barrel for transfer, so that the material liquid can be collected more conveniently.
Example 3
This example provides a method for synthesizing a high-crystallinity nanoscale solid electrolyte precursor, the target product being Li1.3Al0.3Ti1.7(PO4)3(LATP) comprising the steps of:
(S1) solvent preheating: mixing water and ethylene glycol according to a weight ratio of 2:1 to serve as a solvent, putting the solvent into a reaction kettle body 11, starting a stirring device 12, and preheating to 55 ℃ to obtain a mixture a;
(S2) dispersant dissolution: adding polyvinylpyrrolidone into the mixture a, wherein the addition amount of the polyvinylpyrrolidone is 0.3% of the weight of the solvent, and uniformly stirring to obtain a mixture b;
(S3)AO6octahedral pre-nucleation: adding Ti (OC) to the mixture b4H9)4、Al(NO3)· 9H2O, said Ti4+At a concentration of 18000ppm, said Al (NO)3)·9H2O and the Ti (OC)4H9)4Is 0.4, at this time low speed stirring is used and the microwave generator is turned on in the following way: and (3) turning on the microwave generating units a, c and e for 30s, then turning off, switching on the microwave generating units b, d and f for the same time, and sequentially circulating until the system temperature reaches 75 ℃. At the moment, after the material absorbs microwave energy, suspended matters are gradually generated, the output power of a microwave reaction generator is set to be 1000W, and a mixture c is obtained after the microwave reaction is finished;
(S4)PO4nucleation of regular tetrahedrons: (NH) is added to the mixture c4)H2PO4Said (NH)4)H2PO4The amount of (2) and Ti (OC)4H9)4The weight ratio of the components is 1.02, the pH value of the system is adjusted to 7 by using oxalic acid, the microwave power is adjusted to 1500W, and a high-speed dispersion disc is opened to obtain a mixture d;
(S5) covalent bond Structure [ A2P3O12]-Molding: adding Li (CH) to the mixture d3COO)·2H2O, starting the whole section of microwave, setting the power to be 1800W, taking out the solvent after lasting for 5min, and obtaining a mixture e;
(S6) drying and sintering the material: and (3) freeze-drying the mixture e, ball-milling the obtained precursor for 30min, sieving, and calcining at 900 ℃ for 120min in an air atmosphere.
The method utilizes SEM, XRD and electrochemical test as evaluation means, wherein the electrochemical test is to evaluate the material performance by 2032 button cell.
Comparative example
The comparison example is synthesized by the traditional sol-gel method, and the target product is Li1.3Al0.3Ti1.7(PO4)3(LATP) by the method:
li (CH) is calculated in advance according to the chemical formula of the target product3COO)·2H2O、Al(NO3)·9H2O and (NH)4)H2PO4To CH in a molar ratio of3OCH2CH2In CH, stirring is carried out at normal temperature, and then a small amount of concentrated nitric acid is added to prevent the generation of precipitate. When all solutes were completely dissolved, a small amount of CH was added3COCH2COCH3To prevent the hydrolysis of the butyl titanate, then adding the butyl titanate, and continuously stirring to obtain the sol. And heating the obtained sol at 380 ℃ for 20min to obtain the LATP xerogel precursor. And ball-milling the obtained xerogel for 30min, sieving, and calcining at 900 ℃ for 120min in air atmosphere.
SEM test of the product obtained in example 3 shows that the average particle size of the obtained nano NASICON material is about 30-100 nm and the primary nucleation particles are uniform, as shown in FIG. 5.
The crystal structure was calculated by XRD, and the lattice parameters are shown in table 1, from which the data result shows that the product obtained in example 3 has a better ion conduction structure than the control group.
The electrochemical impedance test of the products of example 3 and the control group is further performed, and the result is shown in fig. 6, that is, the product obtained in example 3 has better ion conductivity than the control product.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A continuous reactor for synthesizing a high-crystallinity nano-scale solid electrolyte precursor, which is characterized in that the continuous reactor (1) comprises a reaction kettle body (11);
the reaction kettle body (11) is provided with a stirring device (12), a heating device (15) and a feeding controller (16); wherein,
the stirring device (12) is used for stirring reaction materials;
the heating device (15) is used for changing the temperature in the reaction process;
the feeding controller (16) is used for adding reaction materials;
the reaction kettle body (11) also comprises a temperature sensor (13) and a pH sensor (14), wherein,
the temperature sensor (13) is arranged inside the reaction kettle body (11), is electrically connected with the heating device (15), and is used for detecting the reaction temperature and controlling the opening and closing of the heating device (15);
the pH sensor (14) is arranged inside the reaction kettle body (11), is electrically connected with the feeding controller (16) and is used for detecting the pH value of the reaction and controlling the on-off of the feeding controller (16).
