CN101964416B - Preparation method of lithium ion battery anode material lithium manganate and automobile lithium ion battery - Google Patents

Preparation method of lithium ion battery anode material lithium manganate and automobile lithium ion battery Download PDF

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CN101964416B
CN101964416B CN201010517845XA CN201010517845A CN101964416B CN 101964416 B CN101964416 B CN 101964416B CN 201010517845X A CN201010517845X A CN 201010517845XA CN 201010517845 A CN201010517845 A CN 201010517845A CN 101964416 B CN101964416 B CN 101964416B
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lithium
sintering
ion battery
lithium manganate
manganate
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CN201010517845XA
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CN101964416A (en
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张瑾瑾
周友元
肖可颂
张勇
匡远泉
赵罡
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湖南长远锂科有限公司
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a preparation technology of a battery anode material and a related automobile battery and particularly discloses a preparation method of lithium ion battery anode material lithium manganate. The method comprises the following steps: using lithium source, Mn3O4 and nanoscale doping metal additive as raw materials for proportioning, then presintering Mn3O4 or the Mn3O4 processed by ball milling, mixing the presintered Mn3O4 with the mixture of lithium source and metal additive; performing the first sintering and second sintering to the mixed raw material; and finally classifying and screening the sintering product to obtain the spinel lithium manganate product with the required grain size. The invention also discloses an automobile lithium ion battery which is assembled by using the spinel lithium manganate prepared by the method of the invention as anode and using graphite as cathode. The preparation method of the invention has simple operation and environmental friend; and the prepared lithium manganate product has excellent product performance.

Description

The preparation method of lithium cell anode material lithium manganate and automobile-used lithium ion battery
Technical field
The present invention relates to a kind of preparation technology and relevant Vehicular battery of cell positive material, relate in particular to a kind of preparation technology and automobile-used lithium ion battery of anode material for lithium-ion batteries.
Background technology
As the new forms of energy lithium electricity positive electrode of energy-saving and environmental protection, the LiMn2O4 Heat stability is good, overcharging resisting is electric, high rate during charging-discharging is superior, has safety guarantee property preferably; And China has abundant manganese resource, and cheap cost of material makes the production of LiMn2O4 have bigger price advantage.The small lithium ion secondary batteries that has been widely used such as portable electronics such as civilian or military mobile communication equipment now, ups power, mine lamp and portable power tool, and lithium manganate material also begins progressively to be applied in this type of small-sized secondary cell.The outstanding advantage of LiMn2O4 on performance and price makes one of its power type lithium-ion battery anode material that becomes tool prospect.
Yet also there are many shortcomings such as capacity is on the low side, loop attenuation big, high-temperature behavior difference in LiMn2O4 at present.Dissolving and the Jahn-Teller effect of Mn in electrolyte is the main cause that causes its loop attenuation.Although there are many researchers to do a lot of work; But multiselect uses manganese dioxide to be raw material, and because of the intrinsic primary particle features of smaller of manganese dioxide, the LiMn2O4 of preparing all presents defectives such as primary particle tiny (be mostly 1 μ m below), uniform particles property be relatively poor; This makes that the contact area of LiMn2O4 and electrolyte is excessive; In long-term circulation, especially in the high temperature circulation process, dissolving takes place and causes lattice defect in Mn in electrolyte.Simultaneously, common LiMn2O4 intrinsic Jahn-Teller effect, greatly reduce the high-temperature behavior and the cycle performance of battery, its application and development in the electrokinetic cell field is restricted.
