CN113247962A - Battery anode material and method for rapidly synthesizing battery anode material - Google Patents

Battery anode material and method for rapidly synthesizing battery anode material Download PDF

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CN113247962A
CN113247962A CN202110715081.3A CN202110715081A CN113247962A CN 113247962 A CN113247962 A CN 113247962A CN 202110715081 A CN202110715081 A CN 202110715081A CN 113247962 A CN113247962 A CN 113247962A
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cathode material
temperature
lithium
battery
precursor
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CN113247962B (en
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不公告发明人
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Shenzhen Zhongke Jingyan Technology Co ltd
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    • C01G51/42Cobaltates containing alkali metals, e.g. LiCoO2
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M2220/30Batteries in portable systems, e.g. mobile phone, laptop
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    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a method for rapidly preparing a battery cathode material, which utilizes joule heat to rapidly raise and lower the temperature, obtains a cathode material with fine particles, is uniformly dispersed, and shows almost the same performance as the cathode material prepared by the traditional method, such as the LiCoO without any modification by rapidly preparing the cathode material by the method2First coulombic efficiency of positive electrode material89 percent, the first discharge specific capacity of 140 mAh/g, the coulombic efficiency of 300 cycles at 1C still approaches to 100 percent, and the capacity retention rate within 300 cycles still remains 85 percent. In addition, the method can also design a cathode material of a heterostructure and show excellent electrochemical performance.

Description

Battery anode material and method for rapidly synthesizing battery anode material
Technical Field
The invention relates to a method for rapidly preparing a battery anode material and the anode material prepared by the method. The positive electrode material obtained by the method has fine particles, is uniformly dispersed, and shows almost the same performance as the positive electrode material prepared by the traditional method, and the method can also design the positive electrode material with a heterostructure and show excellent electrochemical performance.
Background
Nowadays, the worldwide demand for energy is increasing day by day, and the acquisition of energy is mainly realized by the consumption of fossil fuel. However, resources such as petroleum, coal, natural gas and the like are increasingly exhausted, and acid rain, greenhouse effect and the like generated by combustion of fossil fuels can also seriously harm our living environment. Therefore, the development of some green energy sources is urgent. Under the large background of developing green energy, as an important energy storage device, a lithium ion battery has been widely used in various electronic products, vehicles, and large-scale energy storage systems. Lithium ion batteries are generally composed of positive electrode materials, negative electrode materials, separators, electrolytes, and battery cases. The cathode material as the core component of the whole battery directly influences the electrochemical performance of the battery. The cathode material prepared by the conventional method has a long time in a low temperature zone due to a slow temperature rise rate during calcination, and the low temperature zone is advantageous for surface diffusion of a crystal structure and causes particle coarsening, resulting in poor battery performance. And for the positive electrode material of the battery, the particles are small, so that the particles are uniformly beneficial to the contact of the positive electrode material with the binder and the conductive agent, and are beneficial to improving the cycle performance of the battery, and in addition, the particles are also beneficial to ion migration and improving the rate capability of the battery. Therefore, it is significant to develop a technology capable of rapidly obtaining a cathode material having small particles and uniform dispersion for improving the performance of a battery.
Disclosure of Invention
The invention overcomes the defects that the anode material prepared by the traditional method has low heating rate and long heat preservation time in the calcining process, causes particle coarsening and causes poor battery performance. The invention adopts joule heat to rapidly prepare the battery anode material, compared with the battery anode material prepared by the traditional method, the invention has high temperature rise rate in the calcining process, the calcining process is mainly in a high-temperature interval which mainly takes grain boundary growth and lattice diffusion, the prepared material has fine particles (can reach 50-100 nm) and uniform dispersion, and can ensure that certain materials obtain a heterojunction structure, the electrochemical performance is excellent, and the method can be used for replacing the traditional method for preparing the battery anode material.
Specifically, the method comprises the steps of rapidly heating a precursor of the anode material by using Joule heat, rapidly cooling after heating to a crystallization temperature, and obtaining the uniformly dispersed anode material, wherein the heating rate is 2200-.
Further, the joule heat is obtained by applying a voltage across the electrothermal layer.
