CN102891307A - Composite anode material of high-voltage lithium ion battery and lithium ion battery - Google Patents
Composite anode material of high-voltage lithium ion battery and lithium ion battery Download PDFInfo
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- CN102891307A CN102891307A CN201210354020XA CN201210354020A CN102891307A CN 102891307 A CN102891307 A CN 102891307A CN 201210354020X A CN201210354020X A CN 201210354020XA CN 201210354020 A CN201210354020 A CN 201210354020A CN 102891307 A CN102891307 A CN 102891307A
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Abstract
The invention discloses a composite anode material of a lithium ion battery. The composite anode material has a core-shell structure, a core layer material is Li1+nAwNi0.5+xCo0.2+yMn0.3+zO2, a shell layer material is Li1+aCo1-bMbO2, and the shell layer material accounts for 0.1-20% of the composite anode material in mass percent. Compared with the prior art, the composite anode material disclosed by the invention has the advantages that because a cladding layer can exert effective gram volume and discharge voltage platform under high voltage, the energy density of the battery is improved, and in addition, the structural stability of an enhancement matrix material of the cladding layer is good for effectively inhibiting the dissolution of Mn among the materials in a cyclic process, and the oxidation of electrolyte by the anode material is reduced; and in addition, the invention further discloses a preparation method of the anode material and the lithium ion battery containing the anode material.
Description
Technical field
The present invention relates to the lithium ion battery field, be specifically related to the high-voltage lithium ion batteries composite positive pole that lithium ion battery and the present invention use nucleocapsid structure.
Background technology
Lithium ion battery generally comprises: positive plate, negative plate, be interval in the barrier film between the positive/negative plate, and electrolyte, wherein, positive plate comprises plus plate current-collecting body and the positive electrode that is distributed on the plus plate current-collecting body, and negative plate comprises negative current collector and the negative material that is distributed on the negative current collector.At present, lithium ion anode material commonly used is LiCoO
2, LiNi
0.5Co
0.2Mn
0.3O
2, LiMn
2O
4, LiFePO
4Deng.
More than several positive electrodes self defective is arranged, such as LiCoO
2Because Co is expensive, overcharge resistance performance is poor, and the gram volume performance is limited; LiNi
0.5Co
0.2Mn
0.3O
2Exist compacted density low, with the poor compatibility of electrolyte, Soft Roll in the problem such as flatulence; LiMn
2O
4High temperature circulation and high temperature storage are not good; LiFePO
4There are the problems such as low temperature, homogeneity of product, patent right.Along with the just day by day lightening development of the consumption electronic product batteries such as mobile phone, flat board, pursuing more, the high-energy-density positive electrode becomes the focus that lithium ion battery develops.And volume energy density=discharge capacity * discharge voltage plateau * compacted density only has LiCoO at present
2, LiNi
0.5Co
0.2Mn
0.3O
2The high-energy-density positive electrode uses in the consumption electronic product battery; Because LiCoO
2Poor stability, safer, more cheap LiNi
0.5Co
0.2Mn
0.3O
2Become gradually the focus of positive electrode development.
Yet, LiNi
0.5Co
0.2Mn
0.3O
2There is following bottleneck in application at the consumption electronic product battery: the first, and the high voltage circulatory problems is with the poor compatibility of electrolyte, LiNi
0.5Co
0.2Mn
0.3O
2Cycle performance is good under button cell (negative pole is the lithium sheet) 4.5V high voltage, and very fast at the capacity attenuation of full battery (negative pole is Delanium) 4.4V circulation time; The second, the high temperature storage problem, because Ni has very strong oxidizability to electrolyte, soft-package battery is when high temperature storage, aerogenesis is larger; For addressing the above problem, need to carry out surface modification treatment to material, lot of domestic and international document and patent report Al
2O
3, AlPO
4, ZrO
2, TiO
2, B
2O
3Deng the oxide clad anode material, they think that the surface texture that coats the raising positive electrode is stable, improve the cycle performance under the high voltage; Reduced the oxidation of positive electrode to electrolyte, suppress the high temperature aerogenesis, but effect has been limited.Can bring counter productive simultaneously, because the metal oxide that coats is the non-electrochemical active material, conductive lithium is ionic very poor, can sacrifice gram volume and the discharge voltage plateau of positive electrode after the coating, has reduced to a certain extent the energy density of positive electrode.We find, use positive electrode to coat and have effectively overcome above-mentioned shortcoming, thereby coat the focus that another kind of positive electrode becomes coating with a kind of positive electrode.
