CN101471441B - Active substance of lithium ion battery anode and preparation method thereof - Google Patents
Active substance of lithium ion battery anode and preparation method thereof Download PDFInfo
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- CN101471441B CN101471441B CN2007103070449A CN200710307044A CN101471441B CN 101471441 B CN101471441 B CN 101471441B CN 2007103070449 A CN2007103070449 A CN 2007103070449A CN 200710307044 A CN200710307044 A CN 200710307044A CN 101471441 B CN101471441 B CN 101471441B
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Abstract
The present invention provides a positive active material of a Li-ion battery. The positive active material contains an oxide IA with a formula of LiNi1-x-yCoxMyO2, wherein x and y are mole fractions; the summation of x and y is not less than 0 and less than 1; and M is selected from one or more of a group including Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and Nb. The positive active material also contains an oxide IB having a formula of Li(NiMn)(1-a-b)/2CoaXbO2, wherein a and b are mole fractions; the summation of a and b is not less than 0 and less than 1; and X is selected from one or more of a group including Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and Nb. In addition, the invention also provides the positive active material preparation method. The positive active material has the advantages of excellent thermal stability, rate discharge performance, circle performance and overcharge performance.
Description
Technical field
The present invention relates to a kind of positive active material and preparation method thereof, relate in particular to a kind of active substance of lithium ion battery anode and preparation method thereof.
Background technology
Lithium ion battery has the energy density height, the operating voltage height, and the life-span is long, memoryless property, advantage such as toxicity is little, so application is extensive.
In the lithium ion battery, the performance of positive active material is one of key of decision battery performance.The positive active material that is most widely used at present is the transition metal oxide LiCoO with layer structure
2, it have synthetic easily, the discharge platform height, therefore advantage such as have extended cycle life, but its lattice costliness, capacity is lower, toxicity is bigger, and have certain safety issue has seriously limited its following application prospect.
It is low that lithium nickelate and derived material thereof have a cost, the specific discharge capacity height, and advantages such as good cycle are a kind of good substitutes of lithium cobalt oxygen material.
But also there are some significant disadvantages in lithium nickelate and derived material thereof, have seriously limited its large-scale commercial applications and have used.Wherein more topmost be it under the high charge state thermal stability and with the compatibility of electrolyte.With Co
4+, Mn
4+Compare Ni
4+Oxidizability stronger, take off under the lithium state at height, redox reaction takes place in also easier and organic electrolyte such as PC or EC.LiNiO for example
2When 4.2V, just can observe gas and produce, and for LiCoO
2, more than 4.8V, just can observe gas and produce.Simultaneously, height takes off the lithium nickelate of lithium state and the oxygen loss reaction also can take place derived material self, after heat and air pressure gather to a certain degree, just may blast the generation security incident.Therefore, adopted the over-charging and the high-temperature behavior of lithium ion battery of lithium nickelate or its derived material relatively poor.
CN 1773763A discloses a kind of lithium rechargeable battery, and this battery is a positive pole with modification lithium nickel oxygen, and is formed with coating layer on described modification lithium nickel oxygen, and described coating layer is indifferent oxide or fast ion conduction glass.But be to use the specific discharge capacity that indifferent oxide or fast ion conduction glass coat can influence lithium ion battery.
In addition, under the high rate charge-discharge situation, because Ni
3+The Jahn-Teller effect and the synergy of lithium ion room ordering, NiO
6Serious distortion takes place in octahedra meeting, hinders the migration of lithium ion, thus the decline of guiding discharge capacity.Therefore, lithium nickelate or its derived material multiplying power discharging property are relatively poor.
CN 1549365A discloses a kind of non-aqueous secondary batteries positive electrode, it is characterized in that, this material is with chemical formula LiNi
1-xCo
xO
2The lithium-nickel-cobalt-oxygen thing of expression is a kernel, and the surface coats one deck LiCoO
2This method has improved LiNi
1-xCo
xO
2The thermal stability of material, multiplying power discharging property, charge-discharge performance have also kept higher specific discharge capacity simultaneously.But LiCoO
2Therefore the thermal stability of material itself and fail safe are just unsatisfactory, adopt the over-charging and the high-temperature behavior of the lithium ion battery that this positive electrode makes still bad.
Summary of the invention
To the objective of the invention is the shortcoming that adopts positive active material thermal stability, multiplying power discharging property, cycle performance, over-charging difference in the prior art in order overcoming, a kind of thermal stability, multiplying power discharging property, cycle performance, positive active material that over-charging is good and preparation method thereof to be provided.
The invention provides a kind of active substance of lithium ion battery anode, this positive active material contains oxide IA, and described oxide IA has the composition shown in the general formula (1):
LiNi
1-x-yCo
xM
yO
2 (1)
Wherein, x and y are molar fraction, 0≤x+y＜1, M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb, it is characterized in that this positive active material also contains oxide IB, described oxide IB has the composition shown in the general formula (2):
Li(NiMn)
(1-a-b)/2Co
aX
bO
2 (2)
Wherein, a and b are molar fraction, 0≤a+b＜1, and X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
The present invention also provides a kind of preparation method of active substance of lithium ion battery anode, wherein, this method is included in oxide IA and organic acid exists down, the aqueous solution that will contain the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of soluble-salt, the nickel of lithium and X stirs and obtains gel, with this gel sintering, obtain containing the positive active material of oxide IA and oxide IB then; Wherein, described oxide IA has the composition shown in the general formula (1):
LiNi
1-x-yCo
xM
yO
2 (1)
Wherein, x and y are molar fraction, 0≤x+y＜1, M be one among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb one or more;
The consumption of the soluble-salt of the soluble-salt of the soluble-salt of lithium, the soluble-salt of nickel, manganese, the soluble-salt of cobalt and X satisfies following condition: with respect to 1 mole lithium, the molal quantity of cobalt is m, and the molal quantity of X is n, the molal quantity of nickel and manganese (1-m-n)/2 of respectively doing for oneself, 0≤m+n＜1
Wherein, X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
The present invention also provides a kind of preparation method of active substance of lithium ion battery anode, wherein, this method is included in ammoniacal liquor and exists down, in the pH value is under the condition of 8-13, the aqueous solution that will contain the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of nickel and X mixes with hydroxide IA1, and filtration obtains containing the solid product of hydroxide IA1 and hydroxide IB1, this solid product is mixed with lithium-containing compound and sintering, obtain containing the positive active material of oxide IA and oxide IB; Wherein, described hydroxide IA1 has the composition shown in the general formula (3):
Ni
1-x-yCo
xM
y(OH)
2 (3)
Wherein, x and y are molar fraction, 0≤x+y＜1, and M is one or more among A1, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb;
The consumption of the soluble-salt of the soluble-salt of described nickel, the soluble-salt of manganese, cobalt and the soluble-salt of X satisfies following condition: with respect to the cobalt of p mole, the molal quantity of X is q, the molal quantity of nickel and manganese (1-p-q)/2 of respectively doing for oneself, 0≤p+q＜1, the molal quantity of the lithium in the lithium-containing compound is the molal quantity sum of hydroxide IA1 and hydroxide IB1
Wherein, X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
The positive active material that makes by method of the present invention has good performance.The battery that adopts this positive active material at normal temperatures behind 400 cycle charge-discharges capability retention only be 85% all more than 92% and adopt the battery of the positive active material that prior art makes.
