CN103594712A - Metal-doped oxidative conductive carbon black cladded lithium manganese phosphate and preparation method thereof - Google Patents
Metal-doped oxidative conductive carbon black cladded lithium manganese phosphate and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
The invention discloses metal-doped oxidative conductive carbon black cladded lithium manganese phosphate which is prepared by taking a lithium source compound, a manganese source compound, a phosphorus source compound, a metal dopant and a carbon source as raw materials, wherein the carbon source is oxidative conductive carbon black; the metal-doped oxidative conductive carbon black cladded lithium manganese phosphate has a chemical formula of LiMxMn[1-x]PO4/C, wherein M is a metal doped element and is not less than 0.001 and not more than 0.1. The metal-doped oxidative conductive carbon black cladded lithium manganese phosphate is high in capacity, excellent in performance, good in circling stability and easy to disperse in water. The invention also provides a preparation method of the metal-doped oxidative conductive carbon black cladded lithium manganese phosphate. The preparation method mainly comprises the following steps: (1) preparing the oxidative conductive carbon black; and (2) preparing the metal-doped oxidative conductive carbon black cladded lithium manganese phosphate. The preparation method is simple in step and low in cost; the prepared metal-doped oxidative conductive carbon black cladded lithium manganese phosphate product is uniform in grain size, high in purity and excellent in electrochemical performance.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, especially relate to coated lithium manganese phosphate of a kind of metal-doped oxidation conductive carbon black and preparation method thereof.
Background technology
The electrode material with electro-chemical activity all can be for the manufacturing of lithium ion battery, and wherein conventional anode material for lithium-ion batteries has cobalt acid lithium, lithium nickelate, spinel lithium manganate, nickel ternary cobalt manganic acid lithium etc. at present.Wherein cobalt acid lithium common use in small-scale lithium ion cell, but cobalt resource is rare, expensive, and large electric current with overcharge under condition unstable, very dangerous; The crystal structural stability of lithium nickelate, but fail safe is poor; The cycle performance of LiMn2O4 particularly under hot conditions cycle performance poor.Above positive electrode is all stratiform or spinel-type metal oxide, and they the reaction of ease oxygen easily occur under high-temperature charging state and dangerous, thereby are difficult to be applied to low cost, high safety, high-capacity dynamical lithium-ion battery.Although LiFePO 4 material has stable olivine crystal structure, fail safe is good, and cycle performance is good especially, and with low cost, is acknowledged as the best positive electrode of manufacturing high safety, low cost, long life lithium batteries, works as and LiCoO
2(4.05V is to Li/Li
+) standard electrode potential while comparing, at LiFePO
4in Fe
3+/ Fe
2+galvanic couple has remarkable lower voltage, and (3.45V is to Li/Li
+), this just greatly reduces and can be used for LiFePO
4the energy of system, and be all the LiMnPO of olivine structural
4, because Mn
3+/ Mn
2+galvanic couple produces 4.05V to Li/Li
+electromotive force, itself and current LiCoO
2standard electrode potential approach and cause concern, but lithium manganese phosphate material conductivity is extremely low, its conductivity even, than LiFePO4 low several order of magnitude also, has limited it directly to apply, therefore, the electric conductivity that how to improve lithium manganese phosphate is urgent problem.
The conductivity that adopt at present conventionally that material with carbon element is coated, the means such as conducting polymer doping and metal nanoparticle doping improves lithium manganese phosphate.
Application publication number CN102709554A, the Chinese patent of Shen Qing Publication day 2012.10.03 discloses the preparation method of manganese phosphate lithium/carbon composite material for a kind of lithium ion cell positive, this preparation method is usingd sucrose (organic substance) as carbon source, in the coated one deck conductive carbon in lithium manganese phosphate surface, but organic pyrolysis product is inhomogeneous, easily cause synthetic lithium manganese phosphate batch stability not good, and organic cracking generation is porous carbon, can cause material specific area large, be unfavorable for the preparation of cell size.
