CN114314551B - Method for preparing high-compaction lithium manganese iron phosphate by explosion method - Google Patents
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Abstract
The application relates to the technical field of lithium manganese iron phosphate, in particular to a method for preparing high-compaction lithium manganese iron phosphate by an explosion method. Method for preparing high-compaction lithium manganese iron phosphate by explosion method, wherein the molecular formula of the lithium manganese iron phosphate is LiMn x Fe 1‑x PO 4 The preparation method comprises the following steps: s1, preparing precursor powder; s2, preparing an emulsified substrate; s3, preparing an explosive package; s4, explosion synthesis; s5, ball milling and refining: and performing dry ball milling on the rough lithium manganese iron phosphate for 2-8 hours to obtain the high-compaction lithium manganese iron phosphate. The preparation method has the advantages of being beneficial to forming high-compaction nanoscale lithium manganese iron phosphate, improving the compaction density of the lithium manganese iron phosphate and further improving the electrochemical performance and energy density of the material. In addition, the explosion method has the advantages of low-cost raw materials, simple synthesis process, short preparation time and low energy consumption, and is beneficial to large-scale preparation.
Description
Technical Field
The application relates to the technical field of lithium manganese iron phosphate, in particular to a method for preparing high-compaction lithium manganese iron phosphate by an explosion method.
Background
Lithium manganese phosphate is a natural mineral or artificially synthesized ternary lithium battery anode material, the material has an olivine crystal structure, li + ions can be inserted into and separated from the crystal, so that the charging and discharging of a lithium ion battery are realized, and due to the unique structure, the stability of a crystal form can be maintained in the process of inserting and separating the lithium ions, and the lithium manganese phosphate has good stability, so that the lithium manganese phosphate has stable physical and chemical properties when being used as an electrode material. The lithium manganese phosphate theoretically has a specific capacity of 171mAh/g and a discharge platform of about 4.1V, so that the lithium manganese phosphate becomes an ideal material of a new-generation lithium ion power battery.
In the related art, the compacted density of lithium manganese iron phosphate is usually 2.1 to 2.2g/cm 3 The specific capacity is between 135 and 150mAh/g, which cannot meet the requirements of power battery manufacturers who need to improve the energy density urgently. In order to improve the energy density of the lithium iron manganese phosphate battery, a three-stage compaction-calcination method is generally adopted to improve the compaction density of the cathode material. But the three-section compaction-calcination method has complex process and long preparation time; the process is not controllable, so that the particle size of the lithium manganese iron phosphate is large and is not uniformly distributed, the compacted density of the lithium manganese iron phosphate is poor, and the electrochemical performance and the energy density of the lithium manganese iron phosphate are poor.
Disclosure of Invention
In order to improve the compaction density of the lithium manganese iron phosphate and further improve the electrochemical performance and the energy density of the lithium manganese iron phosphate, the application provides a method for preparing high-compaction lithium manganese iron phosphate by an explosion method.
The application provides a method for preparing high-compaction lithium manganese iron phosphate by an explosion method, which adopts the following technical scheme:
method for preparing high-compaction lithium manganese iron phosphate by explosion method, wherein lithium manganese iron phosphate has molecular formula LiMn x Fe 1-x PO 4 The preparation method comprises the following steps:
s1, precursor powder preparation:
(1) Mixing and sealing a lithium source, iron phosphate, a manganese source, zirconium beads and a mixed medium, and ball-milling for 2-10 hours at a rotating speed of 200-400r/min at normal temperature after sealing to obtain a mixed material;
(2) Placing the mixed materials in a drying oven, drying at 60-100 ℃, and grinding into powder to obtain precursor powder;
s2, preparing an emulsion matrix:
(1) According to mass ratio NH 4 NO 3 :H 2 O:C 24 H 44 O 6 :C 18 H 38 2.5 4 NO 3 、H 2 O、C 24 H 44 O 6 And C 18 H 38 (ii) a Wherein, C 24 H 44 O 6 As an emulsifier, C 18 H 38 Is a composite wax;
(2) Mixing ammonium nitrate and water, and heating to 103-107 deg.C to obtain water phase;
(3) Mixing emulsifier and composite wax, heating to 90-100 deg.C to obtain oil phase;
(4) Mixing and stirring the oil phase and the water phase to obtain an emulsified matrix;
s3, preparing an explosive package: sequentially adding hollow polystyrene microspheres and precursor powder into an emulsified matrix, and mixing to obtain an explosive package;
s4, explosion synthesis: packing explosive in an explosion container, plugging an industrial electric detonator, connecting a wire, placing the explosion container in an explosion pillbox, closing a safety door of the explosion pillbox for detonation, and collecting and obtaining rough lithium manganese iron phosphate after an explosion product is settled;
s5, ball milling and refining: and performing dry ball milling on the rough lithium manganese iron phosphate for 2-8 hours to obtain the high-compaction lithium manganese iron phosphate.
