CN1559889A - Preparation process of lithium ferrous phosphate for positive pole of lithium ion cell - Google Patents
Preparation process of lithium ferrous phosphate for positive pole of lithium ion cell Download PDFInfo
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- CN1559889A CN1559889A CNA2004100391764A CN200410039176A CN1559889A CN 1559889 A CN1559889 A CN 1559889A CN A2004100391764 A CNA2004100391764 A CN A2004100391764A CN 200410039176 A CN200410039176 A CN 200410039176A CN 1559889 A CN1559889 A CN 1559889A
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Abstract
The invention relates to a method of preparing cathode material LiFePO4 for lithium ion cell, making themolysis on the mixture of lithium salt, ferrite and organic/high-molecular compound additive in a certain proportion under the protection of an inert gas, to obtain the cathode material LiFePO4. Its preparation has the characters of simple conditions, safety and low cost, and the added additive can effectively control the shape and crystal structure of LiFePO4 and can improve conductive property of products, and the prepared cathode material has the advantage of high specific capacity, good high-temperature property, excellent circulating property, etc. The ion cells prepared of this cathode material have a wide application filed.
Description
Technical field:
The present invention relates to technical field of lithium ion, relate in particular to a kind of positive electrode material of lithium ion battery---the preparation method of LiFePO 4.
Background technology:
Lithium ion battery is since the early 1990s in last century comes out, because of its high-energy-density, superpower, excellent cycle performance and retention of charge have obtained widespread use rapidly in mobile communication equipment.
At present, the positive electrode material that is mainly used in lithium ion battery is the embedding lithium transition-metal oxide, research the earliest be to have α-sodium ferrite (α-NaFeO
2) the cobalt acid lithium (LiCoO of type laminate structure
2), lithium nickelate (LiNiO
2), lithium manganate (LiMnO
2) and have the spinel lithium manganate (LiMn of spinel structure
2O
4) and their doped compound.Wherein, LiCoO
2In compact battery, be used widely, but except the restraining factors of cobalt resource, it overcharges insecurity and has limited its application in high capacity cell.People expect spinel LiMn
2O
4Can be with its inexpensive and relative LiCoO
2The advantage of safety plays a role in high capacity cell, but the problem of its lower volume and high temperature circulation aspect has limited its extensive popularization.Stratiform LiMnO
2Although very high embedding lithium capacity is arranged, its crystalline structure in charge and discharge process easily subsides and to the spinel transformation of configuration, causes charge/discharge capacity to descend, and cyclicity is very poor, has restricted its practical application.LiNiO
2Then synthesize difficulty and compare LiCoO because of it
2Worsely overcharge safety problem and limited its application.Therefore, the ideal electrode active material from resource, environmental protection and safety performance aspect continuation searching lithium ion battery is still the challenge that faces of quite a while international energy material circle from now on.
Consider from resource and environmental, be accompanied by the appearance of lithium ion battery, iron system is anodal just to be that people expect to substitute LiCoO always
2Alternative materials, to lamellated ferrous acid lithium (LiFeO
2) many dark people's research [Matsumura T., Kanno R., Inaba Y., Kawamota Y., Takano, M.J.Eelectrochem.Soc., 2002,149 (12): A1509] is arranged, but because Fe
4+/ Fe
3+Fermi level and Li that electricity is right
+The energy level of/Li is separated by too far away, and Fe
3+/ Fe
2+The electricity to energy level again with Li
+The energy level of/Li is separated by too near, simultaneously, and Fe
3+Ionic radius and Li
+The ratio of radius does not meet structural requirement [Yamada A., Chung S.C., Hinokuma K.J.Eelectrochem.Soc., 2001,148 (3): A224], so, the LiFeO that has significant practical applications
2Research never has big progress.1997 Goodenough research group [MasquelierC., Goodenough J.B., Nanjundaswamy K.S., Padhi A.K.US Patent 5910382,1997] synthesized a kind of iron content lithium salts---LiFePO 4 (LiFePO
4), have high theoretical capacity (170mAh/g) with this material as anode material for lithium-ion batteries, surpass the anodal LiCoO of commercialization lithium ion battery
2Actual capacity (140mAh/g).Consider that it is nontoxic, environmentally friendly, abundant, high, the good cycle of specific storage in starting material source, think that this class material will become the desirable positive electrode material of power-type lithium ion battery.
