CN104681814B - A kind of anode material for lithium-ion batteries LiFePO with porous star pattern4And preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries LiFePO with porous star pattern4And preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of anode material for lithium-ion batteries LiFePO with porous star pattern4And preparation method thereof.The preparation method of the present invention comprises the steps：Lithium salts, iron salt and phosphate are mixed into solution, add Morphological control agent and carry out hydro-thermal reaction, then carry out pre-burning, calcining obtains the LiFePO of the present invention4.The present invention has the LiFePO of porous star pattern using one step hydro thermal method by self assembly preparation4, it not only effectively improves the specific surface area of active particle, increases effective electrochemical contact area of active particle, also improves electronic conductivity and the ionic conductance of active particle, overcomes current nanoscale LiFePO simultaneously4The shortcoming that material is easily reunited, thus ensureing LiFePO4While there is high power capacity, its tap density and volume and capacity ratio can be effectively improved, meet the big multiplying power of power lithium-ion battery, the use requirement of fast charging and discharging.
Description
Technical field
The present invention relates to one of field of lithium ion battery has the anode material for lithium-ion batteries of porous star pattern
LiFePO4And preparation method thereof.
Background technology
Energy problem is the common issue of 21st century facing mankind, and electric energy is a kind of energy form of most convenient.Its
Middle lithium ion battery due to have reversible capacity height, voltage platform height, energy density height, good cycle, have extended cycle life, from
The outstanding advantages such as discharge rate is little, memory-less effect and environmental protection, are increasingly becoming the focus of whole world research and development.Meanwhile, lithium from
The constantly improve of sub- battery technology and improvement so that lithium ion battery becomes the main flow of chemical cell, be widely used to mobile phone,
Notebook computer, digital camera, military affairs and field of aerospace etc., and it is expected to neck new in new-energy automobile and wind, light energy storage etc.
Domain plays a significant role.
From goodenough in 1997 first by LiFePO4As anode material for lithium-ion batteries carry out research report with
Come, its aboundresources, cheap, nontoxic, environmental friendliness, safety, overcharging resisting are put, heat stability is good, good cycle, theory
The advantages of capacity height (can reach 170mAh/g), attract everybody extensive concern it is considered to be the lithium-ion electric of great prospect
Pond positive electrode.But, LiFePO4There are two obvious shortcomings：One is that electrical conductivity is low, and wherein electronic conductivity only has 10- 10The S/cm order of magnitude, lithium ion diffusion rate is only 10-14cm2/ s the order of magnitude, leads to high-rate discharge ability poor, actual specific capacity
Low, especially when larger current is discharged, electrode polarization is serious, leads to discharge and recharge irreversible degree to increase, electrochemistry capacitance loses
Seriously；Two is that bulk density is low, leads to volume and capacity ratio low, and this gives LiFePO4Practical application bring certain difficulty.
LiFePO at present4Positive electrode method of modifying mainly has carbon coating, metal cation doping, granule nanorize etc..
