CN102115068A - Method for preparing nanometer-level lithium iron phosphate by ultrasonic wave-microwave alternating method - Google Patents
Method for preparing nanometer-level lithium iron phosphate by ultrasonic wave-microwave alternating method Download PDFInfo
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- CN102115068A CN102115068A CN 201110084204 CN201110084204A CN102115068A CN 102115068 A CN102115068 A CN 102115068A CN 201110084204 CN201110084204 CN 201110084204 CN 201110084204 A CN201110084204 A CN 201110084204A CN 102115068 A CN102115068 A CN 102115068A
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Abstract
The invention provides a method for preparing nanometer-level lithium iron phosphate by an ultrasonic wave-microwave alternating method. The method comprises the steps of: mixing the iron salt, the lithium salt with the phosphate at a certain molar ratio to obtain a mixture A; mixing the mixture A with a conductive carbon source, and dissolving the mixture into dissolvent to obtain a mixed material; performing the ball milling to the mixture at high energy, and putting the mixture into a cavity of an ultrasonic wave-microwave cooperative extracting apparatus; and circularly and repeatedly performing the ultrasonic wave-microwave-ultrasonic wave to prepare a nanometer-level lithium iron phosphate powder material. The method for preparing the nanometer-level lithium iron phosphate powder is simple in technology, short in time consumption, and high in controllability. The obtained lithium iron phosphate grain has the nanometer size and is even in grain diameter.
Description
Technical field
The present invention relates to technical field of chemical power, particularly a kind of ultrasonic-microwave alternative method prepares the method for nano-scale lithium iron phosphate fast.
Background technology
Report since people such as the upright Goodenough of university of Texas, USA LiFePO4 reversibility since the characteristic of the lithium of moving into, lithium iron phosphate positive material has caused numerous concerns.With traditional lithium cobalt oxide of lithium-ion secondary battery cathode materials LiCoO
2, lithium nickelate LiNiO
2With lithium manganate LiMn
2O
4Compare the iron lithium phosphate LiFePO of olivine structural
4Positive electrode material has stable operating voltage and cycle life preferably, and its abundant raw material, cheap, thermostability and chemical stability are good, are the environmental protection energy that has development prospect.
But because pure extremely low electronic conductivity and the lithium ion spread coefficient of iron lithium phosphate self, making it only to discharge and recharge in low range just has high electrochemical performance under the condition, seriously hindered the development of lithium iron phosphate positive material.The iron lithium phosphate particle of synthesis of nano size can improve the velocity of diffusion of lithium ion, and help to weaken polarization, reduce internal resistance, improve large current discharging capability, further improve the chemical property of lithium iron phosphate positive material, so the synthetic preparation of nano ferric phosphate lithium anode material has been subjected to more concern.
The preparation method of nano-grade lithium iron phosphate mainly contains high temperature solid-state method, sol-gel method, hydrothermal synthesis method, coprecipitation method, microwave process for synthesizing, template synthesis method etc. at present.Shortcomings such as high temperature solid-state method technology is simple, is easy to industrialization, carries out scale operation, but exists the gained particle size distribution wide, and granule-morphology is irregular.Sol-gel method gained material granule particle diameter is even, narrowly distributing, and equipment is simple, but the production cycle is long, is unfavorable for industrialization.Hydrothermal synthesis method has advantages such as homogeneous phase is single, process is simple, but to the requirement height of production unit, the difficulty of suitability for industrialized production is bigger.The liquid-phase coprecipitation synthesis temperature is low, is easy to scale operation, but because the sedimentation speed difference of each component can cause departing from inhomogeneous of material composition.Microwave process for synthesizing has weak point heat-up time, and rate of heating is fast, heat energy utilization rate advantages of higher, but the difficult control of reaction process, and suitability for industrialized production is difficult to realize.The template synthesis method can be controlled size, pattern, the structure of synthetic materials and arranging etc., but since the production cost height be not suitable for producing in enormous quantities.
In sum, existing method exists complex process, shortcomings such as length, consistency of performance difference consuming time mostly.Therefore, need simple, the consuming time weak point of a kind of technology of exploitation, the method for preparing nano-grade lithium iron phosphate that controllability is strong.
Summary of the invention
The purpose of this invention is to provide a kind of have simple, consuming time weak point of technology and the strong method for preparing nano-scale lithium iron phosphate of controllability, the iron lithium phosphate particle of gained has nano-scale, and uniform particle diameter.
Technical solution of the present invention is the method that described ultrasonic-microwave alternative method prepares nano-scale lithium iron phosphate fast, its special character is, may further comprise the steps: get molysite, lithium salts and phosphoric acid salt with 0.96～1: 0.96～1: 0.96～1 mixed in molar ratio obtains mixture A; A mixes and is dissolved in solvent with the conduction carbon source that accounts for total mass 9%～16% and obtains mixture; Mixture drops into behind high-energy ball milling in the ultrasonic wave microwave synergistic extraction instrument equipment chamber, carry out ultrasonic-microwave-ultrasonic wave repeatedly Circulation prepare nano-scale lithium iron phosphate.