In addition; Granted publication CN101673819B; the Chinese patent of Granted publication day 2012.02.08 discloses a kind of method of preparing manganese phosphate lithium/carbon composite material with manganese phosphate; the method is first to prepare active manganese phosphate; then active manganese phosphate and lithium source are mixed; and add carbon source; above-mentioned substance is asked after mill; spray dry; dried powder is heat-treated under protective atmosphere, is warming up to 300 ~ 850 ℃, calcines 2 ~ 12 hours; then naturally cooling, obtain manganese phosphate lithium/carbon composite material.Carbon source in the method is a kind of in glucose, fructose, sucrose, lactose, Super P, starch, PAN, PVC, PVB, PVA or phenolic resins, carbon source in the method is organic substance or is inorganic matter, while adopting organic substance as carbon source, still exist pyrolysis product inhomogeneous, easily cause synthetic lithium manganese phosphate batch stability not good, and organic cracking produces is porous carbon, can cause material specific area large, be unfavorable for the problem of the preparation of cell size; While adopting inorganic matter as carbon source, more than the addition of carbon source reaches the 15wt% of synthesis material, the addition of carbon source is too much, although can greatly improve the high rate performance of lithium manganese phosphate, but the hydrophily of inorganic carbon source is poor, be difficult to be scattered in polar solvent water, the abundance of carbon source is also difficult to control, carbon source addition too much can cause the gram volume of synthetic product to reduce simultaneously, affects the capacitance of battery.
Summary of the invention
The present invention is not good in order to solve the coated lithium manganese phosphate batch stability of the material with carbon element of prior art, during slurrying, be difficult for disperseing, carbon source addition is too much, the problem that specific capacity is low, provide a kind of gram volume high, good and the good cycling stability of high rate performance, the metal-doped oxidation conductive carbon black that is easy to be dispersed in water is coated lithium manganese phosphate.
The present invention also provides the preparation method of the coated lithium manganese phosphate of a kind of metal-doped oxidation conductive carbon black, and the method processing step is simple, and cost is low, and the particle size were making is even, and purity is high, and chemical property is good.
To achieve these goals, the present invention is by the following technical solutions:
A kind of metal-doped oxidation conductive carbon black is coated lithium manganese phosphate, the coated lithium manganese phosphate of described metal-doped oxidation conductive carbon black be take Li source compound, manganese source compound, P source compound, metalic contamination and carbon source and is prepared from as raw material, described carbon source is oxidation conductive carbon black, and the chemical formula that this metal-doped oxidation conductive carbon black is coated lithium manganese phosphate is: LiM
xmn
1-xpO
4/ C, wherein M is metal-doped element, 0.001≤M≤0.1.The coated carbon source of lithium manganese phosphate in the present invention is the conductive carbon black through oxidation processes, oxidation conductive black is a kind of conductive carbon black through finishing in fact, more oxygen-containing functional group is contained on its surface, hydrophilicity is good, be easy to be dispersed in water, being coated on lithium manganese phosphate surface makes lithium manganese phosphate be easy to be dispersed in water, be conducive to the preparation of slurry, and only need add a small amount of oxidation conductive black and just can improve greatly the conductivity of material lithium manganese phosphate, and do not affect specific capacity, by metallic element, adulterated in the manganese position of lithium manganese phosphate simultaneously, make the structure cell generation deformation of lithium manganese phosphate, significantly improve electronic conductivity and the lithium ion migration rate of manganese-lithium phosphate anode material, coordinated with oxidation conductive carbon black, can greatly improve capacity and the cycle performance of positive electrode, good cycling stability.
As preferably, described Li source compound is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium dihydrogen phosphate, lithium phosphate.
As preferably, described manganese source compound is one or more in manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese oxalate, manganese phosphate, manganese acetate, manganese nitrate.
As preferably, P source compound is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, phosphoric acid dihydro amine.
As preferably, described metal-doped element is Mg, Ti, V, Bi, Nb, Zn or Al.
As preferably, one or more in the carbonate of the oxide that metalic contamination is metal-doped element, the hydroxide of metal-doped element and metal-doped element.
