CN109167060B - Preparation method of porous lithium iron phosphate electrode material - Google Patents

Preparation method of porous lithium iron phosphate electrode material Download PDF

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CN109167060B
CN109167060B CN201810924854.7A CN201810924854A CN109167060B CN 109167060 B CN109167060 B CN 109167060B CN 201810924854 A CN201810924854 A CN 201810924854A CN 109167060 B CN109167060 B CN 109167060B
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lifepo
ethylene glycol
electrode material
iron phosphate
lithium iron
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CN109167060A (en
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卑凤利
陈均青
余毛省
朱律忠
陈俊辉
储海蓉
侯晶晶
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Nanjing University of Science and Technology
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention disclosesA preparation method of the porous lithium iron phosphate electrode material is provided. The method comprises the steps of taking lithium hydroxide and slightly excessive phosphoric acid as a lithium source and a phosphorus source, synthesizing a lithium phosphate precursor by a precipitation method under the stirring condition, taking ethylene glycol as a dispersing agent of a solvothermal method and an auxiliary agent for generating air holes, uniformly mixing and dispersing the solution of the precursor, taking ferrous sulfate as an iron source and ascorbic acid as a reducing agent, and preparing LiFePO by a hydrothermal reaction4And finally, calcining at high temperature in the nitrogen atmosphere to obtain the nano porous lithium iron phosphate electrode material. The porous lithium iron phosphate electrode material prepared by the invention has excellent rate capability and excellent cycle performance, and the charge-discharge voltage platform is stable and has higher specific capacity.

Description

Preparation method of porous lithium iron phosphate electrode material
Technical Field
The invention belongs to the technical field of electrode material preparation, and relates to a preparation method of a porous lithium iron phosphate electrode material.
Background
As a lithium ion positive electrode material, LiFePO of olivine structure4Has higher theoretical capacity (170mAh g)-1) The method has the advantages of excellent capacity retention rate, environmental friendliness, low cost, safety, no toxicity and the like. However, LiFePO is severely affected by the inherent drawbacks of slow diffusion rate of lithium ions inside the material itself and poor conductivity of external electrons4The multiplying power performance and the cycle performance of the energy storage system greatly restrict the application of the energy storage system.
In order to solve the problem of low electronic conductivity outside the material, the general method is to coat the material with carbon to form a conductive network on the outer surface of the material, so that the electronic conductivity outside the material is greatly improved. However, the carbon coating usually involves high-temperature calcination, and the selection and coating degree of the carbon material, the coating process is complex and the process is complicated. And isThe general coating is a coating part of material, which is microscopically uneven, and the conductive network is disordered. Document 1 (Anoptimized Ni sequenced LiFePO)4/C nanocomposite with excellent rate performance[J]Carbon-coated Ni-doped LiFePO was reported in Electrochimica acta.55 (2010) 5886-4The composite material has excellent cycle performance, high specific capacity and high capacity retention rate under high current, but has complex synthesis conditions, disordered conductive networks and high energy consumption.
At present, the conductivity of the metal ion doped lithium iron phosphate is improved mainly by changing the internal ionic conductivity of the metal ion doped lithium iron phosphate. Doping the metal cations in the lithium position with a hypervalent state can increase the overall conductivity of the material by p-type and n-type conduction. First principles calculations reveal information about LiMPO4(M ═ Fe, Mn, Co, and Ni) Li on a nonlinear pathway+The lowest migration energy, so iron site doping is a more effective method for improving the internal conductivity of the material. Equivalent cation (Mg)2+,Cu2+,Co2+Etc.) are readily available in LiFePO4The Fe site is occupied, the crystal distortion is reduced, and more de-intercalation space is provided for Li. Document 2(Amol Naik, et al, Rapid and simple synthesis of Mn doped porous LiFePO 4/C from icon carbonyl complex [ J]Journal of Energy institute, 2015,1-9) synthesis of Mn-doped mesoporous carbon-coated LiFePO by microwave-assisted solid phase method4/C, wherein Mn: fe is 1:99, and the specific first discharge capacity of 0.1C is 163.2 mAh/g. However, most of the cation doping adopts a solid phase method, and has many disadvantages: if the solid phase raw materials are not uniformly mixed, the product has more impurities; generally, very high temperature is needed, and the energy consumption is large; the low-price metal is easy to be oxidized, and the cost of introducing protective gas is high; the metal doping of the synthesized target product is difficult to accurately control; the appearance is poor, the agglomeration is serious, and an ideal battery anode material cannot be obtained.
