CN102751491A - Method for broadening sintering temperature of lithium iron phosphate and preparation method for lithium iron phosphate - Google Patents
Method for broadening sintering temperature of lithium iron phosphate and preparation method for lithium iron phosphate Download PDFInfo
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Abstract
The invention relates to a method for broadening the sintering range of lithium iron phosphate. The method is characterized in that an iron source in raw materials used for preparation of lithium iron phosphate is composed of different iron compounds and broadening of the sintering range of lithium iron phosphate is realized by adjusting the proportional relationship of the different iron source components. The invention also provides a preparation method for lithium iron phosphate. When the above-mentioned method for broadening the sintering range of lithium iron phosphate is used in preparation of lithium iron phosphate, preparation of lithium iron phosphate in a wide temperature range can be realized, dependence on accuracy and reliability of sintering equipment is reduced and stability of different preparation batches of lithium iron phosphate is improved.
Description
Technical field
The present invention relates to the sintering preparation of lithium ion anode material LiFePO 4, relate in particular to a kind of method of widening the LiFePO 4 sintering temperature, belong to the energy and material preparing technical field.
Background technology
LiFePO 4 since security performance good, have extended cycle life, raw material cheaply is expected to become the first-selected positive electrode of electrokinetic cell.But batch stability of ferrousphosphate lithium material receives denouncing of industry always, except the unstable reason that batch mixing forms, and ferrousphosphate lithium material preparation technology control, particularly the fluctuation of sintering temperature is very big to effect of material performance.Especially for the ferrousphosphate lithium material that coats, organic substance is emitted a large amount of heat in calcination process, can impel the fluctuation of calcining powder local temperature bigger, also is difficult to effectively control temperature even if choose good calciner.
The industrial preparation route of ferrousphosphate lithium material mainly is divided into three kinds according to the difference of raw material: iron oxide red route, ferrous oxalate route and ferric phosphate route.Three kinds of routes all are to mix a certain proportion of raw material earlier, and strict then control sintering temperature and sintering time prepare ferrousphosphate lithium material through high temperature sintering.In order to guarantee that the iron in the product LiFePO 4 is positive divalence, calcination environment is normally carried out in certain reducing atmosphere.Confirming of the calcining heat of ferrousphosphate lithium material mainly is other impurity that guarantee not have in the ferrousphosphate lithium material iron, like iron simple substance and positive ferric iron compound.Though the sintering temperature of every kind of ferrousphosphate lithium material is because of the different slightly minute differences of physicochemical properties of its employed raw material; But the sintering temperature in every kind of synthetic method has only very narrow temperature range to adjust; So narrow temperature range requires ferrousphosphate lithium material sintering stove interior temperature distribution very even; And most of stove is to rely on heat conduction to transmit heat; So the temperature gradient distribution in the stove is an objective reality, the existence of this temperature gradient has caused a major reason of present ferrousphosphate lithium material batch fluctuation.At present the research worker is very thorough after deliberation to the preparation of ferrousphosphate lithium material, and is seldom to the technical study of manufacture of materials.
Therefore, how to widen the sintering temperature of ferrousphosphate lithium material, reduce dependence, have very important realistic meaning, become one of technical problem that lithium ion anode material LiFePO 4 preparation field needs to be resolved hurrily the equipment accuracy and reliability.
Summary of the invention
The objective of the invention is to; A kind of method of widening the LiFePO 4 sintering range is provided; This method is widened the ferrousphosphate lithium material sintering range through the proportionate relationship of adding different sources of iron and regulating different source of iron components; Thereby be implemented in preparation LiFePO 4 in the wider temperature range, help improving the stability of LiFePO 4 preparation batch.
One aspect of the present invention; A kind of method of widening the LiFePO 4 sintering range is provided; It is characterized in that; The source of iron that LiFePO 4 prepares in the raw material is made up of different iron containing compoundses, realizes widening of LiFePO 4 sintering range through the proportionate relationship of regulating different source of iron components.
According to a concrete but nonrestrictive embodiment of the present invention, said source of iron comprises the source of iron of at least a reduction sintering temperature and/or the source of iron of at least a raising sintering temperature.
Particularly, the source of iron that reduces sintering temperature is the organic substance of iron, is preferably ferrous oxalate.
The source of iron that improves sintering temperature is the inorganic matter of iron, is preferably in iron oxide red, ferric phosphate, iron phosphide, ferric pyrophosphate and the peroxophosphoric acid iron one or more.