As preferably: described ultrasonic frequency is 20～35KHz, and microwave power is 800～1500W.
As preferably: described ultrasonic wave action time is 20～40s, and the microwave action time is 10～35s.
As preferably: described ultrasonic-microwave cycle index increases with the increase of mix consumption.
As preferably: described lithium salts is one or more in lithium hydroxide, Quilonum Retard, lithium nitrate, Lithium Sulphate and the lithium chloride.
As preferably: described phosphoric acid salt is one or more in phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate and the tertiary iron phosphate.
As preferably: described molysite is one or more in tertiary iron phosphate, iron nitrate, Ferrox and the ferric oxide.
As preferably: described conduction carbon source is one or more in acetylene black, the dextrose plus saccharose.
As preferably: described solvent is ethanol or acetone.
Compared with prior art, the present invention fully utilizes the strong and ultrasonic wave of microwave heating effect and quickens the advantage of chemical reaction, and time of synthesis nano iron lithium phosphate can be effectively shortened in the use of working in coordination of two kinds of technology; In addition, the present invention uses ultrasonic wave microwave extracting instrument, has realized the combination of two kinds of reactivitys in a reactor, optimized reaction system, avoid because of complex steps pollutes or ferrous oxidation, and whole process implementation automatization control, have the advantages that technology is simple, controllability is strong; The iron lithium phosphate particle of gained has nano-scale, and uniform particle diameter.
Embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
Quilonum Retard 3.7g, iron nitrate 24.2g and primary ammonium phosphate 11.5g mixed mutually obtain mixture A.Mixture A mixed and be dissolved in ethanol with sucrose 4.3g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 25KHz, microwave power is 1000W, with ultrasonic wave effect 30s, the microwave action 20s reaction that hockets, obtain powder after 20 circulations, detect with X-ray powder diffraction (XRD) behind the naturally cooling and be LiFePO
4, median size is about 80nm, and is evenly distributed.
Embodiment 2
Lithium hydroxide 2.4g and tertiary iron phosphate 14.8g mixed mutually obtain mixture A.Mixture A mixed and be dissolved in ethanol with glucose 2.7g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 25KHz, microwave power is 1500W, with ultrasonic wave effect 40s, the microwave action 10s reaction that hockets, obtain powder after 25 circulations, detect with X-ray powder diffraction (XRD) behind the naturally cooling and be LiFePO
4, median size is about 30nm, and is evenly distributed.
Embodiment 3
Lithium nitrate 6.7g, ferric oxide 8g and primary ammonium phosphate 11.2g mixed mutually obtain mixture A.Mixture A mixed and be dissolved in acetone with acetylene black 3.9g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 30KHz, microwave power is 800W, with ultrasonic wave effect 35s, the microwave action 25s reaction that hockets, obtain powder after 25 circulations, detect with X-ray powder diffraction (XRD) behind the naturally cooling and be LiFePO
4, median size is about 50nm, and is evenly distributed.
Embodiment 4
Sulfur acid lithium 5.4g, iron nitrate 24g and primary ammonium phosphate 11.5g mixed mutually obtain mixture A.Mixture A mixed and be dissolved in acetone with acetylene black 4.5g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 35KHz, microwave power is 1000W, with ultrasonic wave effect 20s, the microwave action 35s reaction that hockets, obtain powder after 25 circulations, detect with X-ray powder diffraction (XRD) behind the naturally cooling and be LiFePO
4, median size is about 60nm, and is evenly distributed.
Embodiment 5
To contain lithium nitrate 6.7g, ferric oxide 8g mixes mutually with primary ammonium phosphate 11.2g and obtains mixture A.Mixture A mixed and be dissolved in acetone with acetylene black 3.6g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 30KHz, microwave power is 1200W, with ultrasonic wave effect 30s, the microwave action 20s reaction that hockets, obtain powder after 25 circulations, detect with X-ray powder diffraction (XRD) behind the naturally cooling and be LiFePO
4, median size is about 30nm, and is evenly distributed.
Embodiment 6
Sulfur acid lithium 27g, iron nitrate 121g and primary ammonium phosphate 57.5g mixed mutually obtain mixture A.Mixture A mixed and be dissolved in acetone with sucrose 20.6g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 30KHz, microwave power is 1200W, with ultrasonic wave effect 35s, the microwave action 20s reaction that hockets, obtain powder after 40 circulations, detect with X-ray powder diffraction (XRD) behind the naturally cooling and be LiFePO
4, median size is about 40nm, and is evenly distributed.
Embodiment 7
To contain lithium chloride 43.5g, Ferrox 144g mixes mutually with primary ammonium phosphate 115g and obtains mixture A.Mixture A mixed and be dissolved in acetone with sucrose 30.1g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 30KHz, microwave power is 800W, with ultrasonic wave effect 35s, the microwave action 20s reaction that hockets, obtain powder after 40 circulations, detect with X-ray powder diffraction (XRD) behind the naturally cooling and be LiFePO
4, median size is about 100nm, and is evenly distributed.
