CN111908442A - Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof - Google Patents

Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof Download PDF

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CN111908442A
CN111908442A CN202010788662.5A CN202010788662A CN111908442A CN 111908442 A CN111908442 A CN 111908442A CN 202010788662 A CN202010788662 A CN 202010788662A CN 111908442 A CN111908442 A CN 111908442A
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CN111908442B (en
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杭道金
陆君
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Shanghai Huayi Group Corp
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • 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
    • 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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    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

Manganese iron phosphate, manganese iron phosphate and preparation methods thereof are provided. Amorphous iron manganese phosphate powders have the following general formula: (Mn)1‑xFex)aPO4Wherein: x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1; it is prepared by the following method: reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture; filtering to obtain a filter cake containing (Mn) as the main component1‑xFex)aPO4·H2O crystals; heat-treating the crystal at 200-500 ℃ for 2-10 hours to obtain amorphous (Mn)1‑xFex)aPO4And (3) powder.

Description

Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof
Technical Field
The invention relates to a precursor material manganese (III) iron (III) phosphate of a lithium ion battery anode material, a lithium iron manganese phosphate of a lithium ion battery anode material and preparation methods thereof. The lithium iron manganese phosphate lithium ion battery anode material prepared by the method has high tap density, so that the lithium ion battery prepared by the lithium iron manganese phosphate lithium ion battery anode material has improved battery capacity.
Technical Field
As a lithium ion battery anode material, a phosphate material represented by lithium iron phosphate has the advantages of long cycle life, high safety, rich resources, environmental friendliness, low cost and the like, and plays an important role in a lithium ion battery anode material system. The synthesis process of phosphate series anode materials can be divided into a hydrothermal method, an oxalate method, a metal oxide method, a phosphate method and the like. The phosphate anode material prepared by the phosphate method has the advantages of high compaction density, high electrochemical activity, simple preparation process, good product batch stability and the like.
Compared with lithium iron phosphate, lithium manganese iron phosphate has the advantages of improved voltage level, long cycle life, abundant resources and the like, and is gradually promoted in recent years. However, compared with lithium iron phosphate, lithium iron manganese phosphate has fewer precursor sources, and a stable and reliable synthesis process route is still needed. In order to overcome the above disadvantages, the currently published documents propose the following synthetic processes:
CN102781827B discloses a process route for preparing lithium iron manganese phosphate by a hydrothermal method. The route core comprises the following steps: a first step of obtaining an aqueous slurry by a neutralization reaction of the raw material mixed solution; subjecting the slurry obtained in the first step to hydrothermal treatment to obtain LiMn of the compound1-xFexPO4(x is more than or equal to 0.05 and less than or equal to 0.5) after a certain condition is met, a second procedure of cleaning the compound; and coating and heat treating the product obtained in the second procedure to obtain the carbon-coated lithium manganese iron phosphate product.
CN103762362B discloses a hydrothermal synthesis method of lithium iron manganese phosphate. According to the method, mixed liquor containing Mn, Fe, Ti and P is pumped into mixed liquor containing Li and P at a certain temperature for hydrothermal reaction, then the mixed liquor is cooled, washed and precipitated, mixed with an organic carbon source, spray-dried to obtain powder, and then subjected to heat treatment to obtain the product.
CN1632970A discloses a method for preparing spherical lithium iron phosphate and lithium manganese iron phosphate. And (3) coprecipitating Mn, Fe, P and ammonium ions by a coprecipitation means to obtain a spherical manganese iron ammonium phosphate precursor, mixing the spherical manganese iron ammonium phosphate precursor with lithium carbonate, and performing heat treatment to obtain a product.
CN107311853A discloses a method for synthesizing battery-grade manganese iron oxalate. The method comprises the steps of obtaining ferrous sulfate through the reaction of iron and dilute sulfuric acid, adding manganese sulfate to obtain a ferromanganese mixed solution, and precipitating ferromanganese to obtain ferromanganese oxalate serving as a precursor of lithium ferromanganese phosphate by taking the mixed solution of oxalic acid and ammonium oxalate as a precipitating agent.
The methods comprise a hydrothermal method, an oxalate method, a manganese ferric ammonium phosphate precursor method and the like, all of which relate to the production and treatment of wastewater, the investment for environmental protection is high, and the quality of the product is not stable.
CN105355885A discloses a method for preparing lithium iron manganese phosphate by a high-energy ball milling method. In the method, manganese, iron, phosphorus and an organic carbon source are uniformly mixed and then subjected to high-energy ball milling treatment, then the mixture is subjected to heat treatment to obtain carbon-coated manganese iron pyrophosphate, and then the mixture is mixed with a lithium source and subjected to heat treatment to obtain a product. The process belongs to a high-energy ball milling process, elements are difficult to uniformly distribute, and the batch stability of the product is poor.