The coated lithium manganese phosphate preparation method of oxidation conductive carbon black, comprise the following steps:
(1) oxidation conductive carbon black preparation
(1) conductive black is annealed at 270 ~ 290 ℃ 12 ~ 15h.This is one of committed step of the present invention, and the 12 ~ 15h that anneals at 270 ~ 290 ℃ to be to remove impurity and the free carbon in conductive carbon black, otherwise is unfavorable for the finishing of conductive carbon black in subsequent step, and can bring impurity to product.
(2) conductive carbon black obtaining in step (1) is added in strong oxidizer and soaked, after filtration, filter residue is cleaned to pH and be neutral, finally dry and obtain oxidation conductive carbon black.Conductive carbon black soaks in strong oxidizer, can produce gas, between conductive carbon black, mutually peel off, structure changes, and forms the structure of similar Graphene, more oxygen-containing functional group is contained on its surface simultaneously, hydrophilicity is good, process the oxidation conductive carbon black obtaining and be not only easy to be dispersed in water, and the more common conductive carbon black of electric conductivity has obtained larger lifting through strong oxidizer, its mechanism is still not clear, and may be that the change of conductive carbon black structure is more easily transmitted electronics.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
(a) first weigh Li source compound, manganese source compound, P source compound and metalic contamination, wherein, elemental lithium: manganese element: P elements: the mol ratio of metal-doped element is 1:(1-x): 1:x, weigh again carbon source, the addition of carbon source is Li source compound, manganese source compound, 2 ~ 8% of P source compound and metalic contamination gross mass, finally by the Li source compound taking, manganese source compound, P source compound, after mixing, metalic contamination and carbon source be scattered in the mixed solvent of water or water and organic solvent composition, after high-speed stirred or ultrasonic dispersion or ball milling, obtain slurry.Because oxidation conductive carbon black has better electric conductivity, with respect to the organic carbon source or the inorganic carbon source that need cracking, its addition greatly reduces, and only needs 2 ~ 8%, can not impact battery capacity.
(b) dry being placed in protective atmosphere of the slurry spraying obtaining in step (a) is warming up to 500 ~ 800 ℃ of constant temperature sintering 3 ~ 12h, pulverizes, sieve after being cooled to room temperature, obtain the coated lithium manganese phosphate of metal-doped oxidation conductive carbon black.
As preferably, the salpeter solution that described in step (2), strong oxidizer is 10mol/L, 10mol/L salpeter solution and the 10mol/L sulfuric acid solution mixed solution that 1:2 ~ 3 form in mass ratio, the H that quality percentage composition is 10%
2o
2solution or mass concentration are the ammonium persulfate solution of 20g/L, and when strong oxidizer is salpeter solution, the mass ratio of conductive carbon black and salpeter solution is 1:30 ~ 40, and soaking temperature is 60 ~ 80 ℃; When strong oxidizer is the mixed solution of salpeter solution and sulfuric acid solution composition, the mass ratio of conductive carbon black and mixed solution is 1:30 ~ 40, and soaking temperature is 60 ~ 80 ℃; When strong oxidizer is H
2o
2during solution, conductive carbon black and H
2o
2the mass ratio of solution is 1:20 ~ 40, and soaking temperature is 20 ~ 25 ℃; When strong oxidizer is ammonium persulfate solution, the mass ratio of conductive carbon black and ammonium persulfate solution is 1:50 ~ 70, and soaking temperature is 20 ~ 25 ℃.
As preferably, in step (a), the mass ratio of water and organic solvent or volume ratio are 40 ~ 50:1, and described organic solvent is ethanol.Organic solvent just has ethanol, and cost is low, environmental protection.
As preferably, in step (b), heating rate is 2 ~ 4 ℃/min.Heating rate is too fast, in preparation process, can produce the phenomenon of explosion, the particle size were obtaining is inhomogeneous, the local irregularity of lattice, and reactant can not all change into product, can bring other impurity, the product chemical property obtaining is poor, and heating rate is excessively slow, preparation efficiency is low, can reduce lattice constant simultaneously, unit cell volume is shunk, lithium ion passage is diminished, there is difficulty in the de-embedding of lithium ion, can reduce the initial capacity of product, in the present invention, heating rate is controlled at 2 ~ 4 ℃/min, the product out-degree obtaining is high, particle diameter is even, lattice is regular, discharge capacity is high, cycle performance is good.
