CN106340645A - Preparation method of hydroxyl iron phosphate-based battery material with novel morphology - Google Patents
Preparation method of hydroxyl iron phosphate-based battery material with novel morphology Download PDFInfo
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- CN106340645A CN106340645A CN201610809344.6A CN201610809344A CN106340645A CN 106340645 A CN106340645 A CN 106340645A CN 201610809344 A CN201610809344 A CN 201610809344A CN 106340645 A CN106340645 A CN 106340645A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 preparation method of a hydroxyl iron phosphate-based battery material with novel morphology. The preparation method comprises the following steps of dissolving soluble iron salt in water, stirring and dispersing to prepare a 0.1-0.3 M solution, adding trisodium phosphate according to a mole ratio of soluble iron salt to trisodium phosphate as 1:(0.8-1.2), continuously stirring for 10-30 min, adding to-be-doped salt according to the mass ratio of trisodium phosphate to the to-be-doped salt as 1:(0.004-0.02), continuously stirring for 5 min, transferring an obtained mixed solution to a 100 ml reaction kettle, placing in an oven, performing reaction at 140-180 DEG C for 18-36 h, performing suction filtration after the reaction finishes, and putting in the oven at 80-100 DEG C for drying treatment for 4-10 h to form the material. According to the method, the large-scale hydroxyl iron phosphate material with the standardized morphology, good dispersity and uniform dimension is prepared by a simple hydrothermal method.
Description
Technical field
The present invention relates to battery material preparation field and in particular to a kind of novelty pattern di iron-based battery material
Preparation method.
Background technology
Current with coal, oil, the big main energy sources reserves of natural gas three increasingly minimizing, and the environment thus causing is dirty
Going from bad to worse of the problems such as dye and global warming, develops cleaning Renewable resource, such as solar energy, wind energy, tide energy etc., receives
The highest attention of numerous scholars.But the effect of these regenerative resources possesses discontinuous feature it is desirable to utilize on a large scale
These regenerative resources, then must possess matched energy storage device.
Lithium ion battery has that energy density is high, self discharge stream is little, safe because of it, can high current charge-discharge, circulation
Often, the advantages of life-span length, it is increasingly being applied to mobile phone, notebook computer, digital camera, electric automobile, aviation boat
My god, the multiple fields such as military equipment.And the LiFePO 4 material possessing olivine structural possesses extraordinary safety, circulation longevity
The features such as life long, with low cost, environmental protection, it is considered the head that cobalt acid lithium can be replaced to become anode material for lithium-ion batteries of future generation
Choosing.
Iron phosphate is the de- lithium product of lifepo4, can as the presoma of this material, thus be synthesizing iron lithium phosphate material
One of main raw material of material.The structure of iron phosphate is close with LiFePO4, as long as controlling the structure of iron phosphate, shape well
And granular size, the just performance of energy indirect control LiFePO 4 material.Currently prepare LiFePO4 method mainly have solid phase method,
Colloidal sol -- gel method, coprecipitation etc..Although solid phase method process is simple, low cost, obtained material electrochemical stability
Difference, crystal morphology are uncontrollable, distribution of sizes is uneven.And additive method complex operation, relatively costly.A kind of letter is therefore provided
Single, convenient prepare extensive pattern to unify di ferrum to be necessary.
Content of the invention
For solving the above problems, the invention provides a kind of preparation side of the di iron-based battery material of novelty pattern
Method, by simple hydro-thermal method, is prepared for extensive regular appearance, possesses the di ferrum of good dispersion, size uniformity
Material.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of preparation method of the di iron-based battery material of novelty pattern, comprises the steps:
S1, soluble ferric iron salt is dissolved in water, dispersed with stirring, prepare the solution of 0.1--0.3m；
S2, the ratio addition tertiary sodium phosphate being 1: 0.8--1.2 in the mol ratio of soluble ferric iron salt and tertiary sodium phosphate, continue
Stirring 10--30min；
S3, the ratio addition desire doping salts being 1:0.004--0.02 in the mass ratio of tertiary sodium phosphate and salt to be adulterated, hold
Continuous stirring 5min；
S4, the mixed solution of step s4 gained is transferred in 100ml reactor, and is positioned over baking oven, in 140--180
18--36h is reacted at DEG C；
After s5, reaction terminate, sucking filtration, it is placed in drying and processing 4--10h in 80--100 DEG C of baking oven, obtain material.
