CN103151520A - Lithium ion battery anode material and preparation method thereof - Google Patents
Lithium ion battery anode material and preparation method thereof Download PDFInfo
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- CN103151520A CN103151520A CN2013100896109A CN201310089610A CN103151520A CN 103151520 A CN103151520 A CN 103151520A CN 2013100896109 A CN2013100896109 A CN 2013100896109A CN 201310089610 A CN201310089610 A CN 201310089610A CN 103151520 A CN103151520 A CN 103151520A
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Abstract
The invention belongs to the technical field of the lithium ion battery and especially relates to a lithium ion battery anode material. The lithium ion battery anode material comprises a nuclear layer and a shell layer covering the nuclear layer, wherein the general formula of the material of the nuclear layer is LiNixMn2-xO4, wherein x is greater than 0 and less than 0.2; the general formula of the material of the shell layer is LiNiyCozMnwMrO2, wherein r is less than 0.1 and y/w is greater than 1 and less than 4; and the mass ratio of the material of the shell layer to the material of the nuclear layer is (0.1-3): 10. Compared with the prior art, the lithium ion battery anode material is characterized in that nickel is doped in spinel type lithium manganate, so that the octahedral position of the spinel type lithium manganate can be stabilized and the valence state of manganese can be increased, and the change of the lithium manganate structure and dissolution of manganese in the charge/discharge process can be reduced, and the nickel-doped spinel type lithium manganate is covered with a layer of nickel-cobalt lithium manganate so that dissolution of manganese can be effectively prevented; in such a way, attenuation of the capacity of the material can be effectively reduced, and the electrochemical performance and the cycle life of the lithium ion battery employing the anode material are improved.
Description
Technical field
The invention belongs to technical field of lithium ion, relate in particular to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Along with the continuous increase of various circles of society to the demand of high performance lithium ion battery, the specific capacity of positive electrode becomes the key factor that restriction lithium ion battery overall performance further improves, affect capacity, high-temperature stability and other chemical properties of lithium ion battery, this is because the specific capacity of the positive electrode in present commercial lithium-ion batteries is far smaller than the specific capacity of negative material.Lithium manganate having spinel structure (LiMn
2O
4) positive electrode due to have aboundresources, low price, the advantage such as environmentally friendly, synthesis technique is simple and fail safe is good, be acknowledged as one of most promising positive electrode of lithium ion battery of new generation.
But there is poplar-Taylor effect in lithium manganate having spinel structure, and Mn
4+Have the hyperoxia voltinism, manganese wherein is easily dissolving also, makes the capacity of lithium manganate having spinel structure can occur to decay slowly.Under higher temperature, the initial capacity of lithium manganate having spinel structure can descend, the cycle performance variation.In addition, single lithium manganate having spinel structure conductivity is lower.Therefore people wish the part-structure by changing lithium manganate having spinel structure or decay that entire infrastructure suppresses its capacity and change the too low problem of its conductivity.
In view of this, the necessary a kind of anode material for lithium-ion batteries and preparation method thereof that provides, this positive electrode is by the nickel that adulterates in lithium manganate having spinel structure, and coat one deck nickle cobalt lithium manganate on its surface, can effectively reduce the capacity attenuation of this positive electrode, improve chemical property, conductivity and the cycle life of material.
Summary of the invention
One of purpose of the present invention is: for the deficiencies in the prior art, and provide a kind of anode material for lithium-ion batteries, this positive electrode is by the nickel that adulterates in lithium manganate having spinel structure, and coat one deck nickle cobalt lithium manganate on its surface, can effectively reduce the capacity attenuation of this positive electrode, improve chemical property and the cycle life of material, to overcome the deficiency that lithium manganate having spinel structure capacity of the prior art is easily decayed, conductivity is lower, cycle life is not satisfactory.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of anode material for lithium-ion batteries, and comprise stratum nucleare and be coated on the outer shell of described stratum nucleare, the general formula of stratum nucleare material is LiNi
xMn
2-xO
4, 0＜x＜0.2 wherein, the general formula of Shell Materials is LiNi
yCo
zMn
wM
rO
2, wherein r＜0.1, and 1＜y/w＜4, M is at least a in Al, Mg, Ti, Cr, Zr, Pt, Au, Pd, Ce, Pr and Nd, the mass ratio of described Shell Materials and described stratum nucleare material is (0.1-3): 10.
