CN113148969B - Doped lithium iron manganese phosphate-carbon composite material and preparation method thereof - Google Patents

Doped lithium iron manganese phosphate-carbon composite material and preparation method thereof Download PDF

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CN113148969B
CN113148969B CN202110375629.4A CN202110375629A CN113148969B CN 113148969 B CN113148969 B CN 113148969B CN 202110375629 A CN202110375629 A CN 202110375629A CN 113148969 B CN113148969 B CN 113148969B
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manganese
doped
lithium
phosphate
composite material
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CN113148969A (en
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马寅
龚政
吕佳乐
郭永楠
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Jiangsu Lithitech Co ltd
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    • C—CHEMISTRY; METALLURGY
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/625—Carbon or graphite
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a doped lithium iron manganese phosphate-carbon composite material and a preparation method thereof. The method comprises the following steps: (1) preparing pre-doped manganese oxalate; (2) Adding an iron source, a lithium source, a phosphorus source, an organic carbon source and the pre-doped manganese oxalate into water, and mixing and grinding to obtain precursor slurry; (3) Drying and granulating the precursor slurry to obtain precursor powder; (4) Sintering the precursor powder under a protective atmosphere to obtain a sintered material; (5) And crushing the sintered material to obtain the doped lithium iron manganese phosphate-carbon composite material. The preparation method has simple process, and the prepared composite material has high specific capacity, excellent cycle performance and better rate performance.

Description

Doped lithium iron manganese phosphate-carbon composite material and preparation method thereof
Technical Field
The invention relates to a positive active material and a preparation method thereof, in particular to a doped lithium iron manganese phosphate-carbon composite material and a preparation method thereof.
Background
The lithium ion battery is one of common chemical power sources, has the advantages of high specific energy, high specific power, long cycle life, no memory effect and the like, and is an ideal power source for electric vehicles, digital products and various electric tools.
Lithium manganese iron phosphate is a positive electrode active material for lithium ion batteries. Like lithium iron phosphate, lithium manganese iron phosphate also belongs to a phosphate-based positive active material, and has the advantages of good cycle performance, excellent safety performance, environmental friendliness and the like. Common synthesis methods of lithium iron manganese phosphate include a high-temperature solid phase method, a hydrothermal method, a sol-gel method and the like. However, in the synthesis and preparation processes, the high-quality lithium iron manganese phosphate has higher control requirements on the aspects of the types of raw materials, the composition of precursors, the proportion of key elements, the preparation method, process parameters and the like. The main approaches for improving the performance of the material are to realize the nanoscale of active particles, increase the specific surface area of reactants, modify the material by doping, strengthen the uniformity of carbon coating and the like, and finally achieve the purposes of improving the conductivity, the lithium ion conductivity and the electrochemical performance of the material.
Chinese patent application CN102769131a discloses a method for preparing a doped lithium iron manganese phosphate-carbon composite material. The method takes ammonium dihydrogen phosphate, a lithium source, a manganese source, an iron source, a carbon source and a doped metal element compound as raw materials, and obtains the doped lithium iron manganese phosphate-carbon composite material after the process steps of mixing, high-speed ball milling, drying and high-temperature sintering. The doped lithium iron manganese phosphate-carbon composite material has a specific discharge capacity of 142 mAh.g under a discharge rate of 0.1C -1 。
From the view point of the preparation method, the basic preparation idea is to directly mix the lithium source, the manganese source, the iron source, the phosphorus source, the carbon source and the compound containing the doping elements, and then obtain the doped lithium iron manganese phosphate-carbon composite material through the process steps of grinding, drying, sintering and the like. Such methods have a problem in that it is difficult to obtain a uniform mixture of elemental compositions by simultaneously mixing a plurality of raw materials. Such mixing processes are generally solid-liquid mixing processes in which a plurality of solid phases are simultaneously dispersed in a liquid phase. Particularly, the doping element compound with lower component is easy to adsorb or react on the surface of other solid phase raw materials, which causes the problem of uneven distribution of the doping element. Further, the electrochemical performance of the obtained composite material is low.
Disclosure of Invention
Technical problem
In order to solve the problems in the existing preparation method, the invention aims to provide a novel method for preparing a doped lithium iron manganese phosphate-carbon composite material, and the obtained composite material has high specific capacity, excellent cycle performance and better rate performance.
Another object of the present invention is to provide a doped lithium iron manganese phosphate-carbon composite material prepared by the above method.