Adopt the battery of positive active material of the present invention to have good over-charging and high-temperature behavior.For example, adopt the battery of positive active material of the present invention when the over-charging test of carrying out 1C/5V, phenomenons such as swell, blast not to take place all, adopt the battery of positive active material of the prior art that phenomenons such as swell, blast then take place.
In addition, adopt the discharge capacitance of battery battery behind 45 ℃ of following 300 cycle charge-discharges of positive active material of the present invention all more than 80%; And battery is less at the swell value of thickness direction.The discharge capacitance of battery only is 75% behind 300 cycle charge-discharges of battery of positive active material of the prior art and adopt, and battery is also obviously higher at the swell value of thickness direction.
Embodiment
Active substance of lithium ion battery anode of the present invention contains oxide IA, and described oxide IA has the composition shown in the general formula (1):
LiNi
1-x-yCo
xM
yO
2 (1)
Wherein, x and y are molar fraction, 0≤x+y＜1, M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb, wherein, this positive active material also contains oxide IB, and described oxide IB has the composition shown in the general formula (2):
Li(NiMn)
(1-a-b)/2Co
aX
bO
2 (2)
Wherein, a and b are molar fraction, 0≤a+b＜1, and X is one or more among A1, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
In order to make described positive active material have good thermal stability, multiplying power discharging property, cycle performance, over-charging, under the preferable case, 0.1≤x≤0.2,0≤y≤0.1,0.1≤a≤0.33,0≤b≤0.1.
When making that described positive active material has good thermal stability, multiplying power discharging property, cycle performance, over-charging, also has good specific discharge capacity, the mol ratio of described oxide IA and oxide IB is preferably 100: 1-15, more preferably 100: 5-10.
The mean particle diameter of oxide IA of the present invention is preferably the 10-15 micron, and the mean particle diameter of described oxide IB is preferably 10 nanometers to 1 micron.
The invention provides first kind of execution mode that is used to prepare active substance of lithium ion battery anode of the present invention, the preparation method of this active substance of lithium ion battery anode is included in oxide IA and organic acid exists down, the aqueous solution that will contain the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of soluble-salt, the nickel of lithium and X stirs and obtains gel, with this gel sintering, obtain containing the positive active material of oxide IA and oxide IB then; Wherein, described oxide IA has the composition shown in the general formula (1):
LiNi
1-x-yCo
xM
yO
2 (1)
Wherein, x and y are molar fraction, 0≤x+y＜1, and M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb;
The consumption of the soluble-salt of the soluble-salt of the soluble-salt of described lithium, the soluble-salt of nickel, manganese, the soluble-salt of cobalt and X satisfies following condition: with respect to 1 mole lithium, the molal quantity of cobalt is m, and the molal quantity of X is n, the molal quantity of nickel and manganese (1-m-n)/2 of respectively doing for oneself, 0≤m+n＜1
Wherein, X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
Need to prove, according to oxide IA and oxide IB in the positive active material of first kind of execution mode preparation of the present invention is admixture, the XRD of this positive active material (X-ray diffraction) collection of illustrative plates is the combination of the XRD figure spectrum of independent oxide IA or independent oxide IB, there are not other assorted peaks, because the XRD figure spectrum of independent oxide IA and independent oxide IB is extremely approaching, therefore can't come strictly to distinguish them by the XRD figure spectrum that oxide IA and oxide IB mix the active material of forming.But those skilled in the art can judge that easily the positive active material that method of the present invention makes contains oxide IA and oxide IB according to general knowledge.Because in first kind of execution mode, described oxide IA is lithiumation, can not react with other composition of the soluble-salt of lithium, the soluble-salt of nickel, the soluble-salt of manganese, the soluble-salt of cobalt and the soluble-salt of X etc.Simultaneously, prove by experiment, under the situation that does not have oxide IA, the material that makes according to first kind of execution mode is oxide IB of the present invention, therefore, according to judging as mentioned above, the positive active material that is obtained by first kind of execution mode of the present invention contains oxide IA and oxide IB.In addition, draw by XRD (X-ray diffraction) analysis, the XRD diffraction pattern of positive active material of the present invention is the combination of the XRD diffraction pattern of independent oxide IA or independent oxide IB, there is no other assorted peaks, can analyze the kind and the content of each element in the positive active material in addition by the ICP atomic emission spectrometry, simultaneously in conjunction with the general formula of oxide IA and the consumption of oxide IA, can draw the kind of other composition except oxide IA in the positive active material and the general formula that content meets oxide IB, thereby can judge that the positive active material that first kind of execution mode of the present invention makes is the mixture of oxide IA and oxide IB.
In order to make described positive active material have good thermal stability, multiplying power discharging property, cycle performance, over-charging, under the preferable case, 0.1≤x≤0.2,0≤y≤0.1,0.1≤m≤0.33,0≤n≤0.1.
When making that described positive active material has good thermal stability, multiplying power discharging property, cycle performance, over-charging, also has good specific discharge capacity, under the preferable case, the mol ratio of the lithium ion in the soluble-salt of described oxide IA and lithium is 100: 1-15.Further under the selection condition, the mol ratio of the lithium ion in the soluble-salt of described oxide IA and lithium is 100: 5-10.Under this preferable case, oxide IA in the positive active material that finally obtains and the mol ratio of oxide IB are 100: between the 1-15.
The soluble-salt of the soluble-salt of the soluble-salt of described lithium, the soluble-salt of nickel, manganese, the soluble-salt of cobalt and X can be one or more in nitrate, citrate, maleate, acrylates, lactate, malate, succinate, tartrate, sorbate, salicylate, stearate, caprylate, palmitate, glycollate, oxalate, the acetate separately, is preferably nitrate.In addition, need to prove that when described X was boron, the soluble-salt of described X was meant boric acid.
