CN105406056A - Long-cycle and high-safety power lithium ion battery positive electrode material and preparation method thereof - Google Patents

Long-cycle and high-safety power lithium ion battery positive electrode material and preparation method thereof Download PDF

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Publication number
CN105406056A
CN105406056A CN201511015572.8A CN201511015572A CN105406056A CN 105406056 A CN105406056 A CN 105406056A CN 201511015572 A CN201511015572 A CN 201511015572A CN 105406056 A CN105406056 A CN 105406056A
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ion battery
lithium
anode material
preparation
battery anode
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杨邦成
唐泽勋
商士波
常敬杭
刘洪金
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HUNAN SOUNDDON NEW ENERGY CO Ltd
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HUNAN SOUNDDON NEW ENERGY CO Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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 long- cycle and high-safety power lithium ion battery positive electrode material and a preparation method thereof. The positive electrode material can be shown as a general formula LiNi<(1-a-b-c)>Co<a>Mn<b>M<c>O2.xLiM<1>O<y>, wherein a is greater than 0 and less than 1, b is greater than 0 and less than 1, a+b+c is greater than 0 and less tan 1, x is greater than 0 and less than 0.1, and y is greater than 1 and less than 5; LiNi<(1-a-b-c)>Co<a>Mn<b>M<c>O2 is a primary active crystalline particle of the positive electrode material, and is a lithiated composite oxide composed of nickel cobalt manganese and doping element M; and the LiM<1>O<y> is a coating layer coating crystal boundary of the primary active crystalline particle and surface of a polycrystalline secondary particle. The positive electrode material provided by the invention has high stability of crystalline main body, surface and crystal boundary, has good compatibility with electrolyte and is not liable to generate side reaction. The material provided by the invention is used for batteries, has long cycle life, high over-charging resisting capability, good high temperature and high voltage performance and high integral safety, and is particularly suitable for power batteries.

Description

Power type lithium-ion battery anode material of the high safety of long circulating and preparation method thereof
Technical field
The invention belongs to cathode material for lithium ion battery field, more specifically relate to power type lithium-ion battery anode material of the high safety of long circulating and preparation method thereof.
Background technology
The emerging strategic industry that new-energy automobile develops as state key, has entered the fast-developing nurturing period, has instantly solved the course continuation mileage of battery, safety and cycle life very urgent.Existing power battery anode material has LiFePO4, spinel lithium manganate, cobalt nickel lithium manganate ternary material, because the theoretical gram volume of LiFePO4 (169.9mAh/g) and LiMn2O4 (148.2mAh/g) is low, growing continuation of the journey requirement can not be met, can be replaced by the cobalt nickel lithium manganate ternary material of high gram volume (276.8mAh/g) gradually, and ternary material will obtain the approval of consumer comprehensively, the short slab that fail safe is low, cycle life is poor just must be overcome.
Cobalt nickel lithium manganate ternary material is stratiform hexagonal closs packing structure, belong to R3m space group, transition metal occupies 3a position, lithium accounts for 3b position, oxygen accounts for 6c position, when de-lithium amount is greater than 50%, structure becomes very fragile, in lattice, active metal and oxygen are subjected to displacement, reach certain high temperature high voltage, atomic rearrangement again structure progressively aggravates, there is larger change mutually in crystal particle volume and thing, on the other hand, chemistry and electrochemical action is there is with electrolyte, cause the easy deoxidation of material, transition metal dissolution, a series of side reactions such as electrolyte generation decomposition and aggregation, the conduction resistance of lithium ion and electronics is increased, interfacial electrochemistry conversion reaction weakens, and carry out with discharge and recharge, caloric value increases, structure is, usually, thermically destroyed further, the composition and structure at interface is changed further.
In order to rock-steady structure improving SNR, domestic and international researcher finds, apply the performance that bulk phase-doped replacement and Surface coating can promote material, as the positive electrode that patent ZL201110222403.7 uses solid phase method adulterated al to prepare, high-temperature lithium ion battery security performance and cycle characteristics can be improved, but solid phase method doping, batch mixing is difficult to evenly, solid-state diffusion speed is slow, and product exists larger difference in structure, composition etc., thus causes its chemical property not good enough.