It is still another object of the present invention to provide a positive electrode active material comprising the above composite material, a positive electrode comprising the positive electrode active material, and a lithium ion battery comprising the positive electrode.
Technical scheme
According to an aspect of the present invention, there is provided a method of preparing a doped lithium iron manganese phosphate-carbon composite material, the method comprising the steps of:
(1) Preparation of Pre-doped manganese oxalate
1a, mixing a manganese source and a doping agent containing doping elements to obtain mixed powder;
1b, dissolving oxalic acid in water to obtain an oxalic acid solution;
1c, adding the mixed powder into the oxalic acid solution for reaction to obtain a manganese oxalate suspension containing doped elements;
1d, filtering and drying the manganese oxalate suspension to obtain pre-doped manganese oxalate;
(2) Adding an iron source, a lithium source, a phosphorus source, an organic carbon source and the pre-doped manganese oxalate into water, and mixing and grinding to obtain precursor slurry;
(3) Drying and granulating the precursor slurry to obtain precursor powder;
(4) Sintering the precursor powder under a protective atmosphere to obtain a sintered material;
(5) And crushing the sintered material to obtain the doped lithium iron manganese phosphate-carbon composite material.
According to another aspect of the invention, a doped lithium iron manganese phosphate-carbon composite material is provided, wherein the composite material is prepared by the method.
According to another aspect of the present invention, there is provided a positive electrode active material comprising the above composite material, a positive electrode comprising the positive electrode active material, and a lithium ion battery comprising the positive electrode.
Advantageous effects
Compared with the prior art, the preparation method of the invention mixes the manganese source and the doping agent in advance, and reacts with oxalic acid to obtain the pre-doped manganese oxalate as an intermediate product; and then adding an iron source, a lithium source, a phosphorus source and a carbon source, and carrying out the process steps of mixing, grinding, drying, granulating, sintering, crushing and the like to obtain the doped lithium iron manganese phosphate-carbon composite material.
Compared with the doped lithium iron manganese phosphate-carbon composite material prepared by the conventional technology, the composite material prepared by the invention has the advantages of high specific capacity, excellent cycle performance and better rate capability.
The preparation method of the invention has the following advantages:
(1) When the pre-doped manganese oxalate is prepared, high-salinity wastewater cannot be generated. Manganese oxalate is conventionally prepared by a precipitation reaction of a soluble divalent manganese salt, such as manganese sulfate, with an oxalate to produce manganese oxalate and by-product another soluble salt, thereby producing high-salinity wastewater. In the invention, when manganese dioxide, manganese hydroxide and manganese carbonate are used as manganese sources and react with the oxalic acid solution, the generated by-product is carbon dioxide or water, so that a large amount of by-products cannot be generated in a liquid phase, and the problem that how to treat high-salinity wastewater needs to be considered in the conventional preparation method does not exist.
(2) The manganese oxalate is not easy to agglomerate in the sintering process, and the formation of an impurity phase is avoided. The oxalate has coordination complexing action and reducibility, can reduce the microscopic scale of reactant particles, improve the specific surface area and activity of the reactant, and avoid the oxidation of divalent manganese ions. Moreover, oxalate is converted into conductive carbon and carbon dioxide gas, and thus, impurities are not left in the product.
(3) The doping elements are uniformly distributed, and the doping effect is better. The invention pre-dopes manganese oxalate in solution phase; in the reaction process, manganese element and doping elements in the doping agent react with oxalate to form manganese oxalate precipitate containing the doping elements, so that the doping elements and the manganese element can be premixed, local agglomeration of the doping elements is avoided, and the doping effect is improved.
(4) Wide raw material source and low cost. The raw materials used in the invention are common inorganic chemical raw materials, the market price is low and stable, and the raw materials can be used for preparing the pre-doped manganese oxalate and further preparing the doped lithium iron manganese phosphate-carbon composite material, so that the raw material cost can be reduced.
In addition, the preparation method has simple process and the obtained composite material has better comprehensive performance.
Drawings
The drawings of the present specification show preferred embodiments of the present invention and together with the above summary of the invention serve to further clarify the technical idea of the present invention, and therefore the present invention should not be construed as being limited to the contents described in the drawings.
