CN103151520B - 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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- CN103151520B CN103151520B CN201310089610.9A CN201310089610A CN103151520B CN 103151520 B CN103151520 B CN 103151520B CN 201310089610 A CN201310089610 A CN 201310089610A CN 103151520 B CN103151520 B CN 103151520B
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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, particularly relate to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Along with various circles of society are to the continuous increase of the demand of high performance lithium ion battery, the specific capacity of positive electrode becomes the key factor restricting lithium ion battery overall performance and improve further, affect the capacity of lithium ion battery, high-temperature stability and other chemical properties, this is because the specific capacity of positive electrode at present in commercial lithium-ion batteries is far smaller than the specific capacity of negative material.Lithium manganate having spinel structure (LiMn
2o
4) positive electrode owing to having 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 lithium manganate having spinel structure exists poplar-Taylor effect, and Mn
4+have high oxidative, manganese wherein also easily dissolves, and makes the capacity of lithium manganate having spinel structure can occur to decay slowly.At relatively high temperatures, the initial capacity of lithium manganate having spinel structure can decline, and cycle performance is deteriorated.In addition, single lithium manganate having spinel structure conductivity is lower.Therefore people wish that part-structure or entire infrastructure by changing lithium manganate having spinel structure suppress the decay of its capacity and change the too low problem of its conductivity.
In view of this, necessaryly provide a kind of anode material for lithium-ion batteries and preparation method thereof, this positive electrode by adulterating nickel in lithium manganate having spinel structure, and at its Surface coating one deck nickle cobalt lithium manganate, effectively can reduce the capacity attenuation of this positive electrode, improve the chemical property of material, conductivity and cycle life.
Summary of the invention
An object of the present invention is: for the deficiencies in the prior art, and a kind of anode material for lithium-ion batteries is provided, this positive electrode by adulterating nickel in lithium manganate having spinel structure, and at its Surface coating one deck nickle cobalt lithium manganate, effectively can 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 shell outside described stratum nucleare, the general formula of core layer material is LiNi
xmn
2-xo
4, wherein 0 < x < 0.2, the general formula of Shell Materials is LiNi
yco
zmn
wm
ro
2wherein r < 0.1, and 1 < y/w < 4, M is at least one in Al, Mg, Ti, Cr, Zr, Pt, Au, Pd, Ce, Pr and Nd, the mass ratio of described Shell Materials and described core layer material is (0.1-3): 10.
Because nickel ion doped easily occurs platform when 5V, thus make the capacity of positive electrode when 4.25V on the low side, therefore need strictly to control the content (0 < x < 0.2) that nickel replaces manganese, thus suppress the appearance of 5V platform.The advantages such as energy density is high although nickle cobalt lithium manganate has, advantage of lower cost and cycle performance are excellent, but it has the compacted density shortcoming such as poor relative to fail safe on the low side simultaneously, in order to ensure that positive electrode of the present invention has relatively high compacted density and fail safe, the proportion of Shell Materials should be controlled.
One as anode material for lithium-ion batteries of the present invention is improved, in described positive electrode, ratio [(x+y)+(2-x+w)+z+r]/(x+y) >9, i.e. (x+y) < 1/3 of the mole summation of elemental nickel, element manganese, element cobalt and element M and the mole of elemental nickel.
One as anode material for lithium-ion batteries of the present invention is improved, and the mass ratio of described Shell Materials and described core layer material is (1-2.5): 10.
One as anode material for lithium-ion batteries of the present invention is improved, and the mass ratio of described Shell Materials and described core layer material is 1:5.
One as anode material for lithium-ion batteries of the present invention is improved, and the median particle diameter D50 of described core layer 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 making positive electrode have good chemical property, memory property and security performance simultaneously.
One as anode material for lithium-ion batteries of the present invention is improved, and the specific area of described positive electrode is 0.20 ~ 0.60 m
2/ g.Excessive surface area by the reaction of aggravation electrolyte on positive electrode surface, thus worsens the chemical property of battery; Too little surface area will cause larger grain diameter, thus affect the dynamic behavior of lithium ion reversible deintercalation in positive electrode.
