CN105576192A - Lithium ion battery positive pole material, preparation method of lithium ion battery positive pole material and lithium ion battery - Google Patents
Lithium ion battery positive pole material, preparation method of lithium ion battery positive pole material and lithium ion battery Download PDFInfo
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Abstract
The invention relates to a lithium ion battery positive pole material, a preparation method of the lithium ion battery positive pole material and a lithium ion battery. The lithium ion battery positive pole material has a chemical formula of LiNi0.5-yMn1.5-2yAl2yO4, wherein y is greater than 0 and is less than or equal to 0.3. In the lithium ion battery positive pole material, Al<3+> can easily replace Ni<2+> and Mn<3+> and does not cause crystal form change. Through combination of Al and O, an oxygen loss in high temperature calcining is reduced and lithium ion battery positive pole material stability is improved. The content of Mn is reduced through Al so that 4V discharge plateau is reduced, 5V discharge plateau is increased and a lithium ion battery positive pole material specific capacity is improved. The lithium ion battery positive pole material can prevent lithium ion battery positive pole material particle disintegration so that cycle stability is high.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, its preparation method and lithium ion battery.
Background technology
Lithium ion battery is because high operating voltage, high-energy-density, memory-less effect, have extended cycle life, self discharge is low, advantages of environment protection is shown one's talent in numerous energy-storage battery, is successfully used in the digital products such as mobile phone, camera, notebook computer and other portable electronic equipments, is expected in the near future be widely used in the fields such as power vehicle (EV), hybrid vehicle (HEV) and Aero-Space.
Along with the update of the day by day serious of energy and environment problem and digital product, its energy density to lithium ion battery requires more and more higher.Positive electrode is the key material determining lithium ion battery energy density.The energy density improving lithium ion battery mainly contains two approach: one is the specific capacity improving material, and another one approach is exactly improve the charging/discharging voltage of material.
Common positive electrode has LiCoO
2, LiNi
0.8co
0.2o
2, LiNi
l/3co
l/3mn
1/30
2and LiFePO
4deng, discharge voltage plateau, lower than 4V, obtain high voltage, many cells of need connecting, and causing safeguarding the problems such as inconvenient, security performance is bad also can affect power density and the energy density of battery.LiMn
2o
4though discharge voltage has 4.1V, there is Jahn-Teller effect, cause capacity and cyclical stability all undesirable.Transition metal doped spinel type LiMn2O4 LiMn
2-xm
xo
4(M=Ge, Fe, Co, Zn, Ni, Cr, Cu) has the high voltage platform of about 5V, and capacity is higher.Wherein, spinel-type LiNi
0.5mn
1.5o
4the same with LiMn2O4 is the positive electrode with three-dimensional lithium ion tunnel, reversible capacity is 146.7mAh/g, similar with LiMn2O4, but voltage platform is about 4.7V, to more than 15% be exceeded than the 4V voltage platform of LiMn2O4, and the cyclical stability under high temperature has also had the lifting of matter than original LiMn2O4, be considered to a kind of potential lithium ion battery with high energy density positive electrode.But, LiNi
0.5mn
1.5o
4in charge and discharge cycles, and LiMn
2o
4the same, the dissolving of contingent Mn and bursting apart of material granule, the cyclical stability be degrading.
Summary of the invention
Based on this, be necessary to provide the good anode material for lithium-ion batteries of a kind of stable circulation performance, its preparation method and lithium ion battery.
A kind of anode material for lithium-ion batteries, the chemical formula of described anode material for lithium-ion batteries is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein 0<y≤0.3.
