CN109678127A - A kind of titanium phosphate manganese iron and preparation method thereof - Google Patents
A kind of titanium phosphate manganese iron and preparation method thereof Download PDFInfo
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- CN109678127A CN109678127A CN201811487746.4A CN201811487746A CN109678127A CN 109678127 A CN109678127 A CN 109678127A CN 201811487746 A CN201811487746 A CN 201811487746A CN 109678127 A CN109678127 A CN 109678127A
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of titanium phosphate manganese iron, the chemical formulas of the titanium phosphate manganese iron are as follows: Fe(1‑x‑y)TixMnyPO4, wherein x=0.05~0.01, y=0.005~0.001.By including the following steps: that (1) dissolves source of iron, titanium source, manganese source and phosphorus source, mixed solution is obtained；(2) mixed solution is first heated to 30~50 DEG C, and hydrogen peroxide is added, and is then heated to 90 DEG C or more, and phosphoric acid is added, and after reaction system bleaches, insulation reaction 1~3 hour, then adjusts the pH value of reaction system to 4~5, continues insulation reaction 0.5~1.5 hour；(3) the obtained product of step (2) reaction is washed, dry, calcining, obtain described in titanium phosphate manganese iron.Have many advantages, such as that electronic conductivity is high, electrochemical specific capacity is big using the titanium phosphate manganese iron as the titanium phosphate manganese iron lithium of precursor synthesis, and cryogenic property is good.
Description
Technical field
The present invention relates to a kind of titanium phosphate manganese iron and preparation method thereof.
Background technique
Iron manganese phosphate for lithium is a kind of lithium ion battery material developed on lithium manganese phosphate and LiFePO4 basis, phosphorus
The advantages of sour manganese iron lithium has both lithium manganese phosphate and LiFePO4, theoretical specific capacity is identical as LiFePO4 (170mAh/g), but energy
Metric density is higher, the disadvantage is that the ionic conductivity of iron manganese phosphate for lithium is poor.Based on iron manganese phosphate for lithium is mainly produced with solid phase method, generally
It is produced by iron manganese phosphate, lithium salts and microcosmic salt by solid phase method.Therefore, the presoma iron manganese phosphate of iron manganese phosphate for lithium is doped
Modification is to be effectively improved one of mode of its performance.
CN106816584A discloses a kind of iron manganese phosphate for lithium class material and preparation method thereof, which has
LiMnxFe1-x-yMyPO4The structure of/C, wherein 0 < x≤1,0≤y≤0.2, the M are magnesium, zinc, vanadium, titanium, cobalt and nickel
In it is one or more, and the basic flowing energy BFE of the iron manganese phosphate for lithium class material in 600mJ hereinafter, especially energy of flow SE exist
10mJ/g is hereinafter, comprehensive powder flowing coefficient FF >=2.The material is prepared using high temperature solid-state method, includes the following steps: to provide
Lithium source, manganese source, source of iron, phosphorus source, the optional source M and carbon source, wherein the powder basic flowing energy BFE of the manganese source exists
1100mJ hereinafter, especially energy of flow SE in 15mJ/g hereinafter, comprehensive powder flowing coefficient FF is greater than 2；The powder base of the source of iron
This energy of flow BFE in 1300mJ hereinafter, especially energy of flow SE in 20mJ/g hereinafter, comprehensive powder flowing coefficient FF is greater than 1.5；Institute
It is one or more in magnesium, zinc, vanadium, titanium, cobalt and nickel for stating M element in the source M；By lithium source, manganese source, source of iron, phosphorus source, the optional source M,
And carbon source mixes drying after point spreading in a solvent and forms precursor powder；It is sintered the precursor powder and forms carbon-coated phosphorus
Sour manganese iron lithium class material.Above-mentioned technical proposal is mainly to be with it to improve by improving the mobility of iron manganese phosphate for lithium class material
The normal-temperature circulating performance and high temperature cyclic performance of the battery of positive electrode do not provide and how to improve iron manganese phosphate for lithium electronics electricity
The technical inspiration for the property led.