Existing method for coating has two kinds, one is at presoma second particle Surface coating, two is sintering the second particle Surface coating of lithium-transition metal composite oxide into, all at second particle Surface coating, and it is coated uneven, but more it is worth noting, in electrochemical reaction, along with de-lithium amount increases, particularly under high temperature high voltage, the lithium salts of solvent and solvation is easy in the room structure cell after diffusing into de-lithium, make the lattice solvation of positive electrode, special more at dangling bonds, defect is more, the low crystal boundary face of degree of crystallinity is more easily by electrolyte permeability, simultaneously in film-making nipping process, the fragile easy crushed cracking of crystal boundary, expose highly active primary particle surface, circulation time, be out of shape with lattice reciprocal telescopic, produce stress, cause second particle obvious in the efflorescence of grain boundaries cracking, all aggravate the side reaction of electrolyte and active material, therefore except polycrystalline second particle surface, once intercrystalline crystal boundary is also very weak place, has a strong impact on circulation and the security performance of material.
summary of the invention:
For solving the problem, make nickel-cobalt-manganese ternary material as power type lithium-ion battery anode material, large-scale application is in new-energy automobile, power type lithium-ion battery anode material of the high safety of the long circulating that the present invention proposes and preparation method thereof, this positive electrode is modified the crystal boundary of once active crystal grain and polycrystalline second particle surface by inertia coating layer, the side reaction of electrolyte and storeroom can be reduced, strengthen anti-roll-in cracking ability, second particle cracking efflorescence after preventing from circulating, and then, improve high temperature, high voltage capability, strengthen overcharging resisting ability, extend cycle life, further raising fail safe.
Above-mentioned purpose of the present invention is achieved by the following technical solution:
The power type lithium-ion battery anode material of the high safety of a kind of long circulating, the presoma of this positive electrode is a kind of aggregate, this aggregate is formed by the spray-dried accumulation of the primary particle that inert layer predecessor is coated, through high temperature sintering after being mixed with certain proportion with lithium salts by this presoma, the polycrystalline second particle positive electrode crystal boundary of once active crystal grain and polycrystalline second particle surface modified by inertia coating layer can be obtained; The general formula of this positive electrode is LiNi (1-a-b-c)co amn bm co 2.xLiM 1oy, wherein 0<a<1,0<b<1,0<c<1,0<a+b+c<1,0<x<0.1,1<y<5, M cand M 1be one or more metallic element, more preferably, M is one or more in magnesium, aluminium, titanium, zinc, iron, chromium; M 1for one or more in gallium, indium, molybdenum, tungsten, zirconium, yttrium, aluminium, niobium, lanthanum, cerium, barium, calcium.
Further, described inert layer predecessor, for comprising M 1hydroxide or oxyhydroxide.
Further, described once active crystal grain, be the lithiumation composite oxides of nickel cobalt manganese and doped chemical M, molecular formula can use general formula LiNi (1-a-b-c)co amn bm co 2represent, wherein 0<a<1,0<b<1,0<c<1,0<a+b+c<1, M are one or more in magnesium, aluminium, titanium, zinc, iron, chromium.
Further, described inertia coating layer, for comprising M 1lithiated oxide, molecular formula can use general formula xLiM 1oy represents, wherein 0<x<0.1,1<y<5, M 1for one or more in gallium, indium, molybdenum, tungsten, zirconium, yttrium, aluminium, niobium, lanthanum, cerium, barium, calcium.