CN105185993A discloses a method for preparing lithium iron manganese phosphate, which comprises, as described in example 3, mixing manganese dioxide and iron oxalate in a ball mill (rotation speed 200rpm, time 1H), adding H, and mixing with phosphoric acid and polyvinyl pyrrolidone2O2Stirring, aging, washing to pH 7.0, filtering, and drying at 80 deg.C to obtain yellow white manganese element-doped iron phosphate (Fe)0.97Mn0.03PO4·2H2O). The iron phosphate is used as a raw material, lithium carbonate is used as a lithium source, cane sugar is added, and the LiFePO is synthesized by heat preservation for 8 hours at 750 ℃ in high-purity nitrogen4And C, material.
In the prior art, a lithium iron manganese phosphate material with high electrochemical activity and high tap density still needs to be developed, and a lithium ion battery prepared from the material has high energy density. The invention also needs to develop a manufacturing method of the material.
Disclosure of Invention
The invention aims to provide a ferromanganese phosphate precursor material and a preparation method thereof.
The invention also aims to provide lithium iron manganese phosphate and a preparation method thereof, wherein the lithium iron manganese phosphate material has high tap density, and a lithium ion battery prepared from the lithium iron manganese phosphate material has high electrochemical activity.
Accordingly, one aspect of the present invention relates to an amorphous iron manganese phosphate powder having the general formula:
(Mn1-xFex)aPO4，
wherein: x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
it is prepared by the following method:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200-500 ℃ to obtain amorphous (Mn)1-xFex)aPO4And (3) powder.
Another aspect of the present invention relates to a method for preparing amorphous iron manganese phosphate powders having the general formula:
(Mn1-xFex)aPO4，
wherein: x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
it includes:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200-500 ℃ to obtain amorphous (Mn)1-xFex)aPO4And (3) powder.
Another aspect of the invention relates to an amorphous lithium manganese iron phosphate having the general formula:
Li(Mn1-xFex)aPO4/kC；
wherein x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
k is the content of carbon accounting for the total weight of the amorphous lithium manganese iron phosphate, and is 0.5 to 4 weight percent;
the amorphous lithium manganese iron phosphate is prepared by the following method:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200-500 ℃ to obtain amorphous (Mn)1-xFex)aPO4Powder is obtained;
grinding stoichiometric amounts of the amorphous powder, lithium source and carbon source to obtain D50Particles of 0.1 to 2 microns; followed by firing.
Yet another aspect of the invention relates to a method for preparing amorphous lithium manganese iron phosphate having the following general formula:
Li(Mn1-xFex)aPO4/kC；
wherein x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
k is the content of carbon accounting for the total weight of the amorphous lithium manganese iron phosphate, and is 0.5 to 4 weight percent;
it includes:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200-500 ℃ to obtain amorphous (Mn)1-xFex)aPO4Powder is obtained;
grinding stoichiometric amounts of the amorphous powder, lithium source and carbon source to obtain D50Particles of 0.1 to 2 microns; followed by firing.
Drawings
The invention is further described with reference to the accompanying drawings, in which:
FIG. 1 shows Mn as a general formula obtained by one embodiment of the present invention0.85Fe0.15PO4·H2XRD pattern of O precursor;
FIG. 2 is an XRD pattern of the amorphous powder of the precursor of FIG. 1 after heat treatment;
FIG. 3 is an SEM image of an amorphous powder of the precursor of FIG. 1 after heat treatment;
fig. 4 is an XRD pattern of lithium iron manganese phosphate product powder obtained according to an example of the present invention;
FIG. 5 is a charge-discharge diagram of a lithium iron manganese phosphate product powder made from the precursor obtained in FIG. 1;
FIG. 6 is a graph showing the charging and discharging of lithium iron manganese phosphate product powder obtained according to an embodiment of the present invention;
FIG. 7 is a charge/discharge diagram of the lithium iron manganese phosphate product powder obtained in comparative example 1;
fig. 8 is an XRD pattern of the non-pure phase lithium manganese iron phosphate obtained in comparative example 1.
Detailed Description
1. Amorphous precursor powder
The amorphous manganese iron phosphate powder has the following general formula:
(Mn1-xFex)aPO4，
wherein: 0.15. ltoreq. x.ltoreq.0.45, preferably 0.18. ltoreq. x.ltoreq.0.42, more preferably 0.22. ltoreq. x.ltoreq.0.38, preferably 0.25. ltoreq. x.ltoreq.0.35, preferably 0.28. ltoreq. x.ltoreq.0.32;
a is more than or equal to 0.95 and less than or equal to 1, preferably more than or equal to 0.96 and less than or equal to 1, more preferably more than or equal to 0.97 and less than or equal to 0.99;
the preparation method of the amorphous ferromanganese phosphate precursor powder comprises the following steps:
a) reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture
The reducing agent suitable for use in the method of the present invention is not particularly limited as long as it does not adversely affect the reaction. From the viewpoint of product purity, the reducing agent is preferably selected from hydrogen peroxide, oxalic acid, ascorbic acid or a mixture thereof, and hydrogen peroxide is preferred.
In one embodiment of the invention, water is used as the reaction medium.
In one embodiment of the invention, the reaction is carried out by physical dispersion, milling with the aid of ultrasound, wet milling or high-speed homogenizers.
The temperature of the reaction is not particularly limited and may be a conventional reaction temperature known in the art. In one embodiment of the invention, the reaction is carried out at a temperature of between 50 and 90 ℃ and preferably between 60 and 80 ℃.
