CN102249208A - Hydrothermal synthesis method for lithium ferromanganese phosphate anode material of lithium ion battery - Google Patents
Hydrothermal synthesis method for lithium ferromanganese phosphate anode material of lithium ion battery Download PDFInfo
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Abstract
The invention relates to a hydrothermal synthesis method for lithium ferromanganese phosphate anode material of a lithium ion battery, belonging to the technical field of lithium ion batteries. The method has the following processing steps of: step 1, preparing LiMnxFe1-xPO4 through a hydrothermal synthesis reaction: mixing an aqueous lithium hydroxide solution, an aqueous ferrous sulfate solution and phosphoric acid under a stirring condition, after sealing, heating to 150 DEG C to 180 DEG C within 0.5 to 2 h, reacting for 0.5-4 h under the pressure of 0.48-1.0 Mpa, cooling to less than 80 DEG C, and filtering; step 2, mixing with organic matters and drying: mixing a wet filter cake with a soluble carbon source organic matter, and carrying out spray drying or expansion drying; and step 3, carrying out carbon-coated processing: roasting LiMnxFe1-xPO4 carbon source compound powder at a temperature between 600 DEG C and 750 DEG C for 4-6 h under an insert gas condition, and cooling to less than 150 DEG C to obtain a carbon-coated lithium ferromanganese phosphate anode material of the lithium ion battery. The hydrothermal synthesis method disclosed by the invention has the advantages of simple and controllable technology, convenience for operation, low cost, high crystallization degree of products, uniform dispersion, high specific capacity, high conservation rate of the cycling capacity, and the like.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of hydrothermal synthesis method of ion battery positive pole material manganese lithium phosphate iron lithium.
Background technology
At present, be the positive electrode material with olivine structural of representative with the iron lithium phosphate, have characteristics such as security, inexpensive property, environment friendly because of it.Along with the adjustment of energy structure, the energy storage field is to the demands for higher performance of positive electrode material, and promptly material not only will have high specific storage, also will have high specific energy.In the existing method of iron lithium phosphate being carried out modification, useful transition metal as doping agent to improve the method for its chemical property.But the gained material has only a discharge platform.Proposed the preparation method of transition element lithium position doped iron lithium phosphate powder as CN1785799A, improved the high rate performance and the cycle performance of iron lithium phosphate, but the specific storage of this method gained material has been lower, discharge voltage plateau is 3.4V, and specific energy is not improved.CN101212049A discloses positive electrode material of doped iron phosphate lithium active substance and carbon composition and preparation method thereof, and the sparking voltage of this material is at 2.8V, and the specific energy of material is on the low side.
In the external document, Jiajun Chen, Shijun Wang, M.Stanley Whitlingham(Hydrothermal synthesis of cathode materials[J]. Journal of Power Sources 174 (2007): 442-448) reported with the synthetic LiMn of hydrothermal method
xFe
1-xPO
4, during x=0, obtain the LiFePO of pure phase at 180 ℃ of reaction 5h
4, product is a diamond platy, the thick about 100nm of sheet, length of side 1-3um.During x=1,, obtain pure phase LiMnPO 200 ℃ of reactions 2 days
4, its pattern is by the hundreds of nanometers of diameter, the diameter that the rod-shpaed particle of long 3 μ m is formed is a 25-50 μ m cluster shape ball.During x=0.5, the pattern of product is the cluster of being made up of the crystal grain of square.This material existence does not have technical problems such as high capacity and specific energy.
Summary of the invention
The present invention provides a kind of hydrothermal synthesis method of ion battery positive pole material manganese lithium phosphate iron lithium for solving the technical problem that exists in the known technology.
The purpose of this invention is to provide a kind of technology simple controllable that has, easy to operate, with low cost, product crystallization degree height, thing is mutually single, particle is tiny, is uniformly dispersed, and product has the hydrothermal synthesis method of the ion battery positive pole material manganese lithium phosphate iron lithium of characteristics such as higher specific storage and circulation volume conservation rate.
The present invention has higher discharge platform and than the ion battery positive pole material manganese lithium phosphate iron lithium technology of preparing of height ratio capacity, use the Hydrothermal Preparation material, realize that elemental iron and manganese dissolve each other in solid product, by the granular size of CONTROL PROCESS condition control material, provide a kind of and have the nano-micrometer structure, have the high specific storage and the anode material for lithium-ion batteries of specific energy.
The present invention passes through the composition of the proportioning of control reactant with control material, thereby controls the formation speed of nucleus and then control granular size with stirring velocity by controlling to feed in raw material; Control the crystalline pattern by the control heat-up rate.
