CN111525102A - Preparation method of carbon quantum dot modified LiFePO4 positive electrode material - Google Patents
Preparation method of carbon quantum dot modified LiFePO4 positive electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon quantum dot modified LiFePO4 positive electrode material, which belongs to the field of preparation methods of lithium ion battery positive electrode materials, and discloses a preparation method of a carbon quantum dot modified LiFePO4 positive electrode material, wherein chitosan is used as a carbon source to modify and modify the surface of lithium iron phosphate with carbon quantum dots, and a microwave ultrasonic and hydrothermal carbonization two-step method is used to modify the surface of the lithium iron phosphate with carbon quantum dots, so that the preparation method is simple, the prepared material has uniform particle size and uniform distribution, and the material has a large specific surface area; and the carbon quantum dots can expose more active sites for the surface modification of the lithium iron phosphate, so that more spaces are provided for the storage of lithium ions, the conductivity of the lithium iron phosphate is better improved, the lithium iron phosphate has excellent rate performance, and in addition, the self-disinfection magnetic stirrer with the safe disinfection cover used in the manufacturing process can play a disinfection role in the reaction environment inside the container, so that the safety of operators in the manufacturing process is improved.
Description
Technical Field
The invention relates to the field of preparation methods of lithium ion battery anode materials, in particular to a preparation method of a carbon quantum dot modified LiFePO4 anode material.
Background
The main constituent materials of the lithium ion battery include electrolyte, isolating material, anode and cathode materials and the like. The positive electrode material occupies a large proportion (the mass ratio of the positive electrode material to the negative electrode material is 3: 1-4: 1), because the performance of the positive electrode material directly influences the performance of the lithium ion battery, the cost directly determines the cost of the battery. The novel microwave drying technology is adopted to dry the lithium battery anode material, so that the problems that the conventional lithium battery anode material drying technology is long in time, the capital turnover is slow, the drying is not uniform, and the drying depth is not enough are solved.
In summary, the development direction of the positive electrode material of the lithium ion battery is lithium iron phosphate. Although the research and development of domestic lithium iron phosphate cathode materials are vigorous, the original innovative technology is lacked. Lithium ion battery negative electrode materials have two development directions in the future, namely lithium titanate materials and silicon-based materials. The silicon-based materials developed in recent years in China basically meet the requirements of high specific capacity, high power characteristic and long cycle life, but the industrialization still needs to break through the restrictions in the aspects of process, cost and environment. China has achieved certain achievement in the aspect of localization of lithium ion battery diaphragms, but a long way is still needed to realize large-scale production of high-end products.
The air pollution and resource exhaustion are caused by the mass combustion of fossil fuel, and the dependence of people on the fossil fuel can be greatly reduced by the application of the lithium ion secondary battery. The research on the positive electrode material of the lithium ion battery as a lithium source supplier and a core component of the battery has an important role in improving the overall capacity of the battery. The lithium iron phosphate material has wide raw material distribution, is safe and pollution-free, and is widely applied to the anode material of the lithium ion battery. But its development is limited by its low electronic conductivity and low lithium ion diffusion rate.
The lithium iron phosphate is in an orthogonal olivine structure, and the space group is Pnma. In 1997, Goodenough et al discovered this structure and applied it to lithium ion batteries. The structural stability of the LiFePO4 is ensured because the P-O bond of the PO4 tetrahedron is stronger. But the diffusion channel is single, so that the ion diffusion rate is low and is less than 10 < -9 > S.cm < -1 > at room temperature and far lower than LiCoO2(10 < -3 > S.cm < -1 >) and LiMn2O4(10 < -5 > S.cm < -1 >). The low ion diffusion rate and electron conductivity make the material have poor rate capability, and severely limit its development. Therefore, it becomes crucial to select a suitable conductive material to increase the conductivity of lithium iron phosphate.