Preferably, described salt to be adulterated be mgcl2 6h2o, mncl2 4h2o, cocl2 6h2o, nicl2 6h2o,
One or more in alcl3 6h2o, nh4vo3, sncl4 5h2o, licl.
Preferably, described soluble ferric iron salt is trivalent iron salt, such as ferric chloride, ferric nitrate.
Preferably, the hydrothermal temperature in described step s4 be 140--180 DEG C, the time be 18--36h.
The method have the advantages that
First pass through the di ferrum after hydro-thermal method directly prepares di ferrum or doping, then pass through low concentration again
Hydrochloric acid carry out short time post processing be prepared for that pattern on a large scale is regular, possess good dispersion, the di of size uniformity
Iron material；Preparation process is simple, product that is with low cost, obtaining possess good dispersibility, soilless sticking phenomenon, and size is equal
One, regular appearance.After the present invention adds desire dopant ion in water-heat process, product morphology and dispersibility will not occur larger
Change.And this product can be readily available LiFePO4 by carbothermic method.
Brief description
Fig. 1 is prepared di ferrum scanning electron microscope (SEM) photograph in the embodiment of the present invention 1.
Fig. 2 is prepared di ferrum xrd curve chart in the embodiment of the present invention 1.
Fig. 3 is prepared di ferrum scanning electron microscope (SEM) photograph in the embodiment of the present invention 2.
Fig. 4 is prepared di ferrum scanning electron microscope (SEM) photograph in the embodiment of the present invention 3.
Fig. 5 is prepared di ferrum scanning electron microscope (SEM) photograph in the embodiment of the present invention 4.
Fig. 6 is prepared mg/mn/co/ni/v/sn/li doping di ferrum scanning electron microscope in the embodiment of the present invention 5
Figure；
In figure: a, b, c, d, e, f, g, h be respectively adulterate sncl4 5h2o, nicl2 6h2o, zn (no3) 2 6h2o,
Mgcl2 6h2o, cocl2 6h2o, nh4vo3, mncl2 4h2o, 1%licl, 20%licl.
Specific embodiment
In order that objects and advantages of the present invention become more apparent, with reference to embodiments the present invention is carried out further
Describe in detail.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to limit this
Bright.
Embodiment 1
With fecl3 6h2o and na3po4 12h2o as raw material, fe:p carries out dispensing for 1:1 to the present embodiment in molar ratio,
Di ferrum is prepared using hydro-thermal method.It is specific as follows: the fecl3 6h2o weighing 5.406g is dissolved in a small amount of deionized water,
Then add the na3po4 12h2o of 7.602g, after continuously stirred 20 minutes, add appropriate amount of deionized water so that entirely molten
Liquid amasss as 100ml.Obtained solution is transferred in politef lining, hydro-thermal 24h at 140 DEG C.Afterwards by it
Centrifugation, washing simultaneously dry 2h at 80 DEG C.The product obtaining after drying is re-dissolved in the hydrochloric acid solution of the 1mol/l of 100ml
In, it is centrifuged after continuously stirred 30min, washs and drying obtains final product trihydroxy iron phosphate again.
, as shown in figure 1, we can be observed how from figure, the pattern of product is very for prepared trihydroxy iron phosphate pattern
Regular and unified, it is layered laminate corner star looks.In addition also very unified in its size.Fig. 2 is the xrd analysis chart of product,
From in figure, we can draw product in nature, is trihydroxy iron phosphate really.
