CN106784686A - A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof - Google Patents

A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof Download PDF

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CN106784686A
CN106784686A CN201611191227.4A CN201611191227A CN106784686A CN 106784686 A CN106784686 A CN 106784686A CN 201611191227 A CN201611191227 A CN 201611191227A CN 106784686 A CN106784686 A CN 106784686A
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salt
class monocrystalline
lithium
multicomponent
ion battery
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张伟
周舟
程洁
王训才
陈玉超
崔云龙
苏善金
丁雪娇
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Yantai Zhuoneng Lithium Battery Co., Ltd.
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Yantai Zhuoneng Battery Material Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/46Metal oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to anode material for lithium-ion batteries technical field, a kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof is specifically disclosed.The present invention is modified to nickel-cobalt-manganese ternary material, when preparing presoma, mixes M source metals to reduce material sintering temperature, improves material tap density, makes Ni2+In Li+Mixing degree substantially weakens in layer;Crystal structure is further stabilized through high temperature sintering and tempering process using multi-element composite material presoma obtained in coprecipitation, and suppress metal ion dissolving in material by Surface coating, the side reaction of same electrolyte is inhibited, the stability and chemical property of active material is further increased.Obtained crystal structure of the finished product with stabilization of the invention, compacted density higher, good high rate performance, cycle performance, security performance further improve the specific capacity and charging/discharging voltage of material;It is simple to operate, it is easy to control and this method doping is small, it is widely applicable, it is produced on a large scale.

Description

A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, and in particular to a species monocrystalline polynary positive pole material and Its preparation method.
Background technology
With global energy shortage and the increasingly raising of environmental requirement, electric vehicle development is increasingly received with popularization and application To the attention of countries in the world government, lithium-ion-power cell is also received more and more attention as dynamical system core component. The composition of lithium ion battery mainly including positive pole, barrier film, electrolyte, negative pole and several parts etc. shell, due to current negative material It is main to be relatively low than relatively low, Capacity Ratio graphite material higher, and price using current potential.So, positive electrode grinds It is one of key technology that lithium ion battery improves chemical property to study carefully.
Traditional anode material for lithium-ion batteries uses cobalt acid lithium and LiFePO 4 material, the LiFePO4 material of olivine-type Material poorly conductive, generally improves its electric conductivity using carbon coating, but LiFePO4 tap density in itself is just very low, carbon bag Covering rear particularly evident, low tap density is greatly lowered its volume and capacity ratio, so as to limit its application.Cobalt acid lithium is included Spinel structure and layer structure, the cobalt acid lithium of spinel structure are applied to large-sized power battery, but it holds in use Quickly, particularly cycle performance is very poor under high temperature for amount decay.The cobalt acid lithium of layer structure is commercial relatively early, and in lithium ion battery Positive electrode occupation rate of market is larger, its simple production process, mature preparation process.But, because cobalt resource is rare, price is high, Toxicity is larger, and the defect in terms of cobalt acid lithium battery security difference, constrains the development of its industrialization;And, followed in high voltage During ring, because the lithium ion deviate from is excessive, the layer structure as the cobalt acid lithium of main flow positive active material is very unstable, Especially during charging, the lithium concentration gradient of presence, particle top layer lithium concentration are very low in cobalt acid lithium particle, Very easy recurring structure is collapsed, and causes the cycle performance severe exacerbation of battery.As the requirement to battery energy density is more next Higher, cobalt acid lithium material and LiFePO 4 material cannot meet requirement of the electric automobile to course continuation mileage.
Existing crystal Li-like ions polynary positive pole material includes mono-crystalline structures and polycrystalline structure, the polynary material of polycrystalline structure Expect structural instability under high voltages, exacerbate the reaction of same electrolyte, deteriorate cycle performance.Monocrystalline type ternary material, energy It is enough meet charge under high voltages, have the advantages that specific capacity is high, good cycle, be a kind of more economical, safer lithium from Sub- cell positive material, will replace traditional cobalt acid lithium and LiFePO 4 material, the development side as following power battery material To.
Nickel-cobalt-manganese ternary material has energy density higher compared to LiFePO4, and development prospect is wide.Stratiform Li- Ni-Co-Mn-O oxides are proposed by professor Liu Zhaolin of university of Singapore as anode material for lithium-ion batteries, the material Material fully combines LiNiO2Height ratio capacity, LiCoO2Good high rate performance and LiMnO2High safety stability and low The advantages of cost, form LiNiO2-LiCoO2-LiMnO2Ternary eutectic system, its combination property is better than any one-component Compound, is electrode material that a class has trielement synergistic effect.Secondly, the advantage of ternary material is that can improve material Energy density, improves battery energy density mainly by improving the charging voltage of battery, can so be lived in battery is not increased The capacity of battery is significantly improved under conditions of property material.But nickel-cobalt-manganese ternary material is in security performance, cycle performance and forthright again Energy aspect is still present problems, causes its security performance and cycle performance poor because the layer structure of its material is unstable, Corrosion resistance to electrolyte is also poor;Especially discharge material structure is easily caved under high magnification, causes to be circulated under high magnification Hydraulic performance decline;Overcharge and easily cause safety problem.The B of patent CN 102157725 disclose " microwave sintering synthesis nickel-cobalt-manganese multi The method of anode material for lithium-ion batteries ", the patent using heating using microwave and sintering method prepare structure relatively stablize, change Learn the relatively uniform LiNi of compositionxCoyMn1-x-yO2Nickel-cobalt-manganese multi lithium ion battery crystal positive electrode, it is not in the material It is middle to add the metallic compound for adulterating, anode material for lithium-ion batteries cannot be still met for high rate performance, cycle performance and peace The requirement of full aspect of performance.Therefore, in terms of specific capacity and voltage also there is very big Improvement requirement in ternary material.
At present, doping and coating modification are concentrated mainly on to the modified of existing ternary material, coating modification can only be reduced Erosion of the electrolyte to positive active material, and suppress the decomposition of electrolyte under high voltage, improve its cyclical stability and multiplying power Performance, but the agent structure and capacity of material will not be changed.The doping vario-property of proper proportion can play support to layer structure and add Solid effect, the structure of material is more stablized, and in the side reaction of lightening material and electrolyte to a certain degree, improve material Circulation and heat endurance.
Common ternary material preparation method has high temperature solid-state method, sol-gal process and spray drying process, wherein, high temperature is solid Phase method is simple to operate, but products obtained therefrom purity is low, and the content overproof of general sodium has a strong impact on the performance of material;Sol-gal process With the material particle size prepared by spray drying process uniformly, purity is very high, but operational sequence is complicated, it is extremely difficult to realize extensive raw Produce.Existing dopant material is mainly metal oxide or metallic salt is directly incorporated into sintering process, and the technique is prepared Polynary positive pole material still suffer from the defect of aspect of performance.The A of patent CN 105161714 disclose a kind of " calcium analysis lithium ion Battery tertiary cathode material and preparation method thereof ", the patent is obtained calcium analysis lithium using solid phase method and high temperature solid-phase sintering method Ion battery tertiary cathode material;The A of patent CN 104201371 disclose a kind of " system of nickel cobalt lithium manganate Preparation Method ", the addition that the patent passes through bonding agent enhances the frit reaction between particle, improves the bulk density of product; After high-temperature fusion, the bonding agent for remaining in nickel cobalt lithium manganate surface comes between barrier material and electrolyte to occur Side reaction;The A of patent CN 104282901 disclose " a kind of high conductivity electrokinetic cell nickel-cobalt-manganternary ternary anode material Manufacture method ", using the metal-doped raising Li+ of M in the intracell migration velocity of ternary, TCO gels cladding improves three to the patent First positive electrode electron transfer rate and improve to the surface characteristic of ternary material;But due to Ni2+With Li+Ionic radius relatively connect Closely, easily there is cation mixing phenomenon so that material is susceptible to analyse lithium phenomenon in atmosphere, causes the electrochemistry of material Can be deteriorated.There is certain defect in current doping techniques:On the one hand, the doping of inert matter element can cause the appearance of battery Amount loss;On the other hand, using spherical or spherical second particle more than tertiary cathode material, battery is two during discharge and recharge Secondary particle surface and electrolyte contacts, positive electrode active particle surface occur fluoride erosion and transition metal ions it is molten Solution, causes surface texture to cave in, and cycle performance deteriorates.And, in existing process, doped chemical can also cause positive electrode Discharging efficiency is low first, the defect, the lithium ion diffusion of material such as the specific capacity of lithium ion battery is relatively low and cycle performance is poor Coefficient, electrical conductivity, compacted density, high rate performance and security performance etc. need further raising.Therefore, prior art does not have also Efficiently solve method.
