CN107732176B - Preparation method of nano-grade lithium ion battery anode material - Google Patents
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Abstract
The invention discloses a preparation method of a nano-scale lithium ion battery anode material. The preparation method of the nano-scale lithium ion battery anode material comprises the following steps: preparing a lithium ferric manganese phosphate precursor solution; preparing a conductive coating layer precursor solution; mixing the lithium ferric manganese phosphate precursor solution with a conductive coating layer precursor solution to form a mixture solution; and performing ball milling and drying treatment on the mixture solution, and then performing calcination treatment in a protective atmosphere. The preparation method of the invention ensures that the particle size of the generated nano-grade lithium ion battery anode material is nano-grade, the coating layer is complete, and the conductivity is good.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a nano-scale lithium ion battery anode material.
Background
Under the condition that global energy and environmental problems are more and more severe, vehicles are gradually changed to use an energy storage battery as a main power source, and a lithium ion battery is used as a high-performance secondary green battery, has the advantages of high voltage, high energy density (including volume energy and mass specific energy), low self-discharge rate, wide service temperature range, long cycle life, environmental protection, no memory effect, large-current charging and discharging and the like, and is considered to be one of the best choices of high-energy, high-density, high-power and low-cost batteries.
However, one of the bottlenecks restricting the mass popularization and industrialization of lithium ion batteries is the anode material, and the anode material which is mainly and widely applied at present is lithium cobaltate (LiCoO) with a layered structure2) Lithium nickel cobalt manganese oxide (LiNi)1-x-yCoxMnyO2) Manganic acidLithium (LiMnO)2) Lithium manganate (LiMn) having spinel structure2O4) And the like. However, the cobalt is toxic and limited in resources, the cycle performance and safety performance of the nickel cobalt lithium manganate are poor, the cycle performance and high-temperature performance of the lithium manganate are poor, and the like, so that the application and development of the nickel cobalt lithium manganate are restricted. Therefore, development of a novel high-energy and low-cost cathode material is important for development of lithium ion batteries.
Nano lithium iron phosphate (LiFePO)4) The lithium battery positive electrode material has an olivine structure and has a characteristic of reversibly releasing and inserting lithium. Compared with the traditional lithium ion secondary battery anode material, the raw material has wider source, lower price, no toxicity and no environmental pollution, and especially the safety performance and the cycle life of the lithium ion secondary battery anode material are not comparable with those of other materials. However, LiFePO4The material has the defects that the material cannot overcome, such as low voltage platform, generally 3.2V, poor low-temperature performance, low energy density and the like.
With LiFePO4LiMnPO having the same structure4The electrode potential relative to Li +/Li is 4.1V, which is much higher than LiFePO4And is within the electrochemical stability window of existing electrolyte systems, and is therefore of great interest. However, since LiMnPO4Is considered to be an insulator, resulting in LiMnPO4The electrochemical performance of the electrolyte is extremely poor, and the development and application of the electrolyte are limited.
Lithium iron manganese phosphate LiFe1-xMnxPO4(0<x<1) Is in LiMnPO4Developed on the basis of modification, although Fe2+The introduction of the manganese phosphate can improve the conductivity of the lithium manganese phosphate, but the improvement range is limited, and the electrochemical performance of the material is difficult to be fully exerted.
In order to solve the defect of poor conductivity of the lithium manganese iron phosphate, the method for coating the lithium manganese iron phosphate with a conductive coating layer to improve the conductivity of the lithium manganese iron phosphate is provided at present, for example, in the presently disclosed preparation method for preparing the graphene-coated lithium manganese iron phosphate positive electrode material by in-situ reaction, a manganese source and a phosphorus source are firstly adopted to prepare MnPO4·H2O nano powder, and preparing iron source and phosphorus sourceFePO4·2H2O nano powder, then MnPO4·H2O nanopowder, FePO4·2H2The method comprises the steps of ultrasonically dispersing O nano powder and a graphene oxide solution, then dropwise adding a lithium source for mixing, drying and sintering to obtain the graphene-coated lithium manganese iron phosphate material, but researches show that the existing lithium manganese iron phosphate cathode material coated by a conductive layer still has low coating rate of a coating layer, and the electrochemical performance is not ideal due to limited improvement of conductivity.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a nano-scale lithium ion battery anode material. The method solves the technical problems of low coating rate and unsatisfactory electrochemical performance of the existing lithium manganese iron phosphate material with a coating structure.