Therefore, the present invention has following beneficial effect:
(1) by metallic element, adulterated in the manganese position of lithium manganese phosphate, adopt oxidation conductive carbon black to be coated lithium manganese phosphate, by both synergies, make lithium manganese phosphate be easy to be dispersed in water, be conducive to slurrying, can greatly improve capacity and the cycle performance of lithium manganese phosphate simultaneously;
(2) through strong oxidizer, process the more common conductive carbon black of oxidation conductive carbon black electric conductivity obtaining and obtained larger lifting, can reduce the addition of carbon source, the product capacitance obtaining is high;
(3) when preparation oxidation conductive carbon black, first conductive carbon black is carried out annealing in process to remove impurity and the free carbon in conductive carbon black, be conducive to the finishing of conductive carbon black and the raising of product purity in subsequent step;
(4) when preparation is calcined, heating rate is controlled at 2 ~ 4 ℃/min, and the product out-degree obtaining is high, and particle diameter is even, and lattice is regular, and discharge capacity is high, and cycle performance is good;
(5) processing step is simple, and cost is low, and the particle size were making is even, and purity is high, and chemical property is good.
Accompanying drawing explanation
Fig. 1 is the SEM figure that oxidation conductive carbon black metal-doped in embodiment 1 is coated lithium manganese phosphate.
Fig. 2 is the XRD figure that oxidation conductive carbon black metal-doped in embodiment 1 is coated lithium manganese phosphate.
Fig. 3 is the half-cell made of the coated lithium manganese phosphate of oxidation conductive carbon black metal-doped in embodiment 1 discharge curve first.
Fig. 4 is the finished product cycle performance of battery figure that the coated lithium manganese phosphate of oxidation conductive carbon black metal-doped in embodiment 1 is made.
Embodiment
Below by specific embodiment, the present invention will be further described.
In the present invention, if not refer in particular to, all percentage is unit of weight, and all devices and raw material all can be buied from market or the industry is conventional, and the method in following embodiment, if no special instructions, is this area conventional method.
(1) oxidation conductive carbon black preparation
(1) conductive black is annealed at 270 ℃ 15h.
(2) conductive carbon black obtaining in step (1) is added in strong oxidizer and soaked, strong oxidizer is the salpeter solution of 10mol/L, soaking temperature is 60 ℃, the mass ratio of conductive carbon black and salpeter solution is 1:40, after filtration, filter residue is cleaned to pH and be neutral, finally dry and obtain oxidation conductive carbon black.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
(a) in elemental lithium: manganese element: P elements: the ratio that the mol ratio of metal-doped element is 1:0.999:1:0.001 weighs Li source compound, manganese source compound, P source compound and metalic contamination, wherein Li source compound is lithium dihydrogen phosphate, manganese source compound is manganese dioxide, P source compound is phosphoric acid, metalic contamination is magnesium hydroxide, then weighing quality is Li source compound, manganese source compound, the oxidation conductive carbon black of P source compound and metalic contamination gross mass 2%, finally by lithium dihydrogen phosphate, manganese dioxide, phosphoric acid, after mixing, magnesium hydroxide and oxidation conductive carbon black be scattered in water, slurry after ball milling.
(b) be placed on the heating rate with 2 ℃/min in protective atmosphere and be warming up to 500 ℃ of constant temperature sintering 12h the slurry spraying obtaining in step (a) is dry, pulverize, sieve after being cooled to room temperature, obtaining chemical formula is LiMg
0.001mn
0.999pO
4the coated lithium manganese phosphate of metal-doped oxidation conductive carbon black of/C.
one, Micro-Structure Analysis
The coated lithium manganese phosphate of metal-doped oxidation conductive carbon black that utilizes electron microscope observation to obtain, the microscopic pattern obtaining as shown in Figure 1.