Particularly granule nanorize has the advantages that the evolving path of shortening lithium ion, specific surface area are high, conducts electricity very well, and can significantly carry
The chemical property of high material, but the shortcomings of have that tap density is low, volume capacity density is low, easily reunite during smear.Cause
This, while ensureing its tap density, preparation has the micron order of loose structure, and the material particularly with special appearance becomes
For synthesizing LiFePO4Development new direction.Porous anode material can be greatly enhanced the surface area of active particle, increases activity
Effective electrochemical contact area of particle, then improves electron conductivity and the ionic conductance of active particle, meets power lithium
The use requirement greatly to high rate performance and fast charging and discharging for the ion battery, in hybrid vehicle and pure electric automobile and energy storage
Field has preferable application prospect.Yang Lin etc. utilizes sol-gel process to synthesize LiFePO4/ C porous anode material, synthesis
Material is mainly existed with 2 kinds of forms：One is the larger porous support of granule, and two is the nano-particle of particle diameter very little；This 2 kinds of patterns
Can be fully contacted with electrolyte well, improve stock utilization.This material electrochemical performance is preferable, under 1C multiplying power first
Discharge capacity is 139.5mAh/g, and after circulating 50 weeks, capability retention is 94.6%.R.Dominko etc. utilizes collosol and gel legal system
Standby porous LiFePO4/ C micron scale construction material, has loose structure, is conducive to the infiltration of electrolyte, and carbon solid is deposited on
On hole wall, improve the electric conductivity of material, this material surface and inside are all loose structure, reach in 0.5C multiplying power discharge capacity
140mAh/g, cyclical stability is preferable.Xia etc. prepares self assembly spindle-type mesopore LiFePO by adjusting pH value4；
Goodenough etc. synthesizes Semen Juglandiss type using ethylene glycol as chelating agen, ethylenediamine as cosolvent and petal-shaped is spherical
LiFePO4；Wang etc. passes through to add nitrilotriacetic acid (NTA) surfactant successfully to synthesize nano wire LiFePO4Material,
In addition as bar-shaped, lamellar, rectangle prismatic, fusiform, prismatic, bulk, ball-type, nucleocapsid structure, hollow shape and pencil all in succession by
Researcher is successfully prepared.
But, there is the LiFePO of porous star pattern4There is not been reported, and the present invention adopts simple one step hydro thermal method to lead to
Cross the LiFePO that self assembly preparation has porous star pattern4, both can solve LiFePO4Tap density and volume and capacity ratio are relatively low
Problem, can reach again and improve LiFePO4The purpose of chemical property.
Content of the invention
It is an object of the invention to provide a kind of lithium ion battery anode material lithium iron phosphate with porous star pattern
(LiFePO4) and preparation method thereof.
The anode material for lithium-ion batteries LiFePO with porous star pattern provided by the present invention4It is characterised in that
LiFePO4The size tunable of powder, mean diameter is 1～30 μm, the star pattern uniformly and in porous for the particle size distribution, star
The length of shape is 5～30 μm.
The above-mentioned anode material for lithium-ion batteries LiFePO with porous star pattern4Preparation method, including following
Step：
(1) first the lithium salts of certain mol proportion, iron salt and phosphate are dissolved in deionized water and obtain mixed solution, wherein
Iron concentration is less than 0.1mol/L；
(2) structure inducer (or Morphological control agent) is slowly added in step (1) resulting solution, stirs into solution；
(3) step (2) resulting solution loading hydrothermal reaction kettle (is made the stainless steel water thermal response of liner with politef
Kettle) in, the compactedness of solution is 40%～70%, and controlling reaction temperature is 160～190 DEG C, successive reaction 3～24 hours, instead
After should terminating, reacted solution is stirred in 80 DEG C of oil bath pans, obtain green precipitate thing；
(4) step (3) gained sediment is dried 10～48 hours under the conditions of 80～120 DEG C, obtains LiFePO4Forerunner
Body powder, by powder in protective atmosphere in 350～500 DEG C of pre-burnings 6～8 hours, after natural cooling grind obtain pre-burning product；
(5) step (4) gained pre-burning product is mixed homogeneously with carbon source, control final carbon content to be less than 5wt.% (weight
Percentage ratio), sinter 8～10 hours in 600～700 DEG C in protective atmosphere, grind after natural cooling and obtain carbon coating
LiFePO4/ C positive electrode material.
Further, Li in described step (1) mixed solution+、Fe3+、PO4 3-Mol ratio be 0.95～1.05:0.95～
1.05:1.
Further, the lithium salts of described step (1) is one of Quilonorm (SKB), Lithium hydrate, lithium carbonate or two or more；Institute
Stating iron salt is one of ferric nitrate, iron chloride, iron sulfate or two or more；Described phosphate is ammonium dihydrogen phosphate, phosphoric acid hydrogen
One of diammonium, ammonium phosphate or phosphoric acid or two or more.
