CN102969505A - LiFePO4 precursor hollow sphere and preparation method thereof - Google Patents
LiFePO4 precursor hollow sphere and preparation method thereof Download PDFInfo
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- CN102969505A CN102969505A CN2012105328494A CN201210532849A CN102969505A CN 102969505 A CN102969505 A CN 102969505A CN 2012105328494 A CN2012105328494 A CN 2012105328494A CN 201210532849 A CN201210532849 A CN 201210532849A CN 102969505 A CN102969505 A CN 102969505A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a LiFePO4 precursor hollow sphere and a preparation method thereof. The outer diameter of a precursor hollow sphere which is used as a LiFePO4 anode material of a lithium ion secondary battery is 10 nm-100 mu m and the wall thickness is 1 nm-10 mu m. A LiFePO4 anode material precursor with a hollow spherical structure is obtained through carrying out ultrasonic atomization drying on a solution prepared from a lithium compound, an iron compound, a phosphorus compound, a complexing agent and a carbon source. According to the LiFePO4 precursor hollow sphere and the preparation method thereof, a foundation of preparing the LiFePO4 anode material precursor with the hollow spherical structure is laid; and the structure is good for sufficiently contacting the LiFePO4 anode material with electrolyte, reducing a dispersion route of lithium ions and improving the rapid charging/discharging performance of the LiFePO4 anode material.
Description
Technical field
The present invention relates to LiFePO
4Be the lithium rechargeable battery manufacturing technology field of positive electrode, particularly a kind of LiFePO with special appearance
4Positive electrode presoma hollow ball and synthetic method thereof.
Background technology
LiFePO
4Be one of first-selected positive electrode of power lithium-ion rechargeable battery, vigorously promoted the use by various countries in recent years to have lot of advantages, as: fast charging and discharging performance, high security, have extended cycle life, pollution-free, high-energy-density, memory-less effect.But affect LiFePO
4Move towards the poorly conductive that practical shortcoming is it, be not suitable for high current charge-discharge.Present improving one's methods is to improve its electron conduction and accelerate the lithium ion diffusion rate, and with LiFePO
4The research that positive electrode is prepared into hollow ball-shape seldom.
The LiFePO of hollow ball-shape
4Material can fully contact with electrolyte, the very thin thickness of hollow ball, the lithium ion of material internal only need to move very short circuit journey and just can enter in the electrolyte, and this has reduced the time that lithium ion embeds and deviates from widely, has improved the fast charging and discharging performance of lithium rechargeable battery.
LiFePO
4The preparation of positive electrode generally is to be obtained through high-temperature calcination by presoma, and the pattern of presoma is LiFePO
4The basis of material pattern.Control presoma hollow ball pattern is preparation hollow ball shape LiFePO
4The precondition of material.Existing preparation LiFePO
4Material presoma method has a lot, and such as solid-phase ball milling method, sol-gal process, coprecipitation etc., but these methods all are difficult to obtain the LiFePO of hollow ball-shape
4Presoma.
Summary of the invention
The object of the invention is to provide a kind of hollow ball-shape LiFePO
4Presoma and preparation method are by the LiFePO of preparation hollow ball-shape
4Positive electrode can improve the diffusion rate of lithium rechargeable battery lithium ion in charge and discharge process.
The technical solution used in the present invention is as follows:
A kind of LiFePO
4The presoma hollow ball, the external diameter 10 nm-100 μ m of its hollow ball, wall thickness 1 nm-10 μ m.
A kind of LiFePO of the present invention
4The preparation method of presoma hollow ball, may further comprise the steps: with lithium compound, iron compound, phosphorus compound, complexing agent and carbon source with the certain proportion wiring solution-forming after, through ultrasonic atomizatio (can make simultaneously solution because hyperacoustic effect mixes being atomized into droplet), wind send droplet to pass through high temperature process furnances, the tube furnace temperature is more than 100 ℃ the time, solvent evaporation in the droplet, the electrodeposition substance that stays gets off, and obtains hollow ball shape LiFePO
4Precursor powder.Can prepare fast hollow ball shape LiFePO with the method
4Precursor powder, and resulting hollow ball shape LiFePO
4The external diameter of presoma and wall thickness can be adjustable in very large scope, and external diameter is adjustable to 100 μ m from 10 nm, and wall thickness is adjustable to 10 μ m from 1 nm.
