CN108321390B - Three-dimensional flower-shaped single crystal lithium iron phosphate and preparation method thereof - Google Patents
Three-dimensional flower-shaped single crystal lithium iron phosphate and preparation method thereof Download PDFInfo
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- CN108321390B CN108321390B CN201810062558.0A CN201810062558A CN108321390B CN 108321390 B CN108321390 B CN 108321390B CN 201810062558 A CN201810062558 A CN 201810062558A CN 108321390 B CN108321390 B CN 108321390B
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H01M10/05—Accumulators with non-aqueous electrolyte
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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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Abstract
The invention discloses three-dimensional flower-shaped monocrystal lithium iron phosphate and a preparation method thereof, wherein the microcosmic appearance is a three-dimensional flower-shaped structure surrounded by nanometer flaky lithium iron phosphate with the thickness of 10-100 nm, the length of 500-4000 nm and the width of 200-1000 nm, and the direction of each piece of lithium iron phosphate perpendicular to the thickness is [010 ]. The preparation method comprises the following steps: dissolving urea and sodium carbonate in ethylene glycol, adding a phosphorus source and an iron source, uniformly mixing, carrying out hydrothermal reaction, filtering, washing and drying a product after the reaction is finished, then mixing the obtained precursor with a lithium source, and carrying out high-temperature calcination under the protection of inert gas to obtain the three-dimensional flower-shaped monocrystal lithium iron phosphate. The method adopts a simple hydrothermal method and a simple calcination method to synthesize the three-dimensional flower-shaped lithium iron phosphate single crystal, and has the advantages of low energy consumption, wide applicability, simple steps, easy control, easy repetition and amplification and the like.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to three-dimensional flower-shaped single crystal lithium iron phosphate and a preparation method thereof.
Background
The lithium ion battery is a common energy storage device, and has the advantages of high energy density, long service life, low self-discharge rate, wide working temperature range, no memory effect, environmental friendliness and the like, so that the lithium ion battery is of great concern for application in the fields of portable electronic products, electric vehicles, large-scale power supplies, aviation, aerospace, national defense, energy storage and the like. The lithium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. The positive electrode material and the negative electrode material are important components of the lithium ion battery and have a decisive influence on the performance of the lithium ion battery. Currently, lithium cobaltate, lithium manganate and lithium iron phosphate are commonly used as cathode materials in commerce. Because the lithium iron phosphate has the advantages of low price, no toxicity and higher theoretical specific capacity (170mAh g)-1) The lithium ion battery anode material has the advantages of high working voltage, good environmental compatibility, long cycle life, good high-temperature performance and safety performance and the like, so that the lithium ion battery anode material is distinguished from a plurality of anode materials, is considered as a new generation of lithium ion battery anode material with great application potential, and can be widely applied to the field of power systems.
LiFePO4Has an orderly and regular olivine structure, belongs to an orthorhombic system, and has the advantages of rich raw material source, low price, no toxicity, environmental friendliness and stable structureHigher theoretical capacity (170mAh g)-1) High and stable working voltage (3.4V vs. Li/Li)+) The lithium ion battery positive electrode material has the advantages of good thermal stability, excellent cycle performance, high safety and the like, and is regarded as a new generation of lithium ion battery positive electrode material with the most development potential. LiFePO4LiFePO participates in the reaction in the charging and discharging process4And FePO4Two phases, the charge-discharge reaction of which is as follows:
charging reaction: LiFePO4-xLi+-xe-→xFePO4+(1-x)LiFePO4
Discharging reaction: FePO4+xLi++xe-→(1-x)FePO4+xLiFePO4
As can be seen from the charge-discharge reaction, lithium ions are derived from LiFePO during charging4De-intercalation in the lattice to form FePO4On discharge, lithium ions are intercalated into FePO4Formation of LiFePO in the crystal lattice4. Thus, during charging and discharging, LiFePO4With FePO4Two phases coexist. Due to FePO4With LiFePO4The structure is similar and the volume is similar, so the volume change of the material is small in the lithium desorption process, namely LiFePO in the charging and discharging process4With FePO4The two-phase transformation does not produce a volume effect which has a severe influence on the electrochemical properties of the material, which is also LiFePO4The reason for the excellent cycle stability.
