CN102942167A - Anhydrous ferric phosphate, lithium iron phosphate prepared from the anhydrous ferric phosphate and use of the lithium iron phosphate - Google Patents
Anhydrous ferric phosphate, lithium iron phosphate prepared from the anhydrous ferric phosphate and use of the lithium iron phosphate Download PDFInfo
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- CN102942167A CN102942167A CN2012101801027A CN201210180102A CN102942167A CN 102942167 A CN102942167 A CN 102942167A CN 2012101801027 A CN2012101801027 A CN 2012101801027A CN 201210180102 A CN201210180102 A CN 201210180102A CN 102942167 A CN102942167 A CN 102942167A
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- iron phosphate
- anhydrous iron
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- 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 invention discloses an anhydrous ferric phosphate, a lithium iron phosphate prepared from the anhydrous ferric phosphate and a use of the lithium iron phosphate. A preparation method of the anhydrous ferric phosphate comprises the following steps of 1, mixing Fe2O3 and P2O5 according to a mole ratio of Fe: P of 1: (1-1.12), and fully grinding until uniform mixing, and 2, putting the mixture obtained by the step 1 into a tube furnace, sintering at a temperature of 400 to 700 DEG C in air for 5 to 24 hours, cooling to a room temperature, and grinding to obtain the anhydrous ferric phosphate. The lithium iron phosphate is prepared from the anhydrous ferric phosphate. The lithium iron phosphate has good conductivity and a first discharge capacity close to a theoretical value, can be used as a lithium ion battery anode material and can be widely used for the field of power-type lithium ion batteries.
Description
(1) technical field
The present invention relates to a kind of anhydrous iron phosphate by solid phase method preparation, by the application as anode material for lithium-ion batteries of the LiFePO 4 of this anhydrous iron phosphate preparation and LiFePO 4.
(2) background technology
Tertiary iron phosphate is faint yellow or the ivory buff powder, tap density: 1.13 ~ 1.59g/cm
3, loose density 0.75 ~ 0.97g/cm
3, be dissolved in hydrochloric acid during heating, be insoluble in other acid, water-soluble, acetic acid, alcohol exist with the vivianite form at occurring in nature hardly.
At present, lithium ion battery market is fast-developing, and tertiary iron phosphate is one of raw material of preparation lithium ion battery anode material lithium iron phosphate, and the tertiary iron phosphate presoma of excellent property has decisive role to the performance of iron lithium phosphate.
The synthetic method of tertiary iron phosphate has a variety of, as mixing with DAP solution with ferrous sulfate, with the reaction solution ultrasonic radiation, obtain tertiary iron phosphate product (Hirokazu Okawa*, Junpei Yabuki, Youhei Kawamura, Ichiro Arise, Mineo Sato.Synthesis of FePO
4Cathode material for lithium ion batteries by a sonochemical method.J.materials research bulletin.2008), the method shortcoming is high to the production unit requirement, energy consumption is large, and cost is high, is not suitable for scale operation.
For another example with Iron sulfuret, dilute phosphoric acid, sodium chlorate and sodium hydroxide reaction preparation tertiary iron phosphate, reaction equation: 6FeSO
4+ 6H
3PO
4+ NaClO
3+ 12NaOH → 6FePO
42H
2O+6Na
2SO
4+ NaCl+3H
2The O(horse extensively becomes, Ding Shiwen, Li Weiping *. the synthetic and performance study .J. coatings industry .1998.12 of tertiary iron phosphate) and, the shortcoming of the method is that step is complicated, raw material consumption is large, cost is high.
In addition, also useful sodium phosphate and ferric sulfate direct reaction, the pH value less than 2 condition under synthetic tertiary iron phosphate, the method reaction not exclusively, impurity phase is more.
The tertiary iron phosphate of above method preparation contains all that crystal water, particle distribution range are wide, agglomeration is serious between particle, cause surfactivity lower, for the preparation of lithium ferrous phosphate as anode material of lithium ion battery, have that capacity is low, the problem such as poorly conductive and unstable product quality, directly affected the performance of lithium ion battery.
(3) summary of the invention
First purpose of the present invention provides a kind of anhydrous iron phosphate with high reaction activity, and it is simple to operate, with low cost, combined coefficient is high, environmentally friendly, is easy to realize industrialization.
