CN101794881A - Method for preparing anode material of lithium ion batteries by one-step microwave sintering - Google Patents
Method for preparing anode material of lithium ion batteries by one-step microwave sintering Download PDFInfo
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- CN101794881A CN101794881A CN201010128729A CN201010128729A CN101794881A CN 101794881 A CN101794881 A CN 101794881A CN 201010128729 A CN201010128729 A CN 201010128729A CN 201010128729 A CN201010128729 A CN 201010128729A CN 101794881 A CN101794881 A CN 101794881A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for preparing a LiFePO4/C anode material of lithium ion batteries, which comprises: weighing a lithium source compound, an iron source compound and a phosphoric acid in a Li to Fe to P molar ratio of 1:0.8-1.2:0.8-1.2, and adding a carbon source compound which accounts for 4 to 40 percent of the prepared anode material; and mixing the materials to obtain a paste precursor and placing the paste precursor in a non-metal container to perform microwave baking on the paste precursor to prepare LiFePO4/C. The method has the advantages that: a solid-liquid combined method is adopted, so raw material mixing in the early stage is more uniform, metal doping is easier, the process is simpler and the sintering process is free from inert gas protection; due to the microwave heating, synthesis time is reduced and energy is saved; and tests show that the primary discharge capacity is 120 to 130.6mAh/g and the discharge capacity after 10 times of circulation 112-125.8mAh/g, the battery capacity is 3,100 to 3,300mAh, the internal resistance is 20 milliohms, and discharge can be performed continuously within 10 hours.
Description
One, technical field:
The present invention relates to a kind of preparation method of active substance of lithium ion battery anode, particularly relate to a kind of one-step method microwave sintering anode material for lithium-ion batteries LiFePO
4The preparation method of/C.
Two, background technology:
Ferric phosphate lithium ion battery is with LiFePO4 (LiFePO
4, being called for short LFP) and material is made the lithium ion battery of anode, is the newcomer of lithium ion battery family.The main advantage of ferric phosphate lithium cell has: at first be to use safety, the adhesion of phosphate radical chemical bond is stronger than traditional transition metal oxide structural chemistry key, so structure is more stable, and be difficult for discharging oxygen, LiFePO4 has solved the security hidden trouble of cobalt acid lithium and LiMn2O4 fully, ferric phosphate lithium cell is at present global unique lithium ion battery that is perfectly safe, and stability at high temperature can reach 400-500 ℃, has guaranteed the high security of battery inherence; Not can because of overcharge, temperature is too high, short circuit, bump produce blast or burning; Secondly, this battery life overlength, recycle the number of times height, at room temperature the 1C charge and discharge cycles reaches 2000 times, and capability retention is more than 2 times of present lithium ion battery more than 80%, this battery does not contain any heavy metal and rare metal simultaneously, nontoxic (SGS authentication by), pollution-free meets European RoHS regulation, is absolute environmental protection battery.
Because the geneogenous Stability Analysis of Structures characteristic of LiFePO4, particularly has incomparable advantage aspect fail safe and the cycle performance, so adopt the battery of lithium iron phosphate positive material to be mainly used in Large Electric vehicle (as train, bus, fork truck, sight spot tourist coach, hybrid vehicle and pure electric vehicle etc.), military and space field (steamer, submarine, panzer, rocket, space car etc.).But because LiFePO
4The restriction of crystal structure own, ionic conductivity is low, and high-rate charge-discharge capability is poor, does not reach requirement of actual application.There are some researches show, at LiFePO
4The carbon that middle interpolation or coating have conductivity can effectively improve its conductivity.
