CN108417832A - A kind of method that equimolar ratio prepares LiFePO4 - Google Patents
A kind of method that equimolar ratio prepares LiFePO4 Download PDFInfo
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- CN108417832A CN108417832A CN201810110426.0A CN201810110426A CN108417832A CN 108417832 A CN108417832 A CN 108417832A CN 201810110426 A CN201810110426 A CN 201810110426A CN 108417832 A CN108417832 A CN 108417832A
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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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Abstract
The invention discloses a kind of methods that equimolar ratio prepares LiFePO4, belong to field of lithium ion battery anode, and step weighs phosphoric acid iron stabilizers including (1) and is dissolved in deoxidation distilled water, stirs and be added ferrous source, form mixed liquor A；(2) according to Fe2+：Li+=1:1 weighs LiH2PO4 dissolvings, forms solution B；(3) it by mixed liquor A and solution B mixing, is added in autoclave, adjusts pH=6~8；It is passed through inert gas, wave heats reaction kettle to 160~200 DEG C of 4~6h of heat preservation, and cooled to room temperature is filtered, washed, is dried in vacuo, and obtains positive electrode LiFePO4.LiFePO4 positive electrodes made from this method are had excellent performance, and 0.2C specific discharge capacities reach 152mAh/g.
Description
Technical field
The present invention is patent of invention《A kind of method that hydro-thermal method equimolar prepares LiFePO4》(2016101558847)
Divisional application is related to a kind of field of lithium ion battery anode, and especially a kind of hydro-thermal method equimolar prepares LiFePO4
Method.
Background technology
In recent years, lithium ion battery causes more and more concerns in the application of new energy field, therewith, as lithium from
One of the core of sub- battery, positive electrode have become the hot spot of research.And LiFePO 4 material have derive from a wealth of sources, cost
Low, small toxicity is easily recycled, is had a safety feature, the advantages that service life is long and specific capacity is high, is most popular at present and reliable time
Select one of positive electrode.
Currently, in the preparation method and chemical property of numerous LiFePO4s are improved, solid phase method, sol-gel method, water
Hot method and carbon coating, metal ion mixing etc. occupy an important position.Such as：Wang etc. (Electrochem Acta, 2005,
50,14) solid reaction process is used to be prepared for the positive electrode LiFe of Fe doping0.9Mg0.1PO4；(the J Power such as Jin
Sources, 2008,178) utilize hydro-thermal method synthesis LiFePO4, with LiOH, FeSO4, H3PO4For raw material, molar ratio 3:1:1, first
Phosphoric acid and ferrous sulfate are mixed, a small amount of distilled water stirring is added, then lithium hydroxide solution is added in mixed solution, stirs
It is then transferred in reaction kettle, is heated 5 hours at 180 DEG C in drying box；Lithium source in this method：Source of iron：Phosphorus source is 3:1:1,
Lithium source largely excessively neutralizes extra anion in solution, and cost of material is caused to waste, and metal iron ion is easy and phosphate radical
Reaction occurs to reunite and be deposited in autoclave base, insufficient contact with lithium ion, causes reaction impurities content height, cost high
It is expensive, it is complicated for operation.
Therefore, lithium source utilization rate can be improved to greatest extent by being badly in need of one kind, prepared by the LiFePO4 for reducing finished product impurity
Method.
Invention content
The technical assignment of the present invention is to be directed to the above the deficiencies in the prior art, provides a kind of equimolar ratio and prepares ferric phosphate
The method of lithium.
The present invention the technical solution to solve the technical problem is that：A kind of method that equimolar ratio prepares LiFePO4,
It is characterized in that, step includes：
(1) it takes phosphoric acid iron stabilizers to dissolve in deoxygenating in distilled water, ferrous source is slowly added under stirring, form mixed liquor A；
(2) according to Fe2+：Li+=1:1 weighs LiH2PO4, it is dissolved in deoxidation distilled water, and stir, forms solution B；
(3) mixed liquor A and solution B are mixed and stirred for, are added in autoclave, PH=6~8 are adjusted with ammonium hydroxide；It is logical
Enter high purity inert gas, wave heats reaction kettle to 160~200 DEG C of 4~6h of heat preservation, and cooled to room temperature is filtered, washed
It washs, be dried in vacuo, obtain positive electrode LiFePO4；The wave heats 1 DEG C/min of heating speed in order to control, heating
45min stops heating, and same heating speed continues to heat 45min after temperature declines 15 DEG C, and it is in wave to make temperature repeatedly
Formula rises to target temperature.
