CN103904311A - Surface coating and compounding lithium-rich manganese-based positive electrode material and preparation method of positive electrode material - Google Patents

Surface coating and compounding lithium-rich manganese-based positive electrode material and preparation method of positive electrode material Download PDF

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CN103904311A
CN103904311A CN201210585820.2A CN201210585820A CN103904311A CN 103904311 A CN103904311 A CN 103904311A CN 201210585820 A CN201210585820 A CN 201210585820A CN 103904311 A CN103904311 A CN 103904311A
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lithium
manganese
rich manganese
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based anode
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卢华权
庄卫东
卢世刚
王�忠
孙学义
谭翱
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China Automotive Battery Research Institute Co Ltd
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Beijing General Research Institute for Non Ferrous Metals
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract

The invention provides a positive electrode material which is applicable to lithium secondary batteries with high capacity, high charging and discharging efficiency and excellent rate capability. The positive electrode material which is applicable to the lithium secondary batteries is a surface coating and compounding lithium-rich manganese-based positive electrode material. The surface coating and compounding lithium-rich manganese-based positive electrode material is characterized in that an inner layer is made of a lithium-rich manganese-based material; a surface coating and compounding layer is made of a lithium iron phosphate material; the lithium iron phosphate of the surface coating and compounding layer is a novel phase which is generated in a coating and compounding process; a lithium source is selected from the lithium-rich manganese-based positive electrode material and is expressed by a general formula shown as Li[Li<x/3-y>Me<1-x>Mn<>2x/3.yLiFePO4; in the general formula, x is greater than 0 and less than 0.8; y is greater than 0 and less than x/3; Me is selected from at least one of chemical elements comprising Ni, Co, Mn, Cr, Fe, Zn, Al, Mg and Cd. The invention also provides a preparation method of the positive electrode material and a lithium ion secondary battery positive electrode and a lithium-ion secondary battery using the positive electrode material.

Description

Lithium-rich manganese-based anode material that a kind of surface is coated compound and preparation method thereof
Technical field
The present invention relates to lithium ion secondary battery anode material of a kind of high power capacity and preparation method thereof
Background technology
Lithium ion battery has that energy density is high, the feature such as have extended cycle life, and is considered to following electric automobile and hybrid electric vehicle field important " green energy resource ".At present, the energy density of lithium ion battery still can not meet the user demand of pure electric automobile, and development lithium ion battery with high energy density, improves pure electric automobile continual mileage, the key of ev industry development.The positive electrode that adopts height ratio capacity is to improve lithium ion battery energy density the most simply and effective method.
At present, lithium-rich manganese-based anode material is subject to extensive concern because having higher specific capacity (being greater than 200mAh/g).Lithium-rich manganese-based anode material is the Li by stratiform 2mnO 3and LiMO 2(M=Mn, Ni, Co) presses the solid solution that different proportion forms, and its chemical formula can be write as xLi 2mnO 3(1-x) LiMeO 2or Li[Li x/3me 1-xmn 2x/3] O 2.Although lithium-rich manganese-based anode material has higher specific capacity, also there are some problems, as very low in first charge-discharge efficiency, high rate performance is not good etc.First charge-discharge efficiency is low, and the reason of the poor generation of high rate performance is its initial charge during to 4.5V, is arranged in the Li of its layer structure transition metal layer with Li 2o only deviates from from structure, follows O simultaneously 2generation and the rearrangement of structure, and the Li that this part is deviate from only 2o cannot return in lattice, has produced larger irreversible capacity and lower first charge-discharge efficiency.In addition, in structural rearrangement process, part lithium room is occupied by metal ion, causes lithium ion diffusion admittance to be obstructed, and therefore causes the decline of high rate performance.
In recent years, in order to improve first charge-discharge efficiency and the multiplying power discharging property of lithium-rich manganese-based material, the main technology adopting is that surface is coated, be coated the side reaction of the release, minimizing and the electrolyte that suppress oxygen by surface, increase surperficial conductivity simultaneously, thereby improve the problem that rich lithium material efficiency for charge-discharge is low, high rate performance is poor.A.Manthiram etc. adopt Al (OH) 3, Al 2o 3, TiO 2, ZrO 2, MnO 2be coated on material surface (Electrochimica Acta50 (2005) 4784 – 4791 Deng material, Journalof Power Sources159 (2006) 1334 – 1339, J.Mater.Chem., 2009,19,4965 – 4972) improve to a certain extent first charge-discharge efficiency and the high rate performance of material.But simple surface is coated can only be from suppressing the performance of reacting and increase conductivity aspect part and improve lithium-rich manganese-based material of material and electrolyte, can not fundamentally reduce or suppress Li in transition metal layer with Li 2o deviates from, and therefore cannot solve its first charge-discharge efficiency completely on the low side, the problem that material high rate performance is poor.