By adopting the technical scheme, the raw materials are firstly mixed and ball-milled into smaller particle size in the step S1, and then the mixture is dried and ground into powder to prepare precursor powder. And then, preparing a water phase and an oil phase through the step S2, and mixing and stirring the water phase and the oil phase to obtain the emulsified base. Next, through step S3, the hollow styrene microspheres and the precursor powder are added to the emulsified base, thereby preparing the explosive package. And then carrying out explosion reaction in the step S4 to obtain the rough manganese lithium iron phosphate. And finally, performing dry ball milling on the rough lithium manganese iron phosphate through the step S5 to finally prepare the high-compaction lithium manganese iron phosphate with smaller particle size.
The explosion reaction has instantaneity and exothermicity, in the process of generating the rough lithium manganese iron phosphate under the action of explosion, the nucleation particles of the rough lithium manganese iron phosphate cannot grow in time in the rapid cooling process and present a uniform and regular microspheric shape, and recombination of raw materials of the rough lithium manganese iron phosphate occurs in an atomic or molecular degree, so that the formation of high-compaction nanoscale lithium manganese iron phosphate is facilitated, the compaction density of the lithium manganese iron phosphate is improved, and the electrochemical performance and the energy density of the material can be further improved. Meanwhile, the explosion method has the advantages of cheap raw materials, simple synthesis process, short preparation time, low energy consumption and contribution to large-scale preparation.
Preferably, in step S1 (1), n (lithium source)/n (iron phosphate + manganese source) =1.02-2.
By adopting the technical scheme, the lithium source has a large proportion and a proper range, so that the loss caused by lithium volatilization due to a high-temperature state in the explosion synthesis process is supplemented, the sufficiency of the explosion reaction is improved, the formation of high-compaction nanoscale lithium manganese iron phosphate is further facilitated, and the electrochemical performance and the energy density of the high-compaction nanoscale lithium manganese iron phosphate are improved.
Preferably, in the step (4) of the step S2, the mixing and stirring process includes: maintaining the temperature of the oil phase and the water phase, stirring the oil phase at a rotating speed of 180-220 r/min, slowly pouring the water phase into the oil phase, increasing the stirring speed to 1300-1700 r/min after the water phase is poured, and continuously stirring for 1-5min.
By adopting the technical scheme, the temperature of the oil phase and the water phase is maintained, so that the oil phase and the water phase are both fluid with better fluidity, and the oil phase and the water phase are convenient to mix. The oil phase is stirred at a low speed firstly, so that all parts of the oil phase are uniform in state and are not easy to condense, and then the water phase is slowly poured into the oil phase. After the water phase is poured, the rotating speed is increased to a high speed, so that the oil phase and the water phase can be mixed uniformly, a good combination can be formed, and a uniform and stable emulsion matrix can be obtained, therefore, the uniformity of the finally prepared high-compaction lithium manganese iron phosphate can be improved, and the electrochemical performance and the energy density of the high-compaction lithium manganese iron phosphate can be further improved.
Preferably, the mixing medium in step S1 (1) is at least one of deionized water and industrial alcohol.
