CN109607505A - A kind of preparation method for the LiFePO4 improving cryogenic property - Google Patents
A kind of preparation method for the LiFePO4 improving cryogenic property Download PDFInfo
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- CN109607505A CN109607505A CN201811552187.0A CN201811552187A CN109607505A CN 109607505 A CN109607505 A CN 109607505A CN 201811552187 A CN201811552187 A CN 201811552187A CN 109607505 A CN109607505 A CN 109607505A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The present invention relates to field of lithium ion battery anode, specially a kind of preparation method for the LiFePO4 for improving cryogenic property.Source of iron, phosphorus source, carbon source are mixed in a certain ratio ball milling, then it is drying, after drying object is sintered by certain sintering schedule in a nitrogen atmosphere, furnace cooling obtains ferrous pyrophosphate presoma, and the presoma of synthesis has spherical pattern, ideal size distribution, higher tap density.Presoma and Li source compound, doped compound are mixed, lithium iron phosphate positive material is made after double sintering in a nitrogen atmosphere.Synthesis technology of the present invention is simple, process is easily controllable, low energy consumption, high-efficient, suitable industrialization production low in cost, and obtained LiFePO4 granularity is small, even particle distribution improves the low temperature performance of LiFePO 4 material by compounded carbons and doping and nanosizing.
Description
Technical field
The present invention relates to field of lithium ion battery anode, specially a kind of lithium ion battery for improving cryogenic property is used
The preparation method of LiFePO 4 material.
Background technique
Currently, there are many system for being investigated as anode material for lithium-ion batteries, but real heavy industrialization also only has
Bore sour lithium (LiCoO2)、LiMn2O、LiFePO4, ternary compound oxides.LiCoO2It is expensive, poor safety performance, LiMn2O4
Compared with LiCoO2Raw material relative moderate, material thermal stability are slightly higher, but LiMn2O4Capacity it is lower, high-temperature behavior is poor.Novel
Ternary compound oxides LiNi1/3Co1/3Mn1/3O2With LiCoO2Structure having the same, it has high-energy density, but three
The security performance performance of first material is poor, this is that the problem of perplexing entire battery industry always, thorough solution is not yet received so far.
1997, the seminar of Goodenough reported lithium ion anode material LiFePO for the first time4, theoretical specific capacity 170mAh/
G, greater than the LiCoO being commercialized2Actual discharge specific capacity.Moreover, LiFePO4With good cycle performance, in 3.45V
Nearby there is stable discharge platform.LiFePO4It is that main electrode material to be used, major advantage have electricity in current driving force battery
Flattening bench is stablized, and raw material inexpensively enriches, environmental-friendly, hypotoxicity and since good high-temperature stability makes it have higher peace
Quan Xing.
LiFePO4For orthorhombic system olivine-type structure, belong to Pmnb space group, lattice constant LiFePO4Crystal
Structure is still able to maintain stabilization at 400 DEG C, greatly improves its cycle performance and safety.Lithium ion is in LiFePO4In lattice
Along one-dimensional channel migration, its diffusion rate is limited significantly, and one-dimensional channel is easy to the appearance due to impurity defect and blocks,
Further decrease its ionic conductivity.Since the associative key of O atom and Fe and P is very strong, so that LiFePO4Structure with
LiCoO2Etc. layer structures compare, have good high-temperature stability.However, strong P-O key also results in ion diffusion rates (10-13~10-16cm-2·s-1) and electronic conductivity (~10-9cm·s-1) reduce.
LiFePO4Lower ionic conductivity and electronic conductivity reduce its practical discharge capacity, and polarization phenomena are tight
Weight, high rate performance are also very unsatisfactory.People carry out extensive and in-depth research to it, can improve its electrification by reducing partial size
Learn performance；One layer of conductive agraphitic carbon net is coated on its surface, electronic conductivity can not only be improved and crystal grain can also be inhibited
Grow up, and then effectively improve ionic conductivity；People to Li or Fe progress high-valence cationics also by adulterating to form p-
Type semiconductor improves its conductivity.These modification modes all generate very big shadow to its ionic conductivity and electronic conductivity
It rings, to improve its discharge capacity, cycle life and high rate performance.