LiFePO 4 is the compound of a kind olivine structural, and spacer is Pmna, and crystal is by FeO
6Octahedron and PO
4Tetrahedron constitutes spatial skeleton, and Fe and Li then are filled in octahedral space.Fe occupies octahedra M2 (010) position at common angle, and Li then occupies octahedra M1 (100) position on common limit.FeO in the lattice
6Common angles by the bc face couples together, LiO
6Then form axial length of side chain altogether along b.A FeO
6Octahedron and two LiO
6Octahedron and a PO
4Tetrahedron is the limit altogether, and PO
4Tetrahedron then with a FeO
6Octahedron and two LiO
6Octahedra limit altogether.Owing to there is not successive FeO
6Be total to the octahedra network in limit, thus electronic conduction can not be formed, simultaneously, because the PO between the octahedron
4Tetrahedron has limited the variation of lattice volume, thereby makes Li
+Embedding deviate from motion and be affected.So with traditional positive electrode material stratiform LiCoO
2, LiNiO
2, LiMnO
2With spinel LiMn
2O
4Compare LiFePO
4Has extremely low electronic conductivity and ion diffusion speed [Thackeray M.Nature Mater., 2002,1:81], charge/discharge capacity is very low under high current density, so can only discharge and recharge under minimum electric current, this has just limited its application in practice greatly.Therefore how to improve LiFePO
4Electronic conductivity be the focus of current chemical power source circle.Improve LiFePO at present
4The research of electroconductibility mainly concentrates on carbon coating and metal or metal ion mixing two aspects [Croce F., Epifanio A.D., Hassoun J., et al Electrochem.and Solid State Lett., 2002,5 (3): A47; Chung S.Y., Bloking J.T., Chang Y.M.Nature Mater.2002,2:123].The applicant once adopted the method synthesizing lithium ferrous phosphate of materials such as carbon-black doped, made that the chemical property of product is greatly improved [Zhou Henghui, Chen Jitao, Xu Xiaoming, Chinese invention patent, publication number: CN 1401559A, 2003].
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of active substance ferrous lithium phosphate as lithium-ion battery anode, this method is simple to operate, be easy to control, and prepared product has good conductivity.
The LiFePO 4 preparation method who the present invention relates to, its step is as follows:
1, lithium salts, ferrous salt, phosphoric acid salt and additive are mixed in proportion, wherein Li: Fe: the P mol ratio is (0.95-1.10): (0.97-1.03): 1, and the add-on of additive is 1～20% of a mixture total mass; Additive is selected from the organic or macromolecular compound that can be decomposed into the carbon class material with good electric conductivity through pyrolysis;
2, (mixing process can be at the mixing equipment of routine, as mixing in inclined mill, cone-type mixer, the three-dimensional mixer 1～10 hour the material that mixes to be put into Equipment for Heating Processing; Also available wet chemical method mixes as solution-gel method, spray-drying process; Any can all can use in the Equipment for Heating Processing of even heating reaction mixture under the atmosphere protection; as the tubular type atmosphere furnace; rotation atmosphere furnace or atmosphere protection continuous tunnel furnace; box-type furnace etc.); at flow velocity is heat treated in 0.01～50 liter/minute the inert gas protection; temperature rise rate is 1～20 ℃/minute; when temperature to be heated rises to 200～400 ℃; holding temperature is constant; thermostatically heating 1～30 hour; continue then to heat up; carry out high-temperature heat treatment, temperature maintenance is at 500～850 ℃, and heat treatment time is 10～48 hours; be cooled to room temperature then, the material that so makes is ferrous phosphate doping lithium anode material.