By adopting the technical scheme, the deionized water and the industrial alcohol enable the lithium source, the ferric phosphate and the manganese source to realize wet grinding, so that the mixing uniformity of the lithium source, the ferric phosphate and the manganese source is improved, and uniform and stable precursor powder is convenient to form. The deionized water is selected to reduce the introduction of impurities, so that the electrochemical performance of the high-compaction lithium manganese iron phosphate is improved. In addition, the deionized water and the industrial alcohol have the characteristics of low price and convenient purchase.
Preferably, the lithium source in step S1 (1) is at least one of lithium carbonate, lithium hydroxide, lithium acetate, and lithium oxalate.
By adopting the technical scheme, except lithium element, only carbon, hydrogen and oxygen elements exist in lithium carbonate, lithium hydroxide, lithium acetate and lithium oxalate, carbon dioxide and oxygen generated in the reaction process are removed, and impurities are not easily introduced, so that the purity of high-compaction lithium manganese iron phosphate is improved, and the electrochemical performance of the high-compaction lithium manganese iron phosphate is improved. And lithium carbonate, lithium hydroxide, lithium acetate and lithium oxalate are widely applied and are easy to obtain.
Preferably, the manganese source in step S1 (1) is at least one of manganese carbonate, manganese hydroxide and manganese oxalate.
By adopting the technical scheme, the manganese carbonate, the manganese hydroxide and the manganese oxalate only contain carbon, hydrogen and oxygen except manganese elements, carbon dioxide and oxygen generated in the reaction process are removed, and impurities are not easily introduced, so that the purity of the high-compaction lithium manganese iron phosphate is improved, and the electrochemical performance of the high-compaction lithium manganese iron phosphate is improved. And the manganese carbonate, the manganese hydroxide and the manganese oxalate are widely applied and are easy to obtain.
Preferably, the mass of the hollow polystyrene microsphere in the step S3 is 0.5-1% of that of the emulsion matrix.
By adopting the technical scheme, the hollow polystyrene microspheres are used as a sensitizer, and the ratio of the mass of the hollow polystyrene microspheres to the mass of the emulsified matrix within the range can properly introduce sensitized bubbles to form an emulsion body, so that the detonation performance index is improved, the explosion reaction is facilitated, the completeness of the explosion reaction is improved, and the formation of high-compaction lithium manganese iron phosphate with smaller and uniform particle size is facilitated.
Preferably, the mass of the precursor powder in the step S3 is 10% to 40% of the mass of the emulsified base.
By adopting the technical scheme, the mass of the precursor powder is 10-40% of that of the emulsified matrix, so that the explosive reaction is facilitated, the completeness of the explosive reaction is improved, and the formation of high-compaction lithium manganese iron phosphate with small and uniform particle size is facilitated.
In summary, the present application has the following beneficial effects:
1. according to the method, the explosion reaction has instantaneity and exothermicity, in the process of generating the rough manganese lithium iron phosphate under the explosion effect, the nucleation particles of the rough manganese lithium iron phosphate cannot grow in time in the rapid cooling process and are in a uniform and regular microspheric shape, recombination in atomic or molecular degree occurs between raw materials of the rough manganese lithium iron phosphate, high-compaction nanoscale manganese lithium iron phosphate is favorably formed, the compaction density of the manganese lithium iron phosphate is improved, and further the electrochemical performance and the energy density of the material can be improved. Meanwhile, the explosion method has the advantages of cheap raw materials, simple synthetic process, short preparation time and low energy consumption, and is beneficial to large-scale preparation.
2. According to the method, the proportion of n (lithium source)/n (iron phosphate + manganese source) =1.02-2, and the lithium source is large, so that loss caused by volatilization of lithium due to a high-temperature state in an explosion synthesis process is supplemented, the sufficiency of explosion reaction is improved, high-compaction nanoscale lithium manganese iron phosphate is further facilitated to be formed, and the electrochemical performance and the energy density of the high-compaction nanoscale lithium manganese iron phosphate are improved.