Further, the electrothermal layer is selected from: carbon cloth, carbon felt, carbon paper, carbon film and carbon block.
In order to achieve a suitable rate of temperature increase, the art may set the current according to the heating rate of the selected electric heating layer, which is the rate of heat generated by the current passing through the conductor per unit time. Or different currents are applied to a specific electric heating layer, and the electric heating layer is tested by combining an infrared thermal imager to determine a feasible current interval.
Further, the method can also be provided with a barrier layer for preventing the flash-off of the precursor and the reaction of the precursor and the electrothermal layer on the electrothermal layer.
Further, the barrier layer is selected from Al2O3、SiO2、CaO、ZrO2
Further, the rapid cooling is realized by means of cutting off the power supply to stop the current.
The battery cathode material prepared by the method of claim 1, wherein the particle size of the cathode material is 50-100 nm.
Further, the positive electrode material is lithium cobaltate, the temperature is raised to 750 ℃ at 2200 ℃/min in the rapid synthesis process, the temperature is lowered to room temperature at 750 ℃/min, and the particle size of the obtained lithium cobaltate positive electrode material is 50-100 nm.
Further, the anode material is lithium iron phosphate, in the rapid synthesis process, the temperature is raised to 1000 ℃ at 80000 ℃/min, the temperature is kept for 24s, then the temperature is reduced to room temperature at 10000 ℃/min, and the particle size of the obtained lithium iron phosphate anode material is 50-100 nm.
Further, the certain battery positive electrode materials have a heterojunction structure.
Further, the positive electrode material is a lithium-rich material, and in the process of rapid synthesis, the temperature is raised to 600 ℃ at 83000 ℃/min, the temperature is kept for 14s, and then the temperature is reduced to room temperature at 9300 ℃/min; the obtained lithium-rich cathode material has a heterojunction structure, and the particle size of the lithium-rich cathode material is 50-100 nm.
The preparation of the precursor of the battery positive electrode material belongs to the common knowledge in the field, and can be prepared by a combustion method, a ball milling method and the like, and the preparation method specifically comprises the following steps:
(1) the method for preparing the precursor by adopting a combustion method and preparing the battery anode material by utilizing joule heat comprises the following steps:
step 1, dissolving a certain amount of metal acetate in a certain amount of solvent according to a stoichiometric ratio to form a solution A, and dissolving a certain amount of citric acid in a certain amount of solvent to form a solution B.
And 2, adding a certain amount of solvent which is the same as that in the step 1 into the three-neck flask, putting the three-neck flask into an oil bath pot for heating, dropwise adding the solution A and the solution B into the three-neck flask at a certain speed at the same time, and stirring at a constant speed in the titration process. After the end of the titration, the heating temperature of the oil bath was raised and stirred to dryness, after which the three-necked flask was placed in an air-forced drying oven for drying for a while.
And 3, fully grinding the dried precursor to obtain fine powder, quickly heating the powder by using Joule heat, keeping the temperature for a short time to obtain the battery anode material with fine and uniform particles, and heating the battery anode material by using specific heating equipment in the process.
(2) The method for preparing the battery anode material by using the precursor prepared by the ball milling method through joule heat comprises the following steps:
step 1, weighing a certain amount of Li according to stoichiometric ratio2CO3、FeC2O4、NH4H2PO4And sucrose. Weighing a certain amount of steel balls according to the ball-to-material ratio of 20: 3. Grinding the mixture for 3 to 6 hours by using a ball mill, wherein the rotating speed is kept at 300-450r/min in the ball milling process.
Step 2, grinding the ball-milled precursor powder, and then putting the grinded precursor powder into a vacuum drying oven for drying to obtain LiFePO4And (3) precursor powder.
And 3, rapidly heating and preserving heat for a short time by using the Joule heat generated by the substrate to obtain the battery cathode material with fine and uniform particles.
(3) LiFePO prepared directly by commercialized spray drying method4And the precursor powder is subjected to rapid heating and short-time heat preservation by using the Joule heat generated by the substrate, so that the battery cathode material with fine and uniform particles is obtained.
