CN109244462A - A kind of preparation method of high conductivity LiFePO 4 material - Google Patents
A kind of preparation method of high conductivity LiFePO 4 material Download PDFInfo
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- CN109244462A CN109244462A CN201811381141.7A CN201811381141A CN109244462A CN 109244462 A CN109244462 A CN 109244462A CN 201811381141 A CN201811381141 A CN 201811381141A CN 109244462 A CN109244462 A CN 109244462A
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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
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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
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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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods of high conductivity LiFePO 4 material.This method prepares lithium iron phosphate/carbon composite material using two-step method, on the one hand by once sintered, coats the organic carbon source of one layer of carbohydrate breakdown on LiFePO4 surface, belongs to in-stiu coating, control lithium iron phosphate particles size, prepare the carbon-coated LiFePO of single layer4Material；Still further aspect, pass through double sintering, it introduces gas phase deposition technology (CVD), during the sintering process by way of vapor deposition, form cracking carbon, the higher Pintsch process carbon of one layer of degree of graphitization is coated again on lithium iron phosphate/carbon surface, is finally prepared the LiFePO 4 material of high conductivity, low internal resistance, is reduced the internal resistance of material.
Description
Technical field
The present invention relates to field of lithium ion battery anode, it is specifically related to a kind of high conductivity LiFePO 4 material
Preparation method.
Background technique
LiFePO4 is as a kind of positive electrode, relative to materials such as ternarys in safety, circulation, in price all with bright
Aobvious advantage, and environmentally friendly, has been widely used for the markets such as electric car, energy storage, be current mainstream lithium ion just
One of pole material.
With the continuous promotion to deepen continuously with market demands that LiFePO 4 material is studied, at present for LiFePO4
It is required that be concentrated mainly on two aspect, one be energy density promotion, another be reduce internal resistance, hoisting power density.
Due to LiFePO4 LiFePO4Lower conductivity (10-9) and lithium ion diffusion coefficient (1.8 × 10 S/cm-14cm2/ s) these
Intrinsic disadvantage causes the power-performance of LiFePO4 relatively low, and internal resistance is bigger than normal.
Traditional mainstream improved method is that simple carbon coating is carried out to LiFePO4, and mainly carbohydrate breakdown carries out organic packet
It covers and directly addition inorganic carbon carries out inorganic carbon source cladding, although organic carbon source is evenly coated but degree of graphitization
Low, conductivity is inclined, and inorganic carbon source cladding can not be evenly coated at LiFePO4 surface again, all there is certain defect.For example, patent
CN106848222A discloses a kind of preparation method of LiFePO4/double-layer carbon clad composite material, and this method passes through an earnest
Source of iron, phosphorus source and the lithium source of the amount ratio of matter are added reducing agent and dissolve, and add the mode of mesoporous carbon by being sintered disposable shape
At LiFePO4/double-layer carbon clad composite material, disadvantage is that double carbon-coatings are once formed, and mesoporous carbon belongs to inorganic carbon source, distribution
It is difficult uniformly, therefore there are certain shortcomings to electronic conductivity promotion effect.For another example, patent CN107240696A is disclosed
The preparation method and carbon-coated LiFePO 4 for lithium ion batteries and ion battery of a kind of carbon-coated LiFePO 4 for lithium ion batteries, this method first by part carbon source and
Ferric phosphate mixing carries out pre-burning, obtains Preburning material, then Preburning material is mixed with lithium source and part carbon source, obtains LiFePO4 material
Material, the disadvantages of this method is that while it is carbon coated twice, but the mode of carbon coated is consistent with principle twice, is only graphitized
Twice, the effect for improving conductivity is relatively limited for the similar carbon source cladding of degree.
Summary of the invention
To overcome above-mentioned shortcoming and deficiency existing in the prior art, the present invention prepares lithium iron phosphate/carbon using two-step method
Composite material coats the organic carbon source of one layer of carbohydrate breakdown on LiFePO4 surface, belongs to original position on the one hand by once sintered
Cladding controls lithium iron phosphate particles size, prepares the carbon-coated LiFePO of single layer4Material；Still further aspect passes through secondary burning
Knot introduces gas phase deposition technology (CVD), during the sintering process by way of vapor deposition, cracking carbon is formed, in ferric phosphate
Lithium/carbon surface coats the higher Pintsch process carbon of one layer of degree of graphitization again, finally prepares the phosphoric acid of high conductivity, low internal resistance
Iron lithium material reduces the internal resistance of material.
