阅读说明：本技术 一种片状磷酸铁锂材料的制备方法 (Preparation method of flaky lithium iron phosphate material ) 是由 陈永信 李意能 孔令涌 刘龙 陈晓东 陈振绳 于 2021-05-31 设计创作，主要内容包括：本发明提供了一种片状磷酸铁锂材料的制备方法。所述制备方法包括如下步骤：(1)锂源、磷源和铁源溶于酸性溶液中,得到混合液；(2)在密闭环境中,将混合液进行溶剂自热蒸发反应,得到磷酸铁锂前驱体；(3)在保护性气体下,对得到的磷酸铁锂前驱体进行烧结,得到所述片状磷酸铁锂材料。利用本发明提供的制备方法能够得到片状磷酸铁锂材料,并且得到的片状磷酸铁锂材料具有较高的倍率性能,低温充放电性能良好。(The invention provides a preparation method of a flaky lithium iron phosphate material. The preparation method comprises the following steps: (1) dissolving a lithium source, a phosphorus source and an iron source in an acid solution to obtain a mixed solution; (2) in a closed environment, carrying out solvent self-heating evaporation reaction on the mixed solution to obtain a lithium iron phosphate precursor; (3) and sintering the obtained lithium iron phosphate precursor under protective gas to obtain the flaky lithium iron phosphate material. The flaky lithium iron phosphate material can be obtained by the preparation method provided by the invention, and the obtained flaky lithium iron phosphate material has high rate performance and good low-temperature charge and discharge performance.)

1. A preparation method of a sheet-shaped lithium iron phosphate material is characterized by comprising the following steps:

(1) dissolving a lithium source, a phosphorus source and an iron source in an acid solution to obtain a mixed solution;

(2) in a closed environment, carrying out solvent self-heating evaporation reaction on the mixed solution to obtain a lithium iron phosphate precursor;

(3) and sintering the obtained lithium iron phosphate precursor under protective gas to obtain the flaky lithium iron phosphate material.

2. The method of claim 1, wherein the solvent autothermal evaporation reaction comprises:

when the acid solution is an oxidizing acid solution, adding a reducing carbon source into the mixed solution to perform autothermal evaporation reaction; when the acid solution is a non-oxidizing acid solution, adding a reducing carbon source and hydrogen peroxide into the mixed solution to perform an autothermal evaporation reaction;

preferably, the non-oxidizing acid is selected from any one or more of hydrochloric acid, dilute sulfuric acid, phosphoric acid or acetic acid;

preferably, the pH of the acidic solution is less than 3;

preferably, the acidic solution of step (1) is an oxidizing acidic solution, preferably the oxidizing acid comprises any one or more of nitric acid, hypochlorous acid, perchloric acid or nitrous acid.

3. The method of claim 1, wherein the solvent autothermal evaporation reaction further comprises:

and when the pressure of the closed environment reaches 0.2-0.6MPa, releasing the pressure, and then continuously carrying out self-heating evaporation reaction under normal pressure to obtain the lithium iron phosphate precursor.

4. The preparation method according to claim 2 or 3, wherein the addition amount of the reducing carbon source is 0.1-50% of the total mass of the mixed solution;

and/or the reducing carbon source is a reducing organic carbon source, and further preferably comprises one or more of sucrose, starch, dextrin, glucose, fructose, amino acid, citric acid and malic acid.

5. The production method according to any one of claims 1 to 4, wherein a surfactant and/or a phase transfer catalyst is further added to the mixed solution;

preferably, the addition amount of the surfactant and/or the phase transfer catalyst is 0.01 to 70% by mass of the mixed solution.

6. The preparation method according to claim 5, wherein the surfactant is selected from any one or more of polyethylene glycol and derivatives thereof, polyvinyl alcohol and derivatives thereof, polyacrylic acid and derivatives thereof;

and/or, the phase transfer catalyst is a positive charge phase transfer catalyst or a negative charge phase transfer catalyst, further preferably, the positive charge phase transfer catalyst comprises any one or more of cetyl trimethyl ammonium bromide and derivatives thereof, tetramethyl ammonium hydroxide and derivatives thereof, tetrabutyl ammonium bromide and derivatives thereof, and tetrabutyl ammonium hydroxide and derivatives thereof, further preferably, the negative charge phase transfer catalyst comprises any one or more of sodium dodecyl benzene sulfonate and derivatives thereof, calixarene and derivatives thereof, and crown ethers and derivatives thereof.