2. The continuous reactor for synthesizing the high-crystallinity nanoscale solid electrolyte precursor according to claim 1, wherein the outer side of the reaction kettle body (11) is wrapped with a cooling liquid interlayer (111), and the cooling liquid interlayer (111) can be filled with cooling liquid; the cooling liquid interlayer (111) is communicated with a cooling inlet (112) and a cooling outlet (113), the cooling inlet (112) is located at the bottom of the cooling liquid interlayer (111), and the cooling outlet (113) is located at the top of the cooling liquid interlayer (111).
3. The continuous reactor for synthesizing a highly-crystalline nanoscale solid-state electrolyte precursor according to claim 1, wherein the stirring device (12) comprises a stirring driving device (121) and a stirring execution device; the stirring driving device (121) is arranged at the top of the reaction kettle body (11), and the stirring executing device is arranged inside the reaction kettle body (11); the output end of the stirring driving device (121) is connected with the stirring execution device through a stirring rod; the bottom of the stirring driving device (121) is provided with a driving cooling liquid inlet (1211), and the top of the stirring driving device is provided with a driving cooling liquid outlet (1212); the driving cooling liquid inlet (1211) and the driving cooling liquid outlet (1212) respectively introduce and flow out cooling liquid, and the cooling liquid is used for cooling the stirring driving device (121); stirring final controlling element includes from last multiunit stirring rake (122) that sets gradually extremely down, and is adjacent be perpendicular setting along the puddler direction between stirring rake (122).
4. The continuous reactor for synthesizing highly crystalline nanoscale solid-state electrolyte precursor according to claim 1, wherein said heating device (15) is a microwave generator; the microwave generator comprises a plurality of groups of microwave generating units (151), wherein the microwave generating units (151) are arranged on the inner side of the reaction kettle body (11) and are uniformly arranged along the circumferential direction of the reaction kettle body (11).
5. The continuous reactor for synthesizing highly crystalline nanoscale solid-state electrolyte precursor according to claim 1, wherein said continuous reactor (1) further comprises a display (17); the display (17) is connected with the temperature sensor (13) and the pH sensor (14) and is used for displaying the reaction temperature and the pH value.
6. The continuous reactor for synthesizing highly crystalline nanoscale solid electrolyte precursor according to claim 1, wherein the continuous reactor (1) further comprises an output filtering device (18) and a liftable foot rest (19), wherein,
the discharging filtering device (18) is arranged at an outlet at the bottom of the reaction kettle body (11) and is used for filtering impurities in the material liquid during discharging;
the lifting foot rest (19) is arranged at the bottom of the reaction kettle body (11) and is used for adjusting the height of the reaction kettle body (11).
7. A synthesis method of a high-crystallinity nanoscale solid electrolyte precursor is characterized by comprising the following steps:
(S1) solvent preheating: putting a polar solvent into a reaction kettle body (11), starting a stirring device (12) and preheating to obtain a mixture a;
(S2) dispersant dissolution: adding a dispersing agent into the mixture a, and uniformly stirring to obtain a mixture b;
(S3)AO6octahedral pre-nucleation: adding metal salt into the mixture b, and starting a heating device (15) until the temperature reaches a set value to obtain a mixture c;
(S4)PO4nucleation of regular tetrahedrons: adding a phosphoric acid compound into the mixture c, and adding an acid-base regulator to regulate the pH value of the system to obtain a mixture d;
(S5) covalent bond Structure [ A2P3O12]-Molding: adding monovalent element salt to the mixture d for continuous reaction to obtain a mixture e;
(S6) drying and sintering the material: and (3) drying and calcining the mixture e in sequence.
8. The method for synthesizing the highly-crystallized nanoscale solid electrolyte precursor according to claim 7, wherein the polar solvent is one or a combination of water, ethanol or ethylene glycol; the dispersing agent is one or a combination of more of polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol; the addition amount of the dispersing agent is 0.1-0.3% of the weight of the solvent.
9. The method for synthesizing a highly-crystallized nanoscale solid-state electrolyte precursor as claimed in claim 7, wherein the metal salt is one or two of a tetravalent element salt or a pre-doped trivalent element salt; the concentration of the tetravalent element salt is 15000-25000 ppm, and the pre-doped trivalent element saltThe mole ratio of the tetravalent element salt is not more than 0.4; the phosphoric acid compound is (NH)4)H2PO4、(NH4)2HPO4Or H3PO4One or a combination of several of (a); the weight ratio of the phosphoric acid compound to the tetravalent element salt is 0.98-1.02; the pH value of the adjusting system is 6-8.
10. The method for synthesizing the highly-crystallized nanoscale solid-state electrolyte precursor according to claim 7, wherein the drying is one of spray granulation drying and freeze drying; the sintering temperature is 500-1200 ℃.
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