CN104253265A - Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof - Google Patents

Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof Download PDF

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CN104253265A
CN104253265A CN201310264937.5A CN201310264937A CN104253265A CN 104253265 A CN104253265 A CN 104253265A CN 201310264937 A CN201310264937 A CN 201310264937A CN 104253265 A CN104253265 A CN 104253265A
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cathode material
ion battery
salt
lithium ion
preparation
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张海朗
杨威
张棪
李红艳
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Jiangnan University
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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
    • H01M4/131—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
    • H01M4/13—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
    • H01M4/48—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 relates to a cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and a preparation method thereof, which belong to the lithium ion battery field. A general chemical formula of the cathode material is LiNi0.4-xM1xCo0.2-yM2yMn0.4-zM3zO2, M1 is Mg, Zn or Cu; M2 is Al or Cr; M3 is Ti, Zr or Mo, x is greater than or equal to 0 and less than or equal to 0.15; y is greater than or equal to 0 and less than or equal to 0.15; and z is greater than or equal to 0 and less than or equal to 0.15. The preparation method comprises the following steps: weighing soluble lithium source, nickel source, manganese source, cobalt source and metal M1 salt, M2 salt and M3 salt according to mol ratio, respectively using deionized water for dissolving, adding a citric acid solution for uniformly mixing and stirring, using concentrated ammonia liquor to adjust pH value, and heating and evaporating to obtain gel, heating and drying the gel, performing twice calcination and grinding to obtain the cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material. The cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material has fine and uniform particles which can reach a nano level, and has high discharge capacity, excellent cycle stability and multiplying power performance, the performance can be kept under high low temperature condition, so that the ternary cathode material is convenient for large scale industrial production and has high practical degree.

Description

Lithium ion battery (4:4:2) type tertiary cathode material of cation doping modification and preparation method thereof
Technical field
Lithium ion battery (4:4:2) type tertiary cathode material that the present invention relates to a kind of cation doping modification and preparation method thereof, belongs to field of lithium ion battery.
Background technology
At present, LiCoO 2because it has, operating voltage is high, capacity large, electric discharge is steady, be applicable to the feature such as heavy-current discharge and good cycle, becomes most widely used positive electrode in business.But cobalt is rare metal, expensive, there is certain pollution to environment.Therefore, the study hotspot of people transfers to and carrys out alternative LiCoO with cheap, other transistion metal compounds environment amenable 2material.LiNiO 2have and LiCoO 2similar structure, has higher actual discharge capacity, and nickel reserves are abundanter and low-cost many than cobalt.But it prepares difficulty, easily generate non-metering than product, and the transformation of crystal structure can occur in charge and discharge process in preparation process, cause its capacity attenuation very fast, cycle performance and thermal stability are all poor.These reasons make LiNiO 2application be very limited.LiMn 2o 4there is the crystal structure of spinelle, with LiCoO 2and LiNiO 2compare, LiMn 2o 4there is plurality of advantages: manganese reserves are large, and with low cost, environmentally friendly, preparation is easier to.But its discharge capacity lower (being about 120mAh/g), Mn 3+the distortion of lattice that causes of Jahn-Teller effect, cause crystal structure generation irreversible transition in charge and discharge process, make LiMn 2o 4when charge and discharge cycles, capacity attenuation is very fast, and especially capacity attenuation is violent under higher than the hot conditions of 45 DEG C.This slows down the process of its industrialization.
LiNi xco ymn 1-x-yo 2the comprehensive LiCoO of tertiary cathode material 2, LiNiO 2, LiMn 2o 4the feature of three class materials, possesses that capacity is high, Stability Analysis of Structures, fail safe is good, low cost and other advantages thus become becomes one of positive electrode having commercialization potentiality most.Patent of the present invention selects mol ratio n (Ni): n (Co): n (Mn)=4: 2: 4 is research system, at the former LiNi of performance 1/3mn 1/3co 1/3o 2under the prerequisite of material advantage, reduce the content of expensive Co, the cost of material and production process can be reduced to a certain extent to the pollution of environment.Ni is maximum to capacity contribution, and the relative increase of Ni content can make material have higher theoretical specific capacity.Meanwhile, the content increasing Mn can improve its security performance further.Thus LiNi 0.4co 0.2mn 0.4o 2it is a kind of tertiary cathode material having more researching value.But current ternary material also remains the shortcoming such as cycle performance and high rate performance deficiency.Doping is a kind of important means improving anode material for lithium-ion batteries performance, and this means are widely used in LiNiO 2, LiMn 2o 4deng on material.Patent of the present invention, on the basis of cation doping, adopts lithium ion battery (4:4:2) the type tertiary cathode material of sol-gal process synthesis nano modification, improves its granule-morphology and chemical property.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, lithium ion battery (4:4:2) the type tertiary cathode material preparation method of a kind of nanoscale cation doping modification is provided, this positive electrode particle is little and even, smooth surface, crystal property is good, has capacity high, and coulombic efficiency is high, good cycle under high/low temperature condition, the advantages such as good rate capability.