Summary of the invention
The present invention is according to the deficiencies in the prior art, on the low side in order to solve material first charge-discharge efficiency, the problem that high rate performance is poor, the present inventors are attentively research discovery repeatedly, for lithium-rich manganese-based anode material, by coated one deck ferric phosphate on surface, simultaneously under inert gas after high-temperature process, can occur a kind of cenotype at lithium-rich manganese-based material surface, find that after testing this cenotype is LiFePO4, in the cenotype of formation, lithium source comes from lithium-rich manganese-based anode material.The appearance of this cenotype has consumed the lithium of " having more than needed " in lithium-rich manganese-based material, thereby has reduced these lithiums of " having more than needed " with Li 2the form of O from structure irreversible deviate from, also make the structure of material keep relative stability in discharging and recharging, the cenotype of the LiFePO4 generating has on the other hand formed stable coating layer at lithium-rich manganese-based material surface, the erosion of electrolyte be can resist, thereby first charge-discharge efficiency, high rate performance and the cycle performance of material significantly improved.
The invention provides a kind of new discharge capacity high, and first charge-discharge efficiency is high, the lithium-rich manganese-based anode material that high rate performance is good.The premium properties of this material is based on the coated compound realization in surface.
Therefore, a kind of surface of the present invention is coated compound lithium-rich manganese-based anode material, it is characterized in that, internal layer is lithium-rich manganese-based material, the coated composite bed in surface is LiFePO 4 material, the LiFePO4 of the coated composite bed in surface is the cenotype generating in coated recombination process, and, from lithium-rich manganese-based anode material, there is LiFePO in lithium source wherein in xrd 4the characteristic diffraction peak of phase.
Above-mentioned surface is coated compound lithium-rich manganese-based anode material, can be represented by general formula below:
Li[Li x/3-yMe 1-xMn 2x/3]O 2y/2·yLiFePO 4
Wherein,
0<x<0.8
0<y<x/3
Me is selected from Ni, Co, Mn, Cr, Fe, Zn, Al, Mg, at least one chemical element in Cd.
Further, above-mentioned surface is coated compound lithium-rich manganese-based anode material, and wherein Me is selected from Ni, Co, Mn, Cr, Fe, Al, at least two kinds of chemical elements in Mg.
Further, above-mentioned surface is coated compound lithium-rich manganese-based anode material, and wherein Me is selected from Ni, Co, Mn, Fe, at least three kinds of chemical elements in Al.
Preferably, above-mentioned surface is coated compound lithium-rich manganese-based anode material, and wherein Me is Ni (1-a-b)co amn b, wherein 0≤a<0.5,0≤b≤0.5, and 0.4≤x≤0.7,0<y≤0.15.
Preferably, above-mentioned surface is coated compound lithium-rich manganese-based anode material, and wherein Me is Ni (1-a-c)co aal c, wherein 0≤a<0.5,0≤c≤0.1, and 0.4≤x≤0.7,0<y≤0.15.
Surface provided by the invention is coated compound lithium-rich manganese-based anode material, and at room temperature between 2.0V to 4.8V, the current density with 20mA/g discharges and recharges, and first charge-discharge capacity is higher than 220mAh/g.
Surface provided by the invention is coated compound lithium-rich manganese-based anode material, and at room temperature between 2.0V to 4.8V, the current density with 20mA/g discharges and recharges, and first charge-discharge efficiency is higher than 80%.
The present invention also provides a kind of surface to be coated compound lithium-rich manganese-based anode material, it is characterized in that, can prepare according to following steps:
1) Li[Li x/3me 1-xmn 2x/3] O 2preparation
By Li source compound, manganese source compound, and Me source compound takes corresponding raw material by stoichiometric proportion, doubly adds deionized water to grind by the 3-19 of pressed powder weight, and the meta particle diameter that is ground to raw material is less than 0.3 micron.Adopt spray-dired mode to be dried in ground slurry, dried material carries out roasting, and sintering temperature is 800～1100 ° of C, roasting time 5～40h, and obtaining chemical formula is Li[Li x/3me 1-xmn 2x/3] O 2lithium-rich manganese-based anode material.
