CN103594712B - A kind of metal-doped coated lithium manganese phosphate of oxidation conductive carbon black and preparation method thereof - Google Patents
A kind of metal-doped coated lithium manganese phosphate of oxidation conductive carbon black and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of metal-doped coated lithium manganese phosphate of oxidation conductive carbon black, it with Li source compound, manganese source compound, P source compound, metalic contamination and carbon source for raw material is prepared from, described carbon source is oxidation conductive carbon black, and the chemical formula of this metal-doped coated lithium manganese phosphate of oxidation conductive carbon black is: LiM
xmn
1-xpO
4/ C, wherein M is metal-doped element, 0.001≤M≤0.1, and metal-doped oxidation conductive carbon black coated lithium manganese phosphate gram volume of the present invention is high, and the good and good cycling stability of high rate performance, is easy to be dispersed in water.Present invention also offers a kind of preparation method of the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black, mainly comprise the following steps: the preparation of (one) oxidation conductive carbon black; (2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black.The method processing step is simple, and cost is low, and obtained particle size is even, and purity is high, and chemical property is good.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, especially relate to a kind of metal-doped coated lithium manganese phosphate of oxidation conductive carbon black and preparation method thereof.
Background technology
The electrode material with electro-chemical activity all may be used for the manufacturing of lithium ion battery, and wherein conventional at present anode material for lithium-ion batteries has cobalt acid lithium, lithium nickelate, spinel lithium manganate, nickel ternary cobalt manganic acid lithium etc.Wherein cobalt acid lithium common use in small-scale lithium ion cell, but cobalt resource is rare, expensive, and in big current and instability under overcharging condition, very dangerous; The crystal structural stability of lithium nickelate, but fail safe is poor; Particularly cycle performance is poor under the high temperature conditions for the cycle performance of LiMn2O4.Above positive electrode is all stratiform or spinel-type metal oxide, and ease oxygen reaction and dangerous easily occurs under high-temperature charging state for they, is thus 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 manufacturing high safety, low cost, long life lithium batteries, works as and LiCoO
2(4.05V is to Li/Li
+) standard electrode potential when comparing, at LiFePO
4in Fe
3+/ Fe
2+galvanic couple has significantly 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 close to and cause concern, but lithium manganese phosphate material conductivity is extremely low, its conductivity is even than LiFePO4 also low several order of magnitude, and limiting it directly applies, and therefore, the electric conductivity how improving lithium manganese phosphate is urgent problem.
Adopt at present usually that material with carbon element is coated, conductivity that the means such as conducting polymer doping and metal nanoparticle doping improve lithium manganese phosphate.
Application publication number CN102709554A, the Chinese patent of Shen Qing Publication day 2012.10.03 discloses a kind of preparation method of lithium ion cell positive manganese phosphate lithium/carbon composite material, this preparation method is using sucrose (organic substance) as carbon source, in lithium manganese phosphate Surface coating one deck conductive carbon, but organic pyrolysis product is uneven, easily cause the lithium manganese phosphate lot stability of synthesis not good, and organic cracking generation is porous carbon, material specific surface area can be caused large, be unfavorable for the preparation of cell size.
In addition; Authorization Notice No. CN101673819B; the Chinese patent of authorized announcement date 2012.02.08 discloses a kind of method preparing manganese phosphate lithium/carbon composite material with manganese phosphate; the method first prepares active manganese phosphate; then by active manganese phosphate and the mixing of lithium source; and add carbon source; after above-mentioned substance is asked mill; carry out spraying dry; dried powder is heat-treated under protective atmosphere, is warming up to 300 ~ 850 DEG C, calcines 2 ~ 12 hours; then naturally cool, obtain manganese phosphate lithium/carbon composite material.Carbon source in the method is the one 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, when adopting organic substance as carbon source, still there is pyrolysis product uneven, easily cause the lithium manganese phosphate lot stability of synthesis not good, and organic cracking generation is porous carbon, material specific surface area can be caused large, be unfavorable for the problem of the preparation of cell size; When adopting inorganic matter as carbon source, the addition of carbon source reaches more than the 15wt% of synthesis material, the addition of carbon source is too much, although the high rate performance of lithium manganese phosphate greatly can be improved, 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 that the coated lithium manganese phosphate lot stability of the material with carbon element in order to solve prior art is not good, not easily disperse during slurrying, 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, is easy to the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black be dispersed in water.
