CN103367746A - Multi-ion-doped carbon-coated lithium iron phosphate battery material and preparation method thereof - Google Patents

Multi-ion-doped carbon-coated lithium iron phosphate battery material and preparation method thereof Download PDF

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CN103367746A
CN103367746A CN2013102976748A CN201310297674A CN103367746A CN 103367746 A CN103367746 A CN 103367746A CN 2013102976748 A CN2013102976748 A CN 2013102976748A CN 201310297674 A CN201310297674 A CN 201310297674A CN 103367746 A CN103367746 A CN 103367746A
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杨志宽
刘登华
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Yantai Zhuoneng Battery Material Co Ltd
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Yantai Zhuoneng Battery Material Co Ltd
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Abstract

The invention discloses a multi-ion-doped carbon-coated lithium iron phosphate battery material and a preparation method thereof. The material has a structure of Li1-x M'x Fe1-y My (PO4)1-zFz/C, wherein x is more than or equal to 0.001 and less than or equal to 0.1, y is more than or equal to 0.001 and less than or equal to 0.1, z is more than or equal to 0.001 and less than or equal to 0.1, M' and M are respectively metal ions doped at the lithium position and the iron position, C is organic matter pyrolysis carbon covered on the surface of lithium iron phosphate, and M' and F come from fluoride M' Fn (n is equal to 1, 2, 3 or 4). The preparation method comprises the steps of: (1) preparing doped iron phosphate containing crystal water by a coprecipitation method; (2) carrying out heat treatment on the iron phosphate containing the crystal water, and removing the crystal water; and (3) mixing the doped iron phosphate, lithium source, the fluoride M' Fn and organic carbon source, carrying out ball-milling, drying and roasting to obtain the multi-ion-doped carbon-coated lithium iron phosphate battery material. The preparation method is simple and easy in technology, and the prepared lithium iron phosphate is high in specific discharge capacity and excellent in rate capability, thus having application prospect in the field of a power battery.

Description

Carbon-coated LiFePO 4 for lithium ion batteries battery material that a kind of polyion mixes and preparation method thereof
 
Technical field:
The present invention relates to a kind of ferric phosphate lithium cell material and preparation method thereof, relate in particular to carbon-coated LiFePO 4 for lithium ion batteries battery material that a kind of polyion for power lithium-ion battery, energy storage lithium ion battery field mixes and preparation method thereof.
Background technology:
Lithium ion battery has high voltage, high-energy-density, good cycle, memory-less effect, the advantage such as environment friendly and pollution-free, is widely used in the fields such as notebook computer, mobile phone, electronic instrument, electric automobile, electric bicycle, energy storage device.Positive electrode has become the object that various countries' researcher is competitively studied at present as the important component part of lithium ion battery.At present, common positive electrode has cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate and LiFePO4.Wherein, the olivine-type LiFePO4 is excellent owing to cycle performance, security performance good, cheap, anode material for lithium-ion batteries that the raw material wide material sources are considered to have most DEVELOPMENT PROSPECT and potentiality.