Prepare LiFePO at present
4The method of material has: solid-phase synthesis, sol-gel process, oxidation-reduction method, microwave process for synthesizing and hydro thermal method etc.People are to LiFePO
4Solid phase method study on the synthesis many, but the solid phase method generated time is long, the heat energy utilization rate is low, particle is inhomogeneous and be prone to the impurity phase of Fe.To LiFePO
4/ C microwave study on the synthesis is less, and what use is household microwave oven, and output is little, and reaction condition is wayward, is difficult to carry out suitability for industrialized production.And the advantage of sol-gel process is: precursor solution chemical uniformity good (can reach the molecular level level), and the gel heat treatment temperature is low, and the powder handling performance is good, course of reaction is easy to control, equipment is simple, but dry contraction is big, the suitability for industrialized production difficulty is bigger, and synthesis cycle is longer.
ZL200610125124.8, publication number are that the patent of CN1964106 has proposed with FePO
4The method for preparing LiFePO4 comprises lithium-containing compound, FePO
4Mix by certain molar ratio and additive with solid polyethylene glycol, add water furnishing rheology attitude, under inert gas, heat-treat the preparation LiFePO4 then.This method technology is simple, but from course of reaction, still belongs to solid phase method in essence, shows as generated time length, the heat energy utilization rate is low, particle is inhomogeneous and is prone to Fe impurity to equate shortcoming.
Three, summary of the invention:
The technical problem to be solved in the present invention is: overcome the shortcoming of lithium ion battery anode material lithium iron phosphate cost height, poor performance in the prior art, provide a kind of reaction time short, technology is simple, energy consumption is low, with low cost, the preparation method that can be widely used in suitability for industrialized production.
Technical scheme of the present invention:
A kind of anode material for lithium-ion batteries LiFePO
4The preparation method of/C, its step comprises:
(1) be that 1: 0.8～1.2: 0.8～1.2 ratio is measured respectively with Li source compound, Fe source compound and phosphoric acid in the mol ratio of Li: Fe: P, add carbon-source cpd in Li source compound, Fe source compound, its addition is the positive electrode LiFePO of preparation
44～40% of/C weight, mixing and stirring obtains mixture then;
(2) described phosphoric acid is added in the said mixture, stir, obtain the paste presoma;
(3) described paste presoma is placed non-metallic vessel, put into industrial microwave oven and handle, prepare LiFePO through microwave thermal
4/ C.
The metal-doped LiFePO of a kind of anode material for lithium-ion batteries
4The preparation method of/C is characterized in that:
(1) with Li source compound, Fe source compound, phosphoric acid and doped metal salt in Li: Fe: P: the mol ratio of metal ion is that 1: 0.8～1.2: 0.8～1.2: 0.02～0.08 ratio is measured respectively, add carbon-source cpd in Li source compound, Fe source compound, its addition is the positive electrode LiFePO of preparation
44～40% of/C weight, mixing and stirring obtains mixture then;
(2) described phosphoric acid and doped metal salt are mixed, stir, obtain the phosphoric acid solution of metal ion; Again and the mixture of step (1) mix, stir, obtain the paste presoma;
(3) described paste presoma is placed non-metallic vessel, put into industrial microwave oven and handle, prepare metal-doped LiFePO through microwave thermal
4/ C.
Described phosphoric acid is that the phosphoric acid adding deionized water of concentration 85% obtains, and the addition of deionized water is the positive electrode LiFePO of preparation
410～90% of/C weight.
It is to adopt the three-dimensional blender machine with 5～20 rev/mins the speed of mainshaft that the mixing of described step (1) is stirred, and mixes 20～60min; The stirring of described step (2) is to adopt trough mixer with 5～30 rev/mins the speed of mainshaft, mixes 20～60min; It is to utilize microwave to be warming up to 550～700 ℃ with the speed of per minute 2～10 degree that described microwave thermal is handled, and keeps 20～50min under this temperature.
Described Li source compound is lithium hydroxide, lithium carbonate or lithium acetate, and described Fe source compound is ferrous oxalate, di-iron trioxide or tri-iron tetroxide; Described carbon-source cpd is one or more in natural macromolecular material, oxalic acid, citric acid, glucose, sucrose, lactose and the maltose; Described slaine is cobalt nitrate, cobaltous sulfate, cobalt acetate, chromic nitrate, chromium sulfate basic, chromic acetate, magnesium nitrate or nickel nitrate; Described non-metallic vessel is silicon carbide crucible, graphite crucible, glass pot or paper container.