Wherein said lithium source is at least one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, and described manganese source is at least one in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate, oxide, carbonate or its mixture that described Me source is Me.
Or:
Soluble manganese source compound and Me source compound is water-soluble by stoichiometric proportion, take carbonate or hydroxide as precipitation reagent, after reaction, obtain persursor material, and carry out roasting after mixing with lithium source, sintering temperature is 800～1100 ° of C, roasting time 5～40h, and obtaining chemical formula is Li[Li x/3me 1-xmn 2x/3] O 2lithium-rich manganese-based anode material.
Wherein said manganese source compound is at least one in manganese nitrate, manganese sulfate, at least one in nitrate, the sulfate of the solubility that described Me source compound is Me.
2) Li[Li x/3-yme 1-xmn 2x/3] O 2-y2yLiFePO 4preparation
The chemical formula that step 1) is obtained is Li[Li x/3me 1-xmn 2x/3] O 2lithium-rich manganese-based anode material drop in the mixed solution of soluble phosphate, soluble ferric iron salt and glucose (lithium-rich manganese-based anode material: soluble phosphate: soluble ferric iron salt: the mol ratio=1:y:y:0.1y of glucose), be uniformly mixed, use ammoniacal liquor that the pH value of system is adjusted to 5-9.Continue to add thermal agitation until liquid evaporation is complete, after drying, under inert gas atmosphere, heat treatment 2～10h under 300-650 ° of C.Obtain the coated compound lithium-rich manganese-based anode material in surface.
Wherein said soluble phosphate is one at least in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and described soluble ferric iron salt is at least one in ferric nitrate, iron chloride, and described inert atmosphere is Ar or N 2in at least one.
Under inert gas, lithium-rich manganese-based material Li[Li in heat treatment process x/3me 1-xmn 2x/3] O 2in part Li and FePO 4under the effect of reduction carbon, generate LiFePO 4cenotype.This part LiFePO 4cenotype be wrapped in the surface of lithium-rich manganese-based material, consumed in lithium-rich manganese-based material and " had more than needed " on the one hand, formed on the other hand stable surface coating layer, can resist the erosion of electrolyte, thereby significantly improve the chemical property of material.
The present invention also provides a kind of positive pole of lithium ion battery, and it has used the coated compound lithium-rich manganese-based anode material in above-mentioned surface as positive active material.
The present invention also provides a kind of lithium rechargeable battery, and it comprises negative pole, barrier film, electrolyte and above-mentioned positive pole.
Accompanying drawing explanation
Fig. 1 is that in the embodiment of the present invention 1, surface is coated the surperficial XRD comparison diagram that is coated compound lithium-rich manganese-based anode material in compound lithium-rich manganese-based anode material and comparative example 1.
Fig. 2 is that in the embodiment of the present invention 1, surface is coated the surperficial first charge-discharge comparison diagram that is coated compound lithium-rich manganese-based anode material in compound lithium-rich manganese-based anode material and comparative example 1.
Fig. 3 is that in the embodiment of the present invention 1, surface is coated the surperficial multiplying power discharging capacity comparison figure that is coated compound lithium-rich manganese-based anode material in compound lithium-rich manganese-based anode material and comparative example 1.
Embodiment
For the present invention being done to further understanding, below in conjunction with embodiment, the preferred embodiment of the invention is further described, protection scope of the present invention is not limited to the examples, and protection scope of the present invention is decided by claims.
Embodiment 1
Coated compound lithium-rich manganese-based anode material Li[Li 0.15ni 0.13co 0.13mn 0.54] O 1.9750.05LiFePO 4(be Li[Li x/3-yme 1-xmn 2x/3] O 2-y/2yLiFePO 4middle x=0.6, y=0.05, Me=Ni 0.325co 0.325mn 0.35).
1) Li[Li 0.15ni 0.13co 0.13mn 0.54] O 1.9750.05LiFePO 4preparation
5.68g nickel protoxide, 6.10g cobaltosic oxide, 26.69g lithium carbonate, 36.28g manganese carbonate are mixed, add deionized water by 9 times of pressed powder weight, join in grinder and grind, until middle granularity is less than 0.3 micron, the dry mixed powder that obtains 4 kinds of raw materials of then spraying, through 900 ° of C calcination 36h, cooling with stove, subsequently powder is ground and sieved, obtain Li[Li 0.2ni 0.13co 0.13mn 0.54] O 2.