By controlling LiFePO4Morphology and size of, can shorten Li+A diffusion path. LiFePO4Is a crystal with olivine structure, and Li is generated during the charge and discharge of lithium battery+Is along [010]The one-dimensional channel of the direction is diffused, and the charge transfer mainly occurs in the {010} crystal plane, thereby ensuring that{010} crystal orientation improves Li+This requires LiFePO4In [010 ]]Fully grows in the direction. Existing LiFePO4The shapes of the particles are sheet, rod and square, and the corresponding specific capacities are all 140-150 mAh.g-1The ideal shape is sheet-like or quadrangular prism-like. Document 3 (Mn-doped modified {010} plane preferentially-grown lithium iron phosphate nanosheet [ J ]]Journal of western national university 2015.03.021) synthesized a flake-form Mn-doped LiFePO4The material has high first-time circulating specific capacity and excellent circulating performance, but has small specific surface area and poor charge and discharge performance under large current.
Disclosure of Invention
To increase LiFePO4The invention provides a preparation method of a porous lithium iron phosphate electrode material, which has high specific capacity and improved cycle and rate performance.
The technical solution of the invention is as follows:
the preparation method of the porous lithium iron phosphate electrode material comprises the following specific steps:
step 1, adding H3PO4Adding the solution into LiOH solution, and reacting to obtain Li3PO4Adding ethylene glycol, adding FeSO containing ascorbic acid under nitrogen protection4Solution, reaction to obtain LiFePO4Precursor solution of said LiFePO4In the precursor solution, the volume ratio of the ethylene glycol to the water is 3: 7-5: 5;
step 2, LiFePO4Carrying out solvothermal reaction on the precursor solution at 180-200 ℃, washing and drying to obtain LiFePO4；
Step 3, LiFePO in nitrogen atmosphere4Calcining at 550-650 ℃ to obtain the nano porous lithium iron phosphate electrode material.
Preferably, in step 1, the FeSO4:H3PO4The molar ratio of LiOH is 1:1.05: 3.
Preferably, in the step 2, the solvothermal reaction time is 12-18 h.
Preferably, in the step 3, the calcination time is 5-7 h.
Compared with the prior art, the invention has the following advantages:
the invention takes ethylene glycol as a dispersing agent and a pore-producing auxiliary agent, generates nanometer-level micropore on the surface of the material while controlling the shape and the particle size of the material, increases the specific surface area of the material, increases the contact area of the material and electrolyte, and shortens Li+The charge-discharge specific capacity and the charge-discharge efficiency of the material are improved by the de-embedded pore channel, and the first charge-discharge specific capacity of the material reaches 150 mAh.g-1The cycle performance is also very stable (the capacity retention rate is more than 95% after 60 cycles).
Drawings
FIG. 1 shows LiFePO without addition of ethylene glycol 415% ethylene glycol LiFePO430% ethylene glycol LiFePO445% ethylene glycol LiFePO460% ethylene glycol LiFePO4XRD pattern of (a).
FIG. 2 shows LiFePO without addition of ethylene glycol4(a) 15% ethylene glycol LiFePO4(b) 30% ethylene glycol LiFePO4(c) 45% ethylene glycol LiFePO4(d) TEM image of (a).
FIG. 3 is 30% ethylene glycol LiFePO4BET data plots.
FIG. 4 is a 30% ethylene glycol LiFePO4The first charge-discharge curve of the electrode material under different multiplying power conditions.
FIG. 5 shows LiFePO with 0-60% ethylene glycol4And (3) attenuation graphs of the electrode material which is circularly charged and discharged for 70 times under different multiplying factors.
FIG. 6 is pure LiFePO415% ethylene glycol LiFePO430% ethylene glycol LiFePO445% ethylene glycol LiFePO460% ethylene glycol LiFePO40.2C first discharge specific capacity map.
Detailed Description
The invention is further described in detail below with reference to the figures and examples.