The preparation method of the high safe power type lithium-ion battery anode material of above-mentioned long circulating, comprises the steps:
(1) preparation of transition metal mixed liquor
Soluble nickel salt, cobalt salt, manganese salt, M salt are dissolved in deionized water, add dispersant, be mixed with the transition metal mixed liquor that nickel cobalt manganese total concentration is 1.5-4.5mol/L, dispersant concentration is 0.1-0.5mol/L, described soluble nickel salt, cobalt salt, manganese salt and M salt are the one in the nitrate of nickel, cobalt, manganese and M, sulfate, formates, hydrochloride, acetate and citrate, and described dispersant is carboxymethyl cellulose, soluble starch, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, soluble chitosan;
The preparation of (2) two kinds of variable concentrations alkali lye
Compound concentration is the high alkali liquid of 2-8mol/L and concentration is the sig water of 0.2-1mol/L, and described alkali is one or more in NaOH, potassium hydroxide, lithium hydroxide, ammoniacal liquor, sodium carbonate;
(3) preparation of coating layer solution
Compound concentration is the coating layer solution of 0.1-1mol/L, described coating be gallium, indium, molybdenum, tungsten, zirconium, yttrium, aluminium, niobium, lanthanum, cerium, barium, the nitrate of calcium, sulfate, hydrochloride one or more;
(4) precursor synthesis
Add in reactor by transition metal mixed liquor in step (1) and step (2) while high alkali liquid, carry out precipitation reaction, dropwise, after continuing stirring 0.5 ~ 2h, precipitation obtains the primary particle of good dispersion; Then add coating layer solution, drip rear continuation stirring 5 ~ 20min, add the sig water in step (2), continue to stir certain hour, filter, washing, gets upper strata filter cake, join in stirred tank with deionized water, dispersed with stirring filter cake, obtains the dispersion liquid of filter cake, then adopts press atomization granulating and drying machine, carry out spraying dry, obtain spherical precursor particle;
(5) sample synthesis
Step (4) gained spherical precursor particle is mixed with lithium salts, puts into pushed bat kiln, pass into atmosphere, sinter, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain power type lithium-ion battery anode material.
Further, in described step (4), the temperature of precipitation reaction is 45-90 DEG C.
Further, in step (4), the pH that transition metal mixed liquor and high alkali liquid react is 10.2-11.8.
Further, in step (4), it is 11.6-12.5 that sig water joins the pH reacted in coating layer solution.
Further, in step (4), the weight ratio of deionized water and upper strata filter cake is 0.5-5.
Further, in step (4), the condition of described press atomization granulating and drying is: the liquid-drop diameter of press atomization is at 500-1000 μm, and pressure is 0.2-3MPa, and hot air temperature is 250-400 DEG C.
Further, in step (4), spherical precursor particle D50 is 7-16um.
Further, in step (5), described lithium salts is one or more in lithium acetate, lithium carbonate, lithium nitrate, lithium hydroxide, lithia.
Further, in step (5), described atmosphere is the one in air, oxygen.
Further, in step (5), sintering temperature is 700-1200 DEG C.
beneficial effect of the present invention is:
(1) the present invention is coated by carrying out inert layer on primary particle surface, be to once active crystal grain is coated, also be carry out coated to the polycrystalline second particle product of spraying accumulation balling-up presoma and lithium salts sintering, namely only with once coated just reaching, the crystal boundary of once active crystal grain and polycrystalline second particle surface are modified, not only reduce prior art in the coated operation of sintering finished rear needs, and under dispersant effect precipitation and coated, make nickel cobalt manganese and doped chemical M dispersed deposition evenly, coating layer element uniform deposition is on surface, ensure the consistency of modified effect and production well, improve processing characteristics.
(2) the inertia coating layer not having electro-chemical activity prepared by the present invention is applied, have the effect that crystal boundary and the polycrystalline second particle surface of once active crystal grain are modified concurrently, overcome the defect that existing technique is only coated on second particle, the side reaction of electrolyte and storeroom can be reduced, strengthen anti-roll-in cracking ability, second particle cracking efflorescence after preventing from circulating, and then improve high temperature, high voltage capability, strengthen overcharging resisting ability, extend cycle life, greatly improve fail safe, the instructions for use that electrokinetic cell is harsh can be adapted to.Presoma prepared by simultaneously the present invention, by spraying dry balling-up, does not use ammoniacal liquor, reduces the pollution of injury to human body and environment.
(3) positive electrode of the present invention is as power-type lithium ion battery material, has extended cycle life, and security performance is high, is applied to electric motor car, electric bicycle, has better effect.
Accompanying drawing explanation
Fig. 1 is synthesis technique FB(flow block) of the present invention.Fig. 2 is the spherical precursor Electronic Speculum figure of embodiment 1 gained.
