CN110416541A - A kind of preparation method of the modified phosphate iron lithium of morphology controllable - Google Patents
A kind of preparation method of the modified phosphate iron lithium of morphology controllable Download PDFInfo
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- CN110416541A CN110416541A CN201910629765.4A CN201910629765A CN110416541A CN 110416541 A CN110416541 A CN 110416541A CN 201910629765 A CN201910629765 A CN 201910629765A CN 110416541 A CN110416541 A CN 110416541A
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- 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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- 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
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Abstract
The present invention provides a kind of preparation method of the modified phosphate iron lithium of morphology controllable, belongs to power battery anode material technical field.Main technical schemes are that source of iron is distributed in Aqueous Solutions of Polyethylene Glycol, it is dissolved to source of iron, phosphorus source is added in polyglycol solution, the aqueous solution of lithium source is added thereto, add manganese sulfate, coating material is added after finally stirring and forms product, product is transferred in flask, modified phosphate iron lithium is prepared using oil bath heating reaction；The mass ratio of ethylene glycol and water is 0.2-0.8 in the ethylene glycol solution；The lithium source is soluble lithium salt；The source of iron is molysite and ferrous salt.The present invention is controlled by pattern, and the tap density of LiFePO 4 material can achieve 1.8g/cm3。
Description
Technical field
The invention belongs to power battery anode material technical field more particularly to a kind of modified phosphate iron lithiums of morphology controllable
Preparation method.
Background technique
The high circulation performance of lithium iron phosphate positive material, high safety performance, low cost and it is environmental-friendly the features such as make it
There is prominent application prospect in power lithium-ion battery, shortcoming be it poorly conductive and lithium ion diffusion velocity it is slow,
And compacted density is lower, the microscopic appearance and chemical structure of this and lithium iron phosphate positive material have great association.Wherein, ball
Contact area between the lithium iron phosphate particles of shape is smaller, is not susceptible to agglomeration and tap density is high；The ferric phosphate of sheet
The migration path of lithium intermediate ion through-thickness is short, is able to ascend the conductivity of material.The side of main synthesizing iron lithium phosphate at present
Method is ferrous oxalate high temperature solid-state method, can not preferably control the uniform doping and pattern of LiFePO4, and additional amount
It is difficult to control accurately with the time, causes the stability between different batches poor and higher cost.
Summary of the invention
To overcome the shortcomings of existing technologies, the present invention provides a kind of preparation method of the modified phosphate iron lithium of morphology controllable,
The lithium iron phosphate nano material morphology controllable of preparation, and it is at low cost.Technical scheme is as follows: a kind of morphology controllable changes
Property LiFePO4 preparation method, source of iron is distributed in Aqueous Solutions of Polyethylene Glycol, to source of iron dissolve, poly- second two is added in phosphorus source
In alcoholic solution, the aqueous solution of lithium source is added thereto, adds manganese sulfate, coating material is added after finally stirring and forms production
Product is transferred in flask by object, prepares modified phosphate iron lithium using oil bath heating reaction；
The mass ratio of ethylene glycol and water is 0.2-0.8 in the ethylene glycol solution；
The lithium source is soluble lithium salt；
The source of iron is molysite and ferrous salt.
Further: the concentration of the coating material is 0.05-0.1g/mL；The time of the stirring is that 3-5 is small
When；The oil bath temperature is 120-130 DEG C, is reacted 4-5 hours；The pattern of the modified phosphate iron lithium is spherical.
Further: the concentration of the coating material is 0.2-0.25g/mL；The time of the stirring is that 6-8 is small
When；The oil bath temperature is 100-110 DEG C, is reacted 7-9 hours；The pattern of the modified phosphate iron lithium is flower-shaped.
It is further: the phosphorus source be in lithium dihydrogen phosphate, metaphosphoric acid and ammonium metaphosphate any one or a few is mixed
It closes.
Further: the coating material is appointing in polyethylene glycol, acetylactone, octylphenol ether and polyacrylic acid
The one or more of mixing of meaning.
Beneficial effects of the present invention are as follows:
(1) it is controlled by pattern, the tap density of LiFePO 4 material can achieve 1.8g/cm3；Conventional method system at present
The tap density of the LiFePO4 obtained is up to 1.7g/cm3, and it is currently, limitation LiFePO4 application that energy density is lower
Principal element, the raising of tap density can effectively improve the energy density of LiFePO4, expand its application range.
(2) molecular structure of surfactant is presented amphiphilic, can be adsorbed on the surface of solids, the steric hindrance effect of long chain
It should can avoid the reunion of nanoparticle, and micelle, reverse micelle, microemulsion, vesica, liquid crystal can be self-assembly of in the solution
Etc. various ordered aggregations, the microenvironment of these aggregations can be used as microreactor or template, to realize to nano material
The regulation of pattern, due to the addition of surfactant, the reaction time is greatly shortened, and reaction temperature has certain reduction, reaction
Controllable-rate, more evenly, while cost substantially reduces pattern.
