CN107394186B - The process of preparing of shell lithium iron phosphate positive material - Google Patents
The process of preparing of shell lithium iron phosphate positive material Download PDFInfo
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- CN107394186B CN107394186B CN201710756823.0A CN201710756823A CN107394186B CN 107394186 B CN107394186 B CN 107394186B CN 201710756823 A CN201710756823 A CN 201710756823A CN 107394186 B CN107394186 B CN 107394186B
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- carbon phase
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- nodularization
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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 present invention relates to a kind of preparation method of LiFePO 4 material, specifically a kind of preparation method of shell structurre lithium iron phosphate positive material.Steps are as follows: step 1) prepares carbon phase microballoon as preliminary core structure by hydrothermal process, glucose is configured to aqueous solution, 2 microns of carbon phase microballoon is prepared in reaction in merging reaction kettle after washing is dry；Step 2 takes ferric phosphate and lithium source mixture according to molar ratio by lithium source and ferric phosphate, takes soluble carbon source and pure water, carries out emulsification mixing after agitated kettle is added, and forms solid powder by microwave drying；Step 3) preferentially puts into the above carbon phase micro-sphere material 1), and charged material weight accounts for the 2%-5% of entire plan mixed material total weight, is introduced into the solid powder formed in 2), continues nodularization, monitor material particle size, control at 6-12 microns；Material carries out high temperature sintering under nitrogen protection after step 4) nodularization, natural cooling and is sieved after sintering, obtains final shell LiFePO4 finished-product material.
Description
Technical field
The present invention relates to a kind of preparation method of LiFePO 4 material, specifically a kind of shell structurre LiFePO4 is just
The preparation method of pole material.
Background technique
LiFePO4 (LiFePO4) crystal structure is olivine-type structure, belongs to orthorhombic system, space group Pnmb, structure cell
Size are as follows: a=0.6008 nm, b=1.0334 nm, c=0.4693 nm.Lithium iron phosphate positive material has good heat steady because of it
Qualitative and higher theoretical specific capacity, and earnestly paid close attention to by lithium electricity industry technology personnel, even pursuing high capacity density
Current environment, the excellent security performance of LiFePO4, which remains on, can not be substituted.But simultaneously because LiFePO 4 material room temperature
Under electronic conductivity and Li+ diffusion coefficient it is very low, cause its high rate charge-discharge performance bad, affect its actually use model
Farmland, therefore the preparation method multi-pass of current LiFePO 4 material is modified cladding, nanosizing excessively to improve its electric conductivity, common method
Such as carbon coating, be sanded it is broken etc. if come from the purpose.
Conventional carbothermic method also realizes industrialized production because its operation is relatively simple already, pursues in existing market
Under the overall situation of rate charge-discharge and energy force density, more manufacturing enterprises are that solution LiFePO 4 material intrinsic conductivity is low
Problem develops towards the direction of nanosizing always, usually can alleviate material high rate performance by reducing particle size in this way
The problem of difference, but the hidden danger that the parameters such as compacted density drastically reduce also is brought simultaneously.In addition to this, in nanosizing ferric phosphate
When carrying out synthetic reaction with carbon thermal reduction, it is limited to raw material particle size variation, the temperature of high-temperature process is slightly lowered, this is to have
The graphitization and electric conductivity of the decomposition of machine carbon source, reduction reaction or even residual carbon play biggish side effect, deposit on the whole
In very big drawback, the degree of graphitization of carbon source is directly limited by the temperature height of materials synthesis, so, in nanosizing technique item
The degree of graphitization of carbon source is also accordingly reduced with the reduction of sintering temperature under part, to further weaken finished product lithium iron phosphate
The electric conductivity of material.Therefore the contradiction mitigated between material conductivity and multiplying power discharging, energy density increasingly becomes important, this hair
It is bright will by brining together, nodularization, the technical points such as shell improve the processing performance and electric conductivity of LiFePO 4 material.