According to technical scheme provided by the invention, a kind of lithium ion battery (4:4:2) type tertiary cathode material of cation doping modification, the chemical general formula of described positive electrode is LiNi 0.4-xm 1 xco 0.2-ym 2 ymn 0.4-zm 3 zo 2, M 1for Mg, Zn or Cu; M 2for Al or Cr; M 3for Ti, Zr or Mo, 0≤x≤0.15; 0≤y≤0.15; 0≤z≤0.15;
Solubility lithium source, nickel source, manganese source, cobalt source and metal M is taken according to mol ratio 1salt, M 2salt, M 3salt, respectively with after deionized water dissolving, adds citric acid solution mixing and stirring, and after regulating pH with concentrated ammonia liquor, heating evaporation obtains gel.After gel heat drying, obtain lithium ion battery (4:4:2) the type tertiary cathode material of product cation doping modification through twice calcination grinding.
Lithium ion battery (4:4:2) type tertiary cathode material for cation doping modification, step is as follows:
(1) preparation of gel: according to stoichiometric proportion (1.05: 0.4: 0.4: 0.2: x: y: z) take analytically pure lithium source, nickel source, manganese source, cobalt source and metal M 1salt, M 2salt, M 3salt, is dissolved in respectively in deionized water, adds citric acid solution, addition equals the mole sum of transition metal ions, mixing and stirring, by concentrated ammonia liquor adjust ph to 7-8,60-100 DEG C of heating water bath evaporation, and constantly stir, until obtain darkviolet gel;
(2) calcination: get gel dry 8-15 hour at 80-150 DEG C prepared by step (1), and be placed on 300-600 DEG C of pre-calcination process 4-8 hour; Naturally cool to grinding at room temperature and obtain presoma; Powder after grinding is placed in roasting 10-20 hour under 700-1000 DEG C of condition, continues lithium ion battery (4:4:2) the type tertiary cathode material that grinding obtains the modification of product cation doping after cooling.
Further, described lithium source is LiNO 3, CH 3one or more in COOLi, LiOH, described nickel source is Ni (NO 3) 2, Ni (CH 3cOO) 2in one or both, described manganese source is Mn (NO 3) 2, Mn (CH 3cOO) 2in one or both, described cobalt source is Co (NO 3) 2, Co (CH 3cOO) 2in one or both, described metal M 1salt is Mg (NO 3) 26H 2o, Zn (NO 3) 26H 2o or Cu (NO 3) 23H 2o, described metal M 2salt is Al (NO 3) 29H 2o or Cr (NO 3) 29H 2o; Described metal M 3salt is C 16h 36o 4ti, Zr (NO 3) 25H 2o or MoO 3.
Tool of the present invention has the following advantages:
(1) positive electrode even particle size distribution prepared by the present invention, degree of crystallinity is high, smooth surface, and particle dispersion is good;
(2) positive electrode provided by the present invention, due to cationic doping vario-property, material structure is more stable.Thus under making material height temperature condition, all possess higher discharge capacity, excellent cycle performance and high rate performance.And the cost of material needed for doping vario-property is cheap, reduce further the cost needed for positive electrode production, be conducive to advancing commercial process.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of positive electrode prepared by comparative example and embodiment 1,5.
Fig. 2 is the scanning electron microscope (SEM) photograph (in figure, a is embodiment 1, b be embodiment 5, c be embodiment 6, d be embodiment 7) of positive electrode prepared by embodiment 1,5,6,7.
