CN102104143A - Hydrothermal synthesis method of composite material for high-performance power battery - Google Patents
Hydrothermal synthesis method of composite material for high-performance power battery Download PDFInfo
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Abstract
The invention relates to a hydrothermal synthesis method of a composite material for a high-performance power battery, in particular to a hydrothermal synthesis method of a lithium ion battery positive pole material LiFePO4 doped with grapheme, comprising the following steps of: mixing a certain amount of ferrous sulfate, phosphoric acids and ascorbic acids, and then dissolving into a certain amount of deionized water; adding a certain amount of lithium hydroxide solutions; then dispersing the grapheme into ethanol, and then adding to a mixed solution; delivering the mixed solution to a high-pressure reaction kettle, sealing, and carrying out hydrothermal reaction; filtering, washing and drying hydrothermal reaction products; and roasting dried substances under a certain condition. The size distribution of the related material prepared by taking the grapheme as a carbon source is concentrated on a nanoscale, therefore an ion transmission path is effectively shortened; a carbon cladding layer is formed on the granular surface of the material by using the grapheme, therefore the transmission efficiency of electrons is enhanced, and high-power charge and discharge are facilitated.
Description
Technical field
The invention belongs to photovoltaic and energy storage material industrial field, the in-situ doped preparation of Graphene specifically prepares the hydrothermal synthesis method of LiFePO4/C composite material.
Background technology
Lithium rechargeable battery is as the new generation of green secondary energy sources, and characteristics such as have energy density height, environmental friendliness, security performance excellence, have extended cycle life become a kind of alternative energy source of tool potentiality.Anode material for lithium-ion batteries mainly comprises cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2), LiMn2O4 (LiMn
2O
4) and LiFePO4 (LiFePO
4) etc.Because factors such as price, security performances, LiFePO4 is the selection of the best of anode material for lithium-ion batteries.LiFePO4 has the theoretical capacity of 170mAh/g, 3.4V (vs Li/Li
+) platform voltage, excellent security energy and charge and discharge circulation life, cheap, the environmental friendliness of cost of material simultaneously, resource and the environmental issue of having avoided traditional lithium ion battery to face.But LiFePO4 self-conductance rate is lower, 10
-9The order of magnitude of S/m, its crystal structure can only provide the one dimension diffusion admittance for lithium ion, has limited the migration rate of lithium ion.Therefore if the application of realization LiFePO4 just must be carried out study on the modification to LiFePO4, improve the migration rate and the electronic conductivity of its inner lithium ion.Present achievement in research mainly adopts three kinds of methods to carry out modification: preparation has the crystal grain of nanoscale to shorten lithium ion diffusion length; Doped metal ion is to improve its intrinsic conductivity; The coated with conductive material improves conductivity.Among the preparation technology who has reported, the complex process of preparation nano-scale lithium iron phosphate, cost is too high, and particle size and particle size distribution are wayward; The method of doped metal ion exists doping, the unmanageable problem of doping position; Therefore studying maximum is at LiFePO4 surface coated with conductive material with carbon element, major part all is the method for utilization carbon thermal reduction, under hot conditions the organic substance pyrolysis is become carbon, is coated on the surface of LiFePO4, cause too growing up of material grains easily like this, limited the fast transferring of lithium ion.Graphene is the novel two-dimensional nano material with carbon element that a class monolayer carbon atom of discovery in 2004 is formed, it is the thinnest in the world present two-dimensional material, it is the elementary cell that makes up other dimension material with carbon element (as the zero dimension fullerene-based material, one dimension carbon nano-tube, three-dimensional graphite).Discover that Graphene has excellent electrochemical properties, its room temperature electron mobility reaches 10000cm
2/ S, moreover, Graphene also has advantages of excellent stability, the electrochemical window of broad and bigger specific area etc.If Graphene is incorporated in the LiFePO 4 material, utilize graphite rare that excellent performance can effectively improve the conductance of material, increase the contact area of material and electrolyte, thereby can well improve the performance of LiFePO4.
Doping prepares the method for composite ferric lithium phosphate material and preparation technology's patent thereof about Graphene to disclose some both at home and abroad, wherein, patent 200910155316.7 discloses a kind of Graphene or graphene oxide of directly adding in LiFePO4, pass through The high temperature anneal then, finally obtain the lithium iron phosphate anode active material of Graphene modification, but because this doping is not to be to carry out in the process that the LiFePO4 crystal forms, pattern and particle size that can not the better controlled LiFePO4.Patent 2010146161.3 discloses a kind of preparation method with the anode material for lithium-ion batteries that mixes, and he is LiFePO4 and the intercalated graphite alkene that will prepare, and the Graphene of graphene oxide or electronation directly mixes, and passes through annealing in process then.The same with top patent, this method does not fundamentally solve LiFePO4 particle size problem in the process that forms crystal yet.