In order to achieve the above object, in one aspect, the present invention provides a method for preparing a nanoscale lithium ion battery positive electrode material. The preparation method of the nano-scale lithium ion battery anode material comprises the following steps:
preparing a lithium ferric manganese phosphate precursor solution;
preparing a conductive coating layer precursor solution;
mixing the lithium ferric manganese phosphate precursor solution with a conductive coating layer precursor solution to form a mixture solution;
performing ball milling and drying treatment on the mixture solution, and then performing calcination treatment in a protective atmosphere;
the lithium manganese iron phosphate precursor solution also contains an auxiliary agent, and the ratio of the molar content of the auxiliary agent to the total molar content of the lithium manganese iron phosphate precursor is 1: (0.1-10).
Compared with the prior art, the invention mainly has the following technical effects:
firstly, a conductive coating layer precursor solution is coated with lithium manganese iron phosphate in situ, on one hand, in the calcining treatment, the conductive coating layer precursor solution is sintered to form a coating layer material and is uniformly coated on the surface of primary particles of the lithium manganese iron phosphate generated by the calcining treatment, so that the growth of the particle size of the lithium manganese iron phosphate can be inhibited, the particle size of the generated nanoscale lithium ion battery anode material is nanoscale, the migration path of lithium ions and electrons is shortened, and the conductivity of the material is improved; on the other hand, the coating layer has a conductive characteristic, so that a uniform conductive network can be formed on the surface of the lithium manganese iron phosphate secondary particles, and the conductivity of the lithium manganese iron phosphate is effectively improved;
secondly, the addition agent added into the lithium ferric manganese phosphate precursor solution can realize the coordination effect with metal ions, so that the metal ions are uniformly dispersed at the atomic level; meanwhile, the auxiliary agent can play a role in a carbon source besides enabling metal ions to be uniformly dispersed, and can improve the integrity of the coating of the lithium ferric manganese phosphate particles together with other coating source materials of the conductive coating precursor solution while inhibiting the growth of primary particles of the lithium ferric manganese phosphate, so that the prepared lithium ferric manganese phosphate has excellent performance.
In addition, the preparation method has easily controlled process conditions, and the prepared nano-grade lithium ion battery anode material has stable structure and electrochemical performance.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a nanoscale lithium ion battery cathode material according to an embodiment of the present invention;
fig. 2 is an electron microscope scanning picture of the cathode material of the nanoscale lithium ion battery according to the embodiment of the present invention, wherein fig. a is an electron microscope picture of the cathode material of the nanoscale lithium ion battery prepared in example 1, and fig. B is an electron microscope picture of the cathode material of the nanoscale lithium ion battery prepared in comparative example 1;
FIG. 3 is a discharge curve at 0.2C of the cathode materials of the nano-scale lithium ion batteries prepared in example 1 and comparative example 1; wherein, the curve 1 is the discharging curve of the nano-scale lithium ion battery anode material of the embodiment 1 at 0.2 ℃, and the curve 2 is the discharging curve of the nano-scale lithium ion battery anode material of the comparative example 1 at 0.2 ℃;
FIG. 4 is a graph of discharge at 1.0C for the nanoscale lithium ion battery positive electrode materials prepared in example 1 and comparative example 1; wherein, the curve 1 is the discharging curve of the nano-scale lithium ion battery anode material of the embodiment 1 at 1.0 ℃, and the curve 2 is the discharging curve of the nano-scale lithium ion battery anode material of the comparative example 1 at 1.0 ℃;
FIG. 5 is a discharge curve at 0.2C of the cathode materials of the nano-scale lithium ion batteries prepared in example 2 and comparative example 2; wherein, the curve 1 is the discharging curve of the nano-scale lithium ion battery anode material of the embodiment 2 at 0.2 ℃, and the curve 2 is the discharging curve of the nano-scale lithium ion battery anode material of the comparative example 2 at 0.2 ℃;
FIG. 6 is a graph of discharge at 1.0C for the nanoscale lithium ion battery positive electrode materials prepared in example 2 and comparative example 2; wherein, the curve 1 is the discharging curve of the nano-scale lithium ion battery anode material of the embodiment 2 at 1.0 ℃, and the curve 2 is the discharging curve of the nano-scale lithium ion battery anode material of the comparative example 2 at 1.0 ℃;
FIG. 7 is a discharge curve at 0.2C of the cathode materials of the nano-scale lithium ion batteries prepared in example 3 and comparative example 3; wherein, the curve 1 is the discharging curve of the nano-scale lithium ion battery anode material of the embodiment 3 at 0.2 ℃, and the curve 2 is the discharging curve of the nano-scale lithium ion battery anode material of the comparative example 2 at 0.2 ℃;
FIG. 8 is a graph of discharge at 1.0C for the nanoscale lithium ion battery positive electrode materials prepared in example 3 and comparative example 3; wherein, the curve 1 is the discharging curve of the nano-scale lithium ion battery anode material of the embodiment 3 at 1.0 ℃, and the curve 2 is the discharging curve of the nano-scale lithium ion battery anode material of the comparative example 2 at 1.0 ℃;
fig. 9 is a rate test graph of the cathode materials of the nano-sized lithium ion batteries prepared in example 3 and comparative example 3.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a nano-scale lithium ion battery anode material. The process flow of the preparation method of the nano-scale lithium ion battery anode material is shown in figure 1, and comprises the following steps:
s01, preparing a lithium ferric manganese phosphate precursor solution;
s02, preparing a precursor solution of the conductive coating layer;
s03, mixing the lithium ferric manganese phosphate precursor solution with a conductive coating layer precursor solution to form a mixture solution;
and S04, performing ball milling and drying treatment on the mixture solution, and then performing calcination treatment in a protective atmosphere.
