CN104409734A - Lithium iron phosphate battery positive material prepared by using microwave-assisted sol-gel method - Google Patents
Lithium iron phosphate battery positive material prepared by using microwave-assisted sol-gel method Download PDFInfo
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- CN104409734A CN104409734A CN201410823756.6A CN201410823756A CN104409734A CN 104409734 A CN104409734 A CN 104409734A CN 201410823756 A CN201410823756 A CN 201410823756A CN 104409734 A CN104409734 A CN 104409734A
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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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- 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
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Abstract
The invention discloses a lithium iron phosphate battery positive material prepared by using a microwave-assisted sol-gel method and belongs to the technical field of preparation of energy materials. The method comprises the following steps: dissolving a lithium source compound, an iron source compound and a complexing agent in deionized water according to a certain mole ratio to prepare a mixed solution, magnetically stirring the mixed solution, then adding a proper amount of phosphorus source aqueous solution and dropwise adding an alkaline solution to adjust the pH value, then further stirring the mixed solution in a water bath to obtain gel, drying the gel to obtain dried gel; adding a precursor into a gradient furnace, pre-decomposing at low temperature, then putting the precursor in a microwave oven to be sintered at high temperature to obtain a target product which is lithium iron phosphate powder. According to the method, the advantages of the sol-gel method and the microwave method are integrated in the method; the prepared lithium iron phosphate is free of impurity phase; the powder is uniform in particle diameter distribution; the method is simple in process, short in preparation period, free of protection of inert gas and low in cost.
Description
Technical field
The invention belongs to technical field of energy material preparation, particularly a kind of microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate.
Background technology
Lithium ion battery, as the high performance secondary green battery of one, has high voltage, high-energy-density, low self-discharge rate, wide serviceability temperature scope, long cycle life, environmental protection, memory-less effect and can the advantage such as high current charge-discharge.The improvement of performance of lithium ion battery, is decided by the improvement of electrode material performance, especially positive electrode to a great extent.Current research the most widely positive electrode has LiCoO
2, LiNiO
2and LiMn
2o
4deng, but due to the poisonous and resource-constrained of cobalt element, lithium nickelate preparation difficulty, the factors such as the cycle performance of LiMn2O4 and high-temperature behavior, constrain their application and development.Therefore, the development of positive electrode to lithium ion battery of development of new high energy cheapness is most important.1997, Padhi etc. report the LiFePO4 with olivine structural can reversibly doff lithium, and have that specific capacity is high, good cycle, stable electrochemical property, lower-price characteristic, first-selected new generation of green positive electrode, particularly as power lithium-ion battery material.
At present, the method for the preparation of lithium ion battery anode material lithium iron phosphate mainly contains high temperature solid-state method, hydro thermal method, sol-gal process and microwave process for synthesizing etc.High temperature solid-state method technique is simple, is easy to industrialization, but the particle size wider distribution obtained, pattern is also irregular, and in preparation process, need the protection of inert gas.And the solubility of oxygen in hydrothermal system is very little; synthesis for LiFePO4 provides excellent inert environments, and therefore Hydrothermal Synthesis no longer needs inert gas shielding, and product form and particle diameter are easy to control; but hydro thermal method needs high temperature high voltage resistant equipment, suitability for industrialized production difficulty is larger.Sol-gal process can make raw material realize other Homogeneous phase mixing of molecular level, improves reactivity, reduces reaction temperature, obtain and be uniformly distributed and the less product of particle diameter, thus the migration distance of lithium ion when shortening discharge and recharge, improve multiplying power discharging property, but the production cycle is long, be unfavorable for industrialization.Microwave method and high temperature solid-state method similar, just heating means difference to some extent, microwave method adopts microwave heating, Synchronous Heating inside and outside reactant in whole microwave heating process, heat up rapidly, be heated evenly, there is no temperature gradient, shorten heat conduction time, and microwave can also promote that in reactant, molecular motion is accelerated, and increases collision probability, improves reaction speed, but microwave method course of reaction is wayward, be difficult to realize suitability for industrialized production.