Relative to prior art, the present invention by adulterating nickel (nickel exists with the form of divalence in LiMn2O4) in lithium manganate having spinel structure, can stable spinel-type lithium manganate octahedral site and improve manganese valence, reduce the change of LiMn2O4 structure and the dissolving of manganese in charge and discharge process, change in this element adjustment fundamentally changes inherent electron orbit overlapping cases and the surface nature of material, effectively raise the stability of material structure, the cycle performance of the lithium ion battery of this positive electrode of use is improved.In addition, the present invention is by the Surface coating one deck nickle cobalt lithium manganate at the lithium manganate having spinel structure doped with nickel, effectively can prevent the dissolving of manganese, and suppress the catalytic action that the decomposition of the unoccupied orbital of manganese to electrolyte is played, thus effectively reduce the decay of material capacity, and improve the conductivity of material, improve chemical property and the cycle life of the lithium ion battery using this positive electrode.The present invention carries out performance optimization in conjunction with foreign cation and these two kinds of methods of Surface coating to lithium manganate having spinel structure, and make the performance of lithium manganate having spinel structure more good, structure is more stable.And the present invention is by the strict content controlling nickel and replace manganese, restrained effectively the appearance of 5V platform, makes this positive electrode only occur single 4V platform, thus effectively improve the capacity of this positive electrode when 4.25V.
Another object of the present invention is the preparation method providing a kind of anode material for lithium-ion batteries, comprise the following steps: the first step, the oxide of the oxide of manganese, lithium source and nickel 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 DEG C with the programming rate of 3-15 DEG C/min, and heat preservation sintering 2-6h; And then be warming up to 700-900 DEG C with the programming rate of 4-10 DEG C/min, and heat preservation sintering 15-30h, obtain the nickel ion doped presoma of single spinel structure after ball milling.
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 5-20 DEG C/min, and heat preservation sintering 10-20h, obtain anode material for lithium-ion batteries after ball milling.
One as the preparation method of anode material for lithium-ion batteries of the present invention is improved, and described lithium source is Li
2cO
3, Li
2o or LiOH.
Certainly, the preparation method of the nickel ion doped presoma of single spinel structure can also be solid sintering technology, melt-impregnation method, coprecipitation, sol-gel process, spray drying process or combustion method etc.
Relative to prior art, preparation method's technique of the present invention is simple, is easy to realize, easily realizes suitability for industrialized production.Adopt the positive electrode for preparing of the method to have the advantages such as the higher and capacity attenuation of Stability Analysis of Structures, conductivity is little, be applied in lithium ion battery, cycle performance and the chemical property of lithium ion battery can be improved.
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, comprise stratum nucleare and be coated on the shell outside stratum nucleare, the general formula of core layer 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 core layer material is 1:5, and the median particle diameter D50 of core layer 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, comprise stratum nucleare and be coated on the shell outside stratum nucleare, the general formula of core layer 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 core layer material is 1:4, and the median particle diameter D50 of core layer 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, comprise stratum nucleare and be coated on the shell outside stratum nucleare, the general formula of core layer 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 core layer material is 3:10, and the median particle diameter D50 of core layer 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, comprise stratum nucleare and be coated on the shell outside stratum nucleare, the general formula of core layer 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 core layer material is 1:100, and the median particle diameter D50 of core layer 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, comprise stratum nucleare and be coated on the shell outside stratum nucleare, the general formula of core layer 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 core layer material is 1:10, and the median particle diameter D50 of core layer 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, comprise stratum nucleare and be coated on the shell outside stratum nucleare, the general formula of core layer 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 core layer material is 1:20, and the median particle diameter D50 of core layer material is 20um, and the specific area of this positive electrode is 0.20 m
2/ g.
