CN115275144A - Phosphate anode material and preparation method and application thereof - Google Patents

Phosphate anode material and preparation method and application thereof Download PDF

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CN115275144A
CN115275144A CN202210922943.4A CN202210922943A CN115275144A CN 115275144 A CN115275144 A CN 115275144A CN 202210922943 A CN202210922943 A CN 202210922943A CN 115275144 A CN115275144 A CN 115275144A
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life
doped
lithium
treatment
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李鹤
冯国旗
张爱香
李�浩
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Xi'an Hesheng Huili New Materials Co ltd
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Abstract

The invention discloses a phosphate anode material and a preparation method and application thereof. Firstly, sulfate, phosphate and alkaline lithium are used as raw materials, metaphosphate is used as a doping agent, an organic solvent is used as a chelating agent, and the lithium manganese iron phosphate anode material matrix LiFe doped with different elements is prepared by stirring, dissolving and mixing and hydrothermal treatment x Mn y D z PO 4 (x+y+z＝1，0<z<0.2 D is other transition metal elements. And then, taking a carbon-containing compound as a coating precursor, and carrying out carbon coating on the doped lithium manganese iron phosphate material through ball milling and high-temperature treatment to prepare the carbon-coated lithium manganese iron phosphate cathode material. The experimental result shows that the prepared optimal material LiFe 0.6 Mn 0.3 W 0.1 PO 4 After @ C is cycled for 300 circles at 25 ℃ and 1.0C multiplying power, the specific discharge capacity of the material is still as high as 153.2mAh g ‑1 The capacity retention rate was 95.6%, while the discharge capacity of the blank material was only 145.9mAh g ‑1 The corresponding capacity retention was 92.2%. In addition, the electrochemical cycle performance of the modified lithium ferric manganese phosphate material under high rate is also obviously improved.

Description

Phosphate anode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of high-energy battery materials, in particular to a phosphate anode material and a preparation method and application thereof.
Background
Lithium ion batteries, one of the most advanced and widespread energy storage devices at present, have an energy density of from 90Wh kg -1 Gradually increased to 300Wh kg -1 The portable electronic product has helped revolutionize for nearly thirty years, greatly promotes the progress of human civilization, and becomes an indispensable part of our daily life. Lithium ion batteries dominate energy storage products because of their higher energy and power densities, longer cycle life, wider operating temperature range, and lower self-discharge rates than other rechargeable battery systems. Along with the rapid development of material technology and manufacturing process, lithium ion batteries are promoting the rapid growth of the electric automobile market and show good application prospects in large-scale energy storage and aerospace and ships. However, many challenges remain with the development of lithium ion batteries. In the beginning of the 20 th century, the electric vehicle accounts for about 25%, but as the power and the driving mileage of the electric vehicle are still far away from those of the traditional engine fuel vehicle, and the electric vehicle is also at a disadvantage in terms of manufacturing cost and maintenance cost, the popularization degree of the electric vehicle is sharply reduced within 20 years, and finally the fuel engine wins. Therefore, the dominance of the lithium ion battery in the energy storage system is further consolidated, and higher requirements are put forward on the energy density, the service life, the cost and the safety performance of the lithium ion battery.
Lithium manganese iron phosphate material LiFe x Mn 1-x PO 4 (0<x<1,LFMP) is taken as a novel phosphate anode material, and is considered as an ideal substitute material for a lithium iron phosphate anode due to the advantages of high discharge capacity, good cycle performance, high safety and the like. However. Poor rate performance due to poor ion diffusion kinetics and faster at high ratesThe capacity is declined, and the further development of the lithium ferric manganese phosphate material is greatly limited. At present, the research on lithium ferric manganese phosphate materials mainly focuses on the aspect of interface coating, and few reports are made on the modification of the crystal structure of the materials.
Disclosure of Invention
In order to overcome the existing defects and shortcomings of the lithium manganese iron phosphate cathode material, the invention aims to provide a high-stability lithium manganese iron phosphate cathode material which is doped and coated and modified at the same time, in particular to a lithium manganese iron phosphate cathode material and a preparation method and application thereof. The invention introduces doping agent containing similar groups in the process of mixing material precursors, and prepares lithium manganese iron phosphate matrix material LiFe doped with different element lattices through hydrothermal treatment x Mn y D z PO 4 (x+y+z＝1，0<z<0.2 D) is other transition metal elements; and then, preparing the carbon-coated doped lithium manganese iron phosphate cathode material by using a carbon-containing compound as a carbon-coated precursor through ball milling and high-temperature treatment. The element doping is beneficial to improving the lattice structure of the lithium ferric manganese phosphate material, inhibiting the irreversible phase change of the material and protecting the transmission channel of lithium ions in the material lattice, and the carbon coating is beneficial to inhibiting the corrosion of electrolyte to the material interface and improving the lithium ion transmission dynamics of the material interface. Therefore, by the method, the structure and the interface of the lithium ferric manganese phosphate cathode material can be simultaneously modified, and the modified material has excellent electrochemical performance.
