CN109494367B - Hydroxyl lithium iron phosphate/graphene composite cathode material and preparation method thereof - Google Patents
Hydroxyl lithium iron phosphate/graphene composite cathode material and preparation method thereof Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention discloses a preparation method of a lithium iron phosphate hydroxide/graphene composite cathode material. The electrochemical performance was investigated using XRD testing and SEM to analyze the phase composition of the material and using the material as a positive electrode to assemble a lithium ion battery. The result shows that for the hydroxyl lithium iron phosphate/graphene composite material, the specific capacity of 129mAh/g can be obtained at 0.1C, and the coulomb efficiency of 98% is still achieved after 50 times of circulation at 0.5C.
Description
Technical Field
The invention relates to the technical field of electrochemical energy materials, in particular to a lithium iron phosphate hydroxide/graphene composite cathode material and a preparation method thereof.
Background
In recent years, as fossil energy is overused, great harm is caused to the environment, economic development cannot be at the cost of damaging the environment on which people live, and therefore development of environment-friendly and sustainable new energy materials is an energy development hotspot. At present, new energy sources such as solar energy, wind energy and tidal energy have great potential, the new energy sources reduce the environmental problems caused by energy use, but also face the key problem of energy storage, the energy storage technology is a very key step in the energy utilization process, and secondary batteries are the most important energy storage mode. The lithium ion battery has the characteristics of high energy density, long cycle life, environmental friendliness and the like. With the development of science and technology, more and more electronic products have gone into thousands of households, and a lithium ion battery is one of the most important parts in daily life and is widely applied to high-technology fields such as electronic equipment. With the development of electric automobiles, people put higher demands on the aspects of endurance, safety, power density and the like of lithium ion batteries.
Since the first report in 1997, olivine-structured lithium iron phosphate is particularly suitable for application in electric vehicle power sources based on low cost, no toxicity, high capacity and excellent charge-discharge reversibility, has attracted global researchers' attention, and has become an excellent candidate for a lithium ion battery cathode material.
The theoretical specific capacity of the lithium iron phosphate anode material is 170 mAh/g. Because the lithium iron phosphate and the ferric phosphate can stably exist at 400 ℃, the influence of temperature on crystals is not worried about in the charging and discharging process. Currently known methods for synthesizing lithium iron phosphate include a high-temperature solid-phase method, a solvothermal method, a mechano-physical synthesis method, a carbothermic method, and the like. Because the ferric phosphate is similar to the lithium iron phosphate in structure, only one platform is arranged at 3.45V, the platform capacity accounts for about 90% of the theory, and the charging and discharging platform is long, which indicates that the reaction of lithium intercalation and deintercalation is a two-phase reaction.
The charge-discharge reaction is as follows:。
from the above-mentioned charge-discharge reaction process, the key of lithium ion between two phases is the temperature of diffusion reaction, and the size of crystal grain can affect it, and further affect the discharge capacity. Lithium iron phosphate has low conductivity and poor lithium ion diffusion coefficient, which limits its wide application in the field of lithium ion batteries for electric vehicles and hybrid vehicles, particularly at low temperatures.
Disclosure of Invention
The invention aims to provide a lithium iron phosphate hydroxyl/graphene composite cathode material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is a preparation method of a hydroxyl lithium iron phosphate/graphene composite positive electrode material, which comprises the following steps:
(1) reacting LiOH & H2Adding O into the graphene oxide dispersion liquid, and then dropwise adding analytically pure H3PO4Uniformly stirring by using a magnetic stirrer to obtain solution A;
(2) FeSO (ferric oxide) is added4·7H2Adding O into the graphene oxide dispersion liquid, and uniformly stirring by using a magnetic stirrer to obtain a solution B;
(3) slowly adding the solution B into the solution A, stirring for 0.2 ~ 1h, adding ethanol, stirring for 0.2 ~ 1h, transferring the obtained mixed solution into a hydrothermal reaction kettle, reacting at 150 ~ 200 ℃ for 3 ~ 6 h, centrifuging and washing the obtained product, and carrying out freeze drying treatment to obtain the lithium iron hydroxyphosphate/graphene composite anode material.
Preferably, the molar ratio of P to Li to Fe in the mixed solution in the step (3) is 1:3: 1.
Preferably, the volume of ethanol added in the step (3) is 20 ~ 50% of the total volume of the solution A and the solution B.