To achieve the object of the present invention, the preparation of the high conductivity LiFePO 4 material of the present invention, main includes certain metering
The preparation process of the preparation of the single layer carbon-coated LiFePO 4 for lithium ion batteries of chemical ratio and the double-deck carbon-coated LiFePO 4 for lithium ion batteries.Specifically, this
Invent the preparation method of the high conductivity composite ferric lithium phosphate material the following steps are included:
(1) lithium source, source of iron and phosphorus source are carried out to mixing in organic solvent or in deionized water system, by the lithium after mixing
Source, source of iron, phosphorus source and organic carbon source are sequentially added in Ball-stirring mill, obtain mixed material；
(2) it is ground by Ball-stirring mill, the slurry being ground is poured into sand mill and is ground；
(3) after being ground in sand mill, slurry is poured out；
(4) it will be spray-dried by the slurry of sand mill grinding, obtain ferric lithium phosphate precursor；
(5) ferric lithium phosphate precursor obtained by step (4) carries out first time burning in tube furnace under inert gas shielding atmosphere
Knot, obtains single layer carbon-coated LiFePO 4 for lithium ion batteries material；
(6) the single layer carbon-coated LiFePO 4 for lithium ion batteries material prepared in step (5) is transferred in rotary furnace and carries out second of burning
Knot, sintering process are sintered using mixed gas, obtain the double-deck carbon-coated LiFePO 4 for lithium ion batteries material.
Further, lithium source can be selected from lithium carbonate or monohydrate lithium hydroxide, the source of iron and phosphorus in the step (1)
It source can and ammonium dihydrogen phosphate ferrous selected from ferric phosphate or two oxalic acid hydrates.
Further, the organic solvent in the step (1) can be selected from methanol or ethyl alcohol.
Preferably, the elemental mole ratios in the step (1) be Li:Fe=1.025~1.06, Li:P=1.01~
1.05；Preferably, organic carbon source is selected from glucose, polyethylene glycol, ascorbic acid, PVP, citric acid, starch, beta-cyclodextrin, sugarcane
One of sugar is a variety of.
The solid content of mixed material controls between 25%-40% in the step (1).
Slurry granularity is D50 < 2um after Ball-stirring mill grinding in the step (2)；Preferably, abrasive media is zirconium oxide
Ball, zirconium ball is having a size of diameter 1mm.
Slurry Granularity is 400nm < D50 < 600nm after sand mill grinding in the step (3)；Preferably, abrasive media
For zirconia ball, zirconium ball is having a size of 0.4mm.
Spray drying inlet temperature in the step (4) controls between 200-230 DEG C, and outlet temperature is controlled in 80-
Between 120 DEG C.
Inert atmosphere in the step (5) is one of argon gas, nitrogen or two kinds；Preferably, sintering temperature is
730-760 DEG C, sintering time 8-9h.
Mixed gas in the step (6) can be the nitrogen and propylene mixed gas, volume ratio 9:1 of volume ratio 9:1
Nitrogen and propane mixture body, the nitrogen of volume ratio 8:2 and propylene mixed gas, the nitrogen of volume ratio 9:1 and ethyl alcohol mixing
One of the argon gas and propylene mixed gas of gas or volume ratio 9:1；Preferably, sintering temperature is 500-550 DEG C；When sintering
Between be 0.3-0.7h, such as 0.5h.
The beneficial effects of the present invention are:
1) a kind of double-deck carbon-coated LiFePO 4 for lithium ion batteries material is provided, the bilayer carbon-coated LiFePO 4 for lithium ion batteries material is more traditional
Carbon-coated LiFePO 4 for lithium ion batteries material becomes double-layer carbon by original monolayer carbon, and second layer carbon is that the higher CVD of degree of graphitization is split
Carbon is solved, can effectively improve the electronic conductivity of LiFePO4, conductivity value is up to 10-2S/cm-10-1Between S/cm.
2) a kind of double-deck carbon-coated LiFePO 4 for lithium ion batteries material is provided, by double sintering and secondary carbon coating, is improving electricity
While electron conductivity, the chemical property of LiFePO4, especially cryogenic property can be also improved, is held in -20 degree 0.2C electric discharges
It measures up to 120mAh/g.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Embodiment 1
Step 1: 840g deionized water being added in Ball-stirring mill；Lithium carbonate 75.7g is weighed, ferric phosphate 300g carries out mixing；
Carbon source uses glucose, weighs 36g；The weighed lithium source of institute, source of iron, phosphorus source, glucose sugar are added sequentially in Ball-stirring mill.