Specifically, in step S01, the lithium ferric manganese phosphate precursor solution may be prepared according to a method for preparing a conventional lithium ferric manganese phosphate precursor solution. Unlike the conventional method for preparing a lithium manganese iron phosphate precursor solution, an auxiliary is added to the lithium manganese iron phosphate precursor solution in step S01. In one embodiment, the lithium manganese iron phosphate precursor solution further contains an auxiliary agent, and the ratio of the molar content of the auxiliary agent to the total molar content of the lithium manganese iron phosphate precursor is 1: (0.1-10).
In a further embodiment, the method for preparing the lithium ferric manganese phosphate precursor solution is as follows:
mixing the components in a molar ratio of (0.95-1.1): (0.2-0.9): (0.95-1): (0.1-0.8): (0-0.05) a lithium source, an iron source, a phosphorus source, a manganese source, and a doping element source are treated with the aid.
Specifically, a lithium source, an iron source, a phosphorus source, a manganese source and doping elements are dissolved in a solvent according to a proportion to prepare a mixture solution; and then adding an auxiliary agent into the mixture solution and uniformly mixing to prepare the lithium ferric manganese phosphate precursor solution.
Wherein, the auxiliary agent can be at least one of a film forming agent, an active agent or a dispersing agent. In a specific embodiment, the auxiliary agent may be at least one selected from polyvinyl alcohol, polyethylene glycol, stearic acid, citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, succinic acid, glycine, ethylenediaminetetraacetic acid, sucrose, and glucose. The auxiliaries contain coordination functional groups, so that the coordination effect with metal ions can be realized, and the metal ions are uniformly dispersed at the atomic level; meanwhile, the auxiliary agents can also play a role of a carbon source and cooperate with the precursor solution of the conductive coating layer to improve the coating integrity of the lithium manganese iron phosphate particles, so that the prepared lithium manganese iron phosphate has excellent performance. In addition, the auxiliary agents can also be used as a carbon source, so that the auxiliary agents can play a synergistic effect with other coating source materials in the conductive coating precursor solution during calcination, inhibit the growth of primary particles of lithium manganese iron phosphate, and effectively control the particle size of the finally generated lithium ion battery cathode material to be in a nanometer level.
The iron source can be, but not limited to, at least one of iron phosphate, ferrous pyrophosphate, ferrous carbonate, ferrous chloride, ferrous hydroxide, ferrous nitrate, ferrous oxalate, ferric chloride, ferric hydroxide, ferric nitrate, ferric citrate, and ferric oxide.
The phosphorus source can be at least one of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ferric phosphate and lithium dihydrogen phosphate.
The manganese source may be, but not limited to, at least one of manganese dioxide, manganese sesquioxide, manganous oxide, manganese oxalate, manganese acetate, or manganese nitrate.
The doping element source may be, but not limited to, at least one of boron compound, cadmium compound, copper compound, magnesium compound, aluminum compound, zinc compound, titanium compound, zirconium compound, niobium compound, chromium compound, and rare earth element compound. When the lithium ferric manganese phosphate precursor solution prepared in the step S01 contains the doping element sources, the finally prepared nano-scale lithium ion battery positive electrode material contains the doping element, such as at least one of boron, cadmium, copper, magnesium, aluminum, zinc, titanium, zirconium, niobium, chromium and rare earth elements, preferably at least one of boron, cadmium, magnesium and aluminum. By adding the doping elements into the lithium manganese iron phosphate, the disproportionation reaction of manganese is reduced, so that the structure of the generated lithium manganese iron phosphate core body is more stable, and the structural stability of the finally prepared nano-scale lithium ion battery anode material is improved.
In addition, the proper additive is added in the prepared lithium ferric manganese phosphate precursor solutionAn iron source in an amount range such that after the sintering process, Fe2+Substituted part of Mn2+The proportion of (2) can increase unit cell parameters, improve the conductivity of the lithium manganese iron phosphate material, and ensure that the generated lithium manganese iron phosphate material has a high voltage platform.