The materials commonly used at present for improving the electrical conductivity are mainly carbon materials, and carbon sources include glucose, sucrose, ascorbic acid, citric acid, polydopamine and the like. The coating method is divided into an in-situ coating method and an ex-situ coating method. The carbon coating is coated on the surface of the lithium iron phosphate to improve the conductivity of the lithium iron phosphate, but the conductivity improving effect is related to factors such as the graphitization degree of the carbon layer, the expansion coefficient of the carbon layer is very low, the combination effect of the carbon layer and the lithium iron phosphate is mostly not ideal, the initial conductivity is improved well, but after a certain period of charging and discharging, the stability of the conductivity improvement is reduced, the performance under the condition of large-current charging is not ideal, and the multiplying power performance is reduced. Therefore, the development of a more effective method for improving the conductivity of the lithium iron phosphate is crucial to the long-term use of the material and the improvement of the rate capability.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a carbon quantum dot modified LiFePO4 positive electrode material, which adopts chitosan as a carbon source to modify and modify the carbon quantum dots on the surface of lithium iron phosphate, adopts a two-step method of microwave ultrasonic and hydrothermal carbonization to modify the carbon quantum dots on the surface of the lithium iron phosphate, and has the advantages of simple preparation method, uniform particle size and distribution of the prepared material, and large specific surface area of the material; and the carbon quantum dots can expose more active sites for modifying the surface of the lithium iron phosphate, so that more spaces are provided for lithium ion storage, the conductivity of the lithium iron phosphate is better improved, and the lithium iron phosphate has excellent rate capability.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A preparation method of a carbon quantum dot modified LiFePO4 cathode material comprises the following steps:
s1, weighing 5-25g of analytically pure ferrous salt, and dissolving in 50-100mL of distilled water to obtain a solution A;
s2, taking 5-25mL of analytically pure phosphoric acid, and adding distilled water to dilute to 60mL to obtain a phosphoric acid solution B;
s3, weighing 10-30g of analytically pure lithium phosphate, and dissolving in 50-100mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer to be stirred at the rotating speed of 400r/min, simultaneously dripping the solution A and the solution B into the solution C, stirring while dripping, centrifugally separating the generated precipitate, washing the precipitate for 3 times by using distilled water, and drying the precipitate in an oven at the temperature of 60 ℃ to obtain a precipitate D;
s5, weighing 5-10g of chitosan, and dissolving in 50mL of acetic acid solution with the mass fraction of 20-40% to obtain a mixed solution E;
s6, stirring the solution E for 10-60min, pouring into a microwave ultrasonic reaction kettle, centrifugally separating the mixed solution obtained by the reaction, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, and reacting to obtain a product H;
and S9, placing the product H in a freeze dryer, and reacting to obtain a final product I.
In S6, the microwave power of the microwave ultrasonic reaction kettle is controlled to be 800W for 600-.
In S7, the temperature of the hydrothermal kettle is controlled at 160-180 ℃, and the reaction time is 18-24 h.
In S8, the rotating speed of the rotary evaporator is controlled to be 20-80rpm, the temperature is controlled to be 20-80 ℃, and the reaction time is 2-10 h.
In S9, the freeze-drying machine controls the air pressure to be 10Pa, the temperature to be-60 ℃ and the drying time to be 12 h.
According to the scheme, chitosan is used as a carbon source to modify and modify the surface of the lithium iron phosphate with carbon quantum dots, and a microwave ultrasonic and hydrothermal carbonization combined two-step method is used to modify the surface of the lithium iron phosphate with carbon quantum dots, so that the preparation method is simple, the prepared material is uniform in particle size and uniform in distribution, and has a large specific surface area; and the carbon quantum dots can expose more active sites for modifying the surface of the lithium iron phosphate, so that more spaces are provided for lithium ion storage, the conductivity of the lithium iron phosphate is better improved, and the lithium iron phosphate has excellent rate capability.