Step 2: control Ball-stirring mill speed is 800r/min, every 10min detection successively granularity, when granularity is less than 2um, just
Material is dumped into sand mill and is ground.
Step 3: control sand mill speed is 2500r/min, successively granularity is detected every 30min, when granularity reaches 400nm
Just by material discharging between < D50 < 600nm, it is ready for being spray-dried.
Step 4: being spray-dried, control spray drying inlet temperature is 220-230 DEG C, and outlet temperature is controlled in 100-
120 DEG C, obtain presoma.
Step 5: the presoma obtained in step 4 being put into tube furnace and is sintered, entire sintering process uses nitrogen
Atmosphere protection is carried out, sintering temperature is set in 740 DEG C, is sintered 9h, obtains single layer coated LiFePO 4 for lithium ion batteries material.
Step 6: the single layer coated LiFePO 4 for lithium ion batteries material obtained in step 5 being transferred in rotary furnace, revolution furnace temperature is set
530 DEG C are scheduled on, using nitrogen and propylene mixed gas, wherein the ratio of nitrogen and propylene is 9:1, and entire sintering time is
0.5h obtains double-coating LiFePO 4 material.
Embodiment 2
Step 1: 570g methanol being added in Ball-stirring mill；Weigh monohydrate lithium hydroxide (LiOHH2O) 57.59g, ferric phosphate
200g carries out mixing；Carbon source uses glucose and beta-cyclodextrin, weighs 20g and 4g；By the weighed lithium source of institute, source of iron, phosphorus source, Portugal
Sugared and beta-cyclodextrin is added sequentially in Ball-stirring mill.
Step 2: control Ball-stirring mill speed is 800r/min, every 10min detection successively granularity, when granularity is less than 2um, just
Material is dumped into sand mill and is ground.
Step 3: control sand mill speed is 2500r/min, successively granularity is detected every 30min, when granularity reaches 400nm
Just by material discharging between < D50 < 600nm, it is ready for being spray-dried.
Step 4: being spray-dried, control spray drying inlet temperature is 220-230 DEG C, and outlet temperature is controlled in 80-
100 DEG C, obtain presoma.
Step 5: the presoma obtained in step 4 being put into tube furnace and is sintered, entire sintering process uses nitrogen
Atmosphere protection is carried out, sintering temperature is set in 750 DEG C, is sintered 8h, obtains single layer coated LiFePO 4 for lithium ion batteries material.
Step 6: the single layer coated LiFePO 4 for lithium ion batteries material obtained in step 5 being transferred in rotary furnace, revolution furnace temperature is set
540 DEG C are scheduled on, using nitrogen and propylene mixed gas, wherein the ratio of nitrogen and ethyl alcohol is 9:1, and entire sintering time is
0.5h obtains the double-deck carbon-coated LiFePO 4 for lithium ion batteries material.
Embodiment 3
Step 1: 1800g methanol being added in Ball-stirring mill；Weigh lithium carbonate 100g, two oxalic acid hydrates ferrous iron (C2H4FeO6)
468.2g, ammonium dihydrogen phosphate 302.3g carry out mixing；Carbon source uses sucrose, weighs 6g；By the weighed lithium source of institute, source of iron, phosphorus source,
Sucrose is added sequentially in Ball-stirring mill.
Step 2: control Ball-stirring mill speed is 800r/min, every 10min detection successively granularity, when granularity is less than 2um, just
Material is dumped into sand mill and is ground.
Step 3: control sand mill speed is 2500r/min, successively granularity is detected every 30min, when granularity reaches 400nm
Just by material discharging between < D50 < 600nm, it is ready for being spray-dried.
Step 4: being spray-dried, control spray drying inlet temperature is 210-230 DEG C, and outlet temperature is controlled in 80-
100 DEG C, obtain presoma.
Step 5: the presoma obtained in step 4 being put into tube furnace and is sintered, entire sintering process uses argon gas
Atmosphere protection is carried out, sintering temperature is set in 730 DEG C, is sintered 9h, obtains single layer coated LiFePO 4 for lithium ion batteries material.
