CN101654237A - Improved process for synthesizing lithium iron phosphate materials by low-heating solid-state method - Google Patents
Improved process for synthesizing lithium iron phosphate materials by low-heating solid-state method Download PDFInfo
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- CN101654237A CN101654237A CN200910183504A CN200910183504A CN101654237A CN 101654237 A CN101654237 A CN 101654237A CN 200910183504 A CN200910183504 A CN 200910183504A CN 200910183504 A CN200910183504 A CN 200910183504A CN 101654237 A CN101654237 A CN 101654237A
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Abstract
The invention discloses an improved technology for synthesizing lithium iron phosphate materials by low-heating solid-state method. The process comprises the following steps: adding raw materials of lithium source, phosphorus source, iron source and carbon source in a stirring ball mill with an oil bath and a vacuum extractor, and carrying out ball milling and reaction in the stirring ball mill with the vacuum degree of 0.12 to -0.15MPa and the temperature of 165 to 330 DEG C of the oil bath to synthesize the lithium iron phosphate. Carbon-coated lithium iron phosphate materials with stable performance and average grain diameter of less than 200nm can be synthesized in the method through only one production step. The invention adopts the oil bath so that temperature control precision can be enhanced, and the synthesizing temperature only needs 165 to 330 DEG C, and the energy consumption in the synthesizing process can be greatly reduced. The reaction is carried out in the condition close to the vacuum without the protection of inert gas so that cost is saved and reduced, and meanwhile, the produced lithium iron phosphate materials have good batch stability due to the technology stability.
Description
Technical field
The invention belongs to the lithium ion battery field, be specifically related to a kind of synthetic method of lithium ferrous phosphate as anode material of lithium ion battery.
Background technology
The energy and environment are the greatest problem that the present whole world mankind face.How to seek the alternate resources of oil, how to reduce automobile, all make increasing people have an optimistic view of the future of electromobile, and lithium-ion-power cell undoubtedly will become the main force of batteries of electric automobile the dependence of oil and the discharging that reduces tail gas.Ferrousphosphate lithium material is the lithium-ion-power cell material that is expected most at present.Now, whole world automobile year output is about 7,000 ten thousand, conservative estimation, till 2015, if 10% automobile changes the electromobile of ferrous phosphate lithium battery into, then the recoverable amount of battery will reach 7,000,000 groups, lithium ion battery will reach 3,500,000 tons/year to total demand of LiFePO 4, the output value of this industry will reach 80,000,000,000 dollars/year, and the expert estimates, this numeral was expected to above 5,000 hundred million dollars/year to the year two thousand thirty.
As the lithium-ion-power cell positive electrode material, ferrousphosphate lithium material itself still has a lot of defectives to need to solve.Wherein the most outstanding is exactly this material produce complex process, required synthesis condition harshness, and batch stability of product is bad always.The electron conduction of ferrousphosphate lithium material and ionic conductivity are all bad in addition, and the material that need make the agent of small-particle coated with conductive could guarantee its application in battery.Problems such as conventional high-temperature solid state reaction synthesizing lithium iron phosphate materials also faces the temperature of reaction height simultaneously, and synthesis step is many, and technology stability is relatively poor.
Summary of the invention
This law is bright to be exactly at above deficiency, utilizes simple and effective equipment, provides an a kind of step, low-heat solid phase method to synthesize method ultra-fine, that wrap up the LiFePO 4 of carbon material.This method only needs a production stage just can synthesize below the median size 200nm carbon coated, the ferrousphosphate lithium material of stable performance, and the present invention adds the thermal recovery oil bath, can improve temperature-controlled precision, synthesis temperature only needs 165-330 ℃, can reduce the energy consumption in the building-up process greatly; Reacting near under the vacuum condition, need not protection of inert gas, saving reduces cost, while technology stability, the ferrousphosphate lithium material of producing batch good stability.
Purpose of the present invention can reach by following measure:
A kind of technology of improved synthesizing lithium iron phosphate materials by low-heating solid-state, starting material lithium source, phosphorus source, source of iron and carbon source material are added in the agitating ball mill of band oil bath and vacuum extractor, in agitating ball mill vacuum tightness be-0.12～-carry out ball milling and reaction, synthesizing lithium ferrous phosphate under 165～340 ℃ of 0.15MPa and the oil bath temperatures.