The invention has the advantages of greatly shortening the production period of the battery anode material, improving the production efficiency and reducing the energy consumption. Meanwhile, the battery anode material precursor synthesized by all the methods can be used for preparing the battery anode material, and the battery anode material prepared by Joule heating has fine particles and uniform dispersion. In addition, the invention can also design the battery anode material with the heterojunction structure. XRD (X-ray diffraction) characterization results show that the battery anode material prepared by Joule heat has good crystallinity and contains less impurities. The characterization result of a Scanning Electron Microscope (SEM) shows that the synthesized anode material has fine particles and is uniformly dispersed. The battery anode material prepared by the method has electrochemical performance comparable to that of the anode material prepared by the traditional method. The method can replace the traditional method and become a common method for synthesizing the battery anode material.
Drawings
Fig. 1(a) is an XRD spectrum of the lithium-rich manganese-based positive electrode material prepared by the present invention;
fig. 1(b) is an XRD spectrum of the lithium cobaltate positive electrode material prepared in the present invention;
fig. 1(c) is an XRD spectrogram of a lithium iron phosphate precursor prepared by a spray drying method using the lithium iron phosphate positive electrode material prepared by the present invention;
fig. 1(d) is an XRD spectrogram of a lithium iron phosphate precursor prepared by a ball milling method using a lithium iron phosphate positive electrode material prepared by the present invention;
fig. 2(a) is a Scanning Electron Microscope (SEM) image at a smaller magnification of a lithium-rich manganese-based positive electrode material prepared according to the present invention;
fig. 2(b) is a Scanning Electron Microscope (SEM) image at a larger magnification of the lithium-rich manganese-based positive electrode material prepared by the present invention;
fig. 2(c) is a Scanning Electron Microscope (SEM) image at a smaller magnification of a lithium cobaltate positive electrode material prepared according to the present invention;
fig. 2(d) is a Scanning Electron Microscope (SEM) image at a larger magnification of the lithium cobaltate positive electrode material prepared in the present invention;
fig. 2(e) is a Scanning Electron Microscope (SEM) image of a lithium iron phosphate precursor prepared by a spray drying method with a small magnification of the lithium iron phosphate positive electrode material prepared by the present invention;
fig. 2(f) is a Scanning Electron Microscope (SEM) image of a lithium iron phosphate precursor prepared by a spray drying method with a large magnification of the lithium iron phosphate positive electrode material prepared by the present invention;
FIG. 3 is a spherical aberration electron micrograph and an enlarged view and an electron diffraction diagram of a square frame area of the lithium-rich manganese-based positive electrode material prepared by the invention;
FIG. 4(a) is a cycle performance curve of the lithium-rich manganese-based positive electrode material prepared by the present invention at 0.1C;
fig. 4(b) is a charge-discharge curve of the lithium cobaltate positive electrode material prepared by the invention at 0.1C for the first three circles;
fig. 4(C) is a cycle performance curve of the lithium cobaltate positive electrode material prepared by the invention at 1C;
FIG. 4(d) is a graph showing rate performance of a lithium cobaltate positive electrode material prepared according to the present invention;
FIG. 4(e) is LiFePO prepared by spray drying4A cycle performance diagram of a finished product formed after the precursor is quickly calcined under the multiplying power of 1C;
FIG. 4(f) shows LiFePO prepared by spray drying4The charge and discharge curves of the first three cycles of the sample formed by the rapid calcination of the precursor at 0.1C.
Detailed Description
Example 1
(1) The precursor of the lithium-rich manganese-based positive electrode material prepared by a combustion method comprises the following steps:
step 1, 13g of lithium acetate, 5g of nickel acetate and 15g of manganese acetate were dissolved in stoichiometric proportions in 50ml of absolute ethanol to form a solution A. 21g of citric acid was dissolved in 50ml of absolute ethanol to form a solution B.
And 2, adding 250ml of absolute ethyl alcohol into a three-necked flask, putting the three-necked flask into an oil bath pot for heating, simultaneously dropwise adding the solutions A and B into the three-necked flask at a certain speed, and stirring at a constant speed in the titration process, wherein the heating temperature is 80 ℃. After titration, the heating temperature of the oil bath is increased to 100 ℃ and stirred to be dry, and then the three-neck flask is placed in an air-blowing drying oven to be dried for a period of time, wherein the heating temperature is 100 ℃ and the heating time is 12 hours.