The lithium source, source of iron and the phosphorus source that wherein prepare above-mentioned positive active material all do not have special restriction, contain lithium salts or its various mixtures etc. as Quilonum Retard, lithium hydroxide, Trilithium phosphate, lithium oxalate, Lithium Acetate, lithium chloride, lithium nitrate etc. and all can be elected to be the lithium source.Ferrous salts such as Ferrox, Iron diacetate, iron protochloride, ferrous phosphate or its various mixtures can be elected to be source of iron.Phosphorous hydrochlorates such as phosphoric acid ammonia, phosphoric acid hydrogen ammonia, ammonium di-hydrogen phosphate, ferrous phosphate or its various mixtures can be elected to be the phosphorus source.Additive can be selected from the luxuriant and rich with fragrance terpolymer of benzene naphthalene, benzene naphthalene anthracene terpolymer, the luxuriant and rich with fragrance copolymer of benzene, benzene anthracene copolymer, benzene naphthalene dicarboxylic multipolymer, poly-to organism or its mixtures such as benzene, Zulkovsky starch, polyvinyl alcohol, glucose, sucrose, resol, furfuryl resins.Described shielding gas is selected from rare gas element such as nitrogen, argon gas or its mixed gas.
Because adopting to add in the building-up process, the present invention can be decomposed into the organic or macromolecular compound of carbon class material as additive with good electric conductivity through pyrolysis, these additives are distributed between the material granule by mixing, the adding of additive can have the effect of three aspects: (1) organic or macromolecular compound additive can produce the gas of reductibility in the polycondensation process of follow-up high temperature section, as hydrogen, carbon monoxide etc., can work in coordination with and prevent ferrous oxidation, and different additive polycondensation mechanism differences is so can show difference on the result of use of different additive.(2) suppress LiFePO
4The growth of individual particle reduces the particle diameter of individual particle.At the thermal treatment initial stage, additive can evenly spread in the raw material with molecularity under molten state, and in the follow-up heat treatment process, molecularity dispersive additives decompose produces the nano level pyrolytic carbon.The introducing of charcoal is to LiFePO
4The generation of crystal grain has inducing action, the existence of a large amount of nanometer charcoals, the feasible LiFePO that is generated
4Crystal grain quantity increases, so crystal particle diameter reduces; Simultaneously, in the particle growth process, be present in intergranular pyrolytic carbon and also hindered intergranular fusion, suppressed oarse-grained generation, so add the particle diameter that additive can effectively reduce the product individual particle.(3) improve the conductivity of product.At LiFePO
4In the crystal grain forming process, there is part nanometer charcoal to be doped in crystal grain inside.Charcoal is good electronic conductor, charcoal mix the electroconductibility that can improve particle self; Simultaneously, be coated on crystal grain surface or be present in pyrolytic carbon between the particle and also can improve conductivity between the particle effectively.So in building-up process, add additive, can obtain particle diameter little, conduct electricity very well, LiFePO that reversible capacity is high
4Material.
Advantage of the present invention is:
(1) the starting material wide material sources are pollution-free, and cost is low;
(2) preparation methods is simple, security good;
(3) prepared LiFePO 4 has good heavy-current discharge performance (seeing accompanying drawing 2);
(4) prepared LiFePO 4 Stability Analysis of Structures, good with the electrolytic solution consistency, good cyclicity (seeing accompanying drawing 3) is arranged.
Positive electrode material involved in the present invention has purposes widely, and the lithium ion battery that adopts this positive electrode material to prepare can be used for comprising the various electrical appliances of intelligent chip, wireless headset, mobile telephone, notebook computer, digital camera, pick up camera, electronic toy, electric bicycle, battery-operated motor cycle, electromobile etc.
Description of drawings:
Fig. 1, embodiment 1 prepared LiFePO
4The X-ray diffraction figure of sample, Cu target (K
α 1, wavelength is 0.154nm), used instrument is RINT2000, and wide angle diffraction, applied voltage are 40kV, and electric current is 40mA.
Fig. 2, embodiment 1 prepared LiFePO
4Sample sem photograph, applied voltage are 20kV, and transmitter current is 95mA.