(3) presence of ethylene glycol can provide a micro- reaction environment, regulate and control micro- reaction environment by adjusting alcohol water ratio,
The control of alcohol water ratio is so that morphology controllable, by adjusting alcohol water ratio, it can be achieved that in the size control of ball and floriform appearance
The control of the thickness of piece.
(4) it is reacted using oil bath heating, more traditional hydro-thermal reaction, condition is more controllable, and the consistency between batch improves,
Mass production easy to accomplish, and cost reduces.
Detailed description of the invention
Fig. 1 is the picture of spherical LiFePO 4；
Fig. 2 is the picture of flower-shaped LiFePO4.
Specific embodiment
It is clear in order to be more clear purpose, technical solution and the advantageous effects of invention, below in conjunction with specific implementation
Mode, the present invention will be described in further detail.It should be understood that specific embodiment described in this specification is only
It is to be not intended to limit the present invention to explain the present invention.
Embodiment 1
(1) 20mL ethylene glycol is distributed in 20mL second level water, 300rpm magnetic agitation 2min；(2) 2.78g sulfuric acid is sub-
Iron is added in glycol water, after continuing stirring to ferrous sulfate dissolution；0.96g ammonium metaphosphate is added, stirs 10min；
(3) 1.65g lithium sulfate is added to 20mL water to stir to dissolution, pours into above-mentioned solution, is stirred to react
20min；
(4) stirring of reaction system is kept, 0.2g manganese sulfate is added in reaction system, stirs 5min；
(5) 6g polyethylene glycol is added to be added in system, after stirring 5h, oil bath keeps 130 DEG C of 4h of temperature, obtains nanosphere
Shape modified phosphate iron lithium.
Embodiment 2
(1) 35mL ethylene glycol is distributed in 35mL second level water, 300rpm magnetic agitation 2min；
(2) 1.27g frerrous chloride is added in glycol water, after continuing stirring to ferrous sulfate dissolution；It is added
0.80g metaphosphoric acid stirs 10min；
(3) 1.65g lithium sulfate is added to 15mL water to stir to dissolution, pours into above-mentioned solution, is stirred to react
20min；
(4) stirring of reaction system is kept, 0.2g manganese sulfate is added in reaction system, stirs 5min；
(5) 3g acetylactone is added and 3.38g polyethylene glycol is added in system, after stirring 4h, oil bath keeps temperature 125
DEG C reaction 4.5h, obtain the spherical modified phosphate iron lithium of nanometer.
Embodiment 3
(1) 40mL ethylene glycol is distributed in 45mL second level water, 300rpm magnetic agitation 2min；
(2) 1.27g frerrous chloride is added in glycol water, after continuing stirring to ferrous sulfate dissolution；It is added
0.40g metaphosphoric acid and 0.48g ammonium metaphosphate stir 10min；
(3) 1.65g lithium sulfate is added to 10mL water to stir to dissolution, pours into above-mentioned solution, is stirred to react
20min；
(4) stirring of reaction system is kept, 0.2g manganese sulfate is added in reaction system, stirs 5min；
(5) 2g acetylactone is added and 2.75g polyethylene glycol is added in system, after stirring 5h, oil bath keeps temperature 130
DEG C reaction 5h, obtain the spherical modified phosphate iron lithium of nanometer.
Embodiment 4
(1) 10mL ethylene glycol is distributed in 35mL second level water, 300rpm magnetic agitation 2min；(2) 2.78g sulfuric acid is sub-
Iron is added in glycol water, after continuing stirring to ferrous sulfate dissolution；0.96g ammonium metaphosphate is added, stirs 10min；
(3) 1.65g lithium sulfate is added to 20mL water to stir to dissolution, pours into above-mentioned solution, is stirred to react
20min；
(4) stirring of reaction system is kept, 0.2g manganese sulfate is added in reaction system, stirs 5min；
(5) 16.25g polyethylene glycol is added to be added in system, after stirring 8h, oil bath keeps 110 DEG C of reaction 7h of temperature, obtains
To flower-shaped modified phosphate iron lithium.