Fig. 3 is the Electronic Speculum figure of the power type lithium-ion battery anode material of embodiment 1 gained.
Embodiment
Be below that Application Example is described in detail to thought of the present invention, and protection scope of the present invention is not only confined to following examples.Described those skilled in the art, according to above content disclosed by the invention and scope that each parameter is got, all can realize object of the present invention.
Embodiment 1
Be the nickelous sulfate of 4.97:2:3:0.03 by Ni:Co:Mn:Mg mol ratio, cobaltous sulfate, manganese sulfate, magnesium sulfate is mixed with the mixed liquor 1.2m that total concentration is 2mol/L 3, and polyacrylamide is added in mixed liquor, its concentration is made to be 0.2mol/L, the NaOH solution being 4mol/L by mixed liquor and concentration is added dropwise in reactor simultaneously, reactor rotating speed is 500rmp, temperature 50 C, PH is 11.5, dropwise, after continuing to stir 1h, dropwise add the Y2(SO4 that 4.8L concentration is 0.25mol/L) 3 solution, drip rear continuation and stir 10min, drip the NaOH solution that concentration is 0.5mol/L again, until PH stops after 11.8 dripping, continue to stir 30min, then filter, wash 3 times, get upper strata filter cake, filter cake is disperseed for 1:1 adds in stirred tank with deionized water and filter cake weight ratio, obtain the dispersion liquid of filter cake, then spraying dry, obtain the spherical precursor particle that D50 is 10-13um.
Inclined mixer mixing 5h put into by the lithium carbonate taking 100kg presoma and 42.7kg, the compound mixed is put into pusher furnace, pass into oxygen, after 700 DEG C of sintering 5h, be warmed up to 970 DEG C of sintering 9h, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain the sample of modification, be power type lithium-ion battery anode material of the present invention.
The D50=10.6um of gained sample, specific area 0.31m 2/ g, tap density is 2.35g/cm 3.
The test of assembling button cell.Be 92:4:4 by active material, Super-p, PVDF mass ratio, stir be mixed with slurry with appropriate NMP, on coating aluminium foil, vacuumize, punching, compressing tablet obtain positive plate, are metal lithium sheet to electrode, 1molL -1liPF6/EC(ethylene carbonate)+DMC(dimethyl carbonate)+EMC (methyl ethyl carbonate) (volume ratio 1:1:1) be electrolyte, use the 25um barrier film of Cangzhou jewel, be assembled into the button cell test of 2032, be also assembled into soft-package battery test simultaneously.
Embodiment 2
Be the nickelous sulfate of 7:1.5:1.45:0.05 by Ni:Co:Mn:Al mol ratio, cobaltous sulfate, manganese sulfate, aluminum sulfate is mixed with the mixed liquor 1.2m that total concentration is 2mol/L 3, and carboxymethyl cellulose is added in mixed liquor, its concentration is made to be 0.3mol/L, the NaOH solution being 4mol/L by mixed liquor and concentration is added dropwise in reactor simultaneously, reactor rotating speed is 500rmp, temperature 50 C, PH is 11.5, dropwise, after continuing to stir 1h, dropwise add the zirconyl nitrate solution that 4.5L concentration is 0.3mol/L, drip rear continuation and stir 10min, drip the NaOH solution that concentration is 0.5mol/L again, until PH stops after 11.9 dripping, continue to stir 30min, then filter, wash 3 times, get upper strata filter cake, filter cake is disperseed for 2.5:1 adds in stirred tank with deionized water and filter cake weight ratio, obtain the dispersion liquid of filter cake, then spraying dry, obtain the spherical precursor particle that D50 is 9-12um.
Inclined mixer mixing 5h put into by the lithium carbonate taking 100kg presoma and 43.5kg, the compound mixed is put into pusher furnace, pass into oxygen, after 500 DEG C of sintering 1.5h, be warmed up to 850 DEG C of sintering 12h, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain the sample of modification, be power type lithium-ion battery anode material of the present invention.
The D50=10.2um of gained sample, specific area 0.34m 2/ g, tap density is 2.39g/cm 3.