Step 6: the single layer coated LiFePO 4 for lithium ion batteries material obtained in step 5 being transferred in rotary furnace, revolution furnace temperature is set
500 DEG C are scheduled on, using nitrogen and propylene mixed gas, wherein the ratio of argon gas and propylene is 9:1, and entire sintering time is
0.5H obtains double-coating LiFePO 4 material.
Embodiment 4
Step 1: 850g deionized water being added in Ball-stirring mill；Lithium carbonate 75.7g is weighed, ferric phosphate 300g carries out mixing；
Carbon source uses glucose, weighs 36g；The weighed lithium source of institute, source of iron, phosphorus source, glucose sugar are added sequentially in Ball-stirring mill.
Step 2: control Ball-stirring mill speed is 800r/min, every 10min detection successively granularity, when granularity is less than 2um, just
Material is dumped into sand mill and is ground.
Step 3: control sand mill speed is 2500r/min, successively granularity is detected every 30min, when granularity reaches 400nm
Just by material discharging between < D50 < 600nm, it is ready for being spray-dried.
Step 4: being spray-dried, control spray drying inlet temperature is 220-230 DEG C, and outlet temperature is controlled in 100-
120 DEG C, obtain presoma.
Step 5: the presoma obtained in step 4 being put into tube furnace and is sintered, entire sintering process uses nitrogen
Atmosphere protection is carried out, sintering temperature is set in 730 DEG C, is sintered 8h, obtains single layer coated LiFePO 4 for lithium ion batteries material.
Step 6: the single layer coated LiFePO 4 for lithium ion batteries material obtained in step 5 being transferred in rotary furnace, revolution furnace temperature is set
550 DEG C are scheduled on, using nitrogen and propylene mixed gas, wherein the ratio of nitrogen and propylene is 9:1, and entire sintering time is
0.5h obtains double-coating LiFePO 4 material.
Embodiment 5
Step 1: 540g methanol being added in Ball-stirring mill；Weigh monohydrate lithium hydroxide (LiOHH2O) 56.44g, ferric phosphate
196g carries out mixing；Carbon source uses beta-cyclodextrin and starch, weighs 18g and 4g；By the weighed lithium source of institute, source of iron, phosphorus source, β-ring
Dextrin and starch are added sequentially in Ball-stirring mill.
Step 2: control Ball-stirring mill speed is 800r/min, every 10min detection successively granularity, when granularity is less than 2um, just
Material is dumped into sand mill and is ground.
Step 3: control sand mill speed is 2500r/min, successively granularity is detected every 30min, when granularity reaches 400nm
Just by material discharging between < D50 < 600nm, it is ready for being spray-dried.
Step 4: being spray-dried, control spray drying inlet temperature is 220-230 DEG C, and outlet temperature is controlled in 80-
100 DEG C, obtain presoma.
Step 5: the presoma obtained in step 4 being put into tube furnace and is sintered, entire sintering process uses nitrogen
Atmosphere protection is carried out, sintering temperature is set in 730 DEG C, is sintered 9h, obtains single layer coated LiFePO 4 for lithium ion batteries material.
Step 6: the single layer coated LiFePO 4 for lithium ion batteries material obtained in step 5 being transferred in rotary furnace, revolution furnace temperature is set
550 DEG C are scheduled on, using nitrogen and propylene mixed gas, wherein the ratio of nitrogen and propylene is 8:2, and entire sintering time is
0.5h obtains the double-deck carbon-coated LiFePO 4 for lithium ion batteries material.
Comparative example 1
Commercially available Hefei state pavilion lithium iron phosphate/carbon composite material.
Comparative example 2
Commercially available German side's nano-grade lithium iron phosphate/carbon composite.
Conductivity is carried out using the material of the resulting material of embodiment 1-5 and comparative example 1-2 and low temperature -20 spends 0.2C electric discharge
Volume test.The results are shown in Table 1, the commercially available lithium iron phosphate/carbon composite material conductance of the Conductivity Ratio of products obtained therefrom in embodiment
The high 1-2 order of magnitude of rate, low temperature electric performance test will also be higher by 10-20mAh/g.