Method of the present invention can make described oxide IB be coated on the described oxide IA, this clad structure can effectively improve thermal stability, multiplying power discharging property, cycle performance, the over-charging of positive active material, thereby improves the performance that adopts this positive active material.In order to make described oxide IB be coated on the surface of described oxide IA equably, improve the thermal stability of positive active material better, the mean particle diameter of described oxide IA is preferably the 10-15 micron.
In addition, the used oxide IA of the present invention is conventionally known to one of skill in the art, can be commercially available, and also can prepare by the method for routine.For example the hydroxide with the composition shown in the general formula (3) can be mixed with lithium-containing compound and sintering and obtaining.
Ni
1-x-yCo
xM
y(OH)
2 (3)
In the general formula (3), 0≤x+y＜1, M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
The described Ni that consists of
1-x-yCo
xM
y(OH)
2The hydroxide and the consumption of lithium-containing compound make that finally can obtain oxide IA gets final product, those skilled in the art can easily adjust according to general knowledge.The described Ni that consists of
1-x-yCo
xM
y(OH)
2Hydroxide can prepare by the method for routine.For example, can be by under stirring condition, being that complexing agent is obtained by the soluble-salt of nickel, the soluble-salt of cobalt and the soluble-salt of M with ammoniacal liquor.The soluble-salt of described nickel, cobalt, M can be one or more in nitrate, sulfate and the hydrochloride.Described lithium-containing compound can be selected from one or more in lithium carbonate, lithium nitrate, lithium hydroxide, hydronium(ion) oxidation lithium, lithia, lithium peroxide, lithium oxalate, the lithium acetate.
Described organic acid can be the conventional organic acid as complexing agent that uses when preparing positive active material by sol-gel process, for example can be in citric acid, maleic acid, acrylic acid, lactic acid, malic acid, butanedioic acid, tartaric acid, sorbic acid, salicylic acid, stearic acid, sad, palmitic acid, glycolic, ethanedioic acid and the acetate one or more, described organic acid consumption is conventionally known to one of skill in the art, for example can be the total mole number of nickel ion, manganese ion, cobalt ions in the described aqueous solution 0.1-10 doubly, be preferably 0.5-5 doubly.Here, the total mole number of described nickel ion, manganese ion, cobalt ions is meant the total mole number of nickel ion, manganese ion and cobalt ions of soluble-salt of soluble-salt, the cobalt of soluble-salt, the manganese of nickel in the aqueous solution.
As long as in the aqueous solution of the soluble-salt of the soluble-salt of the described soluble-salt that contains lithium, nickel, the soluble-salt of manganese, cobalt and the soluble-salt of X the consumption of water make the described aqueous solution with can obtain gel after oxide IA mixes, generally speaking, the consumption of described water be the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of soluble-salt, the nickel of lithium and X soluble-salt total weight 0.5-5 doubly.
In addition, can form gel state as long as will contain the time that the aqueous solution of the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of soluble-salt, the nickel of lithium and X stirs, those skilled in the art can easily control.Generally, the time of described stirring is to get final product in 10-180 minute, in order to make fully reaction, the more preferably 60-180 minute time of described stirring.The present invention is by obtaining containing the positive active material of oxide IA and oxide IB behind the described gel sintering, the temperature of described sintering can be 700-900 ℃, and the time can be 2-16 hour.Under the preferable case, earlier that described gel is dry under 80-150 ℃, and then carry out described sintering, can shorten the time of sintering like this.
The present invention also provides second kind of execution mode that is used to prepare active substance of lithium ion battery anode of the present invention, this method of the preparation method of this active substance of lithium ion battery anode is included in ammoniacal liquor and exists down, in the pH value is under the condition of 8-13, the soluble-salt that will contain nickel, the soluble-salt of manganese, the aqueous solution of the soluble-salt of cobalt and the soluble-salt of X mixes with hydroxide IA1, and filtration obtains containing the solid product of hydroxide IA1 and hydroxide IB1, this solid product is mixed with lithium-containing compound and sintering, obtain containing the positive active material of oxide IA and oxide IB; Wherein, described hydroxide IA1 has the composition shown in the general formula (3):
Ni
1-x-yCo
xM
y(OH)
2 (3)
Wherein, x and y are molar fraction, 0≤x+y＜1, and M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb;
The consumption of the soluble-salt of the soluble-salt of nickel, the soluble-salt of manganese, cobalt and the soluble-salt of X satisfies following condition: with respect to the cobalt of p mole, the molal quantity of X is q, the molal quantity of nickel and manganese (1-p-q)/2 of respectively doing for oneself, 0≤p+q＜1, the molal quantity of the lithium in the lithium-containing compound is 1-1.04 with the ratio of the molal quantity sum of hydroxide IA1 and hydroxide IB1: 1
Wherein, X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
Need to prove, according to oxide IA and oxide IB in the positive active material of second kind of execution mode preparation of the present invention is admixture, the XRD of this positive active material (X-ray diffraction) collection of illustrative plates is the combination of the XRD figure spectrum of independent oxide IA or independent oxide IB, there are not other assorted peaks, because the XRD figure spectrum of independent oxide IA and independent oxide IB is extremely approaching, therefore can't come strictly to distinguish them by the XRD figure spectrum that oxide IA and oxide IB mix the active material of forming.But those skilled in the art can judge that easily the positive active material that method of the present invention makes contains oxide IA and oxide IB according to general knowledge.Because in second kind of execution mode, described hydroxide IA1 can not react with other composition of the soluble-salt of nickel, the soluble-salt of manganese, the soluble-salt of cobalt and the soluble-salt of X etc.Simultaneously, obtain by experiment, under the situation that does not have described hydroxide IA1, in the presence of ammoniacal liquor, in the pH value is under the condition of 8-13, the aqueous solution that will contain the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of nickel and X stirs and can obtain hydroxide IB1, and the general formula of described hydroxide IB1 is (NiMn)
(1-a-b)/2Co
aX
b(OH)
2(a and b are molar fraction, 0≤a+b＜1, X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb).Therefore, the solid product that described second kind of execution mode obtains contains hydroxide IA1 and hydroxide IB1, will can obtain the mixture of oxide IA of the present invention and oxide IB behind described solid product and the lithium-containing compound mixed sintering.In addition, draw by XRD (X-ray diffraction) analysis, the XRD diffraction pattern of positive active material of the present invention is the combination of the XRD diffraction pattern of independent oxide IA or independent oxide IB, do not have other assorted peaks, kind and the content by each element in the ICP atomic emission spectrometry analysis positive active material conforms to the combination of the general formula of oxide IB with oxide IA in addition.Therefore, the positive active material that makes of second kind of execution mode of the present invention is the mixture of oxide IA and oxide IB.