In one embodiment of the invention, the reaction mixture obtained has a total solids content of between 20 and 55% by weight, preferably between 30 and 45% by weight.
b) Filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystal
The filtration means suitable for the method of the present invention is not particularly limited and may be conventional filtration means known in the art.
In one embodiment of the invention, the water content of the filter cake obtained by filtration is between 30 and 70% by weight, preferably between 35 and 60% by weight, more preferably between 40 and 50% by weight.
The process of the invention optionally comprises a step of drying the filter cake. Suitable drying methods are not particularly limited and may be any drying method known in the art. In one embodiment of the invention, the filter cake is dried at a temperature of 90-130 deg.C, preferably 100-120 deg.C, for a period of 1-5 hours, preferably 2-4 hours.
To determine the composition of the solid obtained by filtration, it was subjected to XRD analysis and TG-DSC analysis to confirm that the obtained cake contained mainly (Mn)1-xFex)aPO4·H2And (4) O crystals.
c) Heat treating the crystal at 200-500 deg.C for 1-24 hr to dehydrate and form amorphous phase to obtain amorphous (Mn)1-xFex)aPO4And (3) powder.
The temperature for heat treatment of the filter cake is 200-500 ℃, preferably 250-480 ℃, more preferably 300-450 ℃, and preferably 350-420 ℃; the treatment time is 1 to 24 hours, preferably 2 to 18 hours, more preferably 3 to 12 hours, further preferably 4 to 8 hours.
The atmosphere in which the crystal is heat-treated is not particularly limited and may be any conventional heat-treating atmosphere known in the art, and for example, may be an air or oxygen atmosphere, preferably an air atmosphere.
In one embodiment of the present invention, the preparation of amorphous (Mn)1-xFex)aPO4The method of powder comprises: weighing manganese dioxide, ferrous oxalate, phosphoric acid and water, adding hydrogen peroxide under stirring, uniformly stirring, heating and maintaining the temperature between 50 and 60 ℃, and reacting the system under the action of ultrasound. And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. Spreading the filter cake in a ceramic sagger, transferring the filter cake into a muffle furnace with oxygen, heating to 100-130 ℃, preferably 110-120 ℃, keeping the temperature for 2-4 hours, preferably 2.5-3.5 hours to evaporate the water, heating to 200-500 ℃, preferably 250-480 ℃, preferably 300-450 ℃, keeping the temperature for 3-6 hours, preferably keeping the temperature for 4-5 hours at the speed of 1-4 ℃/min, preferably 1.5-3.5 ℃/min, more preferably 2-3 ℃/min, and finally obtaining the amorphous precursor material.
2. Amorphous lithium manganese iron phosphate powder
The amorphous lithium iron manganese phosphate powder of the invention has the following general formula:
Li(Mn1-xFex)aPO4/kC；
wherein x and a are as previously described;
k is carbon in an amount of 0.5 to 4 wt%, preferably 0.8 to 3.5 wt%, more preferably 1 to 3 wt%, and most preferably 1.5 to 2.5 wt%, based on the total weight of the amorphous lithium manganese iron phosphate.
The preparation method of the amorphous lithium manganese iron phosphate comprises the following steps:
c') amorphous form (Mn) is provided according to the process described above1-xFex)aPO4Powder; and
d) grinding stoichiometric amounts of the amorphous powder, lithium source and carbon source to obtain D50Particles of 0.1 to 2 microns; followed by firing.
In one embodiment of the invention, the method of the invention comprises, prior to milling, stoichiometrically weighing the lithium source and the amorphous iron manganese phosphate powder, adding water to prepare a suspension, and adding a dispersant and an organic carbon source.
The suitable lithium source is not particularly limited, and may be a conventional lithium source known in the art. For example, the lithium source may be selected from lithium oxalate, lithium hydroxide, lithium carbonate, lithium acetate or a mixture of two or more thereof, preferably lithium carbonate or lithium hydroxide.
In one embodiment of the invention, the molar ratio of Li (Mn + Fe) is between 0.98 and 1.08, preferably between 1.0 and 1.05.
The dispersant suitable for use in the method of the present invention is not particularly limited and may be a conventional dispersant known in the art. In one embodiment of the invention, the dispersant is selected from polyacrylic acid and derivatives thereof, ascorbic acid, citric acid or mixtures thereof.
The amount of the dispersant to be added is not particularly limited as long as the effect of promoting dispersion is satisfied and the reaction is not adversely affected. In one embodiment of the invention, the dispersant is added in an amount of 0.1 to 5 wt%, preferably 0.5 to 4 wt%, more preferably 1 to 3 wt%, based on the total weight of the solid.
The organic carbon source suitable for the method of the present invention is not particularly limited, and may be a conventional organic carbon source known in the art. In one embodiment of the invention, the organic carbon source is selected from glucose, galactose, lactose, sucrose, caramel, ethylcellulose, phenolic resin or a mixture of two or more thereof. Preferably glucose, sucrose, caramel or mixtures thereof.