The even ，Qie lattice of the primary particle particle diameter local structured of the product obtaining as can be seen from Figure 1.
The coated lithium manganese phosphate of metal-doped oxidation conductive carbon black is carried out to X-ray diffraction, and the spectrogram obtaining as shown in Figure 2.
In spectrogram, do not have as can be seen from Figure 2 the base peak of C, illustrate that C exists with amorphous state form, there is no in addition other assorted peaks in spectrogram, illustrate that synthetic product is pure olivine lithium manganese phosphate phase, the purity of product is high.
Other physical indexs to material are tested, and recording the carbon amount that is oxidized conductive carbon in material is 5%, and tap density is 1.1g/cm
3, specific area is 20 m
2/ g, material particle size is normal distribution, D
50it is 3.0 microns.
two, electrochemical property test
By the chemical formula obtaining, be LiMg
0.001mn
0.999pO
4the coated lithium manganese phosphate of metal-doped oxidation conductive carbon black of/C is anodal, and lithium alkoxide is that negative pole is made half-cell, at 20 ± 5 ℃, carries out half-cell test under the condition of 0.2C, and the discharge curve first obtaining as shown in Figure 3.
As can be seen from Figure 3, when 0.2C discharges, the reversible gram volume of material can reach 140mAh/g, illustrates that the capacity of the coated lithium manganese phosphate of the metal-doped oxidation conductive carbon black of the present invention is high.
With the mass ratio of 83:7:10, take respectively the coated lithium manganese phosphate of metal-doped oxidation conductive carbon black, conductive carbon black (SP), the binding agent HSV900 of embodiment 1 gained, in nmp solvent, mix, drying, roll-in, cut-parts, make electrode, negative pole is selected metal lithium sheet, and electrolyte is the LiPF that is dissolved in the 1.0mol/L in ethyl carbonate and carbonic acid diethyl vinegar mixed solvent
6, ethyl carbonate and carbonic acid diethyl vinegar volume ratio 1:1, barrier film is polypropylene microporous film, is assembled into 2016 button cells.The battery obtaining, at 20 ± 5 ℃, is carried out to charge-discharge test with 1C/1C charge-discharge magnification, and the cycle performance figure obtaining as shown in Figure 4.
As can be seen from Figure 4, through 1000 circulations, the capability retention of battery, still in 90% left and right, illustrates that the coated lithium manganese phosphate high rate performance of metal-doped oxidation conductive carbon black of the present invention is good, and good cycling stability.
(1) oxidation conductive carbon black preparation
(1) conductive black is annealed at 280 ℃ 13h.
(2) conductive carbon black obtaining in step (1) is added in strong oxidizer and soaked, strong oxidizer is 10mol/L salpeter solution and the 10mol/L sulfuric acid solution mixed solution that 1:3 forms in mass ratio, soaking temperature is 70 ℃, the mass ratio of conductive carbon black and mixed solution is 1:30, after filtration, filter residue is cleaned to pH and be neutral, finally dry and obtain oxidation conductive carbon black.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
(a) in elemental lithium: manganese element: P elements: the ratio that the mol ratio of metal-doped element is 1:0.9:1:0.1 weighs Li source compound, manganese source compound, P source compound and metalic contamination, wherein Li source compound by lithium dihydrogen phosphate and lithium hydroxide in mass ratio 1:1 mix, manganese source compound is manganese oxalate, P source compound by ammonium phosphate and ammonium dihydrogen phosphate in mass ratio 1:1 mix, metalic contamination is alundum (Al2O3), then weighing quality is Li source compound, manganese source compound, the oxidation conductive carbon black of P source compound and metalic contamination gross mass 8%, finally by lithium dihydrogen phosphate, lithium hydroxide, manganese oxalate, ammonium phosphate, ammonium dihydrogen phosphate, after mixing, alundum (Al2O3) and oxidation conductive carbon black be scattered in water, slurry after ball milling.