Above-mentioned phosphoric acid iron stabilizers are gelatinized starch.
Above-mentioned gelatinized starch preparation method is：Soluble starch is dissolved in deoxidation distilled water, is heated to 60 DEG C and is formed paste
Change starch.
Above-mentioned ferrous source is FeSO4·7H2O or ferrous oxalate.
Compared with prior art, the present invention has advantageous effect following prominent：
1, it is reacted with ferrous sulfate using ammonium pyrophosphate and generates the ferrous pyrophosphate that property is stablized, ferrous pyrophosphate is in high temperature
Hydrolysis release ferrous ion, influences hydrolysis rate by wave computer heating control solution temperature under high fever, effectively reduces anti-
The speed of growth of LiFePO 4 particle during answering plays the effect of refinement LiFePO 4 particle；
2, in solution mixed process, pH to 6~8 is slowly adjusted using 1mol/L ammonium hydroxide, mixed liquid process is avoided Fe occur
(OH)2Precipitation, FePO4Precipitation influences product purity, while ammonium hydroxide can balance extra phosphate anion, maintains solution charge
Balance；
3, existing hydro-thermal method synthesizing iron lithium phosphate, lithium source：Source of iron：Phosphorus source=3:1:1, by reacting 3LiOH+FeSO4+
NH4H2PO4=LiFePO4↓+Li2SO4+NH3+3H2O, in solution Fe and phosphoric acid easily reaction easily generate and easily reunite, cause Li+It is difficult to
Presence into reaction system, and sulfate ion makes solution that electronegativity, Li be presented+It needs to balance extra sulfate ion,
So in fact Li needs 3 times of excess that can just prepare purity LiFePO up to standard4；This programme uses LiH2PO4While as
The lithium source and phosphorus source of the preparation process, and the LiFePO of the amount of commaterial can be produced4, without other impurity containing lithium.I.e.：
LiH2PO4+FeSO4+NH3·H2O+(NH4H)4P2O7=LiFePO4↓+(NH4)2SO4+(NH4)3PO4+NH4H2PO4+2H2O.Using
Macromolecular protects iron ion, ferrous ion, and the control purposive release source of iron of reaction condition contacts to obtain with lithium source, phosphorus source
The LiFePO 4 material that grain is uniform, capacitance is high.LiFePO obtained by the reaction4Crystal, crystalline structure is complete, and particle is small and equal
It is even, it can obtain pure phase LiFePO with X-ray diffraction4, LiFePO obtained through the invention4It is bright on yield, purity, electric property
The aobvious LiFePO prepared better than existing hydro-thermal method4, lithium source material is greatly saved, while cost-effective, reduces environmental pollution, have
There are products pure, at low cost, easy to operate and efficient advantage.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of 1 product of the embodiment of the present invention.
Fig. 2 is X-ray powder diffraction (XRD) figure of 1 product of the embodiment of the present invention.
Specific implementation mode
The present invention is further described with specific implementation mode with reference to the accompanying drawings of the specification.
Comparative example 1：
(1) 1mol FeSO are weighed first4·7H2O is completely dissolved in 300ml distilled water, forms solution and 1mol is added dropwise again
H3PO4Wiring solution-forming A, is added in reaction kettle, seals reaction kettle, and reaction kettle, discharge are purged by intake valve using high pure nitrogen
Inner air；
(2) 3mol LiOHH are weighed2Solution is added dropwise in 300ml distilled water wiring solution-forming B, by reaction kettle inlet valve in O
B；The proportioning that substance is wherein added is molar ratio Li：Fe：P=3.0：1.0：1.0, reaction kettle is warming up to 200 DEG C, keeps the temperature 6h,
It after Temperature fall, filters, washs, it is dry, obtain initial product.