Yet the electronic conductivity of pure phase LiFePO4 is lower, causes its efficiency for charge-discharge and specific discharge capacity lower, and especially high rate performance is relatively poor, has greatly limited the extensive use of LiFePO4.Existing research mainly is the chemical property that improves LiFePO4 by material with carbon-coated surface and ion doping.Material with carbon-coated surface can improve the electronic conductivity of material, promotes the migration of lithium ion, improves efficiency for charge-discharge, improves multiplying power discharging property; Ion doping can change the crystal structure of LiFePO4, makes the lattice distorted, enlarges the lithium ion migrating channels, improves the specific discharge capacity of material.Application number is 201019026104.9 patent of invention " a kind of lithium ion battery cathode material antimony-doped lithium iron phosphate and preparation method ", lithium, iron, antimony, compounds of phosphorus are mixed by stoichiometric proportion, grind to form the slurry that particle is 0.4 ~ 2 μ m, under inert atmosphere, through 100 ~ 200 ℃ of preliminary treatment 6 ~ 12h, then be warming up to 700 ~ 800 ℃ of constant temperature 5 ~ 15h, cooling obtains the LiFePO 4 material that antimony mixes naturally.Application number is 200510132428.2 patent of invention " preparation method of transition element doped iron lithium phosphate powder ", with lithium salts, ferrous salt, phosphate and alloy once weigh, batch mixing, oven dry, low temperature presintering and high temperature secondary calcining, obtain transition element doped iron lithium phosphate powder Li 1-xTR xFePO 4, TR is Ni, Co, Mn.Application number is 200910303488.4 patent of invention " preparation method of the LiFePO4 of doping vario-property ", under the condition that surfactant exists, lithium compound, molysite, phosphate, carbon matrix precursor and alloy are mixed, and adopting the high temperature solid-state method roasting to obtain chemical formula after the ball-milling treatment is LiFe xM 1-xPO 4LiFePO 4 material, wherein M is at least a in Mg, Mn, Co or the Ni oxide.Application number is 200710008713.2 patent of invention " based on P site doped lithium iron phosphate positive material and preparation method thereof ", with ferrous salt, phosphate and alloy through the liquid phase ball milling mix, drying obtains intermediate product, again intermediate product is mixed with lithium salts liquid phase ball milling, drying, at last product roasting under inertia or reducing atmosphere is obtained doped lithium ferric phosphate Li yFe (P 1-xM x) O 4Powder, wherein M is Ge, Sn, Se, Te or Bi.Above-mentioned patented method all to LiFePO4 in the lithium position, iron position or phosphate potential carry out single doping vario-property, though improved to a certain extent the performance of LiFePO4, but it is limited that the performance that single doping brings improves, specific capacity and the indexs such as efficient, active material utilization, high rate performance are on the low side first, still can't satisfy electric automobile to requirements such as electrokinetic cell energy density, power densities, greatly limit the extensive use of ferric phosphate lithium cell material in the electric automobile field.
LiFePO4 is carried out two or multi-position doped research relevant report is also arranged.Application number is 201210050619.4 patent of invention " LiFePO 4 material of a kind of fluorine, vanadium ion-doped and preparation method thereof ", with lithium salts, molysite, phosphate, carbon source mix in proportion with fluorine, vanadium dopant, ball milling, high-temperature calcination, obtain the LiFePO 4 material of fluorine, vanadium ion-doped.Application number is 200810146486.4 patent of invention " multi-position doped lithium iron phosphate positive electrode material preparation method and application thereof ", adopts solid phase method production, through the simple stoving process that mixes, prepares multi-position doped LiFePO 4 material Li 1-xA xFe 1-yB yP 1-zC zO 4D δ, wherein among x, y, z, the δ at least two can not be 0 simultaneously.Though above-mentioned patent has been carried out multi-position doped modification to LiFePO4, but both carry out combination by simple raw material mixing, ball milling, roasting with alloy and host element material, can not guarantee distributing homogeneity and the occupy-place in LiFePO4 lattice thereof of doped chemical in LiFePO 4 material, cause easily the olivine-type crystallographic system structure mutation of LiFePO4, produce dephasign, reduce the material electrical property, do not have on the contrary and improve the effect that improves.
Summary of the invention:
The object of the invention is to overcome the deficiency of prior art and carbon-coated LiFePO 4 for lithium ion batteries battery material that a kind of polyion mixes and preparation method thereof is provided, be intended to improve efficiency for charge-discharge, specific discharge capacity and the high rate performance of LiFePO4, promote LiFePO 4 material in the application in electrokinetic cell field.
Purpose of the present invention can reach by following measure: the carbon-coated LiFePO 4 for lithium ion batteries battery material that a kind of polyion mixes, the structure of material is Li 1-xM` xFe 1-yM y(PO 4) 1-zF z/ C, 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1 wherein, M` and M are respectively the metal ion that mixes in lithium position and iron position, and C is the organic cracking carbon that is coated on the LiFePO4 surface, and M` and F be from same raw material, i.e. fluoride M`F n(n=1,2,3,4).
The preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material that a kind of polyion mixes comprises the steps:
The first step, coprecipitation prepares the ferric phosphate of doped metal ion M: (1) is (1-y) strictly in molar ratio: y, 0.001≤y≤0.1 wherein, accurate weighing solubility source of iron and the material that contains metal ions M, add deionized water, be mixed with the mixed solution A that total concentration of metal ions is 0.05 ~ 5mol/L; Preparation contains PO 4 3-Concentration is the phosphate solution B of 0.05 ~ 5mol/L; The ammonia spirit of preparation 0.5 ~ 10mol/L; (2) with peristaltic pump solution A and solution B are pumped in the reactor of rapid stirring, the control reaction temperature is 40 ~ 95 ℃, and mixing speed is 800 ~ 2500rpm, regulates the pH value between 2 ~ 3 with ammonia spirit, reaction 0.5 ~ 3h; (3) with above-mentioned reaction solution after filtration, washing, drying, obtain the ferric phosphate that is doped with metal ions M that white contains the crystallization water, be expressed as Fe 1-yM yPO 42H 2O.
Second step is heat-treated between 300 ~ 500 ℃ the ferric phosphate of the doped metal ion M that contains the crystallization water of first step preparation, and heating rate is 1 ~ 10 ℃/min, insulation 2 ~ 10h, naturally cool to room temperature, do not contained the ferric phosphate of the doped metal ion M of the crystallization water, be expressed as Fe 1-yM yPO 4
In the 3rd step, the ferric phosphate of the doped metal ion M that the employing second step obtains is pressed structural formula Li 1-xM` xFe 1-yM y(PO 4) 1-zF z/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1 takes by weighing lithium source, fluoride M`F n(n=1,2,3,4), the organic carbon source that adds simultaneously raw material total weight 15 ~ 20%, take alcohol as dispersant, through ball milling mix, the dry processing obtain precursor powder, under high pure nitrogen atmosphere, be raised to 650 ~ 820 ℃ with the heating rate of 1 ~ 10 ℃/min from room temperature and carry out high-temperature roasting, insulation 6 ~ 20h, naturally cool to room temperature, through pulverizing, sieving, obtain the carbon-coated LiFePO 4 for lithium ion batteries battery material that polyion mixes.
Described fluoride M`F n(n=1,2,3,4) are NaF, KF, MgF 2, CaF 2, AlF 3, ZnF 2, TiF 4, VF 4In a kind of.
A kind of in chloride, sulfate, nitrate and the organic salt that the described material that contains metal ions M is Ni, Co, Mn.
Described soluble ferric iron salt is a kind of in ferric sulfate, ferric nitrate, the iron chloride.
Described phosphate is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the ammonium phosphate.
Described lithium source is a kind of in lithium carbonate, lithium hydroxide, the lithium acetate.
Described organic carbon source is a kind of in glucose, sucrose, maltose, starch, the phenolic resins.
The present invention can produce following good effect compared with the prior art:
(1) in coprecipitation presoma ferric phosphate process, namely introduces doped metal ion, so that the easier iron position that enters of doping ion, guaranteed the distributing homogeneity of doped metal ion iron position in the LiFePO4 lattice, remove the crystallization water by heat treatment again, control heating rate and temperature retention time have improved the uniformity of doped metal ion in ferric phosphate and the degree of crystallinity of ferric phosphate;
(2) mix by the difference of substep, guaranteed the uniformity that the doping ion distributes in mutually in material bodies, with single dopant material or not dopant material compare, the LiFePO4 of this invention preparation has not only further improved the electronic conductivity of material, the body that has more improved material mutually in lithium ion at LiFePO 4/ FePO 4Diffusion rate in the two-phase, thus the specific capacity of more excellent high rate performance and Geng Gao had.