The test of assembling button cell.Be 92:4:4 by active material, super-p, PVDF mass ratio, stir be mixed with slurry with appropriate NMP, on coating aluminium foil, vacuumize, punching, compressing tablet obtain positive plate, are metal lithium sheet to electrode, 1molL -1liPF6/EC(ethylene carbonate)+DMC(dimethyl carbonate)+EMC (methyl ethyl carbonate) (volume ratio 1:1:1) be electrolyte, use the 25um barrier film of Cangzhou jewel, be assembled into the button cell test of 2032, be also assembled into soft-package battery test simultaneously.
Embodiment 3
Be the nickel nitrate of 8:1:0.92:0.08 by Ni:Co:Mn:Ti mol ratio, cobalt nitrate, manganese nitrate, titanium tetrachloride be mixed with the mixed liquor 1.5m that total concentration is 2.5mol/L 3, and polyethylene glycol is added in mixed liquor, its concentration is made to be 0.3mol/L, the KOH solution being 6mol/L by mixed liquor and concentration is added dropwise in reactor simultaneously, reactor rotating speed is 600rmp, temperature 65 DEG C, PH is 11.3, dropwise, after continuing to stir 1h, dropwise add Ce (NO3) the 36H2O solution that 5L concentration is 0.28mol/L, drip rear continuation and stir 10min, drip the NaOH solution that concentration is 0.6mol/L again, until PH stops after 12.1 dripping, continue to stir 30min, then filter, wash 3 times, get upper strata filter cake, filter cake is disperseed for 3:1 adds in stirred tank with deionized water and filter cake weight ratio, obtain the dispersion liquid of filter cake, then spraying dry, obtain the spherical precursor particle that D50 is 11-15um.
The lithium hydroxide taking 120kg presoma and 57.2kg puts into inclined mixer mixing 5h, the compound mixed is put into pusher furnace, pass into air, after 600 DEG C of sintering 2h, be warmed up to 930 DEG C of sintering 10h, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain the sample of modification, be the high safe power type lithium-ion battery anode material of long circulating of the present invention.
The D50=11.3um of gained sample, specific area 0.29m 2/ g, tap density is 2.43g/cm 3.
The test of assembling button cell.Be 92:4:4 by active material, super-p, PVDF mass ratio, stir be mixed with slurry with appropriate NMP, on coating aluminium foil, vacuumize, punching, compressing tablet obtain positive plate, are metal lithium sheet to electrode, 1molL -1liPF6/EC(ethylene carbonate)+DMC(dimethyl carbonate)+EMC (methyl ethyl carbonate) (volume ratio 1:1:1) be electrolyte, use the 25um barrier film of Cangzhou jewel, be assembled into the button cell test of 2032, be also assembled into soft-package battery test simultaneously.
Comparative example 1
Be the nickelous sulfate of 4.97:2:3:0.03 by Ni:Co:Mn:Mg mol ratio, cobaltous sulfate, manganese sulfate, magnesium sulfate is mixed with the mixed liquor 1.2m that total concentration is 2mol/L 3, and in mixed liquor, add the polyacrylamide of 0.2mol/L, the NaOH solution being 4mol/L with concentration is added dropwise in reactor simultaneously, reactor rotating speed is 500rmp, temperature 50 C, and PH is 11.5, dropwise, after continuing to stir 1h, filter, wash 3 times, get upper strata filter cake, disperse filter cake with deionized water and filter cake weight ratio for 1:1 adds in stirred tank, obtain the dispersion liquid of filter cake, then spraying dry, obtains the spherical precursor particle that D50 is 9-12um.
Inclined mixer mixing 5h put into by the lithium carbonate taking 100kg presoma and 42.7kg, the compound mixed is put into pusher furnace, pass into oxygen, after 700 DEG C of sintering 5h, be warmed up to 970 DEG C of sintering 9h, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain the sample of modification, be power type lithium-ion battery anode material of the present invention.
The D50=10.2um of gained sample, specific area 0.32m 2/ g, tap density is 2.31g/cm 3.
Sample sets is dressed up button cell and the soft-package battery test of 2032.
