CN109904423A - Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method - Google Patents
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method Download PDFInfo
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Abstract
The present invention relates to fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation methods, it obtains positive electrode as presoma low temperature calcination by using a small amount of lithium hexafluoro phosphate, simple process, operation is easy, energy consumption is lower, raw material are cheap and easily-available, and gained positive electrode chemical property is superior.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to fluorine-ion-doped and lithium fluoride coats phosphorus
The preparation method of sour iron lithium anode material.
Background technique
Lithium ion battery meets the demand of sustainable development, has been widely used for as the conversion equipment of clean energy resource
Every field.In recent years, LiFePO4 (LiFePO4) secondary battery positive electrode material, not only have that cost of material is cheap, environment is friendly
The advantages such as good and safety, and its stable internal structure shows high theoretical discharge specific capacity (170mAh/g), electric discharge
Voltage platform is 3.4V and excellent cycle performance, is one of widest anode material for lithium-ion batteries of current application.
LiFePO4 intrinsic conductivity is lower, ionic diffusion coefficient is low, tap density is smaller, it is therefore necessary to carry out one to it
Fixed surface modification or design of material just can be carried out practical application.People have done largely the chemical property for improving LiFePO4
Work, be generally adopted by the methods of cladding, doping and nanosizing.
The LiFePO4 surface that modern times generally commercially produce, which is coated with it using carbon-coating, improves its conductivity, to make
LiFePO 4 material shows more excellent chemical property, but the lower degree of crystallization of coated with carbon bed can be very big
Covered effect is reduced, and reduces its tap density.It is especially fluorine-ion-doped and about ion doping, it can effectively improve
The high rate performance of LiFePO4, but the increase of simple fluorine ion will lead to current potential and be substantially reduced, and then not be able to satisfy lithium ion
The requirement of power battery.In the prior art, 106,207,113 106450223 A and CN 107946584 of A, CN of Publication No. CN
The Chinese patent application of A individually discloses the preparation method of carbon coating/Fluorin doped iron phosphate lithium positive pole composite material, these
Method is required to be calcined under protective gas atmosphere and/or high temperature, and there are capacity guarantors for the material being prepared by correlation method
Holdup improves the problems such as unobvious, coulombic efficiency is relatively low.And the Chinese patent application of 102610817 A of Publication No. CN is then public
A kind of LiFePO 4 material and preparation method thereof of fluorine-doped tin oxide cladding is opened, this method still needs in protective gas atmosphere
With react a few hours under high temperature.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, fluorine-ion-doped and lithium fluoride is provided and coats phosphorus
The preparation method of sour iron lithium anode material, the method is simple and easy, prepares resulting positive electrode electrochemical performance.
The preparation method of fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode provided by the present invention, including by six
Lithium fluophosphate and LiFePO4 mixture are add to deionized water, and after 20 DEG C~30 DEG C stirring 12h~48h, are put into baking oven
In in 100 DEG C~120 DEG C dry 0.5h~2h, be then placed in again in Muffle furnace in 300 DEG C~400 DEG C calcining 1h~3h；According to
Mass percentage, the lithium hexafluoro phosphate account for the 0.5%~2% of amount of the mixture.
In this preparation method, lithium hexafluoro phosphate meets aquatic products unboiled water solution, generates lithium fluoride and hydrogen fluoride.Lithium fluoride can be made
It is prevented for buffer layer or reduces the side reaction between electrode and electrolyte, while can also be used as and lead because itself containing Li+
Electric layer increases the conduction diffusion of lithium ion.And fluorine ion (the F adulterated-) then non-equivalence instead of O2-, so as to form Li sky
, during charge and discharge cycles, Li+It can not had to stringent along radial migration by Li Vacancy Transition in migration.And
And the weak bonding performance of F is enough in Li+Appropriate adjustment position in transition process, is conducive to Li+Migration.
Further, according to mass percentage, the lithium hexafluoro phosphate account for amount of the mixture 0.5%, 1% or
2%.