In the above embodiments, the solvent used for preparing the lithium ferric manganese phosphate precursor solution may be, but not limited to, at least one of deionized water, distilled water, ethanol, methanol, acetone, dimethylformamide, dimethyl sulfoxide, and ethylene glycol. The concentration of the lithium ferric manganese phosphate precursor solution prepared by the solvents can be 10-80% by weight.
In the above step S02, the preparation of the conductive coating layer precursor solution may be performed according to the following method:
dispersing a carbon source and a conductive agent in a solvent; wherein the weight ratio of the carbon source to the conductive agent is 1: (0.01-10).
Wherein the carbon source can be at least one of asphalt, polyethylene glycol, polyvinyl alcohol, fructose, lactose and starch; the conductive agent can be at least one of Ketjen black, acetylene black, Super P, nano carbon powder, carbon nano tube, graphite, graphene, superconducting carbon and carbon nano fiber. In this way, the precursor solution of the conductive coating layer contains a carbon source and a conductive agent, the carbon source is calcined in the step S04 to form carbon, and can be uniformly coated on the surface of the primary particles of lithium manganese iron phosphate, so that the growth of the particle size of the lithium manganese iron phosphate can be inhibited, and the particle size of the generated lithium ion battery anode material is in a nanometer level, thereby shortening the migration path of lithium ions and electrons, and improving the conductivity of the material. The contained conductive agent can form a uniform conductive network on the surface of the lithium manganese iron phosphate secondary particles, so that the conductivity of the lithium manganese iron phosphate is effectively improved.
In one embodiment, the solvent used for preparing the conductive coating layer precursor solution may be, but not limited to, at least one of water, ethanol, acetone, and ethylene glycol. The concentration of the precursor solution of the conductive coating layer prepared by the solvents can be 1-50%.
In the step S03, the mixing process of the lithium ferric manganese phosphate precursor solution prepared in the step S01 and the conductive coating layer precursor solution prepared in the step S02 may be a process of directly mixing the two together and performing ball milling in the step S04 to fully mix the components; or mixing the two solutions together and then uniformly mixing the two solutions by a conventional mixing method such as stirring. In one embodiment, in the mixture solution formed by mixing the two solutions, the total mass of the carbon source and the conductive agent accounts for 0.5-10% of the mass of the theoretically generated lithium iron manganese phosphate. By controlling the mixing amount of the carbon source and the conductive agent, the coating layer can effectively coat the generated lithium manganese iron phosphate in the subsequent steps, and the coating rate and the integrity of the coating layer are improved under the action of the auxiliary agent contained in the lithium manganese iron phosphate precursor solution.
In the step S04, when the mixture solution prepared in the step S03 is ball-milled, the particle size of each component can be effectively reduced, and the components can be sufficiently and uniformly dispersed. In one embodiment, the mixture solution is ball milled for 10 to 48 hours. In particular embodiments, the ball milling process may, but does not exclusively, perform ball milling in a planetary ball mill.
In step S04, the drying treatment is performed on the mixture solution after the ball milling treatment, for example, the mixture solution after the ball milling treatment is sufficiently dried at a temperature of 80 to 300 ℃, for example, for 2 to 20 hours, in order to remove the solvent in the mixture solution. After the drying treatment, in an embodiment, the drying method further includes crushing the dried mixture to crush the agglomerated mixture during the drying treatment.
In step S04, the sintering process makes the components in the mixture obtained after the drying process react at a high temperature, such as the lithium source, the iron source, the phosphorus source, the manganese source, and the doping element source, to generate the lithium manganese iron phosphate positive electrode material during the sintering process, and when the doping element source component is contained, the doped lithium manganese iron phosphate positive electrode material is generated. At the moment, the components such as the contained auxiliary agent, the carbon source and the like generate carbon in the sintering process, specifically, the auxiliary agent and the carbon source such as pitch are sintered to form amorphous carbon-free carbon, so that the lithium manganese iron phosphate material particles are effectively and completely coated, the contained conductive agent such as Ketjen black is dispersed in lithium manganese iron phosphate crystal grains, and a uniform conductive network is formed on the surface of the lithium manganese iron phosphate, so that the conductivity of the lithium manganese iron phosphate is remarkably improved.
In order to improve the generation of the lithium ferric manganese phosphate cathode material and improve the coating integrity of the conductive coating layer, in an embodiment, the conditions of the calcination treatment are as follows: the heating rate is 1-15 ℃/min, the temperature is 500-900 ℃, and the calcination time is 2-24 hours. In a further embodiment, after the drying treatment and before the calcining treatment, the method further comprises the step of performing a pre-sintering treatment on the mixture obtained after the drying treatment, wherein the temperature of the pre-sintering treatment is 300-500 ℃ and the time is 2-10 hours.