Further, the structure inducer (or Morphological control agent) of described step (2) is can be organic with complexing of metal ion
In amine or/and Organic Alcohol；Organic amine is selected from one of triethylamine, ethylenediamine, triethanolamine or two or more；Organic Alcohol is selected from
One of ethylene glycol, propylene glycol, glycerol, diglycol, tetramethylolmethane or two or more；And described Morphological control
The addition volume of agent is the 0～5% of overall solution volume.
Further, the carbon source of described step (5) is sucrose, glucose, caramel, citric acid, Graphene, CNT, second
One of acetylene black, graphite, Super P (conductive charcoal (carbon) is black) etc. or two or more.
Further, described protective atmosphere is mixed gas, described nitrogen and the hydrogen of nitrogen, argon or nitrogen and hydrogen
In the mixed gas of gas, nitrogen accounts for 80～99V% (volume fraction), and hydrogen accounts for 1～20V%；Or the gaseous mixture of argon and hydrogen
In the mixed gas of body, described argon and hydrogen, argon accounts for 80～99V%, and hydrogen accounts for 1～20V%.
Further, the gas flow rate of described protective atmosphere is 0.1～10L/min.
The present invention has the following technical effect that：
(1) present invention adopts hydro-thermal method synthesizing porous star LiFePO4There is abundant raw material source, cheap, synthesis
Simple for process, safe and reliable, low production cost, yield height, non-environmental-pollution, the suitability is wide, be easy to repeat and give birth in a large number
The advantages of product.
(2) present invention has the LiFePO of porous star pattern using simple one step hydro thermal method by self assembly preparation4,
It can not only effectively improve the specific surface area of active particle, increase effective electrochemical contact area of active particle, then carry
The electronic conductivity of high activity particle and ionic conductance, overcome current nanoscale LiFePO simultaneously4Material is easily reunited
Shortcoming, thus ensureing prepared LiFePO4While there is high power capacity, its tap density and volume ratio can be effectively improved
Capacity, thus meeting the big multiplying power of power lithium-ion battery, the use requirement of fast charging and discharging, in hybrid vehicle and pure electronic
Automobile and energy storage field are respectively provided with good application prospect.
Brief description
Fig. 1 is LiFePO in embodiment 24The XRD figure of/C.
Fig. 2 is LiFePO in embodiment 14The SEM figure of precursor powder entirety pattern.
Fig. 3 is LiFePO in embodiment 14The SEM figure of precursor powder local pattern.
Fig. 4 is LiFePO in embodiment 14The nitrogen adsorption desorption curve of/C.
Fig. 5 is LiFePO in embodiment 14The pore size distribution curve of/C.
Fig. 6 is LiFePO in embodiment 14/ C charging and discharging curve under 0.5C multiplying power as positive pole.
Fig. 7 is LiFePO in embodiment 14/ C charging and discharging curve under 1.0C multiplying power as positive pole.
Fig. 8 is LiFePO in embodiment 14/ C as positive pole 0.5C and 1C cycle performance figure.
Specific embodiment
Further describe the present invention by the following examples, but be not limited to embodiment.
Experimental technique in following embodiments, if no special instructions, is conventional method.
Embodiment 1
With Quilonorm (SKB), Fe(NO3)39H2O, ammonium dihydrogen phosphate is initiation material, according to Li+:Fe3+:PO4 3-=1:1:1
Ratio is made into the solution that iron concentration is 0.025mol/L, is slowly added dropwise triethylamine afterwards, solution is changed into crocus gel, will
Resulting solution loads in 100mL polytetrafluoroethyllining lining, and liner is put into rustless steel water heating kettle, is placed in program control by compactedness 40%
Carry out heat treatment in sweat box, control temperature to be 180 DEG C, successive reaction 3 hours, then by reacted solution in 80 DEG C of oil baths
Stir in pot and dry obtain green precipitate thing.The precipitate obtaining is placed in air dry oven, 120 DEG C of dryings 10 hours, by obtain
Porous star LiFePO4Presoma is placed in Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in mixed gas protected high temperature process furnances
At 500 DEG C, pre-burning 6 hours, are cooled to room temperature.Again pre-burning product is ground, tabletting pelletize, mix then with 5wt.% glucose
It is placed on Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in the high temperature process furnances of mixed atmosphere, in 700 DEG C of roastings 10 hours.Cooling
To room temperature, grind, obtain LiFePO4/ C positive electrode material.
