CN102142557A - Anode active material and preparation method thereof - Google Patents
Anode active material and preparation method thereof Download PDFInfo
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- CN102142557A CN102142557A CN2010101061926A CN201010106192A CN102142557A CN 102142557 A CN102142557 A CN 102142557A CN 2010101061926 A CN2010101061926 A CN 2010101061926A CN 201010106192 A CN201010106192 A CN 201010106192A CN 102142557 A CN102142557 A CN 102142557A
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Abstract
The invention provides an anode active material. The structural formula of the anode active material is LiMnxM1-xPO4, wherein x is more than or equal to 0.2 and less than or equal to 0.8; M is selected from one or more of Fe, Co and Ni; and the specific surface area of the anode active material is 40 to 50m<2>/g. The anode active material has high electric conductivity, excellent high-current charge/discharge property and stable structure. The invention simultaneously provides a preparation method for the anode active material, which comprises the following steps of: adding one or more organic substance monomers of phenylamine, pyridine, furan, thiophene, pyrrole or imidazole into raw materials during preparation of a phosphate precursor, preparing a nano precursor, and preparing the nano anode active material. The anode active material has the advantages of uniform granule diameter, good consistency and no impurity phase; and the preparation method has the advantages of short time, low energy consumption, low cost, high yield, good consistency and simple and controllable process flow, and can realize large-scale industrial clean production.
Description
Technical field
The present invention relates to a kind of positive electrode active materials and preparation method thereof.
Background technology
Lithium ion battery has been widely used in fields such as mobile communication, notebook computer, video camera, camera, portable instrument as the high-energy-density chemical power source, also be the electric automobile studied energetically of various countries, the first-selected supporting power supply of space power system, become the first-selection of the alternative energy.
Anode material for lithium-ion batteries is the focus and the difficult point of prior art research, existing general commercial LiCoO
2, because the rareness and the environmental pollution of cobalt resource cause the battery production cost to cross problems such as height, seeking new material is the existing generally difficult point of research.The focus LiFePO of existing research
4Have good electrochemical, charge and discharge platform is very steady, Stability Analysis of Structures in the charge and discharge process, and having nontoxic, pollution-free, advantage such as security performance is good, can use under hot environment, raw material wide material sources, is the material that current battery circle is competitively developed.But LiFePO
4With respect to Li
+The electrode potential of/Li is 3.4V only, and energy storage density is low, has limited its application and development prospect.And LiMnPO
4With respect to Li
+The electrode potential of/Li is 4.1V, and is positioned at the stable electrochemical window of existing electrolyte system, and theoretical capacity has potential high-energy-density up to 170mAh/g simultaneously.In addition, synthetic LiMnPO
4Cost is low, environmentally friendly.But the existing synthetic LiMnPO that can reversiblely discharge and recharge
4Very difficult, electronics is at LiMnPO
4The middle energy gap that transition takes place is 2eV, the electron conduction extreme difference, and in discharge process, the electrode polarization degree is bigger, and therefore in the discharge middle and later periods, voltage drops to cut-ff voltage fast, causes battery capacity lower.Prior art research adopts element doping to improve this conductivity of electrolyte materials by introduce hetero-atom in material lattice, for example introduces atoms such as Fe, forms LiMn
xFe
1-xPO
4(x 〉=0.5) solid-solution material.
The method of existing synthetic this type of material generally comprises high-temperature solid phase reaction method, liquid-phase coprecipitation, hydro thermal method, sol-gel process, oxidation-reduction method, solid phase microwave method and mechanical ball milling method etc., wet method is owing to the mixing that can realize on the raw molecule level, help controlling the chemical composition and the particle diameter of product, favored by industry.
For example, have by with a certain proportion of molysite compound, the manganese salt compound, lithium salt compound and microcosmic salt compound, and add the organic substance of doping element compound and/or carbon containing therein, add organic acid and regulate the pH value as carrier, preparation organic carbon clad metal doped iron lithium phosphate nanometer presoma, back sintering prepares nano-scale carbon clad metal doped iron lithium phosphate material, but when synthesizing presoma, this method passes through the simple organic carbon source that adds, can not stop growing up of short grained reunion and deposit seed, synthetic presoma particle diameter is still bigger, and particle diameter heterogeneity, particle diameter distribution width is bigger, not only the electric conductivity of material is still undesirable, and influences performances such as the consistency of final material and stability; And this method is difficult to obtain the solid solution LiMn of pure phase
xFe
1-xPO
4, containing dephasigns such as manganese phosphate, ferric phosphate easily, thereby cause the lithium ion the evolving path long, chemical property is not ideal enough, and the specific capacity decay is serious.