Therefore, according to the preparation method of the nanoscale lithium ion battery anode material, the conductive coating layer precursor solution is coated with the lithium manganese iron phosphate in situ, so that on one hand, a uniform conductive network is formed on the surface of the lithium manganese iron phosphate by the conductive coating layer, and the conductivity of the lithium manganese iron phosphate is effectively improved; on the other hand, the conductive coating layer inhibits the growth of the particle size of the lithium ferric manganese phosphate, so that the particle size of the generated nano-scale lithium ion battery anode material is nano-scale, the migration path of lithium ions and electrons is shortened, and the conductivity of the material is improved; in addition, the auxiliary agent added in the lithium ferric manganese phosphate precursor solution can uniformly disperse metal ions on one hand, and can also play a role of a carbon source on the other hand, assist in conducting the precursor solution of the coating layer, improve the coating rate of the coating layer and improve the conducting performance of the prepared nano-scale lithium ion battery anode material.
And preferably, a mixture of a carbon source and a conductive agent is used as a precursor solution of the conductive coating, so that the carbon source and the auxiliary agent form the carbon coating in the sintering treatment process, the integrity of the carbon coating is improved, and the contained conductive agent forms a uniform conductive network on the surface of the lithium manganese iron phosphate, so that the conductivity of the lithium manganese iron phosphate is remarkably improved.
The nano-scale lithium ion battery anode material prepared by the method has nano size, for example, the particle is fine and uniform below 100nm, thereby reducing the nano sizeShortening Li in primary particle size of anode material of meter-class lithium ion battery+And the migration path of electrons, thereby improving the conductivity of the material and improving the electrochemical performance of the material. In addition, the prepared nano lithium ion battery cathode material is high in purity, high in discharge platform (3.95V), and has high energy density, good low-temperature performance, good rate discharge performance and good cycle performance. The 1C discharge gram capacity of the nano-scale lithium ion battery anode material can reach 153mAh/g, the median voltage is 3.95V, and the 3C discharge gram capacity can reach 146 mAh/g. And secondly, the preparation method has easily-controlled preparation process conditions, ensures the stable performance of the generated nano-grade lithium ion battery anode material, has rich raw material sources and high production efficiency, and reduces the production cost of the nano-grade lithium ion battery anode material.
Based on the preparation method of the nanoscale lithium ion battery anode material and the performance test of the generated nanoscale lithium ion battery anode material, the nanoscale lithium ion battery anode material prepared by the method is used as the lithium ion battery prepared from the lithium ion battery anode material, and the lithium ion battery has the advantages of safety, high capacity, super-long service life, high temperature resistance, high-power discharge capacity, quick charging and the like, and has the advantages of higher energy density, better low-temperature performance, higher compaction density and the like.
The present invention will now be described in further detail with reference to specific examples.
Example 1
The embodiment provides a nanoscale lithium ion battery anode material and a preparation method thereof. The preparation method of the nano-scale lithium ion battery anode material comprises the following steps:
s11, preparing lithium ferric manganese phosphate precursor solution by lithium hydroxide, ferric nitrate, ammonium dihydrogen phosphate, manganese nitrate and stearic acid according to the molar ratio of 1:0.4:1:0.6:1, wherein the solvent is water, and the concentration of the solution is 20% by weight;
s12, dispersing the asphalt and the Keqin black in a solvent to prepare a precursor solution of the conductive coating; wherein the weight ratio of the asphalt to the ketjen black is 1: 0.05, the solvent is water, and the concentration of the solution is 5 percent;
s13, mixing the lithium ferric manganese phosphate precursor solution prepared in the step S11 and the electric coating layer precursor solution prepared in the step S12 according to a ratio of 20:1 to form a mixture solution;
s14, ball-milling the mixture solution in a planetary ball mill for 30 hours, carrying out blast drying at 80 ℃ to obtain powder, and crushing the powder by using crushing equipment; and (2) placing the crushed powder into an atmosphere furnace for pretreatment at the temperature of 400 ℃ for 20 hours to obtain a nano lithium manganese iron phosphate/asphalt/ketjen black precursor, calcining the nano lithium manganese iron phosphate/asphalt/ketjen black precursor at the temperature of 700 ℃ for 20 hours under the protection of nitrogen atmosphere, controlling the heating rate at 5 ℃/min, and naturally cooling to obtain the nano asphalt-based amorphous carbon/ketjen black coated nano lithium manganese iron phosphate.