FIG. 1 is a process flow diagram for the preparation of pre-doped manganese oxalate in accordance with one embodiment of the present invention;
FIG. 2 is a process flow diagram for preparing a doped lithium iron manganese phosphate-carbon composite according to one embodiment of the present invention;
FIG. 3 is an SEM photograph of pre-doped manganese oxalate obtained in example 1;
fig. 4 is an XRD spectrum of the pre-doped manganese oxalate obtained in example 1.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. It should be understood that the terms or words used in the specification and claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation.
As used herein, "%" means weight percent unless otherwise specified. In addition, detailed descriptions thereof will be omitted with respect to processes and components well known in the art.
1. Method for preparing doped lithium iron manganese phosphate-carbon composite material
According to an aspect of the present invention, referring to fig. 1 and 2, a method of preparing a lithium iron manganese phosphate-carbon composite material includes the following steps.
Step (1) preparation of pre-doped manganese oxalate
Referring to fig. 1, the step (1) includes the following steps 1a, 1b, 1c and 1d.
1a, mixing a manganese source and a doping agent containing a doping element to obtain mixed powder.
The manganese source may be in the form of a powder. The manganese source may include one or a combination of elemental manganese, manganese monoxide, trimanganese tetroxide, manganese dioxide, manganese hydroxide, manganese carbonate, manganese chloride, manganese nitrate and manganese sulfate, but is not limited thereto. Preferably, the manganese source is manganese dioxide, manganese hydroxide, manganese carbonate or a combination thereof.
The doping element may include one or a combination of titanium, magnesium, aluminum, zinc, cobalt, nickel, tin, niobium, tungsten, zirconium, tantalum, cerium, europium, fluorine, but is not limited thereto.
The dopant may include one or a combination of sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide, etc. containing the doping element, but is not limited thereto.
Doping refers to doping one or more metal and nonmetal elements into the anode material, so as to stabilize the crystal structure of the anode material, promote the transmission of lithium ions and electrons, and improve the electrical property of the material. In particular, the invention selects the element pre-doping of the manganese oxalate, so that the doping elements can be uniformly distributed in the manganese oxalate. Furthermore, in the subsequent sintering process of the lithium iron manganese phosphate precursor powder, the doping elements can uniformly enter the crystal structure of the anode material, so that the doping elements and the reactant are mixed for many times, and the problems of nonuniform doping and impurity formation caused by agglomeration of the doping elements can be effectively solved.
In the mixed powder, the mole percent ratio of the doping element to the manganese element can be 0.001-10.0%,
with the increase of the proportion of the doping elements in the cathode material, the improvement effect of the doping elements is gradually reduced, and particularly, the specific capacity of the cathode material is reduced after excessive addition of some doping elements because some doping elements do not participate in electrochemical reaction. Therefore, the molar percentage ratio of the doping element to the manganese element is preferably 0.01% to 8.0%, more preferably 0.05% to 5.0%, most preferably 0.1% to 3.0%, still more preferably 0.5% to 1.0%, and 1.5% to 2.5%.
Dissolving oxalic acid in water to obtain oxalic acid solution.
The water may be pure water, deionized water, etc.
First, water may be heated to 20 ℃ to 90 ℃, preferably 40 ℃ to 80 ℃, more preferably 50 ℃ to 70 ℃.
Then, oxalic acid is added into water, stirred and dissolved to obtain an oxalic acid solution. The mass fraction of the solute in the oxalic acid solution can be 5.0-60%, preferably 20-50%, and more preferably 30-40%.
The temperature during the oxalic acid dissolution process is maintained at the temperature of water, i.e. 20 ℃ to 90 ℃, preferably 40 ℃ to 80 ℃, more preferably 50 ℃ to 70 ℃.
The solubility of oxalic acid increases with the temperature of the solvent water, and the oxalic acid dissolution process is an endothermic process. The oxalic acid is dissolved by keeping higher water temperature, so that the solubility and the dissolution rate of the oxalic acid in the water can be improved, and the oxalic acid solution with higher concentration can be obtained. In addition, the oxalic acid solution with higher temperature and concentration has stronger reducibility, and the reduction reaction can be rapidly and completely carried out when the oxalic acid solution reacts with a manganese source with the valence of more than two, thereby improving the production efficiency.
And 1c, adding the mixed powder into an oxalic acid solution for reaction to obtain a manganese oxalate suspension containing the doping elements.