1 the performance test results of table
| Number | Conductivity S/cm | Low-temperature test (- 20 DEG C of 0.2C) |
| Embodiment 1 | 1.04×10-1 | 120 |
| Embodiment 2 | 7.05×10-2 | 114 |
| Embodiment 3 | 8.02×10-2 | 118 |
| Embodiment 4 | 6.35×10-2 | 119 |
| Embodiment 5 | 2.02×10-1 | 121 |
| Comparative sample 1 | 3.43×10-3 | 96 |
| Comparative sample 2 | 4.74×10-3 | 101 |
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high conductivity LiFePO 4 material, which is characterized in that the preparation method the following steps are included:
(1) lithium source, source of iron and phosphorus source are carried out to mixing in organic solvent or in deionized water system, by after mixing lithium source,
Source of iron, phosphorus source and organic carbon source are sequentially added in Ball-stirring mill, obtain mixed material；
(2) it is ground by Ball-stirring mill, the slurry being ground is poured into sand mill and is ground；
(3) after being ground in sand mill, slurry is poured out；
(4) it will be spray-dried by the slurry of sand mill grinding, obtain ferric lithium phosphate precursor；
(5) ferric lithium phosphate precursor obtained by step (4) carries out first sintering in tube furnace under inert gas shielding atmosphere,
Obtain single layer carbon-coated LiFePO 4 for lithium ion batteries material；
(6) the single layer carbon-coated LiFePO 4 for lithium ion batteries material prepared in step (5) is transferred in rotary furnace and carries out second of sintering, burnt
Knot process is sintered using mixed gas, obtains the double-deck carbon-coated LiFePO 4 for lithium ion batteries material.
2. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(1) in lithium source be selected from lithium carbonate perhaps monohydrate lithium hydroxide source of iron and phosphorus source be selected from ferric phosphate or two oxalic acid hydrate ferrous irons and
Ammonium dihydrogen phosphate.
3. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(1) organic solvent in is selected from methanol or ethyl alcohol.
4. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(1) elemental mole ratios in are Li:Fe=1.025~1.06, Li:P=1.01~1.05, and organic carbon source is selected from glucose, gathers
One of ethylene glycol, ascorbic acid, PVP, citric acid, starch, beta-cyclodextrin, sucrose are a variety of.
5. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(1) solid content of mixed material controls between 25%-40% in.
6. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(2) slurry granularity is D50 < 2um after Ball-stirring mill grinding in；Preferably, abrasive media is zirconia ball, and zirconium ball is having a size of diameter
1mm。
7. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(3) Slurry Granularity is 400nm < D50 < 600nm after sand mill grinding in；Preferably, abrasive media is zirconia ball, zirconium ball ruler
Very little is 0.4mm.
8. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(4) the spray drying inlet temperature in controls between 200-230 DEG C, and outlet temperature controls between 80-120 DEG C.
9. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(5) inert atmosphere in is one of argon gas, nitrogen or two kinds；Preferably, sintering temperature is 730-760 DEG C, when sintering
Between be 8-9h.
10. the preparation method of high conductivity LiFePO 4 material according to claim 1, which is characterized in that the step
(6) mixed gas in can mix for nitrogen and propylene mixed gas, the nitrogen of volume ratio 9:1 and propane of volume ratio 9:1
Gas, the nitrogen of volume ratio 8:2 and propylene mixed gas, the nitrogen of volume ratio 9:1 and ethyl alcohol mixed gas, volume ratio 9:1
One of argon gas and propylene mixed gas；Preferably, sintering temperature is 500-550 DEG C；Sintering time is 0.3-0.7h, such as
0.5h。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109921003A (en) * | 2019-04-18 | 2019-06-21 | 王东升 | A kind of preparation method of high-pressure solid LiFePO4 |
| CN110085839A (en) * | 2019-05-07 | 2019-08-02 | 佛山市德方纳米科技有限公司 | Iron phosphate compound anode material of lithium and its preparation method and application |
| CN110137476A (en) * | 2019-05-28 | 2019-08-16 | 大连中比动力电池有限公司 | A kind of lithium iron phosphate/carbon composite material and its preparation method and application |
| CN114914413A (en) * | 2022-04-25 | 2022-08-16 | 中南大学 | Carbon-coated sodium ferrous fluorophosphate material, preparation thereof and application thereof in sodium ion battery |
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| CN114914413B (en) * | 2022-04-25 | 2024-03-26 | 湖南钠邦新能源有限公司 | Carbon-coated sodium ferrous fluorophosphate material, preparation method thereof and application thereof in sodium ion battery |
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