Described natural macromolecular material is starch, sawdust, wood powder, bamboo powder, plant straw, chaff shell or shuck, and natural macromolecular material need be pulverized before use, and crosses 200 mesh sieves.
Positive beneficial effect of the present invention:
(1) raw material of technology of the present invention mixes the method that adopts solid-liquid combination, adds to form the paste presoma after deionized water mixes, and this method can make more even, especially metal-doped easier that early stage, raw material mixed.Amount of water is how much relevant with the raw material that adopts during mixing, is as the criterion to form uniform paste presoma.The water yield is big more, and the paste presoma of formation is rare more, and that mixes naturally is even more, reacts also just complete more in the course of reaction afterwards, but brings difficulty for later sintering, so the phosphoric acid amount of water is wanted suitably.
(2) technology of the present invention in mixed process under the liquid phase state some compositions easily react, help synthesizing; The paste presoma that mixes back formation directly enters and carries out sintering in the industrial microwave oven, has omitted the ball milling in the traditional handicraft, dry run, and technology is simplified greatly, and control is simple, can guarantee product quality effectively.Can find out that from the XRD figure of Fig. 3 prepared product is very pure LiFePO4, no dephasign.
(3) carbonization can take place and be oxidized to CO in the organic carbon that adds in the technology of the present invention in sintering process
2Gas, thus the reproducibility atmosphere formed, thereby can not blanketing with inert gas in the sintering process, reduced the requirement of technology to equipment, help producing.
(4) having adopted carbon-source cpd in the technology of the present invention is natural macromolecular material or other organic substances, particularly utilize natural porous structure and hackly surface of natural macromolecular material, after a large amount of deionized water combines, gas can at the uniform velocity spread in heat treatment process, can make reaction more even.In reaction is the process of aqueous vapor effusion in earlier stage, plays the effect of local dip; Reaction is carbon-source cpd carbonization and oxidation, formation originality atmosphere in the later stage, and further plays local dip, sufficient reacting, so the product that obtains is very loose, machinability is good, the quality height.
(5) process using industrial microwave heating of the present invention heats up material self integral body simultaneously, and firing rate is fast, pollution-free, the sample grain refinement of processing, and even structure, microwave heating simultaneously can accurately be controlled, and has shortened generated time.Traditional sintering need be incubated about 20h, and the present invention only need be incubated 20～50min, can reduce generated time, energy savings effectively.
(6) technology of the present invention is simple, and production cost is low, and the favorable reproducibility of different batches product is fit to large-scale industrial production, and can not produce a large amount of pernicious gases such as oxynitrides in sintering process, and is pollution-free, is very beneficial for environmental protection.
(7) the present invention when improving the LiFePO4 conductivity significantly, has improved the charge/discharge capacity and the cycle-index of battery by carbon coated and doped metallic elements effectively.
Be the performance of check product of the present invention, as follows positive electrode of the present invention made positive plate.
At first PVDF and NMP are mixed, be mixed with 8% solution, adopt high speed dispersor to mix then, under the rotating speed of 35 rev/mins of revolution, 1500 rev/mins of rotations, stir 1h, add conductive carbon material, under the rotating speed of 2000 rev/mins of rotational velocities, stir 1h, add LiFePO4 of the present invention, under the speed of rotation more than 2000 rev/mins, stir 3h, add solvent NMP, adjust the viscosity of solution.The final solution composition that forms is as follows: LiFePO4: conductive carbon: PVDF: NMP=100: 1: 3: 70 (weight ratio).