Fig. 2 is the present embodiment gained LiFePO4Overall and local pattern the SEM of precursor powder schemes.Can from Fig. 2
Go out, this powder body has porous star structure, granule is well dispersed, average particulate diameter is about 10 μm.LiFePO by Fig. 44/C
Nitrogen adsorption desorption curve can be seen that LiFePO4There is obvious hysteresis loop in/C-material, show to have micropore and mesoporous in material
Presence, the presence of this structure can promote the transmission of electrolyte ion.Can be obtained by Fig. 5, LiFePO4The aperture of/C-material is
7.8490nm.Tested by BET, the specific surface area of material is 12.5989m2/g.Weigh 0.24gLiFePO4/ C, adds 0.015g
Acetylene black, 0.015g graphite and 0.03g Kynoar, mix homogeneously, add N- N-methyl 2-pyrrolidone N-to be tuned into slurry, equably apply
Overlay in current collector aluminum foil, after 80 DEG C of dryings, volume press flattens, makes the anode thin film of about 200 μm of thickness, just very thin
The disk of diameter 1cm size is gone out on film, is placed on heat treatment more than 12 hours in 110 DEG C of vacuum drying ovens, with vacuum tank
After natural cooling, weigh, as backup electrode.Electrolyte adopts 1mol/L LiPF6Ethylene vinegar (EC)：Carbonic acid diformazan vinegar
(DMC)(1:1) mixed liquor, polypropylene microporous film is barrier film, and metal lithium sheet is as negative pole.The glove box of argon gas atmosphere seals
Packed battery, is aged 6 hours, and discharge and recharge blanking voltage scope is 2.0-4.5V, discharge and recharge under 0.5C and 1C multiplying power.From Fig. 6 and
Fig. 7 shows good chemical property when can be seen that this material as lithium ion cell positive, its first discharge specific capacity
It is up to 154.8 and 139.4mAh/g respectively.As it can be observed in the picture that its stable cycle performance, after 100 discharge and recharges, its specific capacity is protected
Hold respectively 149.1 and 135.6mAh/g.
Embodiment 2
With Lithium hydrate, Fe(NO3)39H2O, ammonium dihydrogen phosphate is initiation material, according to Li+:Fe3+:PO4 3-=1:1:1
Ratio be made into iron concentration be 0.025M solution, be slowly added dropwise triethylamine afterwards, solution is changed into crocus gel, by institute
Obtain solution and load in 100mL polytetrafluoroethyllining lining, compactedness 40%, liner is put into rustless steel water heating kettle, puts into journey afterwards
Carry out heat treatment in controlling temperature case, control temperature to be 190 DEG C, successive reaction 3 hours, then by reacted solution in 80 DEG C of oil
Stir in bath and dry obtain green precipitate thing.The precipitate obtaining is placed in air dry oven, 120 DEG C of dryings 10 hours, will obtain
Porous star LiFePO4Front aggressiveness is placed in Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in mixed gas protected high temperature process furnances
At 500 DEG C, pre-burning 6 hours, are cooled to room temperature.Again pre-burning product is ground, tabletting pelletize, mix then with 5wt.% glucose
It is placed on Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in the high temperature process furnances of mixed atmosphere, in 700 DEG C of roastings 10 hours.It is cooled to
After room temperature, grind, obtain LiFePO4/ C positive electrode material.Size mixing by above-described embodiment 1 and battery manufacturing conditions.It discharges first
Specific capacity respectively up to 149.1 and 140.2mAh/g, stable cycle performance, after 100 discharge and recharges, its specific capacity remains
142.5 and 132.4mAh/g.Fig. 1 is LiFePO in this embodiment4The XRD figure of/C.