Summary of the invention
The present invention is in order to solve the LiMn of prior art for preparing
xFe
1-xPO
4Particle diameter is big, lattice is relatively poor, and electric conductivity is not good, simultaneously Zhi Bei LiMn
xFe
1-xPO
4The shortcoming that contains many dephasigns such as manganese phosphate, ferric phosphate provides a kind of have high electric conductivity and excellent large current density electrical characteristics and constitutionally stable positive electrode active materials, and wherein, the structural formula of positive electrode active materials is LiMn
xM
1-xPO
4, wherein, 0.2≤x≤0.8; M is selected from one or more among Fe, Co or the Ni;
The specific area of positive electrode active materials is 40-50m
2/ g.
The present invention provides the preparation method of above-mentioned positive electrode active materials simultaneously, and step comprises:
A, will comprise that the solution of phosphorus source, manganese source, M source and organic substance monomer mixes, control pH value is 4-6, prepares the phosphate presoma;
B, with the phosphate presoma and the lithium source mixing and ball milling of step a preparation;
C, the roasting under inert atmosphere of step b ball milling gained material is made LiMn
xM
1-xPO
4, wherein, 0.2≤x≤0.8; M is selected from one or more among Fe, Co or the Ni;
Wherein, the organic substance monomer is selected from one or more in aniline, pyridine, furans, thiophene, pyrroles or the phonetic azoles;
The M source is selected from one or more in ferric iron source, trivalent cobalt source or the tetravalence nickel source.
The present inventor is unexpected to be found when preparation phosphate presoma, add aniline, pyridine, furans, thiophene, during organic substance such as pyrroles or phonetic azoles monomer, in cation and anion react the process of growth phosphate (MPO4), these organic substance monomers can polymerization under the oxidizing condition in ferric iron source or trivalent cobalt source or tetravalence nickel source, polymer is attached to particle surface, the generation of this polymerization process and phosphate (MPO4) and particle are grown up and are taken place simultaneously, cover particle surface, shuttle back and forth between particle, between particle, form the side chain network configuration, this three-dimensional net structure has also effectively stoped the continued growth of particle simultaneously, and intercepted the short grained reunion of nanometer, effectively controlled the particle diameter of phosphate presoma; The polymerization of polymer and the generation of deposit seed simultaneously takes place simultaneously, the polymer of particle surface also relatively evenly, not only better controlled the homogeneity and the consistency of product of particle diameter, and well modified particle surface, make the product particle pattern perfection of final preparation; And this kind polymer three-dimensional network configuration is stable, helps being bound by crystalline form further perfect of the nano particle of organic polymer three-dimensional net structure between intermittently, helps preparing the perfect final products of lattice; Organic substance also can be used as carrier simultaneously, the uniformity consistency of the height uniformity consistency of assurance solution and the phosphate precursor of generation, thereby the integrality of assurance sintering reaction, and the product thing of the final preparation of assurance is compared pure, stops dephasign.
This polymer three-dimensional network configuration can not only stop the reunion of nanometer granular precursor, and the reaction in precursor and lithium source is bound by Nano grade, and reaction is more even, more thorough simultaneously; And these polymer can produce reducibility gas when sintering, play reduction, also can further stop the contact and the reunion of nano particle, effectively the product cut size and the pattern of the material of the final preparation of control; At particle surface residue one deck carbon, coated particle when strengthening conductivity, further stoped particle agglomeration, preparation nano particle positive electrode active materials when simultaneously some polymer also can sintering.
The lithium phosphate of the present invention's preparation is nanoscale, once synthetic particle diameter can reach 100-200nm, the particle size distribution homogeneous, improved the conductivity of material, powder resistance can reduce by 3 more than the order of magnitude, the battery of preparation is in the charging and discharging cyclic process, and the electrode polarization degree is low, is not easy to occur local overcharging and overdischarge; This nano particle pattern perfection simultaneously has short lithium ion and takes off the embedding stroke, makes battery the electrode polarization degree is little when high power charging-discharging, reversible capacity is high, has extended cycle life; And the nano particle of the present invention preparation has bigger specific area, and particle voids rate height can provide a large amount of spaces for the migration of taking off embedding and organic solvent molecule of lithium ion, helps improving the big current ratio flash-over characteristic of battery.Particularly Zhi Bei material is the pure phase solid-solution material, and Stability Analysis of Structures helps improving the cycle performance of battery.