Second purpose of the present invention provides a kind of LiFePO 4 that is made by anhydrous iron phosphate, and this LiFePO 4 conductivity is good, and loading capacity is near theoretical value first.
The 3rd purpose of the present invention is as anode material for lithium-ion batteries with described LiFePO 4.
The below does technical scheme of the present invention and specifies.
The invention provides a kind of anhydrous iron phosphate, described anhydrous iron phosphate is to utilize cheap ferric oxide to be the phosphorus source for source of iron, Vanadium Pentoxide in FLAKES, adopts step solid phase method preparation, specifically in accordance with the following steps preparation:
(1) be 1:(1 ~ 1.12 with ferric oxide and Vanadium Pentoxide in FLAKES in the Fe:P mol ratio) ratio mix, fully grind and make it to mix;
(2) step (1) gained mixture is put into tube furnace, under air atmosphere, in 400 ~ 700 ℃ of high temperature sinterings 5 ~ 24 hours, be cooled to room temperature, the levigate anhydrous iron phosphate that obtains.
In the described step (1), can adopt ordinary method that ferric oxide and Vanadium Pentoxide in FLAKES are mixed, for example ground and mixed 4 ~ 20 hours on ball mill.Usually, reach well-mixed effect for making mixture, can add an amount of alcohol before grinding, the adding volume of alcohol is generally 20 ~ 200mL/mol in the mole number of ferric oxide.
In the described step (2), preferred described mixture is warming up to 400 ~ 700 ℃ with 5 ~ 10 ℃/minute speed.Sintering temperature is preferably 650 ℃, and sintering time is preferably 5 ~ 8 hours.
The present invention is concrete to recommend described preparation anhydrous iron phosphate method to carry out in accordance with the following steps:
(1) be 1:(1 ~ 1.12 with ferric oxide and Vanadium Pentoxide in FLAKES in the Fe:P mol ratio) ratio mix, and adding alcohol, the adding volume of alcohol is counted 20 ~ 200mL/mol with the mole number of ferric oxide, then mixes 4 ~ 20 hours at ball mill, makes it to mix;
(2) mixture is put into tube furnace, under the air conditions, be warming up to 400 ~ 700 ℃ with 5 ~ 10 ℃/minute speed, high temperature sintering 5 ~ 8 hours is cooled to room temperature, the levigate anhydrous iron phosphate that obtains.
The tertiary iron phosphate that the present invention makes does not contain crystal water, and median size is 0.2 ~ 2 micron, and tap density is greater than 1.2g/cm
3, at the high power observed under electron microscope, product is the particle of surface irregularity, gauffer, the surface is the porous structure, has improved the reactive behavior of tertiary iron phosphate.
The present invention also provides the LiFePO 4 by the preparation of described anhydrous iron phosphate, and concrete preparation method is: with lithium compound and anhydrous iron phosphate according to Li:FePO
4Mol ratio is (0.95 ~ 1.05): 1 ratio mixes, under reducing atmosphere in 600 ~ 800 ℃ of sintering 4 ~ 30 hours, the levigate LiFePO 4 that obtains after the cooling.Described lithium compound is the compound that contains the lithium source, such as lithium hydroxide, Quilonum Retard, lithium nitrate etc.Also can use the mode (for example on ball mill ball milling 5 ~ 20 hours) of grinding that lithium compound and anhydrous iron phosphate are mixed among the present invention.Described reducing atmosphere is that volume ratio is the N of 5 ~ 9:1
2With H
2Mixed atmosphere or the volume ratio Ar and the H that are 5 ~ 9:1
2Mixed atmosphere.The flow velocity of reductibility air-flow is recommended as 5 ~ 30 liter/mins of clocks.
LiFePO 4 of the present invention can be used as anode material for lithium-ion batteries, is widely used in the fields such as power-type lithium ion battery.
The present invention compared with prior art, its beneficial effect is mainly reflected in:
(1) the present invention takes full advantage of cheap ferric oxide as source of iron, creatively adopts solid phase method to prepare anhydrous iron phosphate.Compare with traditional liquid phase method, technique of the present invention is simple, with low cost, combined coefficient is higher, be easy to realize industrialization, and discharges without waste water and gas in the preparation process, thereby environmentally friendly.