(b) be placed on the heating rate with 3 ℃/min in protective atmosphere and be warming up to 700 ℃ of constant temperature sintering 8h the slurry spraying obtaining in step (a) is dry, pulverize, sieve after being cooled to room temperature, obtaining chemical formula is LiMg
0.1mn
0.9pO
4the coated lithium manganese phosphate of oxidation conductive carbon black that/C is metal-doped.
The SEM figure of the coated lithium manganese phosphate of metal-doped oxidation conductive carbon black that the present embodiment obtains, XRD figure and the half-cell made be equal similar to embodiment 1 of discharge curve and the finished product cycle performance of battery figure that makes first, therefore do not enumerate and repeat at this.
Embodiment 3
(1) oxidation conductive carbon black preparation
(1) conductive black is annealed at 290 ℃ 12h.
(2) conductive carbon black obtaining in step (1) is added in strong oxidizer and soaked, strong oxidizer is that mass concentration is the ammonium persulfate solution of 20g/L, soaking temperature is 25 ℃, the mass ratio of conductive carbon black and mixed solution is 1:50, after filtration, filter residue is cleaned to pH and be neutral, finally dry and obtain oxidation conductive carbon black.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
(a) in elemental lithium: manganese element: P elements: the ratio that the mol ratio of metal-doped element is 1:0.95:1:0.05 weighs Li source compound, manganese source compound, P source compound and metalic contamination, wherein Li source compound is by lithium dihydrogen phosphate, lithium carbonate and lithium hydroxide in mass ratio 1:1:2 mix, manganese source compound by manganese phosphate and manganese sesquioxide managnic oxide in mass ratio 1:3 mix, P source compound is ammonium dihydrogen phosphate, metalic contamination is titanium dioxide, then weighing quality is Li source compound, manganese source compound, the oxidation conductive carbon black of P source compound and metalic contamination gross mass 5%, finally by lithium dihydrogen phosphate, lithium hydroxide, manganese oxalate, ammonium dihydrogen phosphate, after mixing, titanium dioxide and oxidation conductive carbon black be scattered in water, slurry after ball milling.
(b) be placed on the heating rate with 4 ℃/min in protective atmosphere and be warming up to 800 ℃ of constant temperature sintering 3h the slurry spraying obtaining in step (a) is dry, pulverize, sieve after being cooled to room temperature, obtaining chemical formula is LiMg
0.05mn
0.95pO
4the coated lithium manganese phosphate of oxidation conductive carbon black that/C is metal-doped.
The SEM figure of the coated lithium manganese phosphate of metal-doped oxidation conductive carbon black that the present embodiment obtains, XRD figure and the half-cell made be equal similar to embodiment 1 of discharge curve and the finished product cycle performance of battery figure that makes first, therefore do not enumerate and repeat at this.
In other technologies scheme of the present invention, all can implement, therefore do not enumerate at this.
Above-described embodiment is a kind of preferably scheme of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.
Claims (10)
1. a metal-doped oxidation conductive carbon black is coated lithium manganese phosphate, it is characterized in that, the coated lithium manganese phosphate of described metal-doped oxidation conductive carbon black be take Li source compound, manganese source compound, P source compound, metalic contamination and carbon source and is prepared from as raw material, described carbon source is oxidation conductive carbon black, and the chemical formula that this metal-doped oxidation conductive carbon black is coated lithium manganese phosphate is: LiM
xmn
1-xpO
4/ C, wherein M is metal-doped element, 0.001≤M≤0.1.
2. the coated lithium manganese phosphate of a kind of metal-doped oxidation conductive carbon black according to claim 1, is characterized in that, described Li source compound is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium dihydrogen phosphate, lithium phosphate.
3. a kind of metal-doped oxidation conductive carbon black according to claim 1 is coated lithium manganese phosphate, it is characterized in that, described manganese source compound is one or more in manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese oxalate, manganese phosphate, manganese acetate, manganese nitrate.
4. the coated lithium manganese phosphate of a kind of metal-doped oxidation conductive carbon black according to claim 1, is characterized in that, P source compound is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, phosphoric acid dihydro amine.