Summary of the invention
Problem mentioned in the background art, it is an object of the present invention to provide one kind, and iron manganese phosphate for lithium can be improved
The presoma titanium phosphate manganese iron of ionic conductivity.
It is another object of the present invention to provide the preparation methods of above-mentioned titanium phosphate manganese iron.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of titanium phosphate manganese iron, the chemical formula of the titanium phosphate manganese iron are as follows: Fe(1-x-y)TixMnyPO4, wherein x=0.05~
0.01, y=0.005~0.001.
The preparation method of above-mentioned titanium phosphate manganese iron, includes the following steps:
(1) source of iron, titanium source, manganese source and phosphorus source are dissolved, obtains mixed solution；
(2) mixed solution is first heated to 30~50 DEG C, and hydrogen peroxide is added, and is then heated to 90 DEG C or more, phosphoric acid is added, to anti-
After answering system to bleach, insulation reaction 1~3 hour, then adjust the pH value of reaction system to 4-5, continue insulation reaction 0.5~
1.5 hour；
(3) the obtained product of step (2) reaction is washed, dry, calcining, obtain described in titanium phosphate manganese iron.
Preferably, the source of iron is ferrous sulfate, frerrous chloride, ferric sulfate and/or iron chloride；The titanium source is chlorination
Titanium, titanium trichloride and/or titanium sulfate；The manganese source is manganese sulfate and/or manganese chloride；Phosphorus source be ammonium dihydrogen phosphate and/or
Ammonium hydrogen phosphate.
Preferably, in step (1), the iron phosphorus molar ratio of source of iron and phosphorus source is 0.83~0.95:1.
Preferably, in step (1), concentration of the source of iron in mixed solution is 0.5~1 mol/L.
Preferably, in step (2), the dosage of the phosphoric acid is the 0.3~0.4% of mixed liquor volume.
Preferably, in step (3), calcination temperature is 640-680 DEG C, and the time is 1-6 hours, it is highly preferred that calcination time
It is 2-5 hours.
The hydrogen peroxide that step (2) is added plays the role of oxidant, by Fe2+, Mn2+It is oxidized to Fe3+, Mn3+。
From the point of view of from the size, particle diameter distribution of effective control crystal grain, in the synthesis process, element doping ratio very little
When, heterogeneous nucleation easily occurs for system, improves nucleation rate, the speed of growth of nucleus is reduced, to effectively reduce partial size
Size, but a small amount of doping will lead to the inhomogeneous growth of crystal again, and under the action of surface tension, biggish particle continues
It grows and lesser particle fades away, thus while partial size is fined, but the distribution of partial size is still than wider.With
The increase of doping, the trend of inhomogeneous growth weaken.However as continuing growing for doping, forming core number is more and more,
But when again number of nuclei excessively will lead to the inhomogeneous growth of nucleus.
From the point of view of material property, two kinds of titanium, manganese elements form Fe and Li co-dopeds, change to material property
It is kind to show apparent synergistic effect, have electronic conductivity height, electrochemical specific capacity big by the titanium phosphate manganese iron lithium that it is synthesized
The advantages that, electric electron conductivity≤0.06,0.2C specific capacity can reach 165mAh/g, and have good cryogenic property.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
Titanium phosphate manganese iron (Fe0.9539Ti0.0416Mn0.0045PO4) preparation
(1) ferrous sulfate (FeSO is taken4·7H2O) 433.68g, 30wt% titanium trichloride solution 35g, manganese sulfate 1.1g, di(2-ethylhexyl)phosphate
Hydrogen ammonium 198g, is dissolved into 3L mixed aqueous solution.
(2) agitating and heating mixes aqueous to 40 DEG C, and 30wt% hydrogenperoxide steam generator 110ml is added.Continue to be heated to 90 DEG C,
12ml phosphoric acid is added, is kept for 90 DEG C or more react, bleached to reaction system, after continuing heat preservation 2 hours, NaOH regulation system is added
PH value continues heat preservation 1 hour to 4-5.