Embodiment 3
With lithium carbonate, Fe(NO3)39H2O, ammonium dihydrogen phosphate is initiation material, according to Li+:Fe3+:PO4 3-=1:1:1
Ratio is made into the solution that iron concentration is 0.02M, is slowly added dropwise triethylamine afterwards, solution is changed into crocus gel, by gained
Solution loads in 100mL polytetrafluoroethyllining lining, and liner is put into rustless steel water heating kettle, put into program control afterwards by compactedness 50%
Carry out heat treatment in sweat box, control temperature to be 190 DEG C, successive reaction 10 hours, then by reacted solution in 80 DEG C of oil
Stir in bath and dry obtain green precipitate thing.The precipitate obtaining is placed in air dry oven, 120 DEG C of dryings 10 hours, will obtain
Porous star LiFePO4Front aggressiveness is placed in Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in mixed gas protected high temperature process furnances
At 350 DEG C, pre-burning 8 hours, are cooled to room temperature.Again pre-burning product is ground, tabletting pelletize, mix then with 5wt.% glucose
It is placed on Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in the high temperature process furnances of mixed atmosphere, in 700 DEG C of roastings 8 hours.It is cooled to
After room temperature, grind, obtain LiFePO4/ C positive electrode material.Size mixing by above-described embodiment 1 and battery manufacturing conditions.It discharges first
Specific capacity respectively up to 136.3 and 133.9mAh/g, stable cycle performance, after 100 discharge and recharges, its specific capacity keeps respectively
For 135.6 and 130.4mAh/g.
Embodiment 4
With Quilonorm (SKB), Fe(NO3)39H2O, ammonium dihydrogen phosphate is initiation material, according to Li+:Fe3+:PO4 3-=1:1:1
Ratio is made into the solution that iron concentration is 0.02M, is slowly added dropwise glycerol and triethylamine afterwards, and solution is changed into crocus and coagulates
Glue, resulting solution is loaded in 100mL polytetrafluoroethyllining lining, and liner is put into rustless steel water heating kettle, afterwards by compactedness 50%
Put into and in program control temperature case, carry out heat treatment, control temperature to be 190 DEG C, successive reaction 24 hours, then by reacted solution
80 DEG C of oil bath pans stir and dry obtains green precipitate thing.The precipitate obtaining is placed in air dry oven, and 120 DEG C of dryings 10 are little
When, the porous star LiFePO that will obtain4Front aggressiveness is placed in Ar/H2(Ar accounts for 95V%, H2Account for 5V%) mixed gas protected height
At 500 DEG C in warm tube furnace, pre-burning 8 hours, are cooled to room temperature.Again pre-burning product is ground, tabletting pelletize, with 5wt.% sucrose
Then mixing is placed on Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in the high temperature process furnances of mixed atmosphere, in 700 DEG C of roastings 10
Hour.After being cooled to room temperature, grind, obtain LiFePO4/ C positive electrode material.Size mixing by above-described embodiment 1 and battery manufacturing conditions.Its
First discharge specific capacity respectively up to 138.3 and 134.2mAh/g, stable cycle performance, after 100 discharge and recharges, its
Specific capacity keeps being respectively 136.3 and 131.2mAh/g.