Embodiment 5
(1) 15mL ethylene glycol is distributed in 35mL second level water, 300rpm magnetic agitation 2min；
(2) 1.27g frerrous chloride is added in glycol water, after continuing stirring to ferrous sulfate dissolution；It is added
0.80g metaphosphoric acid stirs 10min；
(3) 1.65g lithium sulfate is added to 20mL water to stir to dissolution, pours into above-mentioned solution, is stirred to react
20min；
(4) stirring of reaction system is kept, 0.2g manganese sulfate is added in reaction system, stirs 5min；
(5) 8.15g acetylactone is added and 7.6g polyethylene glycol is added in system, after stirring 7h, oil bath keeps temperature
105 DEG C of reaction 8h, obtain flower-shaped modified phosphate iron lithium.
Embodiment 6
(1) 20mL ethylene glycol is distributed in 35mL second level water, 300rpm magnetic agitation 2min；
(2) 1.27g frerrous chloride is added in glycol water, after continuing stirring to ferrous sulfate dissolution；It is added
0.40g metaphosphoric acid and 0.48g ammonium metaphosphate stir 10min；
(3) 1.65g lithium sulfate is added to 20mL water to stir to dissolution, pours into above-mentioned solution, is stirred to react
20min；
(4) stirring of reaction system is kept, 0.2g manganese sulfate is added in reaction system, stirs 5min；
(5) 6g acetylactone is added and 9g polyethylene glycol is added in system, after stirring 6h, oil bath is kept for 100 DEG C of temperature
9h is reacted, the spherical modified phosphate iron lithium of nanometer is obtained.
Above-described embodiment is only intended to citing and explanation of the invention, and is not intended to limit the invention to described
In scope of embodiments.Furthermore it will be appreciated by persons skilled in the art that the present invention is not limited to the above embodiment, according to this hair
Bright introduction can also make more kinds of variants and modifications, these variants and modifications all fall within present invention model claimed
In enclosing.
Claims (5)
1. a kind of preparation method of the modified phosphate iron lithium of morphology controllable, which is characterized in that source of iron is distributed to polyethylene glycol water
It in solution, is dissolved to source of iron, phosphorus source is added in polyglycol solution, the aqueous solution of lithium source is added thereto, adds sulfuric acid
Manganese is added coating material after finally stirring and forms product, product is transferred in flask, reacts preparation using oil bath heating and is modified
LiFePO4；
The mass ratio of ethylene glycol and water is 0.2-0.8 in the ethylene glycol solution；
The lithium source is soluble lithium salt；
The source of iron is molysite and ferrous salt.
2. the preparation method of the modified phosphate iron lithium of morphology controllable as described in claim 1, it is characterised in that:
The concentration of the coating material is 0.05-0.1g/mL；
The time of the stirring is 3-5 hours；
The oil bath temperature is 120-130 DEG C, is reacted 4-5 hours；
The pattern of the modified phosphate iron lithium is spherical.
3. the preparation method of the modified phosphate iron lithium of morphology controllable as described in claim 1, it is characterised in that: the surface
The concentration of dressing agent is 0.2-0.25g/mL；
The time of the stirring is 6-8 hours；
The oil bath temperature is 100-110 DEG C, is reacted 7-9 hours；
The pattern of the modified phosphate iron lithium is flower-shaped.
4. the preparation method of the modified phosphate iron lithium of morphology controllable as described in claim 1, it is characterised in that: the phosphorus source
For any one or a few mixing in lithium dihydrogen phosphate, metaphosphoric acid and ammonium metaphosphate.
5. the preparation method of the modified phosphate iron lithium of morphology controllable as described in claim 1, it is characterised in that: the surface
Dressing agent is any one or a few mixing in polyethylene glycol, acetylactone, octylphenol ether and polyacrylic acid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102655233A (en) * | 2011-12-14 | 2012-09-05 | 中聚电池研究院有限公司 | Preparation method of LiFePO4/C anode material of lithium ion battery |
| CN107381528A (en) * | 2017-07-27 | 2017-11-24 | 深圳市沃特玛电池有限公司 | A kind of method for controlling LiFePO4 pattern |
| CN108390057A (en) * | 2018-03-07 | 2018-08-10 | 南京理工大学 | The preparation method of additive Mn lithium iron phosphate electrode material |
| CN109742340A (en) * | 2018-12-14 | 2019-05-10 | 南京国轩电池有限公司 | A kind of iron manganese phosphate for lithium composite material and preparation method, application |
-
2019
- 2019-07-12 CN CN201910629765.4A patent/CN110416541A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102655233A (en) * | 2011-12-14 | 2012-09-05 | 中聚电池研究院有限公司 | Preparation method of LiFePO4/C anode material of lithium ion battery |
| CN107381528A (en) * | 2017-07-27 | 2017-11-24 | 深圳市沃特玛电池有限公司 | A kind of method for controlling LiFePO4 pattern |
| CN108390057A (en) * | 2018-03-07 | 2018-08-10 | 南京理工大学 | The preparation method of additive Mn lithium iron phosphate electrode material |
| CN109742340A (en) * | 2018-12-14 | 2019-05-10 | 南京国轩电池有限公司 | A kind of iron manganese phosphate for lithium composite material and preparation method, application |
Non-Patent Citations (3)
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| 万异 等: "锰掺杂磷酸铁锂的合成和电化学性能研究", 《徐州工程学院学报（自然科学版）》 * |
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