7. The production method according to any one of claims 1 to 6, wherein the raw material of lithium iron phosphate includes a lithium source, a phosphorus source, and an iron source;

preferably, in the raw material of the lithium iron phosphate, the molar ratio of the iron element, the phosphorus element and the lithium element is (0.85-1.15): (0.85-1.15): (0.85-1.15).

8. The production method according to claim 7, wherein the lithium source includes any one or more of lithium hydroxide, lithium oxide, lithium chloride, lithium nitrite, lithium nitrate, lithium oxalate, lithium carbonate, lithium acetate, lithium phosphate, lithium dihydrogen phosphate, and lithium dihydrogen phosphate;

and/or the phosphorus source comprises any one or more of phosphoric acid, diammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, iron phosphate, lithium phosphate and lithium dihydrogen phosphate;

and/or the iron source comprises any one or more of ferric oxide, ferric phosphate, ferric chloride, ferric sulfate, ferric hydroxide, ferric nitrate, ferric acetate, ferric citrate, ferric pyrophosphate, ferrous sulfate, ferrous phosphate or ferrous oxalate.

9. The preparation method according to any one of claims 1 to 8, wherein the sintering in step (3) comprises a second sintering, wherein the first sintering is carried out at a temperature of between room temperature and 100 ℃ and 200 ℃ for 1 to 5 hours, and the second sintering is carried out at a temperature of between 550 ℃ and 850 ℃ for 3 to 15 hours, so as to obtain the flaky lithium iron phosphate material.

10. The flaky lithium iron phosphate material obtained by the preparation method according to any one of claims 1 to 9;

preferably, the thickness of the flaky lithium iron phosphate in the flaky lithium iron phosphate material is 30-100 nm.

Technical Field

The invention belongs to the technical field of lithium ion batteries, and relates to a preparation method of a flaky lithium iron phosphate material.

Background

Lithium iron phosphate (LFP) is an anode material with an olivine crystal structure, has excellent safety performance and cycle life, is one of the anode materials of the lithium ion battery with development prospects at present, but the spatial structure of the LFP determines that the LFP only has a one-dimensional lithium ion channel, namely lithium ions can only migrate along a single direction, so that the transmission rate of the lithium ions is low, and the multiplying power performance and the low-temperature performance of the LFP are poor; therefore, how to shorten the migration distance of lithium ions is the key to improve the LFP rate and low temperature performance. In order to shorten the migration distance of lithium ions, a common method at present is to prepare sheet-shaped lithium iron phosphate, and since the conduction of Li in LFP can only be along the direction of the b axis of the crystal, when the b axis is arranged along the thinnest direction of the sheet-shaped LFP, the rate capability of the LFP material can be improved.

CN10845552A discloses a rectangular lithium iron phosphate nanosheet with an exposed crystal face and a preparation method thereof, wherein the nanosheet is of a regular rectangular nanosheet structure, has a width of 100-600nm and a thickness of 20-60nm, and the preparation method of the nanosheet comprises the steps of preparing flaky lithium iron phosphate from a precursor solution of lithium iron phosphate by using a reaction kettle at the temperature of 180-200 ℃; CN102842716A discloses a method for preparing nano-scale lithium iron phosphate, which improves its conductivity by reducing the size of lithium iron phosphate crystal grain to within 100 nm. The preparation method comprises the step of preparing the flaky lithium iron phosphate by heating the reaction solution in a sealed reaction container by using microwaves. Both of the above-mentioned patent applications obtain sheet-like lithium iron phosphate, but still require additional energy to provide the conditions required for the reaction.

Because the sheet LFP has better multiplying power and low-temperature charge and discharge performance, the preparation method which is simple and low in energy consumption is found in the production and preparation process, and the preparation method has important significance for generating the sheet LFP on a large scale.