The solid content of the suspension formed of the lithium source, amorphous powder, and carbon source is not particularly limited, and may be a conventional solid content known in the art. In one embodiment of the invention, the solids content of the suspension is between 20 and 60% by weight, preferably between 30 and 50% by weight.
The applicable grinding method is not particularly limited, and may be a grinding method conventional in the art. D of the milled particles50Is 0.1 to 2 μm, preferably 0.2 to 1.8. mu.m, more preferably 0.3 to 1.6 microns, preferably 0.5 to 1.4 microns, preferably 0.6 to 1.2 microns.
After milling, the process of the invention also comprises a drying step. The drying method to be used is not particularly limited, and may be a conventional drying method known in the art. In one embodiment of the invention, spray drying is employed.
After drying, D is obtained as dry granules50The particle size is 5 to 20 microns, preferably 6 to 18 microns, more preferably 8 to 16 microns, preferably 10 to 12 microns.
The method of the present invention includes the step of calcining the dried particles. In one embodiment of the present invention, the calcination is performed under an inert atmosphere, which may be selected from nitrogen, argon, carbon dioxide, or a mixture thereof. The temperature for calcination is 550-800 deg.C, preferably 600-750 deg.C. The calcination time is between 1 and 12 hours, preferably 1 to 6 hours.
The calcination can also be carried out by a stepwise heating method, for example, in an inert atmosphere, the temperature is raised from the normal temperature to 450 ℃ for 350-.
In one embodiment of the present invention, the method for preparing amorphous lithium manganese iron phosphate comprises: amorphous manganese iron phosphate powder was provided by the method described above, water was added, and the lithium source and organic carbon source were added under stirring and then sanded by a sand mill. During sanding, an aqueous solution of ammonium polyacrylate is suitably added as the viscosity increases. Finally, the grinding is stopped after the median particle diameter D50 measured by a laser particle sizer meets the requirements. And (4) carrying out spray drying on the ground slurry by means of centrifugal disc spray drying to obtain dry powder. Transferring the powder into an atmosphere furnace, heating to 450 ℃ from normal temperature at the speed of 1-5 ℃/min under the nitrogen protection atmosphere, preserving the heat for 3-6 hours, heating to 600 ℃ at the speed of 1-5 ℃/min, preserving the heat for 3-6 hours, naturally cooling, and sieving with a 200-mesh sieve to obtain the product.
The advantage of the present invention is that,
the anhydrous ferromanganese phosphate provided by the invention has the advantages that the manganese and iron elements are uniformly distributed, the product is amorphous, the reaction activity is high, the reaction atom economy is high, the reaction condition is mild, the process is simple, and no sewage is discharged.
The lithium manganese iron phosphate product has high tap compactness and high electrochemical activity.
Examples
The present invention will be further described with reference to specific examples. The electrochemical performance test method of the obtained lithium manganese iron phosphate comprises the following steps:
according to the active substance: conductive agent: mixing active substance, conductive carbon fiber and binder according to the weight ratio of 92.5:3.5:4 and NMP as solvent, and mixing the mixture according to the ratio of-10 mg/cm2The surface density of (a) was coated on one side on an aluminum foil and vacuum dried. And after the pole piece is rounded, a lithium piece is used as a counter electrode, the concentration of lithium hexafluorophosphate is 1.2M, the solution of DMC (DMC: EC) ═ 3:1(V/V) is used as electrolyte, and a PP diaphragm with the thickness of 20 micrometers is used for isolating the positive electrode and the negative electrode, so that the CR2025 button cell is assembled. The rate test was performed according to the following conditions:
and (3) testing temperature: 23 +/-2 ℃;
voltage range: 2.7-4.25V;
the test flow comprises the following steps:
charging: charging at 150mA/g, and stopping at 1.5mA/g constant voltage after 4.5V;
discharging: after a release of 15mA/g active substance and a cut-off after 2.7V.
Example 1
Weighing 1.89kg of battery-grade electrolytic manganese dioxide (with the purity of 92 percent, the same below), 0.635kg of battery-grade ferrous oxalate dihydrate, 2.71kg of 85 percent by weight of industrial-grade phosphoric acid and 1.77kg of purified water, adding 640g of 25 percent by weight of hydrogen peroxide under stirring, uniformly stirring, heating to maintain the temperature between 50 and 60 ℃, putting a 300W ultrasonic probe, and reacting the system under the action of ultrasonic waves. The reaction time is about 3 hours.
And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. The filtrate can beDirectly recycled, and the solid content of a filter cake is determined to be 33 percent. XRD of the filter cake is shown in figure 1 as MnPO4·H2O structure, and the chemical composition of the compound contains a crystal water determined by TG-DSC, so that the structural formula is (Mn)0.85Fe0.15)1.00PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring into a muffle furnace with oxygen, heating to 120 ℃, keeping the temperature for 3 hours to evaporate water, heating to 350 ℃ at the speed of 3 ℃/min, and keeping the temperature for 10 hours. The final product has an amorphous precursor material with XRD shown in FIG. 2, SEM shown in FIG. 3, and chemical composition of (Mn)0.85Fe0.15)1.00PO4。
1.5kg of precursor material was weighed, 2kg of purified water was added, 0.370kg (1.00 times stoichiometric ratio) of battery grade lithium carbonate and 110g of food grade glucose were added under stirring, and the mixture was sanded by a sand mill. During sanding, a 50% aqueous solution of ammonium polyacrylate, amounting to about 100g, is suitably added as the viscosity increases. Finally, the median particle diameter D50, measured by laser particle sizer, was 0.721. mu.m, with a solids content of about 50%.