However, the lithium iron phosphate has the defects of low electronic conductivity and small lithium ion diffusion coefficient, so that the large-current charge and discharge performance of the lithium iron phosphate is influenced, and the large-scale application of the lithium iron phosphate is limited. In order to overcome these disadvantages, researchers have conducted extensive research and proposed many feasible modification methods, mainly including material nanocrystallization, coating methods, and doping methods. Therefore, modification of the lithium iron phosphate cathode material to improve electrochemical properties such as rate capability of the material is a hot research point for the cathode material of the lithium ion battery.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide a three-dimensional flower-like single-crystal lithium iron phosphate, and a second object of the present invention is to provide a method for preparing the lithium iron phosphate.
In order to achieve the first object, the technical scheme of the invention is as follows: a three-dimensional flower-like monocrystal lithium iron phosphate is characterized in that: the microcosmic appearance is a three-dimensional flower-shaped structure surrounded by nanometer flaky lithium iron phosphate with the thickness of 10-100 nm, the length of 500-4000 nm and the width of 200-1000 nm, and the direction of each piece of lithium iron phosphate perpendicular to the thickness is [010 ].
The second object of the present invention is achieved by: the preparation method of the three-dimensional flower-like monocrystal lithium iron phosphate is characterized by comprising the following steps: dissolving urea and sodium carbonate in ethylene glycol, adding a phosphorus source and an iron source into an ethylene glycol solution, uniformly mixing, carrying out hydrothermal reaction, filtering, washing and drying a product after the reaction is finished, then mixing the obtained precursor with a lithium source, and calcining at high temperature under the protection of inert gas to obtain the three-dimensional flower-shaped monocrystal lithium iron phosphate.
Lithium ion in LiFePO4The diffusion in (1) is the most important and decisive control step in the charge-discharge process, and firstly the LiFePO is improved by a material nano-crystallization method4The lithium ion diffusion rate of the material. Due to LiFePO4Having one-dimensional lithium ion diffusion channel ([010 ]]Channels), therefore, we prepared a material having [010] based on the principle of low lattice mismatch]Crystal oriented three-dimensional flower-like monocrystal lithium iron phosphate, i.e. monocrystal nano sieve in [010]The direction has nanometer thickness, thereby effectively shortening the lithium ion diffusion path and improving the lithium ion diffusion rate. Meanwhile, the three-dimensional flower-shaped structure has a large specific surface area and a porous structure, so that the contact area of the material and the electrolyte is increased, and the permeation and infiltration of the electrolyte are promoted. In addition, the three-dimensional flower-like structure can prevent the two-dimensional lithium iron phosphate nanosheets from being attached, and the two-dimensional lithium iron phosphate nanosheets are fully exposed in the electrolyte in the circulation process, so that excellent circulation stability and excellent rate capability are shown. The experimental result shows that the specific capacity of the three-dimensional flower-shaped monocrystal lithium iron phosphate is stabilized at 164mAh g through 4000 charge-discharge cycles at the rate of 1C-1The capacity retention rate is as high as 99%.
In the scheme, the method comprises the following steps:the iron source is selected from Fe (NO)3)3The phosphorus source is Na3PO4、Na2HPO4、NaH2PO4At least one of (1).
In the scheme, the method comprises the following steps: the lithium source is selected from Li3PO4、LiCO3、Li2C2O4And LiOH.
In the scheme, the method comprises the following steps: the mol ratio of urea to sodium carbonate is 1-3: 1.
in the scheme, the method comprises the following steps: the temperature of the hydrothermal reaction is 150-220 ℃, and the time is 12-24 h.
In the scheme, the method comprises the following steps: the high-temperature calcination temperature is 600-760 ℃, and the time is 1-5 h.
Has the advantages that: the three-dimensional flower-shaped monocrystal lithium iron phosphate with the exposed specific crystal face (010) prepared by the invention has regular appearance and uniform size, and as a lithium ion battery cathode material, the unique three-dimensional flower-shaped structure can shorten the transmission distance of lithium ions in the charging and discharging process and can prevent the material from agglomerating, thereby improving the electrochemical performance of the electrode material and enhancing the cycle stability. The method adopts a simple hydrothermal method and a simple calcination method to synthesize the three-dimensional flower-shaped lithium iron phosphate single crystal, and has the advantages of low energy consumption, wide applicability, simple steps, easy control, easy repetition and amplification and the like.
Drawings
Fig. 1 is an XRD analysis chart, and all X-ray powder diffraction peaks can be indicated as lithium iron phosphate crystals.
FIG. 2 is an FE-SEM photograph of example 1.
Fig. 3 shows the high power transmission of a three-dimensional flower-like lithium iron phosphate single crystal.
Fig. 4 is a rate performance graph of the three-dimensional flower-like lithium iron phosphate single crystal of embodiment 1.