Wherein the lithium source material is selected from one or more in Quilonum Retard, monometallic or the Lithium Acetate; Described phosphorus source material is selected from one or more in primary ammonium phosphate, monometallic or the tertiary iron phosphate; Ferrous source material is selected from one or more in ferric oxide, Ferrox or the tertiary iron phosphate; Carbon source material is selected from one or more in super conductive carbon black, sucrose, glucose or the polyoxyethylene glycol.Starting material mix back (promptly adding in the raw-material ball mill) each element Li, Fe, P, and the mol ratio between the Elements C in the carbon source material is (1.00～1.10): 1.0: 1.0: (0.25～3.25).
Abrading-ball generally adds fashionable the adding in the lump in the ball mill at starting material, and the quality of the abrading-ball during ball milling in the agitating ball mill is 1～3 times of starting material total mass; Abrading-ball is preferably the zirconium oxide balls (being diameter 5mm) of φ 5.
The stirring velocity of agitating ball mill is 35～240 rev/mins during ball milling.The time of ball milling and reaction is 2～120h.
A kind of concrete reactions steps is: the zirconium oxide balls of 1～3 times of former material material (comprising the mixture that is pre-mixed or each raw material that is not pre-mixed) and raw-material weight is joined in " oil bath agitating ball mill " agitating ball mill of oil bath and vacuum extractor (promptly with), cover the ball mill loam cake, open vacuum fan, be evacuated to vacuum gauge pressure-0.12～-0.15MPa; Open the oil bath recycle pump, open the oil bath heating system, be adjusted to temperature sensor and show 165～340 ℃; Open the agitating ball mill operating switch, reconcile 35～240 rev/mins of agitator arm rotating speeds.Whole ball-milling reaction time 2～120h after reaction finishes, stops the oil bath heating, reduces mixing speed, reduces to below 50 ℃ until the temperature sensor displays temperature.Discharging separates the gained solid product by screen cloth with zirconium oxide balls.
Also relate to a kind of agitating ball mill with oil bath and vacuum extractor in the method for the present invention, the agitating ball mill of this band oil bath and vacuum extractor comprises ball mill wall, ball mill loam cake and agitator arm, and described agitator arm is positioned at agitating ball mill; In described ball mill wall, be provided with chuck, be provided with the oil bath that has oil bath import and outlet in the chuck around the ball mill wall; Described ball mill loam cake (being sealing cover) covers the agitating ball mill sealing and is provided with bleeding point on ball mill.
Above-mentioned ball mill wall comprises the sidewall and the diapire of ball mill, so oil bath is around the ball mill wall, not only around the sidewall of ball mill, also around the diapire of ball mill.Oil bath can be the barrel-like structure that matches with the ball mill wall of hollow, also can be tubulose and the structure on the ball mill wall.
Also be provided with the vacuum meter that has Presentation Function outside agitating ball mill in the agitating ball mill, vacuum meter is located in the ball mill in the space on the material, to avoid the contacting measurement that influences vacuum tightness with reaction mass.Also be provided with the temperature sensor that outside agitating ball mill, has Presentation Function of test oil temperature in the oil bath, logical temperature sensor control reaction temperature.Wherein vacuum meter and temperature sensor can not only be one.
The ball mill wall can the liner zirconia ceramics, is beneficial to heated oil with direct formation oil bath and passes through.Agitator arm in the ball mill can adopt the stainless steel main body, pastes zirconia ceramics outward, does not also influence reaction process when playing high-speed stirring.
Beneficial effect of the present invention:
1. traditional technology is produced ferrousphosphate lithium material often needs several processing steps such as batch mixing, drying, sintering, pulverizing, size classification, relates to a plurality of critical processes reference mark, and product performance are wayward, and the product batches stability of coming out is bad.The present invention only needs a processing step just can synthesize ferrousphosphate lithium material ultra-fine, carbon coated, and batch stability of product is very good.
2. adopt the LiFePO 4 of the method system of low fever solid phase reaction, can make being lower than under 330 ℃ the temperature, and traditional method generally needs 500-750 ℃ middle high temperature.Greatly reduce production energy consumption, the requirement of equipment is also reduced, low-temp reaction can also reduce the ferrousphosphate lithium material particulate excessively grows up the electroconductibility of strongthener.
3. the present invention need not to feed protection gas when producing ferrousphosphate lithium material, as long as must vacuum tightness in the maintenance equipment, can effectively reduce production costs.
4. the ferrousphosphate lithium material phone performance brilliance that synthesizes of the present invention, gram volume is greater than more than the 160mAh/g, and actual battery 30C discharge capacitance is more than 92%.
Description of drawings
Fig. 1 is the structural representation of the agitating ball mill of band oil bath of the present invention and vacuum extractor.
