CN102897741B - Hydrothermal preparation method for nanometer lithium iron phosphate - Google Patents
Hydrothermal preparation method for nanometer lithium iron phosphate Download PDFInfo
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- CN102897741B CN102897741B CN201110209509.3A CN201110209509A CN102897741B CN 102897741 B CN102897741 B CN 102897741B CN 201110209509 A CN201110209509 A CN 201110209509A CN 102897741 B CN102897741 B CN 102897741B
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- phosphoric acid
- lithium
- organic compound
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Abstract
The present invention provides a preparation method for lithium iron phosphate (LiFePO4). In hydrothermal synthesis, an organic compound having a phosphate end group such as hydroxyethylidene diphosphonic acid is added, wherein the synthesized LiFePO4 material has characteristics of small particle size (nanometer scale), good uniformity and good dispersibility. In addition, the method is simple; raw material cost is low; and characteristics of high specific capacity and good cycle performance are provided when the prepared LiFePO4 material is adopted as a battery positive electrode material.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery anode material lithium iron phosphate, particularly relate to the hydrothermal preparing process of controlledly synthesis nano-grade lithium iron phosphate.
Background technology
Along with widespread use and the fast development of various portable electric appts and electromobile, lithium ion battery is high with its operating voltage, energy density is large, have extended cycle life, the advantages such as self-discharge rate is low, environmental protection, at portable electronics as being widely used in laptop computer, pick up camera, mobile communication, and start aspect the energy storage of hybrid vehicle, electromobile, sun power and wind energy, obtaining application.
Olivine-type iron lithium phosphate (LiFePO
4hereinafter to be referred as LFP) material is owing to possessing height ratio capacity, long circulation life,, more environmental protection safer than other anode material for lithium-ion batteries, the multiple advantage such as more cheap and become the emphasis of recent research are the anode material for lithium-ion batteries of new generation of tool development and application potentiality.LFP was in the news as anode material for lithium-ion batteries first in 1997.LFP has the structure of olivine-type, and spacer is Pnmb (Pnma), and its theoretical capacity is 170mAh/g.
LFP, as cell positive material, has following advantage:
1) higher theoretical specific capacity and operating voltage, and 1mol LFP can deintercalation 1mol Li+, and the service efficiency of material is high, the about 3.4V of its operating voltage;
2) good cycle performance, particularly high temperature cyclic performance, and improve use temperature and can also improve its high-rate discharge ability;
3) superior safety energy;
4) World Iron aboundresources, inexpensive and nontoxic, therefore LFP is considered to a kind of environmentally friendly positive electrode material.
5) volume change of LFP in charge and discharge process is only 6.8%, if use is carbon negative pole, in discharge process, its volume becomes large, just the opposite with positive pole, so just can make the cumulative volume variation of whole inside battery material very little, reduces stress.
Due to its reasons in structure, LFP also has the following shortcoming:
1) relatively low (3.6g/cm of the density of LFP
3), cause its energy density lower;
2) ion of LFP and electron conductivity are very low, and the specific conductivity of pure LFP is 10-9S/cm;
3) in charge and discharge process, occur that phase transformation is (by LiFePO
4change FePO into
4), affect cycle life.
Wherein, the disadvantage that affects LFP application is second point, specific conductivity and ionic conductance that LFP material is extremely low.This has affected LFP material and has brought into play its effect, has limited its performance under high charge-discharge magnification.
US Patent No. 2007190418 has been reported the preparation method of nano level LiFePO 4 material, and elaborated nano-scale lithium iron phosphate material and compare with micron order LiFePO 4 material with submicron, there is higher electronics and ionic conductance, different charge-discharge performance and longer cycle life.Nano-scale lithium iron phosphate material is at Li
+embedding/deintercalation circulation time, LiFePO
4and FePO
4form sosoloid, be conducive to Li
+embedding/deintercalation.And in working cycle, may there is the process that capacity improves in nano-scale lithium iron phosphate material.
The preparation method of the material of above-mentioned patent report is the synthetic high temperature solid-state method used of industry at present.The method mainly comprises that ball milling mixes and two processes of high-temperature firing, has step simple, easy to operate advantage.Its shortcoming length consuming time; State when synthetic is restive; The consistence of synthetic material is not good; Energy consumption is large; Need protection of inert gas etc.In addition, the synthetic LFP material of solid phase method generally contains Fe
2+and Fe
3+pyrophosphate salt dephasign, if temperature of reaction reaches 700 DEG C, also there will be phosphide impurity.