Simultaneously preparation method of the present invention weak point consuming time, energy consumption is low, cost is low, productive rate is high, the material granule of preparation evenly, stable, the technological process simple controllable of material property of preparation, can realize that large-scale industry cleans production.
Description of drawings
Fig. 1 is the LiMn of embodiment 1 preparation
0.5Fe
0.5PO
4The scanning of materials electromicroscopic photograph;
Fig. 2 is the LiMn of embodiment 1 preparation
0.5Fe
0.5PO
4The material XRD figure;
Fig. 3 is the first charge-discharge curve of the simulated battery of embodiment 1 preparation;
Fig. 4 is the LiMn of embodiment 4 preparations
0.8Fe
0.2PO
4The material XRD figure;
Fig. 5 is the first charge-discharge curve of the simulated battery of embodiment 4 preparations.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The invention provides a kind of have high electric conductivity and excellent large current density electrical characteristics and constitutionally stable positive electrode active materials, wherein, the structural formula of positive electrode active materials is LiMn
xM
1-xPO
4, wherein, 0.2≤x≤0.8; M is selected from one or more among Fe, Co or the Ni;
The grain diameter of positive electrode active materials is distributed in the 100-200nm scope substantially, and specific area is 40-50m
2/ g.Grain diameter significantly reduces, and powder resistance significantly reduces, and has improved the specific capacity of material.
The present invention is the conductivity that further improves material, is preferable over surface of active material and also is coated with carbon.
The present invention provides the preparation method of above-mentioned positive electrode active materials simultaneously, and step comprises:
A, will comprise that the solution of phosphorus source, manganese source, M source and organic substance monomer mixes, control pH value is 4-6, prepares the phosphate presoma;
B, with the phosphate presoma and the lithium source mixing and ball milling of step a preparation;
C, with the roasting under inert atmosphere of step b ball milling gained material;
Wherein, the organic substance monomer is selected from one or more in aniline, pyridine, furans, thiophene, pyrroles or the phonetic azoles;
The M source is selected from one or more in ferric iron source, trivalent cobalt source or the tetravalence nickel source.
The further preferred steps a of the present invention will be for after will comprising the phosphorus source and the solution of organic substance monomer will mix earlier, slowly add manganese source and M source again, controlling the pH value with alkaline solution in the process is 4-6, the pH value of promptly can be earlier regulating the mixed solution of phosphorus source and organic substance monomer with ammoniacal liquor is 4-6, slowly add manganese source and M source again, also regulate pH simultaneously in the process that adds, be controlled at 4-6, prepared by co-precipitation phosphate presoma.Even polymerization of organic substance energy and phosphate granular precursor are slowly grown; Polymer can play certain flocculating effect as the carrier of precipitation simultaneously, is easy to separate, and has helped guaranteeing the uniformity and the stability of system.The preferred ammoniacal liquor of alkaline solution the present invention.The present invention also comprises post-processing step, for example filters, and impurity is removed in washing repeatedly, and oven dry, grinding wait and obtain the phosphate presoma.
Wherein, ball milling can adopt and well known to a person skilled in the art ball milling, with the absolute ethyl alcohol medium ball milling in high speed ball mill for example with phosphate presoma and lithium source, high speed ball mill the present invention be not particularly limited, can be and select the capable ball mill of star, agitating ball mill, high energy vibration ball mill etc. for use, the volume ratio of ball, material can be 5-10: 1, and the volume of ball, material can account for the 60-75% of mill tank volume.