Embodiment 2
With fecl3 6h2o and na3po4 12h2o as raw material, fe:p carries out dispensing for 1: 1 to the present embodiment in molar ratio,
Di ferrum is prepared using hydro-thermal method.It is specific as follows: the fecl3 6h2o weighing 5.406g is dissolved in a small amount of deionized water,
Then add the na3po4 12h2o of 7.602g, after continuously stirred 20 minutes, add appropriate amount of deionized water so that entirely molten
Liquid amasss as 100ml.Obtained solution is transferred in politef lining, hydro-thermal 24h at 180 DEG C.Afterwards by it
Centrifugation, washing simultaneously dry 2h at 80 DEG C.The product obtaining after drying is re-dissolved in the hydrochloric acid solution of the 1mol/l of 100ml
In, it is centrifuged after continuously stirred 30min, washs and drying obtains final product trihydroxy iron phosphate again.
, as shown in figure 3, we can be observed how from figure, the pattern of product is very for prepared trihydroxy iron phosphate pattern
Regular and unified, it is Bamboo-shaped cross pattern.
Embodiment 3
With fecl3 6h2o and na3po4 12h2o as raw material, fe:p is 1: 0.85--1.15 to the present embodiment in molar ratio
Carry out dispensing, di ferrum is prepared using hydro-thermal method.Specific as follows: the fecl3 6h2o weighing four parts of 5.406g is molten respectively
In a small amount of deionized water, then it is separately added into the na3po4 12h2o of 6.462g, 7.222g, 7.983g, 8.743g again, hold
After continuous stirring 20 minutes, add appropriate amount of deionized water so that whole liquor capacity is 100ml.Obtained solution is transferred to
In politef lining, hydro-thermal 24h at 140 DEG C.It is centrifuged afterwards, washed and dried 2h at 80 DEG C.After drying
The product obtaining is re-dissolved in the hydrochloric acid solution of the 1mol/l of 100ml, is centrifuged, washs and dry again after continuously stirred 30min
Dry obtain final product.
Prepared di ferrum pattern as shown in figure 4, we can be observed how from figure, the pattern of product with
The change of fecl3 6h2o and na3po4 12h2o mol ratio and occur significantly to change.Add with na3po4 12h2o
The increase of amount, the pattern of product will produce the transformation from ball-type to layered laminate corner star.And, from Fig. 4 it will be seen that no
It is which kind of product by four kinds of products, but its pattern and size are all very unified on extensive.
Embodiment 4
With fe (no) 3 9h2o and na3po4 12h2o as raw material, fe:p is 1: 0.85-- to the present embodiment in molar ratio
1.15 carry out dispensing, prepare di ferrum using hydro-thermal method.Specific as follows: fe (no) 3 9h2o weighing 8.08g is dissolved in less
In amount deionized water, then add the na3po4 12h2o of 6.462g, 7.222g, 7.983g, 8.743g, continuously stirred 20
After minute, add appropriate amount of deionized water so that whole liquor capacity is 100ml.Obtained solution is transferred to polytetrafluoroethyl-ne
In alkene lining, hydro-thermal 24h at 140 DEG C.It is centrifuged afterwards, washed and dried 2h at 80 DEG C.The product obtaining after drying
Thing is re-dissolved in the hydrochloric acid solution of the 1mol/l of 100ml, is centrifuged, washs and drying obtains the most again after continuously stirred 30min
End-product trihydroxy iron phosphate.
, as shown in figure 5, we can be observed how from figure, the pattern of product is with fe for prepared di ferrum pattern
(no) change of 3 9h2o and na3po4 12h2o mol ratio and occur significantly to change.