Take 2.02 nine water ferric nitrates, 0.575g ammonium dihydrogen phosphate and 0.24g glucose are dissolved in 80mL water, take the above-mentioned Li[Li of 8.64g 0.2ni 0.13co 0.13mn 0.54] O 2drop in solution, after being uniformly mixed, use ammoniacal liquor that system pH is adjusted to 7.0, being heated to 80 ° of C, to be stirred to liquid evaporation complete, vacuumize 10h under 80 ° of C, after grinding under Ar atmosphere 500 ° of C heat treatment 5h, obtain Li[Li 0.15ni 0.13co 0.13mn 0.54] O 1.9750.05LiFePO 4.
2) Li[Li 0.15ni 0.13co 0.13mn 0.54] O 1.9750.05LiFePO 4structure
Use XRD to characterize the structure of material, X ray is Cu/K α,
Figure BDA00002680915100041
scanning angle is 10-90 °, and sweep speed is 8 °/min, and walking wide is 0.02 °.The XRD collection of illustrative plates of material as shown in Figure 1, can find out from XRD collection of illustrative plates, and XRD main peak is all the characteristic diffraction peak of rich lithium material, but also occurred low intensive LiFePO 4characteristic diffraction peak, this show through surface coated compound after, the surface of material has formed LiFePO 4cenotype.
Comparative example 1: the not coated compound lithium-rich manganese-based anode material Li[Li in surface 0.2ni 0.13co 0.13mn 0.54] O 2.
Li[Li 0.2ni 0.13co 0.13mn 0.54] O 2preparation method as follows: 5.68g nickel protoxide, 6.10g cobaltosic oxide, 26.69g lithium carbonate, 36.28g manganese carbonate are mixed, add deionized water by 9 times of pressed powder weight, join in grinder and grind, until middle granularity is less than 0.3 micron, the dry mixed powder that obtains 4 kinds of raw materials of then spraying, through 900 ° of C calcination 36h, cooling with stove, subsequently powder is ground and sieved, obtain Li[Li 0.2ni 0.13co 0.13mn 0.54] O 2.
Not coated compound Li[Li 0.2ni 0.13co 0.13mn 0.54] O 2structure use XRD characterize, X ray is Cu/K α,
Figure BDA00002680915100051
scanning angle is 10-90 °, and sweep speed is 8 °/min, and walking wide is 0.02 °.The XRD collection of illustrative plates of material as shown in Figure 1, can find out from XRD collection of illustrative plates, and the XRD of the coated compound material in surface is the characteristic diffraction peak of rich lithium material, there is no the appearance of other diffraction maximums.
Embodiment 2-5: a series of surfaces are coated compound lithium-rich manganese-based anode material Li[Li 0.2-yni 0.13co 0.13mn 0.54] O 2-y/2yLiFePO 4(be Li[Li x/3-yme 1-xmn 2x/3] O 2-y/2yLiFePO 4middle x=0.6, Me=Ni 0.325co 0.325mn 0.35).The value of y is as shown in table 1.
The preparation method of material is identical with the method that embodiment 1 provides, and the proportioning of corresponding raw material calculates by the chemical formula of the present embodiment.
[table 1]
Embodiment Y value Chemical composition
2 0.02 Li[Li 0.18Ni 0.13Co 0.13Mn 0.54]O 1.99·0.02LiFePO 4
3 0.08 Li[Li 0.12Ni 0.13Co 0.13Mn 0.54]O 1.96·0.08LiFePO 4
4 0.10 Li[Li 0.10Ni 0.13Co 0.13Mn 0.54]O 1.95·0.10LiFePO 4
5 0.12 Li[Li 0. 08Ni 0.13Co 0.13Mn 0.54]O 1.94·0.12LiFePO 4
Embodiment 6: coated compound lithium-rich manganese-based anode material: the Li[Li in surface 0.113ni 0.195co 0.195mn 0.477] O 1.990.02LiFePO 4(be Li[Li x/3-yme 1-xmn 2x/3] O 2-y/2yLiFePO 4middle x=0.4, y=0.02, Me=Ni 0.325co 0.325mn 0.35).