The technical scheme that the hydrothermal synthesis method of ion battery positive pole material manganese lithium phosphate iron lithium of the present invention is taked for the technical problem that exists in the solution known technology is:
A kind of hydrothermal synthesis method of ion battery positive pole material manganese lithium phosphate iron lithium, be characterized in: hydrothermal synthesis method may further comprise the steps,
The first step, hydrothermal synthesis reaction prepare base mateiral LiMn
xFe
1-xPO
4
With lithium hydroxide aqueous solution, ferrous sulfate aqueous solution and phosphoric acid, under agitation condition, mix, after the sealing, in 0.5-2.0 hour, be warming up to 150-180 ℃, under 0.48～1.0Mpa pressure, reacted 0.5-4 hour, be cooled to below 80 ℃, filter and obtain filter cake and mother liquor;
In second step, mix and drying with organism
Wet cake mixes with solubility carbon source organism, and the mode of spraying drying or expansion drying obtains LiMn at air drying
xFe
1-xPO
4The carbon source composite powder;
In the 3rd step, carbon coats to be handled
With LiMn
xFe
1-xPO
4The carbon source composite powder in 600～750 ℃ of roastings 4～6 hours, is cooled to below 150 ℃ under inert gas conditions, and discharging obtains the iron manganese phosphate for lithium anode material for lithium-ion batteries that carbon coats.
The hydrothermal synthesis method of ion battery positive pole material manganese lithium phosphate iron lithium of the present invention can also be taked following technical scheme:
The hydrothermal synthesis method of described ion battery positive pole material manganese lithium phosphate iron lithium is characterized in: the concentration of lithium hydroxide aqueous solution is 0.3～3.6 mol/L Li
+, the concentration of ferrous sulfate aqueous solution is 0.1～1.2mol/L Fe
2+, phosphoric acid is 50～85% industrial phosphoric acid; When three kinds of solution mixed, molar ratio was Li:M:P=3.00～3.20:1.00:1.03～1.15, and wherein, M is the mixture in Fe source and Mn source, M=Mn
x+ Fe
1-x, 0.01≤x≤0.80, x represents the mol ratio of manganese element and manganese, ferro element resultant.
The hydrothermal synthesis method of described ion battery positive pole material manganese lithium phosphate iron lithium, be characterized in: lithium hydroxide aqueous solution, ferrous sulfate aqueous solution and phosphoric acid blended under agitation condition has 4 kinds of feed way in proper order: (1) adds phosphoric acid with ferrous sulfate aqueous solution earlier, mix, again lithium hydroxide aqueous solution is added above-mentioned mixed solution, mix; (2) earlier phosphoric acid is added lithium hydroxide aqueous solution, mix, again ferrous sulfate aqueous solution is added above-mentioned mixed solution, mix; Or (3) earlier add phosphoric acid with ferrous sulfate aqueous solution, mixes, and lithium hydroxide aqueous solution added above-mentioned mixed solution again, mixes; Or (4) earlier add ferrous sulfate aqueous solution with phosphoric acid, mixes, and lithium hydroxide aqueous solution added above-mentioned mixed solution again, mixes.
The hydrothermal synthesis method of described ion battery positive pole material manganese lithium phosphate iron lithium is characterized in: in 4 kinds of feed way, during again with the third mixing of materials, finish reinforced under brute force stirs in 2～5 minutes after preceding two kinds of materials mix.
The hydrothermal synthesis method of described ion battery positive pole material manganese lithium phosphate iron lithium is characterized in: stirring velocity 200-400rpm.
The hydrothermal synthesis method of described ion battery positive pole material manganese lithium phosphate iron lithium is characterized in: organism is glucose, sucrose, Zulkovsky starch, solubility phenolic resin, organism and LiMn
xFe
1-xPO
4The butt mass ratio be 10～20:100.
The hydrothermal synthesis method of described ion battery positive pole material manganese lithium phosphate iron lithium, be characterized in: the operational condition of spraying drying or expansion drying is: air atmosphere or stack gas atmosphere, 350 ℃-500 ℃ of opening for feed gas temperatures, 100-200 ℃ of discharge port gas temperature.
The hydrothermal synthesis method of described ion battery positive pole material manganese lithium phosphate iron lithium is characterized in: carbon coats when handling, and takes the naturally cooling mode to be cooled to below 150 ℃, and discharging is sieved with 325 mesh sieves.
Advantage and positively effect that the present invention has are:
The hydrothermal synthesis method of ion battery positive pole material manganese lithium phosphate iron lithium is owing to adopted brand-new technology scheme of the present invention, and compared with prior art, the present invention has the following advantages:
1. reaction raw materials reacts with the solution form, and various materials can reach molecular level to be mixed.The crystallization degree height of product, thing is mutually single, and particle is tiny, is uniformly dispersed, and has nanostructure on the lithium ion dispersal direction, and product has higher specific storage and circulation volume conservation rate.
2. product is corresponding has 4.1V and two charge and discharge platform of 3.45V, and the length of two platforms is than corresponding with the mol ratio of manganese and iron, and product has higher specific energy.
3. control the nucleus formation speed by control feed way, feed rate, stirring velocity, thus by the control heat-up rate with control crystal growth control granular size, help production control and reduce cost.
4. facility investment is little, technology simple controllable, batch good stability of product.