To use behind the static 2h of above positive solution, it is on the thick aluminium foil of 0.020mm that anode sizing agent is coated on thickness equably, adopts 80～150 ℃ hot air circulation oven dry.The surface density of coating is 180g/m
2, precision is at 4g/m
2In; To adopt 300 tons pressure to carry out roll-in with superior pole piece, and make the pole piece compacting, density reaches 2.7g/cm
3, and cut into the strip pole piece of width 55mm, length 1350mm, positive plate and graphite cathode sheet are wound into 26650 batteries.After testing, this battery discharge capacity first is 120～130.6mAh/g, is 112～125.8mAh/g after 10 circulations, and battery capacity can reach 3100～3300mAh, about internal resistance 20 milliohms, can carry out 10C with interior continuous discharge.
Four, description of drawings:
Fig. 1 is LiFePO of the present invention
4The heat treated sem photograph of microwave during 620 ℃ of/C.
Fig. 2 is LiFePO of the present invention
4The heat treated sem photograph of microwave during 700 ℃ of/C.
From Fig. 1 and Fig. 2 as can be seen, the sample particle is tiny, and especially distribution of particles is more even among Fig. 2, and the largest particles is that resulting product cut size is tiny and even, quality better about 10 μ m.
Fig. 3 is LiFePO of the present invention
4The XRD figure of/C.
The 1# sample is that 580 ℃ of microwave thermal are handled 35min among the figure, and the 2# sample is that 600 ℃ of microwave thermal are handled 40min, and the 3# sample is that 680 ℃ of microwave thermal are handled 25min.Can find from the X-ray diffraction spectrum of sample, just can obtain and LiFePO at 580 ℃
4The olivine crystalline structure that/C is identical, (JCPDS card) belongs to the space group of rhombic system, shows that this method can access the LiFePO of pure olivine structural
4/ C phase.
Fig. 4 is LiFePO of the present invention
4Preparation technology's general flow chart of/C.
Five, embodiment:
Embodiment one: anode material for lithium-ion batteries LiFePO
4The preparation method of/C
(1) with 4000 gram LiOHH
2O, 7870 gram Fe
3O
4, 2000 gram wood powders put into the three-dimensional blender machine, mix 30min with 5～20 rev/mins the speeds of mainshaft, mix;
(2) be that 85% phosphoric acid dissolves in 9000 ml deionized water with 11500 gram concentration, shake up;
(3) phosphoric acid solution with step (2) preparation adds in the mixture of step (1) preparation, and the speed of mainshaft with 5～30 rev/mins in trough mixer stirs 40min, stirs, and obtains the paste presoma;
(4) the paste presoma of step (3) is put into the carborundum crucible, again crucible is put into industrial microwave oven, be warmed up to 550 ℃ with the speed of 4 ℃ of per minutes, and insulation 30min, LiFePO obtained
4/ C.
As calculated, the positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
412.5% of/C amount, amount of deionized water is LiFePO
456.3% of/C amount.
Embodiment two: anode material for lithium-ion batteries LiFePO
4The preparation method of/C
(1) with 8000 gram Fe
2O
3, 4000 gram lithium carbonates, 3500 gram wood powders put into the three-dimensional blender machine, mix 60min, mixing with 5～20 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 8000 ml deionized water with 11500 gram concentration, shake up;
(3) phosphoric acid solution with step (2) preparation adds in the mixture of step (1), and the speed of mainshaft with 5～30 rev/mins in trough mixer stirs 55min, mixes, and obtains the paste presoma;
(4) the paste presoma of step (3) is put into the brown paper container, container is put into industrial microwave oven again, be warmed up to 600 ℃ with the speed of 6 ℃ of per minutes, insulation 40min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
422% of/C amount, amount of deionized water is LiFePO
450% of/C amount.