Present invention also offers a kind of preparation method of the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black, the method processing step is simple, and cost is low, and obtained particle size 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 coated lithium manganese phosphate of oxidation conductive carbon black, the described metal-doped coated lithium manganese phosphate of oxidation conductive carbon black with Li source compound, manganese source compound, P source compound, metalic contamination and carbon source for raw material is prepared from, described carbon source is oxidation conductive carbon black, and the chemical formula of this metal-doped coated lithium manganese phosphate of oxidation conductive carbon black 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, its surface is containing more oxygen-containing functional group, 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 the conductivity that a small amount of oxidation conductive black just can improve material lithium manganese phosphate greatly, and do not affect specific capacity, adulterated by the manganese position of metallic element to lithium manganese phosphate simultaneously, make the structure cell generation deformation of lithium manganese phosphate, significantly improve electronic conductivity and the lithium ion mobility speed of manganese-lithium phosphate anode material, with the coordinated of oxidation conductive carbon black, greatly can 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, metalic contamination is one or more in the carbonate of the oxide of metal-doped element, the hydroxide of metal-doped element and metal-doped element.
The coated lithium manganese phosphate preparation method of metal-doped oxidation conductive carbon black, comprises the following steps:
(1) conductive carbon black preparation is oxidized
(1) anneal conductive black at 270 ~ 290 DEG C 12 ~ 15h.This is one of committed step of the present invention, and the 12 ~ 15h that anneals at 270 ~ 290 DEG C to remove impurity in conductive carbon black and free carbon, otherwise is unfavorable for the finishing of conductive carbon black in subsequent step, and can bring impurity to product.
(2) conductive carbon black obtained in step (1) added in strong oxidizer soak, after filtration by filter residue cleaning to pH in neutral, finally dry and obtain oxidation conductive carbon black.Conductive carbon black soaks in strong oxidizer, gas can be produced, mutually peel off between conductive carbon black, structure changes, and forms the structure of similar Graphene, its surface is containing more oxygen-containing functional group simultaneously, hydrophilicity is good, and the oxidation conductive carbon black obtained through strong oxidizer process is not only easy to be dispersed in water, and the more common conductive carbon black of electric conductivity obtains larger lifting, its mechanism is still not clear, and may be that the change of conductive carbon black structure makes electronics more easily transmit.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
A () first weighs 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 carbon source again, the addition of carbon source is Li source compound, manganese source compound, 2 ~ 8% of P source compound and metalic contamination gross mass, the Li source compound finally will taken, manganese source compound, P source compound, be scattered in the mixed solvent that water or water and organic solvent forms after metalic contamination and carbon source mix, slurry is obtained after high-speed stirred or ultrasonic disperse or ball milling.Because oxidation conductive carbon black has better electric conductivity, relative to needing the organic carbon source of cracking or inorganic carbon source, its addition greatly reduces, and only needs 2 ~ 8%, can not impact battery capacity.
B the slurry spraying dry obtained in step (a) is placed in protective atmosphere and is warming up to 500 ~ 800 DEG C of Isothermal sinter 3 ~ 12h by (), pulverize, sieve, obtain the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black after being cooled to room temperature.
As preferably, strong oxidizer described in step (2) is the salpeter solution of 10mol/L, 10mol/L salpeter solution and 10mol/L sulfuric acid solution 1:2 ~ 3 form in mass ratio mixed solution, mass percentage are the H of 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 DEG C; When strong oxidizer be salpeter solution and sulfuric acid solution form mixed solution time, the mass ratio of conductive carbon black and mixed solution is 1:30 ~ 40, and soaking temperature is 60 ~ 80 DEG C; 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 DEG C; 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 DEG C.
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 DEG C/min.Heating rate is too fast, the phenomenon of explosion can be produced in preparation process, the particle size obtained is uneven, lattice local irregularity, and reactant all can not change into product, other impurity can be brought, the product chemical property obtained is poor, and heating rate is excessively slow, preparation efficiency is low, lattice constant can be reduced simultaneously, unit cell volume is shunk, lithium ion tunnel is diminished, there is difficulty in the deintercalation of lithium ion, the initial capacity of product can be reduced, in the present invention, heating rate controls at 2 ~ 4 DEG C/min, the product out-degree obtained is high, uniform particle sizes, lattice is regular, discharge capacity is high, cycle performance is good.
Therefore, the present invention has following beneficial effect:
(1) adulterated by the manganese position of metallic element to lithium manganese phosphate, adopt oxidation conductive carbon black to carry out coated to lithium manganese phosphate, by both synergies, make lithium manganese phosphate be easy to be dispersed in water, be conducive to slurrying, greatly can improve capacity and the cycle performance of lithium manganese phosphate simultaneously;
(2) the more common conductive carbon black of the oxidation conductive carbon black electric conductivity obtained through strong oxidizer process obtains larger lifting, and can reduce the addition of carbon source, the product capacitance obtained is high;
(3) first annealing in process being carried out to remove impurity in conductive carbon black and free carbon to conductive carbon black when preparing oxidation conductive carbon black, being conducive to the finishing of conductive carbon black and the raising of product purity in subsequent step;
(4), during preparation calcining, heating rate controls at 2 ~ 4 DEG C/min, and the product out-degree obtained is high, uniform particle sizes, and lattice is regular, and discharge capacity is high, and cycle performance is good;
(5) processing step is simple, and cost is low, and obtained particle size is even, and purity is high, and chemical property is good.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the coated lithium manganese phosphate of oxidation conductive carbon black metal-doped in embodiment 1.