Summary of the invention
The present invention is designed for the problems such as lithium iron phosphate positive material conductivity is low, multiplying power discharging, micro- by carbon phase
The design of " core " of ball, matches spheroidizing process, and the method for having synthesized the shell lithium iron phosphate positive material of high conductivity is main to walk
It is rapid as follows:
Step 1) prepares carbon phase microballoon as preliminary core structure by hydrothermal process, and glucose is configured to 0.5-
The aqueous solution of 1mol/L, is placed in 180 DEG C -200 DEG C of reactions 4-6 hours in reaction kettle, and it is good that dispersibility is prepared after washing is dry
2 microns good of carbon phase microballoon；
Step 2 is weighed the phosphorus of 2-10kg total weight in lithium source and ferric phosphate according to the ratio that molar ratio is 1.02-1.05:1
Sour iron and lithium source mixture weigh soluble carbon source and pure water according to the ratio that mass ratio is 1:0.4-0.5, after agitated kettle is added
Emulsification mixing 2h is carried out, forms solid powder by microwave drying；
For step 3) in fusion nodularization equipment, the preferential above carbon phase micro-sphere material 1) of investment, charged material weight accounts for entire meter
Draw the 2%-5% of mixed material total weight；After by carbon phase micro-sphere material nodularization 10-30min, it is introduced into the solid powder formed in 2)
End, continues nodularization 1-2h, and process monitoring material particle size controls at 6-12 microns, stops pelletizing operations after reaching requirement；
Step 4) by after nodularization material carry out nitrogen protection under high temperature sintering, 700 DEG C -750 DEG C of temperature setting, time 4-6
Hour, it natural cooling and is sieved after sintering, obtains final shell LiFePO4 finished-product material.
Preferably, fusion pelletizing operations need whole process to carry out under nitrogen atmosphere；
Preferably, the soluble carbon source mentioned in step 2 is glucose or sucrose；
Preferably, the shell cored structure is carbon phase microballoon, quality specific gravity is to account for entire plan mixed material total weight
2%-5%；Plan mixed material refers to ferric phosphate, lithium source, the summation of carbon source and carbon phase microballoon all solids material；
Preferably, granularity is controlled in primary particle size 200-600nm after core material nodularization 10-30min, shell structurre
Outer diameter is at 6-12 microns；
Preferably, the temperature of material high temperature sintering is 700 DEG C -750 DEG C after core material nodularization, time 4-6 hour.
Preparation of the present invention process from internal carbon phase microballoon, the nodularization behaviour of outer layer ferric phosphate and carbon source material after evenly mixing
Make, then passes through high temperature sintering, the internal carbonization of realization is decomposed and the formation of surface layer LiFePO4 object phase；The gradient design in technique
The formation of the shell pattern of final finished is ensured.
The present invention has the advantages that the shell structurre design of 1, LiFePO4 alleviates, material intrinsic conductivity is low to be asked
Topic, the innovative migration thickness that lithium ion in LiFePO 4 material is shortened using shell structurre design, is to be different from sand milling
Novel process means outside process for refining；2, LiFePO4 shell structurre ensure that the processing performance of material, compacted density are higher than
Nanosizing powder body material increases the energy density of single battery；3, interior carbon material at high temperature equally can be with shell inside
Ferric phosphate occur reduction reaction and degradation, it is final to disappear or size reduces, form interior void structure, it is even remaining a small amount of
Carbon material, also can provide help to the electric conductivity of whole Shell Materials.4, non-solid ball design is guaranteeing material compacting
On the basis of the materiel machinings such as density are superior, increase electrolyte effect of impregnation or even interior shell structure has storage on a small quantity
The possibility of electrolyte.
Detailed description of the invention
The SEM of Fig. 1 embodiment 1 schemes,
The SEM of Fig. 2 embodiment 2 schemes,
The SEM of Fig. 3 comparative example 1 schemes,
The SEM of Fig. 4 comparative example 2 schemes,
2 gained shell LiFePO4 of Fig. 5 embodiment and 2 gained entity sphere electrochemical performances of lithium iron phosphate pair of comparative example
Than.