Summary of the invention
A kind of high-performance electrokinetic cell hydrothermal synthesis method of composite material, technical problem to be solved is: become carbon encapsulated material to cause too growing up of material grains easily at the organic substance pyrolysis that exists in the current techniques, the shortcoming of limiting lithium ion fast transferring provides the hydrothermal synthesis method of the in-situ doped synthesizing iron lithium phosphate of a kind of Graphene/C material.In-situ doped by Graphene can control the formation speed of nucleus, thereby the size of control crystal grain finally obtains the crystallization of nano-sheet.The result shows that the LiFePO4 of this sheet/C material has good electrochemical.
The technical solution adopted in the present invention is:
A kind of high-performance electrokinetic cell hydrothermal synthesis method of composite material may further comprise the steps:
The first step, hydro-thermal is synthesized precursor:
Divalent iron salt is dissolved in the deionized water, add microcosmic salt and ascorbic acid, mix, lithium salts is dissolved in forms solution in the deionized water, in the mixed solution above then lithium salt solution being splashed under continuous stirring condition, make mol ratio Li: Fe: P=3: 1: 1, stir after 1～30 minute, add the scattered Graphene dispersion liquid of ethanol, form the mixed liquor of celadon, mixed liquor is transferred to reaction under high pressure mixed liquor is transferred in the autoclave, add magnetic force, sealing was 120～180 ℃ dimethyl-silicon oil bath internal reactions 2～10 hours.
Second step, the filtration of precursor, washing and drying:
Mixed liquor after the hydro-thermal reaction is taken out in reactor, through ageing after 12 hours, outwell supernatant liquor, the sediment of lower floor is used deionized water wash repeatedly, till in detecting, containing sulfate ion less than cleaning solution, then sediment is put in vacuumize in the vacuum drying chamber, baking temperature is 35～80 ℃.
The 3rd step, the precursor calcination process:
The precursor powder of previous step gained is put into little porcelain boat, carry out calcination process under the condition of the not protection of open close inert gas in tube furnace, sintering temperature is 500～800 ℃, and roasting time is 2～10 hours.
Above-mentioned divalent iron salt is for being the solution that raw material is mixed with by ferrous sulfate or frerrous chloride crystal, and concentration is ferrous ion 0.5～2mol/L.
Above-mentioned microcosmic salt is a kind of solution that is mixed with for raw material of phosphoric acid, diammonium hydrogen phosphate or ammonium dihydrogen phosphate, and concentration is phosphate anion 0.5～2mol/L.
Above-mentioned lithium salts is a kind of solution that is mixed with for raw material in lithium hydroxide, lithium carbonate, lithium acetate or the lithium chloride, and concentration is lithium concentration 0.5～2mol/L.
Above-mentioned antioxidant is a kind of solution that is mixed with for raw material in ascorbic acid or the oxalic acid crystal, and concentration is 0.01～0.1mol/L.
The consumption that above-mentioned graphite is rare is to account for 1%～10% of synthesizing iron lithium phosphate Theoretical Mass.
Above-mentioned drying is carried out in vacuum drying chamber, and purpose is for preventing that ferrous ion is oxidized in the predecessor, and baking temperature is 35～80 ℃, and be 10～20 hours drying time.
Above-mentioned inert protective gas is nitrogen or argon gas, and the temperature of roasting is 500～800 ℃ in tube furnace, and roasting time is 2～10 hours.Being set to of temperature programming wherein: the speed according to 10～30 ℃/min is warmed up to 500～800 ℃, is incubated 2～10 hours then, then according to the speed cooling of 1～50 ℃/min.
Beneficial effect:
The nano particle of the LiFePO4/C that makes by the inventive method, pass through the in-situ doped of Graphene, can in the environment of hydrothermal system, form a large amount of nucleus, thereby control the growth of LiFePO4 crystal effectively, finally can obtain the LiFePO4 crystal of nano-sheet, through performance characterization, the synthetic composite material of the method has good charge-discharge performance and cyclical stability, for the application of lithium ion battery provide that a kind of processing technology is simple, with low cost, capacity is high and safety is good anode material for lithium-ion batteries.