3. According to the method, the oil phase is stirred at a low speed, so that all parts of the oil phase are uniform in state and are not easy to condense, and then the water phase is slowly poured into the oil phase; after the water phase is poured, the rotating speed is increased to a high speed, so that the oil phase and the water phase can be uniformly mixed to form good combination, and a uniform and stable emulsion matrix can be obtained, thereby improving the uniformity of the finally prepared high-compaction lithium manganese iron phosphate and further improving the electrochemical performance and the energy density of the high-compaction lithium manganese iron phosphate.
Detailed Description
The present application will be described in further detail with reference to examples.
In the examples of the present application, the drugs used are shown in table 1:
table 1 pharmaceutical products according to embodiments of the present application
Examples
Example 1:
method for preparing high-compaction lithium manganese iron phosphate by explosion method, wherein lithium manganese iron phosphate has molecular formula LiMn x Fe 1-x PO 4 The preparation method comprises the following steps:
s1, precursor powder preparation:
(1) Taking 0.5mol of lithium source, 0.5mol of iron phosphate and 0.5mol of manganese source, putting the lithium source, the iron phosphate and the manganese source into a ball milling tank according to the proportion of n (lithium source)/n (iron phosphate + manganese source) =0.5, adding zirconium beads and 50kg of mixed medium, sealing and then putting into a ball mill, and ball milling at the rotating speed of 200r/min for 2 hours at normal temperature to obtain a mixed material; the mixed medium is tap water; the lithium source is lithium carbonate; the manganese source is manganese carbonate;
(2) Placing the mixed material in a drying oven, pre-drying at 60 ℃, and grinding into powder to obtain precursor powder;
s2, preparing an emulsion matrix:
(1) 83.5kg of NH were weighed 4 NO 3 10kg of water, 2kg of C 24 H 44 O 6 And 4.5kg of C 18 H 38 In mass ratio NH 4 NO 3 :H 2 O:C 24 H 44 O 6 :C 18 H 38 Weighing NH in the ratio of =83.5 4 NO 3 、H 2 O、C 24 H 44 O 6 And C 18 H 38 (ii) a Wherein, C 24 H 44 O 6 Is an emulsifier, C 18 H 38 Is a composite wax;
(2) Adding ammonium nitrate into water in a stainless steel beaker to dissolve and heating to about 103 ℃ to obtain a water phase;
(3) Mixing the emulsifier and the composite wax in another stainless steel cup, and heating to 90 deg.C to obtain oil phase;
(4) Then, maintaining the temperature of the oil phase and the water phase by using a water bath, putting an emulsifier stirring device into the oil phase, and mixing and stirring at the rotating speed of 500r/min for 1min to obtain an emulsified matrix;
s3, preparing an explosive package: sequentially adding hollow polystyrene microspheres and precursor powder into an emulsion matrix, and mixing to obtain an explosive package; the mass of the hollow polystyrene microsphere is 0.2 percent of that of the emulsified base; the mass of the precursor powder is 5% of the mass of the emulsified base.
S4, explosion synthesis: packing explosive in an explosion container, plugging an industrial electric detonator, connecting a wire, placing the explosion container in an explosion pillbox, closing a safety door of the explosion pillbox for detonation, and collecting and obtaining rough lithium manganese iron phosphate after an explosion product is settled;
s5, ball milling and refining: and performing dry ball milling on the rough lithium manganese iron phosphate for 2 hours to obtain the high-compaction lithium manganese iron phosphate.