Described lithium compound be lithium hydroxide, lithium acetate, lithium carbonate, lithium fluoride, lithium nitrate or lithium dihydrogen phosphate etc. at least any one; Described iron compound is di-iron trioxide, ferric nitrate, iron hydroxide, ferric phosphate, iron chloride, ferrous acetate, ferrous oxide, ferrous oxalate or ferrous sulfate etc. at least any one; Described phosphorus compound be phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, ammonium phosphate or lithium dihydrogen phosphate etc. at least any one; Described complexing agent is at least a of citric acid, ascorbic acid, oxalic acid, acetic acid etc.; Described carbon source be in the carbohydrates such as fructose, sucrose, glucose, maltose, lactose, galactolipin, ribose at least any one; Described solvent be water, alkane, alcohol, ether, ketone, ester, aromatic hydrocarbon etc. at least any one.
The molar ratio of described lithium compound, iron compound, phosphorus compound, complexing agent and carbon source is 0.90～1.10 ︰, 0.90～1.10 ︰, 0.90～1.10 ︰, 1.00 ~ 3.00:0.10～1.00.
Described LiFePO
4The presoma hollow ball is used the positive electrode presoma as lithium rechargeable battery.
LiFePO
4Positive electrode is one of preferred material of power lithium-ion rechargeable battery, and the control of presoma pattern is related to high-performance power lithium-ion rechargeable battery manufacturing technology field.The present invention carries out the ultrasonic atomizatio drying by the solution that lithium compound, iron compound, phosphorus compound, complexing agent and carbon source are made into, and obtains having the LiFePO of hollow ball shape structure
4The positive electrode presoma.This is the LiFePO of preparation hollow ball structure
4Positive electrode lays the first stone, and this structure can be conducive to LiFePO
4Positive electrode fully contacts with electrolyte, shortens the diffusion distance of lithium ion, can improve LiFePO
4The fast charging and discharging performance of positive electrode.
Description of drawings
Fig. 1 is device schematic diagram of the present invention.
The sample SEM photo of Fig. 2 for after 150 ℃ of lower dryings of temperature, obtaining.
The sample SEM photo of Fig. 3 for after 200 ℃ of lower dryings of temperature, obtaining.
The sample SEM photo of Fig. 4 for after 250 ℃ of lower dryings of temperature, obtaining.
The sample SEM photo of Fig. 5 for after 350 ℃ of lower dryings of temperature, obtaining.
The sample SEM photo of Fig. 6 for after 450 ℃ of lower dryings of temperature, obtaining.
The sample EDX photo of Fig. 7 for after 250 ℃ of lower dryings of temperature, obtaining.
The sample EDX photo of Fig. 8 for after 350 ℃ of lower dryings of temperature, obtaining.
The sample EDX photo of Fig. 9 for after 450 ℃ of lower dryings of temperature, obtaining.
The sample TEM photo of Figure 10 for after 250 ℃ of lower dryings of temperature, obtaining.
The sample TEM photo of Figure 11 for after 350 ℃ of lower dryings of temperature, obtaining.
The sample TEM photo of Figure 12 for after 450 ℃ of lower dryings of temperature, obtaining.
Embodiment
Embodiment one
1. raw material takes by weighing: take by weighing respectively 1.2 g lithium hydroxides, 4.7 g ferric phosphates, 1.6 g glucose and 9.6 g oxalic acid, measure the 250ml deionized water.
2. mix: the raw material that takes by weighing more than inciting somebody to action and deionized water mix, the heating stirring and dissolving.
3. atomizing: above solution is poured in the ultrasonic atomizer, carried out ultrasonic atomizatio with the 1.7MHz frequency, form droplet.
4. dry: it is dry that wind send droplet to pass through in the high temperature furnace, and baking temperature is 150 ℃, and dry rear the collection obtains random block LiFePO
4Presoma, stereoscan photograph are as shown in Figure 2.The device schematic diagram as shown in Figure 1.
Embodiment two
1. raw material takes by weighing: take by weighing respectively 1.2 g lithium hydroxides, 4.7 g ferric phosphates, 1.6 g glucose and 9.6 g oxalic acid, measure the 250ml deionized water.
2. mix: the raw material that takes by weighing more than inciting somebody to action and deionized water mix, the heating stirring and dissolving.