Comparative example 2：
(1) 1mol FeSO are weighed first4·7H2O is completely dissolved in 300ml distilled water, forms solution and 1mol is added dropwise again
H3PO4Wiring solution-forming A, is added in reaction kettle, seals reaction kettle, and reaction kettle, discharge are purged by intake valve using high pure nitrogen
Inner air；
(2) 1mol LiOHH are weighed2Solution is added dropwise in 300ml distilled water wiring solution-forming B, by reaction kettle inlet valve in O
B；The proportioning that substance is wherein added is molar ratio Li：Fe：P=1.0：1.0：1.0, reaction kettle is warming up to 200 DEG C, keeps the temperature 6h,
It after Temperature fall, filters, washs, it is dry, obtain initial product.
Embodiment 1
(1) 400g ammonium pyrophosphates are weighed first and are deoxygenated in distilled water in 1L and are dissolved, and electromagnetic agitation is slowly added to 1mol's
FeSO4·7H2O is heated to 80 DEG C, keeps the temperature 30min, forms mixed liquor A；
(2) 1mol LiH are weighed2PO4, it is dissolved in 1L deoxidation distilled water, and stir, forms solution B；LiH2PO4Weigh mark
Standard is Fe2+：Li+=1:1；The proportioning that substance is added is molar ratio Li：Fe：P=1：1：1；
(3) mixed liquor A and solution B are mixed and stirred for, are added in autoclave, PH=6 is adjusted with 1mol/L ammonium hydroxide；
It is passed through high pure nitrogen, wave heats reaction kettle to 160 DEG C of heat preservation 6h, and cooled to room temperature is filtered, washed, is dried in vacuo
The dry 4h of 80 DEG C of case, obtains positive electrode LiFePO4。
In the prior art, iron ion is easy to react with phosphate anion in solution, reunites and generates ferric phosphate precipitation, leads to lithium
Ion hardly enters reaction system, must be requested that lithium ion is excessive, and reaction forward could be promoted to move, but excessive element shadow
Ring products pure degree.Therefore, the present invention needs to control the stability of ferric phosphate by phosphoric acid iron stabilizers, influences ferrous ion
Rate of release, effectively reduce reaction process in LiFePO 4 particle the speed of growth.
Selected phosphoric acid iron stabilizers are ammonium pyrophosphate, ferrous source FeSO in the present embodiment4·7H2O, the present embodiment
Reaction system in, pyrophosphate ion first react with ferrous ion generation chemical property stabilization ferrous pyrophosphate, pyrophosphoric acid
Ferrous iron exist in the solution with colloidal particle, protection ferrous ion it is not oxidized, by wave computer heating control hydrolysis temperature into
And the hydrolysis rate of ferrous pyrophosphate is controlled, the final rate of release for influencing ferrous ion effectively reduces phosphoric acid in reaction process
The speed of growth of ferrous lithium particle plays the effect for reducing LiFePO 4 grain graininess.The ferrous pyrophosphate of addition is in temperature
It is hydrolyzed at >=100 DEG C, hydrolyzes the phosphate anion of release and ammonium ion in solution is combined and generates ammonium salt, ammonium salt is soluble in
Water and washed away, finally obtain pure phase LiFePO 4, not will produce carbon residue influence LiFePO 4 purity.
1 DEG C/min of heating speed, heating 45min stop heating to the wave mode of heating in order to control, wait for that temperature declines
Same heating speed continues to heat 45min after 15 DEG C, and temperature is made to rise to target temperature (the present embodiment in wave repeatedly
In be 160 DEG C).