And (3) carrying out spray drying on the slurry by a centrifugal disc spray drying method to obtain a dried powder with a median particle diameter D50 of 16 um. And then transferring the obtained powder into an atmosphere furnace, heating to 400 ℃ from the normal temperature at the speed of 3 ℃/min under the nitrogen protection atmosphere, preserving heat for 5 hours, heating to 550 ℃ at the speed of 3 ℃/min, preserving heat for 5 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product.
The tap density of the product was determined to be 1.27g/cm3Specific surface area of 22m2The carbon content is 2.8 wt%, the 0.1C gram capacity of the product is 143mAh/g, and the 1C gram capacity is 135 mAh/g. The charge and discharge characteristics are shown in fig. 5.
Example 2
Weighing 1.51kg of battery-grade electrolytic manganese dioxide and 0.72kg of battery-grade ferrous oxalate dihydrate, and adding 2.33kg of 85 wt% of industrial-grade phosphoric acid; the filtrate of example 1 was taken, supplemented with purified water to a total of 3.3kg, and added to the above mixture. Adding 180g of industrial grade anhydrous oxalic acid under stirring, uniformly stirring, heating, keeping the temperature between 60 and 70 ℃, continuously stirring, and enabling the system to continuously react through a homogenizer with the rotation speed of 5000 rpm. The reaction time was about 4 hours.
And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. The filtrate is recycled. The resulting filter cake was determined to have a solids content of 38%. It was confirmed to have MnPO by XRD4·H2O structure, and the chemical composition of the compound contains a crystal water determined by TG-DSC, so that the structural formula is (Mn)0.80Fe0.20)0.99PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring into a muffle furnace with oxygen, heating to 120 ℃, keeping the temperature for 3 hours to evaporate water, heating to 350 ℃ at the speed of 3 ℃/min, and keeping the temperature for 16 hours. Finally obtaining an amorphous precursor material with the chemical composition of (Mn)0.80Fe0.20)0.99PO4。
Weighing 1.5kg of precursor material, adding 3.1kg of purified water, adding 0.428kg (1.02 times of stoichiometric ratio) of battery-grade lithium hydroxide, 107g of food-grade sucrose and 30g of food-grade anhydrous citric acid under stirring, and sanding by using a sand mill. The final median particle diameter D50, as measured by a laser particle sizer, was 0.32 μm with a solids content of about 45%.
The slurry was spray-dried by means of two-fluid spray-drying to obtain a dried powder having a median particle diameter D50 of 12 um. And transferring the obtained powder into an atmosphere furnace, heating to 350 ℃ from normal temperature at the speed of 3 ℃/min under the atmosphere of nitrogen protection, preserving heat for 5 hours, heating to 580 ℃ at the speed of 3 ℃/min, preserving heat for 8 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product. The XRD pattern is shown in FIG. 4.
The tap density of the product was determined to be 1.33g/cm3Specific surface area 19m2The carbon content is 2.4 wt%, the 0.1C gram capacity of the product is 151mAh/g, and the 1C gram capacity is 141 mAh/g.
Example 3
Weighing 1.42kg of battery-grade electrolytic manganese dioxide and 0.90kg of battery-grade ferrous oxalate dihydrate, adding 2.40kg of 85 wt% industrial-grade phosphoric acid and 4.5kg of purified water, uniformly stirring, heating to maintain the temperature between 70 and 80 ℃, continuously stirring, and enabling the system to continuously react through a homogenizer with the rotation speed of 5000 rpm. The reaction time was about 6 hours.
And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. The filtrate is recycled. The resulting filter cake was determined to have a solids content of 37%. It was confirmed to have MnPO by XRD4·H2O structure, and the chemical composition of the compound contains a crystal water determined by TG-DSC, so that the structural formula is (Mn)0.75Fe0.25)0.96PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring into a muffle furnace with oxygen, heating to 120 ℃, keeping the temperature for 4 hours to evaporate water, heating to 400 ℃ at the speed of 3 ℃/min, and keeping the temperature for 4 hours. Finally obtaining an amorphous precursor material with the chemical composition of (Mn)0.75Fe0.25)0.96PO4。
Weighing 1.5kg of precursor material, adding 3.1kg of purified water, adding 0.436kg of battery-grade lithium hydroxide (1.04 times of stoichiometric ratio), 87g of food-grade caramel and 40g of food-grade ascorbic acid under stirring, and sanding by using a sand mill. The final median particle diameter D50, as measured by laser particle sizer, was 0.54 μm with a solids content of about 40%.
And (3) carrying out spray drying on the slurry by a two-fluid spray drying method to obtain dried powder with the median particle diameter D50 of 9 um. And transferring the obtained powder into an atmosphere furnace, heating to 350 ℃ from normal temperature at the speed of 3 ℃/min under the atmosphere of nitrogen protection, preserving heat for 8 hours, heating to 650 ℃ at the speed of 3 ℃/min, preserving heat for 6 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product.