Fig. 3, Comparative Examples 1 prepared LiFePO
4The sample sem photograph, the same Fig. 2 of used condition.
Fig. 4, press the first charge-discharge graphic representation of the prepared ferrous phosphate doping lithium anode material of embodiment 1, voltage range 2.0～4.1V, concentration is 1molL to electrolytic solution in NSC 11801 (EC) and diethyl carbonate (DEC) (volume ratio 1: the 1) mixed solvent in order to be dissolved in
-1LiPF
6Solution, charging and discharging currents are 0.30mA/cm
2, probe temperature is 25 ℃ ± 1 ℃.
Fig. 5, press the different multiplying discharge curve of the prepared ferrous phosphate doping lithium anode material of embodiment 2, voltage range and the same Fig. 4 of used electrolytic solution, charging current is 0.30mA/cm
2, probe temperature is 25 ℃ ± 1 ℃.Among the figure discharge curve 1,2,3,4,5 pairing current densities be respectively 0.30,1.00,2.00,5.71,11.43mA/cm
2
Fig. 6, press the cycle performance figure of the prepared ferrous phosphate doping lithium anode material of embodiment 3, voltage range and the same Fig. 4 of used electrolytic solution, charging and discharging currents is 0.60mA/cm
2, probe temperature is 25 ℃ ± 1 ℃.Cyclic curve when the cyclic curve when a is 25 ℃ of room temperatures among the figure, b are 60 ℃ of high temperature.
Embodiment:
In order to be illustrated more clearly in the present invention, enumerate following examples, but it does not constitute any limitation of the invention.
0.5 mole of Quilonum Retard, 1 mole of luxuriant and rich with fragrance terpolymer of Ferrox, 1 mole of phosphoric acid hydrogen ammonium and 10g benzene naphthalene are mixed, add in the mixing tank, add the 200g agate ball, the sealing mixing tank mixed 5 hours on the three-dimensional blender machine.
With the raw material that mixes at N
2In the atmosphere protection stove, under the nitrogen atmosphere of 6L/min, rise to 400 ℃ with the speed of 5 ℃/min, keep 10h under this temperature, the speed with 10 ℃/min rises to 600 ℃ then, and under this temperature constant temperature 30h, allow furnace temperature be cooled to room temperature then.Fig. 1 is gained LiFePO
4XRD figure, the adding of additive does not change LiFePO
4Crystalline structure, keep and LiFePO
4Standard x RD spectrum (JCPDS card-190721) identical crystalline structure, all diffraction peaks all can be pointed out by standard spectrum, do not observe the impurity peaks of additive and pyrolysis product thereof.Fig. 2 is gained LiFePO
4Stereoscan photograph, sample topography is 10～20 microns the offspring that particles agglomerate of 0.1～4 micron becomes.Electric conductivity with the two-point method working sample is 2 * 10
-2Scm
-1,
The chemical property of gained sample is measured as follows: take by weighing the 0.85g positive powder, add the 0.7g carbon black, the 0.8g tetrafluoroethylene, after grinding evenly, making electrode, is negative pole with the metal lithium sheet, is dissolved in the 1.0molL in NSC 11801+diethyl carbonate (volume ratio 1: 1) mixed solvent
-1LiPF
6Be electrolytic solution, polypropylene microporous film is a barrier film, is assembled into battery, presses 0.3mA/cm
2Current density battery is discharged and recharged, the charging/discharging voltage scope is 4.1～2.0V.Fig. 4 is the charging and discharging curve first time of this material, and as seen from the figure, institute's synthetic material has favorable charge-discharge voltage platform and high reversible capacity (160mAhg
-1).