Example 1
30% ethylene glycol LiFePO4The preparation method comprises the following steps:
(1) li precipitated by pH adjustment and stirring3PO4: according to the molar ratio of 1:1.05:3Separately weighing FeSO4·7H2O7.06g， H3PO42.6g，LiOH·H2O3.0g, dissolved in deionized water to prepare 50mL solution respectively, and then H is added3PO4Adding the mixture into LiOH to form milky suspension, respectively weighing 25mL, 45mL, 67.5mL and 90mL of ethylene glycol, adding the ethylene glycol into the suspension, and keeping the stirring condition;
(2) synthesis of LiFePO4Precursor: 0.2g ascorbic acid was weighed out and added to the light green FeSO4Dissolving in solution, dropwise adding the light green solution into Li3PO4In a milky white suspension, a dark green precipitate LiFePO is produced4And the precursor, wherein the volume ratio of the ethylene glycol to the water is 15:85, 30:70, 45:55 and 60:40 respectively. In the process, nitrogen is kept introduced to prevent Fe2+Oxidizing, and dropwise adding while keeping stirring condition for 15 min;
(3) the obtained precursor LiFePO4The solution is quickly transferred into 4 polytetrafluoroethylene hydrothermal reaction inner containers with the volume of 80mL, the hydrothermal reaction temperature is 200 ℃ after sealing, and the hydrothermal reaction time is 15 h. Taking out the product after the reaction, washing with water for three times, washing with ethanol for three times, placing in a drying oven at 80 ℃, and drying overnight. Placing the dried sample in a tubular furnace, calcining at the high temperature of 600 ℃ for 5h under the condition of high-purity nitrogen (99.99 percent), naturally cooling to room temperature, and grinding to obtain 15 percent ethylene glycol LiFePO430% ethylene glycol LiFePO445% ethylene glycol LiFePO4。
Comparative example 1
Pure LiFePO4The preparation method comprises the following steps:
(1) precipitation of Li by pH adjustment and stirring3PO4: respectively weighing FeSO according to the molar ratio of 1:1.05:34·7H2O7.06g， H3PO42.6g，LiOH·H2O3.0g, dissolved in deionized water to prepare 50mL solution respectively, and then H is added3PO4Adding into LiOH to form milky suspension;
(2) synthesis of LiFePO4Precursor: 0.2g ascorbic acid was weighed out and added to the light green FeSO4Dissolving in solution, dropwise adding the light green solution into Li3PO4Milky white suspensionIn the turbid solution, a dark green precipitate was produced. In the process, nitrogen is kept introduced to prevent Fe2+Oxidizing, and dropwise adding while keeping stirring condition for 15 min;
(3) the obtained precursor LiFePO4The solution is quickly transferred into 4 polytetrafluoroethylene hydrothermal reaction inner containers with the volume of 80mL, the hydrothermal reaction temperature is 200 ℃ after sealing, and the hydrothermal reaction time is 15 h. Taking out the product after reaction, washing with water for three times, washing with ethanol for three times, placing in a drying oven at 80 ℃, and drying overnight. Placing the dried sample in a tube furnace, calcining at the high temperature of 600 ℃ for 5h under the condition of high-purity nitrogen (99.99 percent), naturally cooling to room temperature, and grinding to obtain LiFePO4。
FIG. 1 shows LiFePO without addition of ethylene glycol 415% ethylene glycol LiFePO430% ethylene glycol LiFePO445% ethylene glycol LiFePO460% ethylene glycol LiFePO4XRD pattern of (a). It can be seen from the figure that pure LiFePO was synthesized4With mesoporous LiFePO added with glycol as an auxiliary agent4Has almost the same XRD peak pattern, and the peak positions correspond to the standard peaks one by one. Illustrating the LiFePO synthesized in the examples4Is phase-pure and the product is LiFePO of olivine type4There are no heterogeneous phases.
The appearance of the product was observed and analyzed by Transmission Electron Microscopy (TEM), and FIG. 2 shows LiFePO without ethylene glycol 415% ethylene glycol LiFePO430% ethylene glycol LiFePO445% ethylene glycol LiFePO4A is LiFePO without addition of ethylene glycol4B is 15% ethylene glycol LiFePO4And c is 30% ethylene glycol LiFePO4D is 45% ethylene glycol LiFePO4. It can be seen that LiFePO was not added with ethylene glycol4Has non-uniform morphology, the length is about 700-800nm, the width is 300-400nm, and LiFePO does not use ethylene glycol as the morphology control machine4The particles of (a) are large, non-uniform, and non-porous structures. And 15% ethylene glycol LiFePO 430% ethylene glycol LiFePO445% ethylene glycol LiFePO4The shapes of the particles are relatively uniform, the particles are irregular segment dry types, the particle size is about 300nm, and the particles are all provided with holes, which is the function of ethylene glycol. Compared with 30% of ethylene glycol LiFePO4And 45 percentEthylene glycol LiFePO 415% ethylene glycol LiFePO4The surface pore size is smaller and is only 2-3nm, while the latter has a pore size of 8-10 nm. The amount of ethylene glycol added can control the pore size, however, too much ethylene glycol is added (60% ethylene glycol LiFePO)4) Instead, more pores are generated on the surface of the material, and the size of the pores is not uniform, which affects the electrochemical performance of the material.