Comparative example 2
Be the nickelous sulfate of 7:1.5:1.45:0.05 by Ni:Co:Mn:Mg mol ratio, cobaltous sulfate, manganese sulfate, magnesium sulfate is mixed with the mixed liquor 1.2m that total concentration is 2mol/L 3, and in mixed liquor, add the carboxymethyl cellulose of 0.3mol/L, the NaOH solution being 4mol/L with concentration is added dropwise in reactor simultaneously, reactor rotating speed is 500rmp, temperature 50 C, and PH is 11.5, dropwise, after continuing to stir 1h, filter, wash 3 times, get upper strata filter cake, disperse filter cake with deionized water and filter cake weight ratio for 2.5:1 adds in stirred tank, obtain the dispersion liquid of filter cake, then spraying dry, obtains the spherical precursor particle that D50 is 8.8-11.5um.
Inclined mixer mixing 5h put into by the lithium carbonate taking 100kg presoma and 43.5kg, the compound mixed is put into pusher furnace, pass into oxygen, after 500 DEG C of sintering 1.5h, be warmed up to 850 DEG C of sintering 12h, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain the sample of modification, be power type lithium-ion battery anode material of the present invention.
The D50=9.5um of gained sample, specific area 0.36m 2/ g, tap density is 2.35g/cm 3.
Sample sets is dressed up button cell and the soft-package battery test of 2032.
Comparative example 3
Be the nickel nitrate of 8:1:0.92:0.08 by Ni:Co:Mn:Ti mol ratio, cobalt nitrate, manganese nitrate, titanium tetrachloride be mixed with the mixed liquor 1.5m that total concentration is 2.5mol/L 3, and in mixed liquor, add the polyethylene glycol of 0.35mol/L, the KOH solution being 6mol/L with concentration is added dropwise in reactor simultaneously, reactor rotating speed is 600rmp, temperature 65 DEG C, and PH is 11.3, dropwise, after continuing to stir 1h, filter, wash 3 times, get upper strata filter cake, disperse filter cake with deionized water and filter cake weight ratio for 3:1 adds in stirred tank, obtain the dispersion liquid of filter cake, then spraying dry, obtains the spherical precursor particle that D50 is 10-14.5um.
The lithium hydroxide taking 120kg presoma and 57.2kg puts into inclined mixer mixing 5h, the compound mixed is put into pusher furnace, pass into air, after 600 DEG C of sintering 2h, be warmed up to 930 DEG C of sintering 10h, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain the sample of modification, be power type lithium-ion battery anode material of the present invention.
The D50=10.9um of gained sample, specific area 0.32m 2/ g, tap density is 2.37g/cm 3.
Sample sets is dressed up button cell and the soft-package battery test of 2032.
Table 1 is safety and the high-temperature behavior of each enforcement and comparative example, Comparative result shows, by the coated once active crystal grain of inert layer, to the positive electrode that crystal boundary and the polycrystalline second particle surface of once active crystal grain are modified, overcharge, acupuncture, hot case all by test, high-temperature storage and high temperature circulation also improve a lot, therefore through the positive electrode of coating decoration, have extended cycle life, high temperature, high voltage, overcharging resisting performance be good, fail safe is high.
the safety of each enforcement of table 1 and comparative example and high-temperature behavior Comparative result

Claims (10)

1. the power type lithium-ion battery anode material of the high safety of long circulating, it is characterized in that, the presoma of this positive electrode is a kind of aggregate, this aggregate is formed by the spray-dried accumulation of the primary particle that inert layer predecessor is coated, through high temperature sintering after being mixed with certain proportion with lithium salts by this presoma, the polycrystalline second particle positive electrode crystal boundary of once active crystal grain and polycrystalline second particle surface modified by inertia coating layer can be obtained; The molecular formula of this positive electrode is LiNi (1-a-b-c)co amn bm co 2.xLiM 1oy, wherein 0<a<1,0<b<1,0<c<1,0<a+b+c<1,0<x<0.1,1<y<5, M cor M 1it is one or more metallic element.
2. the power type lithium-ion battery anode material of the high safety of long circulating according to claim 1, it is characterized in that, described inert layer predecessor comprises M 1hydroxide or oxyhydroxide.
