CN102610811A - Mixed type anode material for lithium ion battery and preparing method of mixed type anode material - Google Patents

Mixed type anode material for lithium ion battery and preparing method of mixed type anode material Download PDF

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CN102610811A
CN102610811A CN2012100939561A CN201210093956A CN102610811A CN 102610811 A CN102610811 A CN 102610811A CN 2012100939561 A CN2012100939561 A CN 2012100939561A CN 201210093956 A CN201210093956 A CN 201210093956A CN 102610811 A CN102610811 A CN 102610811A
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solution
preparation
mixed type
lithium
type anode
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陈勃涛
李旭
徐宁
吴孟涛
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Tianjin B&M Science and Technology Co Ltd
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Tianjin B&M Science and Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a mixed type anode material for a lithium ion battery and a preparing method of the mixed type anode material. The method comprises the following steps: 1) preparing Li ((Ni1-x-y-zCoxMyM'z)1-w(Ni0.5Mn0.5)w)O2; 2) preparing LiCoO2; and 3) preparing the mixed type anode material. The mixed type anode material is high in specific capacity, good in safety performance, long in cycle life and high in rolling density.

Description

Lithium ion battery is with mixed type anode material and preparation method thereof
Technical field
The present invention relates to a kind of lithium ion battery, particularly relate to a kind of lithium ion battery with mixed type anode material and preparation method thereof.
Background technology
Lithium ion battery has obtained using widely at the mobile digital product scope rapidly since coming out because energy density is high.Lithium ion battery mainly is made up of anode pole piece, cathode pole piece, diaphragm material, electrolyte and overpack.Negative pole adopts carbon class material, and its capacity is near the limit at present, so capacity of lithium ion battery and performance mainly receive the influence of positive electrode.On the other hand, the cost of positive electrode accounts for about 30% of lithium ion battery total cost, and exploitation high-performance positive electrode is the key point that improves the lithium-ion electric pool technology.
Since lithium ion battery is born, cobalt acid lithium LiCoO 2Always be the anode material for lithium-ion batteries (hereinafter to be referred as " positive electrode ") of extensive use the most, its share in market once reached more than 90%.The initial specific capacity of cobalt acid lithium material is about 145-150mAh/g, and it is in cycle performance, security performance and roll excellent combination property aspect the density, is widely used in various types of lithium ion batteries.But continuous variation along with downstream product; Cobalt acid lithium material more and more can not satisfy the needs of lithium ion battery to energy density aspect specific capacity, develop that a kind of energy density is high, cycle performance and security performance also preferably the new type lithium ion battery positive electrode be necessary and urgent task very.Nickel-base anode material (being also referred to as nickelic is positive electrode) is to be the modification positive electrode that base growth is got up with the lithium nickelate; Comparing with the cobalt of present extensive use acid lithium has higher specific capacity; 0.1C discharge capacity is more than 180mAhg-1 first; Exceeding closely 40%, is the highest a kind of material of energy density in the commercial anode material for lithium-ion batteries at present, and cost also is lower than LiCoO simultaneously 2Material.But nickelic is the LiNiO on positive electrode surface 2Structure is decomposed, makes the alkaline higher of this material, causes the homogenate difficulty, and drawing abillity is poor.In addition since nickelic be that positive electrode has certain ballooning in cyclic process, therefore be mainly used in box hat or aluminum hull small-scale lithium ion cell, like 18650 type batteries.
In order further to reduce cost, each lithium ion battery production firm adopts ternary layered cobalt nickel oxide manganses lithium material of symmetric form such as LiNi 1/3Co 1/3Mn 1/3O 2Or asymmetric ternary layered cobalt nickel oxide manganses lithium material such as LiNi 0.5Co 0.2Mn 0.3O 2With LiCoO 2The method that material carries out physical mixed prepares the mixed type anode material, at the fail safe and the cycle performance that guarantee to have improved under certain condition that rolls density battery.To so far, still not with nickelic be positive electrode LiNi 1-xCo xO 2With LiCoO 2Be mixed with the precedent of mixed type anode material, mainly be since nickelic be the alkaline higher of positive electrode, with LiCoO 2The whole alkalescence of composite material is raise, cause the processing characteristics of positive electrode to descend, battery has comparatively severe bulging in the cyclic process.
Summary of the invention
An object of the present invention is to provide a kind of processing characteristics better, have higher-security can and the preparation method of the mixed type lithium ion cell positive material of stable circulation performance.