FIG. 3 is 30% ethylene glycol LiFePO4BET data, it can be seen that N2The absorption and desorption curves have smaller hysteresis loops, which shows that a small number of irregular small holes are formed in the material, and compared with a transmission electron microscope, the holes are positioned on the surface of the material, so that the specific surface area of the material can be increased to a certain extent, and Li is shortened+The small number of holes can ensure the stability of the material structure. BET data show 30% ethylene glycol LiFePO4The pore size of the material is approximately 8-10 nm.
FIG. 4 is a 30% ethylene glycol LiFePO4The first charge-discharge curve of the electrode material under different multiplying power conditions. The first discharge specific capacity of the material at 0.2C is 155mAh g-1And the specific discharge capacity under the condition of high multiplying power of 10C can also reach 79 mAh.g-1And the Li of the material is proved by the very high specific discharge capacity of the material under the condition of high rate+The de-intercalation path is short, and the material stability is good.
FIG. 5 is a 30% ethylene glycol LiFePO4And (3) attenuation graphs of the electrode material which is circularly charged and discharged for 70 times under different multiplying factors. The specific discharge capacity of the material in the first 10 discharges is about 150 mAh-g-1After 60 cycles with different multiplying powers, the specific discharge capacity of the material is still kept at 140mAh g-1The retention rate is more than 90%, which shows that the small amount of mesopores of 8-10nm can improve the specific discharge capacity of the material and can not reduce the stability of the material.
FIG. 6 is pure LiFePO 415% ethylene glycol LiFePO 430% ethylene glycol LiFePO445% ethylene glycol LiFePO 460% ethylene glycol LiFePO40.2C first discharge specific capacity map. The discharge capacities were 121, 140, 155, 142, 131mAh · g, respectively-1Visible light is secondThe specific capacity of the material can be improved by regulating the porosity morphology by alcohol, and the electrochemical performance of the material can be reduced by excessive ethylene glycol. 30% ethylene glycol LiFePO4The electrode material has excellent electrochemical performance as the anode material of the lithium ion battery and has wide application prospect.
Comparative example 2
This comparative example is essentially the same as example 1, except that 30% ethylene glycol and a calcination temperature of 700 deg.C are used.
The agglomeration of the material is obvious under the condition of 700 ℃, the material exists in the form of an agglomeration, and the first discharge specific capacity is only 126.7 mAh.g-1And the retention rate of the cyclic capacity of 70 times of different multiplying power is more than 93%. The capacity retention rate for 100 cycles of 10C was 68%.
Comparative example 3
This comparative example is essentially the same as example 1, except that 30% ethylene glycol and a calcination temperature of 500 deg.C are used.
The crystallinity of the prepared material is low, the capacity retention rate is only 84% after 70 cycles with different multiplying factors, and the capacity retention rate is 56% after 100 cycles with 10C.

Claims (3)

1. The preparation method of the porous lithium iron phosphate electrode material is characterized by comprising the following specific steps of:
step 1, adding H3PO4Adding the solution into LiOH solution, and reacting to obtain Li3PO4Adding ethylene glycol, adding FeSO containing ascorbic acid under the protection of nitrogen gas4Solution, reaction to obtain LiFePO4Precursor solution of said LiFePO4In the precursor solution, the volume ratio of the ethylene glycol to the water is 30: 70-45: 55;
in step 1, the FeSO4:H3 PO4The molar ratio of LiOH is 1:1.05: 3;
in step 1, said H3PO4The mass ratio of the ascorbic acid to the water was 2.6 g: 0.2 g;
step 2, LiFePO4Carrying out solvothermal reaction on the precursor solution at 180-200 ℃, washing and drying to obtain LiFePO4；
Step 3, LiFePO in nitrogen atmosphere4Calcining at 550-600 ℃ to obtain the nano porous lithium iron phosphate electrode material.
2. The preparation method according to claim 1, wherein in the step 2, the solvothermal reaction time is 12-18 h.
3. The preparation method according to claim 1, wherein in the step 3, the calcination time is 5-7 h.
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