The present invention can significantly improve the specific storage and the specific energy of material, particularly has great application prospect aspect power lithium-ion battery and the energy-storage battery at secondary lithium battery.
Description of drawings
Fig. 1 is the XRD figure spectrum of products therefrom of the present invention;
LiMn
xFe
1-xPO
4The XRD figure spectrum of/C product, wherein, x=0.6 is the sample of embodiment 1, and x=0.8 is the sample of embodiment 2, and x=0.3 is the sample of embodiment 3, and x=0.02 is the sample of embodiment 5.
Fig. 2 is the stereoscan photograph of products therefrom of the present invention;
Fig. 3 is the discharge curve of products therefrom of the present invention;
LiMn
xFe
1-xPO
4The test condition of the discharge curve of/C: 25 ℃, the 0.2C multiplying power discharging.Wherein, x=0.6 is the sample of embodiment 1, and x=0.8 is the sample of embodiment 2, and x=0.3 is the sample of embodiment 3, and x=0.02 is the sample of embodiment 5, and x=0 is the sample of comparative example 1.
Embodiment
For further understanding technology contents of the present invention, characteristics and effect, exemplify following examples now, and be described with reference to the accompanying drawings as follows:
Embodiment 1
Reactor: useful volume is 1000L, and thermal oil chuck mode heats.
The first step, hydrothermal synthesis reaction prepare base mateiral LiMn
0.6Fe
0.4PO
4(Li:M:P=3.00:1.00:1.03, x=0.6)
Taking by weighing 44.5kg is the FeSO of 0.16kmol
47H
2O and 40.56kg are the MnSO of 0.24kmol
4H
2O is water-soluble, and is diluted to 400L, leave standstill 2 hours after, filter with accurate filter, remove a spot of insolubles; Taking by weighing 47.5kg 85% phosphoric acid is the phosphoric acid of 0.412kmol, is the LiOHH of 1.05kmol with 44.2kg
2O is water-soluble, and is diluted to 400L.Filter standby with accurate filter.
Vacuumize earlier, feed oxide gas again and purge reactor to remove clean air in it, the air outlet adds water seal with sealing autoclave, opens charging valve, under the room temperature, adds phosphoric acid earlier, adds the mixing solutions of ferrous sulfate and manganous sulfate again.Start stirring, rotating speed is 200rpm, and lithium hydroxide solution is added in the reactor, and the reinforced time is 3 minutes.Sealing autoclave then, the temperature of setting thermal oil is 300 ℃, in 1 hour temperature is risen to 150 ℃ (this moment, corresponding autogenous pressure was 0.48Mpa), reacted 4 hours, and be cooled to 80 ℃, open bleeder valve, filter slip, and with deionized water wash to can't check sulfate radical.Mother liquor send storage tank standby (evaporating Lithium Sulphate recycles), and filter cake carries out next-step operation.
In second step, mix and drying with organism.
After measuring the solid content of wet cake, obtain the 62.6kg product in butt.Take by weighing 4kg dextrose anhydrous and 2.3kg water dissolvable starch, mix, add water 226kg water, stir with wet cake, be made into the slip that contains dry labor thing 30%, dry in air atmosphere with centrifugal spraying drying, 350 ℃ of air inlet temperatures, 120 ℃ of air outlet temperatures obtain white powder, i.e. LiMn
0.6Fe
0.4PO
4/ carbon source mixture.
In the 3rd step, carbon coats to be handled
LiMn with the second step gained
0.6Fe
0.4PO
4/ glucose composite powder in 750 ℃ of roastings 6 hours, naturally cools to below 150 ℃ under the oxide gas protection, opens calciner, and discharging behind 325 mesh sieves, obtains the iron manganese phosphate for lithium product LiMn that carbon coats excessively
0.6Fe
0.4PO
4/ C.
Fig. 1 is the X-ray diffracting spectrum of product of the present invention.Wherein the collection of illustrative plates of x=0.6 is the XRD figure spectrum of present embodiment, and it is identical with the standard spectrum (PDF#40-1499) of the top.As can be seen from Figure 1, diffraction peak is sharp-pointed, illustrates that the present embodiment product is the iron manganese phosphate for lithium thing phase of single olivine structural, and the well-crystallized of product.
Fig. 2 is the electron scanning micrograph of present embodiment product, and particle size 0.2～1.0 μ m is uniformly dispersed, and grain refine can shorten the lithium ion the evolving path, helps overcoming the low shortcoming of lithium ion diffusivity of olivine structural material.
The charge-discharge performance test of present embodiment product: with LiMn
0.6Fe
0.4PO
4The mixed that/C, acetylene black, 60% ptfe emulsion are pressed mass ratio 8:1:1 is rolled into the sheet that thickness is 0.10～0.12mm, in 120 ℃ of vacuum-dryings 2 hours, with the blunderbuss cutting-out of φ=10mm, makes the positive pole of battery.With metal lithium sheet is the LiPF of negative pole, 1M
6(NSC 11801: methylcarbonate: Methyl ethyl carbonate=1:1:1) is electrolytic solution to solution, with the barrier film (model 3074) of Ube company, be assembled into button cell with above-mentioned positive pole, under the room temperature (25 ± 2 ℃), discharge and recharge with the 0.2C multiplying power, the voltage range that discharges and recharges is 4.2-2.3V.