Specific embodiment
Make explanation in detail below with reference to process of preparing of the embodiment to shell lithium iron phosphate positive material of the present invention.
Embodiment 1:
1) carbon phase microballoon is prepared as preliminary core structure by hydrothermal process；Glucose is configured to the water of 0.5mol/L
Solution is placed in reaction kettle and reacts 6 hours for 180 DEG C, and 2 microns of the carbon phase that favorable dispersibility is prepared after washing is dry is micro-
Ball.
2) material blends for weighing 2kg total weight according to the ratio that molar ratio is 1.02:1 in lithium source and ferric phosphate, are pressed
Glucose and pure water are weighed according to the ratio that mass ratio is 1:0.4, emulsification mixing 2h is carried out after agitated kettle is added, by microwave drying
Form solid powder.
3) in fusion nodularization equipment, the preferential above carbon phase micro-sphere material 1) of investment, charged material weight accounts for entire plan
The 3% of mixed material total weight；After by core material nodularization 20min, it is introduced into the solid powder formed in 2), continues nodularization 2h, process
Material particle size is monitored, controls at 10 microns, stops pelletizing operations after reaching requirement.
4) by after nodularization material carry out nitrogen protection under high temperature sintering, 710 DEG C of temperature setting, the time 6 hours, after sintering from
After so cooling down and being sieved, final shell LiFePO4 finished-product material is obtained.
Embodiment 2:
1) carbon phase microballoon is prepared as preliminary core structure by hydrothermal process；Glucose is configured to the water-soluble of 1mol/L
Liquid is placed in reaction kettle and reacts 4 hours for 200 DEG C, and 2 microns of carbon phase microballoon of favorable dispersibility is prepared after washing is dry.
2) material blends for weighing 5kg total weight according to the ratio that molar ratio is 1.02:1 in lithium source and ferric phosphate, are pressed
Sucrose and pure water are weighed according to the ratio that mass ratio is 1:0.4, emulsification mixing 2h is carried out after agitated kettle is added, by microwave drying shape
At solid powder.
3) in fusion nodularization equipment, the preferential above carbon phase micro-sphere material 1) of investment, it is mixed that charged material weight accounts for entire plan
Close the 3% of material total weight；After by core material nodularization 20min, it is introduced into the solid powder formed in 2), continues nodularization 2h, process prison
Material particle size is controlled, controls at 6-12 microns, stops pelletizing operations after reaching requirement.
4) by after nodularization material carry out nitrogen protection under high temperature sintering, 750 DEG C of temperature setting, the time 4 hours, after sintering from
After so cooling down and being sieved, final shell LiFePO4 finished-product material is obtained.
Comparative example 1:
Be Li: Fe according to reaction ratio: glucose=1.02: 1: 0.3 ratio weigh the pure FePO4 and Li2CO3 of analysis and
Glucose is added V-type batch mixer mixing 2 hours, then mixes 2 hours in three-dimensional material mixer, 750 DEG C -4 small in pusher furnace
When high temperature sintering, it is cooling after gas powder it is broken, obtain powder LiFePO 4 material.
Comparative example 2
Be Li: Fe according to reaction ratio: carbon source=1.02: 1: 0.3 ratio weighs the pure FePO4 and Li2CO3 of analysis and Portugal
Grape sugar, is added in sand mill, and adding a certain proportion of distilled water makes reaction raw materials solid content 35%, persistently grinds 10 hours, so
Spherical precursor is obtained by spray drying, spherical precursor is carried out 750 DEG C -5 under nitrogen atmosphere protection in sintering furnace
The high temperature sintering of hour, finally cools, and obtains spherical LiFePO4 finished-product material.