Furthermore, the self-disinfection magnetic stirrer comprises a stirring cup body and a safety disinfection cover, wherein a heat insulation baffle ring is fixedly sleeved at the outer end of the stirring cup body, the heat insulation baffle ring is made of nano heat insulation materials, a stirring abdicating hole is drilled in the center of the safety disinfection cover, a plurality of dripping abdicating holes are also drilled in the safety disinfection cover, the stirring abdicating hole and the dripping abdicating hole are both connected with sealing covers, the safety disinfection cover is matched with the heat insulation baffle ring, the inner wall of the safety disinfection cover is connected with a disinfection cross, the disinfection cross is formed by pressing crystal violet and mercury bromored particles, and phosphoric acid has certain toxicity; in the process of dropwise adding and stirring in the S4, the arrangement of the safe disinfection cover can prevent the solution in the stirring cup body from splashing, so that on one hand, the safety of operators in the stirring process can be enhanced, and on the other hand, the problem that the solution quality error is increased because the solution in the stirring cup body is easy to splash can be prevented; in the drying process of the precipitate in the S4, the precipitate can be placed in a stirring cup body, a sealing cover is covered, a certain amount of phosphoric acid gas is released by phosphoric acid during drying, the phosphoric acid gas has certain toxicity, the phosphoric acid gas moves upwards along with steam generated by the precipitate and is accumulated at a safe disinfection cover, the toxic gas is contacted with a disinfection cross, crystal violet and mercury bromored react with the phosphoric acid gas, the disinfection effect is achieved, and the safety of operators in the manufacturing process is improved.
Furthermore, the disinfection cross is clamped with the inner wall of the safe disinfection cover, so that the disinfection cross is convenient to disassemble and replace.
Furthermore, the outer end of the disinfection cross is wrapped with a fastening net, so that crystal violet and mercury bromored particles are not easy to damp and scatter.
Furthermore, the inner side of the safety disinfection cover is provided with an anti-dripping deformation block, the anti-dripping deformation block is positioned at the upper side of the disinfection cross frame, in the drying process of the sediment in S4, the water vapor generated by the sediment moves upwards and is attached to the surface of the anti-dripping deformation block, the anti-dripping deformation block can absorb the water vapor, the water vapor is prevented from forming water drops and reversely dripping on the sediment to be dried, the upper end of the anti-dripping deformation block abuts against the inner bottom end of the safety disinfection cover, the sealing cover is communicated with the inner side of the safety disinfection cover, the inner wall of the sealing cover is adhered with a color-changing coating, after the water vapor permeates the anti-dripping deformation block, redundant water can enter the sealing cover to contact with the color-changing coating, the color-changing coating changes color if the anhydrous copper sulfate powder layer changes blue when encountering water, when the initial water in the sediment is more, the color-changing coating can change when encountering water and then returns to the, at this moment, the precipitate is also completely dried, so that the color-changing coating on the sealing cover is convenient for operators to observe the drying condition of the precipitate, thereby ensuring that the precipitate D and the supernatant F in the S7 react in the hydrothermal kettle to obtain more ideal suspension G, and further improving the quality of the final product I.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) according to the scheme, the carbon quantum dot modification is carried out on the surface of the lithium iron phosphate by adopting a two-step method combining microwave ultrasonic and hydrothermal carbonization, the preparation method is simple, the particle size of the prepared material is uniform, the distribution is uniform, and the material has a large specific surface area.
(2) The carbon quantum dots can expose more active sites for surface modification of the lithium iron phosphate, so that more spaces are provided for lithium ion storage, the conductivity of the lithium iron phosphate is improved better, and the lithium iron phosphate has excellent rate capability.
(3) The carbon source modified by the carbon quantum dots is chitosan, the main component of the chitosan is chitin, free amino groups are contained in molecules, salt formation is easy to occur in an acid solution, active hydroxyl groups and amino groups are contained in macromolecules of the chitosan, and the active hydroxyl groups and the amino groups have strong chemical bonding capacity, so that the carbon quantum dots are more easily modified.
(4) In the process of dropwise adding and stirring in the S4, the arrangement of the safe disinfection cover can prevent the solution in the stirring cup body from splashing, so that on one hand, the safety of operators in the stirring process can be enhanced, and on the other hand, the problem that the solution quality error is increased because the solution in the stirring cup body is easy to splash can be prevented; in the drying process of the precipitate in the S4, the precipitate can be placed in a stirring cup body, a sealing cover is covered, a certain amount of phosphoric acid gas is released by phosphoric acid during drying, the phosphoric acid gas has certain toxicity, the phosphoric acid gas moves upwards along with steam generated by the precipitate and is accumulated at a safe disinfection cover, the toxic gas is contacted with a disinfection cross, crystal violet and mercury bromored react with the phosphoric acid gas, the disinfection effect is achieved, and the safety of operators in the manufacturing process is improved.
