CN105470468A - Fluorine-doped lithium ferric manganese phosphate cathode material and preparation method thereof - Google Patents
Fluorine-doped lithium ferric manganese phosphate cathode material and preparation method thereof Download PDFInfo
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- CN105470468A CN105470468A CN201511008307.7A CN201511008307A CN105470468A CN 105470468 A CN105470468 A CN 105470468A CN 201511008307 A CN201511008307 A CN 201511008307A CN 105470468 A CN105470468 A CN 105470468A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a fluorine-doped lithium ferric manganese phosphate cathode material. A chemical formula of the fluorine-doped lithium ferric manganese phosphate cathode material is LiFe<x>Mn<1-x>(PO<4>)<y>F<1-y>; a preparation method of the fluorine-doped lithium ferric manganese phosphate cathode material comprises the following preparation processes: (1) weighing a lithium source, an iron source, a manganese source, a phosphorus source and a fluorine source to put into a reaction kettle at the molar ratio, heating and warming the raw materials and lastingly stirring the raw materials; (2) adding a carbon source compound to a solution A, and stirring the solution A evenly to form a solution B; (3) adding a surfactant to the solution B; (4) adding EDTA to a solution C and stirring the solution C to obtain a solution D; (5) transferring the solution D into a high-pressure reaction kettle for reaction to obtain a solution E; (6) cooling the solution E and then carrying out vacuum filtration, washing and drying treatment to obtain a fluorine-doped ferric manganese phosphate precursor; and (7) cooling and grinding the fluorine-doped ferric manganese phosphate in an inert gas atmosphere, so as to obtain the fluorine-doped lithium ferric manganese phosphate cathode material.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, particularly relate to a kind of Fluorin doped lithium ferric manganese phosphate positive electrode and preparation method thereof.
Background technology
Along with people are for the reinforcement of environmental protection consciousness; the environmental pollution that vehicle exhaust brings and global warming phenomenon have caused to be paid close attention to widely; day by day reduce to effect a radical cure vehicle exhaust environmental pollution and global warming phenomenon and alleviating petroleum resources the energy crisis brought, the research of the electric automobile of energy-conserving and environment-protective, exploitation and industrialization become the problem paid close attention in the whole world.But the maximum bottleneck of restriction Development of Electric Vehicles is exactly fail safe and the life-span of electrokinetic cell.Lithium ion battery is with its high-energy, high power, long-life, fail safe is good, self discharge is little, the advantage such as environmentally friendly to be known as electric motor car by people electrical source of power.
Anode material for lithium-ion batteries is the important component part of battery, and the focus of research at present mainly concentrates on the fields such as cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4 and nickle cobalt lithium manganate.But the expensive and toxicity of cobalt acid lithium is comparatively large, LiMn2O4 thermal stability is poor, and LiFePO4 high rate performance is poor, and the fail safe of nickle cobalt lithium manganate is poor, limits the application of these materials in lithium ion battery.Transition metal phosphate compound (LiFePO
4, LiMnPO
4) there is the advantages such as cheap, good stability, toxicity are low, environmentally friendly, the important substitution material of positive electrode on market after being considered to.Due to LiFePO
4energy density low, LiMnPO
4chemical property poor, for LiFe
xmn
1-xpO
4research just arise at the historic moment.With LiFePO
4compare, due to the introducing of Mn, LiFe
xmn
1-xpO
4the charge and discharge potential part of positive electrode rises to 4.1V, improves its energy density, the corresponding energy density improving battery; With LiMnPO
4compare, LiFe
xmn
1-xpO
4positive electrode shows excellent chemical property.In order to improve LiFe
xmn
1-xpO
4the conductivity of positive electrode, researchers by doping metals and nonmetalloid to LiFe
xmn
1-xpO
4material carries out modification.
Summary of the invention
The object of this invention is to provide a kind of Fluorin doped lithium ferric manganese phosphate positive electrode and preparation method thereof, be intended to the chemical property improving lithium ferric manganese phosphate, lithium ferric manganese phosphate positive electrode synthetic method of the present invention is simple, and productive rate is high, even particle size distribution, excellent electrochemical performance.
For achieving the above object, the technical solution used in the present invention is: a kind of Fluorin doped lithium ferric manganese phosphate positive electrode, is characterized in that: the chemical formula of described Fluorin doped lithium ferric manganese phosphate positive electrode is LiFe
xmn
1-x(PO
4)
yf
1-y, 0.2 < x < 0.8,0.6 < y < 1.