For this reason, technical scheme of the present invention is following:
A kind of lithium ion battery is used the mixed type anode material, and it is prepared from following components in weight percentage:
Li((Ni 1-x-y-zCo xM yM’ z) 1-w(Ni 0.5Mn 0.5) w)O 2 9.9％～90％
LiCoO 2 9.9％～90％
Property-modifying additive 0.1～5%
Wherein, M, M ' are a kind of in Mn, Al, Mg, Ti, Sr or the Zr element, 0≤x≤0.3,0≤y≤0.1,0≤z≤0.1,0.05≤w≤0.2.
Said property-modifying additive is one or more the mixture in oxide, carbonate compound or the hydroxide of Al, Mg, Ti, Sr and Zr.
A kind of above-mentioned lithium ion battery is used the mixed type anode preparation methods, may further comprise the steps:
1) Li ((Ni 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2Preparation:
(1) Ni: Co: M: M '=(1-x-y-z) in molar ratio: x: y: z preparation salting liquid A makes that concentration of metal ions is 0.5～2.5mol/L among the salting liquid A; Ni: Mn=1 in molar ratio: 1 preparation salting liquid B makes that concentration of metal ions is 0.5～2mol/L among the salting liquid B;
(2) be complexing agent with sodium hydroxide solution and ammoniacal liquor, said concentration of sodium hydroxide solution is 4～12mol/L, is 0.2～0.6 ammoniacal liquor to be joined in the sodium hydroxide solution according to ammonia and NaOH mol ratio;
(3) be that V1 salting liquid A and sodium hydroxide solution are continuously pumped in the agitated reactor that fills deionized water with volume; Solution constantly stirs in the agitated reactor; Fixedly the salting liquid flow velocity is 10.0～12.0 through pH value of solution value in the control sodium hydroxide solution flow velocity control agitated reactor;
(4) after salting liquid A pumps into and finishes, be that the salting liquid B of V2 is continuously pumped in the agitated reactor, feed nitrogen or argon gas simultaneously continuously and protect that after salting liquid B pumps into and finishes, continue to stir 2h～6h, wherein the volume V2 computing formula of solution B is following with volume:
V 2 = w × V 1 × ρ A ( 1 - w ) × ρ B
In the formula: ρ ABe the total mol concentration of metal ion in the solution A, mol/L
ρ BBe the total mol concentration of metal ion in the solution B, mol/L
(5) stop to stir, solution is carried out Separation of Solid and Liquid, it is 8～9 that isolated solid uses the pH value of 20 ℃～60 ℃ deionized water wash to washings;
(6) solidliquid mixture after will washing carries out Separation of Solid and Liquid, and isolated solid obtains (Ni 80 ℃～150 ℃ oven dry down 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w(OH) 2Powder;
(7) with (Ni 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w(OH) 2Powder and lithium salts are according to the mixed of Li/Me=1.0～1.2, wherein Me=Ni+Co+M+M ';
(8) mixture of step (7) is put into kiln, under 600 ℃～1000 ℃, roasting 6h～12h obtains coarse fodder in the air or oxygen atmosphere, and said coarse fodder obtains Li ((Ni after pulverizing 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2Powder;
3) the Li ((Ni that step 1) is made 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2Powder and LiCoO 2, after property-modifying additive mixes in proportion,, obtain the mixed type anode material at 500 ℃～1000 ℃ heat treatment 4～8h.
Said cobalt salt is one or more the mixture in oxide, hydroxide, cobalt acetate and the cobalt carbonate of cobalt.
Said lithium salts is one or more the mixture in lithium carbonate, lithium hydroxide, lithium nitrate and the lithium acetate.
Preferably, the rotating speed of stirring motor is 100～500rpm in the step (3).
The present invention mainly coats LiNi by the surface 0.5Mn 0.5O 2LiNi 1-x-y-zCo xM yM ' zO 2Material and LiCoO 2Material is formed, but two kinds of materials are not that simple physics is mixed, but with the Li ((Ni for preparing 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2With LiCoO 2And after property-modifying additive mixes, mix the back and in air or oxygen atmosphere, mixture is carried out secondary heat treatment, heat treatment temperature is that 500 ℃～1000 ℃, time are 4～8h.At Li ((Ni 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2With LiCoO 2Property-modifying additive is coated on Li ((Ni in the mixed process 1-x-y-zCo xM yM ' z) 1-w-(Ni 0.5Mn 0.5) w) O 2With LiCoO 2Material surface is through obtaining the Li ((Ni that metal oxide coats after the secondary heat treatment 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2With LiCoO 2The mixed type anode material.