The content of the invention
It is an object of the invention to overcome weak point of the prior art, there is provided a kind of doped lithium ion battery class Monocrystalline polynary positive pole material and preparation method thereof, present invention is generally directed to improve existing this master of cell positive material energy density Problem is wanted, nickel-cobalt-manganese ternary material is modified, in the preparation of presoma, be mixed with other one or more metal unit Element reduces the sintering temperature of material, improves the tap density of material, makes Ni2+In Li+Mixing degree in layer substantially weakens; The sintered technique of multi-element composite material presoma being made further carrys out stable crystal structure, and suppresses material by Surface coating The dissolving of metal ion in material, it is suppressed that with the side reaction of electrolyte, improve the stability of active material, further improve The chemical property of ternary material.
To achieve these goals, the technical solution adopted in the present invention is as follows:
It is the invention provides a kind of preparation method of doped lithium ion battery class monocrystalline polynary positive pole material including as follows Step;
S1:Coprecipitation prepares NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma
Nickel salt, cobalt salt, manganese salt, M sources salt are pressed into metal mol ratio for x:y:1-x-y-z:The ratio of z is well mixed, and obtains Mixed solution A, the concentration of solution A is 0.5-2.5mol/L, and solution A and precipitating reagent are together added to the reaction for filling complexing agent Reacted in device, B is precipitated after reaction, precipitate B be aged, washed, filtered, carrying out washing treatment again, obtained NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma;Wherein, the concentration of precipitating reagent is 1-3mol/L, the concentration of complexing agent It is 0.5-2.0mol/L;The consumption sum of precipitating reagent and complexing agent and multi-element composite material presoma NixCoyMn1-x-y-zMz(OH)2 Molar ratio 1-1.07:1;
S2:Dry NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma
By Ni obtained in step S1xCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is carried out very under rich nitrogen environment Sky is dried, Ni after dryingxCoyMn1-x-y-zMz(OH)2Multi-element composite material forerunner body water content is less than 0.4wt%;
S3:Prepare class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Crude product
By the dried Ni of step S2xCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is mixed with lithium source, is obtained To material C, dry NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is 1 with the metal molar ratio of lithium source: 1.020-1.095;The material C for mixing is pre-processed at high temperature, and natural cooling after pretreatment mixes, then put again after grinding In atmosphere sintering furnace inside holding, control oxygen content and furnace pressure are sintered;Material after sintering is in control oxygen content environment Lower slow cooling, is regrind, is classified and sieved, and obtains class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Crude product;
S4:Prepare class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product
By class monocrystalline multicomponent material Li obtained in step S31+xNixCoyMn1-x-y-zMzO2Crude product carries out high tempering treatment, Obtain class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product, finished product is class monocrystalline layered crystal structure, the particle diameter of finished product Distribution D50It is 1-5 μm.
Wherein, 0.6≤x≤0.79,0.1≤y≤0.2,0.01≤z≤0.05, and 0.1≤1-x-y-z≤0.3.
Further, during the step S1 prepares polynary presoma, mixing speed control exists in course of reaction In 10.5-14, the reaction time is 15-36 hours, and reaction temperature is controlled at 40-80 DEG C, ageing for 500-800r/min, PH control Between be 10-30h, washing uses deionized water, and washing times are 2-6 times.
Further, the step S2 dries NixCoyMn1-x-y-zMz(OH)2During multi-element composite material presoma, Drying temperature is 60-80 DEG C, and drying time is 18-30 hours.
Further, the step S3 prepares class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2During, material C is pre-processed 4-7 hours at 400-600 DEG C, and heating rate is 1-10 DEG C/min, and atmosphere during pretreatment is air or oxygen Gas, atmosphere sintering in-furnace temperature is 600-980 DEG C, is incubated 10-25 hours, and the time of grinding is 0.3-1h, oxygen content control In 30-50vol%, in 1.0-2.5MPa, slow rate of temperature fall control is in 1-5 DEG C/min for controling of the pressure of the oven.
Further, it is advanced to nickel salt, cobalt salt, manganese salt and lithium source before combination in the step S1 and the step S3 Row ball milling, rotating speed is 350-450r/min, 50-75min of Ball-milling Time during ball milling.
Further, in the step S1 and the step S3, mixing uses vertical rotary cylinder mixer, and mixed process is: Material is added from top to bottom, and in the presence of high speed centrifugation power, material throws away the material of addition from inner bag, is recycled into again Mixer, repeatedly, finally from downside, hole throws away material for circulation.
Further, sintering furnace includes microwave agglomerating furnace and vacuum sintering furnace in the step S3.
Further, the step S4 prepares class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2During finished product, The temperature of high tempering is 500 DEG C -600 DEG C, and the time of high tempering is 6-8 hours.
Further, the metal of M sources salt is Mg, Ca, Ti, Zr, Al, Fe, Cr, La, Lu, Pr, Sm or transition elements In one or more.
Further, the oxide of metal preferred Ti, Zr, Cr, La, Pr and Sm of M sources salt, inorganic salts or organic salt In one kind.
Further, M sources salt is oxide, inorganic salts or the organic salt of M sources metal, comprising hydroxide, sulfuric acid The mixture of one or more in salt, carbonate, phosphate, acetate, citrate, nitrate or hydrochloride.
Further, the nickel salt, cobalt salt and manganese salt include the one kind in sulfate, carbonate, phosphate or hydrochloride Or several mixtures.
Further, the nickel salt, cobalt salt, manganese salt and M metal inorganic salts or organic salt are soluble-salt.
Further, the lithium source is the inorganic salts or organic salt of lithium, comprising lithium hydroxide, lithium carbonate, lithium sulfate, acetic acid The mixture of one or more in lithium, lithium citrate or lithium nitrate.
Further, the precipitating reagent and complexing agent are soluble alkali solution, 8<The pH value of soluble alkali solution< 13。
Further, the precipitating reagent includes NaOH, disodium ethylene diamine tetraacetate, sodium citrate, sodium lactate, winestone One or more of sour sodium, preferably NaOH.
Further, the complexing agent includes NH3·H2One or more in O, NaOH or LiOH solution, preferably NH3· H2O solution.