Be prone to platform due to the nickel LiMn2O4 when the 5V, thereby make the capacity of positive electrode when 4.25V on the low side, therefore need the strict content (0＜x＜0.2) that nickel replaces manganese of controlling, thereby suppress the appearance of 5V platform.The advantage such as although nickle cobalt lithium manganate has that energy density is high, cost is relatively low and cycle performance is excellent, but it has the compacted density shortcoming such as relatively poor relative to fail safe on the low side simultaneously, in order to guarantee that positive electrode of the present invention has relatively high compacted density and fail safe, should control the proportion of Shell Materials.
A kind of improvement as anode material for lithium-ion batteries of the present invention, in described positive electrode, the ratio [(x+y)+(2-x+w)+z+r]/(x+y) of the mole summation of elemental nickel, element manganese, element cobalt and element M and the mole of elemental nickel〉9, i.e. (x+y)＜1/3.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, the mass ratio of described Shell Materials and described stratum nucleare material is (1-2.5): 10.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, the mass ratio of described Shell Materials and described stratum nucleare material is 1:5.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, the median particle diameter D50 of described stratum nucleare material is 8-20 um.The median particle diameter D50 of positive electrode is to the Li in charge and discharge process
+The evolving path, electrolyte have very large impact in the oxidation Decomposition on positive electrode surface.Control suitable median particle diameter D50, be conducive to make positive electrode to have simultaneously good chemical property, memory property and security performance.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, the specific area of described positive electrode is 0.20 ~ 0.60 m
2/ g.Excessive surface area will aggravate electrolyte in the reaction on positive electrode surface, thereby worsen the chemical property of battery; Too little surface area will cause larger grain diameter, thereby affect lithium ion reversible dynamic behavior that takes off embedding in positive electrode.
With respect to prior art, the present invention is by the nickel that adulterates in lithium manganate having spinel structure (nickel form with divalence in LiMn2O4 exists), octahedral site that can stable spinel-type lithium manganate and improve the valence state of manganese, reduce the variation of LiMn2O4 structure in charge and discharge process and the dissolving of manganese, variation in this element adjustment has fundamentally changed the overlapping situation of inherent electron orbit and the surface nature of material, effectively raise the stability of material structure, use the cycle performance of the lithium ion battery of this positive electrode to be improved.In addition, the present invention is by coating one deck nickle cobalt lithium manganate on the surface doped with the lithium manganate having spinel structure of nickel, can effectively prevent the dissolving of manganese, and the unoccupied orbital that suppresses manganese catalytic action that the decomposition of electrolyte is played, thereby effectively reduce the decay of material capacity, and the conductivity of raising material, chemical property and the cycle life of the lithium ion battery of this positive electrode is used in raising.The present invention carries out performance optimization in conjunction with foreign cation and surface these two kinds of methods of coating to lithium manganate having spinel structure, makes the performance of lithium manganate having spinel structure better, and structure is more stable.And the present invention controls by strict the content that nickel replaces manganese, effectively suppressed the appearance of 5V platform, makes this positive electrode single 4V platform only occur, thereby effectively improves the capacity of this positive electrode when 4.25V.
Another object of the present invention is to provide a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps: the first step, the oxide of oxide, lithium source and the nickel of manganese is placed in batch mixer according to the molar ratio of (2-x): 1:x, after mixing, be placed in Muffle furnace and be warming up to 300-500 ℃ with the programming rate of 3-15 ℃/min, and heat preservation sintering 2-6h; And then being warming up to 700-900 ℃ with the programming rate of 4-10 ℃/min, and heat preservation sintering 15-30h obtains the nickel manganate precursor for lithium of single spinel structure after ball milling.
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
yCo
zMn
wM
rO
2According to mol ratio 10:(0.1-5) add in batch mixer, after mixing, be placed in Muffle furnace and be warming up to 700-1000 ℃ with the programming rate of 5-20 ℃/min, and heat preservation sintering 10-20h, obtain anode material for lithium-ion batteries after ball milling.