LiFePO4Synthesis material is resourceful, at low cost, environmentally friendly, capacity height, good cycle, but its is low
Warm nature can be poor.The cryogenic property and high rate performance for improving LiFePO 4 material are investigation of materials person and the urgent hope with the producer
It hopes, the method for synthesizing iron lithium phosphate has at present: high temperature solid-state method, sol-gel method, hydro-thermal method, carbothermic method, spray pyrolysis
Method etc., but only high temperature solid-state method is widely used in industrial production.
Summary of the invention
The technical problem to be solved in the present invention, which essentially consists in, provides a kind of preparation side of LiFePO4 for improving cryogenic property
Method solves the problems, such as the poor performance at low temperatures of lithium iron phosphate cathode material for lithium ion battery in the prior art.
Technical solution of the present invention is as follows:
It is a kind of improve cryogenic property LiFePO4 preparation method, by source of iron, phosphorus source and carbon source mix, by ball milling,
Drying process, sintering obtain carbon-coated ferrous pyrophosphate presoma, by carbon-coated ferrous pyrophosphate, Li source compound and mix
By ball milling, calcining lithium iron phosphate positive material is made, specifically in ball milling mixing, mixture to the M compound three used mixedly in proportion
Process is as follows:
(1) preparation of ferrous pyrophosphate presoma
A, source of iron, phosphorus source are (0.965~0.98) Fe:P=in molar ratio: 1, carbon source is both source of iron, phosphorus source gross mass
6%~15%；
B, ball mill ball milling is added 5~12 hours in source of iron, phosphorus source and carbon source according to the above ratio, the solvent of ball milling is anhydrous
Ethyl alcohol or deionized water or acetone；
C, the slurry after ball milling is dried in an oven, 80~120 DEG C of drying temperature, drying time 8~12 hours；
D, it by the crushing material after drying, is sintered in nitrogen atmosphere stove, 430~600 DEG C of sintering temperature, sintering time 4
~10 hours, then furnace cooling obtained ferrous pyrophosphate presoma；
(2) preparation of LiFePO 4 material
By presoma, Li source compound and the M compound being doped with, ball milling mixing is abundant in proportion, in reducing atmosphere
It is heated up and is heated with the speed of 0.1~10 DEG C/min, in 600~750 DEG C of 5~25h of calcining at constant temperature, cool to room temperature with the furnace, be made
The lithium iron phosphate cathode material for lithium ion battery of doped metal ion；
Wherein, presoma, Li source compound molar ratio are=1:(1~1.1), the doping of M compound be presoma and
The 0.1~1.5% of both Li source compounds gross mass；In the M compound being doped with, M is metallic element: aluminium, chromium, titanium, zinc,
One of cobalt, molybdenum, magnesium, vanadium or more than one, M compound be M hydroxide, oxide, chloride, acetate, fluorination
One of object or more than one.
The preparation method of the LiFePO4 of the improvement cryogenic property, source of iron are selected from iron oxide, iron powder, ferric acetate, phosphorus
One of sour iron, ferrous oxalate, ferric nitrate or more than one；Phosphorus source is selected from ammonium di-hydrogen phosphate, phosphoric acid, one hydrogen ammonia of phosphoric acid, phosphorus
One of sour iron, lithium dihydrogen phosphate or more than one.
The preparation method of the LiFePO4 of the improvement cryogenic property, Li source compound be selected from a hydronium(ion) lithia,
One of lithium acetate, lithium carbonate, lithium nitrate, lithium fluoride or more than one.
The preparation method of the LiFePO4 of the improvement cryogenic property, carbon source be selected from glucose, phenolic resin, sucrose,
One of conductive black, expansible graphite, polyethylene glycol, citric acid, carbon nanotube, graphene or more than one.
The preparation method of the LiFePO4 of the improvement cryogenic property first prepares carbon-coated ferrous pyrophosphate forerunner
Body, carbon coating layer with a thickness of 1~8 nanometer；Then the phosphorus of low temperature performance excellent is mixed with Li source compound, M compound
Sour iron lithium material, 0.5C discharge capacity is 84% or more of 0.5C discharge capacity under room temperature at -30 DEG C.