Fig. 2 is the XRD figure of the coated lithium manganese phosphate of oxidation conductive carbon black metal-doped in embodiment 1.
Fig. 3 is the half-cell discharge curve first that the coated lithium manganese phosphate of oxidation conductive carbon black metal-doped in embodiment 1 is made.
Fig. 4 is the resultant battery cycle performance 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.
Embodiment 1
(1) conductive carbon black preparation is oxidized
(1) anneal conductive black at 270 DEG C 15h.
(2) conductive carbon black obtained in step (1) is added in strong oxidizer soak, strong oxidizer is the salpeter solution of 10mol/L, soaking temperature is 60 DEG C, the mass ratio of conductive carbon black and salpeter solution is 1:40, it is neutral for being cleaned by filter residue to pH after filtration, finally dries and obtains oxidation conductive carbon black.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
A () is in elemental lithium: manganese element: P elements: the mol ratio of metal-doped element is the ratio weighing Li source compound of 1:0.999:1:0.001, 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, be scattered in water after magnesium hydroxide and the mixing of oxidation conductive carbon black, slurry after ball milling.
B the slurry spraying dry obtained in step (a) is placed in protective atmosphere and is warming up to 500 DEG C of Isothermal sinter 12h with the heating rate of 2 DEG C/min by (), pulverize after being cooled to room temperature, sieve, obtaining chemical formula is LiMg
0.001mn
0.999pO
4the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black of/C.
one, Micro-Structure Analysis
The metal-doped coated lithium manganese phosphate of oxidation conductive carbon black utilizing electron microscope observation to obtain, the microscopic pattern obtained as shown in Figure 1.
As can be seen from Figure 1, the primary particle uniform particle sizes of the product obtained, and lattice local structured.
Carry out X-ray diffraction to the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black, the spectrogram obtained as shown in Figure 2.
Do not have the base peak of C as can be seen from Figure 2 in spectrogram, illustrate that C exists as an amorphous form, do not have other assorted peaks in addition in spectrogram, illustrate that the product of synthesis is pure olivine lithium manganese phosphate phase, the purity of product is high.
Test other physical indexs of material, recording in material the carbon amounts being oxidized conductive carbon 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
Be LiMg by the chemical formula obtained
0.001mn
0.999pO
4the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black of/C is positive pole, and lithium alkoxide is that negative pole makes half-cell, at 20 ± 5 DEG C, carries out half-cell test under the condition of 0.2C, and the discharge curve first obtained 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 oxidation conductive carbon black that the present invention is metal-doped is high.
The metal-doped coated lithium manganese phosphate of oxidation conductive carbon black, conductive carbon black (SP), the binding agent HSV900 of embodiment 1 gained is taken respectively with the mass ratio of 83:7:10, mix in nmp solvent, drying, roll-in, cut-parts, make electrode, negative pole selects metal lithium sheet, and electrolyte is the LiPF of the 1.0mol/L be dissolved 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.To the battery obtained at 20 ± 5 DEG C, carry out charge-discharge test with 1C/1C charge-discharge magnification, the cycle performance figure obtained as shown in Figure 4.
As can be seen from Figure 4, through 1000 circulations, the capability retention of battery, still about 90%, illustrates that metal-doped oxidation conductive carbon black coated lithium manganese phosphate high rate performance of the present invention is good, and good cycling stability.
Embodiment 2
(1) conductive carbon black preparation is oxidized
(1) anneal conductive black at 280 DEG C 13h.
(2) conductive carbon black obtained in step (1) is added in strong oxidizer soak, strong oxidizer is 10mol/L salpeter solution and the 10mol/L sulfuric acid solution mixed solution that forms of 1:3 in mass ratio, soaking temperature is 70 DEG C, the mass ratio of conductive carbon black and mixed solution is 1:30, it is neutral for being cleaned by filter residue to pH after filtration, finally dries and obtains oxidation conductive carbon black.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
A () is in elemental lithium: manganese element: P elements: the mol ratio of metal-doped element is the ratio weighing Li source compound of 1:0.9:1:0.1, 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, be scattered in water after alundum (Al2O3) and the mixing of oxidation conductive carbon black, slurry after ball milling.
B the slurry spraying dry obtained in step (a) is placed in protective atmosphere and is warming up to 700 DEG C of Isothermal sinter 8h with the heating rate of 3 DEG C/min by (), pulverize after being cooled to room temperature, sieve, obtaining chemical formula is LiMg
0.1mn
0.9pO
4the coated lithium manganese phosphate of oxidation conductive carbon black that/C is metal-doped.