(5) After vapor soaks antidrip deformation piece that falls, unnecessary moisture can get into in the sealed lid with the coating contact that discolours, the coating that discolours meets water and discolours, if anhydrous copper sulfate bisque meets water and becomes blue, when initial moisture is more in the precipitate, the coating that discolours can meet water earlier and discolour, then change back original colour again under final drying action, explain this moment the precipitate also thoroughly dry, the event sealed epaxial coating that discolours makes things convenient for operating personnel to observe the dry condition of precipitate, thereby guarantee that deposit D and supernatant F react in hydrothermal kettle and obtain more ideal turbid liquid G in S7, and then improve the quality of final product I.
Drawings
FIG. 1 is a flow chart of a method of the present invention;
FIG. 2 is a graph of rate capability of a carbon quantum dot modified LiFePO4 material;
FIG. 3 is a TEM image of a carbon quantum dot modified lithium iron phosphate material of the present invention;
FIG. 4 is a perspective view of the self-disinfecting magnetic stirrer of the present invention in a stirring state;
FIG. 5 is an exploded view of the self-disinfecting magnetic stirrer of the present invention in a stirring state;
FIG. 6 is a perspective view of the self-disinfecting magnetic stirrer in a drying state;
fig. 7 is a perspective view of the safety cap of the present invention in an inverted state.
The reference numbers in the figures illustrate:
1 stirring cup body, 2 heat-insulating baffle rings, 3 safe disinfection covers, 4 stirring abdicating holes, 5 dripping abdicating holes, 6 sealing covers, 7 disinfection cross frames and 8 anti-dripping deformation blocks.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "top/bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "sleeved/connected," "connected," and the like are to be construed broadly, e.g., "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1:
referring to fig. 1, a method for preparing a carbon quantum dot modified LiFePO4 cathode material includes the following steps:
s1, weighing 5g of analytically pure ferrous salt, and dissolving in 50mL of distilled water to obtain a solution A;
s2, taking 5mL of analytically pure phosphoric acid, and adding distilled water to obtain a phosphoric acid solution B diluted to 60 mL;
s3, weighing 10g of analytically pure lithium phosphate, and dissolving the 10g of analytically pure lithium phosphate in 50mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer at a rotating speed of 400r/min, simultaneously dropwise adding the solution A and the solution B into the solution C, stirring while dropwise adding, centrifugally separating the generated precipitate, washing the precipitate for 3 times with distilled water, and drying in an oven at 60 ℃ to obtain a precipitate D;
s5, weighing 5g of chitosan, and dissolving the chitosan in 50mL of acetic acid solution with the mass fraction of 20% to obtain a mixed solution E;
s6, stirring the solution E for 10min, pouring the solution E into a microwave ultrasonic reaction kettle, controlling the microwave power to be 600W, controlling the reaction temperature to be 160 ℃, controlling the reaction time to be 1.5h and controlling the ultrasonic power to be 1500W, centrifugally separating the obtained mixed solution, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle at 160 ℃ for 24 hours to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, rotating at 20rpm and 20 ℃, and reacting for 10 hours to obtain a product H;
s9, placing the product H in a freeze dryer, wherein the air pressure is 10Pa, the temperature is-60 ℃, and the drying time is 12H, so that the final product I is obtained.
Example 2:
referring to fig. 1, a method for preparing a carbon quantum dot modified LiFePO4 cathode material includes the following steps:
s1, weighing 25g of analytically pure ferrous salt, and dissolving the analytically pure ferrous salt in 100mL of distilled water to obtain a solution A;
s2, taking 25mL of analytically pure phosphoric acid, and adding distilled water to obtain a phosphoric acid solution B diluted to 60 mL;
s3, weighing 25g of analytically pure lithium phosphate, and dissolving the analytically pure lithium phosphate in 80mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer at a rotating speed of 400r/min, simultaneously dropwise adding the solution A and the solution B into the solution C, stirring while dropwise adding, centrifugally separating the generated precipitate, washing the precipitate for 3 times with distilled water, and drying in an oven at 60 ℃ to obtain a precipitate D;
s5, weighing 10g of chitosan, and dissolving in 50mL of acetic acid solution with the mass fraction of 40% to obtain a mixed solution E;
s6, stirring the solution E for 60min, pouring the solution E into a microwave ultrasonic reaction kettle, controlling the microwave power to be 800W, controlling the reaction temperature to be 180 ℃, controlling the reaction time to be 1.5h and controlling the ultrasonic power to be 1000W, centrifugally separating the obtained mixed solution, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle at 180 ℃ for 18h to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, rotating at 80rpm and 80 ℃, and reacting for 5 hours to obtain a product H;
s9, placing the product H in a freeze dryer, wherein the air pressure is 10Pa, the temperature is-60 ℃, and the drying time is 12H, so that the final product I is obtained.