Wherein, phosphorus source, manganese source, ferric iron source, cobalt source, nickel source and the present invention of lithium source can adopt various phosphorus source, manganese source, ferric iron source, cobalt source, nickel source and the lithium source of well known to a person skilled in the art.The preferred phosphorus of the present invention source is selected from one or more in phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or the dibastic sodium phosphate; The manganese source is selected from Mn
2O
3, MnCO
3, Mn (CH
3COO)
24H
2O, MnCl
2, MnSO
4Or Mn (NO
3)
2In one or more; Ferric iron source is selected from one or more in ferric trichloride, ferric nitrate, ironic citrate or the iron hydroxide; Ferric iron source is selected from one or more in ferric trichloride, ferric nitrate, ironic citrate or the iron hydroxide; Trivalent cobalt source is selected from one or more in the sulfate of the acetate of oxalates, cobalt of nitrate, the cobalt of cobalt or cobalt; Tetravalence nickel source is selected from one or more in the sulfate of the acetate of oxyhydroxide, nickel of nitrate, the nickel of nickel or nickel; The lithium source is selected from one or more in lithium hydroxide, lithium acetate, lithium chloride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or the lithium oxalate.The mol ratio in further preferred phosphorus source of the present invention and manganese source is 1: 0.2-0.8; The mol ratio in manganese source and M source is 1: 0.25-4; The mol ratio in lithium source and phosphorus source is 1-1.05.The mol ratio in organic substance monomer and M source is 1-20, more preferably 5-10.Further optimize the thing phase of the material of preparation, preparation pure phase material is avoided the appearance of dephasign.
The present invention also is mixed with carbon source during further preferred steps b ball milling, not only plays reduction, can further increase the conductivity of product at the product particle coated with carbon behind the sintering simultaneously.The preferred conductive acetylene of carbon source the present invention is black, in shitosan, glucose, sucrose, tartaric acid, citric acid or the fructose one or more.
Also be added with phosphorous acid group material during the further preferred steps b ball milling of the present invention, replenish phosphate radical, further make reaction more thorough more fully, avoid dephasign.The preferred phosphorous acid group material of the present invention is selected from one or more in diammonium hydrogen phosphate, ammonium dihydrogen phosphate or the lithium dihydrogen phosphate, and the addition of the phosphorous acid group material of the addition of preferred phosphorous acid group material and the mol ratio in Mn source are 0.2-0.4.
The temperature of the preferred roasting of the present invention is 600-1000 ℃.The temperature-rise period of preferred roasting comprised for two steps, was warming up to 400 ℃ with 5 ℃/min earlier, and insulation 3-5h is warming up to 600-1000 ℃ with 2 ℃/min again, is preferably 750-800 ℃, insulation 12-30h.After finishing, sintering is cooled to annealing at room temperature with 5 ℃/min.
The preferred inert gas of the present invention is gases such as Ar, nitrogen.
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
(1) preparation of positive electrode active materials
With 38.08g NH
4H
2PO
4Be dissolved in the deionized water of 3000ml, stir and regulate pH value to 5 with ammoniacal liquor, the aniline of adding 15ml fully stirs 20min, will contain four hydration manganese acetates and the 44.8g FeCl of 40.5g at last
36H
2The 1500ml solution of O dropwise adds in the above-mentioned solution, fully stirs 6h, gets solution and filters, and with distilled water, the oven dry of ethanol cyclic washing, makes the manganese phosphate presoma that contains ferric phosphate.
Adopt JSM-5610LV type scanning electron microscopy (SEM) to observe the pattern of the phosphate presoma of above-mentioned preparation, observation obtains the grain diameter of phosphate presoma of above-mentioned preparation all about 30nm, and the grain diameter homogeneous, big or small basically identical, no agglomeration.
With the LITHIUM BATTERY lithium acetate is the lithium source, mix with the manganese phosphate nanometer presoma of the above-mentioned phosphoric acid iron that makes, lithium is 1: 1 with the ratio of transition metal manganese, iron mole total amount, and the ammonium dihydrogen phosphate that adds 7.61g compensates phosphate radical in the mixture, thereby form 1: 1 phosphate with transition metal, and the sucrose that adds 25% (wt) is reducing agent, is medium ball milling 2h with the absolute ethyl alcohol in high speed ball mill.The sample that ball milling is good places 80 ℃ of oven dry of vacuum drying chamber, carries out roasting heat at last and handle in box atmosphere furnace, under the Ar Buchholz protection; 400 ℃ of insulation 6h; 750 ℃ of insulation 12h, heating rate is 5 ℃/min, can get black iron manganese phosphate for lithium (LiMn with the stove cooling
0.5Fe
0.5PO
4) positive electrode active materials.