And 3, drying the precursor prepared by the combustion method, fully grinding the dried precursor to obtain fine powder, wherein the grinding time is 15min, and obtaining 0.1mol of precursor.
Step 4, in this example, a carbon cloth of 1 × 3cm size, which is purchased from taiwan carbon technologies, ltd, taiwan, was used for rapid heating2(ii) a In order to ensure that the temperature of the carbon cloth reaches the corresponding temperature rise rate, a temperature rise rate test is carried out on the carbon cloth before heat treatment is carried out to obtain a current-temperature rise rate curve, and finally the temperature rise rate is determined to be 83000 ℃/min under 11A.
Paving part of the precursor powder obtained in the step 3, placing the precursor powder on a carbon cloth substrate, placing the carbon cloth substrate in a tubular furnace, calcining at the temperature of 450 ℃, and preserving heat for 5 hours to fully remove organic matters in the carbon cloth substrate; and grinding by using a mortar, and performing secondary calcination to form crystals after uniform grinding. And (3) paving the secondary calcination on a carbon cloth substrate like the primary calcination, switching in a direct current power supply to electrify, adjusting the power supply gear of the direct current power supply to 11A, controlling the electrifying time to be 15s, and calcining by using Joule heat. The temperature of the secondary calcination is measured by an infrared thermal imager, the temperature is measured by the infrared thermal imager, the temperature rise rate is 83010 ℃/min, and the temperature drop rate is 9300 ℃/min. The brown lithium-rich manganese-based material Li can be obtained after rapid heating and cooling1.2Ni0.2Mn0.6O2(labeled sample 1).
Step 5, calcining part of the precursor powder obtained in the step 3 according to a tubular furnace heating method, wherein the primary calcining temperature is 450 ℃, and preserving heat for 5 hours to fully remove organic matters in the precursor powder (synchronous removal)The treatment of step 4); heating the secondary calcination to 900 ℃ at a speed of 250 ℃/min, and keeping the temperature for 12h to obtain the brown lithium-rich manganese-based material Li1.2Ni0.2Mn0.6O2(labeled sample 2).
As can be seen from the XRD spectrum of fig. 1(a), the lithium-rich manganese-based positive electrode material shown in sample 1 has relatively sharp and intense diffraction peaks, and exhibits better crystallinity. By comparison with standard PDF card, the weak diffraction peak in the range of 20-30 ℃ is originated from monoclinic (C2/m) Li2MnO3The superlattice structure of the phase has a weak hetero-peak around 45 degrees, which is a diffraction peak corresponding to NiO formed in the calcining process. NiO belongs to rock salt phase and has a cubic crystal structure. XRD results show that a lithium-rich and nickel oxide two-phase composite heterojunction structure is successfully prepared by using Joule heat. Lithium-rich manganese-based positive electrode material shown in sample 2 and Li2MnO3And LiNiO2Match the standard PDF card of (1). The XRD results showed that sample 2 had only diffraction peaks of lamellar phase and did not contain diffraction peaks of other phases, so sample 2 had only Li1.2Ni0.2Mn0.6O2This phase, no Li produced1.2Ni0.2Mn0.6O2And a heterojunction structure of NiO.
Fig. 2(a) shows an SEM of a sample of a lithium-rich manganese-based positive electrode material synthesized using the present invention. When the material is observed under the scale of 500nm, the prepared material is small-sized irregular particles with the sizes ranging from tens of nanometers to hundreds of nanometers, and the particles are uniformly distributed and have no agglomeration phenomenon. The sample prepared by the tube furnace is observed under the same scale, the particle size of the sample is larger than that of the sample prepared by the invention, and the particles are mutually aggregated and have serious agglomeration phenomenon.