The preparation method of the LiFePO4 of the improvement cryogenic property, the granularity of ferrous pyrophosphate presoma is 30~40
The particle size range of nanometer, Li source compound and M compound is 6~8 microns.
The preparation method of the LiFePO4 of the improvement cryogenic property, LiFePO4 particle size range are received for 100~120
Rice, even particle distribution.
The preparation method of the LiFePO4 of the improvement cryogenic property, it is preferred that the doping of M compound is presoma
With the 0.4~0.6% of both Li source compounds gross mass.
The preparation method of the LiFePO4 of the improvement cryogenic property, reducing atmosphere are nitrogen；Alternatively, pressing volume hundred
Divide than meter, reducing atmosphere is the mixed gas of 95% argon gas and 5% hydrogen.
Design philosophy of the invention is as follows: with method mechanically and chemically prepare primary particle it is tiny and uniformly have three
The carbon-coated ferrous pyrophosphate presoma of conductive network is tieed up, is then being mixed into lithium salts and dopant M prepares low temperature performance excellent
LiFePO 4 material.
The invention has the advantages and beneficial effects that:
1, the method for the present invention synthesis technology is simple, process is easily controllable, and low energy consumption, high-efficient, suitable industry low in cost
Metaplasia produces, and obtained material granule is small, even particle distribution, and higher tap density passes through compounded carbons and doping metals
Ion improves cryogenic property, is suitble to large-scale industrialization production.
2, the present invention prepares the tiny carbon-coated ferrous pyrophosphate presoma of primary particle using compounded carbons, then exists
It is sintered obtained LiFePO 4 material after presoma is mixed lithium, obtained LiFePO4 granularity is small, even particle distribution, by multiple
It closes carbon source and doping and nanosizing improves the cryogenic property of LiFePO 4 material.
Detailed description of the invention
Fig. 1 is the XRD diagram of 1 sample of embodiment.In figure, abscissa 2Theta represents the angle of diffraction (°), ordinate
Intensity represents relative intensity (a.u.).
Fig. 2 is 1 sample of embodiment in -30 DEG C and room temperature discharge curve.
Fig. 3 is 1 sample SEM of embodiment figure.
Specific embodiment
In the specific implementation process, source of iron, phosphorus source, carbon source are mixed in a certain ratio ball milling by the present invention, are then being dried,
After drying object is sintered by certain sintering schedule in a nitrogen atmosphere, furnace cooling obtains ferrous pyrophosphate presoma,
The presoma of synthesis has spherical pattern, ideal size distribution, higher tap density.By presoma and lithium source chemical combination
Object, doped compound mixing, are made lithium iron phosphate positive material after double sintering in a nitrogen atmosphere.
In the following, being further elaborated on by embodiment and attached drawing to the present invention.
Embodiment 1:
In the present embodiment, improve the LiFePO4 of cryogenic property the preparation method is as follows:
(1) iron oxide 164.9g, ammonium di-hydrogen phosphate 234.6g, DEXTROSE ANHYDROUS 32g are weighed, ball milling mixing 8 hours, is terminated
Mixed material is dried 10 hours as 100 DEG C of baking ovens afterwards, the material of drying is placed in nitrogen atmosphere stove, in nitrogen atmosphere
450 DEG C of heat preservation 5h are warming up to the speed of 2 DEG C/min again in furnace, room temperature is cooled to the furnace, carbon-coated ferrous pyrophosphate is made
Presoma, carbon coating layer with a thickness of 2~5 nanometers.
(2) by ferrous pyrophosphate presoma 142.8g, Li source compound lithium carbonate 37.6g and the titanium dioxide being doped with
0.8g, ball milling mixing is abundant, is then sintered: being heated up and is heated with the speed of 2 DEG C/min in reproducibility nitrogen atmosphere, at 650 DEG C
Calcining at constant temperature 5h, cools to room temperature with the furnace, and the lithium iron phosphate cathode material for lithium ion battery of doped metal ion is made.This reality
Applying a LiFePO4 granularity is 100~120 nanometers, and even particle distribution；Doped metal ion is titanium ion, and titanium can increase
Electric conductivity refines LiFePO4 granularity.