Even the part LiMn2O4 through doping vario-property, increases its cycle performance to some extent, but because of its application target different with purposes; It is not handled raw material, the product sintering schedule is not carried out too much refinement yet, and the product of production has certain crystal defect more; In the high temperature circulation process and under the high-multiplying power discharge condition; Sharply decay can occur, only can use, be difficult to carry out specialization and promote as the electric vehicle lithium manganate material as common manganate cathode material for lithium.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes prior art; Provide that a kind of technology is simple, the preparation method of the lithium cell anode material lithium manganate of environmental friendliness, excellent product performance, also provide a kind of and have extended cycle life, high-temperature behavior and the excellent automobile-used lithium ion battery of multiplying power discharging property.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of preparation method of lithium cell anode material lithium manganate, may further comprise the steps:
(1) batching: (the lithium source is preferably LiOHH with the lithium source 2O or Li 2CO 3), as the Mn in manganese source 3O 4Also prepare burden simultaneously as raw material with nanoscale doping metals additive, make the mol ratio of Li element in the raw material, Mn element and doped metallic elements satisfy x during batching: (2-y): (molecular formula to guarantee the finished product lithium manganate having spinel structure satisfies Li to y xMn 2-yMe yO 4, Me is one or more in the doped metallic elements), 1≤x≤1.2 and 0≤y≤0.45 wherein; Batching of the present invention has been selected rich lithium condition and nano level metal additive for use, and this can play an important role to the raising of positive electrode cycle performance and the improvement of high-temperature behavior;
(2) preliminary treatment: with described Mn 3O 4Perhaps will pass through the Mn after the ball-milling treatment 3O 4(preferably carrying out ball-milling treatment earlier) places pre-burning 1h~10h under 500 ℃~1000 ℃ temperature, accomplishes Mn 3O 4Preliminary treatment; Through raw material is carried out preliminary treatment, can make raw material Mn 3O 4Primary particle grow up; Particle size distribution is more concentrated, and BET reduces greatly, and the follow-up LiMn2O4 product primary particle that makes is bigger with making; Body more evenly, also helps mutually the reduction of product B ET, can produce significant impact equally to the high-temperature behavior and the cycle performance of finished product LiMn2O4;
(3) batch mixing: with above-mentioned pretreated Mn 3O 4Carry out ball mill mixing with said lithium source for preparing and nanoscale doping metals additive, selecting for use of nano level metal additive makes that also whole compounding effect is better, and end product is more even; Ball mill mixing can be carried out in batch mixer, so that raw materials mix evenly is a purpose; Preferably, the ratio of grinding media to material during ball mill mixing can be (1~10): 1, and the time of ball mill mixing is preferably 1h~10h;
(4) sintering: the mixed material after the step (3) is carried out once sintered, (heating rate is preferably 60 ℃/h~240 ℃/h), be incubated 5h~50h then and obtain once sintered appearance to be warming up to 700 ℃~1000 ℃ when once sintered; Again sintering appearance is carried out fragmentation, mixing, carry out double sintering then, (heating rate is preferably 60 ℃/h~240 ℃/h), be incubated 5h~50h again to be warming up to 500 ℃~1000 ℃ during double sintering; Rate of temperature fall after each sintering is accomplished all preferably is controlled at 60 ℃/h~200 ℃/h;
(5) screening: at last the sintering afterproduct is carried out classification, screening (gas flow sizing machine capable of using carries out classification), obtain the lithium manganate having spinel structure product of required particle diameter.
Among the preparation method of above-mentioned lithium cell anode material lithium manganate; Said nanoscale doping metals additive is preferably oxide and/or the hydroxide of doped metallic elements Me, and said doped metallic elements Me is preferably one or more among metallic element Mg, Co, Ti, Al, Ni, the Cr.Through adopting the doping metals additive of nanoscale, small grain size, it is more even that doped metallic elements is mixed with manganese source, lithium source, reacts more complete, makes the interpolation element better to the modified effect of material.
Among the preparation method of each above-mentioned lithium cell anode material lithium manganate, said once sintered, double sintering is preferably having oxygen atmosphere (for example air, ozone or O 2Atmosphere) carry out in, because there is oxygen atmosphere more to help the crystallization effect of product, but at CO 2Or N 2Under the atmosphere, also can control reaction process preferably, promote reaction balanced.Through the heating rate in the sintering process, rate of temperature fall and sintering atmosphere are controlled, can make the crystalline form of sintered sample more become complete.
The method of the invention described above has at first adopted mangano-manganic oxide as the manganese source; After preliminary treatment is carried out in raw material manganese source; Mix the suitably lithium source of mole proportioning again; Add the suitable doping metallic element, and introduce the sintering process of the sintering of optimizing at twice, prepare a kind of body mutually evenly, centralized particle diameter, the perfect lithium manganate having spinel structure of crystallization degree.