Hydrothermal method is a kind of method of carrying out chemical reaction by High Temperature High Pressure in the fluid such as the aqueous solution or water vapor and prepare powder body material.The advantages such as hydrothermal method has thing phase homogeneous, diameter of particle is little, process is simple, have certain advantage aspect synthesizing iron lithium phosphate material.
Chinese patent CN101007630A has reported and a kind of lithium source, source of iron, phosphorus source has been mixed in deionized water or water/alcohol mixing thing, add a certain proportion of additive, as graphite, carbon black, sucrose, tartrate, citric acid etc., carry out at a certain temperature Hydrothermal Synthesis, obtain the method for iron lithium phosphate submicron particles.Its synthetic LiFePO 4 material circulation volume under 0.1C is 145mAh/g, but under high magnification, its capacitance loss is larger, if circulation volume under 4C is 98.18mAh/g.
The inventor sum up reported basis on, carry out research with keen determination, find to use phosphoric acid end group organic compound as additive, use hydrothermal method can synthesize easily nano level LiFePO 4 material, during for anode material for lithium-ion batteries, excellent property, has completed the present invention.
Summary of the invention
The object of this invention is to provide a kind of iron lithium phosphate (LiFePO
4, referred to as LFP) and the hydrothermal preparing process of nano particle, regulate and control easily LiFePO
4the pattern of particulate product and size.Technical scheme of the present invention is to adopt the synthetic LiFePO of hydro-thermal reaction
4time, by adding a certain amount of phosphoric acid end group organic compound, pattern and the size of regulation and control the finished product.Specifically comprise the steps:
(1) after phosphoric acid or aqueous phosphatic are mixed with phosphoric acid end group organic compound, add lithium salts and ferrous salt, after stirring, transfer in hydrothermal reaction kettle;
(2) after logical rare gas element, carry out hydro-thermal reaction;
(3) cooling, solid-liquid separation, washing, dry after, make lithium iron phosphate nano particle.
Wherein said phosphoric acid end group organic compound, can select the easy solvability the aqueous solution obtaining from market good, there is the organic compound of phosphoric acid end group, such compound, for example have from hydroxy ethylene diphosphonic acid (being abbreviated as below HEDP), phenyl-phosphonic acid, Amino Trimethylene Phosphonic Acid (being abbreviated as below ATMP), N-phosphorus carboxylic methylene radical-iminodiethanoic acid (being abbreviated as below PMIDA), N, two (phosphonate group methyl) glycine of N-(also referred to as increasing sweet phosphorus), from price and the easy angle obtaining from market, HEDP, ATMP, PMIDA is better, wherein HEDP is better, it is a kind of conventional water conditioner.In the compound molecule of these types, there is for example phenyl-phosphonic acid that contains 1 phosphate radical, have and contain 2 such as HEDP of phosphate radical, conventionally the amount adding is taking the mole ratio of the mole number of phosphate radical and the amount of iron ion as 5～15: 100 is better, mean the occasion that adds HEDP, the mole number ratio of its HEDP and iron ion is 2.5～7.5: 100 is better, the phosphoric acid end group organic compound adding can be the aqueous solution, can be also solid.Along with the increase adding of for example HEDP of phosphoric acid butt base organic compound, LiFePO4 material particle size reduces, and the distribution of particle diameter is more and more even, and pattern keeps the constant (see photo) of diamond platy.The particle size data of being correlated with mapping is shown in figure below
In step (1), each compound is mixed with the process of solution; as long as can obtain the solution that solvability is good, be beneficial to generation LFP; first by after phosphoric acid or phosphoric acid salt wiring solution-forming; add lithium compound, if use the occasion of phosphoric acid, use the such basic cpd of lithium hydroxide better; both can make the acidity requirement that reaches certain by neutralizing acid; add again ferrous salt better, for anti-oxidation, under protection of inert gas, be operating as.Wherein the ratio of all ingredients can decide by experiment, conventionally lithium salts: ferrous salt: phosphoric acid or phosphoric acid salt: phosphoric acid end group organic compound respectively in lithium ion, iron ion, phosphate radical mole, its mol ratio is 1～3: 1～1.2: 1: 0.05～0.15 is better.
