CN102110808B - Method for preparing high-performance spherical lithium ion secondary battery cathode material - Google Patents
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- CN102110808B CN102110808B CN2009102600381A CN200910260038A CN102110808B CN 102110808 B CN102110808 B CN 102110808B CN 2009102600381 A CN2009102600381 A CN 2009102600381A CN 200910260038 A CN200910260038 A CN 200910260038A CN 102110808 B CN102110808 B CN 102110808B
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Abstract
The invention provides a method for preparing a high-performance spherical lithium ion secondary battery cathode material. The method comprises the steps of synthesizing a NiaCobMn1-a-b(OH)2 precursor through adopting a coprecipitation-crystallization method, coating NicCodMn1-c-d(OH)2NieCofMn1-e-f(oh)2 composite layer on the surface of the precursor through adopting a chemical method, and then fully mixing with lithium salt to prepare a high-performance spherical lithium ion secondary battery cathode material LiNiaCobMn1-a-bO2(LiNicCobMn1)-c-dO2LiNieCofMn1-e-fO2) through stepwise sintering. The cathode material prepared by adopting the method has high density, good activity, and accurate stoichiometric proportion. Malignant interaction between the cathode material and an electrolyte is avoided, capacity decrease caused by non- electrochemical active substances is prevented, and the circulating life of materials is prolonged. The method is easy to control, has a low manufacturing cost, and is convenient for mass production, so as to create conditions for the development of high-capacity lithium ion batteries.
Description
Technical field
The utility model relates to the lithium battery production technology, particularly a kind of preparation method of high performance spherical lithium ion secondary battery cathode material.
Background technology
Energy crisis and environmental pollution be facing mankind sternly complete challenge, seeking clean, reproducible secondary energy sources is needing to be resolved hurrily of the tasks that realize human social.Lithium ion battery has that operating voltage is high in the middle of numerous secondary cell systems, energy density is large, have extended cycle life, the advantages such as self-discharge rate is little, environmental protection, becomes the main trend of secondary cell development.The cathode material of present commercial lithium ion battery has cobalt acid lithium (LiCoO
2), the LiMn2O4 (LiMn of spinel structure
2O
4), ternary material LiNi
ACo
BMn
1-A-BO
2, olivine-type LiFePO4 (LiFePO
4).
LiCoO
2Be the high-lithium ion battery cathode material of commercialization degree at present commonly used, preparation technology is very ripe, better performances.But because of its natural resources shortage, expensive, limited simultaneously the extensive use of cobalt acid lithium as the poor stability of electrokinetic cell etc.The synthetic of lithium transition-metal oxide take nickel (Ni), cobalt (Co), manganese (Mn) and other transition elements as component has been the development trend of current lithium electricity positive electrode at present, and small-scale has begun commercialization production.The ternary material of selling in the market mainly contains two kinds of models: low-nickel type LiNi
cCo
dMn
1-c-dO
2(0≤c≤0.6) and nickelic type LiNi
aCo
bMn
1-a-bO
2(0.6≤u≤1).LiNi wherein
cCo
dMn
1-c-dO
2(0≤c≤0.6) specification capacity is low, and security performance is good, and high-rate discharge ability is outstanding, has extended cycle life, and is applicable to power tool; LiNi
aCo
bMn
1-a-bO
2(0.6≤a≤1) specification capacity is higher, is applicable to various small-sized movable power supplys, as LiCoO
2Substitution material good application prospect is arranged, but its security performance and cycle life are relatively poor, discharge platform is lower, and easily and electrolyte generation deteriorative reaction, causes the battery performance variation.
Summary of the invention
The object of the present invention is to provide a kind of improvement LiNi
aCo
bMn
1-a-bO
2(0.5≤a≤1) security performance and cycle life improves discharge platform, avoids the preparation method with the high performance spherical lithium ion secondary battery cathode material of electrolyte generation deteriorative reaction.