The electrochemical property test of present embodiment product is Fig. 3 and table 1 as a result.As seen from Figure 3, product has two discharge platforms, and respectively at 4.0V and 3.4V, two sections land lengths ratios are corresponding with the ratio of ferromanganese content.
Comparative example 1
The shared ratio of manganous sulfate among the embodiment 1 is become 0, and other is identical.
Products therefrom is LiFePO
4/ C.Its discharge curve has only the discharge platform in 3.4V place, and loading capacity is a little less than the LiMn of embodiment 1
0.02Fe
0.98PO
4/ C.Test result sees Table 1.
Comparative example 2
Order of addition(of ingredients) among the embodiment 1 is changed to: the mixing solutions with ferrous sulfate and manganous sulfate adds reactor earlier, adds lithium hydroxide solution again, starts stirring, and rotating speed is 200rpm, adds phosphoric acid again.The reinforced time is 3 minutes.Other is identical with embodiment 1.
Because iron, mn ion form the low oxyhydroxide of reactive behavior easily under strong alkaline condition, hydro-thermal synthetic product shows slightly brown after drying, has illustrated that unreacted ferrous iron behind ingress of air, has formed ferric compound.The electrochemical property test of product the results are shown in Table 1.
Comparative example 3
Heating-up time among the embodiment 1 is changed to 3 hours, and behind promptly reinforced the finishing, the temperature of setting thermal oil is 250 ℃, and making room temperature to the 150 ℃ temperature-rise period time is 3 hours.Other is with embodiment 1.
Product S EM figure shows that particle is bigger.Explanation is when heating up with lower rate of heating, and product grows up to macrobead easily.Electrochemical property test the results are shown in Table 1.
Comparative example 4
The speed of the hydro-oxidation lithium solution among the embodiment 1 is slack-off, become with 15 minutes lithium hydroxide is added, stirring velocity becomes 100rpm.Other is with embodiment 1.
The electrochemical property test of product the results are shown in Table 1.
Comparative example 5
Hydro-thermal synthetic product LiMn with embodiment 1 gained
0.6Fe
0.4PO
4At first in vacuum drying oven 120 ℃ be dried to constant weight, with micronizer mill it is mixed with the 6.3kg grape again.Carbon coats treating processes with embodiment 1.
The electrochemical property test of product the results are shown in Table 1.
The first step, hydrothermal synthesis reaction prepare base mateiral LiMn
0.8Fe
0.2PO
4
Taking by weighing 2.22kg is the FeSO of 0.008kmol
47H
2O and 5.41kg are the MnSO of 0.032kmol
4H
2O is water-soluble, and is diluted to 400L, leave standstill 10 hours after, filter, remove a spot of insolubles; Taking by weighing 5.3kg 85% phosphoric acid is the phosphoric acid of 0.046kmol, is the LiOHH of 0.128kmol with 5.37kg
2O is water-soluble, and is diluted to 400L.Filter standby.
Vacuumize earlier, feed oxide gas again and purge reactor to remove clean air in it, the air outlet adds water seal with sealing autoclave, under the room temperature, adds phosphoric acid earlier, adds lithium hydroxide solution again.Start stirring, rotating speed is 300rpm, and in the mixing solutions adding reactor with ferrous sulfate and manganous sulfate, the reinforced time is 2 minutes.Sealing autoclave then, the temperature of setting thermal oil is 320 ℃, in 1 hour temperature is risen to 180 ℃ (this moment, corresponding autogenous pressure was 1.0Mpa), reacted 0.5 hour, and be cooled to 80 ℃, open bleeder valve, filter slip, and with deionized water wash to can't check sulfate radical.Mother liquor send storage tank standby (evaporating Lithium Sulphate recycles), and filter cake carries out next-step operation.
In second step, mix and drying with organism.
After measuring the solid content of wet cake, obtain the 6.38kg product in butt.Take by weighing 0.32kg sucrose and 0.32kg water dissolvable starch, with twin screw mixing machine with it with after wet cake mixes, dry in air atmosphere with the Flash Type drying machine, 350 ℃ of air inlet temperatures, 120 ℃ of air outlet temperatures obtain white powder, i.e. LiMn
0.6Fe
0.4PO
4/ carbon source mixture.
In the 3rd step, carbon coats to be handled
LiMn with the second step gained
0.8Fe
0.2PO
4/ glucose composite powder in 750 ℃ of roastings 6 hours, naturally cools to below 150 ℃ under the oxide gas protection, opens calciner, and discharging behind 325 mesh sieves, obtains the iron manganese phosphate for lithium product LiMn that carbon coats excessively
0.8Fe
0.2PO
4/ C.