Embodiment 2
(1) it weighs 200g amphoteric ions polyacrylamide first to deoxygenate in distilled water in 1L, electromagnetic agitation is slowly added to
The ferrous oxalate of 1mol forms mixed liquor A；
(2) 1mol LiH are weighed2PO4It is dissolved in 1L deoxidation distilled water, and stirs, form solution B；LiH2PO4Weigh standard
For Fe2+：Li+=1:1；The proportioning that substance is added is molar ratio Li：Fe：P=1：1：1；
(3) mixed liquor A and solution B are mixed and stirred for, it is rear to be added in autoclave, adjust PH=with 1mol/L ammonium hydroxide
7；It is passed through high pure nitrogen, wave heats reaction kettle to 200 DEG C of heat preservation 4h, and cooled to room temperature is filtered, washed, vacuum is done
The dry 4h of 80 DEG C of dry case.
Wherein selected phosphoric acid iron stabilizers are amphoteric ion polyacrylamide, and ferrous source is ferrous oxalate.Both sexes from
Sub- polyacrylamide is polyelectrolyte, and when dissolving in deionized water, ionization makes counter ion be detached from macromolecule sequence
It is spread to solvent area, though there is cation group in polymer molecular chain, anion is more than cationic in quantity, quiet on strand
Charge is negative, and electrostatic repulsion and hydration make macromolecular chain stretch, be added ferrous ion can neutralizing molecule chain side group charge simultaneously
Shielding action is generated to group charge, to make macromolecular chain electrostatic repulsion weaken, strand is curled, when mixed liquor and lithium ion
Solution mixed high-voltage kettle heats, and the macromolecular chain molecule interlinkage of curling is destroyed and stretches and combined generation ferric phosphate with lithium source phosphorus source
Lithium material.
Embodiment 3
(1) 200g soluble starches are weighed to be dissolved in 1L deoxidation distilled water, are heated to 60 DEG C of formation gelatinized starches, electromagnetism stirs
Mix the FeSO for being slowly added to 1mol4·7H2O forms mixed liquor A；
(2) 1mol LiH are weighed2PO4It is dissolved in 1L deoxidation distilled water, and stirs, form solution B；
(3) mixed liquor A solution B is mixed and stirred for, is added in autoclave, PH=8 is adjusted with ammonium hydroxide；It is passed through high-purity
Argon gas, wave heat reaction kettle to 180 DEG C of heat preservation 5h, and cooled to room temperature is filtered, washed, 80 DEG C of vacuum drying chamber is done
Dry 4h.
Wherein selected phosphoric acid iron stabilizers are soluble starch, since soluble starch heating generation gelatinization is anticaustic,
Intragranular starch molecule is stretched to all directions and is spread, and is dissolved out outside granule, can be mutually connected between the starch molecule spread
Knot, winding form one and netted contain hydrocolloid.When starch enters the particle disintegration stage of gelatinization reaction, solution viscosity is most
Greatly, starch molecule is enable to be coated on LiH2PO4Around, inhibit LiH2PO4With the reaction speed of ferrous sulfate, and inhibit
The LiFePO that the two generates4Particle size and agglomeration, improve the dispersibility of final product, reduce final product particle
Size.
One, yield compares
Comparative example 1, comparative example 2, embodiment 1, embodiment 2,3 lithium source of embodiment yield be shown in Table 1.
Comparison among groups can clearly be found out：
1, raw material needs lithium source under existing preparation method：Source of iron：Phosphorus source is 3:1:1, such as lithium source：Source of iron：Phosphorus source is 1:1:
1, then actual recovery can decline to a great extent (P<0.01).
2, various embodiments of the present invention lithium source, source of iron, phosphorus source 1:1:1, but yield can be with existing lithium source three times excess
It matches in excellence or beauty, no significant difference (P>0.05).