The mixed type anode material of method preparation of the present invention has higher safety performance and stable circulation performance.Li ((Ni wherein 1-x-y-zCo xM yM ' z) (Ni 0.5Mn 0.5) w) O 2For material provides higher ratio capacity, the outer Li (Ni that coats 0.5Mn 0.5) O 2Reduced Li ((Ni 1-x-y-zCo xM yM ' z) O 2Alkalescence, improved Li (Ni 1-x-y-zCo xM yM ' z) O 2Processing characteristics, suppressed the bulging in the battery cyclic process.LiCoO 2Improved the density that rolls of mixed type anode material monolithic.Through after baking, at Li ((Ni 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2And LiCoO 2Material surface has coated metal oxide simultaneously, has further suppressed the bulging that battery produces in the cyclic process.This material and LiCoO 2It is higher to compare specific capacity, has good processing properties again simultaneously, can improve the energy density of lithium ion battery effectively.
Embodiment
Embodiment 1
1) Li (Ni 0.8Co 0.2) 0.8(Ni 0.5Mn 0.5) 0.2O 2Preparation:
Take by weighing nickelous sulfate, cobaltous sulfate (Ni: Co=4: 1) use deionized water dissolving, be mixed with the mixed liquor of 2.0mol/L.Take by weighing nickelous sulfate, manganese sulfate (Ni: Mn=1: 1) spend dried up solution, the mixed solution of preparation 2mol/L.The sodium hydroxide solution of preparation 4mol/L adds ammoniacal liquor, and the ratio (mol ratio) of control ammoniacal liquor and NaOH is 0.2.Nickelous sulfate cobalt liquor and sodium hydroxide solution adopt with measuring pump and the mode of stream joins in the 200L adjustable speed agitated reactor, and the flow velocity of nickel, cobalt sulfate is set at 100ml/min, and reaction temperature is controlled at 40～50 ℃; Reconcile the flow velocity of NaOH/ammonia mixed solution, control pH is 11.6-11.8, and speed of agitator is set at 400rpm, is reflected at N 2Carry out under the atmosphere.After pumping into 100L nickel cobalt sulfate, stop to add nickel cobalt sulfate liquor; Salting liquid is replaced by nickel, mn sulphate solution; Continue to add in the 200L agitated reactor with NaOH/ammonia mixed solution and stream; Nickel, mn sulphate solution flow rate are set at 50ml/min, and it is 11.6～11.8 that adjustment NaOH/ammonia solution flow velocity keeps the pH value, and other process conditions are constant; After pumping into nickel, mn sulphate solution 20L, stop reaction, continue to stir 2h, material is transferred in the rinsing maching with 50 ℃ of washings, wash to washings pH be 8～9 backs, 150 ℃ of oven dry processing 12h in baking oven; With Li: M (M=Ni+Co) ratio 1.0 ratios, take by weighing lithium hydroxide 410g and (Ni 0.8Co 0.2) 0.8(Ni 0.5Mn 0.5) 0.2(OH) 2Powder 1000g mixes 60min in mixer, mixed powder in kiln, in oxygen atmosphere 725 ℃ down behind the insulation 10h, is pulverized and screening obtains Li (Ni sintered product 0.8Co 0.2) 0.8(Ni 0.5Mn 0.5) 0.2O 2
2) LiCoO 2Preparation: according to molar ratio Li: Co=1: 1 takes by weighing Co 3O 41000.0g mix with lithium carbonate 454.0g, mixture at 1020 ℃ of insulation 12h, is pulverized and screening obtains LiCoO sintered product in kiln 2
3) 0.9 [Li (Ni 0.8Co 0.2) 0.8(Ni 0.5Mn 0.5) 0.2O 2] 0.1 [LiCoO 2] preparation: according to molar ratio M 1(M 1=Ni+Co+Mn): Co=9: 1 ratio takes by weighing the Li (Ni of step preparation 0.8Co 0.2) 0.8(Ni 0.5Mn 0.5) 0.2O 21000g and LiCoO 2111.8g mix, mixture is put into kiln, behind insulation 8h under 750 ℃ of oxygen atmospheres, sintered product pulverizing and screening is obtained target product 0.9 [Li (Ni 0.8Co 0.2) 0.8(Ni 0.5Mn 0.5) 0.2O 2] 0.1 [LiCoO 2] positive electrode.