Comparative Examples 1
Except that not adding any additives, all by the method preparation of embodiment 1, Fig. 3 is the stereoscan photograph of prepared comparative example for all the other, and sample topography is 10～30 microns the aggregate that is essentially, and does not observe tangible primary particle; Electric conductivity with the two-point method working sample is 1 * 10
-6Scm
-1Press the method test chemical property of embodiment 1, reversible capacity is 128mAhg
-1
1 molar acetate lithium, 1 molar acetate is ferrous, 1 mole of phosphoric acid ammonium dihydrogen and 40g glucose mix, and add in the mixing tank, add the 200g agate ball, and the sealing mixing tank mixes 10h on the three-dimensional blender machine.
The raw material that mixes in argon gas atmosphere protection stove, under the nitrogen atmosphere of 9L/min, is risen to 300 ℃ with the speed of 10 ℃/min; under this temperature, keep 6h; speed with 20 ℃/min rises to 700 ℃ then, and under this temperature constant temperature 20h, allow furnace temperature be cooled to room temperature then.The gained positive electrode material is pressed embodiment 1 described method and is measured chemical property.Fig. 5 is the discharge curve of this material under different current densities, and as seen from the figure, institute's synthetic material has good heavy-current discharge performance, and discharging current increases nearly 40 times, and its capacity only reduces about 1/5.
With 1.03 mole of phosphoric acid lithiums, 1 mole of phosphoric acid is ferrous and 20g resol mixes, and adds in the mixing tank, adds the 200g agate ball, the sealing mixing tank mixes 4h on the three-dimensional blender machine.
The raw material that mixes in nitrogen atmosphere protection stove, under the nitrogen atmosphere of 2L/min, is risen to 200 ℃ with the speed of 2 ℃/min; under this temperature, keep 30h; speed with 5 ℃/min rises to 600 ℃ then, and under this temperature constant temperature 48h, allow furnace temperature be cooled to room temperature then.The gained positive electrode material is pressed embodiment 1 described method and is measured chemical property.Fig. 6 is the cycle performance figure of this material, and as seen from the figure, institute's synthetic material has the excellent cycle performance, and through 30 circulations, capacity is not decayed.
Be it can also be seen that by Fig. 3 this material has that excellent high-temperature discharges and recharges and cycle performance, when discharging and recharging for 60 ℃, the reversible capacity of material improves about 5% than normal temperature, and keeps good cycle performance.
1 molar nitric acid lithium, 1 mole of Ferrox, 1 mole of phosphoric acid ammonium and 40g sucrose are mixed, add in the mixing tank, add the 200g agate ball, the sealing mixing tank mixes 8h on the three-dimensional blender machine.
The raw material that mixes in nitrogen atmosphere protection stove, under the nitrogen atmosphere of 2L/min, is risen to 350 ℃ with the speed of 2 ℃/min; under this temperature, keep 30h; speed with 5 ℃/min rises to 500 ℃ then, and under this temperature constant temperature 48h, allow furnace temperature be cooled to room temperature then.The gained positive electrode material is pressed embodiment 1 described method and is measured chemical property, and material is not decayed through 30 circulating and reversible capacity.
0.95 mole of lithium chloride, 1 mole of iron protochloride, 1 mole of phosphoric acid ammonium dihydrogen and 25g furfuryl resin are mixed, add in the mixing tank, add the 300g agate ball, the sealing mixing tank mixes 2h on the three-dimensional blender machine.
The raw material that mixes in nitrogen atmosphere protection stove, under the nitrogen atmosphere of 5 liters/min, is risen to 300 ℃ with the speed of 5 ℃/min; under this temperature, keep 30h; speed with 5 ℃/min rises to 800 ℃ then, and under this temperature constant temperature 10h, allow furnace temperature be cooled to room temperature then.The gained positive electrode material is pressed embodiment 1 described method and is measured chemical property, and material is not decayed through 30 circulating and reversible capacity.
Embodiment 6
0.5 mole of lithium oxalate, 1.03 moles of Ferroxs, 1 mole of phosphoric acid ammonium dihydrogen and 15g benzene anthracene copolymers are mixed, other processing and testing method are undertaken by embodiment 1, the gained positive electrode material has excellent electrochemical properties, and material is not decayed through 30 circulating and reversible capacity.