A preparation method for Fluorin doped lithium ferric manganese phosphate positive electrode, is characterized in that: preparation process comprises the following steps:
1) take lithium source, source of iron, manganese source, phosphorus source, fluorine source put in a kettle. in molar ratio, distilled water is added in reactor, be heated to 80-100 DEG C, Keep agitation reaction 6-8h, form solution A, wherein the mol ratio in lithium source, source of iron, manganese source, phosphorus source, fluorine source is 1.0 ~ 1.2:x:1-x:y:1-y, 0.2 < x < 8,0.6 < y < 1;
2) join in solution A by the carbon-source cpd of 5wt% ~ 15wt%, stir formation solution B;
3) in solution B, add Surfactant PEG-6000, stir 0.5h and obtain solution C, wherein the mol ratio in PEG-6000 and lithium source is 0.05 ~ 0.4:1;
4) join in solution C by EDTA, stir 0.5h and obtain solution D, wherein the mol ratio in EDTA and lithium source is 0.5 ~ 2:1;
5) solution D is proceeded in autoclave, carry out hydro-thermal reaction 8 ~ 12h at 160 ~ 190 DEG C and obtain solution E;
6) after vacuum filtration, washing, dry process, obtain the lithium ferric manganese phosphate presoma of Fluorin doped after solution E cooling;
7) put in tube calciner by the lithium ferric manganese phosphate precursor powder of Fluorin doped, in atmosphere of inert gases, calcine 10 ~ 15h at 600 ~ 900 DEG C, after cooling, grinding obtains the coated lithium ferric manganese phosphate positive electrode of carbon of Fluorin doped.
A kind of preparation method of Fluorin doped lithium ferric manganese phosphate positive electrode, it is characterized in that: described lithium source is lithium hydroxide, lithium acetate, one or more in lithium carbonate, described source of iron is ferrous sulfate, ferrous oxalate, iron chloride, one or more of ferric nitrate, described manganese source is manganese sulfate, manganese carbonate, one or more in manganese acetate, described phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, one or more in diammonium hydrogen phosphate, described fluorine source is ammonium fluoride, one or both mixtures in hydrofluoric acid, described carbon source is glucose, starch, sucrose, one or more in ascorbic acid.
In the method, described PEG-6000 is dispersant PEG-4000, and molecular weight is 6000.
In the method, described EDTA is complexing agent ethylenediamine tetra-acetic acid.
In the method, described inert gas be nitrogen, argon gas, helium one or more.
Advantageous effect of the present invention is: utilize the obtained Fluorin doped lithium ferric manganese phosphate of solid phase-liquid phase method to become near-spherical, even particle size distribution owing to using this method; Complexing agent EDTA adds, and better complex reaction can occur with lithium ion, manganese ion, iron ion, phosphate radical particle and fluorine ion, is convenient to form uniform and stable Fluorin doped lithium ferric manganese phosphate presoma; Fluorin doped lithium iron manganese phosphate anode material prepared by the present invention has higher energy density and good chemical property, and preparation method of the present invention is simple simultaneously, and process is easy to control, and is convenient to realize industrialization large-scale production.
Positive electrode of the present invention prepare battery 0.2C first discharge capacity up to 158.1mAh/g, 100 times circulation after capacity be 154.9mAh/g, capability retention is up to 98%.
Accompanying drawing explanation
Fig. 1 is LiFe prepared by the embodiment of the present invention 1
0.5mn
0.5(PO
4)
0.95f
0.05scanning electron microscope (SEM) photograph;
Fig. 2 is LiFe prepared by the embodiment of the present invention 1
0.5mn
0.5(PO
4)
0.95f
0.050.2C charge-discharge performance curve.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described:
As shown in Figure 1, 2, a kind of Fluorin doped lithium ferric manganese phosphate positive electrode, is characterized in that in the present invention: the chemical formula of described Fluorin doped lithium ferric manganese phosphate positive electrode is LiFe
xmn
1-x(PO
4)
yf
1-y, 0.2 < x < 0.8,0.6 < y < 1.