Comparative example 1: the general formula of a kind of anode material for lithium-ion batteries that this comparative example provides is LiNi
0.1mn
1.9o
4, its median particle diameter D50 is 12 um.Namely the positive electrode of this comparative example does not do coated process.
Comparative example 2: a kind of anode material for lithium-ion batteries that this comparative example provides is commercially available spinel-type LiMn
2o
4, its median particle diameter D50 is 12 um.Namely the positive electrode of this comparative example does not do doping and coated process.
Present invention also offers a kind of preparation method of anode material for lithium-ion batteries.
Embodiment 7, present embodiments provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 1 provides, comprises the following steps: the first step, by 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 DEG C with the programming rate of 5 DEG C/min, and heat preservation sintering 4h; And then be warming up to 800 DEG C with the programming rate of 7 DEG C/min, and heat preservation sintering 20h, obtain after ball milling that median particle diameter D50 is 12 um, general formula is LiNi
0.1mn
1.9o
4the nickel ion doped presoma of single spinel structure.
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 8 DEG C/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, present embodiments provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 2 provides, comprises the following steps: the first step, by MnO
2, Li
2o and NiO is placed in batch mixer according to the molar ratio of 1.85:1:0.15, after mixing, is placed in Muffle furnace and is warming up to 450 DEG C with the programming rate of 10 DEG C/min, and heat preservation sintering 3h; And then be warming up to 700 DEG C with the programming rate of 9 DEG C/min, and heat preservation sintering 25h, obtain after ball milling that median particle diameter D50 is 16 um, general formula is LiNi
0.15mn
1.85o
4the nickel ion doped presoma of single spinel structure.
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 12 DEG C/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, present embodiments provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 3 provides, comprises the following steps: the first step, by 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 DEG C with the programming rate of 15 DEG C/min, and heat preservation sintering 2h; And then be warming up to 900 DEG C with the programming rate of 4 DEG C/min, and heat preservation sintering 15h, obtain after ball milling that median particle diameter D50 is 18um, general formula is LiNi
0.05mn
1.95o
4the nickel ion doped presoma of single spinel structure.
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 20 DEG C/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, present embodiments provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 4 provides, comprises the following steps: the first step, by 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 DEG C with the programming rate of 3 DEG C/min, and heat preservation sintering 6h; And then be warming up to 700 DEG C with the programming rate of 10 DEG C/min, and heat preservation sintering 30h, obtain after ball milling that median particle diameter D50 is 10 um, general formula is LiNi
0.18mn
1.82o
4the nickel ion doped presoma of single spinel structure.
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 5 DEG C/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, present embodiments provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 5 provides, comprises the following steps: the first step, by 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 DEG C with the programming rate of 7 DEG C/min, and heat preservation sintering 5h; And then be warming up to 750 DEG C with the programming rate of 7 DEG C/min, and heat preservation sintering 26h, obtain after ball milling that median particle diameter D50 is 8 um, general formula is LiNi
0.03mn
1.97o
4the nickel ion doped presoma of single spinel structure.
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 13 DEG C/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, present embodiments provides the preparation method of the anode material for lithium-ion batteries that a kind of embodiment 6 provides, comprises the following steps: the first step, by 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 DEG C with the programming rate of 13 DEG C/min, and heat preservation sintering 3.5h; And then be warming up to 850 DEG C with the programming rate of 9 DEG C/min, and heat preservation sintering 18h, obtain after ball milling that median particle diameter D50 is 20 um, general formula is LiNi
0.07mn
1.93o
4the nickel ion doped presoma of single spinel structure.
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 17 DEG C/min, and heat preservation sintering 16h, obtaining specific area after ball milling is 0.20m
2the anode material for lithium-ion batteries of/g.
Positive electrode embodiment 1 to 6 and comparative example 1 and 2 provided adds in 1-METHYLPYRROLIDONE with conductive carbon and bonding agent Kynoar respectively makes anode sizing agent, 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, injecting electrolyte, through changing into and capacity etc., making lithium ion battery.Each lithium ion battery number consecutively is S1-S6, D1 and D2.