Gained lithium iron phosphate positive material is dressed up into 13AH battery, cathode is artificial graphite, and diaphragm is U.S. Celgard public
Take charge of the polyethene microporous membrane or microporous polypropylene membrane of production, electrolyte LiPF6It (counts in mass ratio, ethylene carbonate EC: carbonic acid
Dimethyl ester DMC: methyl ethyl ester EMC=1:1:1), measure -30 DEG C for the first time discharge capacity be 11.2Ah, -30 DEG C of electric discharges appearances
Amount is the 86% of room temperature capacity.
As shown in Figure 1, can be seen that the LiFePO4 diffraction pattern that material is standard, material from the XRD diagram of 1 sample of embodiment
Material diffraction maximum more sharply illustrates that the crystallinity of material is preferable, and crystal form is complete, is conducive to the chemical property for improving material.
As shown in Fig. 2, can be seen that the low temperature discharge property of material in -30 DEG C and room temperature discharge curve from 1 sample of embodiment
It can be very well.
As shown in figure 3, from 1 sample SEM of embodiment figure as can be seen that primary particle it is tiny and uniform, material can be improved
Cryogenic property.
Embodiment 2:
In the present embodiment, improve the LiFePO4 of cryogenic property the preparation method is as follows:
(1) iron 56g, phosphatase 11 17.32g are weighed, DEXTROSE ANHYDROUS 12g and PEG (polyethylene glycol) 5g, ball milling mixing 10 is small
When, after mixed material is dried 10 hours as 100 DEG C of baking ovens, the material of drying is placed in nitrogen atmosphere stove,
430 DEG C of heat preservation 8h are warming up to the speed of 2 DEG C/min again in nitrogen atmosphere stove, room temperature is cooled to the furnace, carbon-coated coke is made
Ferrous phosphate presoma, carbon coating layer with a thickness of 3~6 nanometers.
(2) it by ferrous pyrophosphate presoma 71.4g, one hydronium(ion) lithia 21.8g of Li source compound and is doped with inclined
Vanadic acid ammonia 0.585g, ball milling mixing is abundant, is then sintered: it is heated up and is heated with the speed of 2 DEG C/min in reproducibility nitrogen atmosphere,
In 680 DEG C of calcining at constant temperature 5h, room temperature is cooled to the furnace, the lithium ion battery iron phosphate lithium positive pole material of doped metal ion is made
Material.The present embodiment LiFePO4 granularity is 100~120 nanometers, and even particle distribution；Doped metal ion is vanadium ion, is increased
Electric conductivity is added to refine LiFePO4 granularity.
Gained lithium iron phosphate positive material is dressed up into 13AH battery, cathode is artificial graphite, and diaphragm is U.S. Celgard public
Take charge of polyethene microporous membrane, the microporous polypropylene membrane of production, electrolyte LiPF6It (counts in mass ratio, ethylene carbonate EC: carbonic acid
Dimethyl ester DMC: methyl ethyl ester EMC=1:1:1), measure -30 DEG C for the first time discharge capacity be 11Ah, -30 DEG C of discharge capacities
It is the 84.6% of room temperature capacity.
Embodiment 3:
In the present embodiment, improve the LiFePO4 of cryogenic property the preparation method is as follows:
(1) ferrous oxalate 90g, phosphoric acid 59.8g, DEXTROSE ANHYDROUS 9g and carbon nanotube 0.3g are weighed, ball milling mixing 8 is small
When, after mixed material is dried 10 hours as 100 DEG C of baking ovens, the material of drying is placed in nitrogen atmosphere stove,
450 DEG C of heat preservation 6h are warming up to the speed of 2 DEG C/min again in nitrogen atmosphere stove, room temperature is cooled to the furnace, carbon-coated coke is made
Ferrous phosphate presoma, carbon coating layer with a thickness of 2~5 nanometers.
(2) by ferrous pyrophosphate presoma 85.68g, Li source compound lithium carbonate 23g and the titanium dioxide being doped with
0.48g, ball milling mixing is abundant, is then sintered: being heated up and is heated with the speed of 2 DEG C/min in reproducibility nitrogen atmosphere, at 700 DEG C
Calcining at constant temperature 5h, cools to room temperature with the furnace, and the lithium iron phosphate cathode material for lithium ion battery of doped metal ion is made.This reality
Applying a LiFePO4 granularity is 100~120 nanometers, and even particle distribution；Doped metal ion is titanium ion, increases electric conductivity
LiFePO4 granularity can be refined.