The preparation method of the high performance spherical lithium ion secondary battery cathode material of the present invention is as follows:
At first by synthesizing Ni by co-precipitation-crystallisation
aCo
bMn
1-a-b(OH)
2(0.6≤a≤1) spherical precursor, and then coat Ni by chemical method on its surface
cCo
dMn
1-c-d(OH)
2Ni
eCo
fMn
1-e-f(OH)
2The composite bed of (0.1≤c≤0.6,0≤e≤0.5) fully mixes with lithium salts at last again, prepares spherical lithium ion secondary battery cathode material LiNi by step sintering
aCobMn
1-a-bO
2(LiNi
cCo
dMn
1-c-dO
2LiNi
eCo
fMn
1-e-fO
2).
1, the preparation of presoma:
The spherical presoma Ni of lithium rechargeable battery cathode material
aCo
bMn
1-a-b(OH)
2The preparation method, adopt the soluble-salt contain transition elements Ni, Co, Mn to make raw material, add deionized water, according to n
Ni: n
Co: n
Mn=a: b: 1-a-b is mixed with the mixing salt solution A that concentration is 1-3mol/L, then adds appropriate complexing agent and precipitation reagent to carry out co-precipitation.The soluble-salt of transition elements comprises sulfate and chlorate mixed aqueous solution.Take the ammoniacal liquor of 1-15mol/L as complexing agent, the NaOH of 1-10mol/L or KOH are precipitation reagent, controlling its flow velocity mixes with the solubility mixing salt solution A of transition elements and adds in reactor, the temperature of controlling in reaction system is 10-100 ℃, the pH value is 7.5-13.5, the reactor rotating speed is 40-500r/min, after reaction 2-10h, can obtain uniform spherical presoma Ni after washing, filtration (filter cloth order number is the 200-800 order), drying in reactor
aCo
bMn
1-a-b(OH)
2Wherein the flow of solubility mixing salt solution A, complexing agent, precipitation reagent is respectively 0.001-20L/min, 0.001-10L/min and 0.005-15L/min.
2, the coating of presoma:
With the spherical presoma Ni that obtains
aCo
bMn
1-a-b(OH)
2Pour in reactor, then add its quality 1-10 deionized water doubly, make mother liquor B; The soluble-salt that contains transition elements Ni, Co, Mn is made raw material, adds deionized water, according to n
c: n
d: n
1-c-dIt is the mixing salt solution C of 0.1-3mol/L and according to n that=c: d: 1-c-d is mixed with concentration
e: n
f: n
1-e-f=e: f: 1-e-f is mixed with the mixing salt solution D that concentration is 0.1-3mol/L.At first mixing salt solution C is added in reactor by the flow velocity of 0.001-20L/min; The ammoniacal liquor of 0.5-15mol/L is complexing agent simultaneously, 0.5-10mol/L NaOH or KOH be precipitation reagent, add in reactor according to 0.001-10L/min and 0.005-15L/min flow velocity respectively, the temperature of controlling in reaction system is 30-100 ℃, the pH value is 7-14, the reactor rotating speed is 20-1000r/min, reacts 2-10h in reactor, then mixing salt solution D is added in reactor by the flow velocity of 0.001-20L/min; The ammoniacal liquor of 0.5-15mol/L is complexing agent simultaneously, 0.5-10mol/L NaOH or KOH be precipitation reagent, add in reactor according to 0.001-10L/min and 0.005-15L/min flow velocity respectively, the temperature of controlling in reaction system is 40-100 ℃, the pH value is 7-14, the reactor rotating speed is 20-1000r/min, reacts 2-10h in reactor, obtains the surface and coat Ni after washing, filtration (filter cloth order number is the 200-800 order), drying
cCo
dMn
1-c-d(OH)
2Ni
eCo
fMn
1-e-f(OH)
2The spherical precursor Ni of composite bed
aCo
bMn
1-a-b(OH)
2Wherein in mother liquor B in the amount of solute substance and mixing salt solution C, mixing salt solution D the mol ratio of the amount of solute substance at 45: 30: 25-90: between 7.5: 2.5.