The purpose of the invention is realized by the following technical scheme:
a phosphate anode material, which is element-doped lithium ferric manganese phosphate anode material LiFe x Mn y D z PO 4 X + y + z =1, x, y, z cannot be 0;0<z<0.2, D is other transition metal element doped; at least one of Y, W, mg and Al is preferable. Further preferably, the lithium ferric manganese phosphate material comprises LiFe 0.6 Mn 0.3 Y 0.1 PO 4 、LiFe 0.6 Mn 0.3 W 0.1 PO 4 、LiFe 0.6 Mn 0.3 Mg 0.1 PO 4 And LiFe 0.6 Mn 0.3 Al 0.1 PO 4 At least one of (1).
The phosphate anode material is formed by coating a carbon-containing material outside the phosphate anode material.
In the phosphate anode material, other doped transition metal elements adopt metaphosphate as a dopant, and the metaphosphate is treated by a hydrothermal method for doping.
The preparation method of the phosphate cathode material comprises the following steps:
firstly, sulfate, phosphate and alkaline lithium are used as raw materials, metaphosphate is used as a doping agent, an organic solvent is used as a chelating agent, and the element-doped lithium manganese iron phosphate anode material LiFe is prepared by stirring, dissolving and mixing and hydrothermal treatment x Mn y D z PO 4 X + y + z =1, x, y, z cannot be 0;0<z<0.2, D is other transition metal element doped; at least one of Y, W, mg and Al is preferable.
Further preferably, the lithium ferric manganese phosphate material comprises LiFe 0.6 Mn 0.3 Y 0.1 PO 4 、LiFe 0.6 Mn 0.3 W 0.1 PO 4 、LiFe 0.6 Mn 0.3 Mg 0.1 PO 4 And LiFe 0.6 Mn 0.3 Al 0.1 PO 4 At least one of (1).
The preparation method is characterized in that the raw materials are mixed,
and carrying out carbon coating on the doped lithium manganese iron phosphate material by ball milling and high-temperature treatment on the element-doped lithium manganese iron phosphate positive electrode material to prepare the carbon-coated lithium manganese iron phosphate positive electrode material.
The sulfate comprises MnSO 4 ·H 2 O and FeSO 4 ·7H 2 O; said phosphate salt comprises H 3 PO 4 、NH 4 H 2 PO 4 And (NH) 4 ) 2 HPO 4 At least one of; further preferred is H 3 PO 4 . The alkaline lithium includes LiOH and Li 2 CO 3 At least one of (a); further preferred is LiOH.
Said systemThe metaphosphate comprises Y (PO) 3 ) 3 、W(PO 3 ) 3 、Mg(PO 3 ) 2 And Al (PO) 3 ) 3 At least one of (a); further preferably W (PO) 3 ) 3 (ii) a The organic solvent comprises at least one of ethylene glycol, polyethylene glycol 400 and diglycolamine; polyethylene glycol is further preferred.
The preparation method comprises the steps of stirring, dissolving and mixing, wherein the stirring speed is 300-800rad min -1 Preferably 450 to 550rad min -1 (ii) a The stirring time is not more than 3h, preferably 1-2h; the stirring temperature is 20-40 ℃, preferably 25-35 ℃; the hydrothermal treatment temperature is 150-250 ℃, preferably 180-220 ℃; the treatment time is 5-20h, preferably 8-12h.
Furthermore, the preparation method comprises the following stirring and mixing processes: dissolving phosphate in deionized water solution, and adding a chelating agent to prepare solution A; then, mnSO 4 ·H 2 O and FeSO 4 ·7H 2 Dissolving O in the water solution to prepare solution B; dissolving alkaline lithium in deionized water solution, and adding a chelating agent to prepare solution C.
Further, under magnetic stirring, dropwise adding the solution C into the solution A, continuously stirring for a certain time, dropwise adding the solution B into the mixed solution AC, adding a doping agent metaphosphate under continuous stirring to prepare a final mixed solution, transferring the mixed solution into a polytetrafluoroethylene lining for hydrothermal reaction, and carrying out vacuum drying on a product.
Further, the vacuum drying temperature is 30-150 ℃, preferably 60-100 ℃; the treatment time is 10-24h, preferably 14-20h; the vacuum degree is lower than 0.1MPa.
In the preparation method, the carbon-containing compound comprises at least one of sucrose, glucose, polydopamine and citric acid.
The ball milling treatment rotating speed is 200-600rad min -1 Preferably 350 to 450rad min -1 (ii) a The ball-material ratio is 1; the ball milling time is 2-6h, preferably 3-5h.
The high-temperature treatment temperature is 500-800 ℃, preferably 600-700 ℃; the treatment time is 4-10h, preferably 6-8h; high temperature treatment atmosphere is N 2 Ar and Ar/H 2 At least one of the mixed gas.