3. atomizing: above solution is poured in the ultrasonic atomizer, carried out ultrasonic atomizatio with the 1.7MHz frequency, form droplet.
4. dry: it is dry that wind send droplet to pass through in the high temperature furnace, and baking temperature is 200 ℃, and dry rear the collection obtains random block LiFePO
4Presoma, stereoscan photograph are as shown in Figure 3.
Embodiment three
1. raw material takes by weighing: take by weighing respectively 1.2 g lithium hydroxides, 4.7 g ferric phosphates, 1.6 g glucose and 9.6 g oxalic acid, measure the 250ml deionized water.
2. mix: the raw material that takes by weighing more than inciting somebody to action and deionized water mix, the heating stirring and dissolving.
3. atomizing: above solution is poured in the ultrasonic atomizer, carried out ultrasonic atomizatio with the 1.7MHz frequency, form droplet.
4. dry: it is dry that wind send droplet to pass through in the high temperature furnace, and baking temperature is 250 ℃, and dry rear the collection obtains hollow ball-shape LiFePO
4Presoma, hollow ball external diameter are 100nm-5um, and shell is thick to be about 27nm.Stereoscan photograph as shown in Figure 4, energy dispersion X ray spectrum as shown in Figure 7, transmission electron microscope photo is as shown in figure 10.
Embodiment four
1. raw material takes by weighing: take by weighing respectively 1.2 g lithium hydroxides, 4.7 g ferric phosphates, 1.6 g glucose and 9.6 g oxalic acid, measure the 250ml deionized water.
2. mix: the raw material that takes by weighing more than inciting somebody to action and deionized water mix, the heating stirring and dissolving.
3. atomizing: above solution is poured in the ultrasonic atomizer, carried out ultrasonic atomizatio with the 1.7MHz frequency, form droplet.
4. dry: it is dry that wind send droplet to pass through in the high temperature furnace, and baking temperature is 350 ℃, and dry rear the collection obtains hollow ball-shape LiFePO
4Presoma, hollow ball external diameter are 100nm-5um, and shell is thick to be about 31nm.Stereoscan photograph as shown in Figure 5, energy dispersion X ray spectrum as shown in Figure 8, transmission electron microscope photo is as shown in figure 11.
Embodiment five
1. raw material takes by weighing: take by weighing respectively 1.2 g lithium hydroxides, 4.7 g ferric phosphates, 1.6 g glucose and 9.6 g oxalic acid, measure the 250ml deionized water.
2. mix: the raw material that takes by weighing more than inciting somebody to action and deionized water mix, the heating stirring and dissolving.
3. atomizing: above solution is poured in the ultrasonic atomizer, carried out ultrasonic atomizatio with the 1.7MHz frequency, form droplet.
4. dry: it is dry that wind send droplet to pass through in the high temperature furnace, and baking temperature is 450 ℃, and dry rear the collection obtains hollow ball-shape LiFePO
4Presoma, hollow ball external diameter are 100nm-5um, and shell is thick to be about 41nm.Stereoscan photograph as shown in Figure 6, energy dispersion X ray spectrum as shown in Figure 9, transmission electron microscope photo is as shown in figure 12.
Claims (5)
1. LiFePO
4The presoma hollow ball is characterized in that, described LiFePO
4The external diameter of presoma hollow ball is 10 nm-100 μ m, wall thickness 1 nm-10 μ m.
2. a kind of LiFePO as claimed in claim 1
4The preparation method of presoma hollow ball, it is characterized in that, may further comprise the steps: with lithium compound, iron compound, phosphorus compound, complexing agent and carbon source with the certain proportion wiring solution-forming after, through ultrasonic atomizatio, wind send droplet by temperature greater than 100 ℃ of tube furnaces, the powder that deposits is collected in solvent evaporation in the droplet, namely obtains the LiFePO of hollow ball-shape
4Presoma.
3. described LiFePO according to claim 2
4The preparation method of presoma hollow ball is characterized in that, the molar ratio of described lithium compound, iron compound, phosphorus compound, complexing agent and carbon source is 0.90～1.10 ︰, 0.90～1.10 ︰, 0.90～1.10 ︰, 1.00 ~ 3.00:0.10～1.00.