Preferably, LiOH. H in the step (1)2The solid-to-liquid ratio of O to the graphene oxide dispersion liquid is 1 g: 25 ~ 85ml, and the concentration of the graphene oxide in the step (1) is 0.5 ~ 4 mg/ml.
Preferably, FeSO is used in the step (2)4·7H2The solid-to-liquid ratio of O to the graphene oxide dispersion liquid is 1 g: 15 ~ 40ml, and the concentration of the graphene oxide in the step (1) is 0.5 ~ 4 mg/ml.
Preferably, the preparation method of the lithium iron phosphate/graphene composite cathode material comprises the following steps:
(1) 0.2142 g of LiOH. H were weighed2O is added into 12ml of graphene oxide dispersion liquid with the concentration of 1.66 mg/ml, and 0.1962 g of analytically pure H is added dropwise3PO4Uniformly stirring by using a magnetic stirrer to obtain solution A;
(2) 0.4728 g of FeSO were weighed out4·7H2Adding O into 12ml of graphene oxide dispersion liquid with the concentration of 1.66 mg/ml, and uniformly stirring by using a magnetic stirrer to obtain liquid B;
(3) slowly adding the solution B into the solution A, stirring for 0.5 h, adding 8ml of ethanol, stirring for 0.5 h, transferring the obtained mixed solution into a hydrothermal reaction kettle, reacting for 5 h at 180 ℃, centrifuging and washing the obtained product, and performing freeze drying treatment to obtain the lithium iron hydroxyphosphate/graphene composite anode material.
Preferably, the preparation method of the graphene oxide is as follows: 2.5g K2S2O8And 2.5g P2O5Sequentially adding into 50 ml of concentrated sulfuric acid, fully dissolving at 80 ℃, adding 5g of graphite, stirring at constant temperature for 6 h, washing and drying, adding the dried product into 115 ml of concentrated sulfuric acid, and adding 15 g of KMnO under stirring4After mixing uniformly, heatingStirring at constant temperature of 35 deg.C for 3.5 hr, adding 400 ml ultrapure water, and adding 30 ml 30wt% H2O2And uniformly stirring the solution, centrifugally washing, and performing dialysis treatment to obtain the graphene oxide.
The invention has the following beneficial effects: (1) the hydroxyl lithium iron phosphate/graphene composite material is successfully prepared by adopting solvothermal reaction, wherein hydroxyl lithium iron phosphate particles are uniformly distributed and coated in a three-dimensional porous structure of graphene. Compared with the lithium iron phosphate prepared without the participation of graphene oxide, the phase composition and the microscopic morphology of the material are obviously changed, which shows that the graphene oxide plays a role of an oxidant in the preparation process of the composite material and provides active sites for the uniform dispersion of particles. (2) Due to the three-dimensional conductive network formed by the graphene and the introduction of hydroxyl capable of improving the ion diffusion coefficient, the electrochemical performance of the hydroxyl lithium iron phosphate/graphene composite material is far superior to that of a lithium iron phosphate material under the same condition. When the multiplying power is 0.5C, after stable circulation is carried out for 50 times, the specific capacity of 137.8 mAh/g still exists, and the coulomb efficiency can reach 98% after the stability.
Drawings
Fig. 1 is an XRD pattern of the lithium iron phosphate positive electrode material prepared in comparative example 1;
fig. 2 is an XRD pattern of the lithium iron hydroxyphosphate/graphene composite prepared in example 1;
fig. 3 is an SEM image (a) of the lithium iron phosphate hydroxide/graphene composite positive electrode material prepared in example 1 (b) and the lithium iron phosphate positive electrode material prepared in comparative example 1;
fig. 4 shows ac impedance test results of the lithium iron phosphate of comparative example 1 and the lithium iron phosphate hydroxide/graphene composite material of example 1;
fig. 5 shows the results of cycle tests performed on lithium iron phosphate and the lithium iron phosphate hydroxide/graphene composite material of example 1 at 0.5C;
fig. 6 is a graph comparing rate performance of two materials of lithium iron phosphate and the lithium iron hydroxyphosphate/graphene composite material in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples, without however restricting the scope of the invention thereto.