A preparation method for anode material for lithium-ion batteries, comprises the following steps:
Carry out ball milling after adding organic solvent after being mixed according to the stoichiometric proportion of element each in the chemical formula of anode material for lithium-ion batteries in nickel source, manganese source and aluminium source and obtain mixture, the chemical formula of described anode material for lithium-ion batteries is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein 0<y≤0.3;
Described mixture is heated to 550 DEG C ~ 700 DEG C having in oxygen atmosphere, and calcining at constant temperature obtains intermediate product in 2 hours ~ 10 hours;
Be (0.5-y) according to nickel in nickel source and lithium source with the mol ratio of lithium by described intermediate product and lithium source: 1 ~ (0.5-y): 1.1 mix after ball milling obtains premix;
Described premix is being had in oxygen atmosphere, first be heated to 400 DEG C ~ 600 DEG C calcining at constant temperature 2 hours ~ 12 hours, be heated to 750 DEG C ~ 900 DEG C calcining at constant temperature 2 hours ~ 24 hours again, then at being cooled to 500 DEG C ~ 600 DEG C, annealing in process 2 hours ~ 24 hours, obtains described anode material for lithium-ion batteries after cooling.
Wherein in an embodiment, described nickel source is selected from least one in the acetate of the chloride of nickel, the oxide of nickel, the sulfate of nickel, the nitrate of nickel and nickel.
Wherein in an embodiment, described manganese source is selected from least one in the acetate of the chloride of manganese, the oxide of manganese, the sulfate of manganese, the nitrate of manganese and manganese.
Wherein in an embodiment, described aluminium source is selected from least one in aluminium hydroxide, aluminum nitrate, aluminum sulfate and aluminium chloride.
Wherein in an embodiment, by described mixture there being in oxygen atmosphere heating rate when being heated to 550 DEG C ~ 700 DEG C to be 1 DEG C/min ~ 10 DEG C/min.
Wherein in an embodiment, described lithium source is selected from least one in lithium hydroxide, lithium nitrate, lithium acetate and lithium carbonate.
Wherein in an embodiment, also comprise step before being mixed with described lithium source by described intermediate product: ground by described intermediate product.
Wherein in an embodiment, also comprise step: ground by the anode material for lithium-ion batteries obtained.
A kind of lithium ion battery, the electrode material of described lithium ion battery comprises above-mentioned anode material for lithium-ion batteries.
In above-mentioned anode material for lithium-ion batteries, Al
3+ni can be instead of easily
2+and Mn
3+position, and do not cause the change of crystal formation; The combination of Al and O, can reduce the disappearance of oxygen during high-temperature calcination, and improves the stability of anode material for lithium-ion batteries; Simultaneously, by the content using Al to reduce Mn, thus the discharge platform of 4V can be reduced, extend the discharge platform of 5V and increase the specific capacity of anode material for lithium-ion batteries, simultaneously above-mentioned anode material for lithium-ion batteries can be alleviated in lithium ion battery charge and discharge process due to crystal lattice stress that Jahn-Teller effect causes, avoid the disintegration of anode material for lithium-ion batteries particle, thus cyclical stability is higher.
Accompanying drawing explanation
Fig. 1 is the SEM figure of anode material for lithium-ion batteries prepared by embodiment 1;
Fig. 2 is the discharge test curve chart of 2025 type button cells of anode material for lithium-ion batteries assembling prepared by embodiment 1;
Fig. 3 is the first charge-discharge curve chart of 2025 type button cells of anode material for lithium-ion batteries assembling prepared by embodiment 1;
Fig. 4 is the cycle performance figure of 2025 type button cells of anode material for lithium-ion batteries assembling prepared by embodiment 1 ~ 6 and comparative example 1.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with embodiment.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The anode material for lithium-ion batteries of one execution mode, its chemical formula is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein 0<y≤0.3.
In above-mentioned anode material for lithium-ion batteries, Al
3+ni can be instead of easily
2+and Mn
3+position, and do not cause the change of crystal formation; The combination of Al and O, can reduce the disappearance of oxygen during high-temperature calcination, and improves the stability of anode material for lithium-ion batteries; Simultaneously, by the content using Al to reduce Mn, thus the discharge platform of 4V can be reduced, extend the discharge platform of 5V and increase the specific capacity of anode material for lithium-ion batteries, simultaneously above-mentioned anode material for lithium-ion batteries can be alleviated in lithium ion battery charge and discharge process due to crystal lattice stress that Jahn-Teller effect causes, avoid the disintegration of anode material for lithium-ion batteries particle, thus cyclical stability is higher.