Disclosure of Invention

The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention aims to provide a preparation method of a flaky lithium iron phosphate material, the flaky lithium iron phosphate material can be obtained by the preparation method provided by the invention, and the obtained flaky lithium iron phosphate material has high rate performance and good low-temperature charge and discharge performance.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a preparation method of a sheet lithium iron phosphate material, which comprises the following steps:

(1) dissolving a lithium source, a phosphorus source and an iron source in an acid solution to obtain a mixed solution;

(2) in a closed environment, carrying out solvent self-heating evaporation reaction on the mixed solution to obtain a lithium iron phosphate precursor;

(3) and sintering the obtained lithium iron phosphate precursor under protective gas to obtain the flaky lithium iron phosphate material.

The acidic solution of the invention refers to a solution with pH value less than 3 and acidity.

The method utilizes the solvent self-heating evaporation reaction to provide a heat source in the raw materials, and limits the reaction to be carried out in a closed environment, and in the process of the solvent self-heating evaporation, the solvent is evaporated, the pressure intensity is increased, and reaction conditions can be provided for the production of the flaky lithium iron phosphate; the method of the invention does not need an external heat source, can greatly reduce the consumption of external energy supply and is beneficial to industrial production.

In order to enable the solvent to be vaporized autothermally, a redox reaction can be carried out, the reaction is self-exothermic, and specifically, the solvent autothermal vaporization reaction in the step (2) comprises the following steps:

when the acid solution is an oxidizing acid solution, adding a reducing carbon source into the mixed solution to perform autothermal evaporation reaction; and when the acid solution is a non-oxidizing acid solution, adding a reducing carbon source and hydrogen peroxide into the mixed solution to perform autothermal evaporation reaction.

In a preferred embodiment of the present invention, the non-oxidizing acid is selected from any one or more of hydrochloric acid, dilute sulfuric acid, phosphoric acid, and acetic acid.

As a preferable technical solution of the present invention, the pH of the acidic solution is less than 3.

In a preferred embodiment of the present invention, the acidic solution in step (1) is an oxidizing acidic solution, and preferably the oxidizing acid includes one or more of nitric acid, hypochlorous acid, perchloric acid, and nitrous acid.

The invention adopts oxidizing acid to react with reducing carbon, the reaction releases heat automatically, and the pressure of the reaction environment can be increased by matching with a closed environment, thereby providing reaction conditions for generating the flaky lithium iron phosphate.

In order to obtain the sheet lithium iron phosphate material, the solvent self-heating evaporation reaction further comprises the following steps:

when the pressure of the closed environment reaches 0.2-0.6MPa, the pressure is released, and then the solvent self-heating evaporation reaction is continuously carried out under the normal pressure.

The 0.2-0.6MPa can be 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa and the like.

The invention needs to relieve pressure after the closed environment reaches a certain pressure, if the pressure is relieved too early and the pressure is too low, the appearance of the LFP with the sheet structure can not be changed, and only the spherical LFP can be generated; if not, or the pressure is too high, on the one hand, the production safety is affected, and on the other hand, the thickness of the generated sheet LFP is too large due to the too high pressure, and the purpose of controlling the thickness is not achieved. The method can successfully obtain the sheet lithium iron phosphate material with the thickness of 30-100nm only by carrying out the solvent self-heating evaporation reaction in a closed environment at the early stage and in a normal pressure environment at the later stage.

In a preferred embodiment of the present invention, the amount of the reducing carbon source added is 0.1 to 50% by mass, for example, 0.5%, 1%, 5%, 10%, 20%, 30%, 40% by mass of the total mass of the mixed solution.

As a preferred technical solution of the present invention, the reducing carbon source is a reducing organic carbon source, and further preferably includes any one or more of sucrose, starch, dextrin, glucose, fructose, amino acid, citric acid and malic acid.

Further, in order to obtain the sheet-shaped lithium iron phosphate, a surfactant and/or a phase transfer catalyst are added to the mixed solution.

According to the invention, the surfactant and/or the phase transfer catalyst are/is added into the mixed solution containing the reaction raw materials, so that the flaky lithium iron phosphate precursor can be generated, and then the flaky lithium iron phosphate material can be obtained by sintering.