The discharge capacity of this mixed type anode material is 189mAh/g (4.3V), rolls density 3.56g/cm 3, 400 circulation volume conservation rates 85.5%.
Embodiment 2
1) Li (Ni 0.8Co 0.15Al 0.025Mg 0.025) 0.9(Ni 0.5Mn 0.5) 0.1O 2Preparation: take by weighing nickelous sulfate, cobaltous sulfate, aluminum nitrate, magnesium nitrate (Ni: Co: Al: Mg=80: 17: 2.5: 2.5) and use deionized water dissolving, be mixed with the mixed liquor of 2.0mol/L.Take by weighing nickelous sulfate, manganese sulfate (Ni: Mn=1: 1) spend dried up solution, the mixed solution of preparation 1mol/L.The sodium hydroxide solution of preparation 4mol/L adds ammoniacal liquor, and the ratio (mol ratio) of control ammoniacal liquor and NaOH is 0.2.Nickelous sulfate cobalt liquor and sodium hydroxide solution adopt with measuring pump and the mode of stream joins in the 200L adjustable speed agitated reactor, and the flow velocity of nickel, cobalt sulfate is set at 100ml/min, and reaction temperature is controlled at 40～50 ℃; Reconcile the flow velocity of NaOH/ammonia mixed solution, control pH is 11.6-11.8, and speed of agitator is set at 400rpm, is reflected at N 2Carry out under the atmosphere.After pumping into 100L nickel cobalt sulfate, stop to add nickel cobalt sulfate liquor; Salting liquid is replaced by nickel, mn sulphate solution; Continue to add in the 200L agitated reactor with NaOH/ammonia mixed solution and stream; Nickel, mn sulphate solution flow rate are set at 50ml/min, and it is 11.6～11.8 that adjustment NaOH/ammonia solution flow velocity keeps the pH value, and other process conditions are constant; After pumping into nickel, mn sulphate solution 22L, stop reaction, continue to stir 2h, material is transferred in the rinsing maching with 50 ℃ of washings, wash to washings pH be 8～9 backs, 150 ℃ of oven dry processing 12h in baking oven; With Li: M (M=Ni+Co) ratio 1.0 ratios, take by weighing lithium carbonate 410g and (Ni 0.8Co 0.2) 0.9(Ni 0.5Mn 0.5) 0.1(OH) 2Powder 1000g mixes 60min in mixer, mixed powder in kiln, in oxygen atmosphere behind 725 ℃ of insulation 10h, is pulverized and screening obtains Li (Ni sintered product 0.8Co 0.15Al 0.025Mg 0.025) 0.9(Ni 0.5Mn 0.5) 0.1O 2
2) LiCoO 2Preparation side: according to molar ratio Li: Co=1: 1 takes by weighing Co 3O 41000.0g mix with lithium carbonate 460.2g, mixture at 1040 ℃ of insulation 10h, is pulverized and screening obtains LiCoO sintered product in kiln 2
3) 0.6 [Li (Ni 0.8Co 0.15Al 0.025Mg 0.025) 0.9(Ni 0.5Mn 0.5) 0.1O 2] 0.4 [LiCoO 2] preparation: according to molar ratio M 1(M 1=Ni+Co+Mn): Co=1: 1 ratio takes by weighing the Li (Ni of step preparation 0.8Co 0.15Al 0.025Mg 0.025) 0.9(Ni 0.5Mn 0.5) 0.1O 21000g, LiCoO 2666.7g and Sr (OH) 410g, ZrO 210g mixes, and mixture is put into kiln, behind insulation 10h under 720 ℃ of oxygen atmospheres, sintered product pulverizing and screening is obtained target product 0.6 [Li (Ni 0.8Co 0.15Al 0.025Mg 0.025) 0.9(Ni 0.5Mn 0.5) 0.1O 2] 0.4 [LiCoO 2] positive electrode
This positive pole material discharge capacity is 176mAh/g (4.3V), rolls density 3.6g/cm 3, 400 circulation volume conservation rates 88.1%.