When the carbon is coated, the ball milling and high-temperature treatment processes are as follows: carrying out ball milling on the doped lithium iron manganese phosphate material and a carbon-containing compound according to a certain mass ratio, transferring the materials into a tubular furnace after the materials are uniformly mixed, carrying out high-temperature treatment in an inert atmosphere, and then carrying out grinding treatment to obtain the modified lithium iron manganese phosphate cathode material with carbon coating and element doping.
Further, the carbon coating amount is not more than 10wt%.
The invention also provides application of the lithium ferric manganese phosphate anode material in preparation of a lithium ion battery.
In the invention, metaphosphate is used as a doping agent, and the chemical structural property of metaphosphate and phosphate radical is similar, so that uniform element doping can be realized, the element doping is beneficial to improving the lattice property of the lithium manganese iron phosphate material, inhibiting the disproportionation reaction of manganese and reducing the dissolution of metal manganese, thereby improving the structural stability of the material; the carbon material is used as a coating with excellent conductivity, the carbon surface coating is favorable for improving the lithium ion diffusion kinetics of the material interface, and meanwhile, the coating layer can effectively reduce the corrosion of electrolyte to the material interface and improve the stability of the material interface. Therefore, the lithium ferric manganese phosphate material modified by the method can overcome the defects of poor conductivity and poor interface stability of the material, improve the rate capability of the material, and has excellent electrochemical performance and an ultra-stable structure.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention carries out synchronous doping in the synthesis process of the lithium ferric manganese phosphate material for the first time, and is beneficial to realizing the uniform distribution of doping elements. Meanwhile, metaphosphate is used as doping, and by utilizing similar chemical properties of metaphosphate and phosphate, under the same anion environment, transition metal cations can better realize atomic-level mixing and metal occupation, so that the generation of impurity phases such as iron phosphate and manganese phosphate is reduced, and the method is favorable forLiFe in the lifting material x Mn y D z PO 4 Proportion of pure phase. In addition, the surface coating of the carbon material is beneficial to improving the conductivity of the material and the interface stability of the material. Therefore, the invention can simultaneously modify the bulk phase structure and the interface of the lithium ferric manganese phosphate material, thereby greatly improving the electrochemical performance of the material.
Drawings
FIG. 1: XRD patterns of samples prepared in example 1, comparative example 2 and comparative example 3.
FIG. 2: example 1 LiFe prepared 0.6 Mn 0.3 W 0.1 PO 4 SEM image of @ C sample.
FIG. 3: example 1 LiFe prepared 0.6 Mn 0.3 W 0.1 PO 4 TEM image of the @ C sample.
FIG. 4 is a schematic view of: example 2 LiFe prepared 0.6 Mn 0.3 Mg 0.1 PO 4 XRD pattern of the @ C sample.
FIG. 5: example 2 LiFe prepared 0.6 Mn 0.3 Mg 0.1 PO 4 SEM image of @ C sample.
FIG. 6: example 3 prepared LiFe 0.6 Mn 0.3 Al 0.1 PO 4 SEM image of @ C sample.
FIG. 7: example 3 LiFe prepared 0.6 Mn 0.3 Al 0.1 PO 4 TEM image of the @ C sample.
FIG. 8: liFe prepared in comparative example 1 0.6 Mn 0.4 PO 4 SEM image of the sample.
FIG. 9: liFe prepared in comparative example 2 0.6 Mn 0.3 W 0.1 PO 4 SEM pictures of the samples.
FIG. 10: liFe prepared in comparative example 5 0.6 Mn 0.3 W 0.1 PO 4 -1 SEM picture of sample.
Detailed Description
The following examples are intended to further illustrate the present invention and are not to be construed as limiting the scope of the invention.
The materials referred to in the following examples are commercially available.
Example 1
(1) 20mmol H are weighed 3 PO 4 Dissolving in 5mL deionized water, adding 30mL polyethylene glycol, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 6mmol of MnSO 4 ·H 2 O and 12mmol FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol of LiOH H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Adding solution C dropwise into solution A to form suspension mixed solution AC, stirring for 1 hr, adding solution B dropwise into solution AC, and adding 2mmol W (PO) 3 ) 3 To form a mixed solution D. Subsequently, the mixed solution D was transferred to a polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, washing the filtrate for multiple times by using deionized water and absolute ethyl alcohol, and finally, drying the filtrate in vacuum for 16 hours at the temperature of 80 ℃ to obtain the W-doped lithium ferric manganese phosphate material LiFe 0.6 Mn 0.3 W 0.1 PO 4 。
(3) Weighing 5g of LiFe according to the mass ratio of 10 0.6 Mn 0.3 W 0.1 PO 4 And 0.5g polydopamine in a ball milling tank, adding 20mL of absolute ethyl alcohol for wet ball milling, and performing ball milling at 400rad min -1 Ball milling for 4H at the speed of (1), taking out the material and evaporating the ethanol, placing the powder under a tube furnace at 5% Ar/H 2 At 3 deg.C for min under atmosphere -1 Heating to 650 ℃ for treatment for 4h, and grinding to obtain carbon-coated W-doped modified lithium manganese iron phosphate cathode material LiFe 0.6 Mn 0.3 W 0.1 PO 4 @C。
(4) The LiFe obtained in example 1 was subjected to X-ray diffraction (XRD) 0.6 Mn 0.3 W 0.1 PO 4 Test analysis was performed at @ C to obtain the XRD pattern shown in FIG. 1.