SEM figure, the XRD figure of the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black that the present embodiment obtains and the half-cell made be similar all to embodiment 1 of discharge curve and the resultant battery cycle performance figure that makes first, therefore do not enumerate at this and repeat.
Embodiment 3
(1) conductive carbon black preparation is oxidized
(1) anneal conductive black at 290 DEG C 12h.
(2) conductive carbon black obtained in step (1) is added in strong oxidizer soak, the ammonium persulfate solution of strong oxidizer to be mass concentration be 20g/L, soaking temperature is 25 DEG C, the mass ratio of conductive carbon black and mixed solution is 1:50, it is neutral for being cleaned by filter residue to pH after filtration, finally dries and obtains oxidation conductive carbon black.
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
A () is in elemental lithium: manganese element: P elements: the mol ratio of metal-doped element is the ratio weighing Li source compound of 1:0.95:1:0.05, 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, be scattered in water after titanium dioxide and the mixing of oxidation conductive carbon black, slurry after ball milling.
B the slurry spraying dry obtained in step (a) is placed in protective atmosphere and is warming up to 800 DEG C of Isothermal sinter 3h with the heating rate of 4 DEG C/min by (), pulverize after being cooled to room temperature, sieve, obtaining chemical formula is LiMg
0.05mn
0.95pO
4the coated lithium manganese phosphate of oxidation conductive carbon black that/C is metal-doped.
SEM figure, the XRD figure of the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black that the present embodiment obtains and the half-cell made be similar all to embodiment 1 of discharge curve and the resultant battery cycle performance figure that makes first, therefore do not enumerate at this and repeat.
All can implement in other technologies scheme of the present invention, therefore not enumerate at this.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (2)
1. the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black, it is characterized in that, the described metal-doped coated lithium manganese phosphate of oxidation conductive carbon black is with Li source compound, manganese source compound, P source compound, metalic contamination and carbon source are that raw material is prepared from, described Li source compound is lithium carbonate, lithium hydroxide, lithium acetate, lithium dihydrogen phosphate, one or more in lithium phosphate, described carbon source is oxidation conductive carbon black, described manganese source compound is manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese oxalate, manganese phosphate, manganese acetate, one or more in manganese nitrate, described P source compound is phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, one or more in phosphoric acid dihydro amine, described metalic contamination is the oxide of metal-doped element, one or more in the hydroxide of metal-doped element and the carbonate of metal-doped element, described metal-doped element is Mg, Ti, V, Bi, Nb, Zn or Al, the chemical formula of the described metal-doped coated lithium manganese phosphate of oxidation conductive carbon black is: LiM
xmn
1-xpO
4/ C, wherein M is metal-doped element, 0.001≤x≤0.1, and the preparation method of this metal-doped coated lithium manganese phosphate of oxidation conductive carbon black is:
(1) conductive carbon black preparation is oxidized
(1) anneal conductive black at 270 ~ 290 DEG C 12 ~ 15h;
(2) conductive carbon black obtained in step (1) is added in strong oxidizer soak, filter residue is cleaned to pH in neutral after filtration, finally dry and obtain oxidation conductive carbon black, described strong oxidizer is the salpeter solution of 10mol/L, 10mol/L salpeter solution and 10mol/L sulfuric acid solution 1:2 ~ 3 form in mass ratio mixed solution, mass percentage be the H of 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 DEG C; When strong oxidizer be salpeter solution and sulfuric acid solution form mixed solution time, the mass ratio of conductive carbon black and mixed solution is 1:30 ~ 40, and soaking temperature is 60 ~ 80 DEG C; 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 DEG C; 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 DEG C;
(2) the coated lithium manganese phosphate preparation of metal-doped oxidation conductive carbon black
A () first weighs 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 carbon source again, the addition of carbon source is Li source compound, manganese source compound, 2 ~ 8% of P source compound and metalic contamination gross mass, the Li source compound finally will taken, manganese source compound, P source compound, be scattered in the mixed solvent that water or water and organic solvent forms after metalic contamination and carbon source mix, slurry is obtained after high-speed stirred or ultrasonic disperse or ball milling,
B the slurry spraying dry obtained in step (a) is placed in protective atmosphere and is warming up to 500 ~ 800 DEG C of Isothermal sinter 3 ~ 12h with the heating rate of 2 ~ 4 DEG C/min by (); pulverize after being cooled to room temperature, sieve, obtain the metal-doped coated lithium manganese phosphate of oxidation conductive carbon black.
2. a kind of metal-doped coated lithium manganese phosphate of oxidation conductive carbon black according to claim 1, it 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.
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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 |