Embodiment three: anode material for lithium-ion batteries LiFePO
4The preparation method of/C
(1) 18100 gram ferrous oxalates, 4000 gram lithium carbonates, 3000 gram wood powders, 1500 gram oxalic acid, 500 gram citric acids are put into the three-dimensional blender machine, mix 50min, mixing with 5～20 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 11000 ml deionized water with 11500 gram concentration;
(3) mixed liquor of step (2) preparation adds in the mixture of step (1) preparation, and the speed of mainshaft with 5～30 rev/mins in trough mixer stirs 25min, stirs, and obtains the paste presoma;
(4) the paste presoma that step (3) is purchased is put into graphite crucible, and graphite crucible is put into industrial microwave oven, is warmed up to 650 ℃ with the speed of 5 ℃ of per minutes, and insulation 50min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the addition of wood powder, oxalic acid, citric acid is respectively LiFePO
418.8%, 9.4%, 3.1% of/C amount, amount of deionized water is 68.8%.
Embodiment four: anode material for lithium-ion batteries LiFePO
4The preparation method of/C
(1) with 7870 gram Fe
3O
4, 4000 gram lithium carbonates, 2500 gram wood powders put into the three-dimensional blender machine, mix 40min, mixing with 5～20 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 7000 ml deionized water with 11000 gram concentration;
(3) in the mixture of phosphoric acid solution that step (2) is prepared and adding step (1) preparation, the speed of mainshaft with 5～30 rev/mins in trough mixer stirs 50min, stirs, and obtains the paste presoma;
(4) the paste presoma is put into the brown paper container, the brown paper container is put into microwave oven, be warmed up to 700 ℃ with the speed of 8 ℃ of per minutes, insulation 40min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
415.6% of/C amount, amount of deionized water is 44%.
Embodiment five: anode material for lithium-ion batteries LiFePO
4The preparation method of/C, basic identical with embodiment one, difference is: replace wood powder with the bamboo powder.
Embodiment six: anode material for lithium-ion batteries LiFePO
4The preparation method of/C, basic identical with embodiment two, difference is: replace wood powder with powdered rice hulls, also available glucose, sucrose, lactose or maltose etc. replace wood powder.
Embodiment seven: anode material for lithium-ion batteries LiFePO
4The preparation method of/C, basic identical with embodiment three, difference is: replace wood powder with 6340 gram oxalic acid.
Embodiment eight: anode material for lithium-ion batteries LiFePO
4The preparation method of/C
(1) with 7870 gram Fe
3O
4, 11000 gram lithium acetates, 2500 gram wood powders put into the three-dimensional blender machine, mix 40min, mixing with 15 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 7000 ml deionized water with 11000 gram concentration;
(3) phosphoric acid solution with step (2) preparation adds in the mixture of step (1) preparation, and the speed of mainshaft with 20 rev/mins in trough mixer stirs 50min, and stirring obtains the paste presoma;
(4) the paste presoma is put into the brown paper container, the brown paper container is put into microwave oven, be warmed up to 600 ℃ with the speed of 8 ℃ of per minutes, insulation 40min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
415.6% of/C amount, amount of deionized water is 43.8%.
Embodiment nine: Cr
3+Metal-doped LiFePO
4The preparation method of/C
(1) with 4400 gram LiOHH
2O, 7870 gram Fe
3O
4, 2000 gram wood powders put into the three-dimensional blender machine, mix 55min, mixing with 5～20 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 14000 ml deionized water with 11000 gram concentration, add 100 gram Cr (NO then
3)
3, the speed of mainshaft with 5～30 rev/mins in trough mixer stirs 40min, mixes;
(3) mixed liquor with step (2) preparation adds in the mixture of step (1) preparation, and the speed of mainshaft with 5～30 rev/mins in trough mixer stirs 35min, stirs, and obtains the paste presoma;
(4) the paste presoma is put into the carborundum crucible, the carborundum crucible is put into microwave oven, be warmed up to 680 ℃ with the speed of 4 ℃ of per minutes, insulation 30min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
412.5% of/C amount, amount of deionized water is 87.5%.