Oxalic acid is not only a precipitant but also a reducing agent in the reaction process. By utilizing the characteristics of oxalic acid, the manganese element with more than two valences is firstly reduced into bivalent manganese ions by oxalic acid, and carbon dioxide is generated at the same time; and the divalent manganese ions continue to perform precipitation reaction with oxalate ions to generate the manganese oxalate. In addition, in the process of generating the manganese oxalate, the doping agent containing the doping element also simultaneously generates precipitation reaction with oxalate, and by utilizing the reaction process, the doping element can enter the interior of manganese oxalate crystal grains to obtain manganese oxalate suspension containing the doping element. Finally, the aim of pre-doping the manganese oxalate while preparing the manganese oxalate is fulfilled.
According to the valence state of manganese element in the mixed powder material, the ratio of the total mole number of oxalic acid and manganese ion as reactants can be determined to be (2.2-1.0): 1.0.
The reaction temperature may be 20 to 90 ℃, preferably 40 to 80 ℃, and more preferably 50 to 70 ℃.
And 1d, filtering and drying the manganese oxalate suspension to obtain the pre-doped manganese oxalate.
The process is a conventional procedure. Firstly, filtering the manganese oxalate turbid liquid, and primarily realizing solid-liquid separation to obtain a filter cake. Then, the filter cake is further dried to obtain the pre-doped manganese oxalate.
The filtering equipment can be a centrifuge, a plate-and-frame filter press, a leaf filter and the like.
The drying equipment can be a double-cone dryer, a hot air drying box, a disc dryer and the like.
Because the manganese oxalate dihydrate is stable in chemical composition, not easy to absorb moisture or deteriorate and suitable for long-term storage, and the anhydrous manganese oxalate is easy to absorb moisture when exposed to humid air, the pre-doped manganese oxalate prepared and used in the invention is also a dihydrate in consideration of convenience in production and use, but is not limited thereto.
In order to improve the production efficiency of the drying process, the drying temperature may be 50 to 150 ℃, preferably 70 to 130 ℃, more preferably 90 to 110 ℃.
The drying time is not particularly limited and may be determined according to the form of the particular drying apparatus, and may be generally 1.0h to 1.5h.
Step (2) preparation of precursor slurry
Adding an iron source, a lithium source, a phosphorus source, an organic carbon source and the pre-doped manganese oxalate into water according to the proportion that the total mole number of lithium, manganese, iron and phosphorus Li (Mn + Fe) is (0.8-1.2) to P is (0.8-1.2) to (0.8-1.2), mixing and grinding to obtain precursor slurry; the mixing and grinding equipment can be a shearing machine, a ball mill, a sand mill and the like.
The iron source may include one of elemental iron, ferrous oxide, ferric phosphate, ferrous oxalate, ferrous carbonate, or a combination thereof, but is not limited thereto.
The lithium source may include one of lithium carbonate, lithium hydroxide, lithium phosphate, lithium dihydrogen phosphate, or a combination thereof, but is not limited thereto.
The phosphorus source may include one or a combination of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, and phosphoric acid, but is not limited thereto.
The organic carbon source may include one of starch, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, cyclodextrin, citric acid, oxalic acid, xylitol, or a combination thereof, but is not limited thereto.
Wherein, in order to obtain reactant particles close to or reaching the nanometer level, increase the contact area of the reactant particles and reduce the reaction scale, the particle size range of the ground particles can be controlled as the particle size D 50 Is 0.5 to 15.0. Mu.m, preferably 1.0 to 8.0. Mu.m, more preferably 2.0 to 5.0. Mu.m.
Step (3) drying granulation
And drying and granulating the precursor slurry, and removing water in the slurry to obtain precursor powder. The process is a conventional operation step in which a solid or solute-containing material is atomized into fine droplets and then instantaneously contacted with a hot gas stream, and the moisture in the droplets is evaporated and removed by the hot gas stream to obtain dry small solid particles.
The temperature for drying and granulating may be 100 to 300 ℃, preferably 120 to 280 ℃, and more preferably 150 to 250 ℃.
Conventional drying and granulating equipment such as a spray dryer can be used. Atomization forms of the spray dryer may include centrifugal atomization, ultrasonic atomization, air-stream water-jet atomization, or pressure atomization.
Step (4) sintering
Sintering the lithium iron manganese phosphate precursor powder under an anaerobic protective atmosphere to obtain a sintered material.