Further, the LiFePO4 is prepared by the following method:
(1) ammonium dihydrogen phosphate, Fe(NO3)39H2O and glucose are dissolved in deionized water, are heated to 120 DEG C~160
DEG C reaction 3h~9h after, be cooled to room temperature, obtained solid successively through water and ethanol washing, drying, calcining, obtains intermediate；
(2) it by after the intermediate and lithium carbonate mixing and ball milling 2h~4h, in 600 DEG C~800 DEG C calcining 6h~10h, sieves
Get LiFePO4；
Wherein, the molar ratio of the ammonium dihydrogen phosphate, Fe(NO3)39H2O, glucose and lithium carbonate is 1:0.9~1.1:
0.9~1.1:1.0~1.2.
Further, the molar ratio of the ammonium dihydrogen phosphate, Fe(NO3)39H2O, glucose and lithium carbonate is 1:0.9:
0.9:1.0；Or the ammonium dihydrogen phosphate, Fe(NO3)39H2O, glucose and lithium carbonate molar ratio be 1:1:1:1；Or
The ammonium dihydrogen phosphate, Fe(NO3)39H2O, glucose and lithium carbonate molar ratio be 1:1.1:1.1:1.2.
Further, the calcining is in H2-N2It is carried out in atmosphere.
Based on aforementioned preparation process, another aspect of the present invention additionally provides a kind of fluorine-ion-doped and lithium fluoride cladding phosphoric acid
Iron lithium anode material.
Beneficial effects of the present invention:
Of the present invention fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method is by using few
The lithium hexafluoro phosphate of amount obtains positive electrode as presoma low temperature calcination, and mild condition, operates easy, energy consumption at simple process
It is lower, raw material are cheap and easily-available, gained positive electrode chemical property is superior.On the one hand fluoride cladding can repair carbon coating
Integrality and uniformity, the Long Term Contact of LiFePO4 and electrolyte on the other hand can be inhibited to improve its cycle performance, and
It is fluorine-ion-doped, the conduction velocity of electronic conductivity and lithium ion is improved, anion doped can be increased with electronegativity is biggish
Add inside battery potential difference, improves the specific capacity of material.
Specific embodiment
Below in conjunction with the performance that the present invention will be described in detail, but they are not constituted a limitation of the invention, only for example
?.By specific embodiment, the present invention is described in further detail simultaneously.
Embodiment 1
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method, comprising the following steps:
LiFePO4Preparation: NH4H2PO4、Fe(NO3)3·9H2O and glucose are dissolved in deionized water, and mixed liquor is turned
It moves on to and reacts 120 DEG C in reaction kettle, time 3h naturally cools to room temperature, dry with water and ethanol washing, calcining.Calcining
Sample and Li afterwards2CO3Carry out mixing and ball milling 4h, NH4H2PO4: Fe (NO3)3·9H2O:Li2CO3: the molar ratio of glucose is
1:0.9:0.9:1.0.It calcines again, temperature is 600 DEG C, calcination time 6h, and calcining atmosphere is H2-N2Atmosphere, screening obtain
LiFePO4。
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode LiFePO4- 1 preparation: LiPF6、 LiFePO4With
Deionized water mixing, LiPF6Quality in the mixture is 0.5wt%, and the temperature of mixture stirring is 20 DEG C, and mixing time is
12h.100 DEG C, drying time 0.5h are dried in an oven, 300 DEG C are then calcined in Muffle furnace, time 1h obtains fluorine
Ion doping and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode LiFePO4-1。
Embodiment 2
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method, comprising the following steps:
LiFePO4Preparation: NH4H2PO4、Fe(NO3)3·9H2O and glucose are dissolved in deionized water, and mixed liquor is turned
It moves on to and reacts 140 DEG C in reaction kettle, time 6h naturally cools to room temperature, dry with water and ethanol washing, calcining.Calcining
Sample and Li afterwards2CO3Carry out mixing and ball milling 3h, NH4H2PO4: Fe (NO3)3·9H2O:Li2CO3: the molar ratio of glucose is
1:1:1:1.1.It calcines again, temperature is 700 DEG C, calcination time 8h, and calcining atmosphere is H2-N2Atmosphere, screening obtain
LiFePO4。
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode LiFePO4- 2 preparation: LiPF6、 LiFePO4With
Deionized water mixing, LiPF6Quality in the mixture is 1wt%, and the temperature of mixture stirring is 25 DEG C, and mixing time is
24h.In an oven dry 120 DEG C, drying time 1h, then in Muffle furnace calcine 350 DEG C, time 2h, obtain fluorine from
Son doping and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode LiFePO4-2。
Embodiment 3
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method, comprising the following steps:
LiFePO4Preparation method: NH4H2PO4、Fe(NO3)3·9H2O and glucose are dissolved in deionized water, will be mixed
Liquid, which is transferred in reaction kettle, reacts 160 DEG C, and time 9h naturally cools to room temperature, dry with water and ethanol washing, calcining.?