The LiMn2O4 product primary particle size that the present invention makes is even, and pattern is regular, and the primary particle average grain diameter can reach 1 μ m~5 μ m, and specific area is 0.2m 2/ g~1m 2/ g, tap density can reach 2g/cm 3~2.5g/cm 3This lithium manganate material that the present invention makes not only crystal structure is perfect, and circulation and high-temperature behavior are good, and high rate performance is good, is the comparatively ideal positive electrode of electric vehicle lithium ion battery.
As a total technical conceive; The present invention also provides a kind of automobile-used lithium ion battery on above-mentioned preparation method's basis; Said automobile-used lithium ion battery is to be assembled with negative pole by anodal, and said positive pole is that the lithium manganate having spinel structure that makes of above-mentioned each preparation method of employing is as positive electrode (negative material can be selected graphite etc. for use).The primary particle average grain diameter of this lithium manganate having spinel structure is preferably 1 μ m~5 μ m, and specific area is preferably 0.2m 2/ g~1m 2/ g, tap density is preferably 2g/cm 3~2.5g/cm 3
Under the 1C multiplying power, between 2.8V~4.2V, specific discharge capacity can reach more than the 90mAh/g above-mentioned automobile-used lithium ion battery provided by the invention (the 053048Al actual effect battery that for example is assembled into), and 500 all capability retentions are higher than 80%; In 100 weeks of circulation under 55 ℃ of high temperature, its capability retention is more than 88%; Under the 10C multiplying power, specific discharge capacity can reach more than 90% of 1C specific discharge capacity.
Compared with prior art, the invention has the advantages that:
At first, preparation method of the present invention can make body mutually evenly, crystallization degree is perfect, primary particle is big lithium manganate having spinel structure, can see from its X-ray diffraction collection of illustrative plates the spinel structure of pure phase the dephasign diffraction maximum not occurring;
Second; The lithium manganate having spinel structure that preparation method of the present invention makes has excellent cycle performance, good high-temperature performance and outstanding high rate performance; With this LiMn2O4 is that positive pole, graphite are the automobile-used lithium ion battery of the present invention that negative pole is assembled into; Reach more than the 90mAh/g at specific discharge capacity under the 1C multiplying power, between 2.8V~4.2V, 10C multiplying power discharging specific capacity reaches more than 90% of 1C specific discharge capacity; 500 all capability retentions are higher than 80%, 55 ℃ of 100 week of high temperature circulation, and capability retention is more than 88%; It is thus clear that automobile-used lithium ion battery of the present invention all improves a lot on cycle life, high-temperature behavior and multiplying power discharging property, can satisfy the requirement of electric vehicle positive electrode;
The 3rd, technology of the present invention is simple to operation, is the basis with the solid phase method, is easy to large-scale industrial production;
The 4th, technical process of the present invention does not have waste gas, waste water, waste residue generation, environmental friendliness, energy-conserving and environment-protective.
Description of drawings
The X-ray diffraction collection of illustrative plates of the lithium cell anode material lithium manganate that Fig. 1 makes for the embodiment of the invention 1;
The sem photograph of the lithium cell anode material lithium manganate that Fig. 2 makes for the embodiment of the invention 1;
The 053048Al actual effect battery that Fig. 3 is assembled into for the embodiment of the invention 1~embodiment 3 is at the cyclic curve figure in 500 weeks of circulation between 1C multiplying power, 2.8V~4.2V, under the normal temperature;
The 053048Al actual effect battery that Fig. 4 is assembled into for the embodiment of the invention 1 is at the cyclic curve figure in 100 weeks of circulation between 1C multiplying power, 2.8V~4.2V, under 55 ℃ of high temperature;
The 053048Al actual effect battery that Fig. 5 is assembled into for the embodiment of the invention 1 is between 2.8V~4.2V, under the normal temperature, respectively the discharge curve under 0.1C, 1C, 10C, 30C different multiplying.
