CN101630739A - Preparation method of modification doping lithium ferric phosphate - Google Patents
Preparation method of modification doping lithium ferric phosphate Download PDFInfo
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Abstract
The invention discloses a preparation method of modification doping lithium ferric phosphate, which comprises the following steps: under the condition of the existence of surfactant, mixing lithium compounds, ferric salt, phosphate salt, carbon precursor and dopant according to the proportion; milling the mixture; and then, processing the mixture by adopting a high-temperature solid phase method to obtain the lithium ferric phosphate material, the chemical formula of which is LiFe<x>M<1-x>PO4. In the invention, the surfactant is used as an auxiliary additive for uniformly dispersing the precursor in the water solution and carrying out carbonization in the solid phase reaction without influencing the purity of the material, and carbon is uniformly coated around the crystal, thereby improving the conductivity of the material and effectively inhibiting the growth of the crystal. Finally, the uniformly dispersed lithium ferric phosphate material of the nanometer grade is obtained.
Description
Technical field
The invention belongs to a kind of preparation method of anode material for lithium-ion batteries, particularly relate to a kind of method preparing phosphate iron lithium of doping vario-property.
Background technology
Lithium ion battery is the novel green high-power rechargeable battery that occurs early 1990s, has good voltage platform, outstanding cyclical stability and thermal stability, advantage such as cheap, being widely used in mobile phone, notebook computer, portable power tool, electronic instrument etc., is one of positive electrode that has potentiality.Positive electrode is an important component part of lithium ion battery, in the lithium ion battery charge and discharge process, not only be provided in the both positive and negative polarity lithium intercalation compound the needed lithium of back and forth embedding/take off, but also to bear the required lithium of SEI film that the negative material surface forms, therefore, research and develop high performance positive electrode and become particularly important.The LiCoO of present large-scale commercial
2, toxicity is bigger, costs an arm and a leg, and has certain safety problem.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, there is bigger potential safety hazard in poor heat stability.Spinelle LiMn
2O
4Cost is low, and fail safe is good, but capacity is low, and high temperature cyclic performance is poor.Therefore need the positive electrode of the cheap function admirable of development of new to satisfy the growing market demand.And as the rhombic system olivine-type LiFePO of new type lithium ion battery positive electrode
4Have the capacity height, steadily particularly it is cheap for charging/discharging voltage, and fail safe is good, and Heat stability is good, environmentally safe etc. more make it become one of the most potential positive electrode.
LiFePO
4Exist in the form of occurring in nature, have orderly olivine structural with triphylite, belong to rhombic system (D162h, Pmnb).4 LiFePO are arranged in each structure cell
4Its cell parameter of unit
,
With
In LiFePO4, oxygen atom is approximate, and to be six sides tightly packed, and phosphorus atoms is in tetrahedral space, and iron atom, lithium atom are respectively in octahedral space.FeO on crystal b-c plane
6Octahedra concurrent links.A FeO
6Octahedron and two LiO
6Octahedra limit altogether, and a PO
4Tetrahedron then with a FeO
6Octahedron and two LiO
6Octahedra limit altogether.And Li
+Have two-dimentional mobility, in charge and discharge process, can deviate from and embed.Strong P-O covalent bond forms the 3 D stereo chemical bond of delocalization, makes LiFePO
4Has very strong thermodynamics and kinetics stability.According to Goodenough[J.Flectrochem.Soc., 144 (1997) 1188] research group's synthesizing iron lithium phosphate at first.This material has high theoretical specific capacity (170mAh/g) as anode material for lithium-ion batteries, greater than business-like LiCoO
2Actual discharge capacity 140mAh/g, so cause researcher's very big concern.But the electronic conductivity of this material is relatively poor, has limited the application of material under higher current density greatly.The method about raising LiFePO 4 material performance of report mainly contains surperficial coated with conductive material with carbon element or conductive metal particle at present, improves the intergranular electronic conductivity of fertile material; Modification is mixed.Wherein, modification is mixed and mainly is: mix in the lithium position, iron position doping, oxygen place doped, P site doped.(Li mixes in the lithium position
1-xM
xFePO
4) can improve the electronic conductivity of material, and the raising of dopant material conductivity is not to be the reason of ferrophosphorus compound, can this be relevant with doping elements but improve high rate performance, and is also relevant with doping.(LiFe mixes in the iron position
xM
1-xPO
4): mixing in ferroelectric position is multiplying power and reasonable method of cyclicity of improving material, because its preparation is simple, can extensive use.Oxygen place doped (LiFeP (M
xO
4-x)): oxygen place doped is alloy with anionic compound or simple substance, is easy to be implemented in by traditional solid phase method effective doping of parent oxygen position, significantly improves battery capacity and cycle electric performance, very with practical value.P site doped (LiyFe (P
1-xM
x) O
4): P site doped lithium iron phosphate positive material has higher charge/discharge capacity, better high rate performance and good circulation performance, and wherein M is a doped chemical, and M is Ge, Sn, Se, Te or Bi.