As a kind of improvement of the preparation method of anode material for lithium-ion batteries of the present invention, described lithium source is Li
2CO
3, Li
2O or LiOH.
Certainly, the preparation method of the nickel manganate precursor for lithium of single spinel structure can also be solid sintering technology, fused salt infusion process, coprecipitation, sol-gel process, spray drying process or firing method etc.
With respect to prior art, preparation method's technique of the present invention is simple, is easy to realize, easily realizes suitability for industrialized production.The advantage such as adopt that the positive electrode that the method prepares has Stability Analysis of Structures, conductivity is higher and capacity attenuation is little is applied in lithium ion battery, can improve cycle performance and the chemical property of lithium ion battery.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in further detail, but the specific embodiment of the present invention is not limited to this.
The invention provides a kind of anode material for lithium-ion batteries.
Embodiment 1: a kind of anode material for lithium-ion batteries that the present embodiment provides, and comprise stratum nucleare and be coated on the outer shell of stratum nucleare, the general formula of stratum nucleare material is LiNi
0.1Mn
1.9O
4, Shell Materials is LiNi
0.2Co
0.65Mn
0.1Mg
0.05O
2, the mass ratio of Shell Materials and stratum nucleare material is 1:5, and the median particle diameter D50 of stratum nucleare material is 12 um, and the specific area of this positive electrode is 0.50 m
2/ g.
Embodiment 2: a kind of anode material for lithium-ion batteries that the present embodiment provides, and comprise stratum nucleare and be coated on the outer shell of stratum nucleare, the general formula of stratum nucleare material is LiNi
0.15Mn
1.85O
4, Shell Materials is LiNi
0.15Co
0.78Mn
0.05Al
0.02O
2, the mass ratio of Shell Materials and stratum nucleare material is 1:4, and the median particle diameter D50 of stratum nucleare material is 16um, and the specific area of this positive electrode is 0.40 m
2/ g.
Embodiment 3: a kind of anode material for lithium-ion batteries that the present embodiment provides, and comprise stratum nucleare and be coated on the outer shell of stratum nucleare, the general formula of stratum nucleare material is LiNi
0.05Mn
1.95O
4, Shell Materials is LiNi
0.25Co
0.62Mn
0.10Ti
0.03O
2, the mass ratio of Shell Materials and stratum nucleare material is 3:10, and the median particle diameter D50 of stratum nucleare material is 18um, and the specific area of this positive electrode is 0.25 m
2/ g.
Embodiment 4: a kind of anode material for lithium-ion batteries that the present embodiment provides, and comprise stratum nucleare and be coated on the outer shell of stratum nucleare, the general formula of stratum nucleare material is LiNi
0.18Mn
1.82O
4, Shell Materials is LiNi
0.14Co
0.65Mn
0.12Cr
0.09O
2, the mass ratio of Shell Materials and stratum nucleare material is 1:100, and the median particle diameter D50 of stratum nucleare material is 10um, and the specific area of this positive electrode is 0.55 m
2/ g.
Embodiment 5: a kind of anode material for lithium-ion batteries that the present embodiment provides, and comprise stratum nucleare and be coated on the outer shell of stratum nucleare, the general formula of stratum nucleare material is LiNi
0.03Mn
1.97O
4, Shell Materials is LiNi
0.30Co
0.44Mn
0.20Zr
0.06O
2, the mass ratio of Shell Materials and stratum nucleare material is 1:10, and the median particle diameter D50 of stratum nucleare material is 8um, and the specific area of this positive electrode is 0.60 m
2/ g.
Embodiment 6: a kind of anode material for lithium-ion batteries that the present embodiment provides, and comprise stratum nucleare and be coated on the outer shell of stratum nucleare, the general formula of stratum nucleare material is LiNi
0.07Mn
1.93O
4, Shell Materials is LiNi
0.22Co
0.63Mn
0.07Mg
0.05Ce
0.03O
2, the mass ratio of Shell Materials and stratum nucleare material is 1:20, and the median particle diameter D50 of stratum nucleare material is 20um, and the specific area of this positive electrode is 0.20 m
2/ g.