Example 3:
referring to fig. 1, a method for preparing a carbon quantum dot modified LiFePO4 cathode material includes the following steps:
s1, weighing 10g of analytically pure ferrous salt, and dissolving in 75mL of distilled water to obtain a solution A;
s2, taking 15mL of analytically pure phosphoric acid, and adding distilled water to obtain a phosphoric acid solution B diluted to 60 mL;
s3, weighing 15g of analytically pure lithium phosphate, and dissolving the 15g of analytically pure lithium phosphate in 60mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer at a rotating speed of 400r/min, simultaneously dropwise adding the solution A and the solution B into the solution C, stirring while dropwise adding, centrifugally separating the generated precipitate, washing the precipitate for 3 times with distilled water, and drying in an oven at 60 ℃ to obtain a precipitate D;
s5, weighing 5g of chitosan, and dissolving the chitosan in 50mL of acetic acid solution with the mass fraction of 30% to obtain a mixed solution E;
s6, stirring the solution E for 20min, pouring the solution E into a microwave ultrasonic reaction kettle, controlling the microwave power to be 800W, controlling the reaction temperature to be 170 ℃, controlling the reaction time to be 1h and controlling the ultrasonic power to be 1200W, centrifugally separating the obtained mixed solution, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle at 170 ℃ for 24 hours to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, rotating at 60rpm and 60 ℃, and reacting for 4 hours to obtain a product H;
s9, placing the product H in a freeze dryer, wherein the air pressure is 10Pa, the temperature is-60 ℃, and the drying time is 12H, so that the final product I is obtained.
Example 4:
referring to fig. 1, a method for preparing a carbon quantum dot modified LiFePO4 cathode material includes the following steps:
s1, weighing 20g of analytically pure ferrous salt, and dissolving the 20g of analytically pure ferrous salt in 60mL of distilled water to obtain a solution A;
s2, taking 25mL of analytically pure phosphoric acid, and adding distilled water to obtain a phosphoric acid solution B diluted to 60 mL;
s3, weighing 20g of analytically pure lithium phosphate, and dissolving the 20g of analytically pure lithium phosphate in 80mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer at a rotating speed of 400r/min, simultaneously dropwise adding the solution A and the solution B into the solution C, stirring while dropwise adding, centrifugally separating the generated precipitate, washing the precipitate for 3 times with distilled water, and drying in an oven at 60 ℃ to obtain a precipitate D;
s5, weighing 10g of chitosan, and dissolving the chitosan in 50mL of acetic acid solution with the mass fraction of 25% to obtain a mixed solution E;
s6, stirring the solution E for 50min, pouring the solution E into a microwave ultrasonic reaction kettle, controlling the microwave power to be 750W, controlling the reaction temperature to be 165 ℃, controlling the reaction time to be 0.5h and controlling the ultrasonic power to be 1100W, centrifugally separating the obtained mixed solution, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle at 160 ℃ for 24 hours to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, rotating at 30rpm and 70 ℃, and reacting for 8 hours to obtain a product H;
s9, placing the product H in a freeze dryer, wherein the air pressure is 10Pa, the temperature is-60 ℃, and the drying time is 12H, so that the final product I is obtained.