8.2g nickel protoxide, 8.8g cobaltosic oxide, 24.21g lithium carbonate, 30.80g manganese carbonate are mixed, add deionized water by 19 times of pressed powder weight, join in grinder and grind, until middle granularity is less than 0.3 micron, then spray and be dried the mixed powder that obtains 4 kinds of raw materials, through 850 ° of C calcination 25h, cooling with stove, subsequently powder is ground and sieved, obtain Li[Li 0.133ni 0.195co 0.195mn 0.477] O 2.
Take 0.808 nine water ferric nitrate, 0.23g ammonium dihydrogen phosphate and 0.12g glucose are dissolved in 80mL water, take the above-mentioned Li[Li of 8.64g 0.133ni 0.195co 0.195mn 0.477] O 2drop in solution, after being uniformly mixed, use ammoniacal liquor that system pH is adjusted to 7.0, being heated to 80 ° of C, to be stirred to liquid evaporation complete, vacuumize 10h under 80 ° of C, after grinding under Ar atmosphere 500 ° of C heat treatment 6h, obtain Li[Li 0.113ni 0.195co 0.195mn 0.477] O 1.990.02LiFePO 4.
Embodiment 7: coated compound lithium-rich manganese-based anode material: the Li[Li in surface 0.153ni 0.098co 0.098mn 0.565] O 1.960.08LiFePO 4(be Li[Li x/3-yme 1-xmn 2x/3] O 2-y/2yLiFePO 4middle x=0.7, y=0.08, Me=Ni 0.325co 0.325mn 0.35).
4.4g nickel protoxide, 4.73g cobaltosic oxide, 28.22g lithium carbonate, 39.07g manganese carbonate are mixed, add deionized water by 3 times of pressed powder weight, join in grinder and grind, until middle granularity is less than 0.3 micron, then spray and be dried the mixed powder that obtains 4 kinds of raw materials, through 1000 ° of C calcination 12h, cooling with stove, subsequently powder is ground and sieved, obtain Li[Li 0.233ni 0.098co 0.098mn 0.565] O 2.
Take 2.232 nine water ferric nitrates, 0.92g ammonium dihydrogen phosphate and 0.48g glucose are dissolved in 80mL water, take the above-mentioned Li[Li of 8.64g 0.233ni 0.098co 0.098mn 0.565] O 2drop in solution, after being uniformly mixed, use ammoniacal liquor that system pH is adjusted to 7.0, being heated to 80 ° of C, to be stirred to liquid evaporation complete, vacuumize 10h under 80 ° of C, after grinding under Ar atmosphere 500 ° of C heat treatment 6h, obtain Li[Li 0.153ni 0.098co 0.098mn 0.565] O 1.960.08LiFePO 4.
Embodiment 8-12: a series of surfaces are coated compound lithium-rich manganese-based anode material Li[Li 0.2-yni 0.32co 0.06al 0.02mn 0.40] O 2-y/2yLiFePO 4(be Li[Li x/3-yme 1-xmn 2x/3] O 2-y/2yLiFePO 4middle x=0.6, Me=Ni 0.8co 0.15al 0.05).The value of y is as shown in table 2.
[table 2]
? Y value Chemical composition
Embodiment
8 0.02 Li[Li 0.18Ni 0.32Co 0.06Al 0.02Mn 0.40]O 1.99·0.02LiFePO 4
Embodiment 9 0.05 Li[Li 0.15Ni 0.32Co 0.06Al 0.02Mn 0.40]O 1.975·0.05LiFePO 4
Embodiment 10 0.08 Li[Li 0.12Ni 0.32Co 0.06Al 0.02Mn 0.40]O 1.96·0.08LiFePO 4
Embodiment 11 0.10 Li[Li 0.10Ni 0.32Co 0.06Al 0.02Mn 0.40]O 1.95·0.10LiFePO 4
Embodiment 12 0.12 Li[Li 0.08Ni 0.32Co 0.06Al 0.02Mn 0.40]O 1.94·0.12LiFePO 4
The coated compound lithium-rich manganese-based anode material in a series of surfaces in embodiment 8-12, preparation as follows:
According to Li[Li 0.2ni 0.32co 0.06al 0.02mn 0.40] O 2in the stoichiometric proportion sulfate that takes Ni, Co, Al, Mn be dissolved in deionized water, be made into the solution that total concentration is 2mol/L, the sodium hydroxide solution that is 2mol/L by itself and concentration and appropriate ammoniacal liquor drop to reactor and are precipitated, after washing of precipitate is dry, mix with appropriate lithium carbonate, through 950 ° of C calcination 15h, cooling with stove, subsequently powder is ground and sieved, obtain Li[Li 0.2ni 0.32co 0.06al 0.02mn 0.40] O 2.