5. the coated lithium manganese phosphate of a kind of metal-doped oxidation conductive carbon black according to claim 1, is characterized in that, described metal-doped element is Mg, Ti, V, Bi, Nb, Zn or Al.
6. a kind of oxidation conductive carbon black of doped with metal elements is coated lithium manganese phosphate according to claim 1 or 5, it is characterized in that one or more in the carbonate of the oxide that metalic contamination is metal-doped element, the hydroxide of metal-doped element and metal-doped element.
7. the coated lithium manganese phosphate preparation method of metal-doped oxidation conductive carbon black as claimed in claim 1, is characterized in that, comprises the following steps:
(1) oxidation conductive carbon black preparation
(1) conductive black is annealed at 270 ~ 290 ℃ 12 ~ 15h;
(2) conductive carbon black obtaining in step (1) is added in strong oxidizer and soaked, after filtration, filter residue is cleaned to pH and be neutral, finally dry and obtain oxidation conductive carbon black;
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
(a) first weigh Li source compound, manganese source compound, P source compound and metalic contamination, wherein, elemental lithium: manganese element: P elements: the mol ratio of metal-doped element is 1:(1-x): 1:x, weigh again carbon source, the addition of carbon source is Li source compound, manganese source compound, 2 ~ 8% of P source compound and metalic contamination gross mass, finally by the Li source compound taking, manganese source compound, P source compound, after mixing, metalic contamination and carbon source be scattered in the mixed solvent of water or water and organic solvent composition, after high-speed stirred or ultrasonic dispersion or ball milling, obtain slurry,
(b) dry being placed in protective atmosphere of the slurry spraying obtaining in step (a) is warming up to 500 ~ 800 ℃ of constant temperature sintering 3 ~ 12h, pulverizes, sieve after being cooled to room temperature, obtain the coated lithium manganese phosphate of metal-doped oxidation conductive carbon black.
8. metal-doped oxidation conductive carbon black according to claim 7 is coated lithium manganese phosphate preparation method, it is characterized in that the salpeter solution that described in step (2), strong oxidizer is 10mol/L, 10mol/L salpeter solution and the 10mol/L sulfuric acid solution mixed solution that 1:2 ~ 3 form in mass ratio, the H that quality percentage composition is 10%
2o
2solution or mass concentration are the ammonium persulfate solution of 20g/L, and when strong oxidizer is salpeter solution, the mass ratio of conductive carbon black and salpeter solution is 1:30 ~ 40, and soaking temperature is 60 ~ 80 ℃; When strong oxidizer is the mixed solution of salpeter solution and sulfuric acid solution composition, the mass ratio of conductive carbon black and mixed solution is 1:30 ~ 40, and soaking temperature is 60 ~ 80 ℃; When strong oxidizer is H
2o
2during solution, conductive carbon black and H
2o
2the mass ratio of solution is 1:20 ~ 40, and soaking temperature is 20 ~ 25 ℃; When strong oxidizer is ammonium persulfate solution, the mass ratio of conductive carbon black and ammonium persulfate solution is 1:50 ~ 70, and soaking temperature is 20 ~ 25 ℃.
9. the coated lithium manganese phosphate preparation method of metal-doped oxidation conductive carbon black according to claim 8, is characterized in that, in step (a), the mass ratio of water and organic solvent or volume ratio are 40 ~ 50:1, and described organic solvent is ethanol.
10. the coated lithium manganese phosphate preparation method of metal-doped oxidation conductive carbon black according to claim 8, is characterized in that, in step (b), heating rate is 2 ~ 4 ℃/min.
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Denomination of invention: A metal doped oxide conductive carbon black coated manganese lithium phosphate and its preparation method Effective date of registration: 20230522 Granted publication date: 20150916 Pledgee: Dongyang Branch of China Construction Bank Co.,Ltd. Pledgor: HENGDIAN GROUP DMEGC MAGNETICS Co.,Ltd. Registration number: Y2023330000949 |