A preparation method for Fluorin doped lithium ferric manganese phosphate positive electrode, is characterized in that: preparation process comprises the following steps:
1) take lithium source, source of iron, manganese source, phosphorus source, fluorine source put in a kettle. in molar ratio, distilled water is added in reactor, be heated to 80-100 DEG C, Keep agitation reaction 6-8h, form solution A, wherein the mol ratio in lithium source, source of iron, manganese source, phosphorus source, fluorine source is 1.0 ~ 1.2:x:1-x:y:1-y, 0.2 < x < 8,0.6 < y < 1;
2) join in solution A by the carbon-source cpd of 5wt% ~ 15wt%, stir formation solution B;
3) in solution B, add Surfactant PEG-6000, stir 0.5h and obtain solution C, wherein the mol ratio in PEG-6000 and lithium source is 0.05 ~ 0.4:1;
4) join in solution C by EDTA, stir 0.5h and obtain solution D, wherein the mol ratio in EDTA and lithium source is 0.5 ~ 2:1;
5) solution D is proceeded in autoclave, carry out hydro-thermal reaction 8 ~ 12h at 160 ~ 190 DEG C and obtain solution E;
6) after vacuum filtration, washing, dry process, obtain the lithium ferric manganese phosphate presoma of Fluorin doped after solution E cooling;
7) put in tube calciner by the lithium ferric manganese phosphate precursor powder of Fluorin doped, in atmosphere of inert gases, calcine 10 ~ 15h at 600 ~ 900 DEG C, after cooling, grinding obtains the coated lithium ferric manganese phosphate positive electrode of carbon of Fluorin doped.In the present embodiment, described lithium source is one or more in lithium hydroxide, lithium acetate, lithium carbonate, described source of iron be ferrous sulfate, ferrous oxalate, iron chloride, ferric nitrate one or more, described manganese source is manganese sulfate, one or more in manganese carbonate, manganese acetate, described phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, described fluorine source is one or both mixtures in ammonium fluoride, hydrofluoric acid, and described carbon source is one or more in glucose, starch, sucrose, ascorbic acid.In the present embodiment, described PEG-6000 is dispersant PEG-4000, and molecular weight is 6000.In the present embodiment, described EDTA is complexing agent ethylenediamine tetra-acetic acid.In the present embodiment, described inert gas be nitrogen, argon gas, helium one or more.
embodiment 1
First the lithium hydroxide that mol ratio is 1.0 ~ 1.2:0.5:0.5:0.95:0.05 is taken, ferrous sulfate, manganese acetate, phosphoric acid, ammonium fluoride adds in reactor, a certain amount of distilled water is added in reactor, be heated to 80 DEG C, Keep agitation reaction 6h, adding by slaine mass fraction after cooling is the glucose of 10wt%, a period of time is stirred to dissolving completely after ultrasonic disperse, add the Surfactant PEG-6000 of a certain amount of (n (PEG-6000): n (LiOH)=0.1:1) subsequently, stir 0.5h to PEG-6000 to dissolve completely, again add the EDTA of a certain amount of (n (EDTA): n (LiOH)=1:1), stir the solution that 0.5h obtains stable and uniform.Solution is proceeded in autoclave, at 180 DEG C, carry out hydro-thermal reaction 10h, after solution cooling, after vacuum filtration, washing, dry process, obtain Fluorin doped lithium ferric manganese phosphate presoma.Put in tube calciner by Fluorin doped lithium ferric manganese phosphate precursor powder, in nitrogen atmosphere, calcine 12h at 850 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode LiFe of carbon
0.5mn
0.5(PO
4)
0.95f
0.05.
The Fluorin doped lithium ferric manganese phosphate positive electrode prepared for the present invention, its pattern is determined by scanning electron microscopy.As shown in Figure 1, Fluorin doped lithium ferric manganese phosphate has homogeneous pattern, presents near-spherical, and its diameter is about 70-150nm.With the Fluorin doped lithium ferric manganese phosphate of preparation for anode material for lithium-ion batteries, electrically conductive graphite and conductive carbon black are conductive agent, and Kynoar is binding agent, make cell piece, be negative pole with lithium metal, make button cell, carry out lithium ion battery 0.2C charge-discharge test.As shown in Figure 2, the first discharge specific capacity of this material is up to 158.1mAh/g, and after 100 circulations, capacity is 154.9mAh/g, and capability retention, up to 98%, shows excellent chemical property.