According to the chemical composition in table 2 in molar ratio example take nine water ferric nitrates, ammonium dihydrogen phosphate and 0.24g glucose are dissolved in water, add in proportion above-mentioned Li[Li 0.2ni 0.32co 0.06al 0.02mn 0.40] O 2.After being uniformly mixed, use ammoniacal liquor that system pH is adjusted to 7.0, being heated to 80 ° of C, to be stirred to liquid evaporation complete, vacuumize 10h under 80 ° of C, after grinding under Ar atmosphere 500 ° of C heat treatment 5h, obtain the coated compound lithium-rich manganese-based anode material in a series of surface shown in table 2.
Comparative example 2: not coated compound lithium-rich manganese-based anode material: the Li[Li in surface 0.2ni 0.32co 0.06al 0.02mn 0.40] O 2.
Li[Li 0.2ni 0.32co 0.06al 0.02mn 0.40] O 2preparation method as follows: according to Li[Li 0.2ni 0.32co 0.06al 0.02mn 0.40] O 2in the stoichiometric proportion sulfate that takes Ni, Co, Al, Mn be dissolved in deionized water, be made into the solution that total concentration is 2mol/L, the sodium carbonate liquor that is 2mol/L by itself and concentration and appropriate ammoniacal liquor drop to reactor and are precipitated, after washing of precipitate is dry, mix with appropriate lithium carbonate, through 900 ° of C calcination 36h, cooling with stove, subsequently powder is ground and sieved, obtain Li[Li 0.2ni 0.32co 0.06al 0.02mn 0.40] O 2
Embodiment 13-26: a series of surfaces are coated compound lithium-rich manganese-based anode material Li[Li 0.15me 0.4mn 0.4] O 1.9750.05LiFePO 4(be Li[Li x/3-yme 1-xmn 2x/3] O 2-y/2yLiFePO 4middle x=0.6, y=0.05).Wherein Me is selected from Ni, Co, Mn, Cr, Fe, Zn, Al, Mg, at least one chemical element in Cd.The element of choosing of Me forms as shown in table 1.
The preparation method of material is identical with the method that embodiment 1 provides, and the proportioning of corresponding raw material calculates by the chemical formula of the present embodiment, the oxide of the element that wherein Me source comprises from it.
[table 3]
? The element of Me representative Chemical composition
Embodiment 13 Me=Ni 0.5Mn 0.5 Li[Li 0.15N i0.2Mn 0.6]O 1.975·0.05LiFePO 4
Embodiment 14 Me=Ni 0.8Co 0.2 Li[Li 0.15Ni 0.32Co 0.08Mn 0.4]O 1.975·0.05LiFePO 4
Embodiment 15 Me=Ni 0.5Co 0.2Mn 0.3 Li[Li 0.15Ni 0.2Co 0.08Mn 0.52]O 1.975·0.05LiFePO 4
Embodiment 16 Me=Ni 0.6Co 0.2Mn 0.2 Li[Li 0.15Ni 0.24Co 0.08Mn 0.48]O 1.975·0.05LiFePO 4
Embodiment 17 Me=Ni 0.7Co 0.15Mn 0.15 Li[Li 0.15Ni 0.28Co 0.06Mn 0.46]O 1.975·0.05LiFePO 4
Embodiment 18 Me=Ni 0.8Co 0.1Mn 0.1 Li[Li 0.15Ni 0.32Co 0.04Mn 0.44]O 1.975·0.05LiFePO 4
Embodiment 19 Me=Ni 0.4Mg 0.1Mn 0.5 Li[Li 0.15Ni 0.16Mg 0.04Mn 0.6]O 1.975·0.05LiFePO 4
Embodiment 20 Me=Co 0.8Mn 0.1Cr 0.1 Li[Li 0.15Co 0.32Cr 0.04Mn 0.44]O 1.975·0.05LiFePO 4
Embodiment 21 Me=Co 0.8Mn 0.1Cd 0.1 Li[Li 0.15Co 0.32Cd 0.04Mn 0.44]O 1.975·0.05LiFePO 4
Embodiment 22 Me=Co 0.9Fe 0.1 Li[Li 0.15Co 0.36Fe 0.04Mn 0.4]O 1.975·0.05LiFePO 4
Embodiment 23 Me=Co 0.9Zn 0.1 Li[Li 0.15Co 0.36Zn 0.04Mn 0.4]O 1.975·0.05LiFePO 4
Embodiment 24 Me=Co Li[Li 0.15Co 0.4Mn 0.4]O 1.975·0.05LiFePO 4
Embodiment 25 Me=Ni Li[Li 0.15Ni 0.4Mn 0.4]O 1.975·0.05LiFePO 4
Embodiment 26 Me=Ni 0.8Al 0.2 Li[Li 0.15Ni 0.32Al 0.08Mn 0.4]O 1.975·0.05LiFePO 4
Comparative example 3: not coated compound lithium-rich manganese-based anode material: the Li[Li in surface 0.2ni 0.2mn 0.6] O 2.