3, cathode material is synthetic:
Coat Ni with the surface
cCo
dMn
1-c-d(OH)
2Ni
eCo
fMn
1-e-f(OH)
2The spherical precursor Ni of composite bed
aCo
bMn
1-a-b(OH)
2Be raw material, with Li source compound n in molar ratio
Li: (n
Ni: n
Co: n
Mn)=0.9-1.20: 1 carry out batch mixing after, put into high temperature furnace, be under the Oxygen Condition of 1-40L/min at flow, at 450-1000 ℃ of sintering 4-20h, through cooling, rear spherical lithium ion secondary battery cathode material LiNi sieves
aCo
bMn
1-a-bO
2(LiNi
cCo
dMn
1-c-dO
2LiNi
eCo
fMn
1-e-fO
2).A kind of or the many persons mixture in Li source compound lithium carbonate, lithium hydroxide, lithium oxalate, lithium nitrate wherein.
Advantage of the present invention is:
1, the spherical hydroxide of high density type that adopts the present invention to make has density high, active good and can obtain stoichiometric proportion accurately.
2, by the composite bed in precursor surface coating different Ni contents, namely improve security performance and the cycle life of material, improve discharge platform, avoid the pernicious interaction of cathode product and electrolyte, reduce again the Co content in the material surface coating layer, reduced the cost of material.
3, by the reaction in oxygen atmosphere, can avoid being mingled with the lower valency ion of transition metal, reduced the transformation of material irreversible phase structure in charge and discharge process, make more homogeneous of its chemical composition.
4, the manufacture method of the present invention's proposition is easy to control, and production cost is low, easily accomplishes scale production, for condition has been created in the development of high capacity lithium ion battery.
Description of drawings
Fig. 1 is the SEM figure of presoma of preparation method embodiment 1 preparation of the high performance spherical lithium ion secondary battery cathode material of the present invention;
Fig. 2 is the cathode material XRD spectra of preparation method embodiment 1 preparation of the high performance spherical lithium ion secondary battery cathode material of the present invention;
Fig. 3 is the cathode material SEM figure of preparation method embodiment 1 index of the high performance spherical lithium ion secondary battery cathode material of the present invention;
Fig. 4 is the cathode material first charge-discharge curve of preparation method embodiment 1 preparation of the high performance spherical lithium ion secondary battery cathode material of the present invention.
Embodiment
For further setting forth the preparation method of the high performance spherical lithium ion secondary battery cathode material of the present invention, be described in more detail below in conjunction with embodiment.
Embodiment 1:
With synthetic chemistry formula LiNi
0.6Co
0.2Mn
0.2O
2(LiNi
0.5Co
0.25Mn
0.25O
2LiNi
0.4Co
0.3Mn
0.3O