Embodiment
For technological means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1:
The LiFePO that the hydro thermal method synthesizing graphite alkene coats
4The method of nano particle is as follows, and initial feed is LiOHH
2O, FeSO
47H
2O, H
3PO
4, ascorbic acid (vitamin C) and graphene powder.Accurately take by weighing 5.561g FeSO
47H
2O and 0.053g ascorbic acid add the 20mL deionized water in small beaker, be stirred to dissolving fully, accurately measure the H of 1.369mL 85%
3PO
4Be added in the above-mentioned mixed liquor, the back that stirs forms jade-green A solution; Taking by weighing 2.798g LiOHH2O is dissolved in the deionized water of 60mL, LiOH solution slowly is added drop-wise in the above-mentioned A liquid Li that makes: Fe: P=3.0: 1.0: 1.0 (mol ratio), the dropping process is constantly being carried out under the stirring condition, along with the dropping of LiOH, form green muddy B liquid gradually; Accurately take by weighing in the absolute ethyl alcohol of the ultrasonic 20mL of being scattered in of 0.0316g Graphene (make phosphorus content is 1wt% in the product), dispersion liquid slowly is added drop-wise in the above-mentioned B liquid, form the C liquid predecessor of celadon.Then predecessor is transferred in the teflon-lined stainless steel autoclave sealing.Autoclave is put into oil bath, and constantly the following 150 ℃ of reactions of stirring condition are 5 hours.After reactant liquor fully cooled off, with product ageing 12 hours, suction filtration was washed to the greatest extent
After, 50 ℃ of vacuumize 10 hours, with the roasting in nitrogen atmosphere of dried product, 600 ℃ of roastings 5 hours finally obtain the powder of black.
Embodiment 2:
Initial feed is LiOHH
2O, FeSO
47H
2O, H
3PO
4, ascorbic acid (vitamin C) and graphene powder.Accurately take by weighing 5.561g FeSO
47H
2O and 0.053g ascorbic acid add the 20mL deionized water in small beaker, be stirred to dissolving fully, accurately measure the H of 1.369mL85%
3PO
4Be added in the above-mentioned mixed liquor, the back that stirs forms jade-green A solution; Take by weighing 2.798g LiOHH
2O is dissolved in the deionized water of 60mL, LiOH solution slowly is added drop-wise in the above-mentioned A liquid Li that makes: Fe: P=3: 1: 1 (mol ratio), dropping process along with the dropping of LiOH, form green muddy B liquid constantly carrying out under the stirring condition gradually; Accurately take by weighing in the absolute ethyl alcohol of the ultrasonic 20mL of being scattered in of 0.0948g Graphene (make phosphorus content is 3wt% in the product), dispersion liquid slowly is added drop-wise in the above-mentioned B liquid, form the C liquid predecessor of celadon.Then predecessor is transferred in the teflon-lined stainless steel autoclave sealing.Autoclave is put into oil bath, and constantly the following 150 ℃ of reactions of stirring condition are 5 hours.After reactant liquor fully cooled off, with product ageing 12 hours, suction filtration was washed to the greatest extent
After, 50 ℃ of vacuumize 10 hours, with the roasting in nitrogen atmosphere of dried product, 600 ℃ of roastings 5 hours finally obtain the powder of black.
Embodiment 3:
Initial feed is LiOHH
2O, FeSO
47H
2O, H
3PO
4, ascorbic acid (vitamin C) and graphene powder.Accurately take by weighing 5.561g FeSO
47H
2O and 0.053g ascorbic acid add the 20mL deionized water in small beaker, be stirred to dissolving fully, accurately measure the H of 1.369mL85%
3PO
4Be added in the above-mentioned mixed liquor, the back that stirs forms jade-green A solution; Take by weighing 2.798g LiOHH
2O is dissolved in the deionized water of 60mL, LiOH solution slowly is added drop-wise in the above-mentioned A liquid Li that makes: Fe: P=3: 1: 1 (mol ratio), dropping process along with the dropping of LiOH, form green muddy B liquid constantly carrying out under the stirring condition gradually; Accurately take by weighing in the absolute ethyl alcohol of the ultrasonic 20mL of being scattered in of 0.158g Graphene (make phosphorus content is 5wt% in the product), dispersion liquid slowly is added drop-wise in the above-mentioned B liquid, form the C liquid predecessor of celadon.Then predecessor is transferred in the teflon-lined stainless steel autoclave sealing.Autoclave is put into oil bath, and constantly the following 150 ℃ of reactions of stirring condition are 5 hours.After reactant liquor fully cooled off, with product ageing 12 hours, suction filtration was washed to the greatest extent
After, 50 ℃ of vacuumize 10 hours, with the roasting in nitrogen atmosphere of dried product, 800 ℃ of roastings 5 hours finally obtain the powder of black.