Detailed Description
The invention will be further elucidated with reference to the drawings and the detailed description:
example 1
Dissolving urea and sodium carbonate in 30ml of ethylene glycol solution, adding ferric nitrate and sodium dihydrogen phosphate, dissolving in the ethylene glycol solution, mixing, stirring, wherein the concentration of the urea in the obtained mixed solution is 0.10mol/L, the concentration of the sodium carbonate in the mixed solution is 0.10mol/L, the concentration of the ferric nitrate in the mixed solution is 0.15mol/L, and the concentration of the sodium dihydrogen phosphate in the mixed solution is 0.12 mol/L. And transferring the mixed solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction in a 150 ℃ forced air drying oven for 24 hours, centrifugally washing the precipitate obtained by the reaction, and drying to obtain a precursor.
And uniformly mixing the obtained precursor with lithium phosphate (2mmol of lithium phosphate), and calcining in a tubular furnace in an argon atmosphere at 700 ℃ for 2h to obtain the three-dimensional flower-shaped lithium iron phosphate single crystal.
Example 2
Dissolving urea and sodium carbonate in 30ml of glycol solution, adding ferric nitrate and sodium monohydrogen phosphate, dissolving in the glycol solution, mixing, and stirring, wherein the concentration of the urea, the concentration of the sodium carbonate, the concentration of the ferric nitrate and the concentration of the sodium monohydrogen phosphate in the mixed solution are respectively 0.10mol/L, 0.30mol/L and 0.12mol/L, respectively. And transferring the mixed solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction in a forced air drying oven at 220 ℃ for 12 hours, centrifugally washing the precipitate obtained by the reaction, and drying to obtain a precursor.
And uniformly mixing the obtained precursor with lithium carbonate (3mmol of lithium carbonate), and calcining in a tubular furnace in an argon atmosphere at 760 ℃ for 1h to obtain the three-dimensional flower-shaped monocrystal lithium iron phosphate.
Example 3
(1) Dissolving urea and sodium carbonate in 30ml of ethylene glycol solution, adding ferric nitrate and sodium phosphate, dissolving in the ethylene glycol solution, mixing, stirring, wherein the concentration of the urea in the obtained mixed solution is 0.10mol/L, the concentration of the sodium carbonate is 0.20mol/L, the concentration of the ferric nitrate is 0.15mol/L, and the concentration of the sodium phosphate is 0.12 mol/L. And transferring the mixed solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction in a 180 ℃ forced air drying oven for 18 hours, centrifugally washing the precipitate obtained by the reaction, and drying to obtain a precursor.
And uniformly mixing the obtained precursor with lithium oxalate, and calcining in a tubular furnace in an argon atmosphere at the calcining temperature of 600 ℃ for 5 hours to obtain the three-dimensional flower-shaped monocrystal lithium iron phosphate.
Example 4
(1) Dissolving urea and sodium carbonate in 30ml of glycol solution, adding ferric nitrate and sodium dihydrogen phosphate, dissolving in the glycol solution, mixing, stirring, wherein the concentration of urea in the mixed solution is 0.10mol/L, the concentration of sodium carbonate in the mixed solution is 0.15mol/L, the concentration of ferric nitrate in the mixed solution is 0.15mol/L, and the concentration of sodium dihydrogen phosphate in the mixed solution is 0.12 mol/L. And transferring the mixed solution into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction in a 180 ℃ forced air drying oven for 18 hours, centrifugally washing the precipitate obtained by the reaction, and drying to obtain a precursor.
And uniformly mixing the obtained precursor with lithium hydroxide (5mmol of lithium hydroxide), and calcining in a tubular furnace in an argon atmosphere at the calcining temperature of 720 ℃ for 1.5h to obtain the three-dimensional flower-shaped monocrystal lithium iron phosphate.
The three-dimensional flower-like lithium iron phosphate single crystals prepared in examples 1 to 4 were examined to obtain fig. 1 to 4:
wherein fig. 1 is an XRD analysis chart, all X-ray powder diffraction peaks can be indicated as lithium iron phosphate crystals, which illustrates that the synthesized high-purity lithium iron phosphate nanomaterial of examples 1-4.
Fig. 2 is an FE-SEM photograph of example 1, and it can be seen from the photograph that three-dimensional flower-like lithium iron phosphate can be prepared on a large scale.
Fig. 3 shows the high-power transmission of the three-dimensional flower-like lithium iron phosphate single crystal, and it can be seen from fig. 3 that the lattices of the three-dimensional flower-like lithium iron phosphate are continuous, which proves that the three-dimensional flower-like lithium iron phosphate has a single crystal structure.