Embodiment
Embodiment 1
A kind of preparation method of lithium cell anode material lithium manganate of the present invention may further comprise the steps:
(1) batching: with lithium source Li 2CO 3, manganese source Mn 3O 4Also prepare burden simultaneously as raw material with nanoscale doping metals additive; The atomic molar that makes Li element in the raw material, Mn element and doped metallic elements Me during batching is than satisfying 1.05: 1.9: 0.1; Wherein, Doped metallic elements Me is that 0.04: 0.03: 0.03 Al, Co and Ti forms by the atomic molar ratio, and nanoscale doping metals additive then is respectively Al 2O 3, Co 3O 4And TiO 2(perhaps being the hydroxide of doped metallic elements) satisfied Li through batching with the molecular formula that guarantees the finished product lithium manganate having spinel structure 1.05Mn 1.90Al 0.04Co 0.03Ti 0.03O 4
(2) preliminary treatment: earlier to above-mentioned Mn 3O 4Carry out ball milling, then with the Mn behind the ball milling 3O 4Place pre-burning 5h under 800 ℃ of temperature, accomplish Mn 3O 4Preliminary treatment;
(3) batch mixing: with above-mentioned pretreated Mn 3O 4With the lithium source Li for preparing 2CO 3And nanoscale doping metals additive Al 2O 3, Co 3O 4And TiO 2Carry out ball mill mixing; Ball mill mixing is carried out in batch mixer, and the ratio of grinding media to material during ball mill mixing is 5: 1, and the time of ball mill mixing is 5h;
(4) sintering: the mixed material after the step (3) is placed chamber type electric resistance furnace; Bubbling air carries out once sintered, and the heating rate with 100 ℃/h when once sintered is warming up to 900 ℃, is incubated 10h then; Rate of temperature fall is controlled at 70 ℃/h, obtains once sintered appearance; Again sintering appearance is carried out fragmentation, mixing, carry out double sintering then, be warming up to 800 ℃ with the heating rate of 100 ℃/h equally during double sintering, be incubated 8h again, rate of temperature fall is controlled at 70 ℃/h equally;
(5) screening: utilize gas flow sizing machine that the sintering afterproduct is carried out classification, screening at last, obtain the lithium manganate having spinel structure product of required particle diameter.
The X-ray diffraction collection of illustrative plates of the lithium manganate having spinel structure product that present embodiment makes is as shown in Figure 1, can see that by the X-ray diffraction collection of illustrative plates of Fig. 1 product of the present invention is the spinel structure of pure phase, the dephasign diffraction maximum do not occur.The surface sweeping Electronic Speculum picture of the lithium manganate having spinel structure product that present embodiment makes is as shown in Figure 2, and is visible by Fig. 2, and the primary particle size of product of the present invention is even, and pattern is regular, and the primary particle average grain diameter is about 3 μ m, and specific area is 0.5m 2/ g, tap density is 2.2g/cm 3
A kind of automobile-used lithium ion battery of the present invention (053048Al actual effect battery), this lithium ion battery are to obtain after assembling as negative pole as positive pole, with graphite with the lithium manganate having spinel structure that present embodiment makes.With the lithium ion battery of present embodiment under the 1C multiplying power, discharge and recharge test between 2.8V~4.2V, result of the test such as Fig. 3~shown in Figure 5, first discharge specific capacity is 98.1mAh/g, 500 all capability retentions are higher than 84.7% (referring to Fig. 3); In 55 ℃ of 100 weeks of high temperature circulation, capability retention is 88.2% (referring to Fig. 4); Specific discharge capacity reaches more than 90% (referring to Fig. 5) of 1C specific discharge capacity under the 10C multiplying power.