In a preferred embodiment of the present invention, the surfactant and/or the phase transfer catalyst is added in an amount of 0.01 to 70% by mass, for example, 0.1%, 1%, 10%, 40%, 50%, 60% by mass of the mixed solution.

The addition amount of the surfactant and/or the phase transfer catalyst refers to: the total mass of the surfactant and/or the phase transfer catalyst, that is, the mass of the surfactant when only the surfactant is added to the mixed solution, and the mass of the surfactant and the phase transfer catalyst when the surfactant and the phase transfer catalyst are added to the mixed solution.

In a preferred embodiment of the present invention, the surfactant is selected from one or at least two of polyethylene glycol and derivatives thereof, polyvinyl alcohol and derivatives thereof, and polyacrylic acid and derivatives thereof.

As a preferred embodiment of the present invention, the phase transfer catalyst is a positively charged phase transfer catalyst or a negatively charged phase transfer catalyst, and more preferably, the positively charged phase transfer catalyst includes any one or more of cetyltrimethylammonium bromide and its derivatives, tetramethylammonium hydroxide and its derivatives, tetrabutylammonium bromide and its derivatives, and tetrabutylammonium hydroxide and its derivatives, and still more preferably, the negatively charged phase transfer catalyst includes any one or more of sodium dodecylbenzenesulfonate and its derivatives, calixarenes and their derivatives, and crown ethers and their derivatives.

As a preferred technical solution of the present invention, the raw material of the lithium iron phosphate includes a lithium source, a phosphorus source, and an iron source.

In a preferred embodiment of the present invention, in the raw material of the lithium iron phosphate, the molar ratio of the iron element, the phosphorus element, and the lithium element is (0.85-1.15): (0.85-1.15): (0.85-1.15), preferably 1: (0.85-1.15): (0.85-1.15).

In a preferred embodiment of the present invention, the lithium source includes any one or more of lithium hydroxide, lithium oxide, lithium chloride, lithium nitrite, lithium nitrate, lithium oxalate, lithium carbonate, lithium acetate, lithium phosphate, lithium dihydrogen phosphate, and lithium dihydrogen phosphate.

As a preferred embodiment of the present invention, the phosphorus source includes any one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, iron phosphate, lithium phosphate, and lithium dihydrogen phosphate.

In a preferred embodiment of the present invention, the iron source includes one or more of iron oxide, iron phosphate, iron chloride, iron sulfate, iron hydroxide, iron nitrate, iron acetate, iron citrate, iron pyrophosphate, ferrous sulfate, ferrous phosphate, and ferrous oxalate.

As a preferable technical scheme of the invention, the sintering in the step (3) comprises secondary sintering, wherein the first sintering is carried out at the temperature of between room temperature and 100 and 200 ℃ for 1 to 5 hours, and the second sintering is carried out at the temperature of between 550 and 850 ℃ for 3 to 15 hours, so as to obtain the flaky lithium iron phosphate material. The first stage of the sintering treatment is mainly to remove the residual solvent in the precursor of the positive electrode active material, and the second stage is mainly to fully crystallize lithium iron phosphate crystal lattices to obtain a flaky LFP product.

As a specific embodiment of the present invention, the preparation method of the sheet-like lithium iron phosphate material according to the present invention includes the following steps:

(1) dissolving a lithium source, a phosphorus source and an iron source in an acid solution according to a molar ratio of (0.85-1.15) to obtain a mixed solution A;

(2) adding a surfactant and/or a phase transfer catalyst into the mixed solution A, wherein the addition mass of the surfactant and/or the phase transfer catalyst is 0.01-70% of the mass of the mixed solution A, so as to obtain a mixed solution B;

(3) in a closed reaction environment, adding a reducing carbon source into the mixed solution B to perform autothermal evaporation reaction when the acid solution in the step (1) is an oxidizing acid solution; or, if the acid solution in the step (1) does not contain oxidizing acid, adding a reductive carbon source and hydrogen peroxide into the mixed solution to perform an autothermal evaporation reaction, releasing pressure when the pressure of a closed environment reaches 0.2-0.6MPa, and then continuing the autothermal evaporation reaction at normal pressure to obtain the lithium iron phosphate precursor;

(4) and (3) under protective gas, performing secondary sintering on the obtained lithium iron phosphate precursor, wherein the temperature of the first sintering is increased from room temperature to 200 ℃ in the first time, and is kept for 1-5h, and the temperature of the second sintering is increased from the temperature of the first sintering to 850 ℃ in the second time, and is kept for 3-15h, so as to obtain the flaky lithium iron phosphate material.