Embodiment ten: Cr
3+Metal-doped LiFePO
4The preparation method of/C
(1) with 8000 gram Fe
2O
3, 4000 gram lithium carbonates, 3500 gram wood powders put into the three-dimensional blender machine, mix 45min, mixing with 5～20 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 12000 ml deionized water with 11500 gram concentration; Add 160 gram Cr (NO then
3)
3Mix;
(3) phosphoric acid solution with step (2) preparation adds in the mixture of step (1) preparation, stirs 20min for 5～30 rev/mins with the speed of mainshaft in trough mixer, stirs and obtains the paste presoma;
(4) the paste presoma is put into the brown paper container, the brown paper container is put into microwave oven, be warmed up to 700 ℃ with the speed of 6 ℃ of per minutes, insulation 40min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
422% of/C amount, amount of deionized water is 75%.
Embodiment 11: Cr
3+Metal-doped LiFePO
4The preparation method of/C
(1) with 8000 gram Fe
2O
3, 10500 gram lithium acetates, 3500 gram wood powders put into the three-dimensional blender machine, mix 45min, mixing with 5～20 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 12000 ml deionized water with 11500 gram concentration; Add 160 gram Cr (NO then
3)
3Mix;
(3) phosphoric acid solution with step (2) preparation adds in the mixture of step (1) preparation, stirs 20min for 5～30 rev/mins with the speed of mainshaft in trough mixer, stirs, and obtains the paste presoma;
(4) the paste presoma is put into the brown paper container, the brown paper container is put into microwave oven, be warmed up to 650 ℃ with the speed of 6 ℃ of per minutes, insulation 40min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
422% of/C amount, amount of deionized water is 75%.
Embodiment 12: Cr
3+Metal-doped LiFePO
4The preparation method of/C, basic identical with embodiment nine, difference is: use Fe
2O
3Replace Fe
3O
4, replace chromic nitrate with chromium sulfate basic.
Embodiment 13: Cr
3+Metal-doped LiFePO
4The preparation method of/C, basic identical with embodiment nine, difference is: replace chromic nitrate with chromic acetate.
Embodiment 14: Co
3+Metal-doped LiFePO
4The preparation method of/C
(1) with 8000 gram Fe
2O
3, 4000 gram lithium carbonates, 3500 gram wood powders put into the three-dimensional blender machine, mix 25min, mixing with 5～20 rev/mins the speeds of mainshaft;
(2) be that 85% phosphoric acid dissolves in 7000 ml deionized water with 11500 gram concentration; Add 100 gram Co (NO then
3)
3Mix;
(3) phosphoric acid solution with step (2) preparation adds in the mixture of step (1) preparation, and the speed of mainshaft with 5～30 rev/mins in trough mixer stirs 30min, fully mixes, and obtains the paste presoma;
(4) the paste presoma is put into the brown paper container, the brown paper container is put into microwave oven, be warmed up to 620 ℃ with the speed of 6 ℃ of per minutes, insulation 40min obtains LiFePO
4/ C.
The positive electrode LiFePO of this example preparation
4The about 16kg of/C, the wood powder addition is LiFePO
422% of/C amount, amount of deionized water is 44%.
Embodiment 15: Co
3+Metal-doped LiFePO
4The preparation method of/C, the embodiment tetradecyl is originally identical, and difference is: replace cobalt nitrate with cobaltous sulfate, replace wood powder with citric acid, glucose or sucrose.
Embodiment 16: Co
3+Metal-doped LiFePO
4The preparation method of/C, originally identical with the embodiment tetradecyl, difference is: replace cobalt nitrate with cobalt acetate.
Embodiment 17: Co
3+Metal-doped LiFePO
4The preparation method of/C, the embodiment tetradecyl is originally identical, and difference is: replace cobalt nitrate with cobaltous sulfate.Replace wood powder with starch, plant straw, peanut shell or chaff shell.
Embodiment 18: Mg
2+Metal-doped LiFePO
4The preparation method of/C, basic identical with embodiment nine, difference is: replace chromic nitrate with magnesium nitrate.