Further, after the step S4, also including step S5:The class monocrystalline multicomponent material that will be obtained in step S4 Li1+xNixCoyMn1-x-y-zMzO2Finished product is coated, and the chemical general formula after cladding is:Li1+xNixCoyMn1-x-y-zMzO2/ R, bag Coating R is the inorganic salts of the homologous metals of M or the metallic compound of organic salt.
Further, the coating and class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2The ratio of finished product is 0.5-5wt%.
Further, the coating R also includes the gold of the oxide, inorganic salts or organic salt of carbon and the homologous metals of M Category compound.
Further, the ratio of the metallic compound and carbon is 0.1-1:1
Further, the carbon includes fibrous nano carbon material.
Further, the fibrous nano carbon material be CNT, carbon nano-fiber in one or more mix Compound.
Further, when comprising the coating, in the step S1, solution A also includes fibrous nano carbon Material suspension, the preparation process of fibrous nano carbon materials pulp suspension is as follows:Using fibrous nano carbon material as base material, use Used as dispersant, in deionized water solution, ultrasonic disperse forms the fibrous nano carbon material of stabilization to polyvinylpyrrolidone Heating is carried out under suspension, and high-speed stirred with other compositions in solution A to mix, warm temperature is 30-80 DEG C, high-speed stirred Rotating speed is 400-1000r/min.
Present invention also offers a kind of doped lithium ion battery class monocrystalline polynary positive pole material, including stratum nucleare and cladding Layer, the stratum nucleare is multiple elements design lithium salt compound;Its chemical general formula is:Li1+xNixCoyMn1-x-y-zMzO2/ R, wherein, 0.6≤ X≤0.79,0.1≤y≤0.2,0.01≤z≤0.05, and 0.1≤1-x-y-z≤0.3;M sources be Mg, Ca, Ti, Zr, Al, Fe, The mixture of one or more oxides, inorganic salts or organic salt in Cr, La, Lu, Pr, Sm or transition elements, clad R is The inorganic salts of the homologous metals of M or the metallic compound of organic salt.
Further, the ratio of the coating and stratum nucleare is 0.5-5wt%.
Further, the coating R is the inorganic salts or the metallic compound of organic salt of carbon and the homologous metals of M.
Further, the ratio of the metallic compound and carbon is 0.1-1:1.
Further, the inorganic salts or organic salt comprising sulfate, carbonate, phosphate, acetate, citrate, The mixture of one or more in nitrate or hydrochloride.
Further, the lithium source is the inorganic salts or organic salt of lithium, comprising lithium hydroxide, lithium carbonate, lithium sulfate, acetic acid The mixture of one or more in lithium, lithium citrate or lithium nitrate.
Further, in the oxide of described M sources preferred Ti, Zr, Cr, La, Pr and Sm, inorganic salts or organic salt Kind.
Further, the class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2The class monocrystalline of R layers of finished product and its cladding Multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product is in lithium ion battery as the application of positive electrode.
Wherein, the transition elements transition elements are also referred to as transition metal, are from III in the periodic table of elements B races have three elements of series (scandium to nickel, yttrium to palladium and lanthanum to platinum) to the chemical element of the races of V III, and these elements are in atom Common feature in structure is that valence electron is filled on the d tracks of time outer layer successively, and electronics inserts their 3d, 4d and 5d one by one Track.Sometimes people are also included in lanthanide series and actinides among transition elements.In addition, I B races element (copper, silver, gold) D electronics is also using when+2 and+trivalent compound are formed;II B races element (zinc, cadmium, mercury) is forming stabilization complex It is similar to traditional transition elements in ability, therefore, also often I B and II B races element are listed among transition elements.
The present invention has advantages below compared with prior art:
(1) it is contemplated that improving the energy density of anode material for lithium-ion batteries, in modified technique, in the system of presoma In standby, other one or more metallic element is mixed with, the sintering temperature of material is reduced by doping, improve the jolt ramming of material Density, makes Ni2+In Li+Mixing degree in layer substantially weakens;The sintered technique of polynary persursor material being made further is come Stable crystal structure, also suppresses the dissolving of metal ion in material, it is suppressed that with the side reaction of electrolyte by Surface coating, The stability of active material is improve, the chemical property of ternary material is further improved.
(2) doping type class monocrystalline polynary positive pole material of the present invention has the crystal structure of stabilization, and compacted density higher is good High rate performance well, cycle performance and security performance, further improve the specific capacity and charging/discharging voltage of material.
(3) doping is smaller in preparation method of the invention, simple to operate, it is easy to control, and low production cost is suitable for work Industry large-scale production.The multiple battery positive electrode such as lithium ion battery, super capacitor is the composite can be widely applied to, applicability is wide It is general.
Brief description of the drawings
Fig. 1 schematically illustrates the schematic flow sheet of preparation method of the present invention;
Fig. 2 schematically illustrates the X ray diffracting spectrum of embodiment 1;
Fig. 3 schematically illustrates the scanning electron microscope (SEM) photograph of embodiment 1;
Fig. 4 schematically illustrates the loop test curve of embodiment 1.
Specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but technical scheme include but It is not limited to the content of following embodiments.
A kind of preparation method of doped lithium ion battery class monocrystalline polynary positive pole material of the present invention, comprises the following steps;
S1:Coprecipitation prepares NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma
Nickel salt, cobalt salt, manganese salt, M sources salt are pressed into metal mol ratio for x:y:1-x-y-z:The ratio of z is well mixed, and obtains Mixed solution A, the concentration of solution A is 0.5-2.5mol/L, and solution A and precipitating reagent are together added to the reaction for filling complexing agent Reacted in device, in 500-800r/min, in 10.5-14, the reaction time is 15-36 hours for PH controls for mixing speed control, Reaction temperature is controlled at 40-80 DEG C, and B is precipitated after reaction, and precipitate B is aged, and digestion time is 10-30h, washing, Washing uses deionized water, and washing times are 4-6 times, and filtering is washed again, and washing times are 2-5 times, are obtained NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma;Wherein, the concentration of precipitating reagent is 1-3mol/L, the concentration of complexing agent It is 0.5-2.0mol/L;The consumption sum of precipitating reagent and complexing agent and multi-element composite material presoma NixCoyMn1-x-y-zMz(OH)2 Molar ratio 1-1.07:1;
S2:Dry NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma
By Ni obtained in step S1xCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is carried out very under rich nitrogen environment Sky is dried, and is dried, and drying temperature is 60-80 DEG C, and drying time is 18-30 hours, Ni after dryingxCoyMn1-x-y-zMz(OH)2It is many First composite material precursor water content is less than 0.4wt%;
S3:Prepare class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Crude product
By the dried Ni of step S2xCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is mixed with lithium source, is obtained To material C, dry NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is 1 with the metal molar ratio of lithium source: 1.020-1.095;The material C for mixing is pre-processed at high temperature, and pretreatment temperature is 400-600 DEG C, and the time is 4-7 hours, Heating rate is 1-10 DEG C/min, and atmosphere during pretreatment is air or oxygen, and natural cooling is mixed again after grinding 0.3-1h Close, then be placed in atmosphere sintering furnace, atmosphere sintering in-furnace temperature is 600-980 DEG C, is incubated 10-25 hours, oxygen content control In 30-50vol%, in 1.0-2.5MPa, slow rate of temperature fall control is sintered controling of the pressure of the oven in 1-5 DEG C/min;After sintering Material control oxygen content environment under slowly lower the temperature, regrind, be classified and sieved, obtain class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Crude product;
S4:Prepare class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product
By class monocrystalline multicomponent material Li obtained in step S31+xNixCoyMn1-x-y-zMzO2Crude product carries out high tempering treatment, The temperature of high tempering is 500 DEG C -600 DEG C, and the time of high tempering is 6-8 hours, then obtains class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product, finished product is class monocrystalline layered crystal structure, the particle diameter distribution D of finished product50It is 1-5 μm.