Said phosphoric acid root, adopts phosphoric acid or phosphoric acid salt, considers to be used in conjunction with lithium salts etc., considers the OK range of the pH of solution, uses phosphoric acid more convenient; The phosphoric acid solution concentration of preparation is conveniently selected according to acid-base neutralisation in the good solution of preparation solvability and operating process, and general concentration is relatively good near 2molL-1.
Said lithium salts or lithium hydroxide, consider to prepare suitable pH solution with sour neutralization, selects lithium hydroxide more convenient.
Ferrous salt, the angle of the angle of coexisting ion and inhibition hydrolysis from solution, selects phosphoric acid salt iron ammonium more convenient.
The amount of substance ratio of described lithium hydroxide, phosphoric acid and ferrous ammonium sulphate should be 1～3: 1～1.2: 1 is better.
The hydrothermal temperature of step (2) is preferably 150～180 DEG C, and the reaction times is 2.5～4 hours.
In step (3), the liquid of washing use be water or dehydrated alcohol for well, also can wash with mixing solutions.
Add in the present invention and there is phosphoric acid end group organic compound, due to the phosphate radical of the end group phosphate group containing and phosphoric acid with melts combine aspect character have similar part, binding ability is close.Under the organic compound that contains a large amount of phosphate anions and this phosphoric acid butt base exists, generate iron lithium phosphate under hydrothermal condition time, the organic compound of phosphoric acid butt base also participates in reaction, because an end points of phosphate radical has organic group link, therefore stop and be combined into larger lithium iron phosphate particles, therefore, this compounds addition is too little, do not have effect, along with the increase of addition, the particle that should predict synthetic iron lithium phosphate is less, after being increased to a certain degree, causes the phase transformation of lithium iron phosphate particles.Through experiment, addition is taking the ratio of the mole number of phosphate radical and the mole number of iron ion as 5～15: 100 for well, at a preferred example, lithium ion (lithium hydroxide): ferrous ion (ferrous sulfate is pressed): phosphate radical (phosphoric acid): the mol ratio of phosphoric acid end group organic compound is 1～3: 1～1.2: 1: 0.05～0.15, wherein, phosphoric acid end group organic compound is in the mole number of phosphate radical wherein.
Having the organic compound of phosphate radical end group, as noted earlier, is a kind of organic phosphine acids anti-incrustation corrosion inhibitor, can form stable complex compound with the many kinds of metal ions such as iron, copper, zinc, oxide compound that can dissolution of metals surface.By the organic compound of phosphate radical end group, such as HEDP etc. adds in raw material, during with the synthetic LFP of hydrothermal method, HEDP and phosphate anion competition, with the Fe2+ in system, form title complex with the iron of iron lithium phosphate solid particles surface, can stop growth and the reunion of LFP particle, obtained so evenly less LFP of grain diameter.
Said suitable pH, in process for preparation, based on the hydrolysis that need to prevent iron ion, again can not acidity too high, so there is suitable pH scope, can regulate by experiment proportioning to decide, the solution that adopts the above-mentioned compound proportioning of the present invention to obtain, can synthesize iron lithium phosphate easily.
The LFP that the inventive method obtains, along with the amount of adding phosphoric acid end group organic compound increases, particle diameter diminishes, distribution narrow (accompanying drawing 7 and accompanying drawing 8), in a preferred embodiment, present regular diamond platy pattern, particle diameter is about 100nm, for nanometer materials, and evenly (seeing accompanying drawing 2) of size distribution.
Method of the present invention, energy quickly synthesizing nano level iron lithium phosphate, temperature of reaction is low, and less energy consumption is simple to operate, and cost is low.Because surface is the organic compound that contains phosphate radical end group, can in solution, carry out simply the uniform particle of the coated acquisition of carbon.Regular particles, crystal property is good, and specific storage is high, good cycle, high rate performance is good.These regular particles granularities are little, are conducive to the solid phase diffusion of Li+, greatly multiplying power discharging.