For example, publication number is the Japanese patent application of JP 2002-260659, adopts the spinelle LiMn that is doped with metal
2O
4Clad anode material improves its cycle performance at high temperature, i.e. Li
(1+x)Mn
(2-x-y)M
yO
4(M is Fe, Cr, Ni, Rh, Al, and 0＜x＜0.2,0＜y＜0.2).But in charge and discharge process, the valence state of Mn from+3 to+4 valencys change, and easily produce the Jahn-Teller effect, and distortion of lattice occurs, volume contraction or expansion, and structure becomes unstable and subsides; At high temperature, in the high voltage system, the HF of trace can cause Mn in the electrolyte especially
2+Stripping (its chemical equation is: 4HF+2LiMn
2O
4→ 3 γ-MnO
2+ MnF
2+ 2LiF+2H
2O), cause the destruction of spinel structure, greatly accelerated the decay of battery capacity, thereby LiMn
2O
4The positive electrode that coats is not suitable for using when high voltage, high temperature.
In view of this, the necessary positive electrode that provides a kind of surface to be provided with coating layer, the lithium ion battery that contains this positive electrode can use under higher charge cutoff voltage, and has the advantages that cycle life is good, high-temperature storage performance is good.
Summary of the invention
One of purpose of the present invention is: for the deficiencies in the prior art, provide a kind of surface to be provided with the positive electrode of coating layer, so that positive electrode can use under higher charge cutoff voltage, namely the charge cutoff voltage with respect to lithium is 4.3V ~ 4.6V, both improved the volume energy density of lithium ion battery, again can be so that the cycle life under high voltage of the positive electrode after coating be excellent, high temperature storage is good, thus the cycle performance when overcoming positive electrode of the prior art and under the high charge cut-ff voltage, using, high-temperature storage performance is not good enough, the deficiency that discharge capacity is not high.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of high-voltage lithium ion batteries composite positive pole, and this composite positive pole has nucleocapsid structure, and this nucleocapsid structure is made of stratum nucleare material and Shell Materials, and the stratum nucleare material is Li
1+nA
wNi
0.5+xCo
0.2+yMn
0.3+zO
2, wherein-and 0.05≤n＜0.1,0≤w≤0.1 ,-0.05≤x＜0.05 ,-0.05≤y＜0.05 ,-0.05≤z＜0.05, and w+x+y+z=1, wherein A is at least a of Al, Mg, Ti, Zr; Described Shell Materials is Li
1+aCo
1-bM
bO
2, wherein-and 0.05≤a＜0.1,0＜b＜0.1, M is at least a element of Al, Zr, Sr, B, Mo, La; The mass percent that Shell Materials accounts for described composite positive pole is 0.1 ~ 20%.
The inventor studies discovery: adopt identical graphite cathode and electrolyte, positive pole is respectively LiCoO
2, LiNi
0.5Co
0.2Mn
0.3O
2The full battery that forms, LiCoO
2Cycle performance, high-temperature storage performance under the system high voltage are far superior to LiNi
0.5Co
0.2Mn
0.3O
2System.The inventor thinks: on the one hand, in the high voltage cyclic process, just as easy as rolling off a log and electrolyte generation side reaction, LiNi
0.5Co
0.2Mn
0.3O
2The surface is unstable, and side reaction is more, causes more Mn from the surperficial stripping of positive pole, and the Mn ion deposition of stripping destroys anode surface SEI film at anode surface, so that the capacity circulating decay is fast; In addition, Mn stripping meeting causes LiNi
0.5Co
0.2Mn
0.3O
2The serious shrink/expanded of unit cell volume causes lattice to subside, capacity attenuation.On the other hand, during high temperature storage, LiCoO
2Well below the oxidation of Ni to electrolyte, and Ni content is higher to the degree of oxidation of electrolyte for surface-stable, Co, and the soft-package battery aerogenesis is more, and high temperature storage is poorer.Therefore, stratum nucleare is LiNi
0.5Co
0.2Mn
0.3O
2, shell is LiCoO
2Lithium ion battery composite cathode material under high voltage, can bring into play good cycle performance and high-temperature behavior.