(2) anhydrous iron phosphate of the present invention's preparation has high reaction activity, make LiFePO 4 take this anhydrous iron phosphate as raw material through solid phase synthesis, conductivity is good, loading capacity is near theoretical value first, can be used as the anode material for lithium-ion batteries of excellent property, be widely used in the fields such as power-type lithium ion battery.
(4) description of drawings
Fig. 1 is the XRD diffractogram of the prepared anhydrous iron phosphate of embodiment 1.
Fig. 2 is the prepared anhydrous iron phosphate electron scanning micrograph of embodiment 1.
Fig. 3 is the XRD diffractogram of the prepared LiFePO 4 of embodiment 1.
Fig. 4 is the first discharge curve (0.1C) of the lithium ion battery of embodiment 1 making.
Fig. 5 is the alternating-current impedance figure of the lithium ion battery of embodiment 1 making.
(5) specific implementation method
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
0.5 mole of ferric oxide and 0.5 mole of Vanadium Pentoxide in FLAKES are mixed, put into the nylon tank, and add 80 milliliters alcohol, after ball mill mixes 4 hours, put into tube furnace and carry out thermal response, under air atmosphere, rise to 650 ℃ with 5 ℃/minute speed, constant temperature 6 hours, the levigate anhydrous iron phosphate that obtains behind the naturally cooling.Fig. 1 is the XRD diffraction peak of this material.Fig. 2 is the SEM photo of this material, and product is the particle of surface irregularity, gauffer, and the surface is the porous structure, and median size is 0.5 ~ 1 micron, and tap density is 1.43g/cm
3
0.98 mole of LiOH is joined in the anhydrous iron phosphate, and ball milling 10 hours is put into stove at logical N
2With H
2Be warming up to 650 ℃ of insulations 10 hours under the condition of the mixed atmosphere of (volume ratio 9:1), the flow velocity of mixed atmosphere is 10 liter/mins of clocks, the levigate LiFePO 4 that obtains again behind the naturally cooling, and Fig. 3 is its XRD diffractogram.
Make as follows electrode with prepared LiFePO 4.
Mass ratio with 80:10:10 takes by weighing respectively LiFePO 4: acetylene black: tetrafluoroethylene, make electrode after the grinding evenly, and metal lithium sheet is negative pole, electrolytic solution is 1mol/L LiPF
6/ EC – DMC (1:1), polypropylene microporous film is barrier film, is assembled into the simulation lithium ion battery.Fig. 4 is the first discharge curve (0.1C) of respective battery, and its reversible specific capacity arrives 164mAh/g, near theoretical value (170mAh/g).Fig. 5 is the alternating-current impedance figure of battery, and its electrochemical impedance only has 97.1 Ω, and conductivity is fine.
Embodiment 2
0.5 mole of ferric oxide and 0.56 mole of Vanadium Pentoxide in FLAKES are mixed, put into the nylon tank, and add 80 milliliters alcohol, after ball mill mixes 4 hours, put into tube furnace and carry out thermal response, under air atmosphere, rise to 600 ℃ with 5 ℃/minute speed, constant temperature 10 hours, behind the naturally cooling, the levigate anhydrous iron phosphate that obtains.The reference standard card is the intact tertiary iron phosphate of crystal formation, and the products therefrom particle diameter is 0.5 ~ 1 micron, and tap density is 1.46g/cm
3
1.01 moles of LiOH are joined in the anhydrous iron phosphate, and ball milling 10 hours is put into stove at logical Ar and H
2Be warming up to 600 ℃ of insulations 8 hours under the condition of the mixed atmosphere of (volume ratio 9:1), the flow velocity of mixed atmosphere is 5 liter/mins of clocks, the levigate LiFePO 4 that obtains again behind the naturally cooling.Make electrode with prepared LiFePO 4 according to the method for embodiment 1, be assembled into the simulation lithium ion battery, its reversible specific capacity is 158mAh/g, and its electrochemical impedance is 90.5 Ω.