Fig. 3 is positive electrode prepared by comparative example and embodiment 1,5, and cyclic curve figure during normal temperature under 0.2C electric current, charging/discharging voltage scope is 2.0-4.6V.
Fig. 4 is positive electrode prepared by comparative example and embodiment 1,5, and cyclic curve figure when 55 DEG C under different multiplying, charging/discharging voltage scope is 2.0-4.6V.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but embodiments of the present invention are not limited thereto.
The non-Li doped Ni of comparative example 0.4co 0.2mn 0.4o 2the preparation of positive electrode.
Analytically pure CH is taken according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4) 3cOOLi2H 2o, Ni (CH 3cOO) 24H 2o, Co (CH 3cOO) 24H 2o, Mn (CH 3cOO) 4H 2o, fully dissolve with deionized water respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mix rear concentrated ammonia liquor and solution ph is adjusted to about 7.5,80 DEG C of heating water baths stir, and make the abundant complexing of various ion, and make moisture be evaporated to formation darkviolet gel; By gel under 120 DEG C of conditions dry 10 hours, and preliminary treatment 6 hours at being placed on 500 DEG C, grinding after cooling, then within 20 hours, obtain required product in 850 DEG C of roastings.
Embodiment 1
(1) preparation of gel: take analytically pure CH according to stoichiometric proportion (1.05: 0.35: 0.2: 0.4: 0.05) 3cOOLi2H 2o, Ni (CH 3cOO) 24H 2o, Co (CH 3cOO) 24H 2o, Mn (CH 3cOO) 4H 2o, Mg (NO 3) 26H 2o, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mix rear concentrated ammonia liquor and pH value is adjusted to about 7, also constantly stir, until obtain darkviolet gel 60 DEG C of Water Under bath heating;
(2) calcination: get gel prepared by step (1) heat drying 8 hours at 80 DEG C, products therefrom pre-burning at 300 DEG C was cooled grinding after 4 hours, then calcine cooling grinding after 10 hours at 700 DEG C, obtain product LiNi 0.35co 0.2mn 0.4mg 0.05o 2positive electrode.
Embodiment 2
(1) preparation of gel: take analytically pure LiNO according to stoichiometric proportion (1.05: 0.3: 0.2: 0.4: 0.1) 3, Ni (NO 3) 26H 2o, Co (NO 3) 26H 2o, Mn (NO 3) 24H 2o, Cu (NO 3) 23H 2o, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mix rear concentrated ammonia liquor and pH value is adjusted to about 7.5, also constantly stir, until obtain darkviolet gel 80 DEG C of Water Under bath heating;
(2) calcination: calcination: get gel prepared by step (1) heat drying 10 hours at 100 DEG C, products therefrom pre-burning at 400 DEG C was cooled grinding after 5 hours, then calcine cooling grinding after 15 hours at 850 DEG C, obtain product LiNi 0.3co 0.2mn 0.4cu 0.1o 2positive electrode.
Embodiment 3
(1) preparation of gel: take analytically pure LiOHH according to stoichiometric proportion (1.05: 0.25: 0.2: 0.4: 0.15) 2o, Ni (NO 3) 26H 2o, Co (NO 3) 26H 2o, Mn (NO 3) 24H 2o, Zn (NO 3) 26H 2o, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, mix rear concentrated ammonia liquor and pH value is adjusted to about 8, also constantly stir, until obtain darkviolet gel 90 DEG C of Water Under bath heating;
(2) calcination: 2) calcination: get gel prepared by step (1) heat drying 12 hours at 120 DEG C, products therefrom pre-burning at 500 DEG C was cooled grinding after 6 hours, at 900 DEG C, calcine cooling grinding after 18 hours again, obtain product LiNi 0.25co 0.2mn 0.4zn 0.15o 2positive electrode.
Embodiment 4
(1) preparation of gel: take analytically pure CH according to stoichiometric proportion (1.05: 0.4: 0.1: 0.4: 0.1) 3cOOLi2H 2o, Ni (CH 3cOO) 24H 2o, Co (CH 3cOO) 24H 2o, Mn (CH 3cOO) 4H 2o, Al (NO 3) 29H 2o, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, mix rear concentrated ammonia liquor and pH value is adjusted to about 7.5, also constantly stir, until obtain darkviolet gel 100 DEG C of Water Under bath heating;
(2) calcination: get gel prepared by step (1) heat drying 15 hours at 150 DEG C, products therefrom pre-burning at 600 DEG C was cooled grinding after 8 hours, then calcine cooling grinding after 20 hours at 1000 DEG C, obtain product LiNi 0.4co 0.1mn 0.4al 0.1o 2positive electrode.