Embodiment 19: Ni
2+Metal-doped LiFePO
4The preparation method of/C, embodiment ten is basic identical, and difference is: replace chromic nitrate with nickel nitrate.
Claims (10)
1. anode material for lithium-ion batteries LiFePO
4The preparation method of/C is characterized in that:
(1) be that 1: 0.8～1.2: 0.8～1.2 ratio is measured respectively with Li source compound, Fe source compound and phosphoric acid in the mol ratio of Li: Fe: P, add carbon-source cpd in Li source compound, Fe source compound, its addition is the positive electrode LiFePO of preparation
44～40% of/C weight, mixing and stirring obtains mixture then;
(2) described phosphoric acid is added in the said mixture, stir, obtain the paste presoma;
(3) described paste presoma is placed non-metallic vessel, put into industrial microwave oven and handle, prepare LiFePO through microwave thermal
4/ C.
2. preparation method according to claim 1 is characterized in that: described phosphoric acid is to obtain after adding the deionized water dilution by the phosphoric acid of concentration 85%, and the addition of deionized water is the positive electrode LiFePO of preparation
410～90% of/C weight.
3. preparation method according to claim 1 is characterized in that: it is to adopt the three-dimensional blender machine with 5～20 rev/mins the speed of mainshaft that the mixing of described step (1) is stirred, and mixes 20～60min; The stirring of described step (2) is to adopt trough mixer with 5～30 rev/mins the speed of mainshaft, mixes 20～60min; It is to utilize microwave to be warming up to 550～700 ℃ with the speed of per minute 2～10 degree that described microwave thermal is handled, and keeps 20～50min under this temperature.
4. preparation method according to claim 1 is characterized in that: described Li source compound is lithium hydroxide, lithium carbonate or lithium acetate, and described Fe source compound is ferrous oxalate, di-iron trioxide or tri-iron tetroxide; Described carbon-source cpd is one or more in natural macromolecular material, oxalic acid, citric acid, glucose, sucrose, lactose, the maltose; Described non-metallic vessel is carborundum crucible, graphite crucible, glass pot or paper container.
5. preparation method according to claim 4 is characterized in that: described natural macromolecular material is starch, wood powder, bamboo powder, plant straw, chaff shell or shuck, and natural macromolecular material need be pulverized before use, and crosses 200 mesh sieves.
6. metal-doped LiFePO of anode material for lithium-ion batteries
4The preparation method of/C is characterized in that:
(1) with Li source compound, Fe source compound, phosphoric acid and doped metal salt in Li: Fe: P: the mol ratio of metal ion is that 1: 0.8～1.2: 0.8～1.2: 0.02～0.08 ratio is measured respectively, add carbon-source cpd in Li source compound, Fe source compound, its addition is the positive electrode LiFePO of preparation
44～40% of/C weight, mixing and stirring obtains mixture then;
(2) described phosphoric acid and doped metal salt are mixed, stir, obtain the phosphoric acid solution of metal ion; Again and the mixture of step (1) mix, stir, obtain the paste presoma;
(3) described paste presoma is placed non-metallic vessel, put into industrial microwave oven and handle, prepare metal-doped LiFePO through microwave thermal
4/ C.
7. preparation method according to claim 6 is characterized in that: described phosphoric acid is that the phosphoric acid adding deionized water of concentration 85% obtains, and the addition of deionized water is the positive electrode LiFePO of preparation
410～90% of/C weight.
8. preparation method according to claim 6 is characterized in that: it is to adopt the three-dimensional blender machine with 5～20 rev/mins the speed of mainshaft that the mixing of described step (1) is stirred, and mixes 20～60min; The stirring of described step (2) is to adopt trough mixer with 5～30 rev/mins the speed of mainshaft, mixes 20～60min; It is to utilize microwave to be warming up to 550～700 ℃ with the speed of per minute 2～10 degree that described microwave thermal is handled, and keeps 20～50min under this temperature.