Adopt JSM-5610LV type scanning electron microscopy (SEM) to observe the iron manganese phosphate for lithium (LiMn of above-mentioned preparation
0.5Fe
0.5PO
4) pattern of positive electrode active materials, SEM schemes as Fig. 1, observes the iron manganese phosphate for lithium (LiMn that obtains above-mentioned preparation
0.5Fe
0.5PO
4) grain diameter of positive electrode active materials is all in the 100-200nm scope, and the grain diameter homogeneous, big or small basically identical, no agglomeration.
Adopt the XRD tester to test the iron manganese phosphate for lithium (LiMn of above-mentioned preparation
0.5Fe
0.5PO
4) positive electrode active materials the X ray crystallogram (as Fig. 2, Cu target K alpha ray, λ=0.15406nm), the iron manganese phosphate for lithium characteristic peak peak intensity height of the present invention's preparation as can be seen, peak width is narrow, lattice perfection, and do not have the dephasign peak, thing is mutually pure.
Adopt the iron manganese phosphate for lithium (LiMn of the above-mentioned preparation of N2 absorption test
0.5Fe
0.5PO
4) positive electrode active materials specific grain surface long-pending (BET) is 51.2m
2/ g.
(2) preparation of simulated battery:
By quality than iron manganese phosphate for lithium: acetylene black: PVDF=80: 10: 10 mixed evenly back compressing tablet is made, and pole piece is more than 120 ℃ of vacuumize 24h.Simulated battery is negative pole with the metal lithium sheet, is barrier film with the celgard2400 polypropylene porous film, with 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is=1: 1) be electrolyte, the assembling process of all batteries is all carried out in being full of the glove box of argon gas.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare positive electrode active materials and simulated battery, the organic substance monomer of interpolation that different is is a thiophene.
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.5Fe
0.5PO
4) grain diameter of positive electrode active materials is all in the 150-200nm scope, and the grain diameter homogeneous, big or small basically identical, no agglomeration; Lattice perfection, no dephasign; Specific area is 48.7m
2/ g.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare positive electrode active materials and simulated battery, the organic substance monomer of interpolation that different is is an oxolane.
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.5Fe
0.5PO
4) grain diameter of positive electrode active materials is all in the 150-240nm scope, and the grain diameter homogeneous, big or small basically identical, no agglomeration; Lattice perfection, no dephasign; Specific area is 50.5m
2/ g.
Embodiment 4
Adopt the method identical with embodiment 2 to prepare positive electrode active materials and simulated battery, different is that raw material is 38.08g NH
4H
2PO
4Be dissolved in the deionized water of 3000ml, add the thiophene of 22ml, drip four hydration manganese acetates and the 17.91g FeCl of 64.8g
36H
2The 1500ml solution of O fully stirs 6h, gets solution and filters, and with distilled water, the oven dry of ethanol cyclic washing, makes the polymeric precursor 50g of the manganese phosphate of phosphoric acid iron.Elementary analysis records P phosphorus=(14.91%) according to ICP; Mn manganese=(20.95%); Fe iron=(5.32%); Add 25.5g LiCH
3COO2H
2O and 7.61g NH
4H
2PO
4Under the Ar Buchholz protection, 400 ℃ are incubated 6h behind the ball milling 24h, 750 ℃ of insulation 12h, and heating rate is 5 ℃/min, can get black iron manganese phosphate for lithium (LiMn with the stove cooling
0.8Fe
0.2PO
4) positive electrode active materials
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.8Fe
0.2PO
4) grain diameter of positive electrode active materials is all in the 200-280nm scope, and the grain diameter homogeneous, big or small basically identical, no agglomeration; Lattice perfection, no dephasign (XRD figure such as Fig. 4); Specific area is 46.5m
2/ g.
Embodiment 5
Adopt the method identical with embodiment 2 to prepare positive electrode active materials and simulated battery, the addition of different is organic substance monomer is 2.5ml.
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.5Fe
0.5PO
4) grain diameter of positive electrode active materials is all in the 100-300nm scope, and the grain diameter homogeneous, big or small basically identical, no agglomeration; Lattice perfection, no dephasign; Adopt N
2The BET specific area of absorption test is 34.6m
2/ g.
Embodiment 6
Adopt the method identical with embodiment 2 to prepare positive electrode active materials and simulated battery, the addition of different is organic substance monomer is 50ml.
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.5Fe
0.5PO
4) grain diameter of positive electrode active materials is all in the 180-290nm scope, and the grain diameter homogeneous, big or small basically identical, no agglomeration; Lattice perfection, no dephasign; Specific area is 54.6m
2/ g.