(5) The LiFe obtained in example 1 was subjected to Scanning Electron Microscopy (SEM) 0.6 Mn 0.3 W 0.1 PO 4 @ C sample preparationTesting and analyzing to obtain an electron microscope image, which is shown in figure 2.
(6) The LiFe obtained in example 1 was subjected to a Transmission Electron Microscope (TEM) 0.6 Mn 0.3 W 0.1 PO 4 @ C was subjected to test analysis to obtain a TEM image thereof, as shown in FIG. 3.
(7) The LiFe obtained in example 1 was used 0.6 Mn 0.3 W 0.1 PO 4 The 2016 type button cell assembled by the @ C is subjected to charge and discharge tests in a voltage range of 3.0-4.3V.
(8) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
Example 2
(1) 20mmol of NH are weighed 4 H 2 PO 4 Dissolving in 5mL deionized water, adding 30mL polyethylene glycol 400, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 6mmol of MnSO 4 ·H 2 O and 12mmol FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol LiOH. H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Dropwise adding the solution C into the solution A to form a suspension mixed solution AC, continuously stirring for 1h, dropwise adding the solution B into the solution AC, and adding 2mmol of Mg (PO) 3 ) 2 To form a mixed solution D. Subsequently, the mixed solution D was transferred to a polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, washing the filtrate for multiple times by using deionized water and absolute ethyl alcohol, and finally, drying the filtrate in vacuum at the temperature of 80 ℃ for 16 hours to obtain Mg-doped lithium ferric manganese phosphate material LiFe 0.6 Mn 0.3 Mg 0.1 PO 4 。
(3) Weighing 5g of LiFe according to the mass ratio of 10 0.6 Mn 0.3 Mg 0.1 PO 4 And 0.5g of sucrose in a ball milling tank, adding 20mL of absolute ethyl alcohol for wet ball milling at 400rad min -1 Ball milling for 4h at the rotating speed of (1), then taking out the materials and evaporating ethanol, and then mixing the powderPlacing in a tube furnace under 5% Ar atmosphere at 3 deg.C for min -1 Heating to 650 ℃ for treatment for 4h, and grinding to obtain carbon-coated Mg-doped modified lithium manganese iron phosphate positive electrode material LiFe 0.6 Mn 0.3 Mg 0.1 PO 4 @C。
(4) The LiFe obtained in example 2 was subjected to X-ray diffraction (XRD) 0.6 Mn 0.3 Mg 0.1 PO 4 Test analysis was performed at @ C to obtain the XRD pattern, as shown in FIG. 4.
(5) The LiFe obtained in example 2 was subjected to Scanning Electron Microscopy (SEM) 0.6 Mn 0.3 Mg 0.1 PO 4 The @ C sample was subjected to test analysis and its electron micrograph, shown in FIG. 5, was obtained.
(6) The LiFe obtained in example 2 was converted to 0.6 Mn 0.3 Mg 0.1 PO 4 The @ C is assembled into the 2016 type button battery to carry out charging and discharging tests in a voltage range of 3.0-4.3V.
(7) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
Example 3
(1) 20mmol H was weighed 3 PO 4 Dissolving in 5mL deionized water, adding 30mL ethylene glycol, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 6mmol of MnSO 4 ·H 2 O and 12mmol FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol of LiOH H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Dropwise adding the solution C into the solution A to form a suspension mixed solution AC, continuously stirring for 1h, dropwise adding the solution B into the solution AC, and adding 2mmol of Al (PO) 3 ) 3 To form a mixed solution D. Subsequently, the mixed solution D was transferred to a polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, washing the filtrate for multiple times by using deionized water and absolute ethyl alcohol, and finally, drying the filtrate in vacuum at the temperature of 80 ℃ for 16 hours to obtain the Al-doped lithium ferric manganese phosphate material LiFe 0.6 Mn 0.3 Al 0.1 PO 4 。
(3) Weighing 5g of LiFe according to a mass ratio of 10 0.6 Mn 0.3 Al 0.1 PO 4 And 0.5g of citric acid are placed in a ball milling tank, 20mL of absolute ethyl alcohol is added for wet ball milling, and the mixture is subjected to ball milling at 400rad min -1 Ball milling for 4h at the speed of (1), then taking out the material and evaporating the ethanol, placing the powder under a tube furnace at 5% N 2 At 3 deg.C for min under atmosphere -1 Heating to 650 ℃ for treatment for 4h, and grinding to obtain carbon-coated Al-doped modified lithium manganese iron phosphate cathode material LiFe 0.6 Mn 0.3 Al 0.1 PO 4 @C。
(4) The LiFe obtained in example 3 was subjected to Scanning Electron Microscopy (SEM) 0.6 Mn 0.3 Al 0.1 PO 4 The @ C sample was analyzed by measurement to obtain an electron micrograph, as shown in FIG. 6.