Summary of the invention
Existing unitary system Preparation Method mostly also exists consuming time long, complex process, the problems such as cost is higher.Therefore, need to invent a kind of technique simple, with low cost, the short and method preparing LiFePO4 that phase composition is single consuming time.The present invention, in conjunction with the advantage of existing preparation method, provides a kind of microwave radiation technology sol-gal process and prepares lithium iron phosphate positive material.Sol-gal process can make raw material realize the mixing of molecular level, and microwave sintering shortens the time required for material preparation, and sintering process does not need the protection of inert gas, simplifies synthesis technique while cost-saving, is convenient to suitability for industrialized production.
Technical scheme of the present invention
(1) take Li source compound according to the mol ratio of Li:Fe:CA=1 ~ 1.05:1:1, Fe source compound and citric acid complexing agent are dissolved in deionized water, magnetic agitation 2 ~ 5 hours;
(2) take and be dissolved in above-mentioned solution with the ammonium dihydrogen phosphate of citric acid equimolar amounts, dropwise add concentrated ammonia liquor and regulate pH value of solution=2 ~ 6, in 60 ~ 80 DEG C of water-baths, add thermal agitation, obtain gel, dry;
(3) put into gradient furnace after being ground by xerogel and 200 ~ 300 DEG C of predecomposition 3 ~ 6 hours are set, after naturally cooling to room temperature, take out grinding;
(4) step 3 products therefrom is imbedded the Cr filled with for absorbing microwave
2o
3in the crucible of the carbon dust of powder and generation protective atmosphere, chrome green: carbon=1:1(volume ratio);
(5) crucible is put into microwave oven, with the heats 5 ~ 15 minutes of 350W, heat and completely naturally cool to room temperature, after grinding, obtain LiFePO4.
Described lithium source is one or more in lithium acetate, lithium hydroxide and lithium nitrate; Described source of iron is one or more in ferric nitrate, iron chloride and ironic citrate; Described phosphorus source is ammonium dihydrogen phosphate; Described complexing agent is citric acid.
The described material being used for absorbing microwave is Cr
2o
3, the carbon producing protective atmosphere is graphite carbon dust.
Beneficial effect of the present invention
The present invention prepares ferric lithium phosphate precursor by sol-gal process, raw material is made to realize the Homogeneous phase mixing of molecular level, the source of iron wherein used is ferric iron source, uses citric acid as reducing agent and complexing agent, avoids the possibility that ferrous iron in sol-gel process is oxidized.In predecomposition process, the decomposition of citric acid also can produce reducibility gas and effectively stops ferrous oxidation, and the trace carbon simultaneously decomposing generation can effectively stop growing up of LiFePO4 crystal grain, improves its chemical property.In follow-up microwave method heat treatment process, the protective atmosphere using graphite carbon dust to provide prevents ferrous oxidation, and rapidly and reduce costs, the LiFePO4 crystal formation prepared is perfect for sintering, narrow diameter distribution and without dephasign.
Accompanying drawing explanation
The XRD collection of illustrative plates of Fig. 1, LiFePO4.
Fig. 2,5min and 9min microwave sintering obtains the XRD collection of illustrative plates of LiFePO4.
The transmission electron microscope picture of Fig. 3, LiFePO4.
Embodiment
embodiment 1:
By 2.038g lithium acetate, 8.080g ferric nitrate, 4.194g citric acid is dissolved in 40ml deionized water and obtains rufous mixed solution, and pH value is 1.After room temperature lower magnetic force stirs 3 hours, take 2.302g ammonium dihydrogen phosphate and join in mixed solution, dropwise add concentrated ammonia liquor and regulate solution ph and constantly stir, final solution pH is about 5, and concentrated ammonia liquor consumption is 8ml.Solution after adjust ph is placed in 60 DEG C of water-baths constantly to stir, until dry 12h obtains xerogel at putting into 80 DEG C, drying box after forming gel.Take the ferric lithium phosphate precursor 2.000g predecomposition in gradient furnace after grinding, heating rate 5 DEG C/min is set, after 200 DEG C of insulation 5h, naturally cool to room temperature.Imbed and fill chrome green after getting the material after part predecomposition process (quality is 0.285g) grinding: carbon=1:1(volume ratio) in the crucible of mixed-powder, arranging microwave power is 350W, naturally cool to room temperature after heating 9min, take out grinding and obtain LiFePO4 product.The LiFePO4 prepared belongs to rhombic system, and space group is Pnmb, contrasts with standard P DF card, free from admixture peak, and products therefrom is pure phase product.Under transmission electron microscope, lithium iron phosphate particles domain size distribution is at 20 ~ 40nm.