Embodiment 7
1.05 moles of hydrogen Lithium Oxide 98mins, 1 mole of luxuriant and rich with fragrance copolymer of Ferrox, 1 mole of phosphoric acid ammonium dihydrogen and 16g benzene are mixed, other processing and testing method are undertaken by embodiment 1, the gained positive electrode material has excellent electrochemical properties, and material is not decayed through 30 circulating and reversible capacity.
Embodiment 8
0.5 mole of Quilonum Retard, 1 mole of Ferrox, 1 mole of phosphoric acid ammonium dihydrogen and 12g benzene naphthalene dicarboxylic multipolymer are mixed, and other processing and testing method are undertaken by embodiment 1, and the gained positive electrode material has excellent electrochemical properties, and reversible capacity is 149mAhg
-1
Embodiment 9
Press embodiment 8, only additive changes 10 gram ternary benzene naphthalene anthracene multipolymers into, and the reversible capacity of gained positive electrode material is 161mAhg
-1
Embodiment 10
Press embodiment 8, only to change 15g into poly-to benzene for additive, and gained positive electrode material reversible capacity is 140mAhg
-1
Embodiment 11
Press embodiment 8, only additive changes 25 gram polyvinyl alcohol mixing into, and the reversible capacity of gained positive electrode material is 148mAhg
-1
Press embodiment 8, only additive changes the mixing of 30g Zulkovsky starch into, and the reversible capacity of gained positive electrode material is 142mAhg
-1
Claims (7)
1. the preparation method of a lithium ferrous phosphate as anode material of lithium ion battery, its step comprises:
1) lithium-containing compound, ferrous salt, phosphoric acid salt and additive are mixed in proportion, wherein Li: Fe: the P mol ratio is (0.95-1.10): (0.97-1.03): 1, and the add-on of additive is 1～20% of a mixture total mass; Described additive is selected from the organic or macromolecular compound that can be decomposed into the carbon class material with good electric conductivity through pyrolysis;
2) material that mixes is put into Equipment for Heating Processing; at flow velocity is heat treated in 0.01～50 liter/minute the inert gas protection, and temperature rise rate is 1～20 ℃/minute, when temperature to be heated rises to 200～400 ℃; holding temperature is constant; thermostatically heating 1～30 hour continues to heat up then, carries out high-temperature heat treatment; temperature maintenance is at 500～850 ℃; heat treatment time is 10～48 hours, reduces to room temperature then, obtains LiFePO 4.
2, the preparation method of lithium ferrous phosphate as anode material of lithium ion battery as claimed in claim 1 is characterized in that: described lithium-containing compound is selected from Li
2CO
3, LiOH, lithium oxalate, Lithium Acetate, lithium chloride, lithium nitrate, Trilithium phosphate a kind of, perhaps its mixture.
3. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery as claimed in claim 1 is characterized in that: described ferrous salt is selected from a kind of in Ferrox, Iron diacetate, iron protochloride, the ferrous phosphate or its mixture.
4. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery as claimed in claim 1 is characterized in that: described phosphoric acid salt is selected from a kind of of phosphoric acid ammonia, phosphoric acid hydrogen ammonia, ammonium di-hydrogen phosphate, ferrous phosphate, Trilithium phosphate, or its mixture.
5. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery as claimed in claim 1, it is characterized in that: described additive is selected from the luxuriant and rich with fragrance terpolymer of benzene naphthalene, benzene naphthalene anthracene terpolymer, the luxuriant and rich with fragrance copolymer of benzene, benzene anthracene copolymer, benzene naphthalene dicarboxylic multipolymer, poly-a kind of to benzene, Zulkovsky starch, polyvinyl alcohol, glucose, sucrose, resol, furfuryl resin, or its mixture.
6. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery as claimed in claim 1, it is characterized in that: described inert gas flow velocity is 2～10 liters/minute.
7. as the preparation method of claim 1 or 6 described lithium ferrous phosphate as anode material of lithium ion battery, it is characterized in that: described shielding gas is selected from a kind of of nitrogen, argon gas, or its mixed gas.
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