In order to make described positive active material have good thermal stability, multiplying power discharging property, cycle performance, over-charging, under the preferable case, 0.1≤x≤0.2,0≤y≤0.1,0.1≤p≤0.33,0≤q≤0.1.
When making that described positive active material has good thermal stability, multiplying power discharging property, cycle performance, over-charging, also has good specific discharge capacity, under the preferable case, the mol ratio of described hydroxide IA1 and hydroxide IB1 is 100: 1-15.In order further to improve the specific discharge capacity of positive active material, further under the preferable case, the mol ratio of described hydroxide IA1 and hydroxide IB1 is 100: 5-10.Under this preferable case, oxide IA in the positive active material that finally obtains and the mol ratio of oxide IB are 100: between the 1-15.In addition, those skilled in the art can be easily the consumption of soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, manganese by control hydroxide IA1, nickel and X make the mol ratio of described hydroxide IA1 and hydroxide IB1 100: between the 1-15.
The kind of the soluble-salt of the soluble-salt of nickel, the soluble-salt of manganese, cobalt and the soluble-salt of X is narrated in the above and is repeated no more herein.But, need to prove that when described X was boron, the soluble-salt of described X was meant the boric acid of solubility.
Described lithium-containing compound can be selected from one or more in lithium carbonate, lithium nitrate, lithium hydroxide, hydronium(ion) oxidation lithium, lithia, lithium peroxide, lithium oxalate, the lithium acetate.
The method according to this invention, described oxide IB can be coated on the oxide IA, this clad structure can effectively improve thermal stability, multiplying power discharging property, cycle performance, the over-charging of positive active material, thereby improves the performance that adopts this positive active material.In order to make described oxide IB be coated on the surface of described oxide IA equably, improve the thermal stability of positive active material better, the mean particle diameter of described hydroxide IA is preferably the 10-15 micron.
In addition, the used hydroxide IA1 of the present invention is conventionally known to one of skill in the art, can be commercially available, and also can prepare by the method for routine.Described preparation method narrates in the above, repeats no more herein.
Described ammoniacal liquor is as a kind of complexing agent, and its consumption is conventionally known to one of skill in the art.As long as the consumption of the described ammoniacal liquor amount of ammonia in the described ammoniacal liquor of making be the total mole number of nickel ion, manganese ion, cobalt ions in the described aqueous solution 0.1-6 doubly.Here, the total mole number of described nickel ion, manganese ion, cobalt ions is meant nickel ion, manganese ion, the total mole number of cobalt ions of soluble-salt of soluble-salt, the cobalt of soluble-salt, the manganese of nickel in the aqueous solution.Described pH value can be regulated by alkali-metal alkali, and described alkali-metal alkali for example can be NaOH and/or potassium hydroxide.
After filtration obtains described solid product, preferably described solid product is washed with deionized water, remove alkali metal ion, and then carry out sintering with lithium-containing compound.
In addition, to contain time that the aqueous solution of the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of nickel and X mixes with hydroxide IA1 generally is controlled at and got final product in 10-60 minute, in order to make fully reaction, the more preferably 60-180 minute time of described mixing.In addition, the temperature of described sintering can be 500-900 ℃, and the time can be 5-40 hour.Under the preferable case, described sintering carries out in two steps: earlier the mixture of solid product and lithium-containing compound was calcined 1-10 hour down at 500-700 ℃, and then at 700-900 ℃ of following sintering 5-40 hour.
Further specify the present invention below by embodiment.
Comparative Examples 1
The preparation method of the positive active material of this Comparative Examples explanation prior art.
With nickel nitrate, cobalt nitrate and aluminum nitrate Ni: Co: Al=0.80 in molar ratio: 0.15: 0.05 ratio is dissolved into and obtains the aqueous solution in the deionized water, under stirring condition, with peristaltic pump with this aqueous solution with join in the reactor as the ammoniacal liquor and the stream of complexing agent, the molal quantity of ammonia is 0.6 times of total mole number of nickel, cobalt, aluminium in the control reaction system, in reactor, add NaOH solution with servopump, to keep pH value of reaction system is 11, continue to stir after 8 hours, obtain solid product, this solid matter with deionized water washing is extremely neutral.Obtain consisting of Ni
0.80Co
0.15Al
0.05(OH)
2Spheric granules.(Japanese JEOL company JSM-5610LV) measures this Ni by SEM
0.80Co
0.15Al
0.05(OH)
2The particle diameter of particle of 10 zoness of different of spheric granules sample, average then, described mean value is the mean particle diameter of this particle.Following examples and Comparative Examples are all measured mean particle diameter like this.The result measures and obtains this Ni
0.80Co
0.15Al
0.05(OH)
2The mean particle diameter of spheric granules is 14um.
Be the Ni of 14um then with this mean particle diameter
0.80Co
0.15Al
0.05(OH)
2Spheric granules and Li
2CO
3Micro mist is that 1: 1.04 amount is mixed by the molal quantity sum of nickel, cobalt, aluminium and the ratio of the molal quantity of lithium, and under oxygen atmosphere, at 600 ℃ of calcining 6h, then 800 ℃ of sintering of original position are 16 hours then.Obtaining mean particle diameter is the LiNi that consists of of 14um
0.80Co
0.15Al
0.05O
2Oxide D1.
Comparative Examples 2
The preparation method of the positive active material of this Comparative Examples explanation prior art.
With nickel nitrate, cobalt nitrate and aluminum nitrate Ni: Co: Al=0.75 in molar ratio: 0.18: 0.07 ratio is dissolved into and obtains the aqueous solution in the deionized water, under stirring condition, with peristaltic pump with this aqueous solution with join in the reactor as the ammoniacal liquor and the stream of complexing agent, the molal quantity of ammonia is 0.6 times of total mole number of nickel, cobalt, aluminium in the control reaction system, in reactor, add NaOH solution with servopump, to keep pH value of reaction system is 11, continue to stir after 8 hours, obtain solid product, this solid matter with deionized water washing is extremely neutral.Obtain consisting of Ni
0.75Co
0.18Al
0.07(OH)
2Spheric granules.Obtain this Ni according to Comparative Examples 1 described method mensuration
0.75Co
0.18Al
0.07(OH)
2The mean particle diameter of spheric granules is 11um.
With this mean particle diameter is the Ni of 11um
0.75Co
0.18Al
0.07(OH)
2Spheric granules and Li
2CO
3Micro mist is that 1: 1.04 amount is mixed by the molal quantity sum of nickel, cobalt, aluminium and the ratio of the molal quantity of lithium, and under oxygen atmosphere, at 600 ℃ of calcining 6h, then 800 ℃ of sintering of original position are 16 hours then.The general formula that obtains mean particle diameter and be 11um is LiNi
0.75Co
0.18Al
0.07O
2Oxide D2.