In a preferred example, when the HEDP molar weight adding be in system Fe molar weight 7.5% time, nano level LFP material initial charge specific storage under 0.1C of synthesized is 154mAh/g, specific discharge capacity is 134mAh/g; After 20 circulations, capacity increases, and specific discharge capacity is 140mAh/g; After charge-discharge magnification improves, capacity loss is not obvious, under 2C multiplying power, still has the capacity of 126mAh/g.
Brief description of the drawings
Fig. 1 is the XRD figure spectrum of the iron lithium phosphate prepared of the embodiment of the present invention 1
Fig. 2 is the SEM figure of the iron lithium phosphate prepared of the embodiment of the present invention 1
Fig. 3 is the cyclic voltammetric collection of illustrative plates of the iron lithium phosphate prepared of the embodiment of the present invention 1
Fig. 4 is the 0.1C first charge-discharge cycle diagram of the iron lithium phosphate prepared of the embodiment of the present invention 1
Fig. 5 is cycle performance figure under the 0.1C of the iron lithium phosphate prepared of the embodiment of the present invention 1
Fig. 6 is cycle performance figure under the different multiplying of the iron lithium phosphate prepared of the embodiment of the present invention 1
Fig. 7 is the SEM figure of the iron lithium phosphate particle prepared of the embodiment of the present invention 9
Fig. 8 is the maximum particle diameter of iron lithium phosphate grain and the graph of a relation of minimum grain size and HEDP addition recording from the SEM figure of Fig. 7
Embodiment
The method of the present invention being prepared to lithium iron phosphate nano particle below by specific embodiment is described further, and does not form the restriction to described technical scheme.
Embodiment 1
Pipette 0.04mol H
3pO
4, add 20mL distilled water, be formulated as the aqueous solution of 2mol/L, take 0.0030mol HEDP (being accurate to 0.0001g) with electronic balance, join H
3pO
4in solution, be uniformly mixed.Take 0.12mol LiOH, in nitrogen atmosphere, stir on one side, slowly added aforementioned solution on one side, continue to be stirred to the completely dissolve of LiOH particle.Take 0.04mol (NH
4)
2fe (SO
4)
26H
2o, keeps stirring, and slowly adds aforementioned solution, continues stirring until (NH
4)
2fe (SO
4)
26H
2o particle disappears, and mixed solution is moved in 25-ML water heating kettle.
By logical water heating kettle argon deoxygenation 5min, sealing kettle.In air dry oven, be warming up to 180 DEG C with the speed of 1 DEG C/min, insulation 3h, then lower the temperature with 5 DEG C/min.The powder body material obtaining in water heating kettle is filtered, uses clear water and washing with alcohol successively, sample is placed in to vacuum drying oven, dry 12h at 50 DEG C.Sample, through XRD test, is indicated as LFP (accompanying drawing 1).
Adopt that with the following method material to be carried out to carbon coated: take 1～5g LFP material and mix with the glucose of 17wt%, be placed in beaker, add appropriate ethanol, on magnetic stirring apparatus, 150rpm stirs 4h, after LFP and glucose are evenly mixed, move in Rotary Evaporators ethanol evaporate to dryness.After mixture is dried, put into tube furnace, in argon gas atmosphere, 3 DEG C/min is heated to 600 DEG C, insulation 2h carbonization, and then cool to room temperature with the speed of 5 DEG C/min, obtain LFP/C material.
Take in mass ratio active substance (LFP/C matrix material), conductive agent (acetylene black), binding agent PVDF (poly(vinylidene fluoride)) at 60: 30: 10.First PVDF is added in NMP (N-Methyl pyrrolidone) (10g/L), stir 2h at infrared lamp lower magnetic force, PVDF is all dissolved.By even to LFP/C matrix material and acetylene black ground and mixed, add in the nmp solution of PVDF, continue magnetic agitation 2h, make it to mix.Then, mixed solution is coated on coating machine to aluminium foil surface, coating thickness 0.03mm.40 DEG C of oven dry in vacuum drying oven.On roll squeezer, after roll-in, rushing with sheet-punching machine is Φ 15mm disk, then puts into 120 DEG C of oven dry 12h of vacuum drying oven.