Calcined sample and Li2CO3Carry out mixing and ball milling 2h, NH4H2PO4: Fe (NO3)3·9H2O:Li2CO3: mole of glucose
Than for 1:1.1:1.1:1.2.It calcines again, temperature is 800 DEG C, calcination time 10h, and calcining atmosphere is H2-N2Atmosphere, screening
Obtain LiFePO4。
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode LiFePO4- 3 preparation method: LiPF6、
LiFePO4It is mixed with deionized water, LiPF6Quality in the mixture is 2wt%, and the temperature of mixture stirring is 30 DEG C, stirring
Time is 48h.120 DEG C, drying time 2h are dried in an oven, 400 DEG C are then calcined in Muffle furnace, time 3h is obtained
To fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode LiFePO4-3。
Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode electrochemistry prepared by 4 Examples 1 to 3 of embodiment
Performance test
(1) fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode LiFePO4- 1 to LiFePO4- 3 and pure phase
LiFePO4Capacity, capacity retention ratio and coulombic efficiency data under 1C current density after 100 circle of circulation is as shown in table 1:
Table 1: capacity, capacity retention ratio and the coulombic efficiency of each material
From table 1 it follows that F-Doping and LiF coat LiFePO4Capacity after 100 circle of composite material circulation is obvious
Higher than pure phase LiFePO4, capacity retention ratio is compared with pure phase LiFePO48% or so is improved, and coulombic efficiency also significantly improves.
(2) by LiFePO4- 1~LiFePO4- 3 randomly select the battery after 5 chemical conversions, before room temperature storage, charging one
Secondary, electric discharge is primary, recharges once, and the primary capacity of record electric discharge is C1, storage 28 days are stood under room temperature (25 ± 2 DEG C)
Afterwards: electric discharge is primary, recording capacity C2.The C of record1、C2With recovery rate (C2/C1) as shown in table 2:
Table 2: the capacity C 1 and C2 and recovery rate of each material
As can be seen from Table 2, LiFePO4The recovery rate of -1 battery is maintained between 95.6~96.9%, LiFePO4- 2 electricity
The recovery rate in pond is maintained between 97.9~98.9%, LiFePO4The recovery rate of -3 batteries is maintained between 96.9~97.5%,
The battery recovery rate of three is all very good.
The content that this specification is not described in detail belongs to the prior art well known to professional and technical personnel in the field.
Claims (6)
1. fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method, it is characterised in that: including by hexafluoro
Lithium phosphate and LiFePO4 mixture are add to deionized water, and after 20 DEG C~30 DEG C stirring 12h~48h, are put into baking oven
In 100 DEG C~120 DEG C dry 0.5h~2h, then it is placed in again in Muffle furnace in 300 DEG C~400 DEG C calcining 1h~3h；According to matter
Percentage meter is measured, the lithium hexafluoro phosphate accounts for the 0.5%~2% of amount of the mixture.
2. according to claim 1 fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method,
Be characterized in that: according to mass percentage, the lithium hexafluoro phosphate accounts for 0.5%, 1% or the 2% of amount of the mixture.