As a kind of improvement of high-voltage lithium ion batteries composite positive pole of the present invention, the stratum nucleare material of described composite positive pole is that particle diameter 1 ~ 3 μ m particle aggregation forms median particle diameter D
50=6 ~ 18 μ m.
As a kind of improvement of high-voltage lithium ion batteries composite positive pole of the present invention, the BET of described composite positive pole is 0.1 ~ 0.9m
2/ g, the median particle diameter D of described composite positive pole
50Be 6 ~ 22 μ m.BET＞0.9 m
2/ g, positive electrode absorbs water easily, easy gel, the slurry that is difficult to make.
As a kind of improvement of high-voltage lithium ion batteries composite positive pole of the present invention, described Shell Materials is Li
1+aCo
1-bM
bO
2, the mass percent that Shell Materials accounts for described composite positive pole is 0.1 ~ 20%; The preferential mass percent of selecting is 0.1 ~ 10%; Surpass 20%, may have influence on the compacted density of positive electrode, thereby affect the energy density of battery.
With respect to prior art, high-voltage lithium ion batteries composite positive pole of the present invention has following characteristics: as the Li of stratum nucleare material
1+xCo
1-yA
yO
2Have good lithium ion conduction performance, the effective gram volume of performance under high voltage, and can improve discharge voltage plateau, thus improve to a certain extent the energy density of battery; XRD studies discovery: from 3.0 to 4.5V, and LiNi
0.5Co
0.2Mn
0.3O
2Unit cell volume shrink gradually, high voltage circulation time, unit cell volume change aggravation, and form nucleocapsid structure LiNi
0.5Co
0.2Mn
0.3O
2/ Li
1+xCo
1-yA
yO
2Composite positive pole can establishment LiNi
0.5Co
0.2Mn
0.3O
2The stripping of middle Mn has suppressed the variation of unit cell volume, and can reduce side reaction between positive pole and the electrolyte, improves the cycle life of positive electrode under the high voltage; During high temperature storage, can effectively suppress anodal oxidation to electrolyte, reduce battery producing gas, improve high temperature storage.
A kind of preparation method of high-voltage lithium ion battery cathode material may further comprise the steps:
The first step is dissolved in solubility lithium salts, cobalt salt, complexing agent, inorganic salts in the solvent, forms mixed solution, the aluminium salt that described other inorganic salts are solubility, zirconates, strontium salt, boron salt, molybdenum salt, lanthanum salt at least a;
Second step is regulated mixed solution pH=6 ~ 9 in the first step, forms colloidal sol shape Shell Materials solution, the pH of this moment is meta-alkalescence, can reduce acid destruction to the stratum nucleare material, and then the stratum nucleare material is added in the above-mentioned sol solution, and mix, form the stratum nucleare material that is coated by Shell Materials;
The 3rd step is with the stratum nucleare material that is coated by the Shell Materials oven dry that second step obtains, roasting, the lithium ion battery composite cathode material of formation nucleocapsid structure.
As a kind of improvement of the preparation method of high-voltage lithium ion batteries composite positive pole of the present invention, in the first step, described solubility lithium salts is at least a in lithium acetate, lithium nitrate or the lithium hydroxide; Described solubility cobalt salt is cobalt acetate and/or cobalt nitrate; Inorganic salts are aluminium salt, zirconates, strontium salt, boron salt, molybdenum salt, lanthanum salt at least a of solubility; Described solvent is at least a in water, ethanol and the isopropyl alcohol; Described complexing agent is at least a in citric acid and the ammoniacal liquor.
A kind of improvement as the preparation method of high-voltage lithium ion battery cathode material of the present invention, in the 3rd step, composite positive pole after will drying is first calcined 1 ~ 5h under 500 ~ 700 ℃ air atmosphere or oxygen atmosphere, then calcine 2 ~ 20h under 800 ~ 1000 ℃ air atmosphere or oxygen atmosphere.At the low temperature presintering knot, to form lithium and cobalt oxides, then carry out high temperature sintering first, form perfect cobalt acid lithium crystalline phase.Wherein, consider LiNi
0.5Co
0.2Mn
0.3O
2Synthetic better performances in oxygen atmosphere is carried out roasting to material under the preferred oxygen atmosphere.