Embodiment
The structure of the agitating ball mill of band oil bath and vacuum extractor as shown in Figure 1.The shell of agitating ball mill is a circular cylinder body, and barrel has chuck, the interior logical oil bath of giving material heating in the tube, and oil bath is covered with around the barrel and the bottom; The oil-in of oil bath is in the bottom, and outlet is on top.Barrel liner zirconia ceramics.The tube loam cake seals cylindrical shell, covers on tube and leaves bleeding point, connects extraction equipment, for vacuumizing usefulness.High speed rotating partly is an agitator arm in the middle of in the cylindrical shell, adopts the stainless steel main body, pastes zirconia ceramics outward, and agitator arm is driven by the device of being located in the ball mill or ball mill is outer.Table 1 is the vacuum meter of vacuum tightness in the test bucket, and its detecting end is positioned at an internal upper part, and display end is outside tube; Table 2 is the temperature sensor of the temperature of oil in the test chuck, and its detecting end is positioned at oil groove, and display end is outside tube; Dash area is the zirconia ceramics abrading-ball of starting material and φ 5 diameters in the bucket.Below each example all adopt this agitating ball mill.
Embodiment 1.
1. take by weighing the Quilonum Retard of 5.000mol, the primary ammonium phosphate of 10.000mol, the Ferrox of 10.000mol, the super conductive carbon black of 2.5mol (about 30g), φ 5 zirconium oxide balls of 2.6kg (about raw-material weight 1.0 times).Place agitating ball mill, cover sealing cover.
2. bleed, to the vacuum gauge pressure displayed value be-0.12MPa.
3. the oil bath pump is opened in heating oil bath, to the vacuum mixer heating, and to 165 ℃ of temperature sensor demonstrations, and constant near this value (± 0.5 ℃).
4. unlatching agitating ball mill, rotating speed is set to 35 rev/mins.
5. reaction beginning, sustained reaction time 120h; Stop the oil bath heating after reaction finishes, the agitating ball mill rotating speed transfers to 10 rev/mins, and reducing to below 50 ℃ until temperature (needs 3h) approximately.
6. by stainless steel mesh product is separated with zirconium oxide balls.
The median size of laser particle size test product ferrousphosphate lithium material is 0.153 μ m; The loading capacity first that half-cell is tested this material reaches 162mAh/g; Under the full battery testing 30C discharging condition, the loading capacity of battery be under the 1C condition loading capacity 94.2%.
Embodiment 2.
1. take by weighing the Quilonum Retard of 2525mol, the monometallic of 5.000mol, the primary ammonium phosphate of 5.000mol, the Ferrox of 5.000mol, 2.500mol ferric oxide, the super conductive carbon black of 15.000mol (about 180g); 2.6kg φ 5 zirconium oxide balls (about raw-material weight 1.3 times).Place agitating ball mill, cover sealing cover.
2. bleed, to the vacuum gauge pressure displayed value be-0.12MPa.
3. the oil bath pump is opened in heating oil bath, to the vacuum mixer heating, and to 300 ℃ of temperature sensor demonstrations, and constant near this value (± 1 ℃).
4. unlatching agitating ball mill, rotating speed is set to 165 rev/mins.
5. reaction beginning, sustained reaction time 48h; Stop the oil bath heating after reaction finishes, the agitating ball mill rotating speed transfers to 10 rev/mins, and reducing to below 50 ℃ until temperature (needs 3h) more.
6. by stainless steel mesh product is separated with zirconium oxide balls.
The median size of laser particle size test product ferrousphosphate lithium material is 0.167 μ m; The loading capacity first that half-cell is tested this material reaches 162mAh/g; Under the full battery testing 30C discharging condition, the loading capacity of battery be under the 1C condition loading capacity 92.2%.
Embodiment 3.
1. take by weighing the Quilonum Retard of 2.550mol, the monometallic of 5.000mol, the primary ammonium phosphate of 5.000mol, 5.000mol ferric oxide, the super conductive carbon black of 30.000mol (about 360g); 3.2kg φ 5 zirconium oxide balls (about raw-material weight 1.5 times).Place agitating ball mill, cover sealing cover.
2. bleed, to the vacuum gauge pressure displayed value be-0.12MPa.
3. the oil bath pump is opened in heating oil bath, to the vacuum mixer heating, and to 330 ℃ of temperature sensor demonstrations, and constant near this value (± 3 ℃).
4. unlatching agitating ball mill, rotating speed is set to 220 rev/mins.