Embodiment 1
Present embodiment illustrates the preparation method of positive active material of the present invention.
With lithium nitrate, nickel nitrate, manganese nitrate, cobalt nitrate and magnesium nitrate according to mol ratio Li: Ni: Mn: Co: Mg=1.02: 0.3: 0.3: 0.3: 0.1 ratio was dissolved in the deionized water, and 2 times the citric acid of total mole number that adds nickel ion, manganese ion, cobalt ions is as complexing agent.Under 80 ℃, under agitation add the oxide D1 that Comparative Examples 1 makes then, continue to stir 120 minutes, obtain black-and-blue gel.The mol ratio of described oxide D1 and lithium nitrate is 100: 1.02.With this gel 120 ℃ down dry, then under oxygen atmosphere,, obtain positive active material M1 800 ℃ of following sintering 10 hours.Show that by XRD diffraction analysis and ICP Atomic Emission Spectral Analysis it is LiNi that this positive active material M1 contains general formula
0.80Co
0.15Al
0.05O
2Oxide IA and general formula be Li (NiMn)
0.3Co
0.3Mg
0.1O
2Oxide IB, the mol ratio of described oxide IA and oxide IB is 100: 1.
Measuring the mean particle diameter that obtains oxide IA according to Comparative Examples 1 described method is 14um, and the mean particle diameter of oxide IB is 50 nanometers.
Embodiment 2
Method according to embodiment 1 prepares positive active material, and different is to make that by the mol ratio of adjusting described oxide D1 and lithium nitrate in the positive active material M2 that obtains, general formula is LiNi
0.80Co
0.15Al
0.05O
2Oxide IA and general formula be Li (NiMn)
0.3Co
0.3Mg
0.1O
2The mol ratio of oxide IB be 100: 5.The mean particle diameter that mensuration obtains oxide IA is 14um, and the mean particle diameter of oxide IB is 100 nanometers.
Embodiment 3
Method according to embodiment 1 prepares positive active material, and different is to make that by the mol ratio of adjusting described oxide D1 and lithium nitrate in the positive active material M3 that obtains, general formula is LiNi
0.80Co
0.15Al
0.05O
2Oxide IA and general formula be Li (NiMn)
0.3Co
0.3Mg
0.1O
2The mol ratio of oxide IB be 100: 10.The mean particle diameter that mensuration obtains oxide IA is 14um, and the mean particle diameter of oxide IB is 200 nanometers.
Embodiment 4
Method according to embodiment 1 prepares positive active material, and different is to make that by the mol ratio of adjusting described oxide D1 and lithium nitrate in the positive active material M4 that obtains, general formula is LiNi
0.80Co
0.15Al
0.05O
2Oxide IA and general formula be Li (NiMn)
0.3Co
0.3Mg
0.1O
2The mol ratio of oxide IB be 100: 15.The mean particle diameter that mensuration obtains oxide IA is 14um, and the mean particle diameter of oxide IB is 500 nanometers.
Embodiment 5
With lithium nitrate, nickel nitrate, manganese nitrate, cobalt nitrate and magnesium nitrate according to mol ratio Li: Ni: Mn: Co: Mg=1.02: 0.42: 0.42: 0.14: 0.02 ratio was dissolved in the deionized water, and 2 times the ethanedioic acid of total mole number that adds nickel ion, manganese ion, cobalt ions is as complexing agent.Under 80 ℃, under agitation add the oxide D2 that Comparative Examples 2 makes then, continue to stir 180 minutes, obtain black-and-blue gel.The mol ratio of described oxide D1 and lithium nitrate is 20: 1.02.With this gel 120 ℃ down dry, then under oxygen atmosphere,, obtain positive active material M5 850 ℃ of following sintering 6 hours.Show that by XRD diffraction analysis and ICP Atomic Emission Spectral Analysis containing general formula among this positive active material M5 is LiNi
0.75Co
0.18Al
0.07O
2Oxide IA and general formula be Li (NiMn)
0.42Co
0.14Mg
0.02O
2Oxide IB, the mol ratio of described oxide IA and oxide IB is 100: 5.Measuring the mean particle diameter that obtains oxide IA according to Comparative Examples 1 described method is 11um, and the mean particle diameter of oxide IB is 150 nanometers.
Embodiment 6
Present embodiment illustrates the preparation method of positive active material of the present invention.
With nickel nitrate, manganese nitrate, cobalt nitrate and magnesium nitrate Ni: Mn: Co: Mg=0.95/3 in molar ratio: 0.95/3: 0.95/3: 0.05 ratio is dissolved in the deionized water, and adding the mean particle diameter that Comparative Examples 1 makes again is the Ni of 14um
0.80Co
0.15Al
0.05(OH)
2Spheric granules, under stirring condition, add ammoniacal liquor as complexing agent, the molal quantity of the ammonia in the ammoniacal liquor is 0.6 times of total mole number of nickel ion, manganese ion, cobalt ions, regulate pH value to 12 with NaOH solution, continue to stir after 2 hours, obtain solid product, this solid matter with deionized water washing is extremely neutral.By regulating Ni
0.80Co
0.15Al
0.05(OH)
2The addition of spheric granules, in the feasible solid product that finally obtains, Ni
0.80Co
0.15Al
0.05(OH)
2With (NiMnCo)
0.95/3Mg
0.05(OH)
2Mol ratio be 100: 5.
Then with this solid product and Li
2CO
3Micro mist mixes, wherein, and Li
2CO
3In molal quantity and the solid product of lithium in the ratio of molal quantity of hydroxide be 1.04: 1.Under oxygen atmosphere, with this solid product calcining 6 hours, 800 ℃ of sintering of original position were 18 hours then under 600 ℃ then.Obtain positive active material M6.Show that by XRD diffraction analysis and ICP Atomic Emission Spectral Analysis the kind and the content of each element meet LiNi among this positive active material M6
0.80Co
0.15Al
0.05O
2With Li (NiMnCo)
0.95/3Mg
0.05O
2Mol ratio is 100: 5 o'clock element kind and a content, it can be said that it is LiNi that bright this positive active material M6 contains general formula
0.80Co
0.15Al
0.05O
2Oxide IA and general formula be Li (NiMnCo)
0.95/3Mg
0.05O
2Oxide IB, the mol ratio of described oxide IA and oxide IB is 100: 5.Measuring the mean particle diameter that obtains oxide IA according to Comparative Examples 1 described method is 14um, and the mean particle diameter of oxide IB is 200 nanometers.