According to a concrete but nonrestrictive embodiment of the present invention, it is main source of iron that at least a iron containing compounds is arranged in the said source of iron, and wherein main source of iron accounts for the 80-100 quality % of whole source of iron, and other various sources of iron account for the 0-20 quality % of whole source of iron.
According to a concrete but nonrestrictive embodiment of the present invention, be that the sintering range of main source of iron is 670 ℃～800 ℃ with ferric phosphate; Be that the sintering range of main source of iron is 650 ℃～750 ℃ perhaps with ferrous oxalate; Be that the sintering range of main source of iron is 700 ℃～850 ℃ perhaps with iron oxide red.
According to a concrete but nonrestrictive embodiment of the present invention, the ratio of various components is regulated in the sintering time of staying of each section according to the temperature and the material of each section of sintering furnace in the said source of iron.
Another aspect of the present invention provides a kind of preparation method of LiFePO 4, and said LiFePO 4 is widened sintering range through the calcining method preparation with said method.
Beneficial effect of the present invention is mainly reflected in:
1, the present invention through the ratio of adding different sources of iron and regulating different source of iron components to realize widening of ferrousphosphate lithium material sintering range; Thereby can in wider temperature range, prepare LiFePO 4; Reduced dependence, helped improving the stability of LiFePO 4 batch the agglomerating plant accuracy and reliability.
2, the ferrousphosphate lithium material sintering temperature widens; Realized under higher temperature, preparing LiFePO 4; Thereby make the LiFePO 4 crystal development more complete, help improving the life-span that recycles of ferrousphosphate lithium material simultaneously, and other performances of material are not affected.
3, with respect to being the preparation technology of raw material, add inorganic source of iron such as iron oxide red etc. in the raw material, reduced the cost of raw material with pure ferric phosphate or ferrous oxalate.
Description of drawings
Figure 1A is the TG-DSC curve chart of lithium carbonate.
Figure 1B is the TG-DSC curve chart of sucrose.
Fig. 1 C is the TG-DSC curve chart of ferric phosphate.
Fig. 1 D is for being the TG-DSC curve chart of the mixing source of iron of principal phase with the ferric phosphate.
Fig. 2 is the XRD figure spectrum of the ferrous phosphate powder for lithium of the embodiment of the invention 3 usefulness mixing source of iron preparation.
Fig. 3 is the stereoscan photograph that the embodiment of the invention 3 usefulness are mixed the ferrous phosphate powder for lithium of source of iron preparation.
Fig. 4 makes battery for the ferrous phosphate powder for lithium of the embodiment of the invention 3 usefulness mixing source of iron preparation and tests, the battery cyclic curve that obtains, and cycling condition: room temperature, 1C discharges and recharges, and charges to 3.65V, is discharged to 2.5V.
Embodiment
Specify embodiment of the present invention below in conjunction with accompanying drawing.
The inventor of this patent finds that in long-term LiFePO 4 suitability for industrialized production practice the preparation sintering temperature of every kind of ferrousphosphate lithium material is because of the different slightly small difference of physicochemical properties of the raw material of its use.For example, iron oxide red and ferric phosphate are because their chemical property, proportion, particle diameter different, and sintering temperature just has difference.Ferric phosphate is owing to have the structure identical with LiFePO 4, and in the preparation ferrousphosphate lithium material, lithium atom gets into ferric phosphate as embedded mode, so sintering temperature is low than iron oxide red technology.And ferrous oxalate is lower than the sintering temperature of other two kinds of raw materials as the sintering temperature of feedstock production LiFePO 4 by it owing to belonging to metallorganic.The reason of self heat release, ferrous oxalate is to be prepared by oxalic acid and ferrous sulfate reactive crystallization in belonging to the metallorganic calcination process, and the LiFePO 4 particle diameter that therefore makes is littler.