Embodiment 7
Adopt the method identical to prepare positive electrode active materials and simulated battery, the different ammonium dihydrogen phosphates that do not add when being ball milling with embodiment 2.
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.5Fe
0.5PO
4) grain diameter of positive electrode active materials is all in the 110-290nm scope, and the grain diameter homogeneous, big or small basically identical, no agglomeration; Lattice perfection, no dephasign; Specific area is 50.6m
2/ g.
Comparative Examples 1
Adopt the method identical with embodiment 1 to prepare positive electrode active materials and simulated battery, different is not add aniline, the interpolation polyacrylamide.
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.5Fe
0.5PO
4) the particle average grain diameter of positive electrode active materials about 500nm, and a small amount of agglomeration is arranged, the grain diameter heterogeneity; The feature peak-to-peak is weak by force, phosphoric acid manganese, ferric phosphate dephasign; Specific area is 16.4m
2/ g.
Comparative Examples 2
Adopt the method identical with embodiment 1 to prepare positive electrode active materials and simulated battery, different is not add aniline, the interpolation citric acid.
Adopt the method identical with embodiment 1 test iron manganese phosphate for lithium (LiMn
0.5Fe
0.5PO
4) the particle average grain diameter of positive electrode active materials is about 1 μ m, and agglomeration is more serious, the particle size distribution heterogeneity; The feature peak-to-peak is weak by force, phosphoric acid manganese, ferric phosphate dephasign; Specific area is 8.3m
2/ g.
Performance test
First discharge specific capacity test: the battery of embodiment 1-7 and Comparative Examples 1-2 preparation placed carry out the charge-discharge performance test on the charge-discharge test instrument, the discharge voltage interval is 2.7～4.5V, and discharging current is 0.1C.
Cycle performance test: the battery of embodiment 1-7 and Comparative Examples 1-2 preparation placed carry out the charge-discharge performance test on the charge-discharge test instrument, the discharge voltage interval is 2.7～4.5V, and discharging current is 0.5C.Test result such as table 1.
High rate performance test: the battery of embodiment 1-7 and Comparative Examples 1-2 preparation placed carry out the charge-discharge performance test on the charge-discharge test instrument, the discharge voltage interval is 2.7～4.5V, and discharging current is respectively 0.1C, 0.5C, 1C, 2C, 5C, test result such as table 2.
Table 1
| First discharge specific capacity (mAh/g) | The 20th discharge capacity (mAh/g) | The 100th discharge capacity (mAh/g) | |
| Embodiment 1 | 152 | 139 | 137 |
| Embodiment 2 | 155 | 144 | 140 |
| Embodiment 3 | 150 | 139 | 136 |
| Embodiment 4 | 140 | 131 | 128 |
| Embodiment 5 | 134 | 125 | 122 |
| Embodiment 6 | 154 | 151 | 144 |
| Embodiment 7 | 147 | 138 | 134 |
| Comparative Examples 1 | 118 | 106 | 92 |
| Comparative Examples 2 | 104 | 93 | 77 |
Table 2
| 0.1C specific discharge capacity (mAh/g) | 0.5C inferior specific discharge capacity (mAh/g) | 1C specific discharge capacity (mAh/g) | 2C specific discharge capacity (mAh/g) | 5C specific discharge capacity (mAh/g) | |
| Embodiment 1 | 152 | 139 | 135 | 130 | 125 |
| Embodiment 2 | 155 | 140 | 135 | 129 | 122 |
| Embodiment 3 | 150 | 137 | 129 | 121 | 110 |
| Embodiment 4 | 140 | 127 | 115 | 98 | 87 |
| Embodiment 5 | 134 | 122 | 111 | 82 | 64 |
| Embodiment 6 | 154 | 150 | 143 | 132 | 125 |
| Embodiment 7 | 147 | 135 | 129 | 121 | 111 |
| Comparative Examples 1 | 118 | 89 | 62 | 45 | 14 |
| Comparative Examples 2 | 104 | 77 | 42 | 11 | 8 |
From the positive electrode active materials particle size distribution homogeneous of the last preparation of the present invention as can be seen, the pattern perfection does not have and reunites, and specific grain surface is long-pending big, help improving the electric conductivity of material, the battery multiplying power discharging property excellence, particularly high-rate discharge ability excellence of preparation; The height of discharge capacity first of battery simultaneously, battery charging and discharging is stable, and good cycle for the development of excellent positive electrode active materials provides the foundation, helps the application of this kind material and the development of battery.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. a positive electrode active materials is characterized in that, the structural formula of described positive electrode active materials is LiMn
xM
1-xPO
4, wherein, 0.2≤x≤0.8; M is selected from one or more among Fe, Co or the Ni;
The specific area of described positive electrode active materials is 40-50m
2/ g.