Embodiment 3
1) Li (Ni 0.8Co 0.15Sr 0.02Zr 0.03) 07(Ni 0.5Mn 0.5) 0.3O 2Preparation: take by weighing nickelous sulfate, cobaltous sulfate, strontium nitrate, zirconium nitrate (Ni: Co: Sr: Zr=80: 15: 2: 3) and use deionized water dissolving, be mixed with the mixed liquor of 2.5mol/L.Take by weighing nickelous sulfate, manganese sulfate (Ni: Mn=1: 1) spend dried up solution, the mixed solution of preparation 1.5mol/L.The sodium hydroxide solution of preparation 4mol/L adds ammoniacal liquor, and the ratio (mol ratio) of control ammoniacal liquor and NaOH is 0.2.Nickelous sulfate cobalt liquor and sodium hydroxide solution adopt with measuring pump and the mode of stream joins in the 200L adjustable speed agitated reactor, and the flow velocity of nickel, cobalt sulfate is set at 80ml/min, and reaction temperature is controlled at 50 ℃～60 ℃; Reconcile the flow velocity of NaOH/ammonia mixed solution, control pH is 11.6-11.8, and speed of agitator is set at 450rpm, is reflected at N 2Carry out under the atmosphere.After pumping into 100L nickel cobalt sulfate, stop to add nickel cobalt sulfate liquor; Salting liquid is replaced by nickel, mn sulphate solution; Continue to add in the 200L agitated reactor with NaOH/ammonia mixed solution and stream; Nickel, mn sulphate solution flow rate are set at 30ml/min, and it is 11.6～11.8 that adjustment NaOH/ammonia solution flow velocity keeps the pH value, and other process conditions are constant; After pumping into nickel, mn sulphate solution 71.5L, stop reaction, continue to stir 2h, material is transferred in the rinsing maching with 60 ℃ of washings, wash to washings pH be 8～9 backs, 150 ℃ of oven dry processing 12h in baking oven; With Li: M (M=Ni+Co+Mn+Sr+Zr) ratio 1.0 ratios, take by weighing lithium hydroxide 427g and Li (Ni 0.8Co 0.15Sr 0.02Zr 0.03) 07(Ni 0.5Mn 0.5) 0.3O 2Powder 1000g mixes 60min in mixer, mixed powder in kiln, in oxygen atmosphere 900 ℃ down behind the insulation 6h, is pulverized and screening obtains Li (Ni sintered product 0.8Co 0.15Al 0.025Mg 0.025) 0.7(Ni 0.5Mn 0.5) 0.3O 2
2) LiCoO 2Preparation: according to molar ratio Li: Co=1: 1.1 take by weighing Co 3O 41000.0g mix with lithium carbonate 506.2g, mixture at 900 ℃ of insulation 16h, is pulverized and screening obtains LiCoO sintered product in kiln 2
3) 0.1 [Li (Ni 0.8Co 0.15Sr 0.02Zr 0.03) 07(Ni 0.5Mn 0.5) 0.3O 2] 0.9 [LiCoO 2] preparation: according to molar ratio M 1(M 1=Ni+Co+Mn): Co=1: 1 ratio takes by weighing the Li (Ni of step preparation 0.8Co 0.15Sr 0.02Zr 0.03) 07(Ni 0.5Mn 0.5) 0.3O 21000g, LiCoO 28969.8 and MgCO 3350g, TiO 2150g mixes, and mixture is put into kiln, behind insulation 10h under 720 ℃ of oxygen atmospheres, sintered product pulverizing and screening is obtained target product 0.6 [Li (Ni 0.8Co 0.15Al 0.025Mg 0.025) 0.9(Ni 0.5Mn 0.5) 0.1O 2] 0.4 [LiCoO 2] positive electrode.
The discharge capacity of this mixed type anode material is 158mAh/g (4.3V), rolls density 3.95g/cm 3, 400 circulation volume conservation rates 89.7%.
Can be known that by experimental data the mixed type anode material of method of the present invention preparation has the density of rolling height, the advantage of good cycle has reduced the cost of material simultaneously.

Claims (6)

1. a lithium ion battery is used the mixed type anode material, and it is prepared from following components in weight percentage:
Li((Ni 1-x-y-zCo xM yM’ z) 1-w(Ni 0.5Mn 0.5) w)O 2 9.9％～90％
LiCoO 2 9.9％～90％
Property-modifying additive 0.1～5%
Wherein, M, M ' are a kind of in Mn, Al, Mg, Ti, Sr or the Zr element, 0≤x≤0.3,0≤y≤0.1,0≤z≤0.1,0.05≤w≤0.2.