Example 2
The embodiment provides a nanoscale lithium ion battery anode material and a preparation method thereof. The preparation method of the nano-scale lithium ion battery anode material comprises the following steps:
s21, preparing a lithium manganese iron phosphate precursor solution from a lithium nitrate, ferrous nitrate, phosphoric acid, manganese acetate and magnesium nitrate doping element compound and tartaric acid according to a molar ratio of 1.05:0.2:0.98:0.78:0.02:3, wherein the solvent is water-ethanol (1:1), and the concentration of the solution is 80% by weight;
s22, dispersing the asphalt and the Keqin black in a solvent to prepare a precursor solution of the conductive coating; wherein the weight ratio of the asphalt to the ketjen black is 1: 9, the solvent is absolute ethyl alcohol, and the concentration of the solution is 40 percent;
s23, mixing the lithium ferric manganese phosphate precursor solution prepared in the step S21 and the electric cladding layer precursor solution prepared in the step S22 according to a ratio of 25:1 to form a mixture solution;
s24, ball-milling the mixture solution in a planetary ball mill for 30 hours, carrying out blast drying at 120 ℃ to obtain powder, and crushing the powder by using crushing equipment; and (2) placing the crushed powder into an atmosphere furnace, pretreating for 3 hours at the temperature of 450 ℃ to obtain a nano lithium manganese iron phosphate/asphalt/ketjen black precursor, calcining the nano lithium manganese iron phosphate/asphalt/ketjen black precursor for 12 hours at the temperature of 600 ℃ under the protection of nitrogen atmosphere, controlling the heating rate at 8 ℃/min, and naturally cooling to obtain the nano asphalt-based amorphous carbon/ketjen black coated nano lithium manganese iron phosphate.
Example 3
The embodiment provides a nanoscale lithium ion battery anode material and a preparation method thereof. The preparation method of the nano-scale lithium ion battery anode material comprises the following steps:
s31, preparing a lithium manganese iron phosphate precursor solution from a lithium carbonate, ferric oxide, ammonium phosphate, manganese citrate, aluminum nitrate doping element compound and glucose according to the weight ratio of 0.98:0.59:0.98:0.4:0.01:0.8, adjusting the pH of the solution to 3 by using nitric acid, wherein the solvent is acetone, and the concentration of the solution is 10%;
s32, dispersing the asphalt and the Keqin black in a solvent to prepare a precursor solution of the conductive coating; wherein the weight ratio of the asphalt to the ketjen black is 1: 3, the solvent is glycol, and the concentration of the solution is 20 percent;
s33, mixing the lithium ferric manganese phosphate precursor solution prepared in the step S31 and the electric coating layer precursor solution prepared in the step S32 according to a ratio of 50:1 to form a mixture solution;
s34, ball-milling the mixture solution in a planetary ball mill for 30 hours, carrying out blast drying at 350 ℃ to obtain powder, and crushing the powder by using crushing equipment; and (2) placing the crushed powder into an atmosphere furnace, pretreating for 3 hours at the temperature of 450 ℃ to obtain a nano lithium manganese iron phosphate/asphalt/ketjen black precursor, calcining the nano lithium manganese iron phosphate/asphalt/ketjen black precursor for 8 hours at the temperature of 850 ℃ under the protection of nitrogen atmosphere, controlling the heating rate at 3 ℃/min, and naturally cooling to obtain the nano asphalt-based amorphous carbon/ketjen black coated nano lithium manganese iron phosphate.
Comparative example 1
The preparation method of the nanoscale lithium ion battery positive electrode material provided in the comparative example 1 is the same as the preparation method of the nanoscale lithium ion battery positive electrode material provided in the above example 1, except that an auxiliary agent is not added in the step of preparing the lithium ferric manganese phosphate precursor solution in the comparative example, and the rest is kept unchanged.
Comparative example 2
The preparation method of the nanoscale lithium ion battery positive electrode material provided in the comparative example 2 is the same as the preparation method of the nanoscale lithium ion battery positive electrode material provided in the above example 2, except that an auxiliary agent is not added in the step of preparing the lithium ferric manganese phosphate precursor solution in the comparative example, and the rest is kept unchanged.
Comparative example 3
The preparation method of the nanoscale lithium ion battery positive electrode material provided in the comparative example 3 is the same as the preparation method of the nanoscale lithium ion battery positive electrode material provided in the above example 3, except that an auxiliary agent is not added in the step of preparing the lithium ferric manganese phosphate precursor solution in the comparative example, and the rest is kept unchanged.
Lithium ferric manganese phosphate anode material performance test
1. And (3) determining the particle size, the carbon content and the specific surface area of the nano-grade lithium ion battery anode material:
the nanoscale lithium ion battery positive electrode materials provided in examples 1 to 3 and the nanoscale lithium ion battery positive electrode material provided in a comparative example were subjected to the following relevant tests, wherein the relevant performances of the tests of the positive electrode materials of example 1 and comparative example 1 are shown in table 1. In addition, an electron microscope picture of the cathode material prepared in example 1 is shown in fig. 2A, and an electron microscope picture of the cathode material provided in comparative example 1 is shown in fig. 2B.