The collection of illustrative plates of x=0.8 is the XRD figure spectrum of present embodiment among Fig. 1, and it is identical with the standard spectrum (PDF#40-1499) of the top.As can be seen from Figure 1, diffraction peak is sharp-pointed, illustrates that the present embodiment product is the iron manganese phosphate for lithium thing phase of single olivine structural, and the well-crystallized of product.
With the product LiMn that obtains
0.8Fe
0.2PO
4/ C carries out the test of chemical property by embodiment 1 identical method, the results are shown in Figure 3 and table 1.As seen from Figure 3, product has two discharge platforms, and respectively at 4.0V and 3.4V, two sections land lengths ratios are corresponding with the ratio of ferromanganese content.
Comparative example 6
Change the amount of phosphoric acid among the embodiment 2 into 36.9kg(0.32kmol), other is constant.
Test result sees Table 1.
Comparative example 7
Change the amount of lithium hydroxide among the embodiment 2 into 39.0kg(0.928kmol), other is constant.
Test result sees Table 1.
Embodiment 3
The first step, hydrothermal synthesis reaction prepare base mateiral LiMn
0.3Fe
0.7PO
4
Taking by weighing 40.1kg is the FeSO of 0.144kmol
47H
2O and 56.76kg are the MnSO of 0.336kmol
4H
2O is water-soluble, and is diluted to 400L, leave standstill 12 hours after, filter, remove a spot of insolubles; Taking by weighing 58.1kg 85% phosphoric acid is the phosphoric acid of 0.504kmol, is the LiOHH of 1.49kmol with 62.4kg
2O is water-soluble, and is diluted to 400L.Filter standby.
Vacuumize earlier, feed oxide gas again and purge reactor to remove clean air in it, the air outlet adds water seal with sealing autoclave, under the room temperature, earlier the mixing solutions of ferrous sulfate and manganous sulfate is added in the reactor, add phosphoric acid again from charging opening, start stirring, rotating speed is 300rpm, adds lithium hydroxide solution again, and the reinforced time is 5 minutes.Sealing autoclave then, the temperature of setting thermal oil is 305 ℃, in 1 hour temperature is risen to 160 ℃ (this moment, corresponding autogenous pressure was 1.0Mpa), reacted 2 hours, and be cooled to 80 ℃, open bleeder valve, filter slip, and with deionized water wash to can't check sulfate radical.Mother liquor send storage tank standby (evaporating Lithium Sulphate recycles), and filter cake carries out next-step operation.
In second step, mix and drying with organism.
After measuring the solid content of wet cake, obtain the 76kg product in butt.Take by weighing 2.6kg dextrose anhydrous and 5.0kg sucrose, with twin screw mixing machine with it with after wet cake mixes, dry in air atmosphere with the Flash Type drying machine, 350 ℃ of air inlet temperatures, 120 ℃ of air outlet temperatures obtain white powder, i.e. LiMn
0.3Fe
0.7PO
4/ carbon source mixture.
In the 3rd step, carbon coats to be handled
LiMn with the second step gained
0.3Fe
0.7PO
4/ glucose composite powder in 700 ℃ of roastings 6 hours, naturally cools to below 150 ℃ under the oxide gas protection, opens calciner, and discharging behind 325 mesh sieves, obtains the iron manganese phosphate for lithium product LiMn that carbon coats excessively
0.3Fe
0.7PO
4/ C.
The collection of illustrative plates of x=0.3 is the XRD figure spectrum of present embodiment among Fig. 1, and it is identical with the standard spectrum (PDF#40-1499) of the top.As can be seen from Figure 1, diffraction peak is sharp-pointed, illustrates that the present embodiment product is the iron manganese phosphate for lithium thing phase of single olivine structural, and the well-crystallized of product.
With the product LiMn that obtains
0.3Fe
0.7PO
4/ C carries out the test of chemical property by embodiment 1 identical method, the results are shown in Figure 3 and table 1.As seen from Figure 3, product has two discharge platforms, and respectively at 4.0V and 3.4V, two sections land lengths ratios are corresponding with the ratio of ferromanganese content.
Embodiment 4
Change the feed way of material among the embodiment 1 into the 4th kind of feed way, that is, under the room temperature, earlier lithium hydroxide solution is added reactor, add phosphoric acid again, start stirring, rotating speed is 200rpm, adds the mixing solutions of ferrous sulfate and manganous sulfate again.The reinforced time is 3 minutes.Other is identical with embodiment 1.
The electro-chemical test curve of material is identical with embodiment 1, shows two discharge platforms.Test result sees Table 1.
Embodiment 5
The shared ratio of manganous sulfate among the embodiment 1 is become 0.02, and other is constant.
The electro-chemical test curve of product is seen Fig. 3, and test result sees Table 1.As seen from Figure 3, the ratio of manganese element hour does not show the discharge platform at 4.0V place substantially, but is to compare the specific storage maximum of material at 0 o'clock with the manganese element ratio when big with the manganese element ratio.