Embodiment 7
Method according to embodiment 6 prepares positive active material, and different is, by regulating Ni
0.80Co
0.15Al
0.05(OH)
2The addition of spheric granules, in the feasible solid product that finally obtains, Ni
0.80Co
0.15Al
0.05(OH)
2With (NiMnCo)
0.95/3Mg
0.05(OH)
2Mol ratio be 100: 10.
In the positive active material M7 that finally obtains, general formula is LiNi
0.80Co
0.15Al
0.05O
2Oxide IA and general formula be Li (NiMnCo)
0.95/3Mg
0.05O
2The mol ratio of oxide IB be 100: 10.Measuring the mean particle diameter that obtains oxide IA according to Comparative Examples 1 described method is 14um, and the mean particle diameter of oxide IB is 300 nanometers.
Embodiment 8
With nickel nitrate, manganese nitrate, cobalt nitrate and magnesium nitrate Ni: Mn: Co: Mg=0.42 in molar ratio: 0.42: 0.14: 0.02 ratio is dissolved in the deionized water, and adding the mean particle diameter that Comparative Examples 2 makes again is the Ni of 11um
0.75Co
0.18Al
0.07(OH)
2Spheric granules, under stirring condition, add ammoniacal liquor as complexing agent, the molal quantity of the ammonia in the ammoniacal liquor is 1.2 times of total mole number of nickel ion, manganese ion, cobalt ions, regulate pH value to 13 with NaOH solution, continue to stir after 2 hours, obtain solid product, this solid matter with deionized water washing is extremely neutral.By regulating Ni
0.75Co
0.18Al
0.07(OH)
2The addition of spheric granules, in the feasible solid product that finally obtains, Ni
0.75Co
0.18Al
0.07(OH)
2With (NiMn)
0.42Co
0.14Mg
0.02(OH)
2Mol ratio be 100: 5.
Then with this solid product and Li
2CO
3Micro mist mixes, wherein, and Li
2CO
3In molal quantity and the solid product of lithium in the ratio of molal quantity of hydroxide be 1.04: 1.Under oxygen atmosphere, with this solid product calcining 6 hours, 800 ℃ of sintering of original position were 18 hours then under 600 ℃ then.Obtain positive active material M8.Show that by XRD diffraction analysis and ICP Atomic Emission Spectral Analysis the kind and the content of each element meet LiNi among this positive active material M8
0.75Co
0.18Al
0.07O
2With Li (NiMn)
0.42Co
0.14Mg
0.02O
2Mol ratio is 100: 5 o'clock element kind and a content, it can be said that it is LiNi that bright this positive active material M8 contains general formula
0.75Co
0.18Al
0.07O
2Oxide IA and general formula be Li (NiMn)
0.42Co
0.14Mg
0.02O
2Oxide IB, the mol ratio of described oxide IA and oxide IB is 100: 5.Measuring the mean particle diameter that obtains oxide IA according to Comparative Examples 1 described method is 11um, and the mean particle diameter of oxide IB is 200 nanometers.
Embodiment 9
Method according to embodiment 8 prepares positive active material, different is, with nickel nitrate, manganese nitrate, cobalt nitrate and copper nitrate, strontium nitrate Ni: Mn: Co: Cu: Sr=0.42 in molar ratio: 0.42: 0.14: 0.01: 0.01 ratio was dissolved in the deionized water.Show that by XRD diffraction analysis and ICP Atomic Emission Spectral Analysis the kind and the content of each element meet LiNi among the positive active material M9 that finally makes
0.75Co
0.18Al
0.07O
2With Li (NiMn)
0.42Co
0.14Cu
0.01Sr
0.01O
2Mol ratio is 100: 5 o'clock element kind and a content, it can be said that it is LiNi that the bright positive active material M9 that finally makes contains general formula
0.75Co
0.18Al
0.07O
2Oxide IA and general formula be Li (NiMn)
0.42Co
0.14Cu
0.01Sr
0.01O
2Oxide IB, the mol ratio of described oxide IA and oxide IB is 100: 5.Measuring the mean particle diameter that obtains oxide IA according to Comparative Examples 1 described method is 11um, and the mean particle diameter of oxide IB is 180 nanometers.
Embodiment 10
With nickel nitrate, cobalt nitrate, yttrium nitrate, zinc nitrate is Ni in molar ratio: Co: Y: Zn=0.75: 0.18: 0.03: 0.04 ratio is dissolved into and obtains the aqueous solution in the deionized water, under stirring condition, with peristaltic pump with this aqueous solution with join in the reactor as the ammoniacal liquor and the stream of complexing agent, the molal quantity of ammonia is a nickel in the control reaction system, cobalt, 0.6 times of the total mole number of aluminium, in reactor, add NaOH solution with servopump, to keep pH value of reaction system is 11, continue to stir after 7 hours, obtain solid product, this solid matter with deionized water washing is extremely neutral.Obtaining general formula is Ni
0.75Co
0.18Y
0.03Zn
0.04(OH)
2Spheric granules.Obtain this Ni according to Comparative Examples 1 described method mensuration
0.75Co
0.18Y
0.03Zn
0.04(OH)
2The mean particle diameter of spheric granules is 10um.
With this mean particle diameter is the Ni of 10um
0.75Co
0.18Y
0.03Zn
0.04(OH)
2Spheric granules and Li
2CO
3Micro mist is that 1: 1.04 amount is mixed by the molal quantity sum of nickel, cobalt, aluminium and the ratio of the molal quantity of lithium, and under oxygen atmosphere, at 600 ℃ of calcining 6h, then 800 ℃ of sintering of original position are 16 hours then.The general formula that obtains mean particle diameter and be 11um is LiNi
0.75Co
0.18Y
0.03Zn
0.04O
2Oxide.
Then, prepare positive active material according to the method for embodiment 5, different is to be LiNi with the above-mentioned general formula that makes
0.75Co
0.18Y
0.03Zn
0.04O
2The oxide general formula that replaces Comparative Examples 2 to make be LiNi
0.75Co
0.18Al
0.07O
2Oxide D2.
Show that by XRD diffraction analysis and ICP Atomic Emission Spectral Analysis the kind and the content of each element meet LiNi among the positive active material M10 that finally makes
0.75Co
0.18Y
0.03Zn
0.04O
2With Li (NiMn)
0.42Co
0.14Cu
0.01Ti
0.01O
2Mol ratio is 100: 5 o'clock element kind and a content, it can be said that it is LiNi that the bright positive active material M10 that finally makes contains general formula
0.75Co
0.18Y
0.03Zn
0.04O
2Oxide IA and general formula be Li (NiMn)
0.42Co
0.14Cu
0.01Ti
0.01O
2Oxide IB, the mol ratio of described oxide IA and oxide IB is 100: 5.The mean particle diameter that mensuration obtains oxide IA is 11um, and the mean particle diameter of oxide IB is 150 nanometers.