Description of drawings:
Fig. 1 is the X ray diffracting spectrum of the carbon-coated LiFePO 4 for lithium ion batteries that mixes of the polyion of preparation in the embodiment of the invention 1;
Fig. 2 is the stereoscan photograph of the carbon-coated LiFePO 4 for lithium ion batteries that mixes of the polyion of preparation in the embodiment of the invention 1;
Fig. 3 is the first charge-discharge curve of the carbon-coated LiFePO 4 for lithium ion batteries that mixes of the polyion of preparation in the embodiment of the invention 1, and wherein charge-discharge magnification is 0.2C, and voltage range is 2.5V ~ 4.1V;
Fig. 4 is the cycle performance curve of carbon-coated LiFePO 4 for lithium ion batteries under different multiplying that the polyion of preparation in the embodiment of the invention 1 mixes.
Embodiment: following the specific embodiment of the present invention is elaborated:
Embodiment 1:
1, takes by weighing 259.49g FeCl 36H 2O, 10.51g NiSO 46H 2O joins in the 20L deionized water, is mixed with the mixed solution A that total concentration of metal ions is 0.05mol/L; Take by weighing 115.03g NH 4H 2PO 4Join and be mixed with the solution B that concentration is 5mol/L in the 0.2L deionized water; Compound concentration is the ammonia spirit of 10mol/L; With peristaltic pump solution A and solution B are pumped in the reactor of rapid stirring, the control reaction temperature is 40 ℃, mixing speed is 1200rpm, regulating the pH value with ammonia spirit is 2.4, reaction 0.5h, then reaction liquid filtration, washing, drying are obtained containing the ferric phosphate of the Ni doped of the crystallization water, be expressed as Fe 0.96Ni 0.04PO 42H 2O.
2, with step 1 gained Fe 0.96Ni 0.04PO 42H 2O rises to 300 ℃ of heat treatment 10h by room temperature under the heating rate of 5 ℃/min, naturally lower the temperature, and is not contained the ferric phosphate of the Ni doped of the crystallization water, is expressed as Fe 0.96Ni 0.04PO 4
3, accurately take by weighing Li 2CO 336.91g, KF 0.058g, glucose (account for raw material gross mass 20%) 37.57g, the Fe that obtains with step 2 0.96Ni 0.04PO 4Mixing and ball milling, take alcohol as dispersant, drying is processed and is obtained precursor powder.Presoma heating rate with 10 ℃/min under high pure nitrogen atmosphere is raised to 650 ℃ of roasting 20h from room temperature, naturally cools to room temperature, through pulverizing, sieving, obtain consisting of Li 0.999K 0.001Fe 0.96Ni 0.04(PO 4) 0.999F 0.001The ferric phosphate lithium cell material of/C.
The X ray diffracting spectrum of the LiFePO4 that present embodiment obtains can find out that as shown in Figure 1 synthetic LiFePO4 is the rhombic system olivine-type structure, and polyionic doping does not change its crystal structure.
The electrochemical property test of material is tested by the following method, and take iron phosphate powder of the present invention as positive active material, the lithium sheet is negative pole, is assembled into the CR2025 button cell and tests.Positive pole consists of 80% active material, 10% conductive carbon, 10%PVDF; Electrolyte is the LiPF of 1mol/L 6(EC+DMC), in glove box, finish assembling.The battery testing temperature is 25 ℃, and the system of discharging and recharging is: with the 0.2C constant current charge to 4.1V, then with the 4.1V constant voltage charge to electric current less than 0.005mA, leave standstill 2min, constant-current discharge is to 2.5V again.After tested, this material 0.2C initial charge specific capacity is 159.4mAh/g, and specific discharge capacity is 156.1mAh/g, and efficient is 97.9% first.Specific discharge capacity is 156.3mAh/g, 154.0mAh/g, 151.3mAh/g, 144.4mAh/g, 139.9mAh/g, 133.6mAh/g, 122.4mAh/g to material after 10 times respectively circulating under 0.2C, 0.5C, 1C, 2C, 3C, 5C, the 10C multiplying power respectively, and high rate performance is excellent.