Improve the LiFePO4 electric conductivity except modification is mixed and outside the carbon method for coating, can reduce the size of LiFePO4 particle, improve the ionic diffusion coefficient of material.In the LiFePO4 preparation process, in the precursor system, add surfactant, can play good dispersion effect to precursor.Simultaneously surfactant can form micellar structure in system, be coated on around the precursor uniformly, and when sintering the surfactant high temperature cabonization, effectively controlled the size of LiFePO4 crystal.Surfactant has been brought into play good effect with the micellar structure of its uniqueness at aspects such as medicine (target administration), preparation nano metal ions.Domestic existing people adds surfactant and prepares LiFePO4 (such as patent CN200810120092.1), but its preparation method more complicated, and be difficult to industrialization.The present invention uses simple technology, and cheap raw material utilizes solid sintering technology to prepare LiFePO 4 material, and obtained good performance.
Summary of the invention
The present invention is directed to prior art lithium ion anode material LiFePO4 problem such as difficulty on industrial preparation, the solid-phase sintering method of a kind of iron position doped lithium ion battery LiFePO 4 of anode material is provided, makes it have higher charge/discharge capacity and good cycle performance of battery.
The objective of the invention is to be implemented by the following technical programs:
The method preparing phosphate iron lithium step of doping vario-property of the present invention comprises:
A) lithium compound, molysite, phosphate, carbon matrix precursor and alloy are mixed in proportion, join in the aqueous surfactant solution that concentration is 0.5-3.0wt%, behind ball mill container high speed ball milling certain hour, the mixture of gained is dried processing under 80-120 ℃;
B) mixture after then A step oven dry being handled flow velocity be the 10-50 liter/minute inert gas shielding under carry out sintering; programming rate was 2-10 ℃/minute, is warming up to 400-800 ℃, at 400-800 ℃ of following heat treatment 5-20 hour; reduce to room temperature then, carry out pulverization process at last.
The present invention adopts surfactant as auxiliary additive, be made into the certain density aqueous solution as the ball milling solvent, can play the effect of even dispersion presoma, and carbonization in solid phase reaction (can not influence the purity of prepared material) improves material conductivity, and can effectively suppress growing up of crystal, thereby obtain nano level homodisperse LiFePO 4 material.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, described surfactant is at least a in polyethylene glycol, tween series or the AEO series etc.Wherein, tween (being tween, also is the polyoxyethylene sorbitan fatty acid ester) series can be selected as tween-20, tween-40, tween-60, tween-65 etc.; AEO (being AEO) series can be selected as AEO-3, AEO-5, AEO-7, AEO-9, AEO-12, AEO-15 etc.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, described steps A is the mol ratio Li that forms by chemical formula: Fe: M: P=1: x: (1-x): 1 takes by weighing lithium compound, molysite, alloy and phosphate mixes 0.9≤x＜1 in proportion.Carbon precursor addition adds 5-20g carbon by 1 mole of ferric iron source and calculates.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, described lithium compound is Li
2CO
3, at least a in LiOH, lithium oxalate or the lithium acetate.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, described molysite is di-iron trioxide or ferric phosphate or its mixture.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, described phosphate is at least a in triammonium phosphate, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, described carbon matrix precursor is at least a in sucrose, glucose, carbon black, starch or the gelatin.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, described alloy is at least a in Mg, Mn, Co or the Ni oxide.