Preparation method of the present invention fully combines the advantage of liquid phase method and solid phase method, makes the surface of anode material for lithium-ion batteries by LiCoO
2Evenly coat, form the high-voltage lithium ion batteries composite positive pole of nucleocapsid structure; The discharge gram volume of this composite positive pole and discharge platform do not reduce, and use cycle performance and the memory property of lithium ion battery under high voltage of the nucleocapsid structure composite positive pole that preparation method of the present invention makes all to be significantly increased.In addition, this preparation method's technique is simple, is easy to industrialization production.
Another object of the present invention is to provide a kind of lithium ion battery, comprise positive plate, negative plate and be arranged at described positive plate and described negative plate between barrier film, and electrolyte, described positive plate comprises plus plate current-collecting body and the positive electrode active material layer that is arranged on the described plus plate current-collecting body, described positive electrode active material layer comprises positive active material, conductive agent and bonding agent, and described positive active material is lithium ion battery composite cathode material of the present invention.
With respect to prior art, lithium ion battery of the present invention is owing to used the positive electrode that the present invention relates to, thereby very high discharge capacity and excellent cycle performance and high-temperature storage performance arranged under high voltage, the capability retention that the i.e. interior circulation of 3.0 ~ 4.35V is 400 times is increased to 85% ~ 89%, 4.35V high temperature storage flatulence rate by 61% and is reduced to 9% ~ 16% by 60%.And because the raising of charge cutoff voltage so that this battery has higher volume energy density, can be satisfied people to the demand of lithium battery slimming.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.Wherein, below among each embodiment covering amount refer to that Shell Materials accounts for the quality percentage composition of lithium ion battery composite cathode material.
Embodiment 1: the positive electrode that present embodiment provides is that covering amount is the Li of 5wt %
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2/ Li
0.98Co
0.98Al
0.02O
2Composite positive pole, the BET of this composite positive pole is 0.42m
2/ g, D
50=10 μ m.Wherein, Li
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2/ Li
0.98Co
0.98Al
0.02O
2What represent is with Li
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2Be stratum nucleare material, Li
0.98Co
0.98Al
0.02O
2For the positive electrode of Shell Materials, as follows.Its preparation method is as follows: the lithium nitrate, cobalt nitrate, aluminum nitrate and the citric acid that take by weighing respectively certain mass join in the 250 mL ethanol, stir to make it dissolving, form lithium cobalt aluminium mixed solution, and regulator solution pH=6.8; Add 250g stratum nucleare material Li
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2(this stratum nucleare material is that particle diameter is that 1 μ m particle aggregation forms median particle diameter D
50=9 μ m) powder stirs; After the evaporation of above-mentioned mixed solution, oven dry, first roasting 2 hours under 500 ℃ of air atmospheres, then roasting 10 hours under 800 ℃ of air atmospheres obtains the positive electrode of present embodiment.
Embodiment 2: the positive electrode that present embodiment provides is that covering amount is the Li of 10wt %
0.98Mg
0.08Ni
0.46Co
0.16Mn
0.30O
2/ Li
1.02Co
0.995Zr
0.005O
2Composite positive pole, the BET of this positive electrode is 0.38m
2/ g, D
50=15.0 μ m.Its preparation method is as follows: the lithium acetate, cobalt acetate, zirconium acetate and the ammoniacal liquor that take by weighing respectively certain mass join in the 500 mL water, stir to make it dissolving, form lithium cobalt zirconium mixed solution, and regulator solution pH=8.9; Add 250g stratum nucleare material Li
0.98Mg
0.08Ni
0.46Co
0.16Mn
0.30O
2(this stratum nucleare material is that particle diameter is that 1.5 μ m particle aggregations form median particle diameter D
50=13 μ m) powder stirs; After the oven dry of above-mentioned mixed solution, first roasting 4 hours under 650 ℃ of air atmospheres, then roasting 4 hours under 1000 ℃ of air atmospheres obtains the positive electrode of present embodiment.