Embodiment 2:
1, takes by weighing 403.62g Fe (NO 3) 39H 2O, 0.24g CoCl 26H 2O joins in the 1L deionized water, is mixed with the mixed solution A that total concentration of metal ions is 1mol/L; Take by weighing 131.05g (NH 4) 2HPO 4Join and be mixed with the solution B that concentration is 1mol/L in the 1L deionized water; Compound concentration is the ammonia spirit of 8mol/L; With peristaltic pump solution A and solution B are pumped in the reactor of rapid stirring, the control reaction temperature is 80 ℃, and mixing speed is 800rpm, regulating the pH value with ammonia spirit is 3, then reaction 1.5h obtains reaction liquid filtration, washing, drying containing the ferric phosphate of the doping Co of the crystallization water, is expressed as Fe 0.999Co 0.001PO 42H 2O.
2, with step 1 gained Fe 0.999Co 0.001PO 42H 2O rises to 450 ℃ of heat treatment 6h by room temperature under the heating rate of 1 ℃/min, naturally lower the temperature, and is not contained the ferric phosphate of the doping Co of the crystallization water, is expressed as Fe 0.999Co 0.001PO 4
3, accurately take by weighing Li 2CO 335.47g, MgF 22.49g, phenolic resins (account for raw material gross mass 18%) 33.98g, the Fe that obtains with step 2 0.999Co 0.001PO 4Mixing and ball milling, take alcohol as dispersant, drying is processed and is obtained precursor powder.Presoma heating rate with 1 ℃/min under high pure nitrogen atmosphere is raised to 750 ℃ of roasting 13h from room temperature, naturally cools to room temperature, through pulverizing, sieving, obtain consisting of Li 0.96Mg 0.04Fe 0.999Co 0.001(PO 4) 0.92F 0.08The ferric phosphate lithium cell material of/C.
According to the method for testing of embodiment 1, the LiFePO 4 material 0.2C initial charge specific capacity that records this embodiment preparation is 160.8mAh/g, and specific discharge capacity is 156.8mAh/g, and efficient is 97.5% first.Specific discharge capacity is 156.9mAh/g, 154.7mAh/g, 151.5mAh/g, 144.9mAh/g, 140.3mAh/g, 134.0mAh/g, 122.7mAh/g to material after 10 times respectively circulating under 0.2C, 0.5C, 1C, 2C, 3C, 5C, the 10C multiplying power respectively, and high rate performance is excellent.
Embodiment 3:
1, takes by weighing 264.89g FeCl 36H 2O, 5.00g Mn (NO 3) 24H 2O joins in the 4L deionized water, is mixed with the mixed solution A that total concentration of metal ions is 0.25mol/L; Take by weighing 131.05g (NH 4) 2HPO 4Join and be mixed with the solution B that concentration is 0.5 mol/L in the 2L deionized water; Compound concentration is the ammonia spirit of 3mol/L; With peristaltic pump solution A and solution B are pumped in the reactor of rapid stirring, the control reaction temperature is 65 ℃, mixing speed is 2500rpm, regulating the pH value with ammonia spirit is 2.7, reaction 3h, then reaction liquid filtration, washing, drying are obtained containing the ferric phosphate of the doped with Mn of the crystallization water, be expressed as Fe 0.98Mn 0.02PO 42H 2O.
2, with step 1 gained Fe 0.98Mn 0.02PO 42H 2O rises to 400 ℃ of heat treatment 10h by room temperature under the heating rate of 10 ℃/min, naturally lower the temperature, and is not contained the ferric phosphate of the doped with Mn of the crystallization water, is expressed as Fe 0.98Mn 0.02PO 4
3, accurately take by weighing LiOH 21.55g, NaF 4.20g, maltose (account for raw material gross mass 15%) 26.48g, the Fe that obtains with step 2 0.98Mn 0.02PO 4Mixing and ball milling, take alcohol as dispersant, drying is processed and is obtained precursor powder.Presoma heating rate with 5 ℃/min under high pure nitrogen atmosphere is raised to 820 ℃ of roasting 10h from room temperature, naturally cools to room temperature, through pulverizing, sieving, obtain consisting of Li 0.9Na 0.1Fe 0.98Mn 0.02(PO 4) 0.9F 0.1The ferric phosphate lithium cell material of/C.