Example 2
Method for preparing high-compaction lithium manganese iron phosphate by explosion method, wherein lithium manganese iron phosphate has molecular formula LiMn x Fe 1-x PO 4 The preparation method comprises the following steps:
s1, precursor powder preparation:
(1) Taking 0.5mol of lithium source, 0.5mol of iron phosphate and 0.5mol of manganese source, putting the lithium source, the iron phosphate and the manganese source into a ball milling tank according to the proportion of n (lithium source)/n (iron phosphate + manganese source) =0.5, adding zirconium beads and 50kg of mixed medium, sealing and then putting into a ball mill, and ball milling at the rotating speed of 300r/min for 6 hours at normal temperature to obtain a mixed material; the mixed medium is tap water; the lithium source is lithium carbonate; the manganese source is manganese carbonate;
(2) Placing the mixed material in a drying oven, pre-drying at 80 ℃, and grinding into powder to obtain precursor powder;
s2, preparing an emulsion matrix:
(1) 83.5kg of NH were weighed 4 NO 3 10kg of water, 2kg of C 24 H 44 O 6 And 4.5kg of C 18 H 38 In terms of mass ratio NH 4 NO 3 :H 2 O:C 24 H 44 O 6 : C 18 H 38 2.5 4 NO 3 、H 2 O、C 24 H 44 O 6 And C 18 H 38 (ii) a Wherein, C 24 H 44 O 6 As an emulsifier, C 18 H 38 Is a composite wax;
(2) Adding ammonium nitrate into water in a stainless steel beaker to dissolve and heating to about 105 ℃ to obtain a water phase;
(3) Mixing the emulsifier and the composite wax in another stainless steel cup, and heating to 95 ℃ to obtain an oil phase;
(4) Then, maintaining the temperature of the oil phase and the water phase by using a water bath, putting an emulsifier stirring device into the oil phase, and mixing and stirring at the rotating speed of 500r/min for 3min to obtain an emulsified matrix;
s3, preparing an explosive package: sequentially adding hollow polystyrene microspheres and precursor powder into an emulsion matrix, and mixing to obtain an explosive package; the mass of the hollow polystyrene microsphere is 0.2 percent of that of the emulsified matrix; the mass of the precursor powder is 5% of the mass of the emulsified base.
S4, explosion synthesis: packing explosive in an explosion container, plugging an industrial electric detonator, connecting a wire, placing the explosion container in an explosion pillbox, closing a safety door of the explosion pillbox for detonation, and collecting and obtaining rough lithium manganese iron phosphate after an explosion product is settled;
s5, ball milling and refining: and performing dry ball milling on the rough lithium manganese iron phosphate for 5 hours to obtain the high-compaction lithium manganese iron phosphate.
Example 3
Method for preparing high-compaction lithium manganese iron phosphate by explosion method, wherein molecular formula of lithium manganese iron phosphate is LiMn x Fe 1-x PO 4 The preparation method comprises the following steps:
s1, precursor powder preparation:
(1) Taking 0.5mol of lithium source, 0.5mol of iron phosphate and 0.5mol of manganese source, putting the lithium source, the iron phosphate and the manganese source into a ball milling tank according to the proportion of n (lithium source)/n (iron phosphate + manganese source) =0.5, adding zirconium beads and 50kg of mixed medium, sealing and putting into a ball mill, and ball milling for 10 hours at the rotating speed of 400r/min at normal temperature to obtain a mixed material; the mixed medium is tap water; the lithium source is lithium carbonate; the manganese source is manganese carbonate;
(2) Placing the mixed material in a drying oven, pre-drying at 100 ℃, and grinding into powder to obtain precursor powder;
s2, preparing an emulsion matrix:
(1) 83.5kg of NH were weighed 4 NO 3 10kg of water, 2kg of C 24 H 44 O 6 And 4.5kg of C 18 H 38 In mass ratio NH 4 NO 3 :H 2 O:C 24 H 44 O 6 :C 18 H 38 2.5 4 NO 3 、H 2 O、C 24 H 44 O 6 And C 18 H 38 (ii) a Wherein, C 24 H 44 O 6 Is an emulsifier, C 18 H 38 Is a composite wax;
(2) Adding ammonium nitrate into water in a stainless steel beaker to dissolve and heating to about 107 ℃ to obtain a water phase;
(3) Mixing the emulsifier and the composite wax in another stainless steel cup, and heating to 100 deg.C to obtain oil phase;
(4) Then, maintaining the temperature of the oil phase and the water phase by using a water bath, putting an emulsifier stirring device into the oil phase, and mixing and stirring at the rotating speed of 500r/min for 5min to obtain an emulsified matrix;
s3, preparing an explosive package: sequentially adding hollow polystyrene microspheres and precursor powder into an emulsion matrix, and mixing to obtain an explosive package; the mass of the hollow polystyrene microsphere is 0.2 percent of that of the emulsified matrix; the mass of the precursor powder is 5% of the mass of the emulsifying matrix.