Embodiment 3: the positive electrode that present embodiment provides is that covering amount is the Li of 8wt %
1.08Mg
0.03Ti
0.03Ni
0.52Co
0.17Mn
0.27O
2/ Li
1.01Co
0.984Al
0.01B
0.006O
2Composite positive pole, the BET of this positive electrode is 0.21m
2/ g, D
50=18.0 μ m.Its preparation method is as follows: the lithium acetate, cobalt acetate, aluminum nitrate, boric acid and the citric acid that take by weighing respectively certain mass join in the 250mL isopropyl alcohol, stir to make it dissolving, form lithium cobalt aluminium boron mixed solution, and regulator solution pH=7; Add 250g Li
1.08Mg
0.03Ti
0.03Ni
0.52Co
0.17Mn
0.27O
2(this stratum nucleare material is that particle diameter is that 2.5 μ m particle aggregations form median particle diameter D
50=16.5 μ m) powder stirs; After the oven dry of above-mentioned mixed solution, first roasting 5 hours under 700 ℃ of air atmospheres, then roasting 15 hours under 900 ℃ of air atmospheres obtains the positive electrode of present embodiment.
Embodiment 4: the positive electrode that present embodiment provides is that covering amount is the Li of 3wt %
1.02Mg
0.02Zr
0.01Ni
0.48Co
0.20Mn
0.29O
2/ Li
0.97Co
0.993La
0.003Mo
0.004O
2Composite positive pole, the BET of this positive electrode is 0.68m
2/ g, D
50=21.0 μ m.Its preparation method is as follows: the lithium acetate, cobalt nitrate, lanthanum nitrate, nitric acid molybdenum titanium and the ammoniacal liquor that take by weighing respectively certain mass join in the 400 mL water, stir to make it dissolving, form lithium cobalt lanthanum molybdenum mixed solution, and regulator solution pH=7.5; Add 200g Li
1.02Mg
0.02Zr
0.01Ni
0.48Co
0.20Mn
0.29O
2(this stratum nucleare material is that particle diameter is that 2 μ m particle aggregations form median particle diameter D
50=17.5 μ m) powder stirs; After the oven dry of above-mentioned mixed solution, first roasting 3 hours under 600 ℃ of oxygen atmospheres, then roasting 10 hours under 900 ℃ of oxygen atmospheres obtains the positive electrode of present embodiment.
Embodiment 5: the positive electrode that present embodiment provides is that covering amount is the Li of 15wt %
0.95Al
0.01Ti
0.03Ni
0.49Co
0.18Mn
0.29O
2/ Li
1.07Co
0.991Sr
0.004B
0.005O
2Composite positive pole, the BET of this positive electrode is 0.51m2/g, D
50=12.0 μ m.Its preparation method is as follows: the lithium acetate, cobalt nitrate, strontium nitrate, boric acid and the citric acid that take by weighing respectively certain mass join in the 250mL ethanol, stir to make it dissolving, form lithium cobalt strontium boron mixed solution, and regulator solution pH=6.5; Add 250g stratum nucleare material Li
0.95Al
0.01Ti
0.03Ni
0.49Co
0.18Mn
0.29O
2(this stratum nucleare material is that particle diameter is that 1.5 μ m particle aggregations form median particle diameter D
50=10 μ m) powder stirs; After the oven dry of above-mentioned mixed solution, first roasting 2 hours under 650 ℃ of oxygen atmospheres, then roasting 12 hours under 850 ℃ of oxygen atmospheres obtains the positive electrode of present embodiment.
Embodiment 6: with the positive electrode Li of embodiment 1
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2/ Li
0.98Co
0.98Al
0.02O
2As positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Embodiment 7: with the positive electrode Li of embodiment 2
0.98Mg
0.08Ni
0.46Co
0.16Mn
0.30O
2/ Li
1.02Co
0.995Zr
0.005O
2As positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Embodiment 8: with the positive electrode Li of embodiment 3
1.08Mg
0.03Ti
0.03Ni
0.52Co
0.17Mn
0.27O
2/ Li
1.01Co
0.984Al
0.01B
0.006O
2As positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Embodiment 9: with the positive electrode Li of embodiment 4
1.02Mg
0.02Zr
0.01Ni
0.48Co
0.20Mn
0.29O
2/ Li
0.97Co
0.993La
0.003Mo
0.004O
2As positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Embodiment 10: with the positive electrode Li of embodiment 5
0.95Al
0.01Ti
0.03Ni
0.49Co
0.18Mn
0.29O
2/ Li
1.07Co
0.991Sr
0.004B
0.005O
2As positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Comparative example 1: with Li
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2As positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Comparative example 2: with Al
2O
3The Li that coats
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2(Al
2O
3Covering amount be 5wt%) as positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Comparative example 3: with ZrO
2The Li that coats
0.98Mg
0.08Ni
0.46Co
0.16Mn
0.30O
2(ZrO
2Covering amount be 10wt%) as positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Comparative example 4: with Al