(3) the solid product washing and drying for obtaining step (2), 650 DEG C of calcining 4h.
Comparative example 1
(1) ferrous sulfate (FeSO is taken4·7H2O) 433.68g, manganese sulfate 1.1g, ammonium dihydrogen phosphate 198g are dissolved into 3L mixing
Aqueous solution.
(2) agitating and heating mixes aqueous to 40 DEG C, and 30wt% hydrogenperoxide steam generator 110ml is added.Continue to be heated to 90 DEG C,
12ml phosphoric acid is added, is kept for 90 DEG C or more react, bleached to reaction system, after continuing heat preservation 2 hours, NaOH regulation system is added
PH value continues heat preservation 1 hour to 4-5.
(3) the solid product washing and drying for obtaining step (2), 650 DEG C of calcining 4h.
Comparative example 2
(1) ferrous sulfate (FeSO is taken4·7H2O) 433.68g, ammonium dihydrogen phosphate 198g are dissolved into 3L mixed aqueous solution.
(2) agitating and heating mixes aqueous to 40 DEG C, and 30wt% hydrogenperoxide steam generator 110ml is added.Continue to be heated to 90 DEG C,
12ml phosphoric acid is added, is kept for 90 DEG C or more react, bleached to reaction system, after continuing heat preservation 2 hours, NaOH regulation system is added
PH value continues heat preservation 1 hour to 4-5.
(3) the solid product washing and drying for obtaining step (2), 650 DEG C of calcining 4h.
Comparative example 3
Titanium phosphate manganese iron (Fe0.8354Ti0.1607Mn0.0039PO4) preparation
(1) ferrous sulfate (FeSO is taken4·7H2O) 433.68g, 30wt% titanium trichloride solution 154.25g, manganese sulfate 1.1g, phosphorus
Acid dihydride ammonium 198g, is dissolved into 3L mixed aqueous solution.
(2) agitating and heating mixes aqueous to 40 DEG C, and 30wt% hydrogenperoxide steam generator 110ml is added.Continue to be heated to 90 DEG C,
12ml phosphoric acid is added, is kept for 90 DEG C or more react, bleached to reaction system, after continuing heat preservation 2 hours, NaOH regulation system is added
PH value continues heat preservation 1 hour to 4-5.
(3) the solid product washing and drying for obtaining step (2), 650 DEG C of calcining 4h.
Comparative example 4
Titanium phosphate manganese iron (Fe0.48Ti0.02Mn0.5PO4) preparation
(1) ferrous sulfate (FeSO is taken4·7H2O) 207.98g, 30wt% titanium trichloride solution 16g, manganese sulfate 117.78g, phosphoric acid
Ammonium dihydrogen 198g is dissolved into 3L mixed aqueous solution.
(2) agitating and heating mixes aqueous to 40 DEG C, and 30wt% hydrogenperoxide steam generator 110ml is added.Continue to be heated to 90 DEG C,
12ml phosphoric acid is added, is kept for 90 DEG C or more react, bleached to reaction system, after continuing heat preservation 2 hours, NaOH regulation system is added
PH value continues heat preservation 1 hour to 4-5.
(3) the solid product washing and drying for obtaining step (2), 650 DEG C of calcining 4h.
Table 1
| Project | Room temperature electron conductivity | Specific capacity (25 DEG C, 0.2C) | Cryogenic property |
| Embodiment 1 | 0.012 | 156 Wh/kg | 85% |
| Comparative example 1 | 0.0095 | 154 Wh/kg | 80% |
| Comparative example 2 | 0.010 | 145 Wh/kg | 78% |
| Comparative example 3 | 0.012 | 106 Wh/kg | 52% |
| Comparative example 4 | 0.011 | 96 Wh/kg | 54% |
Cryogenic property refers to: -20 DEG C, specific capacity when 0.2C is with 25 DEG C, specific capacity percentage when 0.2C.