embodiment 2:
By 2.039g lithium acetate, 8.088g ferric nitrate, 4.198g citric acid is dissolved in 40ml deionized water and obtains rufous mixed solution, and pH value is 1.After room temperature lower magnetic force stirs 3 hours, take 2.306g ammonium dihydrogen phosphate and join in mixed solution, dropwise add concentrated ammonia liquor and regulate solution ph and constantly stir, final solution pH is about 5, and concentrated ammonia liquor consumption is 8ml.Solution after adjust ph is placed in 60 DEG C of water-baths constantly to stir, until dry 12h obtains xerogel at putting into 80 DEG C, drying box after forming gel.Take the ferric lithium phosphate precursor 1.500g predecomposition in gradient furnace after grinding, heating rate 5 DEG C/min is set, after 200 DEG C of insulation 5h, naturally cool to room temperature.Imbed and fill chrome green after getting the material after part predecomposition process (quality is 0.266g) grinding: carbon=1:1(volume ratio) in the crucible of mixed-powder, arranging microwave power is 350W, naturally cool to room temperature after heating 5min, take out grinding and obtain LiFePO4 product.The LiFePO4 prepared belongs to rhombic system, and space group is Pnmb, as can be seen from Figure 2, when other conditions are constant, the microwave sintering time, when shortening to 5min by 9min, XRD collection of illustrative plates was without obvious difference, and the LiFePO4 that 5min microwave sintering prepares also is pure phase product.
embodiment 3:
By 0.442g lithium hydroxide, 4.038g ferric nitrate, 2.101g citric acid is dissolved in 20ml deionized water and obtains mixed solution, and pH value is 1.After room temperature lower magnetic force stirs 2 hours, take 1.154g ammonium dihydrogen phosphate and join in mixed solution, dropwise add concentrated ammonia liquor and regulate solution ph and constantly stir, final solution pH is 6, and concentrated ammonia liquor consumption is 5ml.Solution after adjust ph is placed in 60 DEG C of water-baths constantly to stir, until dry 12h obtains xerogel at putting into 80 DEG C, drying box after forming gel.Take the predecomposition in gradient furnace of the ferric lithium phosphate precursor after grinding, heating rate 5 DEG C/min is set, after 200 DEG C of insulation 5h, naturally cool to room temperature.Imbed and fill chrome green after getting the grinding of the material after part predecomposition process: carbon=1:1(volume ratio) in the crucible of mixed-powder, arranging microwave power is 350W, naturally cools to room temperature after heating 9min, takes out grinding and obtains LiFePO4 product.
Claims (8)
1. microwave radiation technology sol-gal process prepares the method for anode material for lithium-ion batteries, it is characterized in that comprising the following steps:
(1) take Li source compound according to the mol ratio of Li:Fe:CA=1 ~ 1.05:1:1, Fe source compound and citric acid complexing agent are dissolved in deionized water, magnetic agitation 2 ~ 5 hours;
(2) take and be dissolved in above-mentioned solution with the ammonium dihydrogen phosphate of citric acid equimolar amounts, dropwise add concentrated ammonia liquor and regulate pH value of solution=2 ~ 6, in 60 ~ 80 DEG C of water-baths, add thermal agitation, obtain gel, dry;
(3) put into gradient furnace after being ground by xerogel and 200 ~ 300 DEG C of predecomposition 3 ~ 6 hours are set, after naturally cooling to room temperature, take out grinding;
(4) step 3 products therefrom is imbedded the Cr filled with for absorbing microwave
2o
3in the crucible of the carbon dust of powder and generation protective atmosphere, chrome green: carbon=1:1(volume ratio);
(5) crucible is put into microwave oven, with the heats 5 ~ 15 minutes of 350W, heat and completely naturally cool to room temperature, after grinding, obtain LiFePO4.
2. microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that: described lithium source is one or more in lithium acetate, lithium hydroxide and lithium nitrate.
3. microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that: described source of iron is one or more in ferric nitrate, iron chloride and ironic citrate.
4. microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that: described phosphorus source is ammonium dihydrogen phosphate.
5. microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that: described complexing agent is citric acid.
6. microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that: described water bath heating temperature is 60 ~ 80 DEG C.
7. microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that: in described gradient furnace, predecomposition temperature is 200 ~ 300 DEG C, and the time is 3 ~ 6 hours.
8. microwave radiation technology sol-gal process prepares the method for lithium ion battery anode material lithium iron phosphate according to claim 1, it is characterized in that: described microwave heating power is 350W, and heating time is 5 ~ 15 minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106315651A (en) * | 2016-08-09 | 2017-01-11 | 天津正达科技有限责任公司 | Method for rapidly treating steel chlorohydric acid pickling waste liquid with assistance of microwaves |
| CN107732173A (en) * | 2017-09-25 | 2018-02-23 | 江苏奔拓电气科技有限公司 | A kind of preparation method of anode material for lithium-ion batteries |
| CN113264514A (en) * | 2021-05-17 | 2021-08-17 | 天津森特新材料科技有限责任公司 | Preparation method of lithium ion battery anode material lithium iron phosphate |
| CN113540410A (en) * | 2021-07-12 | 2021-10-22 | 天津大学 | Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method |
| CN114014369A (en) * | 2021-10-29 | 2022-02-08 | 蜂巢能源科技有限公司 | Ferromanganese binary hydroxide precursor, preparation method and application thereof |
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| CN1821064A (en) * | 2006-03-20 | 2006-08-23 | 清华大学 | Method for preparing high density lithium ferric phosphate by microwave heating |
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| CN101941687A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Method for synthetizing lithium ion battery anode material LiFePO4 |
| CN102299327A (en) * | 2011-08-05 | 2011-12-28 | 陕西科技大学 | Preparation method for lithium-aluminum doped carbon cladded lithium iron phosphate anode material |
| CN104022284A (en) * | 2014-06-20 | 2014-09-03 | 郑州德朗能微波技术有限公司 | Method for preparing anode material lithium iron phosphate of lithium ion battery with ion and electron mixed conductive network structure |
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Patent Citations (6)
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| CN1821064A (en) * | 2006-03-20 | 2006-08-23 | 清华大学 | Method for preparing high density lithium ferric phosphate by microwave heating |
| CN101121508A (en) * | 2006-08-08 | 2008-02-13 | 新疆大学 | Method for synthesizing lithium iron phosphate battery anode material by microwave |
| CN101759172A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Microwave sintering method for preparing high-performance iron phosphate lithium |
| CN101941687A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Method for synthetizing lithium ion battery anode material LiFePO4 |
| CN102299327A (en) * | 2011-08-05 | 2011-12-28 | 陕西科技大学 | Preparation method for lithium-aluminum doped carbon cladded lithium iron phosphate anode material |
| CN104022284A (en) * | 2014-06-20 | 2014-09-03 | 郑州德朗能微波技术有限公司 | Method for preparing anode material lithium iron phosphate of lithium ion battery with ion and electron mixed conductive network structure |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106315651A (en) * | 2016-08-09 | 2017-01-11 | 天津正达科技有限责任公司 | Method for rapidly treating steel chlorohydric acid pickling waste liquid with assistance of microwaves |
| CN107732173A (en) * | 2017-09-25 | 2018-02-23 | 江苏奔拓电气科技有限公司 | A kind of preparation method of anode material for lithium-ion batteries |
| CN113264514A (en) * | 2021-05-17 | 2021-08-17 | 天津森特新材料科技有限责任公司 | Preparation method of lithium ion battery anode material lithium iron phosphate |
| CN113540410A (en) * | 2021-07-12 | 2021-10-22 | 天津大学 | Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method |
| CN114014369A (en) * | 2021-10-29 | 2022-02-08 | 蜂巢能源科技有限公司 | Ferromanganese binary hydroxide precursor, preparation method and application thereof |
| CN114014369B (en) * | 2021-10-29 | 2022-12-16 | 蜂巢能源科技有限公司 | Ferromanganese binary hydroxide precursor, preparation method and application thereof |
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Application publication date: 20150311 |