(5) The LiFe obtained in example 3 was subjected to a Transmission Electron Microscope (TEM) 0.6 Mn 0.3 Al 0.1 PO 4 The test analysis was performed @ C, and a TEM image thereof was obtained as shown in FIG. 7.
(6) The LiFe obtained in example 3 0.6 Mn 0.3 Al 0.1 PO 4 The @ C is assembled into the 2016 type button battery to carry out charging and discharging tests in a voltage range of 3.0-4.3V.
(7) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
Comparative example 1
(1) 20mmol H was weighed 3 PO 4 Dissolving in 5mL deionized water, adding 30mL polyethylene glycol, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 8mmol of MnSO 4 ·H 2 O and 12mmol FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol LiOH. H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Adding the solution C into the solution A dropwise to form a suspension mixed solution AC, and continuingAfter stirring for 1h, solution B was added dropwise to solution AC to form mixed solution D. Subsequently, the mixed solution D was transferred to a polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, washing the filtrate for multiple times by using deionized water and absolute ethyl alcohol, and finally, drying the filtrate in vacuum at the temperature of 80 ℃ for 16 hours to obtain the lithium ferric manganese phosphate material LiFe 0.6 Mn 0.4 PO 4 。
(3) The LiFe obtained in comparative example 1 was compared by X-ray diffraction (XRD) 0.6 Mn 0.4 PO 4 The test analysis was carried out to obtain the XRD pattern thereof as shown in FIG. 1.
(4) Comparative example 1 obtained LiFe using Scanning Electron Microscope (SEM) 0.6 Mn 0.4 PO 4 The sample was analyzed by testing to obtain an electron micrograph, as shown in FIG. 8.
(5) The LiFe obtained in comparative example 1 was used 0.6 Mn 0.4 PO 4 The 2016 type button cell is assembled to carry out the charge and discharge test in the voltage range of 3.0-4.3V.
(6) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
Comparative example 2
(1) 20mmol H are weighed 3 PO 4 Dissolving in 5mL deionized water, adding 30mL polyethylene glycol, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 6mmol of MnSO 4 ·H 2 O and 12mmol of FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol LiOH. H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Dropwise adding the solution C into the solution A to form a suspension mixed solution AC, continuously stirring for 1h, dropwise adding the solution B into the solution AC, and adding 2mmol W (PO) 3 ) 3 To form a mixed solution D. Subsequently, the mixed solution D was transferred to a polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, and adding deionized water and absolute ethyl alcoholWashing for multiple times, preferably drying for 16h in vacuum at 80 ℃ to obtain the W-doped lithium ferric manganese phosphate material LiFe 0.6 Mn 0.3 W 0.1 PO 4 。
(3) The LiFe obtained in comparative example 2 was compared by X-ray diffraction (XRD) 0.6 Mn 0.3 W 0.1 PO 4 The test analysis was carried out to obtain the XRD pattern thereof as shown in FIG. 1.
(4) Comparative example 2 obtained LiFe by Scanning Electron Microscope (SEM) 0.6 Mn 0.3 W 0.1 PO 4 The samples were analyzed by testing and their electron micrographs were obtained as shown in FIG. 9.
(6) The LiFe obtained in comparative example 2 was used 0.6 Mn 0.3 W 0.1 PO 4 The 2016 type button cell is assembled to carry out charge and discharge tests in a voltage range of 3.0-4.3V.
(7) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
Comparative example 3
(1) 20mmol H was weighed 3 PO 4 Dissolving in 5mL deionized water, adding 30mL polyethylene glycol, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 8mmol MnSO 4 ·H 2 O and 12mmol of FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol LiOH. H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Dropwise adding the solution C into the solution A to form a suspended mixed solution AC, and after continuously stirring for 1h, dropwise adding the solution B into the solution AC to form a mixed solution D. Subsequently, the mixed solution D was transferred to a polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, washing the filtrate for multiple times by using deionized water and absolute ethyl alcohol, and preferably drying the filtrate for 16 hours in vacuum at the temperature of 80 ℃ to obtain the lithium manganese iron phosphate material LiFe 0.6 Mn 0.4 PO 4 。
(3) Weighing 5g of LiFe according to a mass ratio of 10 0.6 Mn 0.4 PO 4 And 0.5g polydopamine in a ball milling tank, adding 20mL of absolute ethyl alcohol for wet ball milling, and performing ball milling at 400rad min -1 Ball milling for 4H at the speed of (1), taking out the material and evaporating the ethanol, placing the powder under a tube furnace at 5% Ar/H 2 At 3 deg.C for min under atmosphere -1 Heating to 650 ℃ for treatment for 4h, and grinding to obtain carbon-coated lithium manganese iron phosphate cathode material LiFe 0.6 Mn 0.4 PO 4 @C。
(4) The LiFe obtained in comparative example 3 was compared by X-ray diffraction (XRD) 0.6 Mn 0.4 PO 4 The XRD pattern of @ C was obtained by test analysis, as shown in FIG. 1.