Wherein, 0.6≤x≤0.79,0.1≤y≤0.2,0.01≤z≤0.05, and 0.1≤1-x-y-z≤0.3.
Preferably, in the step S1 and the step S3, nickel salt, cobalt salt, manganese salt and lithium source are first carried out before combination Ball milling, rotating speed is 350-450r/min, 50-75min of Ball-milling Time during ball milling.
It is further preferred that in the step S1 and the step S3, mixing uses vertical rotary cylinder mixer, mixed process It is:Material is added from top to bottom, and in the presence of high speed centrifugation power, material throws away the material of addition from inner bag, circulates again Into mixer, repeatedly, finally from downside, hole throws away material for circulation.
It is further preferred that sintering furnace includes microwave agglomerating furnace and vacuum sintering furnace in the step S3.
It is further preferred that the metal of M sources salt is in Mg, Ca, Ti, Zr, Al, Fe, Cr, La, Lu, Pr, Sm or transition elements One or more.
It is further preferred that the metal of M sources salt is oxide, inorganic salts or the organic salt of Ti, Zr, Cr, La, Pr and Sm In one kind.
It is further preferred that M sources salt is oxide, inorganic salts or the organic salt of M sources metal, comprising hydroxide, sulphur The mixture of one or more in hydrochlorate, carbonate, phosphate, acetate, citrate, nitrate or hydrochloride.
It is further preferred that the nickel salt, cobalt salt and manganese salt include in sulfate, carbonate, phosphate or hydrochloride Plant or several mixtures.
It is further preferred that the nickel salt, cobalt salt, manganese salt and M metal inorganic salts or organic salt are soluble-salt.
It is further preferred that inorganic salts or organic salt of the lithium source for lithium, comprising lithium hydroxide, lithium carbonate, lithium sulfate, vinegar The mixture of one or more in sour lithium, lithium citrate or lithium nitrate.
It is further preferred that the precipitating reagent and complexing agent are soluble alkali solution, 8<The pH of soluble alkali solution Value<13.
It is further preferred that the precipitating reagent includes NaOH, disodium ethylene diamine tetraacetate, sodium citrate, sodium lactate, wine One or more of stone acid sodium, preferably NaOH.
It is further preferred that the complexing agent includes NH3·H2One or more in O, NaOH or LiOH solution, preferably NH3·H2O solution.
It is further preferred that after the step S4, also including step S5:The polynary material of class monocrystalline that will be obtained in step S4 Material Li1+xNixCoyMn1-x-y-zMzO2Finished product is coated, and the chemical general formula after cladding is:Li1+xNixCoyMn1-x-y-zMzO2/ R, Clad R is the inorganic salts of the homologous metals of M or the metallic compound of organic salt.
It is further preferred that the coating and class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2The ratio of finished product is 0.5-5wt%.
It is further preferred that the coating R also includes the gold of the oxide, inorganic salts or organic salt of carbon and the homologous metals of M Category compound.
It is further preferred that the ratio of the metallic compound and carbon is 0.1-1:1.
It is further preferred that the carbon includes fibrous nano carbon material.
It is further preferred that the fibrous nano carbon material is mixed for one or more in CNT, carbon nano-fiber Compound.
It is further preferred that when comprising the coating, in the step S1, solution A also includes fibrous nano carbon Material suspension, the preparation process of fibrous nano carbon materials pulp suspension is as follows:Using fibrous nano carbon material as base material, use Used as dispersant, in deionized water solution, ultrasonic disperse forms the fibrous nano carbon material of stabilization to polyvinylpyrrolidone Heating is carried out under suspension, and high-speed stirred with other compositions in solution A to mix, warm temperature is 30-80 DEG C, high-speed stirred Rotating speed is 400-1000r/min.
Present invention also offers a kind of doped lithium ion battery class monocrystalline polynary positive pole material, including stratum nucleare and cladding Layer, the stratum nucleare is multiple elements design lithium salt compound;Its chemical general formula is:Li1+xNixCoyMn1-x-y-zMzO2/ R, wherein, 0.6≤ X≤0.79,0.1≤y≤0.2,0.01≤z≤0.05, and 0.1≤1-x-y-z≤0.3;M sources be Mg, Ca, Ti, Zr, Al, Fe, The mixture of one or more oxides, inorganic salts or organic salt in Cr, La, Lu, Pr, Sm or transition elements, clad R is The inorganic salts of the homologous metals of M or the metallic compound of organic salt.
Preferably, the ratio of the coating and stratum nucleare is 0.5-5wt%.
It is further preferred that the coating R is the inorganic salts or the metallic compound of organic salt of carbon and the homologous metals of M.
It is further preferred that the ratio of the metallic compound and carbon is 0.1-1:1.
It is further preferred that the inorganic salts or organic salt include sulfate, carbonate, phosphate, acetate, citric acid The mixture of one or more in salt, nitrate or hydrochloride.
It is further preferred that inorganic salts or organic salt of the lithium source for lithium, comprising lithium hydroxide, lithium carbonate, lithium sulfate, vinegar The mixture of one or more in sour lithium, lithium citrate or lithium nitrate.
It is further preferred that in the oxide of described M sources preferred Ti, Zr, Cr, La, Pr and Sm, inorganic salts or organic salt one Kind.
It is further preferred that the class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product and with its clad R's Application of the finished product in anode material for lithium-ion batteries.
Embodiment 1
(1) it is 0.75 that nickel salt, cobalt salt, manganese salt, titanium salt press metal mol ratio:0.1:0.1:0.05 ratio mixing, dissolving The mixing salt solution that concentration is 1mol/L is made in deionized water.By mixing salt solution, the precipitating reagent NaOH solution of 2mol/L With complexing agent NH3·H2O solution three's cocurrents, are added to and fill during the NaOH solution that pH is 11.25 is the reactor of bottom liquid, control PH processed remain 11.25 ± 0.05,50 DEG C at stirring reaction 24 hours (nitrogen makees protection gas in course of reaction), overflow must be produced Product slurries, 20h is aged by product slurry, is filtrated to get product in the middle of polynary presoma;
(2) above-mentioned middle product are washed 6 times with 80 DEG C of deionized water, unnecessary foreign ion is washed away, 80 after filtering DEG C drying 24 hours, obtains Ni0.75Co0.1Mn0.1Ti0.05(OH)2Polynary presoma, the granular precursor particle diameter D50 controls for obtaining At 4.5 μm or so;
(3) by above-mentioned polynary presoma and Li2CO3Compare 1 according to metal molar:1.09 ratio is mixed, after insert burning In freezing of a furnace sinter, 580 DEG C pre-process 5 hours, grinding 0.5h after 930 DEG C be calcined 16 hours, oxygen content control 40vol% with On, furnace pressure is 2.0MPa, obtains sintering crude product;
(4) by above-mentioned crude product it is ground, screening after obtain class monocrystalline multicomponent material finished product, chemical formula is Li1.75Ni0.75Co0.1Mn0.1Ti0.05O2, finished product grain size D50Control is at 5 μm ± 0.1.