Wherein, the sintering equipment can be a rotary furnace, a pushed slab kiln or a roller kiln, etc.; the protective atmosphere may be one of nitrogen, argon, or a combination thereof. The sintering temperature may be 300 ℃ to 800 ℃, preferably 400 ℃ to 700 ℃, more preferably 500 ℃ to 650 ℃. The sintering time may be 6 to 20 hours, preferably 8 to 16 hours, and more preferably 10 to 14 hours.
The sintering form can be divided into one-stage sintering or multi-stage sintering, and preferably two-stage sintering.
Step (5) pulverization
And crushing the sintered material to obtain the lithium iron manganese phosphate-carbon composite material.
The sintered material has the phenomena of particle agglomeration, excessive internal pores, irregular shape and overlarge particle size. The purpose of the comminution is to bring the particle size to uniformity. Therefore, on one hand, the tap density and the compaction density of the positive electrode active material can be increased, and on the other hand, when the crushed positive electrode active material is used as a positive electrode of a lithium ion battery, the risk that irregular large particles in the positive electrode active material pierce through a diaphragm to cause internal short circuit of the battery can be reduced.
The pulverization operation may be carried out using a jet mill.
The granularity range of the crushed lithium iron manganese phosphate-carbon composite material can be controlled as follows, and the granularity D 50 0.5-15.0 μm; preferably 1.0 to 8.0 μm; more preferably 2.0 to 5.0. Mu.m.
In the doped lithium iron manganese phosphate-carbon composite material,
the molar ratio of Mn to Fe can be z (1-z), wherein z is more than or equal to 0.6 and less than 1;
the total molar ratio of lithium, manganese, iron and phosphorus Li (Mn + Fe) to P may be (0.8-1.2) to 1.0 (0.8-1.2);
based on the total mass of the doped lithium iron manganese phosphate-carbon composite material, the carbon content of the doped lithium iron manganese phosphate-carbon composite material can be 1.0-10.0%, preferably 1.2-5.0%, and more preferably 1.5-2.5%.
The total mole percentage of the doping element in the manganese element can be 0.001-10.0%.
2. Doped lithium iron manganese phosphate-carbon composite material
According to another aspect of the present invention, the present invention provides a doped lithium iron manganese phosphate-carbon composite material, wherein the doped lithium iron manganese phosphate-carbon composite material is prepared by the above method.
3. Positive electrode active material, positive electrode, and lithium ion battery
According to another aspect of the present invention, there is provided a positive electrode active material comprising the above-described doped lithium iron manganese phosphate-carbon composite material.
According to another aspect of the present invention, there is provided a positive electrode comprising the above positive electrode active material. The positive electrode may further comprise a common current collector.
According to another aspect of the present invention, the present invention provides a lithium ion battery comprising a positive electrode, the positive electrode comprising the above positive electrode active material, and the positive electrode further comprising a conductive agent, a binder, and an aluminum foil. They may be materials commonly used in the art.
In addition, the lithium ion battery may further include an anode including a current collector, an anode active material, a conductive agent, a binder, etc., a separator, an electrolyte, a tab, a battery case, etc. They may be materials commonly used in the art.
In addition, the preparation process of the lithium ion battery comprises the common process steps of size mixing, coating, drying, rolling, cutting, laminating or winding, battery assembly, liquid injection, battery sealing and the like.
Examples
Hereinafter, the present invention will be described in detail with reference to examples to specifically describe the present invention. However, the embodiment of the present invention may be modified into various other forms and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the invention to those of ordinary skill in the art.
The experimental procedures in the following examples and comparative examples are generally conventional in the art or according to the manufacturer's recommendations if specific conditions are not noted; the raw materials and equipment used are those commercially available from conventional markets and the like unless otherwise specified.
Example 1
The doped lithium iron manganese phosphate-carbon composite material is prepared by the following steps.
(1) Preparation of Pre-doped manganese oxalate
1a 32.11kg of manganese carbonate (manganese source) and 0.67kg of magnesium sulfate (dopant) were added to a mixer in such an amount that the mole percent ratio of the doping element magnesium to manganese element was 2.0%, and sufficiently mixed to preliminarily disperse the magnesium sulfate in the manganese carbonate to obtain a mixed powder.
1b, heating 86.28kg of pure water to about 60 ℃ in a reaction kettle, and preserving heat; and adding 36.98kg oxalic acid dihydrate into the pure water, and fully stirring and dissolving to obtain an oxalic acid solution with the solute mass fraction of about 30%.