The protective gas of the present invention includes any one or more of nitrogen, argon, helium.

In a second aspect, the invention provides a sheet-shaped lithium iron phosphate material obtained by the preparation method in the first aspect.

The thickness of the flaky lithium iron phosphate in the flaky lithium iron phosphate material is 30-100nm, such as 35nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm and the like.

Compared with the prior art, the invention has the following beneficial effects:

(1) the method utilizes the solvent self-heating evaporation reaction to provide a heat source in the raw materials, and limits the reaction to be carried out in a closed environment, and in the process of the solvent self-heating evaporation, the solvent is evaporated, the pressure intensity is increased, and reaction conditions can be provided for the production of the flaky lithium iron phosphate;

(2) meanwhile, a surfactant and/or a phase transfer catalyst are added into the reaction solution containing the raw materials, and the reaction solution is matched with a solvent in a closed environment for self-heating evaporation reaction, so that a sheet lithium iron phosphate material with the thickness of 30-100nm can be obtained;

(3) the flaky lithium iron phosphate material prepared by the preparation method provided by the invention has higher rate performance and good low-temperature charge and discharge performance;

(4) the method of the invention does not need an external heat source, has simple process, can greatly reduce the consumption of external energy supply and is beneficial to industrial production.

Drawings

Fig. 1 is a first SEM photograph of the plate-like LFP material prepared in example 1.

Fig. 2 is a second SEM photograph of the plate-like LFP material prepared in example 1.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The embodiment provides a preparation method of a flaky lithium iron phosphate material and the obtained flaky lithium iron phosphate material.

The preparation method comprises the following steps:

(1) lithium nitrate (LiNO)₃1mol)68.95g, iron chloride (FeCl)₃·6H₂O, 1mol)270.30g, 85% phosphoric acid (H)₃PO₄1mol)115.30g and 33g of 63.5% nitric acid (HNO)₃0.33mol) are mixed and dissolved in 300g of water to prepare a mixed solution A;

(2) adding a positive charge phase transfer catalyst (cetyl trimethyl ammonium bromide (CTAB)36.4g) into the mixed solution A, and stirring to obtain a mixed solution B;

(3) adding a carbon source (60 g of glucose) into the mixed solution B, stirring to fully disperse the carbon source to obtain a solution C, transferring the solution C into a high-pressure-resistant reaction kettle, monitoring the air pressure and the reaction temperature, discharging the solution in the reaction kettle when the pressure is increased to 0.4MPa, transferring the solution into a normal-pressure reaction container, and obtaining a solid lithium iron phosphate precursor after the solvent in the system is naturally evaporated;

(4) and (2) carrying out heat treatment on the precursor at 180 ℃ for 2h in a nitrogen atmosphere, then heating from 180 ℃ to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4h, cooling, and grinding to obtain the lithium iron phosphate material.

The microscopic morphology of the lithium iron phosphate material obtained by observation with a scanning electron microscope is shown in fig. 1 and 2, which are SEM photographs of the sheet-like LFP material prepared in example 1, and it can be seen that the lithium iron phosphate in the lithium iron phosphate material obtained by the present invention is microscopically sheet-like in structure and about 48nm in thickness.

Example 2

The embodiment provides a preparation method of a flaky lithium iron phosphate material and the obtained flaky lithium iron phosphate material.