According to the method for testing of embodiment 1, the LiFePO 4 material 0.2C initial charge specific capacity that records this embodiment preparation is 159.9mAh/g, and specific discharge capacity is 155.0mAh/g, and efficient is 96.9% first.Specific discharge capacity is 155.3mAh/g, 153.2mAh/g, 150.0mAh/g, 142.9mAh/g, 138.7mAh/g, 132.6mAh/g, 121.6mAh/g to material after 10 times respectively circulating under 0.2C, 0.5C, 1C, 2C, 3C, 5C, the 10C multiplying power respectively, and high rate performance is excellent.
Embodiment 4:
1, takes by weighing 179.95g Fe 2(SO 4) 3, 17.3g Mn (CH 3COO) 2Join in the 0.2L deionized water, be mixed with the mixed solution A that total concentration of metal ions is 5mol/L; Take by weighing 203.13g (NH 4) 3PO 43H 2O joins and is mixed with the solution B that concentration is 0.05mol/L in the 20L deionized water; Compound concentration is the ammonia spirit of 0.5mol/L; With peristaltic pump solution A and solution B are pumped in the reactor of rapid stirring, the control reaction temperature is 95 ℃, mixing speed is 2000rpm, regulating the pH value with ammonia spirit is 2.0, reaction 1h, then reaction liquid filtration, washing, drying are obtained containing the ferric phosphate of the doped with Mn of the crystallization water, be expressed as Fe 0.9Mn 0.1PO 42H 2O.
2, with step 1 gained Fe 0.9Mn 0.1PO 42H 2O rises to 500 ℃ of heat treatment 2h by room temperature under the heating rate of 6 ℃/min, naturally lower the temperature, and is not contained the ferric phosphate of the doped with Mn of the crystallization water, is expressed as Fe 0.9Mn 0.1PO 4
3, accurately take by weighing CH 3COOLi 63.35g, VF 41.27g, starch (account for raw material gross mass 17%) 36.61g, the Fe that obtains with step 2 0.9Mn 0.1PO 4Mixing and ball milling, take alcohol as dispersant, drying is processed and is obtained precursor powder.Presoma heating rate with 5 ℃/min under high pure nitrogen atmosphere is raised to 680 ℃ of roasting 6h from room temperature, naturally cools to room temperature, through pulverizing, sieving, obtain consisting of Li 0.99V 0.01Fe 0.9Mn 0.1(PO 4) 0.96F 0.04The ferric phosphate lithium cell material of/C.
According to the method for testing of embodiment 1, the LiFePO 4 material 0.2C initial charge specific capacity that records this embodiment preparation is 158.7mAh/g, and specific discharge capacity is 156.0mAh/g, and efficient is 98.3% first.Specific discharge capacity is 156.3mAh/g, 153.8mAh/g, 151.5mAh/g, 143.8mAh/g, 139.1mAh/g, 132.9mAh/g, 121.2mAh/g to material after 10 times respectively circulating under 0.2C, 0.5C, 1C, 2C, 3C, 5C, the 10C multiplying power respectively, and high rate performance is excellent.
Above embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention all should fall in the definite protection range of claims of the present invention.

Claims (8)

1. the carbon-coated LiFePO 4 for lithium ion batteries battery material that mixes of a polyion, the structure that it is characterized in that material is Li 1-xM` xFe 1-yM y(PO 4) 1-zF z/ C, 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1 wherein, M` and M are respectively the metal ion that mixes in lithium position and iron position, and C is the organic cracking carbon that is coated on the LiFePO4 surface, and M` and F be from same raw material, i.e. fluoride M`F n(n=1,2,3,4).
2. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material of a kind of polyion doping claimed in claim 1 is characterized in that comprising the steps:
The first step, coprecipitation prepares the ferric phosphate of doped metal ion M: (1) is (1-y) strictly in molar ratio: y, 0.001≤y≤0.1 wherein, accurate weighing soluble ferric iron salt and the material that contains metal ions M, add deionized water, be mixed with the mixed solution A that total concentration of metal ions is 0.05 ~ 5mol/L; Preparation contains PO 4 3-Concentration is the phosphate solution B of 0.05 ~ 5mol/L; The ammonia spirit of preparation 0.5 ~ 10mol/L; (2) with peristaltic pump solution A and solution B are pumped in the reactor of rapid stirring, the control reaction temperature is 40 ~ 95 ℃, and mixing speed is 800 ~ 2500rpm, regulates the pH value between 2 ~ 3 with ammonia spirit, reaction 0.5 ~ 3h; (3) with above-mentioned reaction solution after filtration, washing, drying, obtain the ferric phosphate that is doped with metal ions M that white contains the crystallization water, be expressed as Fe 1-yM yPO 42H 2O;
Second step is heat-treated between 300 ~ 500 ℃ the ferric phosphate of the doped metal ion M that contains the crystallization water of first step preparation, and heating rate is 1 ~ 10 ℃/min, insulation 2 ~ 10h, naturally cool to room temperature, do not contained the ferric phosphate of the doped metal ion M of the crystallization water, be expressed as Fe 1-yM yPO 4
In the 3rd step, the ferric phosphate of the doped metal ion M that the employing second step obtains is pressed structural formula Li 1-xM` xFe 1-yM y(PO 4) 1-zF z/ C, wherein 0.001≤x≤0.1,0.001≤y≤0.1,0.001≤z≤0.1 takes by weighing lithium source, fluoride M`F n(n=1,2,3,4), the organic carbon source that adds simultaneously raw material total weight 15 ~ 20%, take alcohol as dispersant, through ball milling mix, the dry processing obtain precursor powder, under high pure nitrogen atmosphere, be raised to 650 ~ 820 ℃ with the heating rate of 1 ~ 10 ℃/min from room temperature and carry out high-temperature roasting, insulation 6 ~ 20h, naturally cool to room temperature, through pulverizing, sieving, obtain the carbon-coated LiFePO 4 for lithium ion batteries battery material that polyion mixes.
3. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material of a kind of polyion doping according to claim 1 and 2 is characterized in that described fluoride M`F n(n=1,2,3,4) are NaF, KF, MgF 2, CaF 2, AlF 3, ZnF 2, TiF 4, VF 4In a kind of.
4. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material that mixes of a kind of polyion according to claim 2 is characterized in that a kind of in chloride, sulfate, nitrate and the organic salt that the described material that contains metal ions M is Ni, Co, Mn.
5. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material that mixes of a kind of polyion according to claim 2 is characterized in that described soluble ferric iron salt is a kind of in ferric sulfate, ferric nitrate, the iron chloride.
6. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material that mixes of a kind of polyion according to claim 2 is characterized in that described phosphate is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, the ammonium phosphate.
7. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material that mixes of a kind of polyion according to claim 2 is characterized in that described lithium source is a kind of in lithium carbonate, lithium hydroxide, the lithium acetate.
8. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries battery material that mixes of a kind of polyion according to claim 2 is characterized in that described organic carbon source is a kind of in glucose, sucrose, maltose, starch, the phenolic resins.