The inventor proposes thus in three kinds of synthetic methods-iron oxide red route, ferrous oxalate route and the ferric phosphate route of LiFePO 4; With the used raw material of any one method wherein is primary raw material; Through adding other different sources of iron; And regulate according to actual conditions that various components can reach the purpose of widening the ferrousphosphate lithium material sintering range to reach suitable ratio in the source of iron.The interpolation of some source of iron can reduce the sintering temperature of ferrousphosphate lithium material, and the interpolation of some source of iron then can improve sintering temperature.Wherein, the chemical substance that reduces sintering temperature is mainly the organic compound of some iron, like ferrous oxalate; And the chemical substance of rising LiFePO 4 sintering temperature is mainly some inorganic molysites, like iron oxide red, ferric phosphate, iron phosphide, ferric pyrophosphate, peroxophosphoric acid iron etc.The source of iron that can select to add one or more reductions or improve sintering temperature, the source of iron that also can select to add reduction simultaneously and improve sintering temperature is to widen sintering temperature.For example: if be primary raw material with the ferric phosphate, then can add ferrous oxalate to reduce sintering temperature, perhaps add iron oxide red improving sintering temperature, both also can add simultaneously and widen sintering temperature jointly.If with the iron oxide red is primary raw material, then can add ferrous oxalate or ferric phosphate or both add simultaneously.If with the ferrous oxalate is primary raw material, then can add ferric phosphate or iron oxide red or both add simultaneously.Preferred main source of iron accounts for the 80-100% (by percentage to the quality) of whole source of iron, and other various sources of iron account for the 0-20% (by percentage to the quality) of whole source of iron.
In order to study the rational temperature scope, the inventor has carried out the TG-DSC test to the various raw materials of LiFePO 4 preparation.
At first in the LiFePO 4 preparation as the lithium source with carbon source and raw material-lithium carbonate that often uses and sucrose carry out TG-DSC respectively and tests.Figure 1A is the TG-DSC curve chart of lithium carbonate, finds out that from Figure 1A lithium carbonate begins heat absorption and melts in the time of 736 ℃, along with the further rising of temperature begins to decompose weightlessness.Figure 1B is the TG-DSC curve chart of sucrose, can find out that from Figure 1B sucrose melts at 195 ℃ under nitrogen atmosphere, until about 700 ℃, decomposes fully.
Then ferric phosphate is carried out the TG-DSC test.Fig. 1 C is the TG-DSC curve chart of ferric phosphate, can find out that from Fig. 1 C ferric phosphate experiences the process that dehydration and crystal transform successively under nitrogen atmosphere, just changes into stable crystal structure to 718 ℃.This explanation with single ferric phosphate be source of iron prepare the sintering temperature of LiFePO 4 at least will be at 718 ℃.
Afterwards, the inventor is again to being that the mixing source of iron of principal phase is carried out the TG-DSC test with the ferric phosphate.Fig. 1 D is that ferric phosphate is a main source of iron (ferric phosphate: 90 quality %; Iron oxide red: 8 quality %; Ferrous oxalate: the TG-DSC curve of lithium iron phosphate precursor 2 quality %) under nitrogen atmosphere; Can see that from Fig. 1 D a very long and level and smooth curve is arranged between 670 ℃～800 ℃, weight does not change in this section yet.Adjustment source of iron component and proportion relation; Repeatedly test; Discovery is that the sintering range of mixing source of iron of principal phase is basically at 670 ℃～800 ℃ with the ferric phosphate; With single ferric phosphate is that the sintering temperature (greater than 718 ℃) of source of iron is compared, and the mixing source of iron that adds other source of iron has obviously been widened the sintering range of ferric phosphate source of iron.The inventor mixes the presoma of source of iron at the sintering temperature more than 800 ℃, finds to have occurred in the ferrous phosphate powder for lithium existence of metal iron phase, explains to be higher than the reduction of crossing that this temperature causes source of iron easily.
The inventor uses the same method again and studied is that the sintering range of principal phase is basically at 650 ℃～750 ℃ with the ferrous oxalate; (for example: the ferrous oxalate of 84 quality %; The ferric phosphate and the 6 quality % iron oxide reds that add 10 quality %), widen to some extent as the sintering temperature of source of iron than single ferrous oxalate.
And with iron oxide red be the sintering range of main source of iron basically at 700 ℃～850 ℃, (for example: the iron oxide red of 82 quality % adds the ferrous oxalate of 9 quality %, the ferric phosphate of 9 quality %), widen to some extent as the sintering temperature of source of iron than single iron oxide red.
Utilize the sintering temperature method of widening of the present invention to prepare LiFePO 4, may further comprise the steps:
The first step: raw material configuration
Different sources of iron according to certain proportional arrangement, is mixedly configured into the mixture of 1:1:1.05 (mol ratio) then with phosphorus source, lithium source, and adds deionized water formation slurry.
Second step: drying
The slurry that the first step is formed carries out drying through spraying, forms dry powder.