Preparation method is as follows: according to Li[Li 0.2ni 0.2mn 0.6] O 2in the stoichiometric proportion sulfate that takes Ni, Mn be dissolved in deionized water, be made into the solution that total concentration is 2mol/L, the sodium carbonate liquor that is 2mol/L by itself and concentration and appropriate ammoniacal liquor drop to reactor and are precipitated, after washing of precipitate is dry, mix with appropriate lithium carbonate, through 900 ° of C calcination 36h, cooling with stove, subsequently powder is ground and sieved, obtain Li[Li 0.2ni 0.2mn 0.6] O 2
In order to measure the chemical property of material of embodiment of the present invention 1-26 and comparative example 1-3, above-mentioned material is prepared into electrode, and is assembled into button cell, discharge and recharge experiment, specific experiment step is as follows:
1) by above-mentioned active material, conductive carbon black (superP) and Kynoar (PVDF) in the ratio of 80:10:10 and add METHYLPYRROLIDONE (NMP) to blend together slurry, be evenly coated on aluminium foil, after oven dry, be cut into pole piece.
2) above-mentioned pole piece is after 120 ° of C vacuumize 12h, in the glove box that is full of argon gas, take pour lithium slice as negative pole, take 1mol/L LiPF6EC+DEC+DMC(1:1:1) be electrolyte, take Celgard2300 as barrier film, dress up CR2032 type button experimental cell.
3) experimental cell carries out charge-discharge test computer-controlled discharging and recharging on instrument, charging/discharging voltage interval is 2.0-4.8V, the system of discharging and recharging is: be respectively 20mA/g with current density and charge and discharge circulation 3 weeks, 40mA/g charges and discharge circulation 3 weeks, with 40mA/g charging with 100mA/g discharge cycles 3 weeks, with 40mA/g charging with 200mA/g discharge cycles 3 weeks, with 40mA/g charging with 600mA/g discharge cycles 3 weeks, finally charge and discharge circulation 3 weeks with 20mA/g again, test finishes.
The test result of experimental cell first discharge specific capacity, 3C specific discharge capacity and the first charge-discharge efficiency of preparing is according to the method described above listed in table 4.
Discharge and recharge result known, compared with the coated compound lithium-rich manganese-based anode material in surface of embodiment of the present invention 1-26 is coated compound lithium-rich manganese-based anode material with the not carrying out surface in comparative example 1-3, efficiency first and the 3C discharge capacity of material all have raising in various degree.
Fig. 2 is the first charge-discharge comparison diagram of embodiment 1 and comparative example 1, Fig. 3 is the multiplying power discharging capacity comparison figure of embodiment 1 and comparative example 1, from Fig. 2 and Fig. 3, in both contrasts, can find, after surface is coated, the discharge capacity first of embodiment 1 does not significantly reduce, but efficiency for charge-discharge and heavy-current discharge performance all obviously improve.
The coated compound lithium-rich manganese-based material specific capacity in surface provided by the invention is high, and efficiency is high first, and good rate capability is suitable as the positive electrode of pure electric automobile (EV), plug-in hybrid-power automobile (PHEV) electrokinetic cell very much.
[table 4]
Figure BDA00002680915100101

Claims (11)

1. the coated compound lithium-rich manganese-based anode material in surface, it is characterized in that, its internal layer is lithium-rich manganese-based material, and the coated composite bed in surface is LiFePO4, the LiFePO4 of the coated composite bed in surface is the cenotype generating in coated recombination process, and lithium source is wherein from lithium-rich manganese-based anode material.
2. according to the coated compound lithium-rich manganese-based anode material in surface claimed in claim 1, it is characterized in that it is expressed by the following formula:
Li[Li x/3-yMe 1-xMn 2x/3]O 2-y/2·yLiFePO 4
Wherein,
0<x<0.8
0<y<x/3
Me is selected from Ni, Co, Mn, Cr, Fe, Zn, Al, Mg, at least one in Cd.