By taking above-described embodiment as an example, electrochemical property test is carried out;Finished product obtained above is carried out X-ray respectively to spread out Penetrate, electron-microscope scanning and cyclic curve are tested, as follows in detail:
As shown in Fig. 2 in X ray diffracting spectrum, when the angle of diffraction screen scanning is 2 θ, showing the peak of diffraction maximum Position, peak shape and peak intensity:In nearly 20 (003) positions, there is peak intensity higher, peak shape is preferable;Secondly, 45 (104), 37/39 (006) there is the peak intensity for successively decreasing the position of/(012) and 65 (018)/(110) successively;Show that the crystal of finished product in embodiment 1 spreads out Penetrate functional;
As shown in figure 3, under electron-microscope scanning, the doping type class monocrystalline polynary positive pole material that the present embodiment is made has crystal formation complete Whole full, crystal structure stabilization, compacted density is higher.
As shown in figure 4, test loop curve, discharge and recharge is carried out with 1C multiplying powers, circulate 760 weeks, investigate capability retention, knot Fruit shows:Capability retention is more than 95%, and cycle performance is preferable.
The doping type class monocrystalline polynary positive pole material that the present embodiment is made has the crystal structure of stabilization, and compacting higher is close Degree, good high rate performance, cycle performance and security performance, the specific capacity and charging/discharging voltage of material is higher.
Embodiment 2
(1) nickel salt, cobalt salt, manganese salt, zirconates and lithium source are carried out into ball milling, rotating speed is 400r/min, and the time is 55min;
(2) it is 0.7 that nickel salt, cobalt salt, manganese salt, zirconates press metal mol ratio:0.15:0.12:0.03 ratio mixing, mixing Using vertical rotary cylinder mixer, dissolving is made the mixing salt solution that concentration is 2mol/L in deionized water.By mixing salt solution, The precipitating reagent NaOH solution and complexing agent NH of 4mol/L3·H2O solution three's cocurrents, are added to that to fill the NaOH that pH is 11.55 molten During liquid is the reactor of bottom liquid, control pH remain 11.55 ± 0.05,60 DEG C at stirring reaction 30 hours (in course of reaction Nitrogen makees protection gas), overflow obtains product slurry, and product slurry is aged into 28h, is filtrated to get product in the middle of polynary presoma;
(3) above-mentioned middle product are washed 5 times with 75 DEG C of deionized water, washes away unnecessary foreign ion, filtered, washed again In 75 DEG C of dryings 28 hours after washing 4 times, drying is carried out under the vacuum environment rich in nitrogen, is obtained Ni0.7Co0.15Mn0.12Zr0.03(OH)2Polynary presoma, the granular precursor particle diameter D for obtaining50Control is at 4.0 μm or so;
(4) lithium nitrate after above-mentioned polynary presoma and ball milling is compared 1 according to metal molar:1.095 ratio is mixed Close, mixing uses vertical rotary cylinder mixer, then insert in sintering furnace and sinter, 550 DEG C pre-process 6 hours, and heating rate is 5 DEG C/min, 900 DEG C are calcined 18 hours after grinding 0.7h, and oxygen content is controlled more than 45%, and furnace pressure is 1.5MPa, slow cooling Speed control obtains sintering crude product in 5 DEG C/min;
(5) sintering crude product is carried out into high tempering treatment, temperature is 550 DEG C, and tempering time is 6 hours;
(6) above-mentioned crude product is ground, sieved, obtain class monocrystalline multicomponent material finished product, chemical formula is Li1.7Ni0.7Co0.15Mn0.12Zr0.03O2, finished product is class monocrystalline layered crystal structure, the particle diameter distribution D of finished product50For 4.5 μm ± 0.2。
Embodiment 3
(1) nickel salt, cobalt salt, manganese salt, chromic salts and lithium source are carried out into ball milling, rotating speed is 380r/min, and the time is 60min;
(2) it is 0.65 that nickel salt, cobalt salt, manganese salt, chromic salts press metal mol ratio:0.18:0.15:0.02 ratio mixing, mixes Close and use vertical rotary cylinder mixer, dissolving is made the mixing salt solution that concentration is 1.5mol/L in deionized water.By salt-mixture Solution, the precipitating reagent NaOH solution of 3mol/L and complexing agent NH3·H2O solution three's cocurrents, it is 11.0 to be added to and fill pH During NaOH solution is the reactor of bottom liquid, stirring reaction (was reacted for 20 hours at control pH remains 11.0 ± 0.05,65 DEG C Nitrogen makees protection gas in journey), overflow obtains product slurry, and product slurry is aged into 22h, is filtrated to get product in the middle of polynary presoma;
(3) above-mentioned middle product are washed 5 times with 85 DEG C of deionized water, washes away unnecessary foreign ion, filtered, washed again In 70 DEG C of dryings 30 hours after washing 3 times, drying is vacuum environment under nitrogen protection, obtains Ni0.65Co0.18Mn0.15Cr0.02 (OH)2Polynary presoma, the granular precursor particle diameter D for obtaining50Control is at 3.5 μm or so;
(4) lithium sulfate after above-mentioned polynary presoma and ball milling is compared 1 according to metal molar:1.04 ratio is mixed Close, mixing uses vertical rotary cylinder mixer, then insert in sintering furnace and sinter, 500 DEG C pre-process 6.5 hours, and heating rate is 8 DEG C/min, 950 DEG C are calcined 14 hours after grinding 1h, and oxygen content is controlled more than 40%, and furnace pressure is 2.4MPa, slow cooling speed Rate is controlled in 3 DEG C/min, obtains sintering crude product;
(5) sintering crude product is carried out into high tempering treatment, temperature is 500 DEG C, and tempering time is 6.5 hours;
(6) above-mentioned crude product is ground, sieved, obtain class monocrystalline multicomponent material finished product, chemical formula is Li1.65Ni0.65Co0.18Mn0.15Cr0.02O2, finished product is class monocrystalline layered crystal structure, the particle diameter distribution D of finished product50For 4.0 μm ± 0.1。
Embodiment 4
(1) it is 0.62 that nickel salt, cobalt salt, manganese salt, lanthanum salt press metal mol ratio:0.12:0.22:0.04 ratio mixing, it is molten Solution is made the mixing salt solution that concentration is 0.7mol/L in deionized water.By mixing salt solution, the precipitating reagent of 1.4mol/L NaOH solution and complexing agent NH3·H2O solution three's cocurrents, are added to the reaction for filling that the NaOH solution that pH is 12.0 is bottom liquid In device, stirring reaction 32 hours (nitrogen makees protection gas in course of reaction) at controlling pH to remain 12.0 ± 0.05,45 DEG C is overflow Product slurry is flowed to obtain, product slurry is aged 15h, be filtrated to get product in the middle of polynary presoma;
(2) above-mentioned middle product are washed 5 times with 83 DEG C of deionized water, washes away unnecessary foreign ion, filtered, washed again In 80 DEG C of dryings 26 hours after washing 5 times, it is dried under nitrogen protection, obtains Ni0.62Co0.12Mn0.22La0.04(OH)2It is polynary Presoma, the granular precursor particle diameter D for obtaining50Control is at 4.5 μm or so;
(3) above-mentioned polynary presoma and lithium citrate are compared 1 according to metal molar:1.08 ratio is mixed, rearmounted Enter sintering in sintering furnace, 530 DEG C pre-process 7 hours, 850 DEG C are calcined 22 hours after grinding 0.4h, oxygen content control exists More than 42vol%, furnace pressure is 2.5MPa, obtains sintering crude product;
(4) sintering crude product is carried out into high tempering treatment, temperature is 530 DEG C, and tempering time is 7 hours;
(5) above-mentioned crude product is ground, sieved, obtain class monocrystalline multicomponent material finished product, chemical formula is Li1.62Ni0.62Co0.12Mn0.22La0.04O2, finished product is class monocrystalline layered crystal structure, finished product grain size D50Control is at 5 μm ± 0.1.