Embodiment 5
With Quilonorm (SKB), Fe(NO3)39H2O, ammonium dihydrogen phosphate is initiation material, according to Li+:Fe3+:PO4 3-=1:1:1
Ratio is made into the solution that iron concentration is 0.014M, is slowly added dropwise glycerol and triethylamine afterwards, and solution is changed into crocus and coagulates
Glue, resulting solution is loaded in 100mL polytetrafluoroethyllining lining, and liner is put into rustless steel water heating kettle, afterwards by compactedness 70%
Put into and in program control temperature case, carry out heat treatment, control temperature to be 190 DEG C, successive reaction 10 hours, then by reacted solution
80 DEG C of oil bath pans stir and dry obtains green precipitate thing.The precipitate obtaining is placed in air dry oven, and 120 DEG C of dryings 10 are little
When, the porous star LiFePO that will obtain4Front aggressiveness is placed in Ar/H2(Ar accounts for 95V%, H2Account for 5V%) mixed gas protected height
At 500 DEG C in warm tube furnace, pre-burning 6 hours, are cooled to room temperature.Again pre-burning product is ground, tabletting pelletize, with 5wt.% sucrose
Then mixing is placed on Ar/H2(Ar accounts for 95V%, H2Account for 5V%) little in 700 DEG C of roastings 10 in the high temperature process furnances of mixed atmosphere
When.After being cooled to room temperature, grind, obtain LiFePO4/ C positive electrode material is sized mixing by above-described embodiment 1 and battery manufacturing conditions.It is first
Secondary specific discharge capacity respectively up to 137.6 and 132.3mAh/g, stable cycle performance, after 100 discharge and recharges, its specific capacity is protected
Hold respectively 134.4 and 130.9mAh/g.
Embodiment 6
With Quilonorm (SKB), Fe(NO3)39H2O, ammonium dihydrogen phosphate is initiation material, according to Li+:Fe3+:PO4 3-=1:1:1
Ratio is made into the solution that iron concentration is 0.02M, is slowly added dropwise ethylene glycol and triethylamine afterwards, and solution is changed into crocus and coagulates
Glue, resulting solution is loaded in 100mL polytetrafluoroethyllining lining, and liner is put into rustless steel water heating kettle, afterwards by compactedness 50%
Put into and in program control temperature case, carry out heat treatment, control temperature to be 190 DEG C, successive reaction 8 hours, then reacted solution is existed
Stir in 80 DEG C of oil bath pans and dry obtain green precipitate thing.The precipitate obtaining is placed in air dry oven, 120 DEG C of dryings 10 hours,
The porous star LiFePO that will obtain4Front aggressiveness is placed in Ar/H2(Ar accounts for 95V%, H2Account for 5V%) mixed gas protected high temperature pipe
At 500 DEG C in formula stove, pre-burning 6 hours, are cooled to room temperature.Again pre-burning product is ground, tabletting pelletize, mix with 5wt.% sucrose
Then it is placed on Ar/H2(Ar accounts for 95V%, H2Account for 5V%) in the high temperature process furnances of mixed atmosphere in 700 DEG C of roastings 10 hours.
After being cooled to room temperature, grind, obtain LiFePO4/ C positive electrode material.Size mixing by above-described embodiment 1 and battery manufacturing conditions.It is first
Specific discharge capacity respectively up to 134.3 and 130.2mAh/g, stable cycle performance, after 100 discharge and recharges, its specific capacity keeps
It is respectively 133.3 and 128.2mAh/g.
Claims (8)
1. a kind of anode material for lithium-ion batteries LiFePO with porous star pattern4It is characterised in that：Described LiFePO4
The size tunable of powder, mean diameter is 1～30 μm, the star pattern uniformly and in porous for the particle size distribution, the length of star
Spend for 5～30 μm.
2. the anode material for lithium-ion batteries LiFePO with porous star pattern described in claim 14Preparation method, its
It is characterised by comprising the steps：
(1) first the lithium salts of certain mol proportion, iron salt and phosphate are dissolved in deionized water and obtain mixed solution, wherein ferrum from
Sub- concentration is less than 0.1mol/L；
(2) Morphological control agent is added in step (1) resulting solution, stirs into solution；
(3) step (2) resulting solution is loaded in hydrothermal reaction kettle, the compactedness of solution is 40%～70%, controls reaction temperature
Spend for 160～190 DEG C, successive reaction 3～24 hours, reacted solution is stirred after terminating in 80 DEG C of oil bath pans by reaction,
Obtain green precipitate thing；
(4) step (3) gained sediment is dried 10～48 hours under the conditions of 80～120 DEG C, obtains LiFePO4Precursor
End, by powder in protective atmosphere in 350～500 DEG C of pre-burnings 6～8 hours, after natural cooling grind obtain pre-burning product；
(5) step (4) gained pre-burning product is mixed homogeneously with carbon source, control final carbon content to be less than 5wt.%, in shielding gas
Sinter 8～10 hours in 600～700 DEG C in atmosphere, after natural cooling, grind the LiFePO obtaining carbon coating4/ C positive electrode material.