The preparation method of the anode material for lithium-ion batteries of one execution mode, comprises the following steps:
Step S110, nickel source, manganese source and aluminium source are carried out ball milling and obtained mixture after adding organic solvent after the stoichiometric proportion mixing of element each in the chemical formula of anode material for lithium-ion batteries.
The chemical formula of anode material for lithium-ion batteries is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein 0<y≤0.3.
Preferably, nickel source is selected from least one in the acetate of the chloride of nickel, the oxide of nickel, the sulfate of nickel, the nitrate of nickel and nickel.Further, the nickel element in nickel source is at least one in nickelic and nickelous.
Preferably, manganese source is selected from least one in the acetate of the chloride of manganese, the oxide of manganese, the sulfate of manganese, the nitrate of manganese and manganese.Further, the manganese element in manganese source is at least one in bivalent manganese, tetravalent manganese, sexavalence manganese and septivalency manganese.
Preferably, aluminium source is selected from least one in aluminium hydroxide, aluminum nitrate, aluminum sulfate and aluminium chloride.
Preferably, organic solvent is selected from least one in ethanol and acetone.
Preferably, the mass ratio in organic solvent and nickel source is 0.1:1 ~ 0.2:1.
Preferably, the time of ball milling is 2 hours ~ 10 hours.
Preferably, ball milling adopts planetary ball mill or vertical ball mill.
Preferably, the rotating speed of ball milling is 350r/min-650r/min.
Preferably, ball-milling medium is zirconia ball milling pearl.
Step S120, mixture is heated to 550 DEG C ~ 700 DEG C having in oxygen atmosphere, calcining at constant temperature obtains intermediate product in 2 hours ~ 10 hours.
The intermediate product that this step obtains is the oxide of nickel manganese aluminium.
Preferably, mixture there being in oxygen atmosphere heating rate when being heated to 550 DEG C ~ 700 DEG C to be 1 DEG C/min ~ 10 DEG C/min.
Preferably, oxygen atmosphere is had to be air atmosphere or oxygen atmosphere.
Preferably, the flow of gas in oxygen atmosphere is had to be 3m
3/ h ~ 18m
3/ h.
Preferably, calcine after 2 hours ~ 10 hours and naturally cool to room temperature.
Preferably, calcine and carry out in Muffle furnace.
Step S130, intermediate product to be ground.
Preferably, employing planetary ball mill or vertical ball mill grinding is pulverized.
Preferably, the particle diameter of the intermediate product after pulverizing is 2 ~ 10 μm.
Step S140, be (0.5-y) according to nickel in nickel source and lithium source with the mol ratio of lithium by intermediate product and lithium source: 1 ~ (0.5-y): 1.1 mix after ball milling obtains premix.
Preferably, lithium source is selected from least one in lithium hydroxide, lithium nitrate, lithium acetate and lithium carbonate.
Preferably, the time of ball milling is 2 hours ~ 10 hours.
Preferably, ball milling adopts planetary ball mill or vertical ball mill.
Preferably, the rotating speed of ball milling is 350r/min-650r/min.
Step S150, premix is being had in oxygen atmosphere, first be heated to 400 DEG C ~ 600 DEG C calcining at constant temperature 2 hours ~ 12 hours, be heated to 750 DEG C ~ 900 DEG C calcining at constant temperature 2 hours ~ 24 hours again, then at being cooled to 500 DEG C ~ 600 DEG C, annealing in process 2 hours ~ 24 hours, obtains anode material for lithium-ion batteries after cooling.
In this step, the structural formula of the anode material for lithium-ion batteries obtained is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein 0<y≤0.3.
Preferably, oxygen atmosphere is had to be air atmosphere or oxygen atmosphere.
Preferably, the flow of gas in oxygen atmosphere is had to be 3m
3/ h ~ 18m
3/ h.
Preferably, with the heating rate of 1 DEG C/min ~ 10 DEG C/min, premix is heated to 400 DEG C ~ 600 DEG C.