2) be example, press Ni: Co: Mn=0.6: transition elements nickel, cobalt and the mn sulphate mixed solution of the mol ratio preparation 2mol/L of 0.2: 0.2, and the NaOH solution of 6mol/L ammonia solution and 4mol/L, inject respectively the reactor of 25L according to the flow velocity of 1L/min, 0.5L/min, 1.25L/min, keep reaction temperature at 65 ℃, the pH value is 10.0, after reacting 6h with the 400r/min. rotating speed in reactor, can obtain uniform spherical Ni after washing, filtration, drying
0.6Co
0.2Mn
0.2(OH)
2Presoma.And then it is added in the reactor of 50L, add in the deionized water of 4 times of quality; Press Ni: Co: Mn=0.5: the sulfate mixed solution of transition elements nickel, cobalt and the manganese of the mol ratio preparation 0.5mol/L of 0.25: 0.25, the total amount of substance of sulfate liquor solute is Ni
0.6Co
0.2Mn
0.2(OH)
240%, flow velocity with 1L/min adds in reactor, simultaneously with the NaOH solution of 6mol/L ammonia solution and 4mol/L, flow velocity according to 1L/min, 1.25L/min injects reactor respectively, keep reaction temperature at 85 ℃, the pH value is 11.0, after reacting 4h with the 350r/min. rotating speed in reactor; Press Ni: Co: Mn=0.4: the sulfate mixed solution of transition elements nickel, cobalt and the manganese of the mol ratio preparation 0.5mol/L of 0.3: 0.3, the total amount of substance of sulfate liquor solute is Ni again
0.6Co
0.2Mn
0.2(OH)
225%, flow velocity with 1L/min adds in reactor, simultaneously with the NaOH solution of 5mol/L ammonia solution and 4.5mol/L, flow velocity according to 1L/min, 1.25L/min injects reactor respectively, keep reaction temperature at 95 ℃, the pH value is 11.5, after reacting 4h with the 450r/min. rotating speed in reactor, after filtration, can obtain the surface after washing, drying and coat Ni
0.5Co
0.25Mn
0.25(OH)
2Ni
0.4Co
0.3Mn
0.3(OH)
2The spherical precursor Ni of composite bed
0.6Co
0.2Mn
0.2(OH)
2Its SEM figure sees Fig. 1.
According to n
LiOHH2O: the ratio of n (Ni+Co+Mn)=1.15: 1 takes corresponding LiOHH
2O and surface coat Ni
0.5Co
0.25Mn
0.25(OH)
2Ni
0.4Co
0.3Mn
0.3(OH)
2The spherical precursor Ni of composite bed
0.6Co
0.2Mn
0.2(OH)
2, mix.Mixed sample at 600-900 ℃ of sintering 10-15h, is passed into oxygen (flow velocity 1L/min), through cooling, can obtain lithium rechargeable battery cathode material LiNi after sieving
0.6Co
0.2Mn
0.2O
2(LiNi
0.5Co
0.25Mn
0.25O
2LiNi
0.4Co
0.3Mn
0.3O
2).Its XRD spectra is seen Fig. 2.
This positive electrode particle is spheric granules (its SEM figure sees Fig. 3).Then with it as cathode material for lithium ion battery, acetylene black is conductive agent, polytetrafluoroethylene is bonding agent, positive electrode, conductive agent and bonding agent weight ratio are 85: 10: 5, mix rear take aluminium foil as the collector smear, take metal lithium sheet as reference electrode, with 1.0mol/LiPF
6/ EC+DEC (1: 1Vol.) be electrolyte, be assembled into the simulation button cell in being full of the stainless steel glove box of argon gas.Then test this positive electrode 0.1C capacity and 0.5C cycle life, voltage range 4.25V-2.75V on LAND CT-2001A battery performance detector.Its first discharge capacity be 187mAh/g, lower 300 the circulation volume conservation rates of 0.5C are greater than 85%, its discharge curve is seen Fig. 4.