TABLE 1
As can be seen from FIG. 1 and Table 1, the particle size of the sample added with the aid is significantly smaller, the size of the sample is relatively uniform, the particle size of the sample is below 100nm, and the agglomeration is significantly less; the sample without the addition of the auxiliary agent is particularly obvious in agglomeration, and the particle size of the sample is obviously larger; the sample added with the auxiliary agent enables metal ions to be uniformly dispersed at the atomic level under the action of the auxiliary agent; meanwhile, the added auxiliary agent is slightly excessive, the excessive auxiliary agent can play a role of a carbon source to assist a precursor solution of the conductive coating layer, the coating rate of the coating layer is improved, and the conductive coating layer inhibits the growth of the particle size of lithium ferric manganese phosphate, so that the particle size of the generated nano-scale lithium ion battery anode material is below 100 nm. In addition, the same tests as those described above were performed on the positive electrode materials of the nanoscale lithium ion batteries prepared in examples 2 and 3 and comparative examples 2 and 3, and the results show that the relevant performance of the lithium manganese iron phosphate positive electrode materials prepared in examples 2 and 3 is close to that of the lithium manganese iron phosphate positive electrode material prepared in example 1, and the relevant performance of the lithium manganese iron phosphate positive electrode materials prepared in comparative examples 2 and 3 is close to that of the lithium manganese iron phosphate positive electrode material prepared in comparative example 1. Therefore, the preparation method of the lithium manganese iron phosphate cathode material provided by the embodiment of the invention can ensure that the prepared lithium manganese iron phosphate cathode material has stable related performances such as particle size and carbon content.
2. Relevant electrochemical performance test of nano-scale lithium ion battery anode material
The lithium manganese iron phosphate positive electrode materials provided in examples 1 to 3 and the lithium manganese iron phosphate positive electrode material provided in the comparative example were respectively used as positive electrode active materials, and after weighing the positive electrode active materials, acetylene black and PVDF in a mass ratio of 90:5:5, the positive electrode active materials were ground in a mortar for 20 minutes to be uniformly mixed, and then N-methyl pyrrolidone (NMP) was added and ground for 20 minutes to obtain a uniform black slurry. The black slurry was uniformly coated on an aluminum foil, then dried in a vacuum oven at 120 ℃ for 12 hours, and then punched into a disk with a diameter of 14mm as a positive electrode. A positive plate, a negative plate (a metal lithium plate with the diameter of 14.5 mm), a diaphragm (Celgard 2400 microporous polypropylene film) and an electrolyte (1mo1/L LiPF)6the/EC + DMC (1:1 by volume)) was assembled into a CR2025 button cell in a hydrogen-filled glove box, and the cell was left to stand for 12h before performing electrochemical performance tests. When the electrochemical performance test is carried out, the metallic Li is used as a counter electrode, the charging and discharging voltage range is 2.0-4.3V, the temperature is kept at 25 ℃, the related performance test is carried out as shown in the following table 2, and the test result is shown in the following table 2. Wherein, the discharge curve at 0.2C of the example 1 and the comparative example 1 is shown in FIG. 3, and the discharge curve at 1.0C of the example 1 and the comparative example 1 is shown in FIG. 4; example 2 and comparative example 2 discharge at 0.2CThe curve is shown in fig. 5, and the discharge curves of example 2 and comparative example 2 at 1.0C are shown in fig. 6; the discharge curves of example 3 and comparative example 3 at 0.2C are shown in fig. 7, and the discharge curves of example 3 and comparative example 3 at 1.0C are shown in fig. 8. Further, the rate capability of example 3 and comparative example 3 is shown in fig. 9.
TABLE 2
As can be seen from the test results in table 2 and fig. 3-9, the nanoscale lithium ion battery cathode material provided by the embodiment of the present invention has excellent electrical properties, and therefore, the lithium ion battery prepared by using the nanoscale lithium ion battery cathode material has excellent and stable electrochemical properties.
As can be seen from table 2 and fig. 3 to 8, the discharging capacity of examples 1 to 3 is significantly improved compared with that of comparative examples 1 to 3, that is, the addition of the additive can significantly improve the charging and discharging performance of the synthesized lithium ferric manganese phosphate, the 0.2C and 1.0C median voltages thereof are both significantly improved, and particularly the 1.0C median voltage can be increased by more than 0.2V.