As can be seen from the above embodiments, specific energy LiMnxFe1-xPO4/C(x=0.02-0.8) exceeds 2.9-6.3% than the specific energy of LiFePO4/C.
The Electrochemical results of table 1 product
Claims (8)
1. the hydrothermal synthesis method of an ion battery positive pole material manganese lithium phosphate iron lithium, it is characterized in that: hydrothermal synthesis method may further comprise the steps,
The first step, hydrothermal synthesis reaction prepare base mateiral LiMn
xFe
1-xPO
4
With lithium hydroxide aqueous solution, ferrous sulfate aqueous solution and phosphoric acid, under agitation condition, mix, after the sealing, in 0.5-2.0 hour, be warming up to 150-180 ℃, under 0.48～1.0Mpa pressure, reacted 0.5-4 hour, be cooled to below 80 ℃, filter and obtain filter cake and mother liquor;
In second step, mix and drying with organism
Wet cake mixes with solubility carbon source organism, and the mode of spraying drying or expansion drying obtains LiMn at air drying
xFe
1-xPO
4The carbon source composite powder;
In the 3rd step, carbon coats to be handled
With LiMn
xFe
1-xPO
4The carbon source composite powder in 600～750 ℃ of roastings 4～6 hours, is cooled to below 150 ℃ under inert gas conditions, and discharging obtains the iron manganese phosphate for lithium anode material for lithium-ion batteries that carbon coats.
2. according to the hydrothermal synthesis method of the described ion battery positive pole material manganese lithium phosphate iron of claim 1 lithium, it is characterized in that: the concentration of lithium hydroxide aqueous solution is 0.3～3.6 mol/L Li
+, the concentration of ferrous sulfate aqueous solution is 0.1～1.2mol/L Fe
2+, phosphoric acid is 50～85% industrial phosphoric acid; When three kinds of solution mixed, molar ratio was Li:M:P=3.00～3.20:1.00:1.03～1.15, and wherein, M is the mixture in Fe source and Mn source, M=Mn
x+ Fe
1-x, 0.01≤x≤0.80, x represents the mol ratio of manganese element and manganese, ferro element resultant.
3. according to the hydrothermal synthesis method of the described ion battery positive pole material manganese lithium phosphate iron of claim 1 lithium, it is characterized in that: lithium hydroxide aqueous solution, ferrous sulfate aqueous solution and phosphoric acid blended under agitation condition has 4 kinds of feed way in proper order: (1) adds phosphoric acid with ferrous sulfate aqueous solution earlier, mix, again lithium hydroxide aqueous solution is added above-mentioned mixed solution, mix; Or (2) earlier add lithium hydroxide aqueous solution with phosphoric acid, mixes, and ferrous sulfate aqueous solution added above-mentioned mixed solution again, mixes; Or (3) earlier add phosphoric acid with ferrous sulfate aqueous solution, mixes, and lithium hydroxide aqueous solution added above-mentioned mixed solution again, mixes; Or (4) earlier add ferrous sulfate aqueous solution with phosphoric acid, mixes, and lithium hydroxide aqueous solution added above-mentioned mixed solution again, mixes.
4. according to the hydrothermal synthesis method of the described ion battery positive pole material manganese lithium phosphate iron of claim 3 lithium, it is characterized in that: in 4 kinds of feed way, during again with the third mixing of materials, under brute force stirs, finish reinforced in 2～5 minutes after preceding two kinds of materials mix.
5. according to the hydrothermal synthesis method of the described ion battery positive pole material manganese lithium phosphate iron of claim 4 lithium, it is characterized in that: stirring velocity 200-400rpm.
6. according to the hydrothermal synthesis method of the described ion battery positive pole material manganese lithium phosphate iron of claim 1 lithium, it is characterized in that: organism is glucose, sucrose, Zulkovsky starch, solubility phenolic resin, organism and LiMn
xFe
1-xPO
4The butt mass ratio be 10～20:100.
7. according to the hydrothermal synthesis method of the described ion battery positive pole material manganese lithium phosphate iron of claim 1 lithium, it is characterized in that: the operational condition of spraying drying or expansion drying is: air atmosphere or stack gas atmosphere, 350 ℃-500 ℃ of opening for feed gas temperatures, 100-200 ℃ of discharge port gas temperature.
8. according to the hydrothermal synthesis method of the described ion battery positive pole material manganese lithium phosphate iron of claim 1 lithium, it is characterized in that: carbon coats when handling, and takes the naturally cooling mode to be cooled to below 150 ℃, and discharging is sieved with 325 mesh sieves.