Embodiment 3
0.5 mole of ferric oxide and 0.52 mole of Vanadium Pentoxide in FLAKES are mixed, put into the nylon tank, and add 80 milliliters alcohol, after ball mill mixes 4 hours, put into tube furnace and carry out thermal response, under air atmosphere, rise to 500 ℃ with 5 ℃/minute speed, constant temperature 16 hours, behind the naturally cooling, the levigate anhydrous iron phosphate that obtains.The reference standard card is the intact tertiary iron phosphate of crystal formation, and the products therefrom particle diameter is 1 ~ 2 micron, and tap density is 1.52g/cm
3
With 0.51 mole of Li
2CO
3Join in the anhydrous iron phosphate, ball milling 7 hours is put into stove at logical Ar and H
2Be warming up to 650 ℃ of insulations 10 hours under the condition of the mixed atmosphere of (volume ratio 9:1), the flow velocity of mixed atmosphere is 10 liter/mins of clocks, the levigate LiFePO 4 that obtains again behind the naturally cooling.Make electrode with prepared LiFePO 4 according to the method for embodiment 1, be assembled into the simulation lithium ion battery, its reversible specific capacity is 162mAh/g, and its electrochemical impedance is 101.3 Ω.
Embodiment 4
0.5 mole of ferric oxide and 0.54 mole of Vanadium Pentoxide in FLAKES are mixed, put into the nylon tank, and add 80 milliliters alcohol, after ball mill mixes 4 hours, this mixture is put into tube furnace carry out thermal response, under air atmosphere, rise to 400 ℃ with 5 ℃/minute speed, constant temperature 24 hours, behind the naturally cooling, the levigate anhydrous iron phosphate that obtains.The reference standard card is the intact tertiary iron phosphate of crystal formation, and the products therefrom particle diameter is the 0.2-2 micron, and tap density is 1.49g/cm
3
With 0.495 mole of Li
2CO
3Join in the anhydrous iron phosphate, ball milling 10 hours is put into stove at logical Ar and H
2Be warming up to 750 ℃ of insulations 10 hours under the condition of the mixed atmosphere of (volume ratio 9:1), the flow velocity of mixed atmosphere is 10 liter/mins of clocks, the levigate LiFePO 4 that obtains again behind the naturally cooling.Make electrode with prepared LiFePO 4 according to the method for embodiment 1, be assembled into the simulation lithium ion battery, its reversible specific capacity is 152mAh/g, and its electrochemical impedance is 75.6 Ω.
Claims (10)
1. anhydrous iron phosphate, it is characterized in that: described anhydrous iron phosphate prepares according to following step:
(1) be 1:(1 ~ 1.12 with ferric oxide and Vanadium Pentoxide in FLAKES in the Fe:P mol ratio) ratio mix, fully grind and make it to mix;
(2) mixture of step (1) gained is put into tube furnace, under air atmosphere, in 400 ~ 700 ℃ of high temperature sinterings 5 ~ 24 hours, be cooled to room temperature, the levigate anhydrous iron phosphate that obtains.
2. anhydrous iron phosphate as claimed in claim 1 is characterized in that: describedly fully be ground to: mixed 4 ~ 20 hours at ball mill.
3. anhydrous iron phosphate as claimed in claim 1 or 2 is characterized in that: in the described step (1), before grinding, add alcohol in ferric oxide and Vanadium Pentoxide in FLAKES.
4. anhydrous iron phosphate as claimed in claim 3, it is characterized in that: the adding volume of described alcohol is counted 20 ~ 200mL/mol with the mole number of ferric oxide.
5. anhydrous iron phosphate as claimed in claim 1, it is characterized in that: in the described step (2), mixture is warming up to 400 ~ 700 ℃ with 5 ~ 10 ℃/minute speed.
6. anhydrous iron phosphate as claimed in claim 5 is characterized in that: in the described step (2), mixture was in 400 ~ 700 ℃ of high temperature sinterings 5 ~ 8 hours.