3. according to claim 1 fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method,
Be characterized in that: the LiFePO4 is prepared by the following method:
(1) ammonium dihydrogen phosphate, Fe(NO3)39H2O and glucose are dissolved in deionized water, are heated to 120 DEG C~160 DEG C reactions
It after 3h~9h, is cooled to room temperature, obtained solid successively through water and ethanol washing, drying, calcining, obtains intermediate；
(2) it by after the intermediate and lithium carbonate mixing and ball milling 2h~4h, in 600 DEG C~800 DEG C calcining 6h~10h, sieves
To LiFePO4；
Wherein, the molar ratio of the ammonium dihydrogen phosphate, Fe(NO3)39H2O, glucose and lithium carbonate be 1:0.9~1.1:0.9~
1.1:1.0~1.2.
4. according to claim 3 fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method,
Be characterized in that: the ammonium dihydrogen phosphate, Fe(NO3)39H2O, glucose and lithium carbonate molar ratio be 1:0.9:0.9:1.0；Or
The molar ratio of ammonium dihydrogen phosphate, Fe(NO3)39H2O described in person, glucose and lithium carbonate is 1:1:1:1；Or the di(2-ethylhexyl)phosphate
Hydrogen ammonium, Fe(NO3)39H2O, glucose and lithium carbonate molar ratio be 1:1.1:1.1:1.2.
5. according to claim 3 or 4 fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method,
It is characterized by: the calcining is in H2-N2It is carried out in atmosphere.
6. fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode, which is characterized in that by any in Claims 1 to 5
Item is described fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method obtains.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110931735A (en) * | 2019-11-15 | 2020-03-27 | 中国科学院宁波材料技术与工程研究所 | Modified composite material, preparation method thereof, and positive electrode material and lithium battery comprising modified composite material |
| CN114933336A (en) * | 2022-06-21 | 2022-08-23 | 宜宾锂宝新材料有限公司 | Fluorine-phosphorus chaperone doped ternary precursor, preparation method thereof and ternary material |
| CN116072961A (en) * | 2023-03-07 | 2023-05-05 | 中国科学院宁波材料技术与工程研究所 | Core-shell sulfide solid electrolyte, preparation method and all-solid-state battery |
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| CN102593452A (en) * | 2012-03-22 | 2012-07-18 | 华南师范大学 | Method for preparing carbon-coated lithium iron phosphate material |
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| CN106207113A (en) * | 2016-07-15 | 2016-12-07 | 成都大学 | A kind of carbon-coated LiFePO 4 for lithium ion batteries of Fluorin doped and its preparation method and application |
| CN108511710A (en) * | 2018-03-22 | 2018-09-07 | 中南大学 | Lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof |
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| US20040258836A1 (en) * | 2003-06-23 | 2004-12-23 | Besenhard Jurgen Otto | Method for the synthesis of surface-modified materials |
| CN102593452A (en) * | 2012-03-22 | 2012-07-18 | 华南师范大学 | Method for preparing carbon-coated lithium iron phosphate material |
| CN103855393A (en) * | 2014-03-12 | 2014-06-11 | 桂林理工大学 | Preparation method of lithium iron phosphate with excellent rate performance and cycling performance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110931735A (en) * | 2019-11-15 | 2020-03-27 | 中国科学院宁波材料技术与工程研究所 | Modified composite material, preparation method thereof, and positive electrode material and lithium battery comprising modified composite material |
| CN114933336A (en) * | 2022-06-21 | 2022-08-23 | 宜宾锂宝新材料有限公司 | Fluorine-phosphorus chaperone doped ternary precursor, preparation method thereof and ternary material |
| CN114933336B (en) * | 2022-06-21 | 2023-06-23 | 宜宾锂宝新材料有限公司 | Fluorine-phosphorus chaperone doped ternary precursor, preparation method thereof and ternary material |
| CN116072961A (en) * | 2023-03-07 | 2023-05-05 | 中国科学院宁波材料技术与工程研究所 | Core-shell sulfide solid electrolyte, preparation method and all-solid-state battery |
| CN116072961B (en) * | 2023-03-07 | 2023-11-14 | 中国科学院宁波材料技术与工程研究所 | Core-shell sulfide solid electrolyte, preparation method and all-solid-state battery |
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