2. positive electrode active materials according to claim 1 is characterized in that the particle surface of described positive electrode active materials also is coated with carbon-coating, and the thickness of described carbon-coating is 5-10nm.
3. the preparation method of a positive electrode active materials is characterized in that, step comprises:
A, will comprise that the solution of phosphorus source, manganese source, M source and organic substance monomer mixes, control pH value is 4-6, prepares the phosphate presoma;
B, with the phosphate presoma and the lithium source mixing and ball milling of step a preparation;
C, the roasting under inert atmosphere of step b ball milling gained material is made LiMn
xM
1-xPO
4, wherein, 0.2≤x≤0.8; M is selected from one or more among Fe, Co or the Ni; Described organic substance monomer is selected from one or more in aniline, pyridine, furans, thiophene, pyrroles or the phonetic azoles;
The M source is selected from one or more in ferric iron source, trivalent cobalt source and the tetravalence nickel source.
4. the preparation method of positive electrode active materials according to claim 3, it is characterized in that described step a slowly adds manganese source and M source again for after will comprising the phosphorus source and the solution of organic substance monomer mixes earlier, with alkaline solution control pH value is 4-6, prepared by co-precipitation phosphate presoma.
5. the preparation method of positive electrode active materials according to claim 3 is characterized in that, described phosphorus source is selected from one or more in phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or the dibastic sodium phosphate;
Described manganese source is selected from Mn
2O
3, MnCO
3, Mn (CH
3COO)
24H
2O, MnCl
2, MnSO
4Or Mn (NO
3)
2In one or more;
Described ferric iron source is selected from one or more in ferric trichloride, ferric nitrate, ironic citrate or the iron hydroxide;
Described trivalent cobalt source is selected from one or more in the sulfate of the acetate of oxalates, cobalt of nitrate, the cobalt of cobalt or cobalt;
Described tetravalence nickel source is selected from one or more in the sulfate of the acetate of oxyhydroxide, nickel of nitrate, the nickel of nickel or nickel;
Described lithium source is selected from one or more in lithium hydroxide, lithium acetate, lithium chloride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4 or the lithium oxalate.
6. the preparation method of positive electrode active materials according to claim 3 is characterized in that, the mol ratio in described phosphorus source and manganese source is 1: 0.2-0.8; The mol ratio in described manganese source and M source is 1: 0.25-4;
The mol ratio in described lithium source and phosphorus source is 1-1.05;
The mol ratio in described organic substance monomer and M source is 1-20.
7. the preparation method of positive electrode active materials according to claim 6 is characterized in that, the mol ratio in described organic substance monomer and M source is 5-10.
8. the preparation method of positive electrode active materials according to claim 3 is characterized in that, also is added with phosphorous acid group material during described step b ball milling.
9. the preparation method of positive electrode active materials according to claim 8, it is characterized in that, described phosphorous acid group material is selected from one or more in diammonium hydrogen phosphate, ammonium dihydrogen phosphate or the lithium dihydrogen phosphate, and the mol ratio in the addition of described phosphorous acid group material and Mn source is 0.2-0.4.
10. the preparation method of positive electrode active materials according to claim 3 is characterized in that, also is mixed with carbon source during described step b ball milling.
11. the preparation method of positive electrode active materials according to claim 10 is characterized in that, described carbon source is selected from that conductive acetylene is black, in shitosan, glucose, sucrose, tartaric acid, citric acid or the fructose one or more;
The mol ratio in described carbon source and phosphorus source is 0.1-0.5.
12. the preparation method of positive electrode active materials according to claim 3 is characterized in that, the temperature of described roasting is 600-1000 ℃.
13. the preparation method of positive electrode active materials according to claim 12 is characterized in that, described roasting comprises with 5 ℃/min and is warming up to 400 ℃, insulation 3-5h; Be warming up to 600-1000 ℃ with 2 ℃/min again, insulation 12-30h.
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