The method preparing phosphate iron lithium of above-mentioned doping vario-property, as preferably, the time of ball-milling treatment is 2-10 hour in the described steps A, ball milling speed is 200-800rpm.
The method preparing phosphate iron lithium of above-mentioned doping vario-property as preferably, was warming up to 400-750 ℃ among the described step B, at 400-750 ℃ of following heat treatment 2-10 hour.
The compound that the inventor proposes with Mg, the Mn of transition elements VIIB family, the 8th VIIICo of family, Ni is a doped raw material, utilizes surfactant evenly to disperse, and prepares the nano-grade lithium iron phosphate that mixes in the iron position with solid-phase synthesis then, has improved LiFePO4 LiFePO
4The base batteries performance of positive electrode makes it have higher charge/discharge capacity and good cycle performance of battery.
Material of the present invention compared with prior art has the following advantages:
The present invention adopts surfactant can evenly disperse presoma as auxiliary additive in the aqueous solution, and carries out carbonization in solid phase reaction, does not influence the purity of material.And around the crystal even carbon coated, improved material conductivity, and effectively suppressed growing up of crystal, obtain nano level homodisperse LiFePO 4 material at last.
The present invention utilizes to mix in the iron position and introduces metal ion, can be at the olivine structural that does not change material, kept having improved the conductivity of LiFePO4 greatly under the prerequisite of stable cycle performance, and improved the high rate capability of material.And the present invention uses cheap ferric iron source solid sintering technology to prepare the LiFePO4 of electric conductivity excellence, avoided that the easy oxidation of ferrous salt causes the impure problem of product in other synthetic methods, use ferric iron source to be reduced to divalence, the ferrous iron activity of harsh one-tenth is good, fast with lithium and phosphorus source reaction speed, the LiFePO4 purity height that generates makes the product that makes that good electrochemical be arranged.The lithium ion anode material LiFePO4 molecular formula LiFe that the present invention obtains
xM
1-xPO
4Expression, wherein M is a doped chemical, 0.9≤x＜1.Adopt this method production efficiency height, energy consumption is low, is fit to big suitability for industrialized production, and technological parameter is controlled easily, the batch good stability, and prepared product has good pole piece processing characteristics, electric conductivity and chemical property.
Description of drawings
Fig. 1 is for pressing the XRD figure spectrum of embodiment 1 gained LiFePO 4 material.
Fig. 2 a is by the prepared simulation button cell discharge curve under different charge-discharge magnifications of embodiment 1, Fig. 2 b is by the prepared simulation button cell discharge curve under different charge-discharge magnifications of comparative example 1, voltage range is 2.5-4.2V, charge-discharge magnification is 0.2C, 1C, 2C, 3C, and probe temperature is 30 ℃ ± 1 ℃.
Fig. 3 a is the sem photograph (8k doubly) of the LiFePO4 powder of embodiment 1 gained; Fig. 3 b is the sem photograph (7k doubly) of the LiFePO4 powder of comparative example 1 gained.
Fig. 4 is the LiFePO4 powder particles scatter chart of embodiment 1 gained.
Fig. 5 is the cycle performance figure by 17500 prepared cylindrical lithium ion batteries of embodiment 2.
Embodiment
Below be the specific embodiment of the present invention, technical characterictic of the present invention is described further, but the present invention is not limited to these embodiment.
In the present invention, if not refer in particular to, all part, percentages are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
Embodiment 1:
At first, sand mill is put in 74.27g monohydrate lithium hydroxide LiOHH2O, 133.22g di-iron trioxide Fe2O3,197.47g ammonium dihydrogen phosphate, 40g white granulated sugar and 3.42g magnesium oxide MgO mixing, adding concentration is the polyethylene glycol aqueous solution of 0.5wt%, ball material-water ratio example is 2: 1: 2, high speed ball milling (600rpm) 5 hours; To mix slurry behind the sand milling with 100 ℃ of oven for drying, and carry out pulverization process then and put into the nitrogen atmosphere sintering furnace, under 10 liters/minute high pure nitrogens protection, be warmed up to 750 ℃, be incubated 6 hours, be cooled to room temperature then with 3 ℃/minute speed thereafter.After material behind the sintering pulverized with pulverizer, classification was handled on airflow milling, obtains evengranular LiFePO4.Record that phosphorus content is 4.5% in the material.