Fig. 4 is a rate performance diagram of the three-dimensional flower-like lithium iron phosphate single crystal in embodiment 1, and it can be seen from the diagram that the coulombic efficiency of the three-dimensional flower-like lithium iron phosphate single crystal can still be maintained above 97% after 6000 cycles.
Table one shows the discharge capacity and cycle performance of the lithium battery positive electrode material tests of the three-dimensional flower-like lithium iron phosphate single crystals prepared in the embodiment examples 1 to 4 and the comparative material.
Watch 1
As can be seen from the table I, the performance of the three-dimensional flower-shaped single-crystal lithium iron phosphate prepared by the invention is obviously superior to that of the flake single-crystal lithium iron phosphate and the lithium iron phosphate nano-particles.
The present invention is not limited to the specific embodiments described above, and it should be understood that many modifications and variations can be made by one of ordinary skill in the art in light of the present inventive concept without undue experimentation. In summary, the technical solutions available to those skilled in the art through logic analysis, reasoning or limited experiments based on the prior art according to the concept of the present invention are all within the scope of protection defined by the claims.
Claims (4)
1. A three-dimensional flower-like single crystal lithium iron phosphate is characterized in that: the microcosmic appearance is a three-dimensional flower-shaped structure surrounded by nano flaky lithium iron phosphate with the thickness of 10-100 nm, the length of 500-4000 nm and the width of 200-1000 nm, and the direction of each piece of lithium iron phosphate perpendicular to the thickness is [010]](ii) a The three-dimensional flower-shaped single crystal lithium iron phosphate is prepared by the following method: dissolving urea and sodium carbonate in ethylene glycol, adding a phosphorus source and an iron source into an ethylene glycol solution, uniformly mixing, carrying out a solvothermal reaction, filtering, washing and drying a product after the reaction is finished, then mixing the obtained precursor with a lithium source, and carrying out high-temperature calcination under the protection of inert gas to obtain three-dimensional flower-shaped monocrystal lithium iron phosphate; the iron source is Fe (NO)3)3The phosphorus source is Na3PO4、Na2HPO4、NaH2PO4At least one of; the temperature of the solvothermal reaction is 150 ℃ and the time is 24 h.
2. The method for preparing the three-dimensional flower-like single crystal lithium iron phosphate according to claim 1, which is characterized in that: the lithium source is selected from Li3PO4、LiCO3、Li2C2O4And LiOH.
3. The method for preparing the three-dimensional flower-like single crystal lithium iron phosphate according to claim 2, which is characterized in that: the mol ratio of urea to sodium carbonate is 1-3: 1.
4. the method for preparing the three-dimensional flower-like single crystal lithium iron phosphate according to claim 3, which is characterized in that: the high-temperature calcination temperature is 600-760 ℃, and the time is 1-5 h.
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| US11476462B2 (en) * | 2011-06-22 | 2022-10-18 | National Tsing Hua University | LiFePO4 precursor for manufacturing electrode material of Li-ion battery and method for manufacturing the same |
| CN111646449B (en) * | 2019-03-04 | 2023-02-03 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate material, preparation method and application thereof |
| CN114195115B (en) * | 2021-11-17 | 2023-08-04 | 合肥国轩高科动力能源有限公司 | Modification method of lithium iron phosphate composite material |
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| CN102569791A (en) * | 2010-12-16 | 2012-07-11 | 中国科学院福建物质结构研究所 | Lithium iron phosphate with flower-like structure and preparation method thereof |
| CN104201335A (en) * | 2014-08-18 | 2014-12-10 | 浙江大学 | Nano flake-shaped lithium iron phosphate and preparation method thereof |
| CN104835939A (en) * | 2015-05-05 | 2015-08-12 | 南京理工大学 | Preparation method of high-performance lithium iron phosphate composite material |
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| CN102569791A (en) * | 2010-12-16 | 2012-07-11 | 中国科学院福建物质结构研究所 | Lithium iron phosphate with flower-like structure and preparation method thereof |
| CN104201335A (en) * | 2014-08-18 | 2014-12-10 | 浙江大学 | Nano flake-shaped lithium iron phosphate and preparation method thereof |
| CN104835939A (en) * | 2015-05-05 | 2015-08-12 | 南京理工大学 | Preparation method of high-performance lithium iron phosphate composite material |
Non-Patent Citations (1)
| Title |
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| 单分散花状分级结构LiFePO4 的合成及其电化学性能;龚美丽等;《中南大学学报(自然科学版)》;20150831;第46 卷(第8 期);第2819-2823页 * |
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