Fig. 3 shows a Transmission Electron Microscope (TEM) image of the lithium-rich manganese-based positive electrode material. It is obvious from the results of a spherical aberration electron microscope that the lithium-rich manganese-based positive electrode material prepared by the invention is a composite structure formed by layers and nickel oxide rock salt phases. The nickel oxide is an electrochemical inert substance, can play a role in stabilizing a crystal structure in the lithium-rich manganese-based positive electrode material, and reduces the irreversible transformation from a lamellar state to a spinel phase, so that the cycle performance of the whole material is improved. Similarly, when the internal structure of the sample prepared by the tube furnace is observed by using a TEM, it is clear from the image that the sample only contains a layered structure, and no lattice fringes of the rock salt phase NiO are observed, further indicating that the sample prepared by the tube furnace does not form a heterojunction structure.
Fig. 4(a) shows a cycle performance curve of the lithium-rich manganese-based positive electrode material prepared according to the present invention, and the result shows that the capacity is not attenuated after 45 cycles of cycling at a rate of 0.1C. But the capacity retention rate of the sample prepared by the tube furnace circulating 45 circles under the current density of 0.1C is only 70%.
Example 2
In this embodiment, based on embodiment 1, a joule heat treatment method is also adopted for the removal process of the organic matter in the precursor. Meanwhile, in order to prevent the flash-off of the precursor and the reaction between the precursor and the electrothermal layer, a barrier layer Al is provided in the embodiment2O3(0.65 mm thick, from Xinghua electronics, Foshan).
In this embodiment, the carbon cloth of the same size as that in example 1 is adopted, and due to the arrangement of the barrier layer, the temperature-rise rate is reduced to a certain extent, and before the thermal treatment, a temperature-rise rate test is performed on the carbon cloth provided with the barrier layer to obtain a current-temperature-rise rate curve, and finally it is determined that the temperature-rise rate is 800 at 12A and 2200 ℃/min at 19A; the method comprises the following specific steps:
step 1, lithium acetate and cobalt nitrate are completely dissolved together with ultrapure water according to a stoichiometric ratio (5% excess lithium salt is required to prevent lithium loss) (the concentrations of lithium acetate and cobalt nitrate are both 2M/L), and complexation is performed at 80 ℃ by using a citric acid aqueous solution (the concentration of the citric acid aqueous solution is 2M/L) as a complexing agent. The specific process of the complexing is that the metal salt aqueous solution and the citric acid aqueous solution are simultaneously dripped into a certain amount of ultrapure water (the amount of the ultrapure water is 150mL per 0.1M of the metal salt), the metal salt aqueous solution and the citric acid aqueous solution are continuously stirred at the same time, and after the two solutions are completely dripped, the temperature is raised to 100 ℃ for liquid evaporation. And after the liquid is completely evaporated to dryness, transferring the liquid into an oven to be dried at 100 ℃ overnight, taking out the dried liquid and grinding the dried liquid in a mortar to fine powder, namely the precursor of the lithium cobaltate cathode material.
Step 2, uniformly paving the lithium cobaltate positive electrode material precursor prepared in the step 1 on a barrier layer Al with good heat conductivity2O3And after paving, placing the carbon cloth on a carbon cloth substrate, switching on a direct current power supply for electrifying with an open-circuit voltage of 20V, adjusting the power supply level of the direct current power supply to 12A, controlling the electrifying time to be 30s, calcining by using Joule heat, grinding by using a mortar, uniformly grinding, and then carrying out secondary calcination. And (3) paving the secondary calcination on a barrier layer with good heat conductivity like the primary calcination, switching on a direct current power supply to be electrified, adjusting the power supply gear of the direct current power supply to 19A, controlling the electrifying time to be 18s, and calcining by using Joule heat. The temperature of the two calcinations is measured by an infrared thermal imager, the heating rates are 810 and 2209 ℃/min respectively, and the cooling rates are 700 and 750 ℃/min respectively; and (3) rapidly heating and cooling to obtain the lithium cobaltate cathode material (marked as sample 1).