Gained lithium iron phosphate positive material is dressed up into 13AH battery, cathode is artificial graphite, and diaphragm is U.S. Celgard public
Take charge of polyethene microporous membrane, the microporous polypropylene membrane of production, electrolyte LiPF6It (counts in mass ratio, ethylene carbonate EC: carbonic acid
Dimethyl ester DMC: methyl ethyl ester EMC=1:1:1), measure -30 DEG C for the first time discharge capacity be 11.31Ah, -30 DEG C electric discharge
Capacity is the 87% of room temperature capacity.
Embodiment 4:
In the present embodiment, improve the LiFePO4 of cryogenic property the preparation method is as follows:
(1) iron 56g, di-iron trioxide 80g, phosphoric acid 236.64g, DEXTROSE ANHYDROUS 30g and carbon nanotube 0.6g, ball are weighed
Mill mixing 10 hours, after mixed material is dried 10 hours as 100 DEG C of baking ovens, the material of drying is placed in nitrogen gas
In atmosphere furnace, 470 DEG C of heat preservation 8h are warming up to the speed of 2 DEG C/min again in nitrogen atmosphere stove, cool to room temperature with the furnace, carbon is made
The ferrous pyrophosphate presoma of cladding, carbon coating layer with a thickness of 3~6 nanometers.
(2) by ferrous pyrophosphate presoma 285.6g, Li source compound lithium carbonate 77.1g and the titanium dioxide being doped with
1.6g, ball milling mixing is abundant, is then sintered: being heated up and is heated with the speed of 2 DEG C/min in reproducibility nitrogen atmosphere, at 680 DEG C
Calcining at constant temperature 5h, cools to room temperature with the furnace, and the lithium iron phosphate cathode material for lithium ion battery of doped metal ion is made.This reality
Applying a LiFePO4 granularity is 100~120 nanometers, and even particle distribution；Doped metal ion is titanium ion, increases electric conductivity
LiFePO4 granularity can be refined.
Gained lithium iron phosphate positive material is dressed up into 13AH battery, cathode is artificial graphite, and diaphragm is U.S. Celgard public
Take charge of polyethene microporous membrane, the microporous polypropylene membrane of production, electrolyte LiPF6It (counts in mass ratio, ethylene carbonate EC: carbonic acid
Dimethyl ester DMC: methyl ethyl ester EMC=1:1:1), measure -30 DEG C for the first time discharge capacity be 10.92Ah, -30 DEG C electric discharge
Capacity is the 84% of room temperature capacity.
Claims (9)
1. a kind of preparation method for the LiFePO4 for improving cryogenic property, which is characterized in that source of iron, phosphorus source and carbon source are mixed,
Carbon-coated ferrous pyrophosphate presoma is obtained by ball milling, drying process, sintering, by carbon-coated ferrous pyrophosphate, lithium source
LiFePO4 is being made just by ball milling, calcining in ball milling mixing, mixture in proportion by compound and the M compound three being doped with
Pole material, detailed process is as follows:
(1) preparation of ferrous pyrophosphate presoma
A, source of iron, phosphorus source are (0.965~0.98) Fe:P=in molar ratio: 1, carbon source is the 6% of both source of iron, phosphorus source gross mass
~15%；
B, ball mill ball milling is added 5~12 hours in source of iron, phosphorus source and carbon source according to the above ratio, the solvent of ball milling is dehydrated alcohol
Or deionized water or acetone；
C, the slurry after ball milling is dried in an oven, 80~120 DEG C of drying temperature, drying time 8~12 hours；
D, it by the crushing material after drying, is sintered in nitrogen atmosphere stove, 430~600 DEG C of sintering temperature, sintering time 4~10
Hour, then furnace cooling obtains ferrous pyrophosphate presoma；
(2) preparation of LiFePO 4 material
By presoma, Li source compound and the M compound being doped with, ball milling mixing is abundant in proportion, in reducing atmosphere with
The speed of 0.1~10 DEG C/min, which heats up, to be heated, and in 600~750 DEG C of 5~25h of calcining at constant temperature, is cooled to room temperature with the furnace, is made and mixes
The lithium iron phosphate cathode material for lithium ion battery of miscellaneous metal ion；
Wherein, presoma, Li source compound molar ratio are=1:(1~1.1), the doping of M compound is presoma and lithium source
The 0.1~1.5% of both compounds gross mass；In the M compound being doped with, M is metallic element: aluminium, chromium, titanium, zinc, cobalt, molybdenum,
One of magnesium, vanadium or more than one, M compound be the hydroxide of M, oxide, chloride, acetate, in fluoride
It is one or more kinds of.
2. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that source of iron is selected from
One of iron oxide, iron powder, ferric acetate, ferric phosphate, ferrous oxalate, ferric nitrate or more than one；Phosphorus source is selected from biphosphate
One of ammonia, phosphoric acid, one hydrogen ammonia of phosphoric acid, ferric phosphate, lithium dihydrogen phosphate or more than one.
3. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that lithium source chemical combination
Object be selected from one of a hydronium(ion) lithia, lithium acetate, lithium carbonate, lithium nitrate, lithium fluoride or more than one.
4. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that carbon source is selected from
Glucose, phenolic resin, sucrose, conductive black, expansible graphite, polyethylene glycol, citric acid, carbon nanotube, in graphene
It is one or more kinds of.
5. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that first prepare carbon
The ferrous pyrophosphate presoma of cladding, carbon coating layer with a thickness of 1~8 nanometer；Then it is mixed with Li source compound, M compound
The LiFePO 4 material of low temperature performance excellent is prepared, 0.5C discharge capacity is 84% of 0.5C discharge capacity under room temperature at -30 DEG C
More than.
6. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that pyrophosphoric acid is sub-
For the granularity of iron presoma at 30~40 nanometers, the particle size range of Li source compound and M compound is 6~8 microns.
7. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that LiFePO4
Particle size range is 100~120 nanometers, even particle distribution.
8. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that preferred, M
The doping of compound is the 0.4~0.6% of both presoma and Li source compound gross mass.
9. the preparation method of the LiFePO4 according to claim 1 for improving cryogenic property, which is characterized in that reproducibility gas
Atmosphere is nitrogen；Alternatively, pressing volume percentage, reducing atmosphere is the mixed gas of 95% argon gas and 5% hydrogen.
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| CN110436431A (en) * | 2019-06-29 | 2019-11-12 | 佛山市德方纳米科技有限公司 | A kind of preparation method and lithium ion battery of lithium iron phosphate positive material |
| CN112239227A (en) * | 2020-10-29 | 2021-01-19 | 龙蟒佰利联集团股份有限公司 | Preparation method of conductive titanium dioxide |
| CN112723333A (en) * | 2020-12-11 | 2021-04-30 | 江苏锂源电池材料有限公司 | Method for improving low-temperature performance and compaction density of lithium iron phosphate |
| CN113346075A (en) * | 2021-04-29 | 2021-09-03 | 华中科技大学 | Low-temperature-resistant framework composite precursor-based lithium iron phosphate, and preparation method and application thereof |
| CN113830747A (en) * | 2021-09-17 | 2021-12-24 | 湖北亿纬动力有限公司 | Low-temperature starting type lithium iron phosphate cathode material and preparation method thereof |
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| CN113830747A (en) * | 2021-09-17 | 2021-12-24 | 湖北亿纬动力有限公司 | Low-temperature starting type lithium iron phosphate cathode material and preparation method thereof |
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| CN114314553A (en) * | 2021-12-31 | 2022-04-12 | 欣旺达电动汽车电池有限公司 | Modified lithium iron phosphate, preparation method thereof and lithium ion battery |
| CN115676799A (en) * | 2022-12-28 | 2023-02-03 | 湖南鹏博新材料有限公司 | Preparation method of modified lithium iron phosphate |
| CN115676799B (en) * | 2022-12-28 | 2023-03-31 | 湖南鹏博新材料有限公司 | Preparation method of modified lithium iron phosphate |
| CN116565180A (en) * | 2023-06-27 | 2023-08-08 | 湖北万润新能源科技股份有限公司 | High tap density lithium iron phosphate positive electrode material, and preparation method and application thereof |
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