Comparative Examples 3
The lithium ion battery of the positive active material that present embodiment explanation employing Comparative Examples 1 makes and the performance of this battery.
With 90 gram polyvinylidene fluoride (Atuofeina Corp, 761#PVDF) be dissolved in the 1350 gram N-N-methyl-2-2-pyrrolidone N-solvents and make adhesive solution, in gained solution, add the oxide D1 that 2895 gram Comparative Examples 1 make then, fully mix and make anode sizing agent.This anode sizing agent is uniformly applied on the aluminium foil, through 125 ℃ of dryings 1 hour, calendering then.Be cut into 390 * 44 millimeters positive pole, contain 4.4 gram positive active materials in each positive pole.
With 100 gram negative electrode active composition native graphites, adhesive is that mixture, the 4 gram conductive agent carbon blacks that 1 gram carboxymethyl cellulose and 3 restrains butadiene-styrene rubber join in the 120 gram water, stirs in de-airing mixer then and forms uniform cathode size.This slurry is coated on the Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 500 * 44 millimeters negative pole, wherein contain 2.6 gram active component native graphites.
The polypropylene diaphragm of above-mentioned positive pole, 20 micron thickness and negative pole is overlapping successively and be wound into rectangular lithium ion battery electricity core, in the battery case of packing into, electrolyte is injected battery case with the amount of 3.8g/Ah, LP053450 type lithium rechargeable battery E1 is made in sealing.Described electrolyte contains LiPF
6And nonaqueous solvents, LiPF described in the electrolyte
6Concentration be 1 mol, described nonaqueous solvents is that mass ratio is 1: 1 a ethylene carbonate (EC) and the mixed solvent of diethyl carbonate (DMC).
Performance test
(1) first discharge specific capacity
Use BS-9300R secondary cell device for detecting performance respectively battery E1 to be carried out the discharge capacity test.Test environment is 25 ℃, relative humidity 30%, and assay method is as follows:
With the 0.2C current charges to 4.2V, 20 milliamperes of cut-off currents of charging, then with the 1C current discharge to 3.0V, the record discharge capacity value.And according to the first discharge specific capacity of following formula counting cell.The result is as shown in table 1.
Positive active material weight * 100% of discharge capacity/each positive plate of first discharge specific capacity=first
(2) normal-temperature circulating performance
Constant current with 800mA carries out constant current charge to above-mentioned battery E1, and charging rises to 4.2V at voltage and carries out constant voltage charge later on, by electric current 25mA by voltage 4.2V; Shelved 10 minutes, and to 3.0V, measured the initial discharge capacity that obtains battery with the current discharge of 800mA.After shelving 10 minutes, repeat above step, make continuous charge-discharge test, obtain the discharge battery capacity after battery circulates for 400 times, calculate the discharge capacitance of 400 circulation back batteries according to following formula.The result is as shown in table 1.
Discharge capacitance=400 time circulation back discharge capacity/initial discharge capacity * 100%
(3) multiplying power discharging property
Use BS-9300R secondary cell device for detecting performance respectively battery E1 to be carried out the discharge capacity test.Test environment is 25 ℃, relative humidity 30%, and assay method is as follows:
With the 0.2C current charges to 4.2V, 20 milliamperes of cut-off currents of charging, then with the 1C current discharge to 3.0V, record discharge capacity value F1; With the 0.2C current charges to 4.2V, 20 milliamperes of cut-off currents of charging, then with the 0.2C current discharge to 3.0V, record discharge capacity value F2.And according to the multiplying power discharging property of following formula counting cell.The result is as shown in table 1.
Multiplying power discharging property=F1/F2 * 100%
(4) over-charging test
Battery E1 is overcharged experiment in the over-charge protective cabinet.
1C/5V test: at normal temperatures, the battery E1 that expires electric attitude 4.2V is charged to 5V with 1C, and kept 0.5 hour.Observe the performance of battery in charging and maintenance process.
1C/12V test: at normal temperatures, the battery of expiring electric attitude 4.2V is charged to 12V with 1C, and kept 0.5 hour, observe the performance of battery in charging and maintenance process.
The result is as shown in table 1.
(5) high-temperature behavior
Under 45 ℃, with the constant current of 800mA above-mentioned battery E1 is carried out constant current charge, charging rises to 4.2V at voltage and carries out constant voltage charge later on, by electric current 25mA by voltage 4.2V; Shelved 10 minutes, and to 3.0V, measured the initial discharge capacity that obtains battery with the current discharge of 800mA.After shelving 10 minutes, repeat above step, make continuous charge-discharge test, obtain the discharge battery capacity after battery circulates for 300 times, calculate the discharge capacitance of 300 circulation back batteries according to following formula.The result is as shown in table 1.
45 ℃ of following discharge capacitance=300 time circulation back discharge capacity/initial discharge capacity * 100%
In addition, measure after 300 charge and discharge cycles, constant current with 800mA carries out constant current charge to battery E1 again, charging is by voltage 4.2V, measure the swell value of battery at thickness direction then, described swell value is thickness poor after thickness after battery the 301st time charging and battery charge for the first time.
Comparative Examples 4
Method according to Comparative Examples 3 prepares lithium ion battery, and different is that positive active material is respectively the positive active material D2 that Comparative Examples 2 makes.Finally obtain battery E2.Simultaneously, measure the performance of battery E2 according to the method for Comparative Examples 3.The result is as shown in table 1.
Embodiment 11-20
Method according to Comparative Examples 3 prepares lithium ion battery, and different is that positive active material is respectively the positive active material M1-M10 that embodiment 1-10 makes.Finally obtain battery C1-C10.
Simultaneously, measure the performance of battery C1-C10 according to the method for Comparative Examples 3.The result is as shown in table 1.