1c, keeping the temperature of the oxalic acid solution at about 60 ℃, adding the mixed powder obtained in the step 1a into the oxalic acid solution, and stirring for reaction; and after the addition is finished, continuously stirring for 2.0 hours to ensure that the materials fully react until no bubbles are generated, thereby obtaining the magnesium element doped manganese oxalate suspension.
And 1d, filtering and dehydrating the manganese oxalate turbid liquid in a centrifugal machine until no filtrate flows out of a water outlet. And then drying by a double-cone dryer at the drying temperature of 120 ℃ for about 1.0 h. And then naturally cooling, and discharging when the temperature of the material is lower than 50 ℃ to obtain the pre-doped manganese oxalate.
(2) 50.00kg of the above-mentioned pre-doped manganese oxalate, 21.58kg of ferrous carbonate, 18.06kg of lithium carbonate, 54.63kg of ammonium dihydrogen phosphate and 8.78kg of glucose were added together to 612.18kg of pure water, stirred and mixed uniformly, and ground in a sand mill to obtain a particle size D 50 About 2.5 μm, a precursor slurry was obtained.
(3) And (3) drying and granulating the precursor slurry in centrifugal spray drying equipment, and controlling the heating temperature of an air inlet of the equipment to be 260 ℃ and the temperature of an air outlet of the equipment to be 120 ℃ to obtain precursor powder.
(4) The precursor powder was sintered in a rotary furnace in a nitrogen atmosphere. Sintering is carried out in two stages, the working temperature of the first stage is 400 ℃, and the material retention time is 6.0h; the second stage has a working temperature of 700 ℃ and a material retention time of 15.0h. And then naturally cooling, and discharging when the temperature of the material is reduced to about 50 ℃ to obtain the sintered material.
(5) And crushing the sintered material in a jet mill to obtain the doped lithium iron manganese phosphate-carbon composite material.
Comparative example 1
The doped lithium iron manganese phosphate-carbon composite material is prepared basically according to the process steps of the embodiment 1, except that:
(i) In the preparation process of the manganese oxalate, pre-doping is not carried out, but the conventional manganese oxalate is obtained as an intermediate product;
(ii) The doping was performed in step (2) using magnesium sulfate as a dopant, and the amount of the doping element added was the same as in example 1.
The preparation process of comparative example 1 includes the following steps.
(1) Preparation of conventional manganese oxalate
1a 32.11kg of manganese carbonate (manganese source) was prepared.
1b As in step 1b of example 1, an oxalic acid solution having a solute mass fraction of about 30% was obtained.
1c, keeping the temperature of the oxalic acid solution at about 60 ℃, adding 32.11kg of manganese carbonate into the oxalic acid solution, and stirring for reaction; and when the feeding is finished, continuously stirring for 2 hours to ensure that the materials fully react until no bubbles are generated, thereby obtaining the manganese oxalate suspension without doping elements.
1d conventional manganese oxalate was obtained in the same manner as in step 1d of example 1.
(2) 50.00kg of the above-mentioned conventional manganese oxalate, 0.67kg of magnesium sulfate (dopant), 21.58kg of ferrous carbonate, 18.06kg of lithium carbonate, 54.63kg of ammonium dihydrogen phosphate and 8.78kg of glucose were added together in such an amount that the molar percentage of the doping elements magnesium and manganese was 2.0%, to pure water, stirred and mixed uniformly, and ground in a sand mill to give a particulate matter having a particle size D 50 About 2.5 μm, a precursor slurry was obtained.
(3) - (5) were the same as in steps (3) to (5) of example 1, respectively, to thereby obtain a doped lithium iron manganese phosphate-carbon composite material.
Comparative example 2
The doped lithium iron manganese phosphate-carbon composite material prepared by the method disclosed in chinese patent application CN102769131a is different from the embodiment 1 in that the step of preparing pre-doped manganese oxalate is not performed.
The preparation process of comparative example 2 includes the following steps.
(1) 32.11kg of manganese carbonate (manganese source) and 0.67kg of magnesium sulfate (dopant) were prepared, respectively, in such a manner that the molar percentage of the doping element magnesium to manganese was 2.0%.
(2) Adding the above manganese carbonate and magnesium sulfate directly with 21.58kg ferrous carbonate, 18.06kg lithium carbonate, 54.63kg ammonium dihydrogen phosphate and 8.78kg glucose into pure water, stirring, mixing, and grinding in sand mill to obtain particulate D 50 About 2.5 μm, a precursor slurry was obtained.