In addition, M sources lanthanum salt is also changed to praseodymium or samarium rare-earth oxide, inorganic salts or organic salt etc., praseodymium or samarium M sources pair The lithium source answered respectively lithium hydroxide and lithium acetate, its chemical general formula is:Li1.7Ni0.7Co0.15Mn0.1Pr0.05O2And Li1+ xNi0.75Co0.13Mn0.1Sm0.02O2
In addition, M sources can be several mixing in one kind, or above-claimed cpd of above-mentioned metallic compound Thing, because preparation method is identical, is not repeated herein.
Embodiment 5
In the present invention and above-described embodiment, cladding can be again coated outside the class monocrystalline polynary positive pole material for being made finished product Layer R, the chemical general formula after cladding is:Li1+xNixCoyMn1-x-y-zMzO2/ R, its preparation process is as follows:
In the doping polynary positive pole material Surface coating being made containing titanium oxide (correspondence embodiment 1) 0.5wt% and carbon The compound coating layer of 0.5wt%, drying, 700 DEG C of calcining at constant temperature 10h under ar gas environment, natural cooling, sieving, air-flow dispersion After treatment, the polynary anode material for lithium-ion batteries of doping after being coated.
In the doping polynary positive pole material Surface coating being made containing zirconium oxide (correspondence embodiment 2) 1wt% and carbon 1wt%'s Compound coating layer, drying, 750 DEG C of calcining at constant temperature 8h under ar gas environment, natural cooling after sieving, air-flow decentralized processing, is obtained The polynary anode material for lithium-ion batteries of doping after cladding.
In the doping polynary positive pole material Surface coating being made containing chromium oxide (correspondence embodiment 3) 1.5wt% and carbon 2wt% Compound coating layer, drying, 700 DEG C of calcining at constant temperature 12h under ar gas environment, natural cooling, sieving, after air-flow decentralized processing, The polynary anode material for lithium-ion batteries of doping after being coated.
In the doping polynary positive pole material Surface coating being made containing lanthana (correspondence embodiment 4) 1wt% and carbon 2wt%'s Compound coating layer, drying, 800 DEG C of calcining at constant temperature 12h under ar gas environment, natural cooling after sieving, air-flow decentralized processing, is obtained The polynary anode material for lithium-ion batteries of doping after to cladding.
Wherein, carbon can change CNT or carbon nano-fiber in fibrous nano carbon material etc. into.
In addition, when containing the coating, in the preparation process of presoma, need to be in nickel salt, cobalt salt, manganese salt and M sources Fibrous nano carbon materials pulp suspension is added in mixed solution, the preparation process of fibrous nano carbon materials pulp suspension is as follows:Will Fibrous nano carbon material used as base material, with polyvinylpyrrolidone as dispersant, in deionized water solution, divide by ultrasound Dissipate, form the fibrous nano carbon materials pulp suspension of stabilization, and heating is carried out with other compositions in solution A under high-speed stirred and mix Close, warm temperature is 30-80 DEG C, the rotating speed of high-speed stirred is 400-1000r/min, and preferably heating-up temperature is 60 DEG C, and stirring turns Speed is 600r/min.
The doping type class monocrystalline polynary positive pole material that the above embodiment of the present invention is made has the crystal structure of stabilization, higher Compacted density, good high rate performance, cycle performance and security performance also further improve specific capacity and the charge and discharge of material Piezoelectric voltage.Doping is smaller in preparation method of the present invention, simple to operate, it is easy to control, low production cost, is suitable for industrialization rule Mould is produced.
For the ordinary skill in the art, specific embodiment is that the present invention is exemplarily described, Specific implementation of the present invention is not limited by aforesaid way.The present invention can have various modifications and variations, all of the invention Within spirit and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.

Claims (10)

1. a kind of preparation method of doped lithium ion battery class monocrystalline multicomponent material, it is characterised in that comprise the following steps:
S1, coprecipitation prepare NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma
Nickel salt, cobalt salt, manganese salt, M sources salt are pressed into metal mol ratio for x:y:1-x-y-z:The ratio of z is well mixed, and is mixed Solution A, the concentration of solution A is 0.5-2.5mol/L, and solution A and precipitating reagent are together added in the reactor for filling complexing agent Reacted, B is precipitated after reaction, precipitate B be aged, washed, filtered, carrying out washing treatment again, obtained NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma;Wherein, the concentration of precipitating reagent is 1-3mol/L, the concentration of complexing agent It is 0.5-2.0mol/L;The consumption sum of precipitating reagent and complexing agent and multi-element composite material presoma NixCoyMn1-x-y-zMz(OH)2 Molar ratio 1-1.07:1;
S2, dry NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma
By Ni obtained in step S1xCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma carries out vacuum under rich nitrogen environment and does It is dry, Ni after dryingxCoyMn1-x-y-zMz(OH)2Water content is less than 0.4wt% in multi-element composite material presoma;
S3, preparation class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Crude product
By the dried Ni of step S2xCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is mixed with lithium source, obtains thing Material C, dry NixCoyMn1-x-y-zMz(OH)2Multi-element composite material presoma is 1 with the metal molar ratio of lithium source:1.020- 1.095;The material C for mixing is pre-processed at high temperature, and natural cooling after pretreatment mixes, then be placed in atmosphere again after grinding Sintering furnace inside holding, control oxygen content and furnace pressure are sintered;Material after sintering is slow in the case where oxygen content environment is controlled Cooling, is regrind, is classified and sieved, and obtains class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Crude product;
S4, preparation class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product
By class monocrystalline multicomponent material Li obtained in step S31+xNixCoyMn1-x-y-zMzO2Crude product carries out high tempering treatment, obtains Class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2Finished product, finished product is class monocrystalline layered crystal structure, the particle diameter distribution of finished product D50It is 1-5 μm;
Wherein, 0.6≤x≤0.79,0.1≤y≤0.2,0.01≤z≤0.05, and 0.1≤1-x-y-z≤0.3.
2. the preparation method of doped lithium ion battery class monocrystalline multicomponent material according to claim 1, it is characterised in that
During the step S1 prepares polynary presoma, mixing speed control is in 500-800r/min, PH in course of reaction In 10.5-14, the reaction time is 15-36 hours, and reaction temperature is controlled at 40-80 DEG C, and digestion time is 10-30h, washing for control Using deionized water, washing times are 2-6 times;
The step S2 dries NixCoyMn1-x-y-zMz(OH)2During multi-element composite material presoma, drying temperature is 60- 80 DEG C, drying time is 18-30 hours;
The step S3 prepares class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2During, material C is at 400-600 DEG C Lower pretreatment 4-7 hours, heating rate is 1-10 DEG C/min, and atmosphere during pretreatment is air or oxygen, atmosphere sintering furnace Interior temperature is 600-980 DEG C, is incubated 10-25 hours, and the time of grinding is 0.3-1h, and oxygen content is controlled in 30-50vol%, , in 1.0-2.5MPa, slow rate of temperature fall control is in 1-5 DEG C/min for controling of the pressure of the oven;
The step S4 prepares class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2During finished product, the temperature of high tempering It is 500 DEG C -600 DEG C to spend, and the time of high tempering is 6-8 hours.