The tap density of the product was determined to be 1.27g/cm3Specific surface area 14m2The carbon content is 1.8 wt%, the 0.1C gram capacity of the product is 150mAh/g, and the 1C gram capacity is 144 mAh/g.
Example 4
Weighing 1.98kg of battery-grade electrolytic manganese dioxide and 1.62kg of battery-grade ferrous oxalate dihydrate, adding 3.60kg of 85 wt% industrial-grade phosphoric acid and 13.2kg of purified water, uniformly stirring, heating to maintain the temperature between 80 and 90 ℃, continuously stirring, and carrying out wet grinding treatment to ensure that the system continuously reacts. The reaction time was about 3 hours.
And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. The filtrate is recycled. The resulting filter cake, as determined, had a solids content of 35%. It was confirmed to have MnPO by XRD4·H2O structure, and the chemical composition of the compound contains a crystal water determined by TG-DSC, so that the structural formula is (Mn)0.70Fe0.30)0.96PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring into a muffle furnace with air, heating to 120 ℃, keeping the temperature for 4 hours to evaporate water, heating to 450 ℃ at the speed of 3 ℃/min, and keeping the temperature for 6 hours. Finally obtaining an amorphous precursor material with the chemical composition of (Mn)0.70Fe0.30)0.96PO4。
2.25kg of precursor material was weighed, 5.3kg of purified water was added, 0.661kg (1.05 times stoichiometric ratio) of battery grade lithium hydroxide, 88g of water-soluble phenolic resin and 80g of 50% aqueous ammonium polyacrylate solution were added with stirring, and the mixture was sanded by a sand mill. The final median particle diameter D50, as measured by laser particle sizer, was 0.45 μm with a solids content of about 37%.
And (3) carrying out spray drying on the slurry by a two-fluid spray drying method to obtain a dried powder with the median particle diameter D50 of 11 um. And transferring the obtained powder into an atmosphere furnace, heating to 350 ℃ from normal temperature at the speed of 3 ℃/min under the atmosphere of nitrogen protection, preserving heat for 5 hours, heating to 680 ℃ at the speed of 3 ℃/min, preserving heat for 8 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product.
The tap density of the product was determined to be 1.39g/cm3Specific surface area 11.7m2The carbon content is 1.9 wt%, the 0.1C gram capacity of the product is 154mAh/g, and the 1C gram capacityThe amount was 150 mAh/g.
Example 5
Weighing 1.76kg of battery-grade electrolytic manganese dioxide and 1.80kg of battery-grade ferrous oxalate dihydrate, adding 3.40kg of 85 wt% industrial-grade phosphoric acid and 8.39kg of purified water, uniformly stirring, heating to maintain the temperature between 70 and 80 ℃, continuously stirring, and carrying out wet grinding treatment to ensure that the system continuously reacts. The reaction time was about 3 hours.
And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. The filtrate is recycled. The resulting filter cake, as determined, had a solids content of 35%. It was confirmed to have MnPO by XRD4·H2O structure, and the chemical composition of the compound contains a crystal water determined by TG-DSC, so that the structural formula is (Mn)0.65Fe0.35)0.97PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring into a muffle furnace with air, heating to 120 ℃, keeping the temperature for 4 hours to evaporate water, heating to 450 ℃ at the speed of 3 ℃/min, and keeping the temperature for 5 hours. Finally obtaining an amorphous precursor material with the chemical composition of (Mn)0.65Fe0.35)0.97PO4。
2.25kg of precursor material was weighed, 5.3kg of purified water was added, 0.661kg (1.05 times stoichiometric ratio) of battery grade lithium hydroxide, 99g of food grade lactose, 80g of 50% aqueous ammonium polyacrylate solution were added with stirring, and the mixture was sanded by a sand mill. The final median particle diameter D50, as measured by laser particle sizer, was 0.43 μm with a solids content of about 34%.
And carrying out spray drying on the slurry by a two-fluid spray drying method to obtain a dried powder with the median particle diameter D50 of 10 um. And transferring the obtained powder into an atmosphere furnace, heating to 350 ℃ from normal temperature at the speed of 3 ℃/min under the atmosphere of nitrogen protection, preserving heat for 5 hours, heating to 700 ℃ at the speed of 3 ℃/min, preserving heat for 8 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product.
The tap density of the product was determined to be 1.38g/cm3Specific surface area 9.8m2Per g, carbon content 1.6%wt, the 0.1C gram capacity of the product is 153mAh/g, and the 1C gram capacity is 147 mAh/g.
Example 6
Weighing 1.70kg of battery-grade electrolytic manganese dioxide and 2.16kg of battery-grade ferrous oxalate dihydrate, adding 3.60kg of 85 wt% industrial-grade phosphoric acid and 11.7kg of purified water, uniformly stirring, heating to maintain the temperature between 70 and 80 ℃, continuously stirring, and carrying out wet grinding treatment to ensure that the system continuously reacts. The reaction time was about 3 hours.