embodiment 2
First the lithium hydroxide that mol ratio is 1.0 ~ 1.2:0.6:0.4:0.9:0.1 is taken, ferrous sulfate, manganese acetate, phosphoric acid, hydrofluoric acid adds in reactor, a certain amount of distilled water is added in reactor, be heated to 100 DEG C, Keep agitation reaction 7h, adding by slaine mass fraction after cooling is the glucose of 8wt%, a period of time is stirred to dissolving completely after ultrasonic disperse, add the Surfactant PEG-6000 of a certain amount of (n (PEG-6000): n (LiOH)=0.2:1) subsequently, stir 0.5h to PEG-6000 to dissolve completely, again add the EDTA of a certain amount of (n (EDTA): n (LiOH)=1.5:1), stir the solution that 0.5h obtains stable and uniform.Solution is proceeded in autoclave, at 160 DEG C, carry out hydro-thermal reaction 12h, after solution cooling, after vacuum filtration, washing, dry process, obtain Fluorin doped lithium ferric manganese phosphate presoma.Put in tube calciner by Fluorin doped lithium ferric manganese phosphate precursor powder, in nitrogen atmosphere, calcine 10h at 900 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode LiFe of carbon
0.6mn
0.4(PO
4)
0.9f
0.1.
embodiment 3
First take lithium carbonate that mol ratio is 1.0 ~ 1.2:0.5:0.5:0.8:0.2, ferrous sulfate, manganese carbonate, phosphoric acid, ammonium fluoride add in reactor, a certain amount of distilled water is added in reactor, be heated to 90 DEG C, Keep agitation reaction 8h, adding by slaine mass fraction after cooling is the starch of 15wt%, stirring a period of time after ultrasonic disperse to dissolving completely, adding a certain amount of (n (PEG-6000): n (Li subsequently
2cO
3)=0.4:1) Surfactant PEG-6000, stir 0.5h to PEG-6000 dissolve completely, again add a certain amount of (n (EDTA): n (Li
2cO
3)=2:1) EDTA, stir 0.5h and obtain the solution of stable and uniform.Solution is proceeded in autoclave, at 190 DEG C, carry out hydro-thermal reaction 8h, after solution cooling, after vacuum filtration, washing, dry process, obtain Fluorin doped lithium ferric manganese phosphate presoma.Put in tube calciner by Fluorin doped lithium ferric manganese phosphate precursor powder, in helium atmosphere, calcine 15h at 600 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode LiFe of carbon
0.5mn
0.5(PO
4)
0..8f
0.2.
embodiment 4
First the lithium hydroxide that mol ratio is 1.0 ~ 1.2:0.8:0.2:0.75:0.25 is taken, ferrous sulfate, manganese acetate, phosphoric acid, ammonium fluoride adds in reactor, a certain amount of distilled water is added in reactor, be heated to 100 DEG C, Keep agitation reaction 6h, adding by slaine mass fraction after cooling is the glucose of 5wt%, a period of time is stirred to dissolving completely after ultrasonic disperse, add the Surfactant PEG-6000 of a certain amount of (n (PEG-6000): n (LiOH)=0.3:1) subsequently, stir 0.5h to PEG-6000 to dissolve completely, again add the EDTA of a certain amount of (n (EDTA): n (LiOH)=1.5:1), stir the solution that 0.5h obtains stable and uniform.Solution is proceeded in autoclave, at 180 DEG C, carry out hydro-thermal reaction 12h, after solution cooling, after vacuum filtration, washing, dry process, obtain Fluorin doped lithium ferric manganese phosphate presoma.Put in tube calciner by Fluorin doped lithium ferric manganese phosphate precursor powder, in helium atmosphere, calcine 12h at 750 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode LiFe of carbon
0.8mn
0.2(PO
4)
0..75f
0.25.
Embodiment recited above is only be described the preferred embodiment of the present invention; not design of the present invention and protection range are limited; under the prerequisite not departing from design concept of the present invention; the various modification that in this area, common engineers and technicians make technical scheme of the present invention and improvement, all should fall into protection scope of the present invention.
Claims (10)
1. a Fluorin doped lithium ferric manganese phosphate positive electrode, is characterized in that: the chemical formula of described Fluorin doped lithium ferric manganese phosphate positive electrode is LiFe
xmn
1-x(PO
4)
yf
1-y, 0.2 < x < 0.8,0.6 < y < 1.