Embodiment 2
Titanium phosphate manganese iron (Fe0.9802Ti0.0183Mn0.0015PO4) preparation
(1) ferrous sulfate (FeSO is taken4·7H2O) 433.68g, 30wt% titanium trichloride solution 15g, manganese sulfate 0.35g, di(2-ethylhexyl)phosphate
Hydrogen ammonium 198g, is dissolved into 3L mixed aqueous solution.
(2) agitating and heating mixes aqueous to 40 DEG C, and 30wt% hydrogenperoxide steam generator 110ml is added.Continue to be heated to 90 DEG C,
12ml phosphoric acid is added, is kept for 90 DEG C or more react, bleached to reaction system, after continuing heat preservation 2 hours, NaOH regulation system is added
PH value continues heat preservation 1 hour to 5-6.
(3) the solid product washing and drying for obtaining step (2), 680 DEG C of calcining 4h.
Embodiment 3
Titanium phosphate manganese iron (Fe0.9539Ti0.0416Mn0.0045PO4) preparation
(1) frerrous chloride (FeCl is taken2) 197.73g, 30wt% titanium trichloride solution 35g, manganese chloride (MnCl2) 0.92g, phosphoric acid
Ammonium dihydrogen 198g is dissolved into 3L mixed aqueous solution.
(2) agitating and heating mixes aqueous to 40 DEG C, and 30wt% hydrogenperoxide steam generator 110ml is added.Continue to be heated to 90 DEG C,
12ml phosphoric acid is added, is kept for 90 DEG C or more react, bleached to reaction system, after continuing heat preservation 2 hours, NaOH regulation system is added
PH value continues heat preservation 1 hour to 4-5.
(3) the solid product washing and drying for obtaining step (2), 640 DEG C of calcining 4h.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (8)
1. a kind of titanium phosphate manganese iron, it is characterised in that: the chemical formula of the titanium phosphate manganese iron are as follows: Fe(1-x-y)TixMnyPO4, wherein
X=0.05~0.01, y=0.005~0.001.
2. the preparation method of titanium phosphate manganese iron, includes the following steps: described in claim 1
(1) source of iron, titanium source, manganese source and phosphorus source are dissolved, obtains mixed solution；
(2) mixed solution is first heated to 30~50 DEG C, and hydrogen peroxide is added, and is then heated to 90 DEG C or more, phosphoric acid is added, to anti-
After answering system to bleach, insulation reaction 1~3 hour, then adjust the pH value of reaction system to 4-5, continue insulation reaction 0.5~
1.5 hour；
(3) the obtained product of step (2) reaction is washed, dry, calcining, obtain described in titanium phosphate manganese iron.
3. preparation method according to claim 2, it is characterised in that: the source of iron is ferrous sulfate, frerrous chloride, sulfuric acid
Iron and/or iron chloride；The titanium source is titanium chloride, titanium trichloride and/or titanium sulfate；The manganese source is manganese sulfate and/or chlorination
Manganese；Phosphorus source is ammonium dihydrogen phosphate and/or ammonium hydrogen phosphate.
4. preparation method according to claim 2, it is characterised in that: in step (1), the iron phosphorus molar ratio of source of iron and phosphorus source
For 0.83~0.95:1.
5. preparation method according to claim 2, it is characterised in that: in step (1), concentration of the source of iron in mixed solution
For 0.5~1 mol/L.
6. preparation method according to claim 2, it is characterised in that: in step (2), the dosage of the phosphoric acid is that mixing is molten
The 0.3~0.4% of liquid product.
7. preparation method according to claim 2, it is characterised in that: in step (3), the temperature of calcining is 640-680 DEG C,
Time is 1-6 hours.
8. preparation method according to claim 7, it is characterised in that: the time of calcining is 4-5 hours.
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| CN117756076A (en) * | 2023-12-22 | 2024-03-26 | 湖北虹润高科新材料有限公司 | Titanium-doped anhydrous ferric phosphate material, and preparation method and application thereof |
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| CN117756076A (en) * | 2023-12-22 | 2024-03-26 | 湖北虹润高科新材料有限公司 | Titanium-doped anhydrous ferric phosphate material, and preparation method and application thereof |
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