Embodiment 2
A kind of preparation method of lithium cell anode material lithium manganate of the present invention may further comprise the steps:
(1) batching: with lithium source LiOH, manganese source Mn 3O 4Also prepare burden simultaneously as raw material with nanoscale doping metals additive; The atomic molar that makes Li element in the raw material, Mn element and doped metallic elements Me during batching is than satisfying 1.1: 1.85: 0.15; Wherein, Doped metallic elements Me is that 0.07: 0.05: 0.03 Mg, Co and Ni forms by the atomic molar ratio, and nanoscale doping metals additive then is respectively the oxide of doped metallic elements Mg, Co and Ni, satisfies Li through batching with the molecular formula that guarantees the finished product lithium manganate having spinel structure 1.1Mn 1.85Mg 0.07Co 0.05Ni 0.03O 4
(2) preliminary treatment: earlier to above-mentioned Mn 3O 4Carry out ball milling, then with the Mn behind the ball milling 3O 4Place pre-burning 10h under 600 ℃ of temperature, accomplish Mn 3O 4Preliminary treatment;
(3) batch mixing: with above-mentioned pretreated Mn 3O 4Carry out ball mill mixing with the oxide of the lithium source LiOH for preparing and doped metallic elements Mg, Co and Ni; Ball mill mixing is carried out in batch mixer, and the ratio of grinding media to material during ball mill mixing is 8: 1, and the time of ball mill mixing is 3h;
(4) sintering: the mixed material after the step (3) is placed chamber type electric resistance furnace, feed CO 2Gas carries out once sintered, and the heating rate with 150 ℃/h when once sintered is warming up to 950 ℃, is incubated 6h then, and rate of temperature fall is controlled at 100 ℃/h, obtains once sintered appearance; Again sintering appearance is carried out fragmentation, mixing, carry out double sintering then, be warming up to 850 ℃ with the heating rate of 150 ℃/h equally during double sintering, be incubated 5h again, rate of temperature fall is controlled at 100 ℃/h equally;
(5) screening: utilize gas flow sizing machine that the sintering afterproduct is carried out classification, screening at last, obtain the lithium manganate having spinel structure product of required particle diameter.The primary particle size of this product is even, and pattern is regular, and the primary particle average grain diameter is 5 μ m, and specific area is 0.3m 2/ g, tap density is 2.4g/cm 3
A kind of automobile-used lithium ion battery of the present invention (053048Al actual effect battery), this lithium ion battery are to be assembled with negative pole by anodal, wherein positive pole be the lithium manganate having spinel structure that makes of employing present embodiment as positive electrode, negative pole is a graphite.Under the 1C multiplying power, discharge and recharge test between 2.8V~4.2V, result of the test is as shown in Figure 3 with the lithium ion battery of present embodiment, and first discharge specific capacity is 98.3mAh/g, and 500 all capability retentions are higher than 83.7% (referring to Fig. 3).
Embodiment 3
A kind of preparation method of lithium cell anode material lithium manganate of the present invention may further comprise the steps:
(1) batching: with lithium source Li 2CO 3, manganese source Mn 3O 4Also prepare burden simultaneously as raw material with nanoscale doping metals additive; The atomic molar that makes Li element in the raw material, Mn element and doped metallic elements Me during batching is than satisfying 1.15: 1.80: 0.2; Wherein, Doped metallic elements Me is 0.05: 0.05: 0.04 by the atomic molar ratio: 0.03: 0.03 Mg, Co, Al, Cr and Ni form; Nanoscale doping metals additive then is respectively the oxide (perhaps hydroxide also can) of doped metallic elements Mg, Co, Al, Cr and Ni, satisfies Li through batching with the molecular formula that guarantees the finished product lithium manganate having spinel structure 1.15Mn 1.80Mg 0.05Co 0.05Al 0.04Cr 0.03Ni 0.03O 4
(2) preliminary treatment: earlier to above-mentioned Mn 3O 4Carry out ball milling, then with the Mn behind the ball milling 3O 4Place pre-burning 12h under 500 ℃ of temperature, accomplish Mn 3O 4Preliminary treatment;
(3) batch mixing: with above-mentioned pretreated Mn 3O 4With the lithium source Li for preparing 2CO 3And the oxide of doped metallic elements Mg, Co, Al, Cr and Ni carries out ball mill mixing; Ball mill mixing is carried out in batch mixer, and the ratio of grinding media to material during ball mill mixing is 10: 1, and the time of ball mill mixing is 2h;
(4) sintering: the mixed material after the step (3) is placed chamber type electric resistance furnace, feed O 2(or air) carries out once sintered, and the heating rate with 200 ℃/h when once sintered is warming up to 800 ℃, is incubated 20h then, and rate of temperature fall is controlled at 200 ℃/h, obtains once sintered appearance; Again sintering appearance is carried out fragmentation, mixing, carry out double sintering then, be warming up to 950 ℃ with the heating rate of 200 ℃/h equally during double sintering, be incubated 10h again, rate of temperature fall is controlled at 200 ℃/h equally;
(5) screening: utilize gas flow sizing machine that the sintering afterproduct is carried out classification, screening at last, obtain the lithium manganate having spinel structure product of required particle diameter.The primary particle size of this product is even, and pattern is regular, and the primary particle average grain diameter is 4 μ m, and specific area is 0.4m 2/ g, tap density is 2.3g/cm 3
A kind of automobile-used lithium ion battery of the present invention (053048Al actual effect battery), this lithium ion battery are to obtain after assembling as negative pole as positive electrode, with graphite with the lithium manganate having spinel structure that present embodiment makes.Under the 1C multiplying power, discharge and recharge test between 2.8V~4.2V, result of the test is as shown in Figure 3 with the lithium ion battery of present embodiment, and first discharge specific capacity is 98.9mAh/g, and 500 all capability retentions are higher than 86.5% (referring to Fig. 3).