Preferably, with the heating rate of 1 DEG C/min ~ 10 DEG C/min, premix is heated to 750 DEG C ~ 900 DEG C by 400 DEG C ~ 600 DEG C.
Preferably, with the rate of temperature fall of 1 DEG C/min ~ 10 DEG C/min, premix is cooled to 500 DEG C ~ 600 DEG C by 750 DEG C ~ 900 DEG C.
Preferably, being operating as of cooling: naturally cool to room temperature.
Step S160, the anode material for lithium-ion batteries pulverizing that will obtain.
Preferably, pulverizing adopts planetary ball mill or vertical ball mill to grind to form fine powder.
Preferably, the particle diameter of the anode material for lithium-ion batteries after pulverizing is 5 ~ 15 μm.
Anode material for lithium-ion batteries stability prepared by the preparation method of above-mentioned anode material for lithium-ion batteries better and specific capacity is higher; Preparation method is simple, does not produce waste water, environmentally safe and manufacturing cost is lower.
It is pointed out that, in the preparation method of above-mentioned anode material for lithium-ion batteries, step S130 and step S160 can omit.
Set forth further below by way of specific embodiment.
Embodiment 1
The chemical formula of anode material for lithium-ion batteries prepared by embodiment 1 is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein y=0.3, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.2mn
0.9al
0.6o
4.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) take Nickelous nitrate hexahydrate, four nitric hydrate nickel and aluminium hydroxide in the ratio of elemental mole ratios Ni:Mn:Al=0.2:0.9:0.6 and put into ball grinder, add acetone, the mass ratio in acetone and nickel source is 0.2:1, and with the speed of 650r/min, ball milling 10h obtains mixture;
(2) mixture in step (1) is transferred in Muffle furnace, in air atmosphere, be heated to 700 DEG C with the programming rate of 10 DEG C/min, calcining at constant temperature 10h;
(3) then naturally cool to room temperature, take out sample, grind to form fine powder with planetary ball mill, rotational speed of ball-mill is 650r/min, obtains the oxide of intermediate product nickel manganese aluminium;
(4) by step (3) the oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) that is worth mix according to the ratio that added Ni source and Li source mol ratio are n (Ni): n (Li)=0.3:1.05 with two hydronium(ion) lithias, then transfer to ball milling 10h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, in air atmosphere, 600 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature 12h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 900 DEG C of calcining 24h with the programming rate of 10 DEG C/min, be cooled to 600 DEG C with the cooling rate of 10 DEG C/min afterwards, constant temperature 24h, finally naturally cools to room temperature;
(6) the product planetary ball mill of step (5) is ground to form fine powder, rotational speed of ball-mill is 650r/min, obtains nickel manganese lithium aluminate cathode material LiNi
0.2mn
0.9al
0.6o
4.
Nickel manganese lithium aluminate LiNi prepared by the present embodiment
0.2mn
0.9al
0.6o
4sEM as shown in Figure 1, can observe above SEM, the material scatter prepared by the method is good, particle size uniformity, does not have too many reunion, and domain size distribution is between 5 and 15 mum.
Embodiment 2
The chemical formula of anode material for lithium-ion batteries prepared by embodiment 2 is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein y=0.25, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.25mn
1al
0.5o
4.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) take six hydration nickel sulfate, four hydrated manganese sulfates and Aluminium chloride hexahydrate in the ratio of elemental mole ratios Ni:Mn:Al=0.25:1:0.5 and put into ball grinder, add suitable acetone, the mass ratio in acetone and nickel source is 0.15:1, and with the speed of 650r/min, ball milling 8h obtains mixture;
(2) transferring in Muffle furnace by the mixture in step (1), is 18m at oxygen flow
3in/h atmosphere, be heated to 700 DEG C with the programming rate of 10 DEG C/min, calcining at constant temperature 10h;
(3) then naturally cool to room temperature, take out sample, grind to form fine powder with planetary ball mill, rotational speed of ball-mill is 400r/min, obtains the oxide of intermediate product nickel manganese aluminium
(4) oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) obtained by step (3) is mixed according to the ratio that added Ni source and the mol ratio in Li source are n (Ni): n (Li)=0.25:1.05 with two hydronium(ion) lithias, then transfer to ball milling 8h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, at 18m
3in the oxygen atmosphere of/h flow, 600 DEG C are heated to the programming rate of 10 DEG C/min, constant temperature 12h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 900 DEG C of calcining 24h with the programming rate of 10 DEG C/min, be cooled to 550 DEG C with the cooling rate of 10 DEG C/min afterwards, constant temperature 24h, finally naturally cools to room temperature;
(6) the product ball milling of step (5) is shattered, obtain nickel manganese lithium aluminate cathode material LiNi
0.25mn
1al
0.5o
4.