CN2013102976748A 2013-07-16 2013-07-16 Multi-ion-doped carbon-coated lithium iron phosphate battery material and preparation method thereof Pending CN103367746A (en)

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CN103779565A (en) * 2014-02-12 2014-05-07 云南磷化集团有限公司 Preparation method of lithium iron phosphate composite battery material
CN103887513A (en) * 2014-04-10 2014-06-25 合肥工业大学 Anion and cation doped carbon-coated lithium iron phosphate cathode material and preparation method thereof
CN103956465A (en) * 2014-05-27 2014-07-30 菏泽学院 Method for preparing lithium ion battery positive electrode lithium iron borate material by using coprecipitation technology
CN105152155A (en) * 2015-08-31 2015-12-16 无锡市嘉邦电力管道厂 Multiple ions co-doped lithium iron phosphate material and preparation method thereof
CN105895879A (en) * 2016-05-20 2016-08-24 中国科学院青岛生物能源与过程研究所 Fluorine-doped carbon-coated positive electrode composite material and preparation method and application thereof
CN109244424A (en) * 2018-10-24 2019-01-18 东莞理工学院 A kind of preparation method of alumina-coated additive Mn lithium iron phosphate positive material
CN110021752A (en) * 2019-01-24 2019-07-16 湖北锂诺新能源科技有限公司 A kind of lithium, aluminium and fluorin-doped lithium iron phosphate positive material and preparation method
CN110620233A (en) * 2019-06-30 2019-12-27 湖北虹润高科新材料有限公司 Preparation method of multi-ion modified lithium iron phosphate material
CN113753876A (en) * 2021-07-20 2021-12-07 中南大学 Potassium ion battery negative electrode material and preparation method thereof
CN115050931A (en) * 2022-05-24 2022-09-13 新疆师范大学 Preparation method of nitrogen and sulfur co-doped carbon layer for coating positive electrode of sodium ion battery

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CN103779565A (en) * 2014-02-12 2014-05-07 云南磷化集团有限公司 Preparation method of lithium iron phosphate composite battery material
CN103779565B (en) * 2014-02-12 2016-08-03 云南磷化集团有限公司 A kind of preparation method of LiFePO4 composite battery material
CN103887513B (en) * 2014-04-10 2016-11-09 合肥工业大学 A kind of zwitterion doping carbon-coated LiFePO 4 for lithium ion batteries positive electrode and preparation method thereof
CN103887513A (en) * 2014-04-10 2014-06-25 合肥工业大学 Anion and cation doped carbon-coated lithium iron phosphate cathode material and preparation method thereof
CN103956465A (en) * 2014-05-27 2014-07-30 菏泽学院 Method for preparing lithium ion battery positive electrode lithium iron borate material by using coprecipitation technology
CN105152155A (en) * 2015-08-31 2015-12-16 无锡市嘉邦电力管道厂 Multiple ions co-doped lithium iron phosphate material and preparation method thereof
CN105895879A (en) * 2016-05-20 2016-08-24 中国科学院青岛生物能源与过程研究所 Fluorine-doped carbon-coated positive electrode composite material and preparation method and application thereof
CN105895879B (en) * 2016-05-20 2019-12-31 中国科学院青岛生物能源与过程研究所 Fluorine-doped carbon-coated positive electrode composite material and preparation method and application thereof
CN109244424A (en) * 2018-10-24 2019-01-18 东莞理工学院 A kind of preparation method of alumina-coated additive Mn lithium iron phosphate positive material
CN110021752A (en) * 2019-01-24 2019-07-16 湖北锂诺新能源科技有限公司 A kind of lithium, aluminium and fluorin-doped lithium iron phosphate positive material and preparation method
CN110021752B (en) * 2019-01-24 2022-10-25 湖北锂诺新能源科技有限公司 Lithium, aluminum and fluorine co-doped lithium iron phosphate cathode material and preparation method thereof
CN110620233A (en) * 2019-06-30 2019-12-27 湖北虹润高科新材料有限公司 Preparation method of multi-ion modified lithium iron phosphate material
CN113753876A (en) * 2021-07-20 2021-12-07 中南大学 Potassium ion battery negative electrode material and preparation method thereof
CN113753876B (en) * 2021-07-20 2023-06-27 中南大学 Potassium ion battery anode material and preparation method thereof
CN115050931A (en) * 2022-05-24 2022-09-13 新疆师范大学 Preparation method of nitrogen and sulfur co-doped carbon layer for coating positive electrode of sodium ion battery

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Application publication date: 20131023