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441270A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium manganese phosphate cathode material |
| CN103682333A (en) * | 2012-08-29 | 2014-03-26 | 株式会社电装 | Positive-electrode active material, manufacturing method of the same, and nonaqueous electrolyte rechargeable battery having the same |
| CN103762362A (en) * | 2014-01-27 | 2014-04-30 | 厦门钨业股份有限公司 | Hydrothermal preparation method of nano lithium iron manganese phosphate anode material |
| CN104518216A (en) * | 2013-09-26 | 2015-04-15 | 清华大学 | Preparation method of lithium iron phosphate |
| CN104600294A (en) * | 2014-12-30 | 2015-05-06 | 山东精工电子科技有限公司 | High-capacity microrod lithium manganese iron phosphate material synthesized by hydrothermal process and preparation method thereof |
| CN104603050A (en) * | 2012-08-14 | 2015-05-06 | 科莱恩国际有限公司 | Mixed sulphate containing lithium-manganese-metal phosphate |
| CN105036103A (en) * | 2015-08-03 | 2015-11-11 | 山东威能环保电源科技股份有限公司 | Preparation method of cuboid lithium battery anode lithium ferric manganese phosphate material |
| CN105742610A (en) * | 2016-05-04 | 2016-07-06 | 合肥国轩高科动力能源有限公司 | Method for preparing carbon-coated lithium ferric manganese phosphate thin film type cathode material |
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| CN107720719A (en) * | 2017-11-03 | 2018-02-23 | 山东科技大学 | The method for preparing iron manganese phosphate for lithium using siderite and manganese spar |
| CN108408709A (en) * | 2018-03-30 | 2018-08-17 | 南阳逢源锂电池材料研究所 | A kind of preparation process of pollution-free inexpensive iron manganese phosphate for lithium crystalline material |
| CN110416525A (en) * | 2019-08-08 | 2019-11-05 | 上海华谊（集团）公司 | The composite material and preparation method of phosphoric acid manganese iron lithium with core-shell structure |
| CN111333049A (en) * | 2020-03-23 | 2020-06-26 | 蒋央芳 | Preparation method of lithium iron manganese phosphate |
| CN111816851A (en) * | 2020-06-22 | 2020-10-23 | 南昌大学 | Hierarchical porous LiMnxFe1-xPO4Template-free hydrothermal preparation method of/C composite microsphere cathode material |
| CN113066969A (en) * | 2021-03-26 | 2021-07-02 | 深圳市鹏冠新材料科技有限公司 | Preparation method of conductive polymer coated lithium manganese iron phosphate cathode material |
| CN113078319A (en) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | Preparation method of lithium iron manganese phosphate/carbon composite nanoparticle positive electrode material |
| CN113072049A (en) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | Preparation method of high-compaction-density lithium manganese iron phosphate/carbon composite positive electrode material |
| CN114314552A (en) * | 2021-12-31 | 2022-04-12 | 欣旺达电动汽车电池有限公司 | Lithium iron phosphate, preparation method thereof, lithium ion battery and electric drive device |
| CN114538404A (en) * | 2022-03-15 | 2022-05-27 | �田一弘 | Method for preparing lithium iron phosphate by using titanium dioxide byproduct ferrous sulfate |
| CN114835100A (en) * | 2022-04-26 | 2022-08-02 | 上海兰钧新能源科技有限公司 | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material |
| WO2023197483A1 (en) * | 2022-04-12 | 2023-10-19 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method for nano lithium manganese iron phosphate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621122A (en) * | 2009-08-07 | 2010-01-06 | 珠海市鹏辉电池有限公司 | Preparation method of lithium iron phosphate compound material |
| CN101891180A (en) * | 2010-07-07 | 2010-11-24 | 成都开飞高能化学工业有限公司 | Method for preparing sub-micrometer lithium iron phosphate (LiFePO4) |
-
2011
- 2011-05-06 CN CN2011101161524A patent/CN102249208A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101621122A (en) * | 2009-08-07 | 2010-01-06 | 珠海市鹏辉电池有限公司 | Preparation method of lithium iron phosphate compound material |
| CN101891180A (en) * | 2010-07-07 | 2010-11-24 | 成都开飞高能化学工业有限公司 | Method for preparing sub-micrometer lithium iron phosphate (LiFePO4) |
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| CN104603050A (en) * | 2012-08-14 | 2015-05-06 | 科莱恩国际有限公司 | Mixed sulphate containing lithium-manganese-metal phosphate |
| CN104603050B (en) * | 2012-08-14 | 2017-09-08 | 庄信万丰股份有限公司 | Mixing lithium manganese Metal phosphate containing sulfate |
| CN103682333A (en) * | 2012-08-29 | 2014-03-26 | 株式会社电装 | Positive-electrode active material, manufacturing method of the same, and nonaqueous electrolyte rechargeable battery having the same |
| CN103682333B (en) * | 2012-08-29 | 2016-03-09 | 株式会社电装 | Positive electrode active materials, its manufacture method and the nonaqueous electrolyte rechargeable battery containing it |