The preparation method of graphene oxide used in the following examples is as follows: 2.5g K2S2O8And 2.5g P2O5Sequentially adding into 50 ml of concentrated sulfuric acid, fully dissolving at 80 ℃, adding 5g of graphite, stirring at constant temperature for 6 h, washing and drying, adding the dried product into 115 ml of concentrated sulfuric acid, and adding 15 g of KMnO under stirring4After mixing uniformly, the temperature is raised to 35 ℃, 400 ml of ultrapure water is added after stirring for 3.5 hours at constant temperature, and then 30 ml of 30wt% H is added2O2And uniformly stirring the solution, centrifugally washing, and performing dialysis treatment to obtain the graphene oxide.
Example 1
A preparation method of a hydroxyl lithium iron phosphate/graphene composite cathode material comprises the following steps:
(1) 0.2142 g of LiOH. H were weighed2O is added into 12ml of graphene oxide dispersion liquid with the concentration of 1.66 mg/ml, and 0.1962 g of analytically pure H is added dropwise3PO4（H3PO485 percent) is evenly stirred by a magnetic stirrer to obtain solution A;
(2) 0.4728 g of FeSO were weighed out4·7H2Adding O into 12ml of graphene oxide dispersion liquid with the concentration of 1.66 mg/ml, and uniformly stirring by using a magnetic stirrer to obtain liquid B;
(3) slowly adding the solution B into the solution A, stirring for 0.5 h, adding 8ml of absolute ethyl alcohol, stirring for 0.5 h, transferring the obtained mixed solution into a hydrothermal reaction kettle, reacting for 5 h at 180 ℃, centrifuging and washing the obtained product, and performing freeze drying treatment to obtain the lithium iron hydroxyphosphate/graphene composite anode material.
Comparative example 1
A preparation method of a lithium iron phosphate positive electrode material comprises the following steps: weighing LiOH. H2O of 0.2142 g is put into 12ml of ultrapure water, and 0.1962 g of analytically pure H is added dropwise3PO4（H3PO4Content 85%), stirring well using a magnetic stirrer, thisIs the solution A. 0.4728 g of FeSO were then weighed out4·7H2O was put into 12ml of ultrapure water, and the mixture was stirred uniformly by a magnetic stirrer, thereby obtaining a solution B. Slowly adding the solution B into the solution A, stirring for 0.5 h, adding 8ml of absolute ethyl alcohol, stirring for 0.5 h, transferring the solution into a hydrothermal reaction kettle, and reacting for 5 h at 180 ℃. And centrifugally washing the obtained product, and freeze-drying to obtain the lithium iron phosphate anode material.
Material characterization
The material phase composition and the microstructure were characterized by the following methods. (1) XRD: the equipment model used was DX-2700B, and all samples were tested by XRD with a Cu Ka target at a wavelength of 1.5406 angstroms and a voltage of 40 kV, a tube current of 20 mA, a sweep rate of 6 °/min, and a scan angle of 10 ° -60 °. (2) SEM, FEI Nova SEM 230 type field emission scanning electron microscope was used.
Fig. 1 is an XRD chart of the lithium iron phosphate positive electrode material prepared in comparative example 1, and compared with a standard card, characteristic peaks at 17.120 °, 20.751 °, 22.648 °, 25.524 °, 29.675 °, 32.161 °, and 35.524 ° in 2 θ are matched with crystal faces of lithium iron phosphate standard cards (JCPDS No. 83-2092) 200, 101, 210, 201, 211, 301, and 311, which indicates that a main product lithium iron phosphate is obtained. Impurity peaks of lithium iron hydroxyphosphate appear at 18.592 degrees and 27.238 degrees, and part of ferrous sulfate is possibly oxidized in the preparation process.
Fig. 2 is an XRD chart of the lithium iron hydroxyphosphate/graphene composite material prepared in example 1, and compared with a standard card, the characteristic peaks at 17.822 °, 19.026 °, 27.238 °, 29.385 ° and 36.478 ° at 2 θ are matched with crystal planes of lithium iron hydroxyphosphate standard card (PDF # 0041-. The XRD comparison of the lithium iron phosphate and the lithium iron hydroxyphosphate/graphene composite shows that the phase components of the material are changed due to the introduction of the graphene oxide, and the graphene oxide has oxidability and plays a role of an oxidant in the formation process of the lithium iron hydroxyphosphate. The redox reaction between the graphene oxide and the particles is beneficial to the formation of stronger acting force between the graphene oxide and the particles.