Embodiment 3
The chemical formula of anode material for lithium-ion batteries prepared by embodiment 3 is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein y=0.2, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.3mn
1.1al
0.4o
4.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) take Nickel dichloride hexahydrate, four chloride hydrate manganese and nine water aluminum nitrates in the ratio of elemental mole ratios Ni:Mn:Al=0.3:1.1:0.4 and put into ball grinder, add acetone, the mass ratio in acetone and nickel source is 0.1:1, and with the speed of 500r/min, ball milling 8h obtains mixture;
(2) transferring in Muffle furnace by the mixture in step (1), is 15m at oxygen flow
3in/h atmosphere, be heated to 550 DEG C with the programming rate of 8 DEG C/min, calcining at constant temperature 8h;
(3) then naturally cool to room temperature, take out sample, grind to form fine powder with planetary ball mill, rotational speed of ball-mill is 400r/min, obtains the oxide of intermediate product nickel manganese aluminium.
(4) oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) obtained by step (3) is mixed according to the ratio that added Ni source and the mol ratio in Li source are n (Ni): n (Li)=0.3:1.0 with two hydronium(ion) lithias, then transfer to ball milling 8h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, at 15m
3in the oxygen atmosphere of/h flow, 550 DEG C are heated to the programming rate of 8 DEG C/min, constant temperature 10h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 850 DEG C of calcining 18h with the programming rate of 8 DEG C/min, be cooled to 550 DEG C with the cooling rate of 8 DEG C/min afterwards, constant temperature 18h, finally naturally cools to room temperature;
(6) the product ball milling of step (5) is shattered, obtain nickel manganese lithium aluminate cathode material LiNi
0.3mn
1.1al
0.4o
4.
Embodiment 4
The chemical formula of anode material for lithium-ion batteries prepared by embodiment 4 is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein y=0.15, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.35mn
1.2al
0.3o
4.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) claim four hydrations to get nickel acetate, four hydration manganese acetates and Patent alum in the ratio of elemental mole ratios Ni:Mn:Al=0.35:1.2:0.3 and put into ball grinder, add appropriate ethanol, the mass ratio in ethanol and nickel source is 0.2:1, with the speed of 500r/min, and ball milling 6h;
(2) transferring in Muffle furnace by the mixture in step (1), is 12m at oxygen flow
3in/h atmosphere, be heated to 500 DEG C with the programming rate of 6 DEG C/min, calcining at constant temperature 6h obtains mixture;
(3) then naturally cool to room temperature, take out sample, grind to form fine powder with planetary ball mill, rotational speed of ball-mill is 400r/min, adopts 400 molecules of interest sieves to carry out sieving the oxide obtaining intermediate product nickel manganese aluminium
(4) oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) obtained by step (3) is mixed according to the ratio that added Ni source and the mol ratio in Li source are n (Ni): n (Li)=0.35:1.1 with two hydronium(ion) lithias, then transfer to ball milling 6h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, at 12m
3in the oxygen atmosphere of/h flow, 450 DEG C are heated to the programming rate of 6 DEG C/min, constant temperature 12h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 800 DEG C of calcining 12h with the programming rate of 6 DEG C/min, be cooled to 500 DEG C with the cooling rate of 6 DEG C/min afterwards, constant temperature 12h, finally naturally cools to room temperature;
(6) the product ball milling of step (5) is shattered, obtain nickel manganese lithium aluminate cathode material LiNi
0.35mn
1.2al
0.3o
4.