The tap density that records material is 1.3g/cm
3
The epigranular that records active material is tiny.Fig. 1 is the XRD figure spectrum of present embodiment gained LiFePO 4 material, and visible sample is the monocrystalline rhombic system, and has orderly olivine crystal structure, does not find tangible impurity peaks in collection of illustrative plates.Fig. 3 a is the sem photograph of the LiFePO4 powder of embodiment 1 gained, and the visible material particle is little and be uniformly dispersed and have orderly olivine crystal structure.
The prepared LiFePO 4 material of present embodiment is tested on the laser particle size distribution instrument, its granularity and particle size distribution testing result as shown in Figure 4:
D10＝1.12μm，D50＝4.77μm，D90＝14.35μm。SMD＝2.55μm，VMD＝6.47μm，Sv＝2.36m
2/cm
3，Sm＝8699.05cm
2/g。
Take by weighing the positive electrode of embodiment 1 gained respectively with 80: 10: 10 mass ratioes: acetylene black: PVDF (polyvinylidene fluoride), make electrode after grinding evenly, negative pole is selected metal lithium sheet for use, electrolyte is for being dissolved in the LiPF6 of the 1.0mol/L in ethyl carbonate+diethyl carbonate (volume ratio 1: 1) mixed solvent, barrier film is a polypropylene microporous film, is assembled into battery.Discharge curve under the different charge-discharge magnifications is shown in Fig. 2 a, as shown in the figure: when 0.2C discharged, the reversible gram volume of material can reach 150mAh/g, and the reversible gram volume of material can reach 135mAh/g during the 1C discharge, gram volume can reach 125mAh/g during the 2C discharge, and gram volume can reach 120mAh/g during the 3C discharge.As seen this material gram volume height, discharge platform is stable, superior performance.
Comparative example 1:
With 74.27g monohydrate lithium hydroxide LiOHH
2O, 133.22g di-iron trioxide Fe
2O
3, 197.47g ammonium dihydrogen phosphate, 40g white granulated sugar and 3.42g magnesium oxide MgO mix and put into sand mill, ball material-water ratio example is 2: 1: 2, high speed ball milling (600rpm) 5 hours; To mix slurry behind the sand milling with 100 ℃ of oven for drying, and carry out pulverization process then and put into the nitrogen atmosphere sintering furnace, under 10 liters/minute high pure nitrogens protection, be warmed up to 750 ℃, be incubated 6 hours, be cooled to room temperature then with 3 ℃/minute speed thereafter.After material behind the sintering pulverized with pulverizer, classification was handled on airflow milling.
Discharge curve under the different charge-discharge magnifications is shown in Fig. 2 b, as shown in the figure: when 0.2C discharged, the reversible gram volume of material was 140mAh/g, and the reversible gram volume of material is 125mAh/g during the 1C discharge, gram volume is 110mAh/g during the 2C discharge, and gram volume can reach 100mAh/g during the 3C discharge.Fig. 3 b is the sem photograph of the LiFePO4 powder of comparative example 1 gained, compare with Fig. 3 a, material granule disperses even inadequately, as seen add an amount of surfactant in the reactant and can play even dispersion precursor, suppress the crystal undue growth, obtain the little and homodisperse LiFePO 4 material of particle, and can improve the chemical property of material
Embodiment 2:
At first, with 74.27g monohydrate lithium hydroxide LiOHH
2O, 133.22g di-iron trioxide Fe
2O
3, 197.47g ammonium dihydrogen phosphate, 20g carbon black and 6.55g mangano-manganic oxide Mn
3O
4Mix and to put into sand mill, adding concentration was the AEO9 aqueous solution of 1.0wt.%, adds 1% second absolute alcohol, ball mill high speed ball milling (600rpm) 8 hours.Slurry behind the mixing sand milling with 100 ℃ of oven for drying, is carried out pulverization process then and puts into the nitrogen atmosphere sintering furnace, under 10 liters/minute high pure nitrogens protection, be warmed up to 750 ℃, be incubated 4 hours, be cooled to room temperature then with 3.5 ℃/minute speed.With the material behind the sintering with crusher in crushing after, classification is handled on airflow milling, obtains evengranular LiFePO4.