And 3, calcining part of the precursor powder obtained in the step 1 according to a traditional calcining method, uniformly spreading the precursor in an alumina ceramic boat, putting the alumina ceramic boat into a tube furnace for twice calcining, wherein the primary calcining condition is that the temperature is kept at 450 ℃ for 5 hours, grinding the precursor by using a mortar, and then carrying out secondary calcining, and the secondary calcining condition is that the temperature is kept at 750 ℃ for 10 hours, thus obtaining the lithium cobaltate (marked as sample 2).
As shown in FIG. 1(b), X-ray diffraction (XRD) pattern showed that lithium cobaltate cathode material and LiCoO were rapidly synthesized2Compared with the standard PDF card, the diffraction peaks of the standard PDF card are consistent, and meanwhile, two pairs of bifurcate peaks of the standard PDF card show that the standard PDF card has a good layered structure.
Fast synthesis of LiCoO2Morphology of the particles, rapidly synthesized LiCoO, as shown in FIGS. 2(c) and 2(d)2Particles of positive electrode material and LiCoO synthesized in other documents2Compared with particles, the particles of the positive electrode material are finer (the particle size is 50-100 nm), and the dispersion is more uniform.
FIG. 4(b) is a schematic diagram for preparing LiCoO2Charge and discharge curves of the material, which show a typical LiCoO2Characteristics of the positive electrode materialThe specific sub-discharge capacity is 140 mAh/g, and as shown in FIG. 4(c), the lithium cobaltate cathode material prepared by the process of the present invention has cycle performance (84% of capacity retention rate after 300 cycles under 1 c) comparable to that of the lithium cobaltate cathode material prepared by the conventional process and rate performance as shown in FIG. 4 (d).
Example 3
Rapidly synthesizing a lithium iron phosphate anode material according to the following steps;
step 1, preparing LiFePO by ball milling method4And (3) precursor. The whole ball milling process is specifically operated as follows, firstly, a certain amount of Li is weighed according to the stoichiometric ratio2CO3、FeC2O4、NH4H2PO4And sucrose. Weighing a certain amount of steel balls according to the ball-to-material ratio of 20:3, and grinding the steel balls for 3-6h by using a ball mill, wherein the rotating speed is kept at 300-. After the ball milling is finished, putting the ball-milled precursor powder into a vacuum drying oven to be dried under the vacuum condition, and obtaining LiFePO4a/C precursor powder.
Step 2, in this example, a carbon cloth of 1 × 3cm size, which is purchased from taiwan carbon technologies, ltd, taiwan, was used for rapid heating2(ii) a In order to ensure that the carbon cloth reaches the corresponding heating rate, a heating rate test is carried out on the carbon cloth before heat treatment is carried out to obtain a current-heating rate curve, the heating rate is finally determined to be 81000 ℃/min under 16A,
putting the sample and the experimental device into a glove box filled with inert gas, spreading the precursor powder on the carbon cloth substrate, switching on a direct current power supply for electrifying, wherein the open-circuit voltage is 20V, the current is 16A, the electrifying time is 25s, and calcining by using Joule heat. Measuring the temperature by an infrared thermal imager, wherein the heating rate is 81012 ℃/min; and then preserving the heat for 24s, naturally cooling after power failure, and measuring the temperature by an infrared thermal imager, wherein the cooling rate is 10090 ℃/min. After rapid temperature rise and temperature reduction, LiFePO can be obtained4powder/C (labeled sample 1).
In addition, the lithium iron phosphate precursor prepared by a commercial spray drying method is prepared by adopting a solid phase methodThe similar steps are as follows: and flatly paving the precursor powder on the carbon cloth substrate, switching on a direct current power supply for electrifying, wherein the open-circuit voltage is 20V, the current is 16A, the electrifying time is 25s, the temperature after electrifying reaches 1000 ℃, and calcining by using Joule heat. Measuring the temperature by an infrared thermal imager, wherein the heating rate is 80000 ℃/min; and then preserving the heat for 24s, cooling, and measuring the temperature by an infrared thermal imager, wherein the cooling rate is 10000 ℃/min. After rapid temperature rise and temperature reduction, LiFePO can be obtained4the/C positive electrode material (labeled sample 2).
And 3, marking the positive electrode material of the lithium iron phosphate battery purchased from Tianjin Consted automobile technology Limited liability company as a sample 3.