S4, explosion synthesis: packing the explosive in an explosion container, inserting an industrial electric detonator, connecting a wire, placing the explosion container in an explosion pillbox, closing a safety door of the explosion pillbox for detonation, and collecting and obtaining rough lithium manganese iron phosphate after an explosion product is settled;
s5, ball milling and refining: and performing dry ball milling on the rough lithium manganese iron phosphate for 8 hours to obtain the high-compaction lithium manganese iron phosphate.
Examples 4 to 7: examples 4-7 differ from example 2 in that:
example 4: in the step (1) of the step S1, 1.02mol of a lithium source, 0.5mol of iron phosphate and 0.5mol of a manganese source are taken, and n (lithium source)/n (iron phosphate + manganese source) =1.02;
example 5: in the step (1) of the step S1, 1.5mol of a lithium source, 0.5mol of iron phosphate and 0.5mol of a manganese source are taken, and n (lithium source)/n (iron phosphate + manganese source) =1.5;
example 6: in the step (1) of the step S1, 2mol of a lithium source, 0.5mol of iron phosphate and 0.5mol of a manganese source are taken, and n (lithium source)/n (iron phosphate + manganese source) =2;
example 7: in step S1 (1), 2.5mol of a lithium source, 0.5mol of iron phosphate, and 0.5mol of a manganese source are taken, and n (lithium source)/n (iron phosphate + manganese source) =2.5.
Example 8: the present embodiment is different from embodiment 5 in that:
in this embodiment, (4) of step S2 is: maintaining the temperature of the oil phase and the water phase, stirring the oil phase at a rotating speed of 180 r/min, slowly pouring the water phase into the oil phase, increasing the stirring speed to 1300r/min after the water phase is poured, and continuously stirring for 3 min.
Example 9: the present embodiment is different from embodiment 8 in that:
in this embodiment, (4) of step S2 is: maintaining the temperature of the oil phase and the water phase, stirring the oil phase at a rotating speed of 200r/min, slowly pouring the water phase into the oil phase, increasing the stirring speed to 1500 r/min after the water phase is poured, and continuously stirring for 3 min.
Example 10: the present embodiment is different from embodiment 8 in that:
in this embodiment, (4) of step S2 is: maintaining the temperature of the oil phase and the water phase, stirring the oil phase at a rotating speed of 220r/min, slowly pouring the water phase into the oil phase, increasing the stirring speed by 1700r/min after the water phase is poured, and continuously stirring for 3 min.
Examples 11 to 13: the present example differs from example 9 in that the mixed media are different:
the mixed medium in step S1 (1) of example 11 is deionized water;
the mixed medium in step (1) of step S1 of example 12 is industrial alcohol;
the mixing medium in step S1 (1) of example 13 is deionized water and industrial alcohol, and the mass ratio of deionized water to industrial alcohol is 1.
Examples 14 to 16: examples 14-16 differ from example 13 in that:
the lithium source in step S1 (1) was selected differently, and lithium hydroxide, lithium acetate, and lithium oxalate were used in this order as the lithium source in examples 14 to 16.
Examples 17 to 18: examples 17-18 differ from example 13 in that:
the selection of the manganese source in step S1 (1) is different, and the manganese sources in examples 17 to 18 sequentially use manganese hydroxide and manganese oxalate.
Examples 19 to 22: examples 19-22 differ from example 17 in that:
the hollow polystyrene microspheres of step S3 in examples 19 to 22 were 0.5%, 0.75%, 1%, and 1.3% by mass of the emulsion base in this order.
Examples 23 to 26: examples 23-26 differ from example 20 in that:
the mass of the precursor powder of step S3 in examples 23 to 26 was 10%, 25%, 40%, and 45% of the mass of the emulsified base.