And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. The filtrate is recycled. The resulting filter cake, as determined, had a solids content of 27%. It was confirmed to have MnPO by XRD4·H2O structure, and the chemical composition of the compound contains a crystal water determined by TG-DSC, so that the structural formula is (Mn)0.60Fe0.40)0.97PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring into a muffle furnace with air, heating to 120 ℃, keeping the temperature for 4 hours to evaporate water, heating to 400 ℃ at the speed of 3 ℃/min, and keeping the temperature for 10 hours. Finally obtaining an amorphous precursor material with the chemical composition of (Mn)0.60Fe0.40)0.97PO4。
Weighing 2.25kg of precursor material, adding 5.2kg of purified water, adding 0.661kg of battery grade lithium hydroxide (1.05 times of stoichiometric ratio), 99g of coating grade ethyl cellulose and 50g of food grade anhydrous citric acid water under stirring, and sanding by a sand mill. The final median particle diameter D50, as determined by laser granulometry, was 0.32 μm with a solids content of about 37%.
And (3) carrying out spray drying on the slurry by a two-fluid spray drying method to obtain a dried powder with the median particle diameter D50 of 11 um. And transferring the obtained powder into an atmosphere furnace, heating to 400 ℃ from normal temperature at the speed of 3 ℃/min under the atmosphere of nitrogen protection, preserving heat for 5 hours, heating to 720 ℃ at the speed of 3 ℃/min, preserving heat for 12 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product.
The tap density of the product was determined to be 1.40g/cm3Specific surface area 7.9m2The carbon content is 1.3 percent by weight, the 0.1C gram capacity of the product is 149mAh/g, and the 1C gram capacity is 144 mAh/g.
Example 7
Weighing 2.08kg of battery-grade electrolytic manganese dioxide and 3.24kg of battery-grade ferrous oxalate dihydrate, adding 4.70kg of 85 wt% industrial-grade phosphoric acid and 21.3kg of purified water, uniformly stirring, heating to maintain the temperature between 70 and 80 ℃, continuously stirring, and carrying out wet grinding treatment to ensure that the system continuously reacts. The reaction time was about 3 hours.
And cooling the reaction liquid, filtering, and collecting filtrate and filter cake. The filtrate is recycled. The resulting filter cake, as determined, had a solids content of 22%. It was confirmed to have MnPO by XRD4·H2O structure, and the chemical composition of the compound contains a crystal water determined by TG-DSC, so that the structural formula is (Mn)0.55Fe0.45)0.98PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring into a muffle furnace with air, heating to 120 ℃, keeping the temperature for 4 hours to evaporate water, heating to 400 ℃ at the speed of 3 ℃/min, and keeping the temperature for 14 hours. Finally obtaining an amorphous precursor material with the chemical composition of (Mn)0.55Fe0.45)0.98PO4。
3.00kg of precursor material was weighed, 9.85kg of purified water was added, 0.881kg (1.05 times stoichiometric ratio) of battery grade lithium hydroxide, 88g of food grade sucrose and 50g of food grade anhydrous citric acid water were added under stirring, and the mixture was sanded by a sand mill. The final median particle diameter D50, as measured by laser particle sizer, was 0.29 μm with a solids content of about 29%.
And (3) carrying out spray drying on the slurry by a two-fluid spray drying method to obtain a dried powder with the median particle diameter D50 of 11 um. And transferring the obtained powder into an atmosphere furnace, heating to 400 ℃ from normal temperature at the speed of 3 ℃/min under the atmosphere of nitrogen protection, preserving heat for 5 hours, heating to 750 ℃ at the speed of 3 ℃/min, preserving heat for 12 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product.
The tap density of the product was determined to be 1.45g/cm3Specific surface area of 6.2m2The carbon content is 1.1 percent by weight, the 0.1C gram capacity of the product is 147mAh/g, and the 1C gram capacity is 133 mAh/g. The charge and discharge characteristics are shown in fig. 6.
Comparative example 1(without muffle furnace Heat treatment)
The procedure of example 1 was repeated to obtain a precursor cake comprising mainly (Mn)0.85Fe0.15)1.00PO4·H2O。
Spreading the filter cake in a ceramic sagger, transferring the ceramic sagger into a muffle furnace with oxygen, heating to 120 ℃, and preserving the temperature for 3 hours to evaporate water.
1.5kg of precursor material was weighed, 2kg of purified water was added, 0.370kg (1.00 times stoichiometric ratio) of battery grade lithium carbonate and 110g of food grade glucose were added under stirring, and the mixture was sanded by a sand mill. During sanding, a 50% aqueous solution of ammonium polyacrylate, amounting to about 100g, is suitably added as the viscosity increases. Finally, the median particle diameter D50, measured by laser particle sizer, was 0.721. mu.m, with a solids content of about 50%.
And (3) carrying out spray drying on the slurry by a centrifugal disc spray drying method to obtain a dried powder with a median particle diameter D50 of 16 um. And then transferring the obtained powder into an atmosphere furnace, heating to 400 ℃ from the normal temperature at the speed of 3 ℃/min under the nitrogen protection atmosphere, preserving heat for 5 hours, heating to 550 ℃ at the speed of 3 ℃/min, preserving heat for 5 hours, naturally cooling, and sieving by a 200-mesh sieve to obtain the product.