Embodiment 2
With synthetic chemistry formula LiNi
0.6Co
0.2Mn
0.2O
2(LiNi
0.4Co
0.3Mn
0.3O
2LiNi
0.33Co
0.33Mn
0.33O
2) be example, press Ni: Co: Mn=0.6: transition elements nickel, cobalt and the mn sulphate mixed solution of the mol ratio preparation 1.5mol/L of 0.2: 0.2, and the NaOH solution of 5mol/L ammonia solution and 4mol/L, inject respectively the reactor of 25L according to the flow velocity of 1L/min, 0.5L/min, 1.25L/min, keep reaction temperature at 65 ℃, the pH value is 10.0, after reacting 6h with the 400r/min. rotating speed in reactor, can obtain uniform spherical Ni after washing, filtration, drying
0.6Co
0.2Mn
0.2(OH)
2Presoma.And then it is added in the reactor of 50L, add in the deionized water of 4 times of quality; Press Ni: Co: Mn=0.4: the sulfate mixed solution of transition elements nickel, cobalt and the manganese of the mol ratio preparation 0.75mol/L of 0.3: 0.3, the total amount of substance of sulfate liquor solute is Ni
0.6Co
0.2Mn
0.2(OH)
240%, flow velocity with 1L/min adds in reactor, simultaneously with the NaOH solution of 5mol/L ammonia solution and 4mol/L, flow velocity according to 1L/min, 1.25L/min injects reactor respectively, keep reaction temperature at 80 ℃, the pH value is 11.5, after reacting 4h with the 450r/min. rotating speed in reactor; Press Ni: Co: Mn=0.33: the sulfate mixed solution of transition elements nickel, cobalt and the manganese of the mol ratio preparation 0.5mol/L of 0.33: 0.33, the total amount of substance of sulfate liquor solute is Ni again
0.6Co
0.2Mn
0.2(OH)
225%, flow velocity with 0.75L/min adds in reactor, simultaneously with the NaOH solution of 5mol/L ammonia solution and 4.5mol/L, flow velocity according to 1L/min, 1.25L/min injects reactor respectively, keep reaction temperature at 90 ℃, the pH value is 11.7, after reacting 4h with the 400r/min. rotating speed in reactor, after filtration, can obtain the surface after washing, drying and coat Ni
0.4Co
0.3Mn
0.3(OH)
2Ni
0.33Co
0.33Mn
0.33(OH)
2The spherical precursor Ni of composite bed
0.6Co
0.2Mn
0.2(OH)
2
According to n
LiOHH2O: the ratio of n (Ni+Co+Mn)=1.18: 1 takes corresponding LiOHH
2O and surface coat Ni
0.4Co
0.3Mn
0.3(OH)
2Ni
0.33Co
0.33Mn
0.33(OH)
2The spherical precursor Ni of composite bed
0.6Co
0.2Mn
0.2(OH)
2, mix.Mixed sample at 600-900 ℃ of sintering 8-15h, is passed into oxygen (flow velocity 1L/min), through cooling, can obtain lithium rechargeable battery cathode material LiNi after sieving
0.6Co
0.2Mn
0.2O
2(LiNi
0.4Co
0.3Mn
0.3O
2LiNi
0.33Co
0.33Mn
0.33O
2)
Take the described method of example 1 to test 0.1C capacity and the 0.5C cycle life of this positive electrode, its discharge capacity is that lower 400 the circulation volume conservation rates of 180mAh/g and 0.5C are greater than 85%.
Embodiment 3
With synthetic chemistry formula LiNi
0.7Co
0.15Mn
0.15O
2(LiNi
0.5Co
0.25Mn
0.25O
2LiNi
0.4Co
0.4Mn
0.4O
2) be example, press Ni: Co: Mn=0.7: transition elements nickel, cobalt and the mn sulphate mixed solution of the mol ratio preparation 2.5mol/L of 0.15: 0.15, and the NaOH solution of 7mol/L ammonia solution and 5mol/L, inject respectively the reactor of 50L according to the flow velocity of 1L/min, 0.5L/min, 1.25L/min, keep reaction temperature at 70 ℃, the pH value is 10.5, after reacting 6h with the 350r/min. rotating speed in reactor, can obtain uniform spherical Ni after washing, filtration, drying
0.7Co
0.15Mn
0.15(OH)