Embodiment 5
(1) preparation of gel: take analytically pure LiNO according to stoichiometric proportion (1.05: 0.35: 0.15: 0.4: 0.05: 0.05) 3, Ni (NO 3) 26H 2o, Co (NO 3) 26H 2o, Mn (NO 3) 24H 2o, Mg (CH 3cOO) 4H 2o, Cr (NO 3) 29H 2o, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, mix rear concentrated ammonia liquor and pH value is adjusted to about 7.5, also constantly stir, until obtain darkviolet gel 90 DEG C of Water Under bath heating;
(2) calcination: get gel prepared by step (1) heat drying 14 hours at 100 DEG C, products therefrom pre-burning at 600 DEG C was cooled grinding after 8 hours, then calcine cooling grinding after 20 hours at 950 DEG C, obtain product LiNi 0.35co 0.15mn 0.4mg 0.05cr 0.05o 2positive electrode.
Embodiment 6
(1) preparation of gel: take analytically pure LiNO according to stoichiometric proportion (1.05: 0.37: 0.17: 0.37: 0.03: 0.03: 0.03) 3, Ni (NO 3) 26H 2o, Co (NO 3) 26H 2o, Mn (NO 3) 24H 2o, Zn (NO 3) 26H 2o, Cr (NO 3) 29H 2o, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, add the positive tetrabutyl titanate of stoichiometric proportion afterwards, mix rear concentrated ammonia liquor and pH value is adjusted to about 7.5, also constantly stir, until obtain darkviolet gel 80 DEG C of Water Under bath heating;
(2) calcination: the gel of preparation heat drying 14 hours at 100 DEG C, cools grinding by products therefrom pre-burning at 600 DEG C after 6 hours, then calcine cooling grinding after 18 hours at 850 DEG C, obtain product LiNi 0.37co 0.17mn 0.37zn 0.03cr 0.03ti 0.03o 2positive electrode.
Embodiment 7
(1) preparation of gel: take analytically pure CH according to stoichiometric proportion (1.05: 0.4: 0.2: 0.3: 0.1) 3cOOLi2H 2o, Ni (CH 3cOO) 24H 2o, Co (CH 3cOO) 24H 2o, Mn (CH 3cOO) 4H 2o, Zr (NO 3) 25H 2o, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, mix rear concentrated ammonia liquor and pH value is adjusted to about 7.5, also constantly stir, until obtain darkviolet gel 70 DEG C of Water Under bath heating;
(2) calcination: get gel prepared by step (1) heat drying 13 hours at 120 DEG C, products therefrom pre-burning at 600 DEG C was cooled grinding after 8 hours, then calcine cooling grinding after 20 hours at 900 DEG C, obtain product LiNi 0.4co 0.2mn 0.3zr 0.1o 2positive electrode.
Embodiment 8
(1) preparation of gel: take analytically pure LiNO according to stoichiometric proportion (1.05: 0.4: 0.2: 0.25: 0.15) 3, Ni (NO 3) 26H 2o, Co (NO 3) 26H 2o, Mn (NO 3) 24H 2o, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, then by MoO 3be dissolved in NH 4oH also adds in mixed liquor obtained above, mixes rear concentrated ammonia liquor and pH value is adjusted to about 8, also constantly stirs, until obtain darkviolet gel 90 DEG C of Water Under bath heating;
(2) calcination: get gel prepared by step (1) heat drying 15 hours at 100 DEG C, products therefrom pre-burning at 500 DEG C was cooled grinding after 6 hours, then calcine cooling grinding after 15 hours at 850 DEG C, obtain product LiNi 0.4co 0.2mn 0.25mo 0.15o 2positive electrode.
From accompanying drawing 1 comparative example and embodiment 1,5 X-ray diffracting spectrum in known, in embodiment 1,5, the positive electrode of synthesis has the hexagonal layer structure of high-sequential, there is not the impurity peaks belonging to doped chemical, illustrate that doping does not cause the change of material crystal structure.