(3) - (5) were the same as in steps (3) to (5) of example 1, respectively, to thereby obtain a doped lithium iron manganese phosphate-carbon composite material.
Examples of the experiments
Experimental example 1 evaluation of micro-morphology of Pre-doped manganese oxalate
The microscopic morphology of the pre-doped manganese oxalate in example 1 was observed using a Scanning Electron Microscope (SEM). As shown in fig. 3, the pre-doped manganese oxalate is a secondary particle formed by agglomeration of primary particles, and the primary particles have an irregular sheet-like structure.
And (3) determining the crystal form composition of the pre-doped manganese oxalate by adopting an X-ray diffractometer (XRD). As shown in fig. 4, the characteristic diffraction peaks of manganese oxalate dihydrate appear at the positions of 18.36 °, 18.81 °, 22.67 °, 24.47 °, 29.71 °, 33.37 ° 2 θ angles, and the ratio of the peak intensity height to the half-peak width is larger, which indicates that the crystallinity of the pre-doped manganese oxalate is better.
Experimental example 2 determination of carbon content and particle size of composite Material
The carbon content of the composite materials obtained in example 1 and comparative examples 1 to 2 was measured by a carbon analyzer, and the particle size D of the composite material was measured by a laser particle size analyzer 50 The results are shown in Table 1.
Experimental example 3 measurement of mole percent ratio of doping element to manganese element in composite Material
The composite materials obtained in example 1 and comparative examples 1 and 2 were measured for the content of the doping element magnesium and the content of the manganese element by an inductively coupled plasma spectrometer (ICP-OES), and the mole percent ratio of the magnesium element to the manganese element was calculated, and the results are shown in table 1.
TABLE 1
Figure BDA0003011051250000151
As can be seen from table 1, the composite materials obtained in example 1 and comparative examples 1 to 2 have similar carbon contents and similar particle sizes, and the molar percentage ratios of the doping elements magnesium and manganese are also similar, indicating that the doping amounts of magnesium in the obtained composite materials are substantially the same.
Experimental example 4 electrochemical Property test of composite Material
(1) Preparation of positive pole piece
Weighing 0.3000g of polyvinylidene fluoride binder (PVDF) in 10.8g N-methylpyrrolidone (NMP) with an analytical balance (precision 0.0001 g), stirring and completely dissolving; 2.4000g of the above composite material (from example 1 and comparative examples 1 to 2, respectively) and 0.3000g of carbon black conductive agent (SP) were further added thereto and stirred uniformly to obtain a paste. Wherein the mass ratio of the composite material, the polyvinylidene fluoride binder (PVDF) and the carbon black conductive agent (SP) is 8.
And uniformly coating the paste on an aluminum foil by using a coater, drying in a vacuum drying oven, removing a solvent NMP, and then rolling and punching to obtain a wafer with the diameter of 16.0mm as a positive pole piece.
(2) Assembly of CR2032 button cell
1.0 mol.L of the positive pole piece as the positive pole, the metal lithium piece as the negative pole, the PE-PP composite film as the battery diaphragm -1 LiPF of 6 And (DMC + DMC) as electrolyte, wherein the volume ratio of EC to DMC is 1:1, and assembling the CR2032 button cell.
(3) Electrochemical performance test
The main purpose of the battery performance test is to determine the specific discharge capacity and capacity retention rate of the composite material. And (3) performing a cyclic charge and discharge test on the button cell by using the Shenzhen new Willer cell detection system according to the charge and discharge multiplying power of 0.1C, 1.0C and 5.0C in sequence, wherein the cycle number is 50, the test temperature is 25.0 ℃, and the charge and discharge voltage is 2.0V-4.3V. The results obtained are summarized in table 2 below.
TABLE 2
Figure BDA0003011051250000161
From table 2, it can be found that the specific capacity and the capacity retention rate of the composite material of example 1 are higher under different discharge rates, which indicates that the composite material of example 1 is obviously better than those of comparative examples 1 and 2 in terms of actual specific capacity, rate performance and cycle performance.