(5) The LiFe obtained in comparative example 3 was used 0.6 Mn 0.4 PO 4 The @ C is assembled into the 2016 type button battery to carry out charging and discharging tests in a voltage range of 3.0-4.3V.
(6) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
Comparative example 4
(1) 20mmol of NH are weighed 4 H 2 PO 4 Dissolving in 5mL deionized water, adding 30mL polyethylene glycol 400, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 6mmol of MnSO 4 ·H 2 O and 12mmol of FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol LiOH. H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Dropwise adding the solution C into the solution A to form a suspension mixed solution AC, continuously stirring for 1h, dropwise adding the solution B into the solution AC, and adding 2mmol of Mg (PO) 3 ) 2 To form a mixed solution D. Subsequently, the mixed solution D was transferred to a teflon-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, washing the filtrate for multiple times by using deionized water and absolute ethyl alcohol, and finally, drying the filtrate in vacuum at the temperature of 80 ℃ for 16 hours to obtain Mg-doped lithium ferric manganese phosphate material LiFe 0.6 Mn 0.3 W 0.1 PO 4 -1。
(3) The LiFe obtained in comparative example 4 was used 0.6 Mn 0.3 Mg 0.1 PO 4 The 2016 type button cell is assembled to carry out the charge and discharge test in the voltage range of 3.0-4.3V.
(4) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
Comparative example 5
(1) 20mmol H was weighed 3 PO 4 Dissolving in 5mL deionized water, adding 30mL polyethylene glycol, placing on a magnetic stirring device with 30 deg.C heating, and performing magnetic stirring at 500rad min -1 Stirring to form a solution A; respectively weighing 6mmol of MnSO 4 ·H 2 O and 12mmol FeSO 4 ·H 2 Dissolving O in 10mL of deionized water to form a solution B; weighing 40mmol LiOH. H 2 O was dissolved in 10mL of deionized water and 5mL of diglycolamine was added to form solution C.
(2) Dropwise adding the solution C into the solution A to form a suspension mixed solution AC, continuously stirring for 1h, dropwise adding the solution B into the solution AC, and adding 2mmol W 2 O 3 To form a mixed solution D. Subsequently, the mixed solution D was transferred to a polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal treatment at 200 ℃ for 10 hours. After the hydrothermal treatment is finished, filtering the filtrate, washing the filtrate for multiple times by using deionized water and absolute ethyl alcohol, and finally, drying the filtrate in vacuum at the temperature of 80 ℃ for 16 hours to obtain the W-doped lithium ferric manganese phosphate material LiFe 0.6 Mn 0.3 W 0.1 PO 4 -1。
(3) Weighing 5g of LiFe according to the mass ratio of 10 0.6 Mn 0.3 W 0.1 PO 4 -1 and 0.5g polydopamine are placed in a ball milling tank, 20mL of absolute ethyl alcohol is added for wet ball milling, and the mixture is subjected to 400rad min -1 Ball milling for 4H at the speed of (1), taking out the material and evaporating the ethanol, placing the powder under a tube furnace at 5% Ar/H 2 At 3 deg.C for min under atmosphere -1 Heating to 650 ℃ for treatment for 4h, and grinding to obtain carbon-coated W-doped modified lithium manganese iron phosphate cathode material LiFe 0.6 Mn 0.3 W 0.1 PO 4 -1@C。
(4) The LiFe obtained in comparative example 5 was compared by Scanning Electron Microscope (SEM) 0.6 Mn 0.3 W 0.1 PO 4 -1 the sample was analyzed by testing, and the electron micrograph thereof was obtained as shown in FIG. 10.
(5) The LiFe obtained in comparative example 5 was used 0.6 Mn 0.3 W 0.1 PO 4 -1 and LiFe 0.6 Mn 0.3 W 0.1 PO 4 The 2016 type button cell assembled by the @ C is subjected to charge and discharge tests in a voltage range of 3.0-4.3V.
(6) The test temperature was 25 ℃, the cells were first activated one turn at 0.2C and 0.5C and then cycled at 1.0C and 3C. The test results are shown in tables 1 and 2.