Example 5:
referring to fig. 1, a method for preparing a carbon quantum dot modified LiFePO4 cathode material includes the following steps:
s1, weighing 20g of analytically pure ferrous salt, and dissolving the 20g of analytically pure ferrous salt in 50mL of distilled water to obtain a solution A;
s2, taking 25mL of analytically pure phosphoric acid, and adding distilled water to obtain a phosphoric acid solution B diluted to 60 mL;
s3, weighing 14g of analytically pure lithium phosphate, and dissolving the 14g of analytically pure lithium phosphate in 59mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer at a rotating speed of 400r/min, simultaneously dropwise adding the solution A and the solution B into the solution C, stirring while dropwise adding, centrifugally separating the generated precipitate, washing the precipitate for 3 times with distilled water, and drying in an oven at 60 ℃ to obtain a precipitate D;
s5, weighing 7g of chitosan, and dissolving the chitosan in 50mL of acetic acid solution with the mass fraction of 35% to obtain a mixed solution E;
s6, stirring the solution E for 50min, pouring the solution E into a microwave ultrasonic reaction kettle, controlling the microwave power to be 620W, controlling the reaction temperature to be 175 ℃, controlling the reaction time to be 1.2h and controlling the ultrasonic power to be 1300W, centrifugally separating the obtained mixed solution, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle at 170 ℃ for 24 hours to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, rotating at 65rpm and 55 ℃, and reacting for 5 hours to obtain a product H;
s9, placing the product H in a freeze dryer, wherein the air pressure is 10Pa, the temperature is-60 ℃, and the drying time is 12H, so that the final product I is obtained.
Example 6:
referring to fig. 1, a method for preparing a carbon quantum dot modified LiFePO4 cathode material includes the following steps:
s1, weighing 21g of analytically pure ferrous salt, and dissolving in 76mL of distilled water to obtain a solution A;
s2, taking 17mL of analytically pure phosphoric acid, and adding distilled water to obtain a phosphoric acid solution B diluted to 60 mL;
s3, weighing 18g of analytically pure lithium phosphate, and dissolving in 60mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer at a rotating speed of 400r/min, simultaneously dropwise adding the solution A and the solution B into the solution C, stirring while dropwise adding, centrifugally separating the generated precipitate, washing the precipitate for 3 times with distilled water, and drying in an oven at 60 ℃ to obtain a precipitate D;
s5, weighing 6g of chitosan, and dissolving the chitosan in 50mL of acetic acid solution with the mass fraction of 28% to obtain a mixed solution E;
s6, stirring the solution E for 45min, pouring the solution E into a microwave ultrasonic reaction kettle, controlling the microwave power to be 700W, controlling the reaction temperature to be 180 ℃, controlling the reaction time to be 1h and controlling the ultrasonic power to be 1250W, centrifugally separating the obtained mixed solution, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle at 180 ℃ for 20 hours to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, rotating at the speed of 80rpm and the temperature of 20 ℃, and reacting for 3 hours to obtain a product H;
s9, placing the product H in a freeze dryer, wherein the air pressure is 10Pa, the temperature is-60 ℃, and the drying time is 12H, so that the final product I is obtained.
Referring to fig. 2, a rate performance graph of the carbon quantum dot modified LiFePO4 material prepared under the conditions of this example is shown. As can be seen from the figure, the LiFePO4 electrode modified by the carbon quantum dots has excellent rate capability. When the current density is 50mA · g < -1 >, the capacity is 170mAh · g < -1 >; when the current density is increased to 2000mA · g < -1 >, the capacity is 110mAh · g < -1 >, the rate capability is high, and the coulombic efficiency is stabilized at 30-100%.
Referring to fig. 3, a transmission electron micrograph of the carbon quantum dot modified LiFePO4 material prepared under the conditions of this example shows that black dots in the micrograph are carbon quantum dots, and are uniformly distributed on the surface of the lithium iron phosphate, and the size of the black dots is about 10 nm.
Example 7:
referring to fig. 1, a method for preparing a carbon quantum dot modified LiFePO4 cathode material includes the following steps:
s1, weighing 21g of analytically pure ferrous salt, and dissolving in 76mL of distilled water to obtain a solution A;
s2, taking 17mL of analytically pure phosphoric acid, and adding distilled water to obtain a phosphoric acid solution B diluted to 60 mL;
s3, weighing 18g of analytically pure lithium phosphate, and dissolving in 60mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer at a rotating speed of 400r/min, simultaneously dropwise adding the solution A and the solution B into the solution C, stirring while dropwise adding, centrifugally separating the generated precipitate, washing the precipitate for 3 times with distilled water, and drying in an oven at 60 ℃ to obtain a precipitate D;
s5, weighing 6g of chitosan, and dissolving the chitosan in 50mL of acetic acid solution with the mass fraction of 28% to obtain a mixed solution E;
s6, stirring the solution E for 45min, pouring the solution E into a microwave ultrasonic reaction kettle, controlling the microwave power to be 700W, controlling the reaction temperature to be 180 ℃, controlling the reaction time to be 1h and controlling the ultrasonic power to be 1250W, centrifugally separating the obtained mixed solution, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle at 180 ℃ for 20 hours to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, rotating at the speed of 80rpm and the temperature of 20 ℃, and reacting for 3 hours to obtain a product H;
s9, placing the product H in a freeze dryer, wherein the air pressure is 10Pa, the temperature is-60 ℃, and the drying time is 12H, so that the final product I is obtained.