The all following technique of the above material carries out electrochemical properties test: weighing LiFePO4 material by the mass ratio of 85:10:5
Material, conductive agent and binder are added 6ml ethanol solution and stir into bulk, the pole of 0.1mm or so is compressed into using film laminator
Piece dries 1h under the conditions of 100 DEG C, uniform diaphragm then is made in its blunderbuss using 15mm blunderbuss, its quality is weighed, is put into
Glove box is fabricated to simulation button cell, and tests its electrochemical properties using blue electric system.
Table 1. simulates button cell Electrochemical Detection data and compacted density
The resulting shell LiFePO 4 material of the present invention has higher compared with powder LiFePO 4 material (comparative example 1)
Compacted density, the higher energy density of full battery can be obtained；And relative to the resulting entity sphere structure table of spray drying
Reveal better chemical property, polarizing voltage is small in charge and discharge process, and voltage platform is high, as shown in Figure 2.
Claims (4)
1. a kind of process of preparing of shell lithium iron phosphate positive material, preparation process are broadly divided into following steps:
1) glucose is configured to the aqueous solution of 0.5-1mol/L, merging reaction as preliminary core structure by preparation carbon phase microballoon
2 microns of carbon phase microballoon of favorable dispersibility is prepared in 180 DEG C -200 DEG C of reactions 4-6 hours in kettle after washing is dry；
2) lithium source and ferric phosphate weigh the ferric phosphate and lithium source of 2-10kg total weight according to the ratio that molar ratio is 1.02-1.05:1
Mixture weighs soluble carbon source and pure water according to the ratio that mass ratio is 1:0.4-0.5, and it is mixed to carry out emulsification after addition agitated kettle
2h is closed, forms solid powder by microwave drying；
3) in fusion nodularization equipment, the carbon phase micro-sphere material in step 1) is first put into, charged material weight accounts for entire plan mixture
Expect the 2%-5% of total weight；After by carbon phase micro-sphere material nodularization 10-30min, it is introduced into the solid powder formed in 2), continues ball
Change 1-2h, process monitoring material particle size is controlled at 6-12 microns, stops pelletizing operations after reaching requirement, fusion pelletizing operations need
It wants whole to carry out under nitrogen atmosphere；
4) material after nodularization is subjected to high temperature sintering under nitrogen protection, 700 DEG C -750 DEG C of temperature setting, time 4-6 hour is sintered
It natural cooling and is sieved afterwards, obtains final shell LiFePO4 finished-product material.
2. a kind of process of preparing of shell lithium iron phosphate positive material according to claim 1, it is characterised in that: carbon
Phase microspheres quality specific gravity is the 2%-5% for accounting for entire plan mixed material total weight；Plan mixed material refer to ferric phosphate, lithium source,
The summation of carbon source and carbon phase microballoon all solids material.
3. a kind of process of preparing of shell lithium iron phosphate positive material according to claim 1, it is characterised in that: step
The control of carbon phase microsphere particle size is controlled in granular size 200-600nm, the outer diameter of shell structurre in 6- after nodularization 10-30min in rapid 3
12 microns.
4. a kind of process of preparing of shell lithium iron phosphate positive material according to claim 1, it is characterised in that: can
Dissolubility carbon source is glucose or sucrose.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066280A (en) * | 2012-12-28 | 2013-04-24 | 珠海泰坦能源电子技术有限公司 | Spherical lithium iron phosphate anode material and preparation method thereof |
| CN103367724A (en) * | 2013-07-26 | 2013-10-23 | 烟台卓能电池材料有限公司 | Lithium iron phosphate cell material with core-shell structure, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066280A (en) * | 2012-12-28 | 2013-04-24 | 珠海泰坦能源电子技术有限公司 | Spherical lithium iron phosphate anode material and preparation method thereof |
| CN103367724A (en) * | 2013-07-26 | 2013-10-23 | 烟台卓能电池材料有限公司 | Lithium iron phosphate cell material with core-shell structure, and preparation method thereof |
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