Embodiment 5
With fecl3 6h2o and na3po4 12h2o as raw material, fe:p carries out dispensing for 1: 1 to the present embodiment in molar ratio,
Di ferrum is prepared using hydro-thermal method.It is specific as follows: the fecl3 6h2o weighing 5.406g is dissolved in a small amount of deionized water,
Then add the na3po4 12h2o of 7.602g, after continuously stirred 20 minutes, add 0.122g sncl4 5h2o,
Mgcl2 6h2o, 0.166g's of zn (no3) 2 6h2o, 0.193g of nicl2 6h2o, 0.142g of 0.166g
The licl of licl, 0.6g of mncl2 4h2o, 0.03g of nh4vo3,0.142g of cocl2 6h2o, 0.09g, adds appropriate
Deionized water is so that whole liquor capacity is 100ml.Obtained solution is transferred in politef lining, in 140 DEG C
Lower hydro-thermal 24h.It is centrifuged afterwards, washed and dried 2h at 80 DEG C.The product obtaining after drying is re-dissolved in 100ml's
In the hydrochloric acid solution of 1mol/l, it is centrifuged after continuously stirred 30min, washs and dry again and obtain final product trihydroxy phosphoric acid
Ferrum.
, as shown in fig. 6, we can be observed how from figure, the pattern of product is very for prepared trihydroxy iron phosphate pattern
Regular and unified, it is corner star looks.In addition also very unified in its size.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (4)
1. a kind of preparation method of the di iron-based battery material of novelty pattern is it is characterised in that comprise the steps:
S1, soluble ferric iron salt is dissolved in water, dispersed with stirring, prepare the solution of 0.1-0.3m；
S2, the ratio addition tertiary sodium phosphate being 1:0.8-1.2 in the mol ratio of soluble ferric iron salt and tertiary sodium phosphate, continuously stirred
10-30min；
S3, the ratio addition desire doping salts being 1:0.004-0.02 in the mass ratio of tertiary sodium phosphate and salt to be adulterated, persistently stir
Mix 5min；
S4, the mixed solution of step s4 gained is transferred in 100ml reactor, and is positioned over baking oven, anti-at 140-180 DEG C
Answer 18-36h；
After s5, reaction terminate, sucking filtration, it is placed in drying and processing 4-10h in 80-100 DEG C of baking oven, obtain material.
2. a kind of preparation method of the di iron-based battery material of novelty pattern as claimed in claim 1, its feature exists
In, described salt to be adulterated be mgcl2 6h2o, mncl2 4h2o, cocl2 6h2o, nicl2 6h2o, alcl3 6h2o,
One or more in nh4vo3, sncl4 5h2o, licl.
3. a kind of preparation method of the di iron-based battery material of novelty pattern as claimed in claim 1, its feature exists
In described soluble ferric iron salt is trivalent iron salt.
4. a kind of preparation method of the di iron-based battery material of novelty pattern as claimed in claim 1, its feature exists
In the hydrothermal temperature in described step s4 is 140-180 DEG C, the time is 18-36h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113078328A (en) * | 2021-03-17 | 2021-07-06 | 浙江大学 | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
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| CN103311543A (en) * | 2012-12-10 | 2013-09-18 | 上海电力学院 | Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof |
| CN103539097A (en) * | 2013-10-30 | 2014-01-29 | 渤海大学 | Preparation method of multi-shape alkaline manganese phosphate microcrystal |
| CN103633322A (en) * | 2012-08-23 | 2014-03-12 | 北京有色金属研究总院 | Preparation method for high-density spherical lithium iron phosphate material |
| CN105024073A (en) * | 2015-08-10 | 2015-11-04 | 河南理工大学 | Cathode material Fe<2.95>(PO4)2(OH)2 of lithium ion battery and preparation method thereof |
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2016
- 2016-09-08 CN CN201610809344.6A patent/CN106340645A/en active Pending
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| CN101276910A (en) * | 2008-05-16 | 2008-10-01 | 北京工业大学 | Preparation of Fe5(PO4)4(OH)3 and application thereof |
| CN103633322A (en) * | 2012-08-23 | 2014-03-12 | 北京有色金属研究总院 | Preparation method for high-density spherical lithium iron phosphate material |
| CN103311543A (en) * | 2012-12-10 | 2013-09-18 | 上海电力学院 | Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113078328A (en) * | 2021-03-17 | 2021-07-06 | 浙江大学 | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
| CN113078328B (en) * | 2021-03-17 | 2023-01-31 | 浙江大学 | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
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Application publication date: 20170118 |