As can be seen from FIG. 9, the rate capability of the lithium manganese iron phosphate added with the additive is obviously improved, the 3C discharge gram capacity of the sample added with the additive can reach 146mAh/g, while the 3C discharge gram capacity of the sample without the additive is only 130 mAh/g; and with the increase of the multiplying power, the discharge capacity of the sample added with the auxiliary agent is slowly reduced, while the sample without the auxiliary agent is in a remarkable reduction trend.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. A preparation method of a nano-scale lithium ion battery anode material comprises the following steps:
preparing a lithium ferric manganese phosphate precursor solution;
preparing a conductive coating layer precursor solution;
mixing the lithium ferric manganese phosphate precursor solution with a conductive coating layer precursor solution to form a mixture solution;
performing ball milling treatment on the mixture solution for 10-48 hours, drying the mixture solution, and then performing calcination treatment in a protective atmosphere;
the lithium manganese iron phosphate precursor solution also contains an auxiliary agent, and the ratio of the molar content of the auxiliary agent to the total molar content of the lithium manganese iron phosphate precursor is 1: (0.1-10);
the auxiliary agent is at least one of polyvinyl alcohol, polyethylene glycol, stearic acid, malic acid, tartaric acid, salicylic acid, succinic acid and glycine;
the method for preparing the precursor solution of the conductive coating layer comprises the following steps:
dispersing a carbon source and a conductive agent in a solvent; wherein the weight ratio of the carbon source to the conductive agent is 1: (0.01-10);
the carbon source is asphalt;
in the mixture solution, the total mass of the carbon source and the conductive agent accounts for 0.5-10% of the mass of the theoretically generated lithium iron manganese phosphate;
the conductive agent is at least one of Ketjen black, acetylene black, Super P, nano carbon powder, carbon nano tubes, graphite, graphene, superconducting carbon and carbon nano fibers;
the conditions of the calcination treatment are as follows: the heating rate is 1-15 ℃/min, the temperature is 500-900 ℃, and the calcination time is 2-24 hours;
after the drying treatment, the step of performing a pre-sintering treatment on the mixture obtained after the drying treatment is further included before the calcining treatment, wherein the temperature of the pre-sintering treatment is 300-500 ℃, and the time is 2-10 hours.
2. The method of claim 1, wherein: the method for preparing the lithium ferric manganese phosphate precursor solution comprises the following steps:
mixing the components in a molar ratio of (0.95-1.1): (0.2-0.9): (0.95-1): (0.1-0.8): (0-0.05) a lithium source, an iron source, a phosphorus source, a manganese source, and a doping element source are treated with the aid.
3. The production method according to claim 1 or 2, characterized in that: the iron source is at least one of ferric phosphate, ferrous pyrophosphate, ferrous carbonate, ferrous chloride, ferrous hydroxide, ferrous nitrate, ferrous oxalate, ferric chloride, ferric hydroxide, ferric nitrate, ferric citrate and ferric oxide; and/or
The phosphorus source is at least one of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, iron phosphate and lithium dihydrogen phosphate; and/or
The manganese source is at least one of manganese dioxide, manganous oxide, manganese oxalate, manganese acetate or manganese nitrate; and/or
The doping element source is at least one of a copper compound, a magnesium compound, an aluminum compound, a zinc compound, a manganese compound, a titanium compound, a zirconium compound, a niobium compound, a chromium compound and a rare earth element compound.
4. The method of claim 1, wherein: the primary particle size of the prepared nano-grade lithium ion battery anode material is less than 100 nm.
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| CN111211297B (en) * | 2018-11-22 | 2022-03-18 | 杭州长凯能源科技有限公司 | Preparation of battery active material containing micro-nano conductive network structure |
| CN111559739A (en) * | 2020-03-30 | 2020-08-21 | 桑顿新能源科技有限公司 | High-rate lithium ferric manganese phosphate composite material, preparation method thereof and lithium ion battery |
| CN112047321A (en) * | 2020-09-10 | 2020-12-08 | 江西智锂科技有限公司 | Method for preparing composite phosphate lithium battery anode material |
| CN114464802A (en) * | 2022-01-11 | 2022-05-10 | 中科锂电新能源有限公司 | Modified nano lithium ferric manganese phosphate cathode material and preparation method thereof |
| CN114497540A (en) * | 2022-01-26 | 2022-05-13 | 湖南裕能新能源电池材料股份有限公司 | Embedded lithium ferric manganese phosphate cathode material, preparation method thereof, lithium ion battery and electric equipment |
| CN115020702A (en) * | 2022-07-12 | 2022-09-06 | 东莞凯德新能源有限公司 | Lithium ion battery, positive electrode material with core-shell structure and preparation method of positive electrode material |
| CN115275170B (en) * | 2022-09-02 | 2023-06-30 | 永州昊利新材料科技有限公司 | Preparation method of cerium dioxide modified lithium iron manganese phosphate electrode material |
| CN115548293B (en) * | 2022-09-23 | 2024-01-30 | 长沙学院 | Spherical LiMnFeVPO 4 Composite positive electrode material/C, and preparation method and application thereof |
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