2Presoma.And then it is added in the reactor of 100L, add in the deionized water of 6 times of quality; Press Ni: Co: Mn=0.5: the sulfate mixed solution of transition elements nickel, cobalt and the manganese of the mol ratio preparation 1mol/L of 0.25: 0.25, the total amount of substance of sulfate liquor solute is Ni
0.6Co
0.2Mn
0.2(OH)
240%, flow velocity with 1L/min adds in reactor, simultaneously with the NaOH solution of 6mol/L ammonia solution and 4.5mol/L, flow velocity according to 1L/min, 1.25L/min injects reactor respectively, keep reaction temperature at 75 ℃, the pH value is 11.2, after reacting 4h with the 400r/min. rotating speed in reactor; Press Ni: Co: Mn=0.4: the sulfate mixed solution of transition elements nickel, cobalt and the manganese of the mol ratio preparation 0.75mol/L of 0.3: 0.3, the total amount of substance of sulfate liquor solute is Ni again
0.6Co
0.2Mn
0.2(OH)
225%, flow velocity with 0.75L/min adds in reactor, simultaneously with the NaOH solution of 5.5mol/L ammonia solution and 4mol/L, flow velocity according to 1L/min, 1.25L/min injects reactor respectively, keep reaction temperature at 110 ℃, the pH value is 11.5, after reacting 4h with the 450r/min. rotating speed in reactor, after filtration, can obtain the surface after washing, drying and coat Ni
0.5Co
0.25Mn
0.25(OH)
2Ni
0.4Co
0.4Mn
0.4(OH)
2The spherical precursor Ni of composite bed
0.7Co
0.15Mn
0.15(OH)
2
According to n
LiOHH2O: the ratio of n (Ni+Co+Mn)=1.20: 1 takes corresponding LiOHH
2O and surface coat Ni
0.5Co
0.25Mn
0.25(OH)
2Ni
0.4Co
0.3Mn
0.3(OH)
2The spherical precursor Ni of composite bed
0.7Co
0.15Mn
0.15(OH)
2, mix.Mixed sample at 600-900 ℃ of sintering 8-15h, is passed into oxygen (flow velocity 1.5L/min), through cooling, can obtain lithium rechargeable battery cathode material LiNi after sieving
0.7Co
0.15Mn
0.15O
2(LiNi
0.5Co
0.25Mn
0.25O
2LiNi
0.4Co
0.3Mn
0.3O
2)
Take the described method of example 1 to test 0.1C capacity and the 0.5C cycle life of this positive electrode, its discharge capacity is that lower 250 the circulation volume conservation rates of 193mAh/g and 0.5C are greater than 85%.
Claims (7)
1. the preparation method of a high performance spherical lithium ion secondary battery cathode material, it is characterized in that: described preparation method comprises:
1) by the synthetic Ni of co-precipitation-crystallisation
aCo
bMn
1-a-b(OH)
2Spherical presoma, wherein 0.6≤a≤1;
2) coat Ni by chemical method on its surface again
cCo
dMn
1-c-d(OH)
2Ni
eCo
fMn
1-e-f(OH)
2Composite bed, 0.1≤c≤0.6,0≤e≤0.5 wherein;
3) fully mix with lithium salts more at last, prepare spherical lithium ion secondary battery cathode material LiNi by step sintering
aCo
bMn
1-a-bO
2(LiNi
cCo
dMn
1-c-dO
2LiNi
eCo
fMn
1-e-fO
2).
2. the preparation method of high performance spherical lithium ion secondary battery cathode material according to claim 1, it is characterized in that: the preparation of the spherical presoma of described cathode material, be to adopt the soluble-salt that contains transition elements Ni, Co, Mn to make raw material, add deionized water, according to
Mol ration
Ni: n
co: n
Mn=a: b: 1-a-b is mixed with the mixing salt solution A that concentration is 1-3mol/L, and then adds appropriate complexing agent and precipitation reagent to carry out co-precipitation, filters, and washing can obtain Ni
aCo
bMn
1-a-b(OH)
2Spherical presoma, wherein 0.6≤a≤1.
3. the preparation method of high performance spherical lithium ion secondary battery cathode material according to claim 2, it is characterized in that: described soluble-salt is sulfate, chlorate, nitrate or its mixture.