Table 1
| The battery numbering | First discharge specific capacity (mAh/g) | 400 circulation volume conservation rates of normal temperature (%) | Multiplying power discharging property (%) | Over-charging | High-temperature behavior | ||
| 1C/5V | 1C/12V | The discharge capacitance (%) of 45 ℃ of following 300 circulation back batteries | 45 ℃ of following 300 circulation back cell thickness swell values (mm) | ||||
| E1 | 182 | 85 | 94 | The thickness direction expansion rate is higher than 20% | Blast | 75 | 2.45 |
| E2 | 181 | 83 | 92 | The thickness direction expansion rate is higher than 20% | Blast | 74 | 2.49 |
| C1 | 181 | 92 | 96 | No abnormal | Blast | 80 | 1.92 |
| C2 | 181 | 92 | 98 | No abnormal | No abnormal | 85 | 0.32 |
| C3 | 180 | 93 | 99 | No abnormal | No abnormal | 86 | 0.23 |
| C4 | 172 | 93 | 99 | No abnormal | No abnormal | 89 | 0.20 |
| C5 | 180 | 93 | 99 | No abnormal | No abnormal | 86 | 0.29 |
| C6 | 181 | 92 | 99 | No abnormal | No abnormal | 87 | 0.23 |
| C7 | 180 | 93 | 99 | No abnormal | No abnormal | 88 | 0.22 |
| C8 | 180 | 92 | 99 | No abnormal | No abnormal | 86 | 0.29 |
| C9 | 181 | 92 | 99 | No abnormal | No abnormal | 87 | 0.22 |
| C10 | 181 | 92 | 99 | No abnormal | No abnormal | 87 | 0.25 |
As can be seen from Table 1, the positive active material M1-M10 that makes of the present invention can obviously improve cycle performance, multiplying power discharging property, over-charging and the high-temperature behavior of the battery C1-C10 that adopts this positive active material.In addition, the present invention can make that the battery that adopts positive active material of the present invention has higher discharge simultaneously by the content of oxide IA and oxide IB in the control positive active material must capacity, thereby can improve the combination property of battery greatly.
Claims (16)
1. active substance of lithium ion battery anode, this positive active material contains oxide IA, and described oxide IA has the composition shown in the general formula (1):
LiNi
1-x-yCo
xM
yO
2 (1)
Wherein, x and y are molar fraction, 0≤x+y＜1, M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb, it is characterized in that this positive active material also contains oxide IB, described oxide IB has the composition shown in the general formula (2):
Li(NiMn)
(1-a-b)/2Co
aX
bO
2 (2)
Wherein, a and b are molar fraction, 0≤a+b＜1, and X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
2. positive active material according to claim 1, wherein, 0.1≤x≤0.2,0≤y≤0.1,0.1≤a≤0.33,0≤b≤0.1.
3. positive active material according to claim 1, wherein, the mol ratio of described oxide IA and oxide IB is 100: 5-10.
4. according to claim 1 or 3 described positive active materials, wherein, the mean particle diameter of described oxide IA is the 10-15 micron, and the mean particle diameter of described oxide IB is 10 nanometers to 1 micron.
5. the preparation method of the described active substance of lithium ion battery anode of claim 1, it is characterized in that, this method is included in oxide IA and organic acid exists down, the aqueous solution that will contain the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of soluble-salt, the nickel of lithium and X stirs and obtains gel, with this gel sintering, obtain containing the positive active material of oxide IA and oxide IB then; Wherein, described oxide IA has the composition shown in the general formula (1):
LiNi
1-x-yCo
xM
yO
2 (1)
Wherein, x and y are molar fraction, 0≤x+y＜1, and M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb;
The consumption of the soluble-salt of the soluble-salt of the soluble-salt of described lithium, the soluble-salt of nickel, manganese, the soluble-salt of cobalt and X satisfies following condition: with respect to 1 mole lithium, the molal quantity of cobalt is m, and the molal quantity of X is n, the molal quantity of nickel and manganese (1-m-n)/2 of respectively doing for oneself, 0≤m+n＜1
Wherein, X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
6. method according to claim 5, wherein, 0.1≤x≤0.2,0≤y≤0.1,0.1≤m≤0.33,0≤n≤0.1.
7. method according to claim 5, wherein, the mean particle diameter of described oxide IA is the 10-15 micron.
8. method according to claim 5, wherein, described organic acid is one or more in citric acid, maleic acid, acrylic acid, lactic acid, malic acid, butanedioic acid, tartaric acid, sorbic acid, salicylic acid, stearic acid, sad, palmitic acid, glycolic, ethanedioic acid and the acetate, and the 0.1-10 that described organic acid consumption is the total mole number of nickel ion, manganese ion, cobalt ions in the described aqueous solution doubly.
9. method according to claim 5, wherein, the mol ratio of the lithium ion in the soluble-salt of described oxide IA and lithium is 100: 5-10.
10. method according to claim 5, wherein, the temperature of described sintering is 700-900 ℃, the time is 2-16 hour.
11. the preparation method of the described active substance of lithium ion battery anode of claim 1, it is characterized in that, this method is included in ammoniacal liquor and exists down, in the pH value is under the condition of 8-13, the aqueous solution that will contain the soluble-salt of the soluble-salt of soluble-salt, cobalt of soluble-salt, the manganese of nickel and X mixes with hydroxide IA1, and filtration obtains containing the solid product of hydroxide IA1 and hydroxide IB1, this solid product is mixed with lithium-containing compound and sintering, obtain containing the positive active material of oxide IA and oxide IB; Wherein, described hydroxide IA1 has the composition shown in the general formula (3):
Ni
1-x-yCo
xM
y(OH)
2 (3)
Wherein, x and y are molar fraction, 0≤x+y＜1, and M is one or more among Al, B, Mn, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb;
The consumption of the soluble-salt of the soluble-salt of nickel, the soluble-salt of manganese, cobalt and the soluble-salt of X satisfies following condition: with respect to the cobalt of p mole, the molal quantity of X is q, the molal quantity of nickel and manganese (1-p-q)/2 of respectively doing for oneself, 0≤p+q＜1, the molal quantity of the lithium in the lithium-containing compound is 1-1.04 with the ratio of the molal quantity sum of hydroxide IA1 and hydroxide IB1: 1
Wherein, X is one or more among Al, B, Fe, Ti, Mg, Cr, Ga, Cu, Zn, Y, Sr and the Nb.
12. method according to claim 11, wherein, 0.1≤x≤0.2,0≤y≤0.1,0.1≤p≤0.33,0≤q≤0.1.
13. method according to claim 11, wherein, the mean particle diameter of described hydroxide IA1 is the 10-15 micron.
14. method according to claim 11, wherein, the consumption of described ammoniacal liquor is 0.1-6 a times of the total mole number of nickel ion, manganese ion, cobalt ions in the described aqueous solution.
15. method according to claim 11, wherein, the mol ratio of described hydroxide IA1 and hydroxide IB1 is 100: 5-10.
16. method according to claim 11, wherein, the temperature of described sintering is 500-900 ℃, and the time is 5-40 hour.
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| CN101471441A (en) | 2009-07-01 |
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