TABLE 1 comparison of the Electrical Properties of the example and comparative materials (25 deg.C test, 1.0C cycle)
Figure BDA0003778476130000091
Figure BDA0003778476130000101
TABLE 2 comparison of the Electrical Properties of the example and comparative materials (25 deg.C test, 3.0C cycle)
Figure BDA0003778476130000102
LiFe of the materials obtained for example 1, comparative example 2 and comparative example 3 of the invention 0.6 Mn 0.4 PO 4 、LiFe 0.6 Mn 0.4 PO 4 @C、LiFe 0.6 Mn 0.3 W 0.1 PO 4 And LiFe 0.6 Mn 0.3 W 0.1 PO 4 @ C, as can be seen from XRD in FIG. 1, the characteristic peak of lithium manganese iron phosphate of the material is obvious, which indicates that the experiment successfully prepares the lithium manganese iron phosphate material. In addition, by comparing LiFe 0.6 Mn 0.4 PO 4 And LiFe 0.6 Mn 0.3 W 0.1 PO 4 XRD pattern ofIt can be known that after the material is doped with W, the material has a new obvious diffraction peak at 23-25 °, and at the same time, the characteristic diffraction peak of the material at 25.4 ° has a leftward shift, which is mainly caused by the slight change of the lattice structure of the material due to the doping of W in the lattice of the material, indicating that the W element has been successfully doped in the crystal structure of the material. In addition, by comparing LiFe 0.6 Mn 0.4 PO 4 、LiFe 0.6 Mn 0.4 PO 4 @C、LiFe 0.6 Mn 0.3 W 0.1 PO 4 And LiFe 0.6 Mn 0.3 W 0.1 PO 4 The characteristic peak of the material after carbon coating is found to be sharp by the diffraction peak at 25.4 ℃ of @ C, which is probably because partial impure phases on the surface of the material are eliminated in the high-temperature carbon coating process of the material, and the interface stability of the material is favorably improved.
From the scanning electron microscopes shown in fig. 2, 5, 6, 8 and 9, liFe is observed for the uncoated material 0.6 Mn 0.4 PO 4 And LiFe 0.6 Mn 0.3 W 0.1 PO 4 The material surface is clear and clean, and the particles are distributed uniformly. However, after the material is coated with carbon, the surface of the material is provided with obvious coatings with different shapes and sizes, the coatings are mainly carbon, and the carbon is successfully coated on the surface of the material, so that the lithium ion diffusion kinetics of the material interface are improved.
As can be seen from fig. 3 and 7, the thickness of the coating layer of the carbon coating material prepared by the present invention is about 5-20nm, and the coating thickness is suitable, generally speaking, the coating layer is too thin to withstand the long-term corrosion of the electrolyte, and too thick the coating layer is liable to increase the diffusion resistance of lithium ions at the material interface, which is not favorable for the electrochemical performance of the material.
FIG. 4 is LiFe prepared in example 2 0.6 Mn 0.3 Mg 0.1 PO 4 The XRD pattern of @ C shows that the material has good characteristic diffraction peak of lithium manganese iron phosphate, which indicates that the lithium manganese iron phosphate material is successfully prepared.
FIG. 10 is LiFe of a sample prepared in comparative example 5 0.6 Mn 0.3 W 0.1 PO 4 SEM picture of-1, phaseCompared with a blank sample LiFe 0.6 Mn 0.4 PO 4 (FIG. 8) and W (PO) 3 ) 3 LiFe doped with tungsten source 0.6 Mn 0.3 W 0.1 PO 4 (FIG. 9), liFe 0.6 Mn 0.3 W 0.1 PO 4 -1 the material surface has a significant increase in heterogeneous particles, indicating a decrease in phase purity of the material produced.
As can be seen from tables 1 and 2, the modified lithium ferric manganese phosphate cathode material obtained by the method provided by the invention takes metaphosphate as a dopant, and the electrochemical cycle performance and rate capability of the material are obviously improved compared with those of a blank material after the material is doped with metal elements of W, mg and Al. For the blank material LiFe 0.6 Mn 0.4 PO 4 The material is circulated for 300 circles under the multiplying power of 1C, and the specific discharge capacity of the material is only 145.9mAh g -1 After 300 times of circulation under the 3C multiplying power, the specific discharge capacity is 122.8mAh g -1 . However, for W and Mg doped LiFe 0.6 Mn 0.3 W 0.1 PO 4 And LiFe 0.6 Mn 0.3 Mg 0.1 PO 4 The specific discharge capacity of the material is 130.1mAh g after 300 cycles under 3C -1 And 133.8mAh g -1 . More importantly, after the material is coated by carbon, the electrochemical cycle performance and rate capability of the material are further improved, and the optimal modified material LiFe 0.6 Mn 0.3 W 0.1 PO 4 @ C has a discharge specific capacity of 153.2mAh g after 300 cycles at 1C and 3C -1 And 139.8mAh g -1 Much higher than undoped and only doped or cladding modified materials. Furthermore, use is made of W 2 O 3 As a dopant, there was a significant decrease in the electrochemical performance of the material compared to the blank sample, mainly due to W during doping 2 O 3 The material is difficult to be mixed with phosphate at an atomic level, so that the material impurity phase is increased, and the electrochemical performance of the material is reduced.