3. the power type lithium-ion battery anode material of the high safety of long circulating according to claim 1, it is characterized in that, described once active crystal grain is the lithiumation composite oxides of nickel cobalt manganese and doped chemical M, and general formula is LiNi (1-a-b-c)co amn bm co 2wherein 0<a<1,0<b<1,0<c<1,0<a+b+c<1, M are one or more in magnesium, aluminium, titanium, zinc, iron, chromium.
4. the power type lithium-ion battery anode material of the high safety of long circulating according to claim 1, it is characterized in that, described inertia coating layer comprises M 1lithiated oxide, general formula is xLiM 1oy, wherein 0<x<0.1,1<y<5, M 1for one or more in gallium, indium, molybdenum, tungsten, zirconium, yttrium, aluminium, niobium, lanthanum, cerium, barium, calcium.
5. the preparation method of the power type lithium-ion battery anode material of the high safety of the long circulating described in any one of Claims 1-4, is characterized in that, comprise the steps:
(1) preparation of transition metal mixed liquor
Soluble nickel salt, cobalt salt, manganese salt, M salt are dissolved in deionized water, add dispersant, be mixed with the transition metal mixed liquor that nickel cobalt manganese total concentration is 1.5-4.5mol/L, dispersant concentration is 0.1-0.5mol/L, described soluble nickel salt, cobalt salt, manganese salt and M salt are the one in the nitrate of nickel, cobalt, manganese and M, sulfate, formates, hydrochloride, acetate and citrate, and described dispersant is carboxymethyl cellulose, soluble starch, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, soluble chitosan;
The preparation of (2) two kinds of variable concentrations alkali lye
Compound concentration is the high alkali liquid of 2-8mol/L and concentration is the sig water of 0.2-1mol/L, and described alkali is one or more in NaOH, potassium hydroxide, lithium hydroxide, ammoniacal liquor, sodium carbonate;
(3) preparation of coating layer solution
Compound concentration is the coating layer solution of 0.1-1mol/L, described coating be gallium, indium, molybdenum, tungsten, zirconium, yttrium, aluminium, niobium, lanthanum, cerium, barium, the nitrate of calcium, sulfate, hydrochloride one or more;
(4) precursor synthesis
Add in reactor by transition metal mixed liquor in step (1) and step (2) while high alkali liquid, carry out precipitation reaction, dropwise, after continuing stirring 0.5 ~ 2h, precipitation obtains the primary particle of good dispersion; Then add coating layer solution, drip rear continuation stirring 5 ~ 20min, add the sig water in step (2), continue to stir certain hour, filter, washing, gets upper strata filter cake, join in stirred tank with deionized water, dispersed with stirring filter cake, obtains the dispersion liquid of filter cake, then adopts press atomization granulating and drying machine, carry out spraying dry, obtain spherical precursor particle;
(5) sample synthesis
Step (4) gained spherical precursor particle is mixed with lithium salts, puts into pushed bat kiln, pass into atmosphere, sinter, cooling down, break pair roller through Hubei Province, after crushing and classification, obtain power type lithium-ion battery anode material.
6. the preparation method of power type lithium-ion battery anode material according to claim 5, it is characterized in that, in described step (4), the temperature of precipitation reaction is 45-90 DEG C, the pH that transition metal mixed liquor and high alkali liquid react is 10.2-11.8, and it is 11.6-12.5 that sig water joins the pH reacted in coating layer solution.
7. the preparation method of power type lithium-ion battery anode material according to claim 5, is characterized in that, in step (4), the weight ratio of deionized water and upper strata filter cake is 0.5-5.
8. the preparation method of power type lithium-ion battery anode material according to claim 5, it is characterized in that, in step (4), the condition of described press atomization granulating and drying is: the liquid-drop diameter of press atomization is at 500-1000 μm, pressure is 0.2-3MPa, and hot air temperature is 250-400 DEG C.
9. the preparation method of power type lithium-ion battery anode material according to claim 5, is characterized in that, in step (5), described lithium salts is one or more in lithium acetate, lithium carbonate, lithium nitrate, lithium hydroxide, lithia.
10. the preparation method of power type lithium-ion battery anode material according to claim 5, is characterized in that, in step (5), described atmosphere is the one in air, oxygen; The temperature of sintering is 700-1200 DEG C.
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