Using above-mentioned pole piece as positive pole, by metal lithium sheet, as negative pole, microporous polypropylene membrane is barrier film, electrolytic solution is the LiPF6/EC+DMC+EMC (volume ratio 1: 1: 1) of 1mol/L, barrier film is Celgard2400, in the glove box that is full of argon gas, is assembled into 2025 button cells.
Cyclic voltammetry adopts Im6ex electrochemistry platform.Test condition: adopt two electrode systems, supporting electrode and reference electrode are metal Li, and Electrode is active sample electrode, sweep limit 2.5～4.5V (vs.Li/Li+); Scanning speed is 0.1mV/s.
Battery charging and discharging test macro is detecting electrode material capacity, the most frequently used equipment of cycle performance.In Wuhan, Land CT2001A battery test system carries out charge-discharge test, current density 100mA/g, and charging/discharging voltage scope is 2.5-4.2V.
The XRD figure of synthetic LFP sample is composed (accompanying drawing 1), has shown to obtain the sample of LFP structure, and from the visible synthetic LFP material particle size of SEM figure (accompanying drawing 2), for being about 100nm, size distribution is even, favorable dispersity.Institute's assemble initial charge specific storage under 0.1C is 154mAh/g (accompanying drawing 4), and specific discharge capacity is 134mAh/g; After 20 circulations, capacity increases by (accompanying drawing 5), has the cycle characteristics of nano-scale lithium iron phosphate material; Specific discharge capacity is 140mAh/g; After charge-discharge magnification improves, under 0.5C, 1C, 2C, 5C, circulation volume is respectively 131mAh/g, 126mAh/g, 123mAh/g and 118mAh/g, conservation rate is respectively 93.6%, 90.0%, 87.9%, 84.3%, can be competent at the high-power needs that discharge and recharge (accompanying drawing 6).
Be about 100nm from SEM figure particle diameter, in fact the grain-size of iron lithium phosphate is less.Learn to there is nano level iron lithium phosphate according to mentioned document in US Patent No. 2007190418 and Patents and this patent, the sample preparing or in impulse electricity process sample can produce defective Li
1-xfePO
4with Li
yfePO
4the sosoloid of (x, y is a very little number, for example 0.01,0.02 etc.), circulation volume such as can increase to some extent at the plurality of advantages.
Embodiment 2
Similar to Example 1, difference is that the HEDP amount adding is 0.0020mol.
The LiFePO 4 material first charge-discharge capacity obtaining is respectively 125mAh/g and 118mAh/g.
Embodiment 3
Similar to Example 1, difference is that the HEDP amount adding is 0.0010mol.
The LiFePO 4 material first charge-discharge capacity obtaining is respectively 120mAh/g and 104mAh/g.
Embodiment 4
Similar to Example 1, difference is that the LiOH amount adding is 0.04mol.This HEDP add-on is iron ion 6 % by mole.
The LiFePO 4 material first charge-discharge capacity obtaining is respectively 98mAh/g and 85mAh/g.
Embodiment 5
Similar to Example 1, difference is that the phosphoric acid end group organic compound adding is Amino Trimethylene Phosphonic Acid [ATMP, CAS:6419-19-8], and add-on is 0.0030mol.Be 150 DEG C in the temperature of air dry oven hydro-thermal reaction, the reaction times is 4h.
The LiFePO 4 material first charge-discharge capacity obtaining is respectively 80mAh/g and 67mAh/g.
Embodiment 6
Similar to Example 1, difference is that the phosphoric acid end group organic compound adding is PMIDA, and add-on is 0.0030mol.Be 175 DEG C in the temperature of air dry oven hydro-thermal reaction, the reaction times is 2.5h.
The LiFePO 4 material first charge-discharge capacity obtaining is respectively 84mAh/g and 68mAh/g.
Embodiment 7
Similar to Example 1, difference is that the phosphoric acid end group organic compound adding is for increasing sweet phosphorus, and add-on is 0.0030mol.
The LiFePO 4 material first charge-discharge capacity obtaining is respectively 96mAh/g and 72mAh/g.
Embodiment 8
Similar to Example 1, difference is that the phosphoric acid end group organic compound adding is phenyl-phosphonic acid, and add-on is 0.0030mol.
The LiFePO 4 material first charge-discharge capacity obtaining is respectively 79mAh/g and 60mAh/g.