3. according to the coated compound lithium-rich manganese-based anode material in surface claimed in claim 2, it is characterized in that Me is selected from Ni, Co, Mn, Cr, Fe, Al, in Mg at least two kinds.
4. according to the coated compound lithium-rich manganese-based anode material in surface claimed in claim 3, it is characterized in that Me is selected from Ni, Co, Mn, Fe, in Al at least three kinds.
5. according to the coated compound lithium-rich manganese-based anode material in the surface described in claim 2-4 any one, wherein Me is Ni (1-a-b)co amn b, wherein 0≤a<0.5,0≤b≤0.5, and 0.4≤x≤0.7,0<y≤0.15.
6. according to the coated compound lithium-rich manganese-based anode material in the surface described in claim 2-4 any one, wherein Me is Ni (1-a-c)co aal c, wherein 0≤a<0.5,0≤c≤0.2, and 0.4≤x≤0.7,0<y≤0.15.
7. according to the coated compound lithium-rich manganese-based anode material in the surface described in claim 5 or 6, it is characterized in that under room temperature that the current density with 20mA/g discharges and recharges between 2.0V to 4.8V, first charge-discharge capacity is higher than 220mAh/g.
8. according to the coated compound lithium-rich manganese-based anode material in the surface described in claim 5 or 6, it is characterized in that under room temperature that the current density with 20mA/g discharges and recharges between 2.0V to 4.8V, first charge-discharge efficiency is higher than 80%.
9. according to the preparation method of the coated compound lithium-rich manganese-based anode material in the surface described in claim 1-8 any one, comprise the following steps:
1) Li[Li x/3me 1-xmn 2x/3] O 2preparation
By Li source compound, manganese source compound, and Me source compound is pressed Li[Li x/3me 1-xmn 2x/3] O 2stoichiometric proportion take corresponding raw material, add water to grind; Adopt spray-dired mode to be dried in ground slurry, dried material carries out roasting, and sintering temperature is 800～1100 ° of C, roasting time 5～40h, and obtaining chemical formula is Li[Li x/3me 1-xmn 2x/3] O 2lithium-rich manganese-based anode material; Wherein said Li source compound is at least one in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, described manganese source compound is at least one in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate, oxide, carbonate or its mixture that described Me source compound is Me metal;
Or:
Soluble manganese source compound and soluble M e source compound are pressed to Li[Li x/3me 1-xmn 2x/3] O 2stoichiometric proportion water-soluble, take carbonate or hydroxide as precipitation reagent, after reaction, obtain persursor material, and carry out roasting after mixing with Li source compound, sintering temperature is 800～1100 ° of C, roasting time 5～40h, obtaining chemical formula is Li[Li x/3me 1-xmn 2x/3] O 2lithium-rich manganese-based anode material; Wherein said soluble manganese source compound is at least one in manganese nitrate, manganese sulfate, at least one in nitrate, the sulfate of the solubility that described soluble M e source compound is Me;
2) Li[Li x/3-yme 1-xmn 2x/3] O 2-y/2yLiFePO 4preparation
The chemical formula that step 1) is obtained is Li[Li x/3me 1-xmn 2x/3] O 2lithium-rich manganese-based anode material drop in the mixed solution of soluble phosphate, soluble ferric iron salt and glucose, wherein, lithium-rich manganese-based anode material: soluble phosphate: soluble ferric iron salt: the mol ratio of glucose is 1:y:y:0.1y, be uniformly mixed, use ammoniacal liquor that the pH value of system is adjusted to 5-9, continue to add thermal agitation until liquid evaporation is complete, after drying, under inert gas atmosphere, heat treatment 2～10h under 300-650 ° of C, obtains the coated compound lithium-rich manganese-based anode material in surface; Wherein said soluble phosphate is one at least in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and described soluble ferric iron salt is at least one in ferric nitrate, iron chloride, and described inert atmosphere is Ar or N 2in at least one.
10. a positive pole for lithium rechargeable battery, is characterized in that, it has used the surface of claim 1-8 any one to be coated compound lithium-rich manganese-based anode material as positive active material.
11. 1 kinds of lithium rechargeable batteries, is characterized in that comprising negative pole, barrier film, electrolyte and positive pole claimed in claim 10.
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