2O
3B
2O
3The Li that coats
1.08Mg
0.03Ti
0.03Ni
0.52Co
0.17Mn
0.27O
2(Al
2O
3B
2O
3Covering amount be 8wt%) as positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Comparative example 5: with Al
2O
3ZrO
2The Li that coats
1.02Mg
0.02Zr
0.01Ni
0.48Co
0.20Mn
0.29O
2(Al
2O
3ZrO
2Covering amount be 3wt%) as positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
Comparative example 6: with Li
0.95Al
0.01Ti
0.03Ni
0.49Co
0.18Mn
0.29O
2With Li
1.07Co
0.991Sr
0.004B
0.005O
2Mixture (Li
1.07Co
0.991Sr
0.004B
0.005O
2The mass percent that accounts for this mixture is 15%, below this mixture be abbreviated as LATNCMO
2-LCSBO
2) as positive active material, after making slurry with bonding agent and conductive agent, be coated on the plus plate current-collecting body, make positive plate, make negative plate with Delanium as negative electrode active material, positive plate, negative plate and barrier film are made lithium ion battery with common process, and charge cutoff voltage is 4.35V (positive electrode potential is about 4.43V take Li as benchmark), and theoretical capacity is 1600mAh.
The lithium ion battery that embodiment 6 ~ 10, comparative example 1 ~ 6 are made carries out following assessment test: first discharge capacity test: under 25 ℃, with 0.5C(800mA) constant current charge is to 4.35V, 0.05C(80mA) constant voltage is to 4.35V, leave standstill 5min, then the capacity that is discharged to 3.0V with 0.5C is discharge capacity first, and acquired results sees Table 1.
Discharge voltage plateau test: under 25 ℃, with 0.5C(800mA) constant current charge is to 4.35V, 0.05C(80mA) constant voltage is to 4.35V, leave standstill 5min, then be discharged to 3.0V with 0.5C, test primary discharge capacity and discharge energy, can obtain discharge voltage plateau: discharge voltage plateau=discharge energy/discharge capacity, acquired results sees Table 1.
Cycle life test: under 25 ℃, with 0.5C(800mA) constant current charge is to 4.35V, 0.05C(80mA) constant voltage is to 4.35V, then 0.5C(800mA) be discharged to 3.0V, 400 this charge and discharge cycles repeatedly, measure the discharge capacity of the circulation time first time and the discharge capacity of the 400th circulation time, obtain the capability retention after the circulation: the capability retention after the circulation=(discharge capacity of the 400th circulation time)/(for the first time discharge capacity of circulation time) * 100%, acquired results sees Table 1.
High-temperature storage performance: under 25 ℃, with 0.5C(800mA) constant current charge is to 4.35V, 0.05C(80mA) constant voltage is to 4.35V, and mensuration is stored front cell thickness.Then, with the above-mentioned battery that completely is charged to 4.35V, storage is 30 days in 60 ℃ of baking ovens, the thickness of battery after the test storage while hot, by with storage before the comparison of cell thickness, obtain the expansion rate of the rear battery of storage: the expansion rate of battery after the storage=(thickness of the front battery of the thickness of battery-storage after the storage)/(thickness of battery before the storage) * 100%, acquired results sees Table 1.
As can be seen from Table 1, embodiment 6 can find with the contrast of comparative example 1: the nucleocapsid structure composite positive pole of the present invention's preparation is the lithium ion battery of positive active material, first discharge capacity and discharge platform under the high voltage all are significantly improved, Li before coating
1.01Al
0.02Ni
0.48Co
0.18Mn
0.32O
2First discharge capacity under 3.0 ~ 4.35V and discharge platform are 1605mAh, 3.642V, and the rear discharge capacity of coating and discharge platform significantly increase to 1620mAh, 3.680V, and this is not only because Shell Materials Li
0.98Co
0.98Al
0.02O
2The effective capacity of performance and platform under high voltage, and certain chemical action can occur in building-up process in the stratum nucleare material of this composite material and Shell Materials, the surface forms a kind of stable material, this material effectively reduces the stripping of Mn in oxidation electrolyte in the high temperature storage process, the high voltage cyclic process, so that composite material has preferably high temperature storage and cycle performance under high voltage, battery storage flatulence rate before namely coating is 60%, the circulation volume conservation rate is 61%, and the flatulence rate of storage battery is 12% behind the encasement layer material, and the circulation volume conservation rate is 89%.