4. the preparation method of high performance spherical lithium ion secondary battery cathode material according to claim 3, it is characterized in that: described complexing agent is concentration 1-15mol/L ammoniacal liquor, precipitation reagent is NaOH or the KOH of concentration 1-10mol/L, and wherein solubility mixing salt solution, complexing agent, the precipitation reagent flow that enters reactor is respectively 0.001-20mL/min, 0.001-10mL/min, 0.005-15mL/min; Reaction temperature is 10-100 ℃; The pH value is 7.5-13.5, and the reactor rotating speed is 40-500r/min, and the reaction time is 2-10h, and filter cloth order number is the 200-800 order.
5. the preparation method of high performance spherical lithium ion secondary battery cathode material according to claim 1, is characterized in that: the coating of the spherical presoma of described cathode material: the spherical presoma Ni that will obtain
aCo
bMn
1-a-b(OH)
2Pour in reactor, then add its quality 1-10 deionized water doubly, make mother liquor B; The soluble-salt that contains transition elements Ni, Co, Mn is made raw material, adds deionized water, according to mol ratio n
c: n
d: n
1-c-d=c: d: 1-c-d and n
e: n
f: n
1-e-f=e: f: 1-e-f all is mixed with mixing salt solution C and the D that concentration is 0.1-3mol/L; At first mixing salt solution C is joined in reactor by the flow velocity of 0.001-20L/min, the ammoniacal liquor of 0.5-15mol/L is complexing agent simultaneously, 0.5-10mol/L NaOH or KOH be precipitation reagent, flow velocity according to 0.001-10L/min and 0.005-15L/min adds in reactor respectively, the temperature of controlling in reaction system is 30-100 ℃, the pH value is 7-14, and the reactor rotating speed is 20-1000r/min, at reaction kettle for reaction 2-10h; Again mixing salt solution D is joined in reactor by the flow velocity of 0.001-20L/min, the ammoniacal liquor of 0.5-15mol/L is complexing agent simultaneously, 0.5-10mol/L NaOH or KOH be precipitation reagent, flow velocity according to 0.001-10L/min and 0.005-15L/min adds in reactor respectively, the temperature of controlling in reaction system is 40-100 ℃, and the pH value is 7-14, and the reactor rotating speed is 20-1000r/min, at reaction kettle for reaction 2-10h, obtain the surface and coat Ni after washing, filtration and drying
cCo
dMn
1-c-d(OH)
2Ni
eCo
fMn
1-e-f(OH)
2The presoma Ni of composite bed
aCo
bMn
1-a-b(OH)
2Wherein filter cloth order number is the 200-800 order, and in mother liquor B, mixing salt solution C and D, the mol ratio of the amount of solute substance is between (40: 30: 30)-(95: 2.5: 2.5).
6. the preparation method of high performance spherical lithium ion secondary battery cathode material according to claim 1 is characterized in that: described cathode material synthetic: coat Ni with the surface
cCo
dMn
1-c-d(OH)
2Ni
eCo
fMn
1-e-f(OH)
2The spherical presoma Ni of composite bed
aCo
bMn
1-a-b(OH)
2Be raw material, with Li source compound nLi: n (Ni+Co+Mn)=(0.9-1.20) in molar ratio: 1 carry out batch mixing after, put into high temperature furnace, be under the Oxygen Condition of 1-40L/min at flow, at 450-1000 ℃ of sintering 4-20h, through cooling, can obtain spherical lithium ion secondary battery cathode material LiNi after sieving
aCo
bMn
1-a-bO
2(LiNi
cCo
dMn
1-c-dO
2LiNi
eCo
fMn
1-e-fO
2).
7. the preparation method of high performance spherical lithium ion secondary battery cathode material according to claim 6, it is characterized in that: described Li source compound is a kind of or many persons mixture in lithium carbonate, lithium hydroxide, lithium oxalate and lithium nitrate.
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| CN2009102600381A CN102110808B (en) | 2009-12-23 | 2009-12-23 | Method for preparing high-performance spherical lithium ion secondary battery cathode material |
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| CN102110808B true CN102110808B (en) | 2013-06-12 |
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