3. the anode material for lithium-ion batteries LiFePO with porous star pattern according to claim 24Preparation side
Method it is characterised in that：Li in described step (1) mixed solution+、Fe3+、PO4 3-Mol ratio be 0.95～1.05:0.95～
1.05:1.
4. the anode material for lithium-ion batteries LiFePO with porous star pattern according to claim 24Preparation side
Method it is characterised in that：Described lithium salts is one of Quilonorm (SKB), Lithium hydrate, lithium carbonate or two or more；Described iron salt
For one of ferric nitrate, iron chloride, iron sulfate or two or more；Described phosphate be ammonium dihydrogen phosphate, diammonium phosphate,
One of ammonium phosphate or two or more.
5. the anode material for lithium-ion batteries LiFePO with porous star pattern according to claim 24Preparation side
Method it is characterised in that：Described Morphological control agent is organic amine or/and Organic Alcohol；Described organic amine is selected from triethylamine, second two
One of amine, triethanolamine or two or more；Described Organic Alcohol is selected from ethylene glycol, propylene glycol, glycerol, a contracting diethyl two
One of alcohol, tetramethylolmethane or two or more；The addition volume of described Morphological control agent is the 5% of overall solution volume.
6. the anode material for lithium-ion batteries LiFePO with porous star pattern according to claim 24Preparation side
Method it is characterised in that：Described carbon source is sucrose, glucose, caramel, citric acid, Graphene, CNT, acetylene black, stone
One of ink, Super P or two or more.
7. the anode material for lithium-ion batteries LiFePO with porous star pattern according to claim 24Preparation side
Method it is characterised in that：Described protective atmosphere is nitrogen, mixed gas, described nitrogen and the hydrogen of argon or nitrogen and hydrogen
In the mixed gas of gas, nitrogen accounts for 80～99V%, and hydrogen accounts for 1～20V%；Or the mixed gas of argon and hydrogen, described argon
In the mixed gas of hydrogen, argon accounts for 80～99V%, and hydrogen accounts for 1～20V%.
8. the anode material for lithium-ion batteries LiFePO with porous star pattern according to claim 24Preparation side
Method it is characterised in that：The gas flow rate of described protective atmosphere is 0.1～10L/min.
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| CN107221672B (en) * | 2017-05-08 | 2020-02-28 | 陕西科技大学 | Olive-shaped porous lithium iron phosphate and preparation method thereof |
| CN108451522B (en) * | 2018-03-28 | 2023-05-30 | 广州源康健信息科技有限公司 | Medical equipment |
| CN109461897B (en) * | 2018-08-29 | 2021-11-23 | 北京泰丰先行新能源科技有限公司 | Preparation method of spindle-shaped carbon-coated vanadium-based positive electrode material |
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| CN102496715A (en) * | 2011-12-22 | 2012-06-13 | 中国计量学院 | Solvothermal method used for preparing LiFePO4 |
| CN102881903A (en) * | 2012-10-23 | 2013-01-16 | 兰州理工大学 | Preparation method of porous lithium iron phosphate powder |
| CN103956493A (en) * | 2014-05-16 | 2014-07-30 | 武汉理工大学 | Preparation method of carbon-coated lithium iron phosphate with grade structure |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496715A (en) * | 2011-12-22 | 2012-06-13 | 中国计量学院 | Solvothermal method used for preparing LiFePO4 |
| CN102881903A (en) * | 2012-10-23 | 2013-01-16 | 兰州理工大学 | Preparation method of porous lithium iron phosphate powder |
| CN103956493A (en) * | 2014-05-16 | 2014-07-30 | 武汉理工大学 | Preparation method of carbon-coated lithium iron phosphate with grade structure |
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