Comparative Examples 1: the general formula of a kind of anode material for lithium-ion batteries that this Comparative Examples provides is LiNi
0.1Mn
1.9O
4, its median particle diameter D50 is 12 um.The positive electrode that is this Comparative Examples does not do to coat processing.
Comparative Examples 2: a kind of anode material for lithium-ion batteries that this Comparative Examples provides is commercially available spinel-type LiMn
2O
4, its median particle diameter D50 is 12 um.The positive electrode that is this Comparative Examples is not done doping and coats to process.
The present invention also provides a kind of preparation method of anode material for lithium-ion batteries.
Embodiment 7, and the present embodiment provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 1 provides, and comprises the following steps: the first step, and with MnO
2, Li
2CO
3Be placed in batch mixer with NiO according to the molar ratio of 1.9:1:0.1, after mixing, be placed in Muffle furnace and be warming up to 400 ℃ with the programming rate of 5 ℃/min, and heat preservation sintering 4h; And then be warming up to 800 ℃ with the programming rate of 7 ℃/min, and heat preservation sintering 20h, obtaining median particle diameter D50 after ball milling is that 12 um, general formula are LiNi
0.1Mn
1.9O
4The nickel manganate precursor for lithium of single spinel structure.
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
0.2Co
0.65Mn
0.1Mg
0.05O
2Add in batch mixer according to mol ratio 5:1, after mixing, be placed in Muffle furnace and be warming up to 900 ℃ with the programming rate of 8 ℃/min, and heat preservation sintering 15h, obtaining specific area after ball milling is 0.50 m
2The anode material for lithium-ion batteries of/g.
Embodiment 8, and the present embodiment provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 2 provides, and comprises the following steps: the first step, and with MnO
2, Li
2O and NiO are placed in batch mixer according to the molar ratio of 1.85:1:0.15, and after mixing, be placed in Muffle furnace and be warming up to 450 ℃ with the programming rate of 10 ℃/min, and heat preservation sintering 3h; And then be warming up to 700 ℃ with the programming rate of 9 ℃/min, and heat preservation sintering 25h, obtaining median particle diameter D50 after ball milling is that 16 um, general formula are LiNi
0.15Mn
1.85O
4The nickel manganate precursor for lithium of single spinel structure.
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
0.15Co
0.78Mn
0.05Al
0.02O
2Add in batch mixer according to mol ratio 4:1, after mixing, be placed in Muffle furnace and be warming up to 800 ℃ with the programming rate of 12 ℃/min, and heat preservation sintering 12h, obtaining specific area after ball milling is 0.40 m
2The anode material for lithium-ion batteries of/g.
Embodiment 9, and the present embodiment provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 3 provides, and comprises the following steps: the first step, and with MnO
2, LiOH and NiO be placed in batch mixer according to the molar ratio of 1.95:1:0.05, after mixing, be placed in Muffle furnace and be warming up to 500 ℃ with the programming rate of 15 ℃/min, and heat preservation sintering 2h; And then be warming up to 900 ℃ with the programming rate of 4 ℃/min, and heat preservation sintering 15h, obtaining median particle diameter D50 after ball milling is that 18um, general formula are LiNi
0.05Mn
1.95O
4The nickel manganate precursor for lithium of single spinel structure.
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
0.25Co
0.62Mn
0.10Ti
0.03O
2Add in batch mixer according to mol ratio 10:3, after mixing, be placed in Muffle furnace and be warming up to 1000 ℃ with the programming rate of 20 ℃/min, and heat preservation sintering 10h, obtaining specific area after ball milling is 0.25 m
2The anode material for lithium-ion batteries of/g.
Embodiment 10, and the present embodiment provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 4 provides, and comprises the following steps: the first step, and with MnO
2, Li
2CO
3Be placed in batch mixer with NiO according to the molar ratio of 1.82:1:0.18, after mixing, be placed in Muffle furnace and be warming up to 300 ℃ with the programming rate of 3 ℃/min, and heat preservation sintering 6h; And then be warming up to 700 ℃ with the programming rate of 10 ℃/min, and heat preservation sintering 30h, obtaining median particle diameter D50 after ball milling is that 10 um, general formula are LiNi
0.18Mn
1.82O
4The nickel manganate precursor for lithium of single spinel structure.