9. preparation method according to claim 6 is characterized in that: described Li source compound is lithium hydroxide, lithium carbonate or lithium acetate, and described Fe source compound is ferrous oxalate, di-iron trioxide or tri-iron tetroxide; Described carbon-source cpd is one or more in natural macromolecular material, oxalic acid, citric acid, glucose, sucrose, lactose and the maltose; Described slaine is cobalt nitrate, cobaltous sulfate, cobalt acetate, chromic nitrate, chromium sulfate basic, chromic acetate, magnesium nitrate or nickel nitrate; Described non-metallic vessel is silicon carbide crucible, graphite crucible, glass pot or paper container.
10. preparation method according to claim 9 is characterized in that: described natural macromolecular material is starch, wood powder, bamboo powder, plant straw, chaff shell or shuck, and natural macromolecular material need be pulverized before use, and crosses 200 mesh sieves.
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| CN201010128729A CN101794881A (en) | 2010-03-22 | 2010-03-22 | Method for preparing anode material of lithium ion batteries by one-step microwave sintering |
| PCT/CN2010/072317 WO2011116539A1 (en) | 2010-03-22 | 2010-04-29 | Method for preparing positive electrode material lifepo4/c of lithium ion battery |
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| CN101955176A (en) * | 2010-10-20 | 2011-01-26 | 河南联合新能源有限公司 | Method for preparing anode material lithium vanadium phosphate of lithium ion battery by microwave sintering |
| CN105006548A (en) * | 2015-05-22 | 2015-10-28 | 郑州德朗能微波技术有限公司 | Method for synthesizing sodium-ion battery positive-electrode material NaFePO4 through microwave method |
| CN105529439A (en) * | 2014-10-27 | 2016-04-27 | 深圳市比克电池有限公司 | Method for preparing lithium iron phosphate by hydrothermal method and lithium iron phosphate prepared by method |
| CN105591100A (en) * | 2014-10-27 | 2016-05-18 | 深圳市比克电池有限公司 | Method of preparing lithium iron phosphate cathode material through hydrothermal method, and the cathode material |
| CN106340648A (en) * | 2016-10-19 | 2017-01-18 | 江苏海四达电源股份有限公司 | LiFePO4/C cathode material and preparation method thereof |
| CN106672934A (en) * | 2016-07-01 | 2017-05-17 | 河北安耐哲新能源技术有限公司 | Microwave drying method in process for preparing lithium iron phosphate by wet-process material mixing and lithium iron phosphate preparation process comprising same |
| CN106698382A (en) * | 2015-11-12 | 2017-05-24 | 宁夏际华环境安全科技有限公司 | Production technology of lithium iron phosphate |
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| CN101955176A (en) * | 2010-10-20 | 2011-01-26 | 河南联合新能源有限公司 | Method for preparing anode material lithium vanadium phosphate of lithium ion battery by microwave sintering |
| CN105529439A (en) * | 2014-10-27 | 2016-04-27 | 深圳市比克电池有限公司 | Method for preparing lithium iron phosphate by hydrothermal method and lithium iron phosphate prepared by method |
| CN105591100A (en) * | 2014-10-27 | 2016-05-18 | 深圳市比克电池有限公司 | Method of preparing lithium iron phosphate cathode material through hydrothermal method, and the cathode material |
| CN105006548A (en) * | 2015-05-22 | 2015-10-28 | 郑州德朗能微波技术有限公司 | Method for synthesizing sodium-ion battery positive-electrode material NaFePO4 through microwave method |
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| CN106672934B (en) * | 2016-07-01 | 2020-01-10 | 河北安耐哲新能源技术有限公司 | Microwave drying method in process for preparing lithium iron phosphate by wet mixing and lithium iron phosphate preparation process comprising same |
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| WO2011116539A1 (en) | 2011-09-29 |
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