Embodiment 5
The chemical formula of anode material for lithium-ion batteries prepared by embodiment 5 is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein y=0.1, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.4mn
1.3al
0.2o
4.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) take Nickelous nitrate hexahydrate, four nitric hydrate manganese and aluminium hydroxide in the ratio of elemental mole ratios Ni:Mn:Al=0.4:1.3:0.2 and put into ball grinder, add appropriate ethanol, the mass ratio in ethanol and nickel source is 0.15:1, with the speed of 400r/min, ball milling 2h obtains mixture;
(2) transferring in Muffle furnace by the mixture in step (1), is 6m at oxygen flow
3in/h atmosphere, be heated to 550 DEG C with the programming rate of 2 DEG C/min, calcining at constant temperature 4h;
(3) then naturally cool to room temperature, take out sample, grind to form fine powder with planetary ball mill, rotational speed of ball-mill is 400r/min, obtains the oxide of intermediate product nickel manganese aluminium.
(4) oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) obtained by step (3) is mixed according to the ratio that added Ni source and the mol ratio in Li source are n (Ni): n (Li)=0.4:1.05 with two hydronium(ion) lithias, then transfer to ball milling 4h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, at 6m
3in the oxygen atmosphere of/h flow, 400 DEG C are heated to the programming rate of 2 DEG C/min, constant temperature 4h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 800 DEG C of calcining 6h with the programming rate of 2 DEG C/min, be cooled to 450 DEG C with the cooling rate of 2 DEG C/min afterwards, constant temperature 4h, finally naturally cools to room temperature;
(6) grinding of the product of step (5) is shattered, obtain nickel manganese lithium aluminate cathode material LiNi
0.4mn
1.3al
0.2o
4.
Embodiment 6
The chemical formula of anode material for lithium-ion batteries prepared by embodiment 6 is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein y=0.05, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.45mn
1.4al
0.1o
4.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) take Nickelous nitrate hexahydrate, four nitric hydrate manganese and aluminium chloride in the ratio of elemental mole ratios Ni:Mn:Al=0.45:1.4:0.1 and put into ball grinder, add appropriate ethanol, the mass ratio in ethanol and nickel source is 0.1:1, and with the speed of 350r/min, ball milling 2h obtains mixture;
(2) transferring in Muffle furnace by the mixture in step (1), is 3m at oxygen flow
3in/h atmosphere, be heated to 550 DEG C with the programming rate of 1 DEG C/min, calcining at constant temperature 2h;
(3) then naturally cool to room temperature, take out sample, grind to form fine powder with planetary ball mill, rotational speed of ball-mill is 400r/min, obtains the oxide of intermediate product nickel manganese aluminium.
(4) oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) obtained by step (3) is mixed according to the ratio that added Ni source and the mol ratio in Li source are n (Ni): n (Li)=0.45:1.1 with two hydronium(ion) lithias, then transfer to ball milling 2h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, at 3m
3in the oxygen atmosphere of/h flow, 400 DEG C are heated to the programming rate of 1 DEG C/min, constant temperature 2h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 750 DEG C of calcining 8h with the programming rate of 1 DEG C/min, be cooled to 400 DEG C with the cooling rate of 1 DEG C/min afterwards, constant temperature 2h, finally naturally cools to room temperature;
(6) grinding of the product of step (5) is shattered, obtain nickel manganese lithium aluminate cathode material LiNi
0.45mn
1.4al
0.1o
4.