Fig. 3 is an SEM image (a) of the lithium iron phosphate hydroxide/graphene composite positive electrode material (b) prepared in example 1 and the lithium iron phosphate positive electrode material prepared in comparative example 1. As can be seen from fig. 3a, the prepared lithium iron phosphate without graphene oxide is in a sheet stacking state, the particle size is not uniform, and the agglomeration phenomenon is severe. As can be seen from fig. 3b, in the lithium iron hydroxyphosphate/graphene composite material, the lithium iron hydroxyphosphate is regular columnar particles, has the same size, and is uniformly dispersed; the graphene forms a porous three-dimensional network structure, and most of the hydroxyl lithium iron phosphate particles are encapsulated in the conductive network. Therefore, the introduction of the graphene not only forms a graphene coating structure beneficial to stable structure, but also plays an important role in controlling the particle size and improving the particle dispersibility.
Electrochemical performance test
(1) Assembling the battery: firstly, 1-methyl-2-pyrrolidone (NMP) is used as a solvent to prepare 5% PVDF, 0.1 g of lithium iron phosphate (or hydroxyl lithium iron phosphate/graphene) is weighed and placed in a 5ml beaker, the lithium iron phosphate (or hydroxyl lithium iron phosphate/graphene) is added according to the mass ratio of the lithium iron phosphate (or hydroxyl lithium iron phosphate/graphene) to the super P: PVDF of 8: 1, the mixture is stirred for 4 hours by magnetic force, stirred into a slurry mixture, coated on an aluminum sheet, then kept stand for 2 hours and placed in a vacuum drying oven to be dried for 12 hours at the temperature of 80 ℃. Cutting into electrode pieces with diameter of 14 mm, and drying in a vacuum drying oven at 60 deg.C for 12 hr. And (5) making the battery in a vacuum glove box. And then packaged at a pressure of 120 kpa.
(2) And (3) testing alternating current impedance: the materials are assembled into a battery, and after the battery is cycled for 5 times at 0.1C rate by using a blue battery test system, an impedance test is carried out by using a CHI604ed electrochemical workstation, wherein the frequency range is 1 Hz-1000 kHz.
(3) And (3) charge and discharge test: and (3) using a blue battery test system under the conditions of constant temperature of 25 ℃, firstly charging to 4.2V at a multiplying power, standing for 15 minutes, and then discharging to 2V at the multiplying power.
The AC impedance test results of the lithium iron phosphate and hydroxyl lithium iron phosphate/graphene composite material are shown in the specificationAs shown in fig. 4, after hydroxyl and graphene are introduced to lithium iron phosphate, in a high-frequency region, the half-circle ratio of the lithium iron phosphate/graphene composite material is LiFePO4The smaller the area (A) indicates that the lithium iron phosphate hydroxide/graphene composite material has smaller capacitive impedance and ohmic impedance after being activated.
The lithium iron phosphate and lithium iron hydroxyphosphate/graphene composite material were subjected to a cycle test at 0.5C, and the results are shown in fig. 5, and after introduction of hydroxyl and graphene, the cycle performance of the lithium iron hydroxyphosphate/graphene composite material was superior to that of lithium iron phosphate. Fig. 5a shows that the first discharge specific capacity of the lithium iron phosphate/graphene composite material is up to 137.8 mAh/g, and the discharge specific capacity of 137 mAh/g is still obtained after 50 times of circulation, while the first discharge specific capacity of the lithium iron phosphate is only 34.9 mAh/g, and the discharge specific capacity of 33.7 mAh/g is obtained after 50 times of circulation. Fig. 5b shows that the first coulombic efficiency of the lithium iron phosphate/graphene composite material is 87%, after the circulation is stable, the efficiency is improved to 98%, and the effect of the lithium iron phosphate is only 76%. The introduction of hydroxyl and graphene obviously improves the lithium storage capacity and cycle reversibility of the material.
Fig. 6 is a graph comparing rate performance of two materials of lithium iron phosphate and lithium iron hydroxyphosphate/graphene composite material. As can be seen from fig. 6, the rate capability of the lithium iron phosphate/graphene composite material is significantly better than that of lithium iron phosphate, and when the rate is as high as 5C, 89 mAh/g of specific capacity can still be released, and at this time, only 22 mAh/g of specific capacity remains in the lithium iron phosphate. When the multiplying power returns to 0.1C, the specific capacity of the composite material can also return to 129mAh/g, and excellent reversibility is shown. The excellent electrochemical performance of the lithium iron phosphate hydroxide/graphene composite material is attributed to the three-dimensional porous network structure formed by the graphene and the introduction of hydroxyl, the former forms an internally staggered conductive network which can effectively improve the electronic conductive capability of the material, and the latter can improve the ion diffusion efficiency of the material.