2. a preparation method for Fluorin doped lithium ferric manganese phosphate positive electrode, is characterized in that: preparation process comprises the following steps:
1) take lithium source, source of iron, manganese source, phosphorus source, fluorine source put in a kettle. in molar ratio, distilled water is added in reactor, be heated to 80-100 DEG C, Keep agitation reaction 6-8h, form solution A, wherein the mol ratio in lithium source, source of iron, manganese source, phosphorus source, fluorine source is 1.0 ~ 1.2:x:1-x:y:1-y, 0.2 < x < 8,0.6 < y < 1;
2) join in solution A by the carbon-source cpd of 5wt% ~ 15wt%, stir formation solution B;
3) in solution B, add Surfactant PEG-6000, stir 0.5h and obtain solution C, wherein the mol ratio in PEG-6000 and lithium source is 0.05 ~ 0.4:1;
4) join in solution C by EDTA, stir 0.5h and obtain solution D, wherein the mol ratio in EDTA and lithium source is 0.5 ~ 2:1;
5) solution D is proceeded in autoclave, carry out hydro-thermal reaction 8 ~ 12h at 160 ~ 190 DEG C and obtain solution E;
6) after vacuum filtration, washing, dry process, obtain the lithium ferric manganese phosphate presoma of Fluorin doped after solution E cooling;
7) put in tube calciner by the lithium ferric manganese phosphate precursor powder of Fluorin doped, in atmosphere of inert gases, calcine 10 ~ 15h at 600 ~ 900 DEG C, after cooling, grinding obtains the coated lithium ferric manganese phosphate positive electrode of carbon of Fluorin doped.
3. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 2, it is characterized in that: described lithium source is lithium hydroxide, lithium acetate, one or more in lithium carbonate, described source of iron is ferrous sulfate, ferrous oxalate, iron chloride, one or more of ferric nitrate, described manganese source is manganese sulfate, manganese carbonate, one or more in manganese acetate, described phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, one or more in diammonium hydrogen phosphate, described fluorine source is ammonium fluoride, one or both mixtures in hydrofluoric acid, described carbon source is glucose, starch, sucrose, one or more in ascorbic acid.
4. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 3, it is characterized in that: described PEG-6000 is dispersant PEG-4000, molecular weight is 6000.
5. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 4, is characterized in that: described EDTA is complexing agent ethylenediamine tetra-acetic acid.
6. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 5, is characterized in that: described inert gas be nitrogen, argon gas, helium one or more.
7. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 3, it is characterized in that: preparation process comprises the following steps: first take the lithium hydroxide that mol ratio is 1.0 ~ 1.2:0.5:0.5:0.95:0.05, ferrous sulfate, manganese acetate, phosphoric acid, ammonium fluoride adds in reactor, distilled water is added in reactor, be heated to 80 DEG C, Keep agitation reaction 6h, adding by slaine mass fraction after cooling is the glucose of 10wt%, a period of time is stirred to dissolving completely after ultrasonic disperse, add the Surfactant PEG-6000 of (n (PEG-6000): n (LiOH)=0.1:1) subsequently, stir 0.5h to PEG-6000 to dissolve completely, again add the EDTA of (n (EDTA): n (LiOH)=1:1), stir the solution that 0.5h obtains stable and uniform, solution is proceeded in autoclave, at 180 DEG C, carry out hydro-thermal reaction 10h, after solution cooling, after vacuum filtration, washing, dry process, obtain Fluorin doped lithium ferric manganese phosphate presoma, put in tube calciner by Fluorin doped lithium ferric manganese phosphate precursor powder, in nitrogen atmosphere, calcine 12h at 850 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode of carbon.
8. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 3, it is characterized in that: preparation process comprises the following steps: first take the lithium hydroxide that mol ratio is 1.0 ~ 1.2:0.6:0.4:0.9:0.1, ferrous sulfate, manganese acetate, phosphoric acid, hydrofluoric acid adds in reactor, distilled water is added in reactor, be heated to 100 DEG C, Keep agitation reaction 7h, adding by slaine mass fraction after cooling is the glucose of 8wt%, be stirred to after ultrasonic disperse and dissolve completely, add the Surfactant PEG-6000 of (n (PEG-6000): n (LiOH)=0.2:1) subsequently, stir 0.5h to PEG-6000 to dissolve completely, again add the EDTA of (n (EDTA): n (LiOH)=1.5:1), stir the solution that 0.5h obtains stable and uniform, solution is proceeded in autoclave, at 160 DEG C, carry out hydro-thermal reaction 12h, after solution cooling, after vacuum filtration, washing, dry process, obtain Fluorin doped lithium ferric manganese phosphate presoma, put in tube calciner by Fluorin doped lithium ferric manganese phosphate precursor powder, in nitrogen atmosphere, calcine 10h at 900 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode of carbon.
9. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 3, it is characterized in that: preparation process comprises the following steps: first take lithium carbonate that mol ratio is 1.0 ~ 1.2:0.5:0.5:0.8:0.2, ferrous sulfate, manganese carbonate, phosphoric acid, ammonium fluoride add in reactor, distilled water is added in reactor, be heated to 90 DEG C, Keep agitation reaction 8h, adding by slaine mass fraction after cooling is the starch of 15wt%, be stirred to after ultrasonic disperse and dissolve completely, add (n (PEG-6000): n (Li subsequently
2cO
3)=0.4:1) Surfactant PEG-6000, stir 0.5h to PEG-6000 dissolve completely, again add (n (EDTA): n (Li
2cO
3)=2:1) EDTA, stir the solution that 0.5h obtains stable and uniform, solution is proceeded in autoclave, hydro-thermal reaction 8h is carried out at 190 DEG C, after solution cooling, after vacuum filtration, washing, dry process, obtain Fluorin doped lithium ferric manganese phosphate presoma, Fluorin doped lithium ferric manganese phosphate precursor powder is put in tube calciner, in helium atmosphere, calcine 15h at 600 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode of carbon.
10. the preparation method of a kind of Fluorin doped lithium ferric manganese phosphate positive electrode according to claims 3, it is characterized in that: preparation process comprises the following steps: first take the lithium hydroxide that mol ratio is 1.0 ~ 1.2:0.8:0.2:0.75:0.25, ferrous sulfate, manganese acetate, phosphoric acid, ammonium fluoride adds in reactor, distilled water is added in reactor, be heated to 100 DEG C, Keep agitation reaction 6h, adding by slaine mass fraction after cooling is the glucose of 5wt%, be stirred to after ultrasonic disperse and dissolve completely, add the Surfactant PEG-6000 of (n (PEG-6000): n (LiOH)=0.3:1) subsequently, stir 0.5h to PEG-6000 to dissolve completely, again add the EDTA of (n (EDTA): n (LiOH)=1.5:1), stir the solution that 0.5h obtains stable and uniform, solution is proceeded in autoclave, hydro-thermal reaction 12h is carried out at 180 DEG C, through vacuum filtration after solution cooling, washing, Fluorin doped lithium ferric manganese phosphate presoma is obtained after dry process, Fluorin doped lithium ferric manganese phosphate precursor powder is put in tube calciner, in helium atmosphere, 12h is calcined at 750 DEG C, after cooling, grinding obtains the coated Fluorin doped lithium ferric manganese phosphate positive electrode of carbon.
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| CN106450223A (en) * | 2016-11-18 | 2017-02-22 | 电子科技大学 | Fluorine-doped and carbon-coated lithium iron phosphate and preparation and application thereof |
| CN114373912A (en) * | 2021-12-31 | 2022-04-19 | 江苏贝特瑞纳米科技有限公司 | Fluorine-doped lithium manganese iron phosphate cathode material and preparation method thereof |
| CN114394584A (en) * | 2021-12-14 | 2022-04-26 | 云南润久科技有限公司 | Method for preparing ferric manganese phosphate lithium battery anode material by coprecipitation-solid phase combination |
| CN116443842A (en) * | 2023-04-18 | 2023-07-18 | 东莞市创明电池技术有限公司 | Fluorine-doped porous lithium iron manganese phosphate, preparation method thereof, positive electrode and battery |
| WO2023197483A1 (en) * | 2022-04-12 | 2023-10-19 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method for nano lithium manganese iron phosphate |
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| CN114394584A (en) * | 2021-12-14 | 2022-04-26 | 云南润久科技有限公司 | Method for preparing ferric manganese phosphate lithium battery anode material by coprecipitation-solid phase combination |
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| WO2023197483A1 (en) * | 2022-04-12 | 2023-10-19 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method for nano lithium manganese iron phosphate |
| CN116443842A (en) * | 2023-04-18 | 2023-07-18 | 东莞市创明电池技术有限公司 | Fluorine-doped porous lithium iron manganese phosphate, preparation method thereof, positive electrode and battery |
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