The battery being numbered S1-S6, D1 and D2 is tested as follows: (1) test battery is at 45 DEG C, cycle performance under 4.25V voltage: 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 3.0V with the discharge-rate constant-current discharge of 0.5C; Discharge capacity attenuation in record circulating battery process, and calculate the capability retention after 300 circulations, acquired results is in 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 use the multiplying power constant-current discharge of 0.2C, 0.5C, 1C to 3.0V successively; The ratio of record 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, the lithium ion battery of positive electrode of the present invention is used to have better cycle performance and high rate performance (chemical property), this is because adulterate in lithium manganate having spinel structure nickel can stable spinel-type lithium manganate octahedral site and improve manganese valence, reduce the change of LiMn2O4 structure and the dissolving of manganese in charge and discharge process, effectively raise the stability of material structure, the cycle performance of the lithium ion battery of this positive electrode of use is improved.And at Surface coating one deck nickle cobalt lithium manganate of the lithium manganate having spinel structure doped with nickel, effectively can prevent the dissolving of manganese, and suppress the catalytic action that the decomposition of the unoccupied orbital of manganese to electrolyte is played, thus effectively reduce the decay of material capacity, and improve the conductivity of material, improve chemical property and the cycle life of the lithium ion battery using this positive electrode.The present invention carries out performance optimization in conjunction with foreign cation and these two kinds of methods of Surface coating to lithium manganate having spinel structure, and make the performance of lithium manganate having spinel structure more good, structure is more stable.
It should be noted that, according to the above description the announcement of book and instruction, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention equivalent modifications more of the present invention and change.Although employ some specific terms in addition in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (6)
1. an anode material for lithium-ion batteries, comprises stratum nucleare and is coated on the shell outside described stratum nucleare, it is characterized in that: the general formula of core layer material is LiNi
xmn
2-xo
4, wherein 0 < x < 0.2, the general formula of Shell Materials is LiNi
yco
zmn
wm
ro
2wherein r < 0.1, and 1 < y/w < 4,0.44≤z≤0.78, M is at least one in Al, Mg, Ti, Cr, Zr, Pt, Au, Pd, Ce, Pr and Nd, and the mass ratio of described Shell Materials and described core layer material is (0.1-3): 10;
In described positive electrode, ratio [(x+y)+(2-x+w)+z+r]/(x+y) >9 of the mole summation of elemental nickel, element manganese, element cobalt and element M and the mole of elemental nickel;
Its preparation method comprises the following steps:
The first step, is placed in batch mixer by the oxide of the oxide of manganese, lithium source and nickel according to the molar ratio of (2-x): 1:x, after mixing, is placed in Muffle furnace and is warming up to 300-500 DEG C with the programming rate of 3-15 DEG C/min, and heat preservation sintering 2-6h; And then be warming up to 700-900 DEG C with the programming rate of 4-10 DEG C/min, and heat preservation sintering 15-30h, obtain the nickel ion doped presoma of single spinel structure after ball milling;
Second step, the nickel ion doped presoma that the first step is obtained and LiNi
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 DEG C with the programming rate of 5-20 DEG C/min, and heat preservation sintering 10-20h, obtain anode material for lithium-ion batteries after ball milling.
2. anode material for lithium-ion batteries according to claim 1, is characterized in that: the mass ratio of described Shell Materials and described core layer material is (1-2.5): 10.
3. anode material for lithium-ion batteries according to claim 2, is characterized in that: the mass ratio of described Shell Materials and described core layer material is 1:5.
4. anode material for lithium-ion batteries according to claim 1, is characterized in that: the median particle diameter D50 of described core layer material is 8-20 μm.
5. anode material for lithium-ion batteries according to claim 1, is characterized in that: the specific area of described positive electrode is 0.20 ~ 0.60m
2/ g.
6. anode material for lithium-ion batteries according to claim 1, is characterized in that: described lithium source is Li
2cO
3, Li
2o or LiOH.
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