The preparation method comprises the following steps:

(1) lithium nitrate (LiNO)₃1mol)68.9g, iron nitrate (Fe (NO)₃)₃·9H₂O, 1mol)404.0g, diammonium hydrogen phosphate ((NH)₄)₂HPO₄1mol)132.0g and 39.4g of 48% nitric acid (0.3mol) are mixed and dissolved in 300g of water to prepare a mixed solution A;

(2) adding a negative charge phase transfer catalyst (17.4 g of sodium hexadecylbenzene sulfonate (SDBS)) into the mixed solution A, and stirring to obtain a mixed solution B;

(3) adding a carbon source (80 g of citric acid) into the mixed solution B, stirring to fully disperse the carbon source to obtain a solution C, transferring the solution C into a high-pressure-resistant reaction kettle, monitoring the air pressure and the reaction temperature, discharging the solution in the reaction kettle when the pressure is increased to 0.6MPa, transferring the solution into a normal-pressure reaction container, and obtaining a solid lithium iron phosphate precursor after the solvent in the system is naturally evaporated;

(4) and (2) carrying out heat treatment on the precursor at 180 ℃ for 2h in a nitrogen atmosphere, then heating from 180 ℃ to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4h, cooling, and grinding to obtain the lithium iron phosphate material.

Example 3

The embodiment provides a preparation method of a flaky lithium iron phosphate material and the obtained flaky lithium iron phosphate material.

The preparation method comprises the following steps:

(1) lithium carbonate (Li)₂CO₃0.5mol)36.9g of iron oxide (molecular formula Fe)₂O₃0.5mol)79.85g, ammonium dihydrogen phosphate (formula NH)₄H₂PO₄1mol)132.0g and 131.25g of 48% nitric acid (1mol) are mixed and dissolved in 300g of water to prepare a mixed solution A;

(2) adding 5.36g of surfactant (polyethylene glycol (PEG)) into the mixed solution A, and stirring to obtain mixed solution B;

(3) adding a carbon source (30 g of starch) into the mixed solution B, stirring to fully disperse the carbon source to obtain a solution C, transferring the solution C into a high-pressure-resistant reaction kettle, monitoring the air pressure and the reaction temperature, discharging the solution in the reaction kettle when the pressure is increased to 0.2MPa, transferring the solution into a normal-pressure reaction container, and obtaining a solid lithium iron phosphate precursor after the solvent in the system is naturally evaporated;

(4) and (2) carrying out heat treatment on the precursor at 180 ℃ for 2h in a nitrogen atmosphere, then heating from 180 ℃ to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4h, cooling, and grinding to obtain the lithium iron phosphate material.

Example 4

The embodiment provides a preparation method of a flaky lithium iron phosphate material and the obtained flaky lithium iron phosphate material.

The preparation method comprises the following steps:

(1) lithium carbonate (Li)₂CO₃0.5mol)36.9g, iron chloride (FeCl)₃·6H₂O, 1mol)270.30g, ammonium dihydrogen phosphate (formula NH)₄H₂PO₄1mol)132.0g and 91.25g of 40% hydrochloric acid (1mol) to prepare a mixed solution A;

(2) adding 25.3g of surfactant (tetrabutylammonium bromide (TBAB)) into the mixed solution A, and stirring to obtain mixed solution B;

(3) adding carbon source (sucrose 130g) and oxidant 30% H into the mixed solution B₂O₂Stirring 12.8g of solution to fully disperse a carbon source to obtain solution C, transferring the solution C into a high-pressure-resistant reaction kettle, monitoring the air pressure and the reaction temperature, discharging the solution in the reaction kettle when the pressure is increased to 0.2MPa, transferring the solution into a normal-pressure reaction container, and obtaining a solid lithium iron phosphate precursor after the solvent in the system is naturally evaporated;

(4) and (2) carrying out heat treatment on the precursor at 180 ℃ for 2h in a nitrogen atmosphere, then heating from 180 ℃ to 680 ℃ at the speed of 5 ℃/min, preserving heat for 4h, cooling, and grinding to obtain the lithium iron phosphate material.

Comparative example 1

The comparative example provides a preparation method for preparing a flaky lithium iron phosphate material by adopting a high-pressure hydrothermal reaction kettle and the flaky lithium iron phosphate material.