The 3rd step: sintering
The temperature of each humidity province of sintering furnace is set, powder is got in the stove according to certain speed carry out sintering.
The 4th step: classification, packing
The particle classifying of sintering is also packed on request.
The ratio of mixing various components in the source of iron need be adjusted to suitable ratio according to practical application; Usually can regulate the ratio of each component in the source of iron in the sintering time of staying of each section according to the temperature of each section of sintering furnace and material, wherein the sintering time of staying equal a control temperature section length divided by fltting speed.
With the ferric phosphate is that principal phase, the mixing source of iron that adds iron oxide red and ferrous oxalate are example; Suppose that sintering stove length is 40 meters; The push pedal fltting speed is 1.2 meters/hour; It is 120 ℃, 200 ℃, 500 ℃, 580 ℃, 700 ℃, 700 ℃, 740 ℃, 740 ℃, 760 ℃, 760 ℃, 600 ℃, 400 ℃, 200 ℃, 50 ℃ that pushed bat kiln temperature section temperature is set; Then mix each component of source of iron according to ferric phosphate: 80-90 quality %, iron oxide red: 1-6 quality %, ferrous oxalate: but the ratio of 9-14 quality % is regulated the good LiFePO 4 of processability.
Below in conjunction with specific embodiment the present invention is further set forth, but following embodiment should not be construed as the concrete qualification to protection range of the present invention.
With raw material after the super-dry preliminary treatment; Join stirring in the stirring mill that contains the 120kg deionized water after accurately taking by weighing 60.00kg ferric phosphate, 4.80kg iron oxide red, 1.08kg ferrous oxalate, 19.50kg lithium carbonate, 13.80kg phosphoric acid dihydro amine, the mixing of 7.50kg sucrose; Rotating speed is controlled at 100 rev/mins; Stir after 4 hours the slurry spray drying; Powder is divided into three parts, three kinds of pushed bat kiln temperature section temperature is set also calcines, three kinds of temperature section temperature are set are respectively through pushed bat kiln (long 40 meters of kiln):
A：120℃、200℃、500℃、580℃、680℃、680℃、720℃、720℃、740℃、740℃、600℃、400℃、200℃、50℃；
B：120℃、200℃、500℃、580℃、700℃、700℃、740℃、740℃、760℃、760℃、600℃、400℃、200℃、50℃；
C：120℃、200℃、500℃、580℃、670℃、670℃、700℃、700℃、720℃、720℃、600℃、400℃、200℃、50℃。
The push pedal fltting speed is set to 1.2 meters/hour, classification behind the sintering, and the numbering of powder is followed successively by LFP1, LFP2, LFP3 behind three kinds of temperature sintering, and the test result of three kinds of powders is as shown in the table:
Test result shows: the mixing source of iron of forming with different sources of iron is a raw material, under different temperature, calcines, and can prepare the very approaching LiFePO 4 powder body material of performance, thereby has improved the stability of LiFePO 4 batch.
With raw material after the super-dry preliminary treatment; Join stirring in the stirring mill that contains the 45kg deionized water after accurately taking by weighing 2.00kg ferric phosphate, 1.60kg iron oxide red, 18.00kg ferrous oxalate, 5.00kg lithium carbonate, 13.80kg phosphoric acid dihydro amine, the mixing of 2.50kg sucrose; Rotating speed is controlled at 100 rev/mins; Stir after 4 hours the slurry spray drying, and calcine through pushed bat kiln (long 40 meters of kiln), the temperature that each section is set is respectively 120 ℃, 200 ℃, 500 ℃, 580 ℃, 680 ℃, 680 ℃, 720 ℃, 720 ℃, 740 ℃, 740 ℃, 600 ℃, 400 ℃, 200 ℃, 50 ℃; The push pedal fltting speed is set to 1.2 meters/hour; Classification obtains the ferrous phosphate powder for lithium behind the sintering, and function admirable is batch stable.