Referring to fig. 4 and 5, the self-disinfecting magnetic stirrer comprises a stirring cup body 1 and a safe disinfecting cover 3, wherein the outer end of the stirring cup body 1 is fixedly sleeved with a heat-insulating baffle ring 2, the heat-insulating baffle ring 2 is made of nano heat-insulating material, a stirring abdicating hole 4 is formed in the center of the safe disinfecting cover 3, a plurality of dripping abdicating holes 5 are formed in the safe disinfecting cover 3, referring to fig. 6, sealing covers 6 are respectively connected to the stirring abdicating hole 4 and the dripping abdicating hole 5, the safe disinfecting cover 3 is matched with the heat-insulating baffle ring 2, referring to fig. 7, a disinfecting cross 7 is connected to the inner wall of the safe disinfecting cover 3, the disinfecting cross 7 is formed by pressing crystal violet and mercury bromored particles, and phosphoric acid has certain toxicity; in the process of dropwise adding and stirring in the S4, the arrangement of the safe disinfection cover 3 can prevent the solution in the stirring cup body 1 from splashing, so that on one hand, the safety of operators in the stirring process can be enhanced, and on the other hand, the situation that the solution is easy to splash out and the solution quality error is increased can be prevented; in the drying process of the precipitate in the S4, the precipitate can be placed in the stirring cup body 1, the sealing cover 6 is covered, a certain amount of phosphoric acid gas is released by phosphoric acid during drying, the phosphoric acid gas has certain toxicity, the phosphoric acid gas moves upwards along with steam generated by the precipitate and is accumulated at the safe disinfection cover 3, the toxic gas is in contact with the disinfection cross 7, crystal violet and mercury bromored react with the phosphoric acid gas, the disinfection effect is achieved, and the safety of operators in the manufacturing process is improved.
The disinfection cross 7 is clamped with the inner wall of the safety disinfection cover 3, so that the disinfection cross 7 is convenient to disassemble and replace; the outer end of the disinfection cross 7 is wrapped with a fastening net, so that crystal violet and mercury bromored particles are not easy to be affected with damp and scattered.
Referring to fig. 7, the inner side of the safety disinfection cover 3 is provided with an anti-dripping deformation block 8, the anti-dripping deformation block 8 is located on the upper side of the disinfection cross 7, during the drying process of the precipitate in S4, the water vapor generated by the precipitate moves upwards and is attached to the surface of the anti-dripping deformation block 8, the anti-dripping deformation block 8 is an internal porous material, such as a sponge, capable of absorbing the water vapor, preventing the water vapor from forming water drops and inversely dripping on the precipitate to be dried, the upper end of the anti-dripping deformation block 8 abuts against the inner bottom end of the safety disinfection cover 3, the sealing cover 6 is communicated with the inner side of the safety disinfection cover 3, the inner wall of the sealing cover 6 is adhered with a color-changing coating, after the water vapor soaks the anti-dripping deformation block 8, the excessive water can enter the sealing cover 6 to contact with the color-changing coating, if the anhydrous copper sulfate powder layer turns blue when the initial water content in the precipitate is large, the, and then the color of the precipitate is changed back to the original color under the final drying action, and the precipitate is completely dried at the moment, so that the color-changing coating on the sealing cover 6 is convenient for operators to observe the drying condition of the precipitate, thereby ensuring that the precipitate D and the supernatant F in S7 react in a hydrothermal kettle to obtain more ideal suspension G, and further improving the quality of the final product I.