Embodiment 4
Initial feed is CH
3COOLi2H
2O, FeCl
24H
2O, (NH
4)
2HPO
4, ascorbic acid (vitamin C) and graphene powder.Accurately take by weighing 4.968g FeCl
24H
2O and 0.053g ascorbic acid add the 20mL deionized water in small beaker, be stirred to dissolving fully, accurately take by weighing 3.302g (NH
4)
2HPO
4Be added in the above-mentioned mixed liquor, the back that stirs forms jade-green A solution; Take by weighing 7.652gCH
3COOLiH
2O is dissolved in the deionized water of 60mL, LiOH solution slowly is added drop-wise in the above-mentioned A liquid Li that makes: Fe: P=3.0: 1.0: 1.0 (mol ratio), the dropping process is constantly being carried out under the stirring condition, along with the dropping of LiOH, form green muddy B liquid gradually; Accurately take by weighing in the absolute ethyl alcohol of the ultrasonic 20mL of being scattered in of 0.0316g Graphene (make phosphorus content is 1wt% in the product), dispersion liquid slowly is added drop-wise in the above-mentioned B liquid, form the C liquid predecessor of celadon.Then predecessor is transferred in the teflon-lined stainless steel autoclave sealing.Autoclave is put into oil bath, and constantly the following 150 ℃ of reactions of stirring condition are 5 hours.After reactant liquor fully cooled off, with product ageing 12 hours, suction filtration was washed to the greatest extent
After, 50 ℃ of vacuumize 10 hours, with the roasting in nitrogen atmosphere of dried product, 600 ℃ of roastings 5 hours finally obtain the powder of black.
Embodiment 5:
Initial feed is CH
3COOLi2H
2O, FeCl
24H
2O, (NH
4)
2HPO
4, ascorbic acid (vitamin C) and graphene powder.Accurately take by weighing 4.968g FeCl
24H
2O and 0.053g ascorbic acid add the 20mL deionized water in small beaker, be stirred to dissolving fully, accurately take by weighing 3.302g (NH
4)
2HPO
4Be added in the above-mentioned mixed liquor, the back that stirs forms jade-green A solution; Take by weighing 7.652gCH
3COOLiH
2O is dissolved in the deionized water of 60mL, LiOH solution slowly is added drop-wise in the above-mentioned A liquid Li that makes: Fe: P=3.0: 1.0: 1.0 (mol ratio), the dropping process is constantly being carried out under the stirring condition, along with the dropping of LiOH, form green muddy B liquid gradually; Accurately take by weighing in the absolute ethyl alcohol of the ultrasonic 20mL of being scattered in of 0.1580g Graphene (make phosphorus content is 5wt% in the product), dispersion liquid slowly is added drop-wise in the above-mentioned B liquid, form the C liquid predecessor of celadon.Then predecessor is transferred in the teflon-lined stainless steel autoclave sealing.Autoclave is put into oil bath, and constantly the following 150 ℃ of reactions of stirring condition are 5 hours.After reactant liquor fully cooled off, with product ageing 12 hours, suction filtration was washed to the greatest extent
After, 50 ℃ of vacuumize 10 hours, with the roasting in nitrogen atmosphere of dried product, 800 ℃ of roastings 5 hours finally obtain the powder of black.
The powder of gained black is finished product combination electrode slurry in the above-described embodiments, and it is of good quality, the purity height.Be fit to be used for doing the high-performance electrokinetic cell.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. the hydrothermal synthesis method of a high-performance electrokinetic cell usefulness composite material is characterized in that, may further comprise the steps:
The first step, hydro-thermal is synthesized precursor
Divalent iron salt is dissolved in the deionized water, add microcosmic salt and ascorbic acid, mix, lithium salts is dissolved in forms solution in the deionized water, in the mixed solution above then lithium salt solution being splashed under continuous stirring condition, make mol ratio Li: Fe: P=3: 1: 1, stir after 1～30 minute, add the scattered Graphene dispersion liquid of ethanol, form the mixed liquor of celadon, mixed liquor is transferred to reaction under high pressure mixed liquor is transferred in the autoclave, add magnetic force, sealing was 120～180 ℃ dimethyl-silicon oil bath internal reactions 2～10 hours;
Second step, the filtration of precursor, washing and drying
Mixed liquor after the hydro-thermal reaction is taken out in reactor, through ageing after 12 hours, outwell supernatant liquor, the sediment of lower floor is used deionized water wash repeatedly, till in detecting, containing sulfate ion less than cleaning solution, then sediment is put in vacuumize in the vacuum drying chamber, baking temperature is 35～80 ℃;
The 3rd step, the precursor calcination process
The precursor powder of previous step gained is put into little porcelain boat, carry out calcination process under the condition of the not protection of open close inert gas in tube furnace, sintering temperature is 500～800 ℃, and roasting time is 2～10 hours.