Embodiment 3
With raw material after the super-dry preliminary treatment; Join stirring in the stirring mill that contains the 80kg deionized water after accurately taking by weighing 2.00kg ferric phosphate, 16.00kg iron oxide red, 3.60kg ferrous oxalate, 8.75kg lithium carbonate, 25.3kg phosphoric acid dihydro amine, the mixing of 4.50kg sucrose; Rotating speed is controlled at 100 rev/mins; Stir after 4 hours the slurry spray drying; And calcine through pushed bat kiln (kiln 40 meters in length), the temperature that each section is set is respectively 120 ℃, 200 ℃, 500 ℃, 580 ℃, 680 ℃, 680 ℃, 720 ℃, 720 ℃, 740 ℃, 740 ℃, 600 ℃, 400 ℃, 200 ℃, 50 ℃, and the push pedal fltting speed is set to 1.2 meters/hour; Classification obtains the ferrous phosphate powder for lithium behind the sintering, and the XRD figure spectrum of powder is as shown in Figure 2.As can beappreciated from fig. 2, meet the spinelle result by the ferrousphosphate lithium material that mixes the source of iron preparation, and crystal development is complete.
The stereoscan photograph of powder is as shown in Figure 3.As can beappreciated from fig. 3, identical basically by the particle diameter of the ferrous phosphate crystalline lithium that mixes the source of iron preparation with the particle diameter of laser particle analyzer detection, basically below 2.0 μ m, and formed intact coating.
The ferrous phosphate powder for lithium that will be prepared by the mixing source of iron of embodiment 3: the proportional arrangement of conductive agent: bonding agent=90:4:6 becomes powder mixture, and then adds the N-pyrrolidones according to the ratio of solid content 45%, stirs; Coating, film-making, fluid injection; Change into, be assembled into battery.Fig. 3 is the cycle life curve chart of battery under the 1C circulation, and cycling condition is a room temperature, 1C, 100%DOD.As can beappreciated from fig. 3, be 93.4% at 1300 circulation back capability retentions, explain by the cycle performance of battery of the ferrous phosphate material that mixes the source of iron preparation good.
Below only be concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (10)
1. method of widening the LiFePO 4 sintering range; It is characterized in that; The source of iron that LiFePO 4 prepares in the raw material is made up of different iron containing compoundses, realizes widening of LiFePO 4 sintering range through the proportionate relationship of regulating different source of iron components.
2. according to the method for claim 1, it is characterized in that said source of iron comprises the source of iron of at least a reduction sintering temperature and/or the source of iron of at least a raising sintering temperature.
3. according to the method for claim 2, it is characterized in that the source of iron that reduces sintering temperature is the organic substance of iron.
4. according to the method for claim 3, it is characterized in that the source of iron that reduces sintering temperature is a ferrous oxalate.
5. according to the method for claim 2, it is characterized in that the source of iron that improves sintering temperature is the inorganic matter of iron.
6. according to the method for claim 5, it is characterized in that the source of iron that improves sintering temperature is one or more in iron oxide red, ferric phosphate, iron phosphide, ferric pyrophosphate and the peroxophosphoric acid iron.
7. according to arbitrary described method among the claim 1-6, it is characterized in that it is main source of iron that at least a iron containing compounds is arranged in the said source of iron, wherein main source of iron accounts for the 80-100 quality % of whole source of iron, and other various sources of iron account for the 0-20 quality % of whole source of iron.
8. according to the method for claim 7, it is characterized in that, is that the sintering range of main source of iron is 670 ℃～800 ℃ with ferric phosphate; Be that the sintering range of main source of iron is 650 ℃～750 ℃ perhaps with ferrous oxalate; Be that the sintering range of main source of iron is 700 ℃～850 ℃ perhaps with iron oxide red.
9. according to the method for claim 1, it is characterized in that the ratio of various components is regulated in the sintering time of staying of each section according to the temperature and the material of each section of sintering furnace in the said source of iron.
10. the preparation method of a LiFePO 4, said LiFePO 4 is widened sintering range through the calcining method preparation with arbitrary described method among the claim 1-9.
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| CN101339991A (en) * | 2008-08-07 | 2009-01-07 | 华南理工大学 | Composite coated modified high vibrancy solid lithium ionic battery positive electrode, preparation and application thereof |
| CN102502562A (en) * | 2011-11-14 | 2012-06-20 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of lithium iron phosphate, lithium ion battery and anode material and anode thereof |
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| CN101339991A (en) * | 2008-08-07 | 2009-01-07 | 华南理工大学 | Composite coated modified high vibrancy solid lithium ionic battery positive electrode, preparation and application thereof |
| CN102502562A (en) * | 2011-11-14 | 2012-06-20 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of lithium iron phosphate, lithium ion battery and anode material and anode thereof |
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| CN108695512A (en) * | 2018-06-14 | 2018-10-23 | 东北大学秦皇岛分校 | The acid washing iron red purposes as negative material |
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