Generally, because metaphosphate is used as a doping agent and polydopamine is used as a coating precursor to modify lithium manganese iron phosphate, the prepared LiFe 0.6 Mn 0.3 W 0.1 PO 4 The @ C material has excellent electrochemical performance mainly because metaphosphate is used for doping, and by utilizing the similar chemical properties of metaphosphate and phosphate, under the same anion environment, transition metal cations can better realize atomic-level mixing and metal occupation, so that the generation of impurity phases such as iron phosphate and manganese phosphate is reduced, and the promotion of LiFe in the material is facilitated x Mn y D z PO 4 The proportion of pure phases; the crystal structure of the lithium ferric manganese phosphate material is improved by doping the element W, and the introduction of a W-O bond can improve the bond energy of increasing anionic oxygen, thereby being beneficial to inhibiting the release of lattice oxygen and the dissolution of metal; the carbon coating improves the lithium ion transmission capability of the lithium ferric manganese phosphate material interface, greatly improves the diffusion transmission of lithium ions on the material interface, and is beneficial to inhibiting the increase of interface impedance and slowing down the corrosion of electrolyte to the material. In general, the method can improve the internal crystal structure and the interface of the material and improve the electrochemical performance of the material simultaneously through simple treatment.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A phosphate positive electrode material characterized in that: liFe serving as element-doped lithium ferric manganese phosphate anode material x Mn y D z PO 4 X + y + z =1, x, y, z cannot be 0;0<z<0.2, D is other transition metal element doped; at least one of Y, W, mg and Al is preferable.
2. The phosphate positive electrode material according to claim 1, characterized in that: the phosphate anode material is coated with a carbon-containing material.
3. The phosphate positive electrode material according to claim 1, characterized in that: and the other doped transition metal elements adopt metaphosphate as a dopant, and are doped by hydrothermal treatment.
4. A preparation method of a phosphate cathode material is characterized by comprising the following steps: the method comprises the following steps:
firstly, sulfate, phosphate and alkaline lithium are used as raw materials, metaphosphate is used as a doping agent, an organic solvent is used as a chelating agent, and the element-doped lithium manganese iron phosphate anode material LiFe is prepared by stirring, dissolving and mixing and hydrothermal treatment x Mn y D z PO 4 X + y + z =1, x, y, z cannot be 0;0<z<0.2, D is other transition metal element doped; at least one of Y, W, mg and Al is preferable.
5. The production method according to claim 4,
and carrying out carbon coating on the doped lithium manganese iron phosphate material by ball milling and high-temperature treatment on the element-doped lithium manganese iron phosphate positive electrode material to prepare the carbon-coated lithium manganese iron phosphate positive electrode material.
6. The method of manufacturing according to claim 4, characterized in that: said sulfate comprises MnSO 4 ·H 2 O and FeSO 4 ·7H 2 O; said phosphate salt comprises H 3 PO 4 、NH 4 H 2 PO 4 And (NH) 4 ) 2 HPO 4 At least one of; the alkaline lithium includes LiOH and Li 2 CO 3 At least one of (a).
7. The method of claim 4, wherein: the metaphosphate comprises Y (PO) 3 ) 3 、W(PO 3 ) 3 、Mg(PO 3 ) 2 And Al (PO) 3 ) 3 At least one of (a); the organic solvent comprises at least one of ethylene glycol, polyethylene glycol 400 and diglycolamine.
8. The method of claim 4, wherein: the stirring, dissolving and mixing treatment is carried out, and the stirring speed is 300-800rad min -1 Preferably 450 to 550rad min -1 (ii) a The stirring time is not more than 3h, preferably 1-2h; the stirring temperature is 20-40 ℃, preferably 25-35 ℃; the hydrothermal treatment temperature is 150-250 ℃, preferably 180-220 ℃; the treatment time is 5-20h, preferably 8-12h.
9. The production method according to claim 5, characterized in that: the carbon-containing compound comprises at least one of sucrose, glucose, polydopamine and citric acid;
the ball milling treatment rotating speed is 200-600rad min -1 Preferably 350 to 450rad min -1 (ii) a The ball-material ratio is 1; the ball milling time is 2-6h, preferably 3-5h;
the high-temperature treatment temperature is 500-800 ℃, preferably 600-700 ℃; the treatment time is 4-10h, preferably 6-8h; high temperature treatment atmosphere of N 2 Ar and Ar/H 2 At least one of the mixed gas.
10. Use of the lithium manganese iron phosphate positive electrode material of any one of claims 1 to 3, or the lithium manganese iron phosphate positive electrode material of any one of claims 4 to 9, in the preparation of a lithium ion battery.
CN202210922943.4A 2022-08-02 2022-08-02 Phosphate anode material and preparation method and application thereof Pending CN115275144A (en)

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