In particular, the specific capacity and capacity retention rate of the composite material of comparative example 2 are low at different discharge rates, indicating that the actual specific capacity, rate performance and cycle performance are poor.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (17)

1. A method of preparing a doped lithium iron manganese phosphate-carbon composite, the method comprising the steps of:
(1) Preparing pre-doped manganese oxalate;
1a, mixing a manganese source and a doping agent containing doping elements to obtain mixed powder,
wherein the manganese source comprises one or the combination of manganese monoxide, manganous manganic oxide, manganese dioxide, manganese hydroxide, manganese carbonate and manganese sulfate,
in the mixed powder, the mole percent ratio of the doping element to the manganese element is 0.001-10.0%;
1b, dissolving oxalic acid in water to obtain an oxalic acid solution;
1c, adding the mixed powder into the oxalic acid solution for reaction to obtain a manganese oxalate suspension containing doped elements;
1d, filtering and drying the manganese oxalate suspension to obtain pre-doped manganese oxalate;
(2) Adding an iron source, a lithium source, a phosphorus source, an organic carbon source and the pre-doped manganese oxalate into water, and mixing and grinding to obtain precursor slurry;
(3) Drying and granulating the precursor slurry to obtain precursor powder;
(4) Sintering the precursor powder under a protective atmosphere to obtain a sintered material;
(5) And crushing the sintered material to obtain the doped lithium iron manganese phosphate-carbon composite material.
2. The method according to claim 1, wherein, in step 1a,
the doping element comprises one or the combination of titanium, magnesium, aluminum, zinc, cobalt, nickel, tin, niobium, tungsten, zirconium, tantalum, cerium, europium and fluorine.
3. The method of claim 2, wherein the manganese source is one of manganese dioxide, manganese hydroxide, manganese carbonate or a combination thereof,
the doping agent comprises one of sulfate, chloride, nitrate, organic acid salt, oxide and hydroxide containing the doping element or the combination of the sulfate, the chloride, the nitrate and the organic acid salt.
4. The method of claim 1, wherein, in step 1b,
the water is pure water, and the water is pure water,
the mass fraction of the solute of the oxalic acid solution is 5.0-60 percent,
the temperature during the dissolution process is kept at 20-90 ℃.
5. The method of claim 1, wherein, in step 1c,
adding the mixed powder into the oxalic acid solution for reaction according to the molar ratio of oxalic acid to manganese element of (2.2-1.0) to 1.0;
the reaction temperature is 20-90 ℃.
6. The method according to claim 1, wherein in step 1d, the drying temperature is 50 ℃ to 150 ℃.
7. A process according to claim 1, wherein, in the pre-doped manganese oxalate obtained in step 1d,
the total mole percentage of the doping elements in the manganese element is 0.001-10.0%.
8. The method according to claim 1, wherein, in step (2),
the iron source comprises one or the combination of simple substance iron, ferrous oxide, ferric phosphate, ferrous oxalate and ferrous carbonate,
the lithium source comprises one of lithium carbonate, lithium hydroxide, lithium phosphate and lithium dihydrogen phosphate or the combination of the lithium carbonate, the lithium hydroxide, the lithium phosphate and the lithium dihydrogen phosphate,
the phosphorus source comprises one or the combination of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid,
the organic carbon source comprises one or more of starch, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, cyclodextrin, citric acid, oxalic acid and xylitol,
the water is pure water.
9. The method according to claim 1, wherein, in step (2),
in the precursor slurry, the particle size D of the particulate matter 50 0.5-15.0 μm.
10. The method according to claim 1, wherein, in the step (3), the temperature of the dry granulation is 100 ℃ to 300 ℃.
11. The method according to claim 1, wherein, in step (4),
the protective atmosphere is one or the combination of nitrogen and argon;
the sintering temperature is 300-800 ℃;
the sintering time is 6-20 h.
12. The method according to claim 1, wherein, in the composite material obtained in step (5),
particle size D of the composite 50 0.5-15 μm.
13. The method according to claim 1, wherein, in the composite material obtained in step (5),
the molar ratio of Mn to Fe is (1-z), wherein z is more than or equal to 0.6 and less than 1;
the total mole number of Li, mn, fe and P is Li (Mn + Fe), P is (0.8-1.2) 1.0 (0.8-1.2);
based on the total mass of the composite material, the carbon content of the composite material is 1.0-10%;
the total mole percentage of the doping element accounts for 0.001-10.0% of the mole percentage of the manganese element.
14. A doped lithium iron manganese phosphate-carbon composite, wherein the composite is made by the method of any one of claims 1 to 13.
15. A positive electrode active material comprising the doped lithium iron manganese phosphate-carbon composite of claim 14.
16. A positive electrode comprising the positive electrode active material according to claim 15.
17. A lithium ion battery comprising the positive electrode of claim 16.
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