3. the preparation method of doped lithium ion battery class monocrystalline multicomponent material according to claim 1, it is characterised in that
In the step S1 and the step S3, ball milling is first carried out to nickel salt, cobalt salt, manganese salt and lithium source before combination, during ball milling Rotating speed is 350-450r/min, 50-75min of Ball-milling Time;
In the step S1 and the step S3, mixing uses vertical rotary cylinder mixer, and mixed process is:Add from top to bottom Material, in the presence of high speed centrifugation power, material is thrown away the material of addition from inner bag, and mixer is recycled into again, and circulation is anti- Multiple, finally from downside, hole throws away material.
4. the preparation method of doped lithium ion battery class monocrystalline multicomponent material according to claim 1, it is characterised in that
The metal of M sources salt is the one kind or several in Mg, Ca, Ti, Zr, Al, Fe, Cr, La, Lu, Pr, Sm or transition elements Kind;It is preferred that one or more in Ti, Zr, Cr, La, Pr and Sm;
M sources salt is oxide, inorganic salts or the organic salt of above-mentioned metal, is soluble-salt, comprising hydroxide, sulfuric acid The mixture of one or more in salt, carbonate, phosphate, acetate, citrate, nitrate or hydrochloride;
The soluble nickel salt, cobalt salt and manganese salt include one or more in sulfate, carbonate, phosphate or hydrochloride Mixture;
The lithium source for lithium inorganic salts or organic salt, comprising lithium hydroxide, lithium carbonate, lithium sulfate, lithium acetate, lithium citrate or The mixture of one or more in lithium nitrate.
5. the preparation method of doped lithium ion battery class monocrystalline multicomponent material according to claim 1, it is characterised in that
The precipitating reagent and complexing agent are soluble alkali solution, 8<The pH value of soluble alkali solution<13;
The precipitating reagent comprising NaOH, disodium ethylene diamine tetraacetate, sodium citrate, sodium lactate, one kind of sodium tartrate or It is several, preferred NaOH;
The complexing agent includes NH3·H2One or more in O, NaOH or LiOH solution, preferably NH3·H2O solution.
6. the preparation method of doped lithium ion battery class monocrystalline multicomponent material according to claim 1, it is characterised in that
After the step S4, also including step S5:The class monocrystalline multicomponent material Li that will be obtained in step S41+ xNixCoyMn1-x-y-zMzO2Finished product is coated, and the chemical general formula after cladding is:Li1+xNixCoyMn1-x-y-zMzO2/ R, clad R It is the inorganic salts or the metallic compound of organic salt of the homologous metals of M;
The coating and class monocrystalline multicomponent material Li1+xNixCoyMn1-x-y-zMzO2The ratio of finished product is 0.5-5wt%.
7. the preparation method of doped lithium ion battery class monocrystalline multicomponent material according to claim 6, it is characterised in that
The coating R also includes the metallic compound of the oxide, inorganic salts or organic salt of carbon and the homologous metals of M;
The ratio of the metallic compound and carbon is 0.1-1:1;
The carbon includes fibrous nano carbon material;
The fibrous nano carbon material is one or more mixtures in CNT, carbon nano-fiber.
8. a kind of doped lithium ion of doped lithium ion battery class monocrystalline multicomponent material as described in claim 1-7 is any is electric Pond class monocrystalline multicomponent material is in lithium ion battery as the application of positive electrode.
9. a kind of doped lithium ion battery class monocrystalline multicomponent material, it is characterised in that including stratum nucleare and clad;
The stratum nucleare is multiple elements design lithium salt compound;Its chemical general formula is:Li1+xNixCoyMn1-x-y-zMzO2/ R, wherein, 0.6 ≤ x≤0.79,0.1≤y≤0.2,0.01≤z≤0.05, and 0.1≤1-x-y-z≤0.3;M sources be Mg, Ca, Ti, Zr, Al, The mixture of one or more oxides, inorganic salts or organic salt in Fe, Cr, La, Lu, Pr, Sm or transition elements, clad R is the inorganic salts of the homologous metals of M or the metallic compound of organic salt;
The ratio of the coating and stratum nucleare is 0.5-5wt%.
10. doped lithium ion battery class monocrystalline multicomponent material according to claim 8, it is characterised in that
The coating R is the inorganic salts or the metallic compound of organic salt of carbon and the homologous metals of M;
The ratio of the metallic compound and carbon is 0.1-1:1.
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CN107403913A (en) * 2017-07-11 2017-11-28 中国科学院成都有机化学有限公司 A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof
CN107706414A (en) * 2017-11-13 2018-02-16 桑顿新能源科技有限公司 A kind of preparation technology of high power capacity, macrocyclic nickelic positive electrode
CN107732232A (en) * 2017-10-18 2018-02-23 重庆特瑞新能源材料有限公司 A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material
CN107808952A (en) * 2017-10-13 2018-03-16 深圳力合厚浦科技有限公司 A kind of preparation method of the compound nickel, cobalt and manganese oxide ternary anode material for lithium-ion batteries of high-tap density high power capacity
CN107978752A (en) * 2017-11-30 2018-05-01 宁波容百锂电材料有限公司 A kind of high security lithium ion positive electrode for battery material and preparation method thereof
CN108550833A (en) * 2018-05-18 2018-09-18 宁德新能源科技有限公司 A kind of positive electrode and lithium ion battery
CN108923041A (en) * 2018-05-29 2018-11-30 深圳市德方纳米科技股份有限公司 Tertiary cathode material and preparation method thereof and lithium ion battery
CN110182857A (en) * 2019-06-04 2019-08-30 浙江帕瓦新能源股份有限公司 A kind of high activity petal-shaped nickel-cobalt-manganese ternary presoma and preparation method thereof
CN110867573A (en) * 2018-08-28 2020-03-06 比亚迪股份有限公司 Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile
CN111029556A (en) * 2019-12-31 2020-04-17 河北科技大学 Multi-modified nickel-rich ternary material and preparation method and application thereof
CN111422924A (en) * 2020-03-31 2020-07-17 蜂巢能源科技有限公司 Calcium-doped lithium-rich carbonate precursor and preparation method and application thereof
CN112542576A (en) * 2019-09-23 2021-03-23 荆门市格林美新材料有限公司 Coated LiFePO4Preparation method of Al-doped nickel-cobalt-manganese ternary cathode material of coating
CN112750994A (en) * 2019-10-31 2021-05-04 深圳市贝特瑞纳米科技有限公司 Positive electrode material, preparation method and application thereof
CN113113594A (en) * 2021-04-07 2021-07-13 湖南工程学院 Doped large-particle nickel cobalt lithium manganate and preparation method and application thereof
CN113258055A (en) * 2021-04-25 2021-08-13 浙江帕瓦新能源股份有限公司 Strontium-doped battery quaternary positive electrode material precursor and preparation method thereof
CN113328262A (en) * 2021-05-31 2021-08-31 青岛科技大学 Preparation method of manganese oxide @ Ni-Co/graphite carbon nanocomposite
CN113451567A (en) * 2021-06-25 2021-09-28 浙江帕瓦新能源股份有限公司 Multi-element doped nickel-rich quaternary anode material precursor and preparation method thereof