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
0.14Co
0.65Mn
0.12Cr
0.09O
2Add in batch mixer according to mol ratio 100:1, after mixing, be placed in Muffle furnace and be warming up to 750 ℃ with the programming rate of 5 ℃/min, and heat preservation sintering 20h, obtaining specific area after ball milling is 0.55m
2The anode material for lithium-ion batteries of/g.
Embodiment 11, and the present embodiment provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 5 provides, and comprises the following steps: the first step, and with MnO
2, Li
2CO
3Be placed in batch mixer with NiO according to the molar ratio of 1.97:1:0.03, after mixing, be placed in Muffle furnace and be warming up to 350 ℃ with the programming rate of 7 ℃/min, and heat preservation sintering 5h; And then be warming up to 750 ℃ with the programming rate of 7 ℃/min, and heat preservation sintering 26h, obtaining median particle diameter D50 after ball milling is that 8 um, general formula are LiNi
0.03Mn
1.97O
4The nickel manganate precursor for lithium of single spinel structure.
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
0.30Co
0.44Mn
0.20Zr
0.06O
2Add in batch mixer according to mol ratio 10:1, after mixing, be placed in Muffle furnace and be warming up to 850 ℃ with the programming rate of 13 ℃/min, and heat preservation sintering 12h, obtaining specific area after ball milling is 0.60m
2The anode material for lithium-ion batteries of/g.
Embodiment 12, and the present embodiment provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 6 provides, and comprises the following steps: the first step, and with MnO
2, Li
2CO
3Be placed in batch mixer with NiO according to the molar ratio of 1.93:1:0.07, after mixing, be placed in Muffle furnace and be warming up to 450 ℃ with the programming rate of 13 ℃/min, and heat preservation sintering 3.5h; And then be warming up to 850 ℃ with the programming rate of 9 ℃/min, and heat preservation sintering 18h, obtaining median particle diameter D50 after ball milling is that 20 um, general formula are LiNi
0.07Mn
1.93O
4The nickel manganate precursor for lithium of single spinel structure.
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
0.22Co
0.63Mn
0.07Mg
0.05Ce
0.03O
2Add in batch mixer according to mol ratio 20:1, after mixing, be placed in Muffle furnace and be warming up to 950 ℃ with the programming rate of 17 ℃/min, and heat preservation sintering 16h, obtaining specific area after ball milling is 0.20m
2The anode material for lithium-ion batteries of/g.
The positive electrode that embodiment 1 to 6 and Comparative Examples 1 and 2 are provided adds with conductive carbon and bonding agent Kynoar respectively makes anode sizing agent in 1-METHYLPYRROLIDONE, then anode sizing agent is coated on plus plate current-collecting body, through drying, colding pressing and cut and make positive plate, each positive plate is coiled into battery core with negative plate and membrane coil respectively, then each battery core is placed in packaging bag, inject electrolyte, through changing into capacity etc., make lithium ion battery.Each lithium ion battery number consecutively is S1-S6, D1 and D2.
The battery that is numbered S1-S6, D1 and D2 is carried out following test: the cycle performance of (1) test battery under 45 ℃, 4.25V voltage: wherein charge step for first with the rate of charge constant current charge of 0.7C to 4.25V, and then constant voltage charge is until electric current is down to 0.05C; Discharge step is that discharge-rate constant-current discharge with 0.5C is to 3.0V; Record the discharge capacity attenuation in the circulating battery process, and calculate the capability retention after circulation 300 times, acquired results sees Table 1.
(2) test battery high rate performance at room temperature: wherein charge step be first with the rate of charge constant current charge of 0.7C to 4.25V, and then constant voltage charge is until electric current is down to 0.05C; Discharge step is to use successively the multiplying power constant-current discharge of 0.2C, 0.5C, 1C to 3.0V; Record the ratio of battery 0.5C and 1C discharge capacity and 0.2C discharge capacity, acquired results is shown in table 1.
Table 1: the cycle performance and the high rate performance test result that are numbered the battery of S1-S6, D1 and D2.