In addition, embodiment 6 also can find with the contrast of comparative example 5 with comparative example 4, embodiment 9 with comparative example 3, embodiment 8 with comparative example 2, embodiment 7: i.e. conventional oxide Al
2O
3, ZrO
2, Al
2O
3B
2O
3, Al
2O
3ZrO
2Coat Li
1+nA
wNi
0.5+xCo
0.2+yMn
0.3+zO
2Positive electrode, discharge capacity under 3.0 ~ 4.35V is respectively 1590mAh, 1596mAh, 1600mAh, 1601mAh, discharge platform is respectively 3.630V, 3.638V, 3.620V, 3.625V, flatulence rate after the storage is respectively 30%, 45%, 35%, 35%, and capability retention is respectively 72%, 74%, 78%, 80% after the circulation; And adopt Li of the present invention
0.98Co
0.98Al
0.02O
2, Li
1.02Co
0.995Zr
0.005O
2, Li
1.01Co
0.984Al
0.01B
0.006O
2, Li
0.97Co
0.993La
0.003Mo
0.004O
2Coat Li
1+nA
wNi
0.5+xCo
0.2+yMn
0.3+zO
2Composite positive pole, discharge capacity under 3.0 ~ 4.35V is respectively 1590mAh, 1596mAh, 1600mAh, 1601mAh, discharge platform is respectively 3.680V, 3.676V, 3.669V, 3.658V, flatulence rate after the storage is respectively 12%, 13%, 8%, 16%, and capability retention is respectively 89%, 85%, 86%, 85% after the circulation.Although conventional aluminium oxide, zirconia and boron oxide clad anode material can improve high temperature storage and cycle performance under the high voltage, but can significantly reduce its discharge capacity and voltage platform, this is because aluminium oxide, zirconia and boron oxide are the non-electrochemical active material, it is very poor to lead lithium ion, thereby can sacrifice to a certain extent the energy density of battery, this is general oxide coated defective place.Yet, at Li
1+nA
wNi
0.5+xCo
0.2+yMn
0.3+zO
2The surface coats Li
1+aCo
1-bM
bO
2Form the composite positive pole of nucleocapsid structure, not only be significantly improved on discharge capacity and the discharge platform, and can bring into play good high-temperature storage performance and cycle performance under the high voltage.This be because: in the high temperature storage process, as the Li of Shell Materials
1+aCo
1-bM
bO
2Reduced the contact area of ternary material and electrolyte, and surperficial formed stable material, effectively suppressed the oxidation of Ni to electrolyte, suppress the generation of flatulence; In the high voltage cyclic process, as the Li of Shell Materials
1+aCo
1-bM
bO
2And good compatibility is arranged between the electrolyte, the formed stable material in surface, strengthened the structural stability of basis material, and suppressed side reaction between positive pole and the electrolyte, reduce anodal surface metal ion Mn stripping, the lattice that suppresses high voltage circulation time material subsides, thereby can improve cycle performance under the high voltage.By contrast, we find that the stratum nucleare material is Li
1.01Co
0.984Al
0.01B
0.006O
2, Li
1.07Co
0.991Sr
0.004B
0.005O
2Battery storage flatulence rate smaller (＜10%) is thought B
2O
3Be electron withdraw group, in the high temperature storage process, the side reaction between energy " absorption " positive pole and the electrolyte suppresses aerogenesis, thereby shows excellent high-temperature storage performance.
In addition, embodiment 10 can find with the contrast of comparative example 6: LATNCMO
2-LCSBO
2(Li
0.95Al
0.01Ti
0.03Ni
0.49Co
0.18Mn
0.29O
2With Li
1.07Co
0.991Sr
0.004B
0.005O
2Mixture) with the Li of nucleocapsid structure
0.95Al
0.01Ti
0.03Ni
0.49Co
0.18Mn
0.29O
2/ Li
1.07Co
0.991Sr
0.004B
0.005O
2As positive active material similar discharge capacity and discharge platform are arranged, but LATNCMO
2-LCSBO
2Relatively poor aspect high temperature storage and cycle performance.LATNCMO
2-LCSBO
2In Li
0.95Al
0.01Ti
0.03Ni
0.49Co
0.18Mn
0.29O
2With Li
1.07Co
0.991Sr
0.004B
0.005O
2Just carry out simple physical mixed and process, obviously do not reduce Ni to the oxidation of electrolyte, also do not suppress the Mn stripping, more do not suppress Lattice Contraction, subside, thereby obviously do not improve storage, cycle performance under the high voltage.