The preparation method comprises the following steps:

(1) lithium nitrate (LiNO)₃1mol)68.95g, iron chloride (FeCl)₃·6H₂O, 1mol)270.30g, 85% phosphoric acid (H)₃PO₄1mol)115.30g, glucose 13g and CTAB 5g are mixed and dissolved in 300g of water to prepare mixed solution A;

(2) adding the solution A into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 5 hours, carrying out suction filtration, and drying;

(3) and (2) carrying out heat treatment on the precursor at 180 ℃ for 2h in a nitrogen atmosphere, then heating from 180 ℃ to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4h, cooling, and grinding to obtain the lithium iron phosphate material.

The lithium iron phosphate material obtained in comparative example 1 was observed by SEM to have a sheet-like structure with a thickness of about 130 nm.

Comparative example 2

The comparative example provides a preparation method of a flaky lithium iron phosphate material and the obtained flaky lithium iron phosphate material.

The difference from example 1 is that the solvent autothermal evaporation reaction of this comparative example was carried out at normal pressure, specifically, step (3) was: and adding a carbon source (60 g of glucose) into the mixed solution B, stirring to fully disperse the carbon source to obtain a solution C, carrying out self-heating evaporation on the solution C in a normal-pressure reaction container, and obtaining a solid lithium iron phosphate precursor after the solvent in the system is naturally evaporated.

The sample was SEM tested and showed that spherical LFP particles were obtained without a plate-like structure.

Comparative example 3

The comparative example provides a preparation method of a flaky lithium iron phosphate material and the obtained flaky lithium iron phosphate material.

The difference from example 1 is that this example does not add a positive charge phase transfer catalyst, i.e. step (2) is omitted.

The samples were tested using SEM and showed an average plate-like LFP thickness of 310nm, with no control of thickness.

Performance testing

The lithium iron phosphate materials obtained in the embodiment and the comparative example are prepared into the lithium ion battery by the same method, and the method comprises the following steps:

the positive plate is prepared as follows: according to the mass ratio LFP: SP: PVDF: NMP 93.5:2.5: 4: 100, stirring for 2 hours by a ball mill stirrer, uniformly mixing to obtain anode slurry, adding the prepared anode slurry on an aluminum foil, uniformly scraping by using a scraper, drying an anode plate at 130 ℃, rolling under the pressure of 10Mpa to obtain a rolled plate, cutting a phi 15mm wafer in the middle area, weighing, measuring the thickness, and calculating the compaction density.

The battery assembly process is as follows: the prepared conductive adhesive for the positive electrode is pasted on a metal shell of the positive electrode, a metal lithium sheet is used as a negative electrode, a Celgard 2400 microporous membrane is used as a diaphragm, and 1.0mol/LLiPF₆The solution of (2) is used as an electrolyte, the solvent of the electrolyte is a mixture of Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1, and the mixture is assembled into a button cell in a glove box.

The electrochemical performance of the button cell is tested by using a LAND electrochemical tester, the charge termination voltage is 4.2V, and the discharge cut-off voltage is 2.0V.

The following performance tests were performed on the obtained lithium ion battery:

(1) charge-discharge multiplying power: the battery was subjected to 1C rate charge-discharge test.

(2) Low temperature performance: and (3) carrying out 1C charge-discharge test at the temperature of minus 20 ℃, and calculating the ratio of the low-temperature capacity to the normal-temperature capacity and recording the ratio as the low-temperature retention rate.

The test results are shown in table 1:

TABLE 1

As can be seen from table 1, the lithium ion battery prepared from the flaky lithium iron phosphate material obtained by the preparation method of the present invention has excellent rate performance and low-temperature charge and discharge performance.

As can be seen from the comparison between the embodiment 1 and the comparative example 1, the method provided by the invention can not only omit an external heat source and reduce the consumption of external energy supply, but also can enable the thickness of the obtained lithium iron phosphate to be about 30-100nm, so that the prepared lithium ion battery has excellent rate capability and low-temperature charge and discharge performance.

As can be seen from the comparison between example 1 and comparative examples 2 to 3, the solvent autothermal evaporation reaction of the present invention needs to be performed in a closed environment, then the pressure is released after reaching 0.2 to 0.6MPa, and a surfactant and/or a phase transfer catalyst needs to be added to the mixed solution, so that the thickness of the obtained lithium iron phosphate material can be 30 to 100nm, and the obtained battery has excellent performance.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.