4. described LiFePO according to claim 3
4The preparation method of presoma hollow ball is characterized in that, described lithium compound is the one or more combination in lithium hydroxide, lithium acetate, lithium carbonate, lithium fluoride, lithium nitrate, the lithium dihydrogen phosphate; Described iron compound is the one or more combination in di-iron trioxide, ferric nitrate, iron hydroxide, iron chloride, ferrous acetate, ferrous oxide, ferrous oxalate, the ferrous sulfate; Described phosphorus compound is the one or more combination in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, ammonium phosphate, the lithium dihydrogen phosphate; Described carbon source is the one or more combination in graphite microparticles, organic pyrolytic carbon, conductive carbon black, carbon nano-tube, carbon fiber, carbon cloth, carbon nano powder, the Graphene; Described solvent is the one or more combination in water, alkane, alcohol, ether, ketone, ester, the aromatic hydrocarbon.
5. described LiFePO of claim 1
4The application of presoma hollow ball is characterized in that, described LiFePO
4The presoma hollow ball is as the positive electrode presoma of lithium rechargeable battery.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274480A (en) * | 2013-06-06 | 2013-09-04 | 南通瑞翔新材料有限公司 | Precursor of polynary positive electrode material for lithium ion battery, and preparation method thereof |
| CN103337604A (en) * | 2013-07-06 | 2013-10-02 | 北京化工大学 | Hollow spherical NiMn2O4 lithium ion battery cathode material and preparation method thereof |
| CN103682339A (en) * | 2013-12-24 | 2014-03-26 | 中南大学 | Preparation method of lithium vanadyl phosphate anode material |
| CN103700851A (en) * | 2013-07-19 | 2014-04-02 | 合肥国轩高科动力能源股份公司 | Improved iron oxide red process for preparing lithium iron phosphate cathode material |
| CN105552370A (en) * | 2016-02-24 | 2016-05-04 | 苏州太阳源纳米科技有限公司 | Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material |
| CN105806674A (en) * | 2016-03-08 | 2016-07-27 | 武汉水天成环保科技有限公司 | Preparation method of acid nanoparticles for calibration |
| CN111564320A (en) * | 2020-05-20 | 2020-08-21 | 新昌县希亭科技有限公司 | Nano MnO2Supercapacitor electrode material of modified carbon cloth and preparation method thereof |
| US11101457B2 (en) * | 2017-11-08 | 2021-08-24 | Korea Basic Science Institute | Manufacturing method for cathode active material complex, and lithium secondary battery including the cathode active material complex |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274480A (en) * | 2013-06-06 | 2013-09-04 | 南通瑞翔新材料有限公司 | Precursor of polynary positive electrode material for lithium ion battery, and preparation method thereof |
| CN103337604A (en) * | 2013-07-06 | 2013-10-02 | 北京化工大学 | Hollow spherical NiMn2O4 lithium ion battery cathode material and preparation method thereof |
| CN103700851A (en) * | 2013-07-19 | 2014-04-02 | 合肥国轩高科动力能源股份公司 | Improved iron oxide red process for preparing lithium iron phosphate cathode material |
| CN103700851B (en) * | 2013-07-19 | 2016-03-02 | 合肥国轩高科动力能源有限公司 | A kind of iron oxide red preparation technology improving lithium iron phosphate positive material |
| CN103682339A (en) * | 2013-12-24 | 2014-03-26 | 中南大学 | Preparation method of lithium vanadyl phosphate anode material |
| CN105552370A (en) * | 2016-02-24 | 2016-05-04 | 苏州太阳源纳米科技有限公司 | Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material |
| CN105552370B (en) * | 2016-02-24 | 2019-04-12 | 苏州太阳源纳米科技有限公司 | Spherical lithium ion secondary battery positive electrode and preparation method thereof |
| CN105806674A (en) * | 2016-03-08 | 2016-07-27 | 武汉水天成环保科技有限公司 | Preparation method of acid nanoparticles for calibration |
| US11101457B2 (en) * | 2017-11-08 | 2021-08-24 | Korea Basic Science Institute | Manufacturing method for cathode active material complex, and lithium secondary battery including the cathode active material complex |
| CN111564320A (en) * | 2020-05-20 | 2020-08-21 | 新昌县希亭科技有限公司 | Nano MnO2Supercapacitor electrode material of modified carbon cloth and preparation method thereof |
| CN111564320B (en) * | 2020-05-20 | 2023-01-31 | 新昌县希亭科技有限公司 | Nano MnO 2 Supercapacitor electrode material of modified carbon cloth and preparation method thereof |
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