The according to the above description announcement of book and instruction, 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 modifications and changes more of the present invention.In addition, although used 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. a high-voltage lithium ion batteries composite positive pole is characterized in that, this composite positive pole has nucleocapsid structure, and this nucleocapsid structure is made of stratum nucleare material and Shell Materials, and the stratum nucleare material is Li
1+nA
wNi
0.5+xCo
0.2+yMn
0.3+zO
2, wherein-and 0.05≤n＜0.1,0≤w≤0.1 ,-0.05≤x＜0.05 ,-0.05≤y＜0.05 ,-0.05≤z＜0.05, and w+x+y+z=1, wherein A is at least a of Al, Mg, Ti, Zr; Described Shell Materials is Li
1+aCo
1-bM
bO
2, wherein-and 0.05≤a＜0.1,0＜b＜0.1, M is at least a element of Al, Zr, Sr, B, Mo, La; The mass percent that Shell Materials accounts for described composite positive pole is 0.1 ~ 20%.
2. high-voltage lithium ion batteries composite positive pole according to claim 1, it is characterized in that: the stratum nucleare material of described composite positive pole is that particle diameter 1 ~ 3 μ m particle aggregation forms median particle diameter D
50=6 ~ 18 μ m.
3. high-voltage lithium ion batteries composite positive pole according to claim 1, it is characterized in that: the specific area of described composite positive pole (BET) is 0.1 ~ 0.9m
2/ g, median particle diameter D
50Be 6 ~ 22 μ m.
4. high-voltage lithium ion batteries composite positive pole according to claim 1, it is characterized in that: the stratum nucleare material is Li
1.08Mg
0.03Ti
0.03Ni
0.52Co
0.17Mn
0.27O
2Described Shell Materials is Li
1.01Co
0.984Al
0.01B
0.006O
2
5. high-voltage lithium ion batteries composite positive pole according to claim 1, it is characterized in that: its preparation method may further comprise the steps:
The first step is dissolved in solubility lithium salts, cobalt salt, complexing agent, inorganic salts in the solvent, forms mixed solution;
Second step, mixed solution to pH value is 6～9 in the adjusting first step, forms the Shell Materials solution of colloidal sol shape, again with the stratum nucleare material, adds in the above-mentioned colloidal sol shape solution, mixes, and makes Shell Materials evenly be coated on the surface of stratum nucleare material;
The 3rd step is with the stratum nucleare material that is coated by the Shell Materials oven dry that second step obtains, roasting, the lithium ion battery composite cathode material of formation nucleocapsid structure.
6. high-voltage lithium ion batteries composite positive pole according to claim 5 is characterized in that: in the first step, described solubility lithium salts is at least a in lithium acetate, lithium nitrate or the lithium hydroxide; Described solubility cobalt salt is cobalt acetate and/or cobalt nitrate; Inorganic salts are aluminium salt, zirconates, strontium salt, boron salt, molybdenum salt, lanthanum salt at least a of solubility, and described solvent is at least a in water, ethanol and the isopropyl alcohol; Described complexing agent is at least a in ammoniacal liquor and the citric acid.
7. high-voltage lithium ion batteries composite positive pole according to claim 5, it is characterized in that: in the 3rd step, positive electrode after will drying is first calcined 1 ~ 5h under 400 ~ 700 ℃ air or oxygen atmosphere, then calcine 2 ~ 20h under 800 ~ 1000 ℃ air or oxygen atmosphere.
8. lithium ion battery, comprise positive plate, negative plate and be arranged at described positive plate and described negative plate between barrier film, and electrolyte, described positive plate comprises plus plate current-collecting body and the positive electrode active material layer that is arranged on the described plus plate current-collecting body, described positive electrode active material layer comprises positive active material, conductive agent and bonding agent, it is characterized in that: described positive active material is each described anode material for lithium-ion batteries of claim 1 to 4.
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