FIGS. 1(c) and 1(d) show LiFePO prepared by spray drying and ball milling4XRD pattern of sample after rapid calcination of/C precursor. The main diffraction peaks of sample 1, sample 2 and sample 3 can be matched with olivine-type LiFePO4PDF card (NO. 83-2092) is corresponding to the standard, and no other obvious impurity peaks are observed, which indicates that the method prepares purer LiFePO4And C, a positive electrode material.
FIGS. 2(e) and 2(f) show LiFePO prepared by spray drying4the/C precursor powder was prepared using joule heating for Scanning Electron Microscope (SEM) spectroscopy of the resulting sample 2. It can be seen from the figure that the sample prepared by the present invention has a particle size of about 50-100nm, which is smaller than that of sample 3. Such fine particles facilitate the subsequent lithium ion intercalation and deintercalation process.
FIG. 4(f) shows LiFePO prepared by spray drying4Charge and discharge curves at 0.1C for samples formed by rapid calcination of the/C precursor. LiFePO appears in the figure4Distinct voltage plateau (3.45V vs. li)+/Li), the electrochemical reaction can be expressed as: FePO4+xLi++xe-→Li1-XFePO4This is typical of LiFePO4Two-phase transformation characteristics, indicating that the purity of the synthesized sample is higher. And from this figure a rapidly prepared LiFePO can be obtained4The specific discharge capacity of the first circle under 0.1C can reach 142 mAh/g. FIG. 4(e) shows LiFePO prepared by spray drying4And (3) a cycle performance diagram of a finished product formed by the precursor after rapid calcination under the multiplying power of 1C. Fast-preparing LiFePO4When the battery is cycled at the rate of 1C for nearly 160 circles, the capacity retention rate can reach 88%, when the battery is cycled for nearly 200 circles, the capacity retention rate can reach 85%, and the charge-discharge efficiency of each circle can reach 99%. Has excellent electrochemical performance.

Claims (11)

1. The method for rapidly synthesizing the battery anode material is characterized by comprising the following steps: the method comprises the steps of rapidly heating a precursor of the anode material by using Joule heat, rapidly cooling after heating to a crystallization temperature, and obtaining the uniformly dispersed anode material, wherein the heating speed is 2200-.
2. The method of claim 1, wherein the joule heating is obtained by applying a voltage across an electrothermal layer.
3. The method of claim 2, wherein the electrically heated layer is a carbon cloth, carbon felt, carbon paper, carbon film, or carbon block.
4. The method according to claim 2, further comprising providing a barrier layer on the electrically heated layer for preventing flash-off of the precursor and for preventing reaction of the precursor with the electrically heated layer.
5. The method of claim 4, wherein the barrier layer is Al2O3、SiO2CaO or ZrO2
6. The method of claim 1, wherein the rapid cooling is achieved by shutting off power to stop current flow.
7. The battery cathode material prepared by the method of claim 1, wherein the particle size of the cathode material is 50-100 nm.
8. The battery cathode material according to claim 7, wherein the cathode material is lithium cobaltate, and during the rapid synthesis process, the temperature is raised to 750 ℃ at 2200 ℃/min, and then is lowered to room temperature at 750 ℃/min, and the particle size of the obtained lithium cobaltate cathode material is 50-100 nm.
9. The battery cathode material according to claim 7, wherein the cathode material is lithium iron phosphate, the temperature is raised to 1000 ℃ at 80000 ℃/min during the rapid synthesis process, the temperature is maintained for 24s and then lowered to room temperature at 10000 ℃/min, and the particle size of the obtained lithium iron phosphate cathode material is 50-100 nm.
10. The battery positive electrode material according to claim 7, wherein the battery positive electrode material has a heterojunction structure.
11. The battery cathode material according to claim 10, wherein the cathode material is a lithium-rich material, and during the rapid synthesis process, the temperature is raised to 600 ℃ at 83000 ℃/min, and the temperature is lowered to room temperature at 9300 ℃/min after being maintained for 14 s; the obtained lithium-rich material cathode material has a heterojunction structure, and the particle size of the lithium-rich material cathode material is 50-100 nm.
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