The product is non-pure-phase lithium manganese iron phosphate, the capacity of 0.1C gram is 102mAh/g, and the product is non-pure-phase lithium manganese iron phosphate with manganese pyrophosphate Mn2P2O7The charge-discharge diagram of the hetero-phase is shown in FIG. 7, and the XRD diagram thereof is shown in FIG. 8.

Claims (10)

1. An amorphous iron manganese phosphate powder having the general formula:
(Mn1-xFex)aPO4，
wherein: x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
it is prepared by the following method:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200 to 500 ℃ to obtain amorphous (Mn)1-xFex)aPO4And (3) powder.
2. A process for the preparation of amorphous iron manganese phosphate powders having the general formula:
(Mn1-xFex)aPO4，
wherein: x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
it includes:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200 to 500 ℃ to obtain amorphous (Mn)1-xFex)aPO4And (3) powder.
3. The amorphous iron manganese phosphate powder of claim 1 or the process of claim 2, characterized in that 0.18. ltoreq. x.ltoreq.0.42, more preferably 0.22. ltoreq. x.ltoreq.0.38, preferably 0.25. ltoreq. x.ltoreq.0.35, preferably 0.28. ltoreq. x.ltoreq.0.32; a is more than or equal to 0.96 and less than or equal to 1, and more preferably more than or equal to 0.97 and less than or equal to 0.99.
4. The amorphous iron manganese phosphate powder of claim 1 or the process of claim 2 wherein said reducing agent is selected from the group consisting of hydrogen peroxide, oxalic acid, ascorbic acid or mixtures thereof.
5. The amorphous iron manganese phosphate powder of claim 1 or the process of claim 2 wherein the filter cake is heat treated at a temperature of 250 to 480 ℃, preferably 300 to 450 ℃, preferably 350 to 420 ℃; the treatment time is 1 to 24 hours, preferably 2 to 18 hours, more preferably 3 to 12 hours, further preferably 4 to 8 hours.
6. An amorphous lithium iron manganese phosphate having the general formula:
Li(Mn1-xFex)aPO4/kC；
wherein x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
k is the content of carbon accounting for the total weight of the amorphous lithium manganese iron phosphate, and is 0.5 to 4 weight percent;
the amorphous lithium manganese iron phosphate is prepared by the following method:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200 to 500 ℃ to obtain amorphous (Mn)1-xFex)aPO4Powder;
grinding stoichiometric amounts of the amorphous powder, lithium source and carbon source to obtain D50Particles of 0.1 to 2 microns; followed by firing.
7. A method for preparing amorphous lithium manganese iron phosphate with the following general formula:
Li(Mn1-xFex)aPO4/kC；
wherein x is more than or equal to 0.15 and less than or equal to 0.45, and a is more than or equal to 0.95 and less than or equal to 1;
k is the content of carbon accounting for the total weight of the amorphous lithium manganese iron phosphate, and is 0.5 to 4 weight percent;
it includes:
reacting stoichiometric amounts of manganese dioxide, ferrous oxalate and phosphoric acid in the presence of a reducing agent to obtain a reaction mixture;
filtering to obtain a filter cake containing (Mn) as the main component1-xFex)aPO4·H2O crystals;
heat-treating the crystal at a temperature of 200 to 500 ℃ to obtain amorphous (Mn)1-xFex)aPO4Powder;
grinding stoichiometric amounts of the amorphous powder, lithium source and carbon source to obtain D50Particles of 0.1 to 2 microns; followed by firing.
8. The amorphous lithium iron manganese phosphate of claim 6 or the method of claim 7, wherein said step of milling stoichiometric amounts of said amorphous powder, lithium source and carbon source comprises:
weighing a lithium source and the amorphous manganese iron phosphate powder according to a stoichiometric amount, adding water to prepare a suspension, and adding a dispersing agent and an organic carbon source;
the dispersant is selected from polyacrylic acid and its derivatives, ascorbic acid, citric acid or their mixture.
9. The amorphous lithium iron manganese phosphate of claim 6 or the method of claim 7, wherein:
the temperature for heat treatment of the filter cake is 250-480 ℃, preferably 300-450 ℃, and preferably 350-420 ℃; the treatment time is 1 to 24 hours, preferably 2 to 18 hours, more preferably 3 to 12 hours, preferably 4 to 8 hours;
the roasting is carried out in an inert atmosphere, and the roasting temperature is 550-800 ℃, preferably 600-750 ℃; the calcination time is between 1 and 12 hours, preferably 1 to 6 hours.
10. The amorphous lithium iron manganese phosphate or the method as claimed in claim 9, wherein the baking is performed by raising the temperature from room temperature to 450 ℃ at a rate of 1-5 ℃/min, preferably 2-4 ℃/min, preferably 380 ℃ to 420 ℃, keeping the temperature for 3-6 hours, raising the temperature to 800 ℃ at a rate of 1-5 ℃/min, preferably 600 ℃ to 750 ℃, keeping the temperature for 3-6 hours, and naturally cooling.
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