As can be seen from Table 1: under the same conditions, use the lithium ion battery of positive electrode of the present invention to have better cycle performance and high rate performance (chemical property), this is because the octahedral site that doping nickel can stable spinel-type lithium manganate in lithium manganate having spinel structure and improve the valence state of manganese, reduce the variation of LiMn2O4 structure in charge and discharge process and the dissolving of manganese, effectively raise the stability of material structure, use the cycle performance of the lithium ion battery of this positive electrode to be improved.And coat one deck nickle cobalt lithium manganate on the surface doped with the lithium manganate having spinel structure of nickel, can effectively prevent the dissolving of manganese, and the unoccupied orbital that suppresses manganese catalytic action that the decomposition of electrolyte is played, thereby effectively reduce the decay of material capacity, and the conductivity of raising material, chemical property and the cycle life of the lithium ion battery of this positive electrode is used in raising.The present invention carries out performance optimization in conjunction with foreign cation and surface these two kinds of methods of coating to lithium manganate having spinel structure, makes the performance of lithium manganate having spinel structure better, and structure is more stable.
Need to prove, the announcement of book and instruction according to the above description, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention equivalent modifications more of the present invention and change.Although used in addition some specific terms in this specification, these terms do not consist of any restriction to the present invention just for convenience of description.
Claims (8)
1. an anode material for lithium-ion batteries, comprise stratum nucleare and be coated on the outer shell of described stratum nucleare, and it is characterized in that: the general formula of stratum nucleare material is LiNi
xMn
2-xO
4, 0＜x＜0.2 wherein, the general formula of Shell Materials is LiNi
yCo
zMn
wM
rO
2, wherein r＜0.1, and 1＜y/w＜4, M is at least a in Al, Mg, Ti, Cr, Zr, Pt, Au, Pd, Ce, Pr and Nd, the mass ratio of described Shell Materials and described stratum nucleare material is (0.1-3): 10.
2. anode material for lithium-ion batteries according to claim 1, it is characterized in that: in described positive electrode, the ratio [(x+y)+(2-x+w)+z+r]/(x+y) of the mole summation of elemental nickel, element manganese, element cobalt and element M and the mole of elemental nickel〉9.
3. anode material for lithium-ion batteries according to claim 1 is characterized in that: the mass ratio of described Shell Materials and described stratum nucleare material is (1-2.5): 10.
4. anode material for lithium-ion batteries according to claim 3, it is characterized in that: the mass ratio of described Shell Materials and described stratum nucleare material is 1:5.
5. anode material for lithium-ion batteries according to claim 1, it is characterized in that: the median particle diameter D50 of described stratum nucleare material is 8-20um.
6. anode material for lithium-ion batteries according to claim 1, it is characterized in that: the specific area of described positive electrode is 0.20 ~ 0.60 m
2/ g.
7. the preparation method of the described anode material for lithium-ion batteries of claim 1 to 6 any one, is characterized in that, comprises the following steps:
The first step is placed in batch mixer with the oxide of oxide, lithium source and the nickel of manganese according to the molar ratio of (2-x): 1:x, and after mixing, be placed in Muffle furnace and be warming up to 300-500 ℃ with the programming rate of 3-15 ℃/min, and heat preservation sintering 2-6h; And then being warming up to 700-900 ℃ with the programming rate of 4-10 ℃/min, and heat preservation sintering 15-30h obtains the nickel manganate precursor for lithium of single spinel structure after ball milling;
Second step, nickel manganate precursor for lithium and LiNi that the first step is obtained
yCo
zMn
wM
rO
2According to mol ratio 10:(0.1-5) add in batch mixer, after mixing, be placed in Muffle furnace and be warming up to 700-1000 ℃ with the programming rate of 5-20 ℃/min, and heat preservation sintering 10-20h, obtain anode material for lithium-ion batteries after ball milling.
8. the preparation method of anode material for lithium-ion batteries according to claim 7 is characterized in that: described lithium source is Li
2CO
3, Li
2O or LiOH.
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| CN103730654A (en) * | 2014-01-18 | 2014-04-16 | 南通瑞翔新材料有限公司 | High-capacity high-stability lithium manganate positive electrode material and preparation method thereof |
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