2. lithium ion battery according to claim 1 is used the mixed type anode material, it is characterized in that: said property-modifying additive is one or more the mixture in oxide, carbonate compound or the hydroxide of Al, Mg, Ti, Sr and Zr.
3. the said lithium ion battery of claim 1 is used the mixed type anode preparation methods, may further comprise the steps:
1) Li ((Ni 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2Preparation:
(1) Ni: Co: M: M '=(1-x-y-z) in molar ratio: x: y: z preparation salting liquid A makes that concentration of metal ions is 0.5～2.5mol/L among the salting liquid A; Ni: Mn=1 in molar ratio: 1 preparation salting liquid B makes that concentration of metal ions is 0.5～2mol/L among the salting liquid B;
(2) be complexing agent with sodium hydroxide solution and ammoniacal liquor, said concentration of sodium hydroxide solution is 4～12mol/L, is 0.2～0.6 ammoniacal liquor to be joined in the sodium hydroxide solution according to ammonia and NaOH mol ratio;
(3) be that V1 salting liquid A and sodium hydroxide solution are continuously pumped in the agitated reactor that fills deionized water with volume; Solution constantly stirs in the agitated reactor; Fixedly the salting liquid flow velocity is 10.0～12.0 through pH value of solution value in the control sodium hydroxide solution flow velocity control agitated reactor;
(4) after salting liquid A pumps into and finishes, be that the salting liquid B of V2 is continuously pumped in the agitated reactor, feed nitrogen or argon gas simultaneously continuously and protect that after salting liquid B pumps into and finishes, continue to stir 2h～6h, wherein the volume V2 computing formula of solution B is following with volume:
V 2 = w × V 1 × ρ A ( 1 - w ) × ρ B
In the formula: ρ ABe the total mol concentration of metal ion in the solution A, mol/L
ρ BBe the total mol concentration of metal ion in the solution B, mol/L
(5) stop to stir, solution is carried out Separation of Solid and Liquid, it is 8～9 that isolated solid uses the pH value of 20 ℃～60 ℃ deionized water wash to washings;
(6) solidliquid mixture after will washing carries out Separation of Solid and Liquid, and isolated solid obtains (Ni 80 ℃～150 ℃ oven dry down 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w(OH) 2Powder;
(7) with (Ni 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w(OH) 2Powder and lithium salts are according to the mixed of Li/Me=1.0～1.2, wherein Me=Ni+Co+M+M ';
(8) mixture of step (7) is put into kiln, under 600 ℃～1000 ℃, roasting 6h～12h obtains coarse fodder in the air or oxygen atmosphere, and said coarse fodder obtains Li ((Ni after pulverizing 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2Powder;
3) the Li ((Ni that step 1) is made 1-x-y-zCo xM yM ' z) 1-w(Ni 0.5Mn 0.5) w) O 2Powder and LiCoO 2, after property-modifying additive mixes in proportion,, obtain the mixed type anode material at 500 ℃～1000 ℃ heat treatment 4～8h.
4. preparation method according to claim 3 is characterized in that: said cobalt salt is one or more the mixture in oxide, hydroxide, cobalt acetate and the cobalt carbonate of cobalt.
5. preparation method according to claim 3 is characterized in that: said lithium salts is one or more the mixture in lithium carbonate, lithium hydroxide, lithium nitrate and the lithium acetate.
6. preparation method according to claim 3 is characterized in that: the rotating speed of stirring motor is 100～500rpm in the step (3).
CN2012100939561A 2012-03-29 2012-03-29 Mixed type anode material for lithium ion battery and preparing method of mixed type anode material Pending CN102610811A (en)

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YANG-KOOK SUN,ET AL: "Synthesis of Spherical Nano- to Microscale Core-Shell Particles Li[(Ni0.8Co0.1Mn0.1)1-x(Ni0.5Mn0.5)x]O2 and Their Applications to Lithium Batteries", 《CHEM.MATER.》, vol. 509, no. 30, 21 September 2006 (2006-09-21), pages 7985 - 7992 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103490051A (en) * 2013-09-18 2014-01-01 成都晶元新材料技术有限公司 Multi-element anode lithium battery material suitable for high voltage and preparation method for material
CN103490051B (en) * 2013-09-18 2015-10-28 成都晶元新材料技术有限公司 One is applicable to high-tension multielement cathode lithium electric material and preparation method thereof
EP4063328A1 (en) * 2021-03-25 2022-09-28 SK On Co., Ltd. Cathode active material for lithium secondary battery and lithium secondary battery including the same

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