According to the scheme, chitosan is used as a carbon source to modify and modify the surface of the lithium iron phosphate with carbon quantum dots, and a microwave ultrasonic and hydrothermal carbonization combined two-step method is used to modify the surface of the lithium iron phosphate with carbon quantum dots, so that the preparation method is simple, the prepared material is uniform in particle size and uniform in distribution, and has a large specific surface area; and the carbon quantum dots can expose more active sites for the surface modification of the lithium iron phosphate, so that more spaces are provided for the storage of lithium ions, the conductivity of the lithium iron phosphate is better improved, the lithium iron phosphate has excellent rate performance, and in addition, the self-disinfection magnetic stirrer with the safe disinfection cover 3 used in the manufacturing process can play a disinfection role in the reaction environment inside the container, so that the safety of operators in the manufacturing process is improved.
The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (10)
1. A preparation method of a carbon quantum dot modified LiFePO4 positive electrode material is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing 5-25g of analytically pure ferrous salt, and dissolving in 50-100mL of distilled water to obtain a solution A;
s2, taking 5-25mL of analytically pure phosphoric acid, and adding distilled water to dilute to 60mL to obtain a phosphoric acid solution B;
s3, weighing 10-30g of analytically pure lithium phosphate, and dissolving in 50-100mL of distilled water to obtain a solution C;
s4, placing the solution C on a self-disinfecting magnetic stirrer to be stirred at the rotating speed of 400r/min, simultaneously dripping the solution A and the solution B into the solution C, stirring while dripping, centrifugally separating the generated precipitate, washing the precipitate for 3 times by using distilled water, and drying the precipitate in an oven at the temperature of 60 ℃ to obtain a precipitate D;
s5, weighing 5-10g of chitosan, and dissolving in 50mL of acetic acid solution with the mass fraction of 20-40% to obtain a mixed solution E;
s6, stirring the solution E for 10-60min, pouring into a microwave ultrasonic reaction kettle, centrifugally separating the mixed solution obtained by the reaction, and taking supernatant F;
s7, placing the precipitate D in the supernatant F, and reacting in a hydrothermal kettle to obtain a suspension G;
s8, placing the suspension G in a rotary evaporator, and reacting to obtain a product H;
and S9, placing the product H in a freeze dryer, and reacting to obtain a final product I.
2. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 1, wherein: in S6, the microwave power of the microwave ultrasonic reaction kettle is controlled to be 800W for 600-.
3. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 1, wherein: in S7, the temperature of the hydrothermal kettle is controlled at 160-180 ℃, and the reaction time is 18-24 h.
4. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 1, wherein: in S8, the rotating speed of the rotary evaporator is controlled to be 20-80rpm, the temperature is controlled to be 20-80 ℃, and the reaction time is 2-10 h.
5. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 1, wherein: in S9, the freeze-drying machine controls the air pressure to be 10Pa, the temperature to be-60 ℃ and the drying time to be 12 h.
6. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 1, wherein: from disinfection magnetic stirrers includes stirring cup (1) and safe disinfection lid (3), the fixed cover of stirring cup (1) outer end has connect thermal-insulated fender ring (2), thermal-insulated fender ring (2) is nanometer thermal insulation material, safe disinfection lid (3) center department cuts a hole (4) of stepping down in the stirring, it has a plurality of droppings hole (5) of stepping down to still cut on safe disinfection lid (3), hole (4) of stepping down in the stirring and dropwise stepping down hole (5) department all are connected with sealed lid (6), safe disinfection lid (3) and thermal-insulated fender ring (2) phase-match, and safe disinfection lid (3) inner wall connection has disinfection cross (7).
7. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 6, wherein: the disinfection cross (7) is clamped with the inner wall of the safe disinfection cover (3).
8. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 6, wherein: the disinfection cross (7) is formed by pressing crystal violet and mercury bromored particles.
9. The method for preparing the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 8, wherein: the outer end of the disinfection cross (7) is wrapped with a fastening net.
10. The preparation method of the carbon quantum dot modified LiFePO4 cathode material as claimed in claim 6, wherein: safe disinfection lid (3) inboard is provided with antidrip deformation piece (8), antidrip deformation piece (8) are located disinfection cross (7) upside, and antidrip deformation piece (8) upper end offsets with safe disinfection lid (3) interior bottom, sealed lid (6) are linked together with safe disinfection lid (3) inboard, sealed lid (6) inner wall is stained with the coating that discolours.
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