7. anhydrous iron phosphate as claimed in claim 1, it is characterized in that: described anhydrous iron phosphate prepares in accordance with the following steps:
(1) be 1:(1 ~ 1.12 with ferric oxide and Vanadium Pentoxide in FLAKES in the Fe:P mol ratio) ratio mix, and adding alcohol, the adding volume of alcohol is counted 20 ~ 200mL/mol with the mole number of ferric oxide, then mixes 5 ~ 20 hours at ball mill, makes it to mix;
(2) mixture is put into tube furnace, under air atmosphere, be warming up to 400 ~ 700 ℃ with 5 ~ 10 ℃/minute speed, high temperature sintering 5 ~ 8 hours is cooled to room temperature, the levigate anhydrous iron phosphate that obtains.
8. LiFePO 4 by anhydrous iron phosphate claimed in claim 1 preparation, described iron lithium phosphate is by the following method preparation specifically: with lithium compound and anhydrous iron phosphate according to Li:FePO
4Mol ratio is (0.95 ~ 1.05): 1 ratio mixes, under reducing atmosphere in 600 ~ 800 ℃ of sintering 4 ~ 30 hours, the levigate LiFePO 4 that obtains after the cooling; Described lithium compound is lithium hydroxide, Quilonum Retard or lithium nitrate.
9. LiFePO 4 as claimed in claim 8, it is characterized in that: described reducing atmosphere is that volume ratio is the N of 5 ~ 9:1
2With H
2Mixed atmosphere or the volume ratio Ar and the H that are 5 ~ 9:1
2Mixed atmosphere.
10. LiFePO 4 as claimed in claim 8 is as the application of anode material for lithium-ion batteries.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014184533A1 (en) | 2013-05-14 | 2014-11-20 | Faradion Limited | Metal-containing compounds |
| CN105800580A (en) * | 2016-05-13 | 2016-07-27 | 贵州安达科技能源股份有限公司 | Anhydrous ferric phosphate and preparation method thereof, lithium iron phosphate, positive electrode of lithium-ion battery and lithium-ion battery |
| CN106586996A (en) * | 2017-01-25 | 2017-04-26 | 上海应用技术大学 | Preparation method of anhydrous iron phosphate |
| CN106809810A (en) * | 2017-01-25 | 2017-06-09 | 上海应用技术大学 | A kind of preparation method of anhydrous ferric orthophosphate |
| CN108101016A (en) * | 2017-12-27 | 2018-06-01 | 山东东佳集团股份有限公司 | The method that titanium white by product ferrous sulfate prepares LiFePO4 |
| CN110316712A (en) * | 2019-08-01 | 2019-10-11 | 湖北昊瑞新能源有限公司 | A method of LiFePO4 is prepared with nanoscale iron phosphate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014184533A1 (en) | 2013-05-14 | 2014-11-20 | Faradion Limited | Metal-containing compounds |
| CN105800580A (en) * | 2016-05-13 | 2016-07-27 | 贵州安达科技能源股份有限公司 | Anhydrous ferric phosphate and preparation method thereof, lithium iron phosphate, positive electrode of lithium-ion battery and lithium-ion battery |
| CN105800580B (en) * | 2016-05-13 | 2017-03-29 | 贵州安达科技能源股份有限公司 | Anhydrous iron phosphate and preparation method thereof, LiFePO4, lithium ion cell positive and lithium ion battery |
| CN106586996A (en) * | 2017-01-25 | 2017-04-26 | 上海应用技术大学 | Preparation method of anhydrous iron phosphate |
| CN106809810A (en) * | 2017-01-25 | 2017-06-09 | 上海应用技术大学 | A kind of preparation method of anhydrous ferric orthophosphate |
| CN106586996B (en) * | 2017-01-25 | 2019-05-24 | 上海应用技术大学 | A kind of preparation method of anhydrous iron phosphate |
| CN108101016A (en) * | 2017-12-27 | 2018-06-01 | 山东东佳集团股份有限公司 | The method that titanium white by product ferrous sulfate prepares LiFePO4 |
| CN108101016B (en) * | 2017-12-27 | 2021-05-07 | 山东东佳集团股份有限公司 | Method for preparing lithium iron phosphate by using ferrous sulfate as titanium dioxide byproduct |
| CN110316712A (en) * | 2019-08-01 | 2019-10-11 | 湖北昊瑞新能源有限公司 | A method of LiFePO4 is prepared with nanoscale iron phosphate |
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Application publication date: 20130227 |