Comparative example
Comparative example 1: this comparative example differs from example 2 in that:
in this comparative example, step S5 and ball milling refinement were not provided.
Performance test
Testing of electrochemical Performance
According to the detection of GB/T39861-2021 lithium manganate electrochemical performance test discharge platform capacity ratio and cycle life test method, the lithium manganate is replaced by the high-compaction lithium manganese iron phosphate in each embodiment and comparative example in the application, and the discharge capacity at 25 ℃ is measured.
Testing of energy Density
The detection is carried out according to the standard test methods (trial implementation) of related technical indexes of energy density power cells and fuel cells.
TABLE 2 Performance test Table
Examples 1-3 were compared, except that examples 1-3 were different in the process conditions for preparing highly compacted lithium manganese iron phosphate, and the process conditions for example 2 were the best as the energy density and discharge capacity were the highest in example 2.
Comparing examples 2 and 4 to 7, the difference between examples 2 and 4 to 7 is that in step S1, n (lithium source)/n (iron phosphate + manganese source) is different, and since examples 4 to 6 have higher energy density and discharge capacity than examples 2 and 7, it is described that the n (lithium source)/n (iron phosphate + manganese source) has better value, the ratio of the lithium source is larger, and the range is suitable, so that loss caused by volatilization of lithium due to high temperature during explosive synthesis can be compensated, and the sufficiency of explosive reaction is improved, thereby further facilitating formation of high-compaction nanoscale lithium manganese iron phosphate, and improving the electrochemical performance and energy density of the high-compaction nanoscale lithium iron phosphate.
Comparing examples 8-10 with example 5, the difference between examples 8-10 and example 5 is (4) of step S2, and since the energy density and discharge capacity of examples 8-10 are higher than those of example 5, it is shown that the oil phase is stirred at a low speed first, so that each part of the oil phase is uniform and not easy to coagulate, then the water phase is slowly poured into the oil phase, and after the water phase is poured, the rotation speed is increased to a high speed, so that the oil phase and the water phase are uniformly mixed, a good combination is formed, a uniform and stable emulsion matrix is obtained, the uniformity of the finally prepared high-compaction lithium manganese iron phosphate is improved, and further the electrochemical performance and energy density of the high-compaction lithium manganese iron phosphate are improved, so that the scheme of the application is better. And the energy density and discharge capacity of example 9 were the highest, indicating that the process conditions of step (4) of step S2 in example 9 were the best.
Comparing examples 11-13 with example 9, examples 11-13 differ from example 9 in the mixed medium, which means that the embodiments 11-13 are better in the solution according to the application, since the energy density and discharge capacity are higher in examples 11-13 than in example 9. The highest energy density and discharge capacity of example 13 are shown, indicating that the mixed medium of example 13 is the best.
Examples 14-16 were compared to example 13, and examples 14-16 differed from example 13 in the selection of the lithium source, indicating that the lithium source of example 13 was the best because of the highest energy density and discharge capacity of example 13.
Examples 17-18 were compared to example 13, and examples 17-18 differed from example 13 in the selection of the manganese source, which was the best illustrated for example 17 because of the highest energy density and discharge capacity of example 17.
Comparing examples 19-22 with example 17, examples 19-22 differ from example 17 in the percentage of the mass of hollow polystyrene microspheres to the mass of the emulsified matrix, which is better demonstrated by the higher energy density and discharge capacity of examples 19-21 than examples 17 and 22. And the energy density and discharge capacity of example 20 were the highest, indicating that the percentage of the mass of the hollow polystyrene microspheres of example 20 to the mass of the emulsified base was the best.
Comparing examples 23-26 with example 20, examples 23-26 differ from example 20 in the mass of the precursor powder and the percentage of the mass of the emulsified matrix, and the solution of the present application is better illustrated as the energy density and discharge capacity of examples 23-25 are higher than those of examples 20 and 26. The energy density and discharge capacity of example 24 were the highest, indicating that the percentage of the mass of the precursor powder to the mass of the emulsifying base in example 24 was the best.