| TWI612716B (en) * | 2013-05-08 | 2018-01-21 | 台灣立凱電能科技股份有限公司 | Preparation method of battery composite material and precursor thereof |
| US10096832B2 (en) | 2013-05-08 | 2018-10-09 | Advanced Lithium Electrochemistry Co., Ltd. | Preparation method of battery composite material and precursor thereof |
| CN103441270A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium manganese phosphate cathode material |
| CN104518216B (en) * | 2013-09-26 | 2017-09-01 | 清华大学 | The preparation method of LiFePO4 |
| CN104518216A (en) * | 2013-09-26 | 2015-04-15 | 清华大学 | Preparation method of lithium iron phosphate |
| US9822014B2 (en) | 2013-09-26 | 2017-11-21 | Tsinghua University | Method for making lithium iron phosphate |
| CN103762362B (en) * | 2014-01-27 | 2016-04-13 | 厦门钨业股份有限公司 | A kind of hydrothermal preparing process of nano lithium iron manganese phosphate anode material |
| CN103762362A (en) * | 2014-01-27 | 2014-04-30 | 厦门钨业股份有限公司 | Hydrothermal preparation method of nano lithium iron manganese phosphate anode material |
| CN104600294A (en) * | 2014-12-30 | 2015-05-06 | 山东精工电子科技有限公司 | High-capacity microrod lithium manganese iron phosphate material synthesized by hydrothermal process and preparation method thereof |
| CN105036103B (en) * | 2015-08-03 | 2017-08-01 | 山东威能环保电源科技股份有限公司 | A kind of preparation method of cuboid-type anode material of lithium battery lithium ferric manganese phosphate |
| CN105036103A (en) * | 2015-08-03 | 2015-11-11 | 山东威能环保电源科技股份有限公司 | Preparation method of cuboid lithium battery anode lithium ferric manganese phosphate material |
| CN105742610A (en) * | 2016-05-04 | 2016-07-06 | 合肥国轩高科动力能源有限公司 | Method for preparing carbon-coated lithium ferric manganese phosphate thin film type cathode material |
| CN106784813A (en) * | 2016-11-19 | 2017-05-31 | 天津赫维科技有限公司 | A kind of preparation method of iron manganese phosphate lithium material |
| CN107720719A (en) * | 2017-11-03 | 2018-02-23 | 山东科技大学 | The method for preparing iron manganese phosphate for lithium using siderite and manganese spar |
| CN108408709A (en) * | 2018-03-30 | 2018-08-17 | 南阳逢源锂电池材料研究所 | A kind of preparation process of pollution-free inexpensive iron manganese phosphate for lithium crystalline material |
| CN110416525A (en) * | 2019-08-08 | 2019-11-05 | 上海华谊（集团）公司 | The composite material and preparation method of phosphoric acid manganese iron lithium with core-shell structure |
| CN111333049A (en) * | 2020-03-23 | 2020-06-26 | 蒋央芳 | Preparation method of lithium iron manganese phosphate |
| CN111816851B (en) * | 2020-06-22 | 2022-07-01 | 南昌大学 | Hierarchical porous LiMnxFe1-xPO4Template-free hydrothermal preparation method of/C composite microsphere cathode material |
| CN111816851A (en) * | 2020-06-22 | 2020-10-23 | 南昌大学 | Hierarchical porous LiMnxFe1-xPO4Template-free hydrothermal preparation method of/C composite microsphere cathode material |
| CN113066969A (en) * | 2021-03-26 | 2021-07-02 | 深圳市鹏冠新材料科技有限公司 | Preparation method of conductive polymer coated lithium manganese iron phosphate cathode material |
| CN113078319A (en) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | Preparation method of lithium iron manganese phosphate/carbon composite nanoparticle positive electrode material |
| CN113072049A (en) * | 2021-03-26 | 2021-07-06 | 天津斯科兰德科技有限公司 | Preparation method of high-compaction-density lithium manganese iron phosphate/carbon composite positive electrode material |
| CN113072049B (en) * | 2021-03-26 | 2023-01-31 | 天津斯科兰德科技有限公司 | Preparation method of high-compaction-density lithium manganese iron phosphate/carbon composite positive electrode material |
| CN114314552A (en) * | 2021-12-31 | 2022-04-12 | 欣旺达电动汽车电池有限公司 | Lithium iron phosphate, preparation method thereof, lithium ion battery and electric drive device |
| CN114314552B (en) * | 2021-12-31 | 2023-07-14 | 欣旺达电动汽车电池有限公司 | Lithium iron phosphate, preparation method thereof, lithium ion battery and electric driving device |
| CN114538404A (en) * | 2022-03-15 | 2022-05-27 | �田一弘 | Method for preparing lithium iron phosphate by using titanium dioxide byproduct ferrous sulfate |
| WO2023197483A1 (en) * | 2022-04-12 | 2023-10-19 | 深圳沃伦特新能源科技有限公司 | Hydrothermal synthesis method for nano lithium manganese iron phosphate |
| CN114835100A (en) * | 2022-04-26 | 2022-08-02 | 上海兰钧新能源科技有限公司 | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material |
| CN114835100B (en) * | 2022-04-26 | 2023-11-17 | 上海兰钧新能源科技有限公司 | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material |
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