From accompanying drawing 2 embodiment 1-4 scanning electron microscope (SEM) photograph in known (in figure a be in embodiment 1 synthesis material, b is the material of synthesis in embodiment 2, c is the material of synthesis in embodiment 3, d is the material of synthesis in embodiment 4), the material synthesized in embodiment all has the more tiny and even particle size distribution of particle, and smooth surface, the good advantage of degree of crystallinity.
Application Example 1
By the positive electrode powder synthesized in embodiment 1-8, acetylene black, poly-inclined tetrafluoroethene (PVDF) mixes than 80: 12: 8 by mass fraction, uniform sizing material is ground to form after adding appropriate pyrrolidones, be spread evenly across on aluminium foil, dry at 100 DEG C, blunderbuss is cut (diameter 14mm), 3MPa rolls, make pole piece, use after 12 hours through 80 DEG C of vacuumizes, button (CR2032) test battery is assembled in the glove box being full of argon gas, negative electricity is lithium sheet very, electrolyte is LB315 [m (DMC): m (EMC): m (EC)=1: 1: 1] solution, barrier film is Celgard2325 hole film.The battery LAND-CT2001A assembled is carried out charge-discharge test.Discharge and recharge interval is 2.0-4.6V.
It should be noted that, concrete when implementing of the present invention, because Li element in the positive electrode that obtains is volatile when high-temperature calcination, have the Li loss of about 5%, therefore the actual mole dosage of lithium salts comparatively theoretical amount want high by about 5%.
The battery that is assembled into of positive electrode of comparative example and embodiment 1-8 synthesis 0.2C current density under point as shown in table 1 in the Electrochemical Characterization result of normal temperature and 55 DEG C.
The battery that the positive electrode of comparative example and embodiment 1,5 is assembled, the cyclic curve figure when normal temperature under 0.2C electric current is as shown in Figure 3; The battery that the positive electrode of comparative example and embodiment 1,5 is assembled, the cyclic curve figure 55 DEG C time under different multiplying electric current as shown in Figure 4.
Under table 10.2C current density, each embodiment charge-discharge performance test result is as shown in the table:

Claims (7)

1. lithium ion battery (4:4:2) type tertiary cathode material for cation doping modification, is characterized in that: described positive electrode is LiNi 0.4-xm 1 xco 0.2-ym 2 ymn 0.4-zm 3 zo 2, M 1for Mg, Zn or Cu; M 2for Al or Cr; M 3for Ti, Zr or Mo, 0≤x≤0.15; 0≤y≤0.15; 0≤z≤0.15.
Solubility lithium source, nickel source, manganese source, cobalt source and metal M is taken according to mol ratio 1salt, M 2salt, M 3salt, respectively with after deionized water dissolving, adds citric acid solution mixing and stirring, and after regulating pH with concentrated ammonia liquor, heating evaporation obtains gel.After gel heat drying, obtain lithium ion battery (4:4:2) the type tertiary cathode material of product cation doping modification through twice calcination grinding.
2. lithium ion battery (4:4:2) type tertiary cathode material for cation doping modification, step is as follows:
(1) preparation of gel: according to stoichiometric proportion (1.05: 0.4: 0.4: 0.2: x: y: z) take analytically pure lithium source, nickel source, manganese source, cobalt source and metal M 1salt, M 2salt, M 3salt, is dissolved in respectively in deionized water, adds citric acid solution, addition equals the mole sum of transition metal ions, mixing and stirring, by concentrated ammonia liquor adjust ph to 7-8,60-100 DEG C of heating water bath evaporation, and constantly stir, until obtain darkviolet gel;
(2) calcination: get gel dry 8-15 hour at 80-150 DEG C prepared by step (1), and be placed on 300-600 DEG C of pre-calcination process 4-8 hour; Naturally cool to grinding at room temperature and obtain presoma; Powder after grinding is placed in roasting 10-20 hour under 700-1000 DEG C of condition, continues lithium ion battery (4:4:2) the type tertiary cathode material that grinding obtains the modification of product cation doping after cooling.