CN113443659A (en) * 2021-06-25 2021-09-28 浙江帕瓦新能源股份有限公司 Wet-method doping and carbon-coating co-modified quaternary anode material and preparation method thereof
CN113571680A (en) * 2021-07-27 2021-10-29 浙江帕瓦新能源股份有限公司 Double-modified ternary cathode material
CN113651374A (en) * 2021-10-20 2021-11-16 浙江帕瓦新能源股份有限公司 Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor
CN113683126A (en) * 2021-08-12 2021-11-23 武汉理工大学 Palladium-doped nickel-cobalt spinel and preparation method thereof
CN114314692A (en) * 2021-12-28 2022-04-12 中伟新材料股份有限公司 Ternary positive electrode material precursor, preparation method, positive electrode material, positive electrode slurry, lithium ion battery, positive electrode and electric equipment
CN114709417A (en) * 2021-12-07 2022-07-05 北京当升材料科技股份有限公司 Multi-element anode material and preparation method and application thereof
CN114804225A (en) * 2022-03-15 2022-07-29 远景动力技术(江苏)有限公司 Ternary material precursor and application thereof
CN114843504A (en) * 2022-06-08 2022-08-02 中南大学 Single-crystal-morphology lithium ion battery ternary positive electrode material and preparation method and application thereof
EP4089055A3 (en) * 2021-09-02 2023-03-08 XTC New Energy Materials (Xiamen) Ltd. Ternary positive material of large monocrystal-like particles, method for preparing the same, and lithium-ion battery having the same

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CN107403913A (en) * 2017-07-11 2017-11-28 中国科学院成都有机化学有限公司 A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof
CN107808952A (en) * 2017-10-13 2018-03-16 深圳力合厚浦科技有限公司 A kind of preparation method of the compound nickel, cobalt and manganese oxide ternary anode material for lithium-ion batteries of high-tap density high power capacity
CN107732232A (en) * 2017-10-18 2018-02-23 重庆特瑞新能源材料有限公司 A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material
CN107706414A (en) * 2017-11-13 2018-02-16 桑顿新能源科技有限公司 A kind of preparation technology of high power capacity, macrocyclic nickelic positive electrode
CN107978752A (en) * 2017-11-30 2018-05-01 宁波容百锂电材料有限公司 A kind of high security lithium ion positive electrode for battery material and preparation method thereof
CN108550833B (en) * 2018-05-18 2021-06-29 宁德新能源科技有限公司 Cathode material and lithium ion battery
CN108550833A (en) * 2018-05-18 2018-09-18 宁德新能源科技有限公司 A kind of positive electrode and lithium ion battery
CN108923041B (en) * 2018-05-29 2020-12-08 深圳市德方纳米科技股份有限公司 Ternary cathode material, preparation method thereof and lithium ion battery
CN108923041A (en) * 2018-05-29 2018-11-30 深圳市德方纳米科技股份有限公司 Tertiary cathode material and preparation method thereof and lithium ion battery
CN110867573A (en) * 2018-08-28 2020-03-06 比亚迪股份有限公司 Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile
CN110182857A (en) * 2019-06-04 2019-08-30 浙江帕瓦新能源股份有限公司 A kind of high activity petal-shaped nickel-cobalt-manganese ternary presoma and preparation method thereof
CN112542576A (en) * 2019-09-23 2021-03-23 荆门市格林美新材料有限公司 Coated LiFePO4Preparation method of Al-doped nickel-cobalt-manganese ternary cathode material of coating
CN112750994A (en) * 2019-10-31 2021-05-04 深圳市贝特瑞纳米科技有限公司 Positive electrode material, preparation method and application thereof
CN112750994B (en) * 2019-10-31 2023-08-29 深圳市贝特瑞纳米科技有限公司 Positive electrode material, preparation method and application thereof
CN111029556B (en) * 2019-12-31 2021-02-02 河北科技大学 Multi-modified nickel-rich ternary material and preparation method and application thereof
CN111029556A (en) * 2019-12-31 2020-04-17 河北科技大学 Multi-modified nickel-rich ternary material and preparation method and application thereof
CN111422924A (en) * 2020-03-31 2020-07-17 蜂巢能源科技有限公司 Calcium-doped lithium-rich carbonate precursor and preparation method and application thereof
CN111422924B (en) * 2020-03-31 2023-03-21 蜂巢能源科技有限公司 Calcium-doped lithium-rich carbonate precursor and preparation method and application thereof
CN113113594B (en) * 2021-04-07 2022-04-08 湖南工程学院 Doped large-particle nickel cobalt lithium manganate and preparation method and application thereof
CN113113594A (en) * 2021-04-07 2021-07-13 湖南工程学院 Doped large-particle nickel cobalt lithium manganate and preparation method and application thereof
CN113258055A (en) * 2021-04-25 2021-08-13 浙江帕瓦新能源股份有限公司 Strontium-doped battery quaternary positive electrode material precursor and preparation method thereof
CN113328262A (en) * 2021-05-31 2021-08-31 青岛科技大学 Preparation method of manganese oxide @ Ni-Co/graphite carbon nanocomposite
CN113451567A (en) * 2021-06-25 2021-09-28 浙江帕瓦新能源股份有限公司 Multi-element doped nickel-rich quaternary anode material precursor and preparation method thereof
CN113443659B (en) * 2021-06-25 2022-05-03 浙江帕瓦新能源股份有限公司 Wet-method doping and carbon-coating co-modified quaternary anode material and preparation method thereof
CN113443659A (en) * 2021-06-25 2021-09-28 浙江帕瓦新能源股份有限公司 Wet-method doping and carbon-coating co-modified quaternary anode material and preparation method thereof
CN113571680A (en) * 2021-07-27 2021-10-29 浙江帕瓦新能源股份有限公司 Double-modified ternary cathode material
CN113683126A (en) * 2021-08-12 2021-11-23 武汉理工大学 Palladium-doped nickel-cobalt spinel and preparation method thereof
EP4089055A3 (en) * 2021-09-02 2023-03-08 XTC New Energy Materials (Xiamen) Ltd. Ternary positive material of large monocrystal-like particles, method for preparing the same, and lithium-ion battery having the same
CN113651374B (en) * 2021-10-20 2021-12-21 浙江帕瓦新能源股份有限公司 Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor
CN113651374A (en) * 2021-10-20 2021-11-16 浙江帕瓦新能源股份有限公司 Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor
CN114709417A (en) * 2021-12-07 2022-07-05 北京当升材料科技股份有限公司 Multi-element anode material and preparation method and application thereof
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CN114709417B (en) * 2021-12-07 2024-01-26 北京当升材料科技股份有限公司 Multielement positive electrode material, preparation method and application thereof
KR102646171B1 (en) 2021-12-07 2024-03-08 베이징 이스프링 머티리얼 테크놀로지 컴퍼니 리미티드 Multi-element cathode materials and their manufacturing methods and applications
KR20230086637A (en) * 2021-12-07 2023-06-15 베이징 이스프링 머티리얼 테크놀로지 컴퍼니 리미티드 Multi-component cathode material and manufacturing method and application thereof
CN114314692A (en) * 2021-12-28 2022-04-12 中伟新材料股份有限公司 Ternary positive electrode material precursor, preparation method, positive electrode material, positive electrode slurry, lithium ion battery, positive electrode and electric equipment
CN114314692B (en) * 2021-12-28 2023-01-24 中伟新材料股份有限公司 Ternary positive electrode material precursor, preparation method, positive electrode material, positive electrode slurry, lithium ion battery, positive electrode and electric equipment
CN114804225A (en) * 2022-03-15 2022-07-29 远景动力技术(江苏)有限公司 Ternary material precursor and application thereof
CN114843504A (en) * 2022-06-08 2022-08-02 中南大学 Single-crystal-morphology lithium ion battery ternary positive electrode material and preparation method and application thereof

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