5. reaction beginning, sustained reaction time 2h; Stop the oil bath heating after reaction finishes, the agitating ball mill rotating speed transfers to 10 rev/mins, and reducing to below 50 ℃ until temperature (needs 3h) more.
6. by stainless steel mesh product is separated with zirconium oxide balls.
The median size of laser particle size test product ferrousphosphate lithium material is 0.166 μ m; The loading capacity first that half-cell is tested this material reaches 161mAh/g; Under the full battery testing 30C discharging condition, the loading capacity of battery be under the 1C condition loading capacity 93.2%.
Claims (10)
1, a kind of technology of improved synthesizing lithium iron phosphate materials by low-heating solid-state, it is characterized in that starting material lithium source, phosphorus source, source of iron and carbon source material are added in the agitating ball mill of band oil bath and vacuum extractor, in agitating ball mill vacuum tightness be-0.12～-carry out ball milling and reaction, synthesizing lithium ferrous phosphate under 165～340 ℃ of 0.15MPa and the oil bath temperatures.
2, technology according to claim 1 is characterized in that described lithium source material is selected from one or more in Quilonum Retard, monometallic or the Lithium Acetate; Described phosphorus source material is selected from one or more in primary ammonium phosphate, monometallic or the tertiary iron phosphate; Ferrous source material is selected from one or more in ferric oxide, Ferrox or the tertiary iron phosphate; Carbon source material is selected from one or more in super conductive carbon black, sucrose, glucose or the polyoxyethylene glycol.
3, technology according to claim 1 and 2 it is characterized in that starting material mix back each element Li, Fe, P, and the mol ratio between the Elements C in the carbon source material is (1.00～1.10): 1.0: 1.0: (0.25～3.25).
4, technology according to claim 1, the quality of the abrading-ball when it is characterized in that ball milling in the agitating ball mill are 1～3 times of starting material total mass.
5, technology according to claim 4 is characterized in that described abrading-ball is the zirconium oxide balls of φ 5.
6, technology according to claim 1, the stirring velocity of agitating ball mill is 35～240 rev/mins when it is characterized in that ball milling.
7, technology according to claim 1 is characterized in that the time of ball milling and reaction is 2～120h.
8, a kind of agitating ball mill with oil bath and vacuum extractor comprises ball mill wall, ball mill loam cake and agitator arm, and described agitator arm is positioned at agitating ball mill; It is characterized in that in described ball mill wall, being provided with chuck, be provided with the oil bath that has oil bath import and outlet in the chuck around the ball mill wall; Described ball mill loam cake seals agitating ball mill, covers on ball mill and is provided with bleeding point.
9, the agitating ball mill of band oil bath according to claim 8 and vacuum extractor is characterized in that also being provided with in the agitating ball mill vacuum meter that has Presentation Function outside agitating ball mill.
10, the agitating ball mill of band oil bath according to claim 8 and vacuum extractor is characterized in that also being provided with in the oil bath temperature sensor that has Presentation Function outside agitating ball mill of test oil temperature.
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| CN200910183504A CN101654237A (en) | 2009-09-22 | 2009-09-22 | Improved process for synthesizing lithium iron phosphate materials by low-heating solid-state method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474653A (en) * | 2012-06-08 | 2013-12-25 | 四川新国荣能源材料有限责任公司 | Preparation method for lithium iron phosphate |
| CN104786666B (en) * | 2014-01-19 | 2017-03-15 | 佛山市顺德区高宝实业发展有限公司 | The manufacturing process of printer ink-providing sponge and dye ink-stick machine |
| CN112512694A (en) * | 2018-05-29 | 2021-03-16 | 迪西尔有限公司 | Three-dimensional grinding machine, method for implementing same and use thereof |
-
2009
- 2009-09-22 CN CN200910183504A patent/CN101654237A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474653A (en) * | 2012-06-08 | 2013-12-25 | 四川新国荣能源材料有限责任公司 | Preparation method for lithium iron phosphate |
| CN104786666B (en) * | 2014-01-19 | 2017-03-15 | 佛山市顺德区高宝实业发展有限公司 | The manufacturing process of printer ink-providing sponge and dye ink-stick machine |
| CN112512694A (en) * | 2018-05-29 | 2021-03-16 | 迪西尔有限公司 | Three-dimensional grinding machine, method for implementing same and use thereof |
| CN112512694B (en) * | 2018-05-29 | 2022-12-06 | 迪西尔有限公司 | Three-dimensional grinding machine, method for implementing same and use thereof |
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Open date: 20100224 |