Example 2
A preparation method of a hydroxyl lithium iron phosphate/graphene composite cathode material comprises the following steps:
(1) 0.2142 g of LiOH. H were weighed2O is added into 18ml of oxidized stone with the concentration of 0.5 mg/mlTo the graphene dispersion, 0.1962 g of analytical grade H was added dropwise3PO4（H3PO485 percent) is evenly stirred by a magnetic stirrer to obtain solution A;
(2) 0.4728 g of FeSO were weighed out4·7H2Adding O into 18ml of graphene oxide dispersion liquid with the concentration of 0.5 mg/ml, and uniformly stirring by using a magnetic stirrer to obtain liquid B;
(3) slowly adding the solution B into the solution A, stirring for 0.2 h, adding 8ml of absolute ethyl alcohol, stirring for 1h, transferring the obtained mixed solution into a hydrothermal reaction kettle, reacting for 6 h at 150 ℃, centrifuging and washing the obtained product, and performing freeze drying treatment to obtain the lithium iron hydroxyphosphate/graphene composite anode material.
Example 3
A preparation method of a hydroxyl lithium iron phosphate/graphene composite cathode material comprises the following steps:
(1) 0.2142 g of LiOH. H were weighed2O is added into 8ml of graphene oxide dispersion liquid with the concentration of 3.5 mg/ml, and 0.1962 g of analytically pure H is added dropwise3PO4（H3PO485 percent) is evenly stirred by a magnetic stirrer to obtain solution A;
(2) 0.4728 g of FeSO were weighed out4·7H2Adding O into 8ml of graphene oxide dispersion liquid with the concentration of 3.5 mg/ml, and uniformly stirring by using a magnetic stirrer to obtain liquid B;
(3) slowly adding the solution B into the solution A, stirring for 1h, adding 8ml of absolute ethyl alcohol, stirring for 0.2 h, transferring the obtained mixed solution into a hydrothermal reaction kettle, reacting for 3 h at 200 ℃, centrifuging and washing the obtained product, and performing freeze drying treatment to obtain the lithium iron hydroxyphosphate/graphene composite anode material.
Claims (2)
1. A preparation method of a hydroxyl lithium iron phosphate/graphene composite cathode material is characterized by comprising the following steps:
(1) 0.2142 g of LiOH. H were weighed2O is added into 12ml of graphene oxide dispersion liquid with the concentration of 1.66 mg/ml, and 0.1962 g of analytically pure H is added dropwise3PO4Uniformly stirring by using a magnetic stirrer to obtain solution A; the preparation method of the graphene oxide comprises the following steps: 2.5g K2S2O8And 2.5g P2O5Sequentially adding into 50 ml of concentrated sulfuric acid, fully dissolving at 80 ℃, adding 5g of graphite, stirring at constant temperature for 6 h, washing and drying, adding the dried product into 115 ml of concentrated sulfuric acid, and adding 15 g of KMnO under stirring4After being mixed uniformly, the mixture is heated to 35 ℃, stirred for 3.5 hours at constant temperature, added with 400 ml of ultrapure water and then added with 30 ml of H2O2Stirring uniformly, centrifuging, washing and then dialyzing to obtain graphene oxide;
(2) 0.4728 g of FeSO were weighed out4·7H2Adding O into 12ml of graphene oxide dispersion liquid with the concentration of 1.66 mg/ml, and uniformly stirring by using a magnetic stirrer to obtain liquid B;
(3) and adding the solution B into the solution A, stirring for 0.5 h, adding 8ml of ethanol, stirring for 0.5 h, transferring the obtained mixed solution into a hydrothermal reaction kettle, reacting for 5 h at 180 ℃, centrifuging and washing the obtained product, and performing freeze drying treatment to obtain the lithium iron hydroxyphosphate/graphene composite anode material.
2. The lithium iron phosphate hydroxyl/graphene composite positive electrode material prepared by the method of claim 1.
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