Two, charge-discharge performance test and comparison
LiFePO prepared by comparative example, embodiment4Carry out charge-discharge performance test, anode prepared material, second
Acetylene black and Kynoar (PVDF) are made by weight 8: 1: 1, and cathode uses metal lithium sheet, diaphragm to use Celgard2400,
Electrolyte is that 1mol/L lithium hexafluoro phosphates are dissolved in ethylene carbonate, the mixed liquor (volume of dimethyl carbonate and diethyl carbonate
Than EC: DMC: DEC=1: 1: 1), making button cell.It tests, comparative example 1,2, implements through BTS high accuracy battery detecting systems
1,2,3 charge-discharge performance of example test such as table 1；
The charge-discharge performance test result of 1 product of table
It can be obtained by table 1, the specific discharge capacity at 0.2C and 1C of embodiment 1,2,3 is above comparative example 1,2；Fig. 1 is this
The SEM figures for the LiFePO 4 that inventive embodiments 1 synthesize, it is seen that the ferrous pyrophosphate lithium grain size of synthesis is less than 1 micron, grain size point
Cloth is uniform, crystal favorable dispersibility.Fig. 2 is the XRD diagram of the embodiment of the present invention 1, shows to obtain LiFePO 4 crystal structure
Product.
It should be noted that the present invention particular embodiment to the present invention have been described in detail, for ability
For the technical staff in domain, its various of progress is obviously changed without departing from the spirit and scope of the present invention
Become all within protection scope of the present invention.
Claims (4)
1. a kind of method that equimolar ratio prepares LiFePO4, which is characterized in that step includes：
(1) it takes phosphoric acid iron stabilizers to dissolve in deoxygenating in distilled water, ferrous source is slowly added under stirring, form mixed liquor A；
(2) according to Fe2+：Li+=1:1 weighs LiH2PO4, it is dissolved in deoxidation distilled water, and stir, forms solution B；
(3) mixed liquor A and solution B are mixed and stirred for, are added in autoclave, PH=6~8 are adjusted with ammonium hydroxide；It is passed through height
Pure inert gas, wave heat reaction kettle to 160~200 DEG C of 4~6h of heat preservation, and cooled to room temperature is filtered, washed, very
Sky is dry, obtains positive electrode LiFePO4；1 DEG C/min of heating speed, heating 45min stop in order to control for the wave heating
Heating, same heating speed continues to heat 45min after temperature declines 15 DEG C, and temperature is made to rise to mesh in wave repeatedly
Mark temperature.
2. the method that equimolar ratio according to claim 1 prepares LiFePO4, it is characterised in that：The ferric phosphate is steady
It is gelatinized starch to determine agent.
3. the method that equimolar ratio according to claim 2 prepares LiFePO4, it is characterised in that：The gelatinization is formed sediment
Powder, preparation method thereof is：Soluble starch is dissolved in deoxidation distilled water, is heated to 60 DEG C of formation gelatinized starches.
4. the method that equimolar ratio according to claim 1 prepares LiFePO4, it is characterised in that：The ferrous source is
FeSO4·7H2O or ferrous oxalate.
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| CN201810110426.0A CN108417832B (en) | 2016-03-18 | 2016-03-18 | Method for preparing lithium iron phosphate in equimolar ratio |
| CN201610155884.7A CN105680044B (en) | 2016-03-18 | 2016-03-18 | A kind of method that hydro-thermal method equimolar prepares LiFePO4 |
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| CN113097591A (en) * | 2021-02-26 | 2021-07-09 | 云南航开科技有限公司 | Method for recovering anode material of lithium iron phosphate battery |
| CN115028153A (en) * | 2022-04-18 | 2022-09-09 | 福州华复新能源科技有限公司 | Low-cost equimolar lithium resource-saving hydrothermal method for producing lithium iron phosphate |
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| CN114702019A (en) * | 2022-04-18 | 2022-07-05 | 福州华复新能源科技有限公司 | Method for producing lithium iron phosphate by pure liquid phase mixing and solid phase sintering |
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| CN113097591A (en) * | 2021-02-26 | 2021-07-09 | 云南航开科技有限公司 | Method for recovering anode material of lithium iron phosphate battery |
| CN115028153A (en) * | 2022-04-18 | 2022-09-09 | 福州华复新能源科技有限公司 | Low-cost equimolar lithium resource-saving hydrothermal method for producing lithium iron phosphate |
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| CN108417832B (en) | 2020-11-24 |
| CN108390061B (en) | 2021-07-02 |
| CN105680044A (en) | 2016-06-15 |
| CN108390061A (en) | 2018-08-10 |
| CN105680044B (en) | 2018-03-20 |
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