Embodiment 9
Similar to Example 1 in the process of synthesizing iron lithium phosphate particle, the HEDP molar content of the amount that the HEDP amount that difference is to add is iron ion is respectively 0%, 1%, 2%, 3%, 4%, 5%, 6%, 9%.After good lithium iron phosphate particles, take SEM image.According to the largest particle diameter of iron lithium phosphate in figure and smallest particles diameter mapping (accompanying drawing 7).The LiFePO4 material particle size of visible synthesized reduces along with the increase of HEDP content, and the distribution of particle diameter is more and more even, and from SEM figure, visible pattern keeps diamond platy constant.
Table 1
Claims (7)
1. the hydrothermal preparing process of a lithium iron phosphate nano particle, it is characterized by the reaction by phosphoric acid or phosphoric acid salt, lithium salts, ferrous salt synthesizing iron lithium phosphate under hydrothermal condition, add phosphoric acid end group organic compound, wherein phosphoric acid end group organic compound is selected from hydroxy ethylene diphosphonic acid, phenyl-phosphonic acid, Amino Trimethylene Phosphonic Acid, N-phosphorus carboxylic methylene radical-iminodiethanoic acid, N, two (phosphonate group methyl) glycine of N-, add phosphoric acid end group organic compound and iron ion taking phosphate radical and iron ion mole mol ratio as 5～15:100.
2. the hydrothermal preparing process of a kind of lithium iron phosphate nano particle as claimed in claim 1, comprises the steps:
(1) after phosphoric acid or aqueous phosphatic are mixed with phosphoric acid end group organic compound, add lithium compound and ferrous salt, after stirring, transfer in hydrothermal reaction kettle;
(2) after logical rare gas element, carry out hydro-thermal reaction;
(3) cooling, solid-liquid separation, washing, dry after, make lithium iron phosphate nano particle.
3. the hydrothermal preparing process of a kind of lithium iron phosphate nano particle as claimed in claim 1 or 2, wherein phosphoric acid end group organic compound is hydroxy ethylene diphosphonic acid.
4. the hydrothermal preparing process of a kind of lithium iron phosphate nano particle as described in one of claims 1 to 3, wherein said phosphoric acid or phosphoric acid salt are phosphoric acid, and lithium compound is lithium hydroxide, and ferrous salt is ferrous ammonium sulphate.
5. the hydrothermal preparing process of a kind of lithium iron phosphate nano particle as claimed in claim 2, lithium compound in wherein said step (1): ferrous salt: phosphoric acid or phosphoric acid salt: mole its mol ratio taking lithium ion, iron ion, phosphate radical of phosphoric acid end group organic compound is as 1～3: 1～1.2: 1: 0.05～0.15.
6. the hydrothermal preparing process of a kind of lithium iron phosphate nano particle as claimed in claim 2, the temperature of wherein said step (2) hydro-thermal reaction is 150～180 DEG C, the reaction times is 2.5～4 hours.
7. the hydrothermal preparing process of a kind of lithium iron phosphate nano particle as claimed in claim 2, wherein in step (3), the solvent of washing use is one or the mixed solvent of water or dehydrated alcohol.
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| CN105084338A (en) * | 2015-07-29 | 2015-11-25 | 南开大学 | Method for preparing anode material lithium ion cell lithium iron phosphate |
| CN106505186B (en) * | 2016-11-28 | 2019-04-05 | 湖南大学 | A kind of lithium iron phosphate positive material and preparation method thereof of in-stiu coating graphene film |
| CN106744773B (en) * | 2016-12-20 | 2018-11-09 | 芜湖华欣诺电化学科技有限公司 | A kind of nanometer of anhydrous iron phosphate and its synthetic method |
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| CN1803590A (en) * | 2005-12-22 | 2006-07-19 | 上海交通大学 | Method for preparing lithium ion battery anode material lithium ion phosphate |
| CN101740778A (en) * | 2008-11-19 | 2010-06-16 | 南京大学 | Low-temperature hydrothermally synthesized organic phosphonic acid lithium battery anode material LixMmR(PO3)n |
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| CN1803590A (en) * | 2005-12-22 | 2006-07-19 | 上海交通大学 | Method for preparing lithium ion battery anode material lithium ion phosphate |
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