Send lithium ion battery factory to be prepared into electrode slice embodiment 2 gained materials and be assembled into battery, under the charge-discharge magnification of 0.2C, the cycle performance that records material as shown in Figure 5.
At first, with 74.27g monohydrate lithium hydroxide LiOHH
2O, 133.22g di-iron trioxide Fe
2O
3, 197.47g ammonium dihydrogen phosphate, 40g white granulated sugar and 6.37g cobalt oxide CoO mix and put into sand mill, adding concentration was the AEO9 aqueous solution of 0.8wt.%, ball mill high speed ball milling (700rpm) 4 hours.Slurry behind the mixing sand milling with 100 ℃ of oven for drying, is carried out pulverization process then and puts into the nitrogen atmosphere sintering furnace, under 10 liters/minute high pure nitrogens protection, be warmed up to 750 ℃, be incubated 6 hours, be cooled to room temperature then with 5 ℃/minute speed.After the fragmentation of the usefulness of the material behind sintering pulverizer, classification is handled on airflow milling, obtains evengranular LiFePO4.
The phosphorus content that records active material is 5.12%, presses the method preparation simulation button cell of embodiment 1, be assembled into battery after, reversible gram volume is more than the 145mAh/g when recording the 0.2C rate charge-discharge.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some instantiations as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (10)
1. the method preparing phosphate iron lithium of a doping vario-property, it comprises the steps:
A) lithium compound, molysite, phosphate, carbon matrix precursor and alloy are mixed in proportion, join in the aqueous surfactant solution that concentration is 0.5-3.0wt%, the mixture that ball-milling treatment obtains is dried processing under 80-120 ℃;
B) mixture after then A step oven dry being handled flow velocity be the 10-50 liter/minute inert gas shielding under carry out sintering; programming rate was 2-10 ℃/minute, is warming up to 400-800 ℃, at 400-800 ℃ of following heat treatment 5-20 hour; reduce to room temperature then, carry out pulverization process at last.
2. preparation method according to claim 1, it is characterized in that, described steps A is the mol ratio Li that forms by chemical formula: Fe: M: P=1: x: (1-x): 1 takes by weighing lithium compound, molysite, alloy and phosphate mixes in proportion, 0.9≤x＜1, carbon precursor addition add 5-20g carbon by 1 mole of ferric iron source and calculate.
3. preparation method according to claim 1 is characterized in that, described surfactant is at least a among polyethylene glycol, tween series or the AEO.
4. preparation method according to claim 1 is characterized in that, described lithium compound is at least a in Li2CO3, LiOH, lithium oxalate or the lithium acetate.
5. preparation method according to claim 1 is characterized in that, described molysite is that di-iron trioxide is or/and ferric phosphate.
6. preparation method according to claim 1 is characterized in that, described microcosmic salt is at least a in triammonium phosphate, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate.
7. preparation method according to claim 1 is characterized in that, described carbon matrix precursor is at least a in sucrose, glucose, carbon black, starch or the gelatin.
8. preparation method according to claim 1 is characterized in that, described alloy is at least a in Mg, Mn, Co or the Ni oxide.
9. preparation method according to claim 1 is characterized in that, the time of ball-milling treatment is 2-10 hour in the described steps A, and ball milling speed is: 200-800rpm.
10. preparation method according to claim 1 is characterized in that, is warming up to 400-750 ℃ among the described step B, at 400-750 ℃ of following heat treatment 2-10 hour.
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| CN101891176A (en) * | 2010-06-24 | 2010-11-24 | 复旦大学 | Method for preparing iron phosphate by using nonionic surfactant |
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| CN115020855B (en) * | 2022-06-24 | 2023-10-17 | 广东邦普循环科技有限公司 | Recycling method of lithium iron phosphate waste batteries |
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