Comparative example 1
The chemical formula of anode material for lithium-ion batteries prepared by comparative example 1 is Li
mni
1-x-ymn
xal
yo
2, wherein x=0.15, y=0.05, m=1.0, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.8mn
1.5al
0.05o
4.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) take Nickelous nitrate hexahydrate, four nitric hydrate manganese and aluminium chloride in the ratio of elemental mole ratios Ni:Mn:Al=80:15:5 and put into ball grinder, add appropriate ethanol, the mass ratio in ethanol and nickel source is 0.1:1, and with the speed of 650r/min, ball milling 10h obtains mixture;
(2) mixture in step (1) is transferred in Muffle furnace, be in air atmosphere at oxygen flow, be heated to 600 DEG C with the programming rate of 51 DEG C/min, calcining at constant temperature 6h;
(3) then naturally cool to room temperature, take out sample, shatter the oxide obtaining intermediate product nickel manganese aluminium; With planetary ball mill, 400r/min grinds to form fine powder.
(4) by step (3) the oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) that is worth mix according to the ratio that elemental mole ratios is n (Li): n (Ni+Mn+Al)=10:9 with lithium hydroxide, then transfer to ball milling 6h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, in air atmosphere, 500 DEG C are heated to the programming rate of 5 DEG C/min, constant temperature 5h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 850 DEG C of calcining 8h with the programming rate of 5 DEG C/min, be cooled to 500 DEG C with the cooling rate of 10 DEG C/min afterwards, constant temperature 5h, finally naturally cools to room temperature;
(6) product of step (5) is shattered, obtain nickel manganese lithium aluminate cathode material LiNi
0.8mn
1.5al
0.05o
2.
Comparative example 2
The chemical formula of anode material for lithium-ion batteries prepared by comparative example 2 is LiNi
0.5-xmn
0.5-xal
2xo
2, wherein x=0.025, the chemical formula of the anode material for lithium-ion batteries namely prepared is LiNi
0.475mn
0.475al
0.05o
2.
The preparation method of above-mentioned anode material for lithium-ion batteries comprises the following steps:
(1) take Nickelous nitrate hexahydrate, four nitric hydrate manganese and aluminium chloride in the ratio of elemental mole ratios Ni:Mn:Al=0.475:0.475:0.05 and put into ball grinder, add appropriate ethanol, the mass ratio in ethanol and nickel source be 0.1:1 with the speed of 650r/min, ball milling 10h obtains mixture;
(2) mixture in step (1) is transferred in Muffle furnace, be in air atmosphere at oxygen flow, be heated to 600 DEG C with the programming rate of 51 DEG C/min, calcining at constant temperature 6h;
(3) then naturally cool to room temperature, take out sample, shatter the oxide obtaining intermediate product nickel manganese aluminium; With planetary ball mill, 400r/min grinds to form fine powder.
(4) by step (3) the oxide of intermediate product nickel manganese aluminium (Ni-Mn-Al) that is worth mix according to the ratio that elemental mole ratios is n (Li): n (Ni+Mn+Al)=10:9 with lithium hydroxide, then transfer to ball milling 6h on ball mill;
(5) product of step (4) is transferred in Muffle furnace, in air atmosphere, 500 DEG C are heated to the programming rate of 5 DEG C/min, constant temperature 5h is to burn the residual organic substance in product, improve the purity of product, and then be heated to 850 DEG C of calcining 8h with the programming rate of 5 DEG C/min, be cooled to 500 DEG C with the cooling rate of 10 DEG C/min afterwards, constant temperature 5h, finally naturally cools to room temperature;
(6) product of step (5) is shattered, obtain nickel manganese lithium aluminate cathode material LiNi
0.475mn
0.475al
0.05o
2.
Performance test:
The assembling of 2025 type button cells: the anode material for lithium-ion batteries prepared by embodiment 1 ~ 6 and comparative example 1 ~ 2 is mixed according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent PVDF (Kynoar) respectively, solvent is made with NMP (1-Methyl-2-Pyrrolidone), after ball milling mixing, be coated on aluminium foil and be prepared into electrode.Before packed battery, be cut into the little pole piece of 1cm × 1cm, 120 DEG C of vacuumize 12h.In glove box, (MBraun) assembles CR2025 type battery, and with pure Li sheet for negative pole, Celgard2300 is barrier film, EC:DMC (1:1 volume ratio, 1molL
-1liPF
6, Samsung) and be electrolyte.With Land, charge-discharge test is carried out to battery;
Charge-discharge test: by the high performance lithium ion battery anode material LiNi prepared by embodiment 1
0.2mn
0.9al
0.6o
4be assembled into 2025 type button cells under 0.5C charging, discharge under 0.5C, 1C, 2C, 5C, 10C multiplying power.Test result as shown in Figure 2.