Claims (7)

1. the preparation method of a lithium cell anode material lithium manganate may further comprise the steps:
(1) batching: with the lithium source, as the Mn in manganese source 3O 4Also prepare burden simultaneously as raw material with nanoscale doping metals additive, make the mol ratio of Li element in the raw material, Mn element and doped metallic elements satisfy x during batching: (2-y): y, wherein 1≤x≤1.2 and 0≤y≤0.45;
(2) preliminary treatment: with described Mn 3O 4Perhaps will pass through the Mn after the ball-milling treatment 3O 4Place pre-burning 1h~12h under 500 ℃~1000 ℃ temperature, accomplish Mn 3O 4Preliminary treatment;
(3) batch mixing: with above-mentioned pretreated Mn 3O 4Carry out ball mill mixing with said lithium source for preparing and nanoscale doping metals additive;
(4) sintering: the mixed material after the step (3) is carried out once sintered, be warming up to 700 ℃~1000 ℃ when once sintered, be incubated 5h~50h then and obtain once sintered appearance; Again sintering appearance is carried out fragmentation, mixing, carry out double sintering then, be warming up to 500 ℃~1000 ℃ during double sintering, be incubated 5h~50h again; Heating rate during said once sintered, double sintering is 60 ℃/h~240 ℃/h, and the rate of temperature fall after each sintering is accomplished all is controlled at 60 ℃/h~200 ℃/h;
(5) screening: at last the sintering afterproduct is carried out classification, screening, obtain the lithium manganate having spinel structure product of required particle diameter.
2. the preparation method of lithium cell anode material lithium manganate according to claim 1, it is characterized in that: said lithium source is LiOHH 2O or Li 2CO 3
3. the preparation method of lithium cell anode material lithium manganate according to claim 1; It is characterized in that: said nanoscale doping metals additive is oxide and/or the hydroxide of doped metallic elements Me, and said doped metallic elements Me is one or more among metallic element Mg, Co, Ti, Al, Ni, the Cr.
4. the preparation method of lithium cell anode material lithium manganate according to claim 1, it is characterized in that: in the said batch mixing step, the ratio of grinding media to material during ball mill mixing is (1~10): 1, the time of ball mill mixing is 1h~10h.
5. according to the preparation method of each described lithium cell anode material lithium manganate in the claim 1~4, it is characterized in that: said once sintered, double sintering is in oxygen atmosphere is arranged, to carry out.
6. automobile-used lithium ion battery, said automobile-used lithium ion battery are to be assembled with negative pole by anodal, it is characterized in that: said positive pole is that the lithium manganate having spinel structure that makes of each said preparation method of employing claim 1~5 is as positive electrode.
7. automobile-used lithium ion battery according to claim 6 is characterized in that: said primary particle average grain diameter as anodal lithium manganate having spinel structure material is 1 μ m~5 μ m, and specific area is 0.2m 2/ g~1m 2/ g, tap density is 2g/cm 3~2.5g/cm 3
CN201010517845XA 2010-10-25 2010-10-25 Preparation method of lithium ion battery anode material lithium manganate and automobile lithium ion battery CN101964416B (en)

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