Finally, comparative example 1 was compared with example 2, and comparative example 1 was different from example 2 in that comparative example 1 was not provided with step S5, ball milling refinement. The higher energy density and discharge capacity of example 2 indicates that the scheme of the present application is better.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The method for preparing high-compaction lithium manganese iron phosphate by using an explosion method is characterized in that the molecular formula of the lithium manganese iron phosphate is LiMn x Fe 1-x PO 4 The preparation method comprises the following steps:
s1, precursor powder preparation:
(1) Mixing and sealing a lithium source, iron phosphate, a manganese source, zirconium beads and a mixed medium, and ball-milling for 2-10 hours at a rotating speed of 200-400r/min at normal temperature after sealing to obtain a mixed material;
(2) Placing the mixed materials in a drying oven, drying at 60-100 ℃, and grinding into powder to obtain precursor powder;
s2, preparing an emulsion matrix:
(1) According to mass ratio NH 4 NO 3 :H 2 O:C 24 H 44 O 6 :C 18 H 38 Weighing NH in the ratio of =83.5 4 NO 3 、H 2 O、C 24 H 44 O 6 And C 18 H 38 (ii) a Wherein, C 24 H 44 O 6 Is an emulsifier, C 18 H 38 Is a composite wax;
(2) Mixing ammonium nitrate and water, and heating to 103-107 deg.C to obtain water phase;
(3) Mixing emulsifier and composite wax, heating to 90-100 deg.C to obtain oil phase;
(4) Mixing and stirring the oil phase and the water phase to obtain an emulsified matrix;
s3, preparing an explosive package: sequentially adding hollow polystyrene microspheres and precursor powder into an emulsion matrix, and mixing to obtain an explosive package;
s4, explosion synthesis: packing the explosive in an explosion container, inserting an industrial electric detonator, connecting a wire, placing the explosion container in an explosion pillbox, closing a safety door of the explosion pillbox for detonation, and collecting and obtaining rough lithium manganese iron phosphate after an explosion product is settled;
s5, ball milling and refining: and performing dry ball milling on the rough lithium manganese iron phosphate for 2-8 hours to obtain the high-compaction lithium manganese iron phosphate.
2. The method for preparing high-compaction lithium manganese iron phosphate by an explosion method according to claim 1, which is characterized by comprising the following steps: in step S1 (1), n (lithium source)/n (iron phosphate + manganese source) =1.02-2.
3. The method for preparing high-compaction lithium manganese iron phosphate by an explosion method according to claim 1, which is characterized by comprising the following steps: in the step (4) of the step S2, the mixing and stirring process includes: maintaining the temperature of the oil phase and the water phase, stirring the oil phase at a rotating speed of 180-220 r/min, slowly pouring the water phase into the oil phase, increasing the stirring speed to 1300-1700 r/min after the water phase is poured, and continuously stirring for 1-5min.
4. The method for preparing high-compaction lithium manganese iron phosphate by an explosion method according to claim 1, which is characterized by comprising the following steps: the mixed medium in step (1) of step S1 is at least one of deionized water and industrial alcohol.
5. The method for preparing high-compaction lithium manganese iron phosphate by an explosion method according to claim 1, which is characterized by comprising the following steps: the lithium source in step (1) of step S1 is at least one of lithium carbonate, lithium hydroxide, lithium acetate, and lithium oxalate.
6. The method for preparing high-compaction lithium manganese iron phosphate by an explosion method according to claim 1, which is characterized by comprising the following steps: the manganese source in step (1) of step S1 is at least one of manganese carbonate, manganese hydroxide, and manganese oxalate.
7. The method for preparing high-compaction lithium manganese iron phosphate by an explosion method according to claim 1, which is characterized by comprising the following steps: the mass of the hollow polystyrene microsphere in the step S3 is 0.5-1% of that of the emulsified base.
8. The method for preparing high-compaction lithium iron manganese phosphate by using the explosion method according to claim 1, characterized by comprising the following steps: the mass of the precursor powder in the step S3 is 10-40% of that of the emulsified base.
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