Positive electrode prepared by embodiment 1 ~ 6 and comparative example 1 is assembled into 2025 type button cells 25 DEG C time, discharge and recharge under 0.5C current density, the voltage of discharge and recharge is 3.5-5.0V, and the test data of discharge cycles and cycle performance figure are respectively as shown in table 1 and Fig. 4.
Wherein, by the high performance lithium ion battery anode material LiNi prepared by embodiment 1
0.2mn
0.9al
0.6o
4be assembled into 2025 type button cells under 5C current density, voltage be the first charge-discharge curve of 3.5-5.0V as shown in Figure 3.As can be seen from Figure 3, LiNi
0.2mn
0.9al
0.6o
4material has very high specific discharge capacity when 0.5C discharges, and specific discharge capacity is 173mAh/g.
Table 1
As can be seen from Table 1, the capability retention of embodiment 1 ~ 6 all remains on more than 95%, higher than 93.4% of comparative example 1, the stable circulation performance of 2025 type button cells of anode material for lithium-ion batteries prepared by embodiment 1 ~ 6 is all better than 2025 type button cells of the anode material for lithium-ion batteries using comparative example 1 to prepare.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an anode material for lithium-ion batteries, is characterized in that, the chemical formula of described anode material for lithium-ion batteries is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein 0<y≤0.3.
2. a preparation method for anode material for lithium-ion batteries, is characterized in that, comprises the following steps:
Carry out ball milling after adding organic solvent after being mixed according to the stoichiometric proportion of element each in the chemical formula of anode material for lithium-ion batteries in nickel source, manganese source and aluminium source and obtain mixture, the chemical formula of described anode material for lithium-ion batteries is LiNi
0.5-ymn
1.5-2yal
2yo
4, wherein 0<y≤0.3;
Described mixture is heated to 550 DEG C ~ 700 DEG C having in oxygen atmosphere, and calcining at constant temperature obtains intermediate product in 2 hours ~ 10 hours;
Be (0.5-y) according to nickel in nickel source and lithium source with the mol ratio of lithium by described intermediate product and lithium source: 1 ~ (0.5-y): 1.1 mix after ball milling obtains premix;
Described premix is being had in oxygen atmosphere, first be heated to 400 DEG C ~ 600 DEG C calcining at constant temperature 2 hours ~ 12 hours, be heated to 750 DEG C ~ 900 DEG C calcining at constant temperature 2 hours ~ 24 hours again, then at being cooled to 500 DEG C ~ 600 DEG C, annealing in process 2 hours ~ 24 hours, obtains described anode material for lithium-ion batteries after cooling.
3. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, described nickel source is selected from least one in the acetate of the chloride of nickel, the oxide of nickel, the sulfate of nickel, the nitrate of nickel and nickel.
4. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, described manganese source is selected from least one in the acetate of the chloride of manganese, the oxide of manganese, the sulfate of manganese, the nitrate of manganese and manganese.
5. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, described aluminium source is selected from least one in aluminium hydroxide, aluminum nitrate, aluminum sulfate and aluminium chloride.
6. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, by described mixture there being in oxygen atmosphere heating rate when being heated to 550 DEG C ~ 700 DEG C to be 1 DEG C/min ~ 10 DEG C/min.
7. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, described lithium source is selected from least one in lithium hydroxide, lithium nitrate, lithium acetate and lithium carbonate.
8. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, also comprises step: ground by described intermediate product with described lithium source before being mixed by described intermediate product.
9. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, also comprises step: ground by the anode material for lithium-ion batteries obtained.
10. a lithium ion battery, is characterized in that, the electrode material of described lithium ion battery comprises anode material for lithium-ion batteries according to claim 1.
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