2. a kind of high-performance electrokinetic cell according to claim 1 is characterized in that with the hydrothermal synthesis method of composite material described divalent iron salt is for being the solution that raw material is mixed with by ferrous sulfate or frerrous chloride crystal, and concentration is ferrous ion 0.5～2mol/L.
3. a kind of high-performance electrokinetic cell according to claim 1 hydrothermal synthesis method of composite material, it is characterized in that, described microcosmic salt is a kind of solution that is mixed with for raw material of phosphoric acid, diammonium hydrogen phosphate or ammonium dihydrogen phosphate, and concentration is phosphate anion 0.5～2mol/L.
4. a kind of high-performance electrokinetic cell according to claim 1 hydrothermal synthesis method of composite material, it is characterized in that, described lithium salts is a kind of solution that is mixed with for raw material in lithium hydroxide, lithium carbonate, lithium acetate or the lithium chloride, and concentration is lithium concentration 0.5～2mol/L.
5. a kind of high-performance electrokinetic cell according to claim 1 is characterized in that with the hydrothermal synthesis method of composite material, and described antioxidant is a kind of solution that is mixed with for raw material in ascorbic acid or the oxalic acid crystal, and concentration is 0.01～0.1mol/L.
6. a kind of high-performance electrokinetic cell according to claim 1 is characterized in that with the hydrothermal synthesis method of composite material the consumption that described graphite is rare is to account for 1%～10% of synthesizing iron lithium phosphate Theoretical Mass.
7. a kind of high-performance electrokinetic cell according to claim 1 is characterized in that with the hydrothermal synthesis method of composite material described dry run is carried out in vacuum drying chamber, baking temperature is 35～80 ℃, and be 10～20 hours drying time.
8. a kind of high-performance electrokinetic cell according to claim 1 hydrothermal synthesis method of composite material; it is characterized in that; described inert protective gas is nitrogen or argon gas; the temperature of roasting is 500～800 ℃ in tube furnace; roasting time is 2～10 hours; being set to of temperature programming wherein: the speed according to 10～30 ℃/min is warmed up to 500～800 ℃, is incubated 2～10 hours then, then according to the speed cooling of 1～50 ℃/min.
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| CN102299326A (en) * | 2011-08-04 | 2011-12-28 | 浙江工业大学 | Graphene modified lithium iron phosphate/carbon composite material and its application |
| CN102299336A (en) * | 2011-07-20 | 2011-12-28 | 彩虹集团公司 | Preparation method of lithium ion battery anode material lithium iron phosphate |
| CN102544489A (en) * | 2012-01-09 | 2012-07-04 | 上海交通大学 | Method for preparing graphene-coated olivine type lithium ferric phosphate composite material |
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| CN102299326B (en) * | 2011-08-04 | 2014-01-29 | 浙江工业大学 | Graphene modified lithium iron phosphate/carbon composite material and its application |
| CN102299326A (en) * | 2011-08-04 | 2011-12-28 | 浙江工业大学 | Graphene modified lithium iron phosphate/carbon composite material and its application |
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| US10090525B2 (en) | 2011-10-04 | 2018-10-02 | Hydro-Quebec | Positive-electrode materials: methods for their preparation and use in lithium secondary batteries |
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| CN102544489B (en) * | 2012-01-09 | 2014-12-10 | 上海交通大学 | Method for preparing graphene-coated olivine type lithium ferric phosphate composite material |
| CN102751496A (en) * | 2012-07-17 | 2012-10-24 | 中国科学院上海硅酸盐研究所 | Preparation method of lithium iron phosphate/graphene nano composite material |
| CN102751486A (en) * | 2012-07-18 | 2012-10-24 | 中国科学院福建物质结构研究所 | Method for preparing lithium cobalt oxide nanosheets |
| CN102751486B (en) * | 2012-07-18 | 2015-12-16 | 中国科学院福建物质结构研究所 | A kind of preparation method of cobalt acid lithium nanometer sheet |
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| WO2014169411A1 (en) * | 2013-04-16 | 2014-10-23 | 成都牧甫生物科技有限公司 | Graphene-lithium iron phosphate with polycrystalline composite structure and preparation method therefor |
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