Comparative Examples 1
Sulfur acid lithium 5.2g, iron nitrate 24g and primary ammonium phosphate 11.5g mixed mutually obtain mixture A.Mixture A mixed and be dissolved in acetone with acetylene black 4.5g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting ultrasonic frequency is 25KHz, to obtain homogenate behind the ultrasonic wave effect 25min, it is comparatively impure that product is detected with X-ray powder diffraction (XRD) in the oven dry back.
Comparative Examples 2
To contain lithium chloride 4.35g, Ferrox 14.4g mixes mutually with phosphatase 79 .6g and obtains mixture A.Mixture A mixed and be dissolved in acetone with acetylene black 3.2g obtain mixture, mixture is through high-energy ball milling, putting into ultrasonic wave microwave extracting machine then reacts, the setting microwave power is 1000W, to obtain powder behind the microwave action 25min, detecting with X-ray powder diffraction (XRD) behind the naturally cooling is LiFePO
4, median size is about 25 μ m, and distributes than heterogeneity.
The above only is preferred embodiment of the present invention, and all equalizations of being done according to claim scope of the present invention change and modify, and all should belong to the covering scope of claim of the present invention.
Claims (9)
1. a ultrasonic-microwave alternative method prepares the method for nano-scale lithium iron phosphate fast, it is characterized in that, may further comprise the steps: get molysite, lithium salts and phosphoric acid salt and obtain mixture A with the mixed in molar ratio of 0.96～1:0.96～1:0.96～1; A mixes and is dissolved in solvent with the conduction carbon source that accounts for total mass 9%～16% and obtains mixture; Mixture drops into behind high-energy ball milling in the ultrasonic wave microwave synergistic extraction instrument equipment chamber, carry out ultrasonic-microwave-ultrasonic wave repeatedly Circulation prepare nano-scale lithium iron phosphate.
2. prepare the method for nano-scale lithium iron phosphate fast according to the described ultrasonic-microwave alternative method of claim 1, it is characterized in that: described ultrasonic frequency is 20～35KHz, and microwave power is 800～1500W.
3. prepare the method for nano-scale lithium iron phosphate according to the described ultrasonic-microwave alternative method of claim 1 fast, it is characterized in that: described ultrasonic wave action time is 20～40s, and the microwave action time is 10～35s.
4. prepare the method for nano-scale lithium iron phosphate fast according to the described ultrasonic-microwave alternative method of claim 1, it is characterized in that: described ultrasonic-microwave cycle index increases with the increase of mix consumption.
5. prepare the method for nano-scale lithium iron phosphate fast according to the described ultrasonic-microwave alternative method of claim 1, it is characterized in that: described lithium salts is one or more in lithium hydroxide, Quilonum Retard, lithium nitrate, Lithium Sulphate and the lithium chloride.
6. prepare the method for nano-scale lithium iron phosphate fast according to the described ultrasonic-microwave alternative method of claim 1, it is characterized in that: described phosphoric acid salt is one or more in phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate and the tertiary iron phosphate.
7. prepare the method for nano-scale lithium iron phosphate fast according to the described ultrasonic-microwave alternative method of claim 1, it is characterized in that: described molysite is one or more in tertiary iron phosphate, iron nitrate, Ferrox and the ferric oxide.
8. prepare the method for nano-scale lithium iron phosphate according to the described ultrasonic-microwave alternative method of claim 1 fast, it is characterized in that: described conduction carbon source is one or more in acetylene black, the dextrose plus saccharose.
9. prepare the method for nano-scale lithium iron phosphate fast according to the described ultrasonic-microwave alternative method of claim 1, it is characterized in that: described solvent is ethanol or acetone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322167A (en) * | 2015-11-03 | 2016-02-10 | 山东精工电子科技有限公司 | Pressure-controlling deaggregating synthetic method for lithium iron phosphate positive electrode material |
| CN116041986A (en) * | 2022-12-22 | 2023-05-02 | 山西盛达威科技有限公司 | Preparation method of water-soluble carbon black |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555004A (en) * | 2009-05-15 | 2009-10-14 | 中山大学 | Method for rapidly preparing lithium iron phosphate by intermittent microwave |
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2011
- 2011-04-02 CN CN 201110084204 patent/CN102115068A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555004A (en) * | 2009-05-15 | 2009-10-14 | 中山大学 | Method for rapidly preparing lithium iron phosphate by intermittent microwave |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322167A (en) * | 2015-11-03 | 2016-02-10 | 山东精工电子科技有限公司 | Pressure-controlling deaggregating synthetic method for lithium iron phosphate positive electrode material |
| CN105322167B (en) * | 2015-11-03 | 2018-01-02 | 山东精工电子科技有限公司 | A kind of pressure control de-agglomerated synthetic method of lithium iron phosphate positive material |
| CN116041986A (en) * | 2022-12-22 | 2023-05-02 | 山西盛达威科技有限公司 | Preparation method of water-soluble carbon black |
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Application publication date: 20110706 |