3. the preparation method of the ternary cathode material of lithium ion battery of cation doping modification as claimed in claim 2, is characterized in that: described lithium salts is LiNO 3, CH 3one or more in COOLi, LiOH.
4. the preparation method of the ternary cathode material of lithium ion battery of cation doping modification as claimed in claim 2, is characterized in that: described nickel salt is Ni (NO 3) 2, Ni (CH 3cOO) 2in one or both.
5. the preparation method of the ternary cathode material of lithium ion battery of cation doping modification as claimed in claim 2, is characterized in that: described manganese salt is Mn (NO 3) 2, Mn (CH 3cOO) 2in one or both.
6. the preparation method of the ternary cathode material of lithium ion battery of cation doping modification as claimed in claim 2, is characterized in that: described cobalt salt is Co (NO 3) 2, Co (CH 3cOO) 2in one or both.
7. the preparation method of the ternary cathode material of lithium ion battery of cation doping modification as claimed in claim 2, is characterized in that: described metal M 1salt is Mg (NO 3) 26H 2o, Zn (NO 3) 26H 2o or Cu (NO 3) 23H 2o, described metal M 2salt is Al (NO 3) 29H 2o or Cr (NO 3) 29H 2o; Described metal M 3salt is C 16h 36o 4ti, Zr (NO 3) 25H 2o or MoO 3.
CN201310264937.5A 2013-06-28 2013-06-28 Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof Pending CN104253265A (en)

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CN105489842A (en) * 2015-12-18 2016-04-13 浙江天能能源科技有限公司 Lithium-rich manganese-based cathode material and preparation method thereof
CN106410183A (en) * 2016-10-21 2017-02-15 中国科学院长春应用化学研究所 Low-temperature lithium ion battery anode material and method for preparing same
CN106784801A (en) * 2016-12-30 2017-05-31 惠州龙为科技有限公司 A kind of preparation method of the modified NCA positive electrodes of power type, high power capacity
CN106784786A (en) * 2016-12-16 2017-05-31 欣旺达电子股份有限公司 Ternary anode material precursor, synthetic method and lithium ion battery
CN107293721A (en) * 2017-07-07 2017-10-24 淮安新能源材料技术研究院 A kind of 523 type nickel-cobalt-manganternary ternary anode material method for preparing solid phase and products thereof
CN107689451A (en) * 2016-08-04 2018-02-13 中信国安盟固利动力科技有限公司 A kind of ternary material and preparation method thereof of synthesized-power type, nanofiber
CN108539159A (en) * 2018-04-04 2018-09-14 南京理工大学 The preparation method of multielement codope LiMn2O4 composite material
CN112340785A (en) * 2020-10-26 2021-02-09 广东邦普循环科技有限公司 Doped high-nickel ternary material and preparation method thereof
CN114105209A (en) * 2021-11-22 2022-03-01 江南大学 Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof

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CN105489842A (en) * 2015-12-18 2016-04-13 浙江天能能源科技有限公司 Lithium-rich manganese-based cathode material and preparation method thereof
CN105489842B (en) * 2015-12-18 2018-03-23 浙江天能能源科技股份有限公司 A kind of lithium-rich manganese-based anode material and preparation method thereof
CN107689451A (en) * 2016-08-04 2018-02-13 中信国安盟固利动力科技有限公司 A kind of ternary material and preparation method thereof of synthesized-power type, nanofiber
CN106410183A (en) * 2016-10-21 2017-02-15 中国科学院长春应用化学研究所 Low-temperature lithium ion battery anode material and method for preparing same
CN106784786A (en) * 2016-12-16 2017-05-31 欣旺达电子股份有限公司 Ternary anode material precursor, synthetic method and lithium ion battery
CN106784801A (en) * 2016-12-30 2017-05-31 惠州龙为科技有限公司 A kind of preparation method of the modified NCA positive electrodes of power type, high power capacity
WO2018121100A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing power-type and high-capacity modified nca anode material
CN107293721A (en) * 2017-07-07 2017-10-24 淮安新能源材料技术研究院 A kind of 523 type nickel-cobalt-manganternary ternary anode material method for preparing solid phase and products thereof
CN108539159A (en) * 2018-04-04 2018-09-14 南京理工大学 The preparation method of multielement codope LiMn2O4 composite material
CN112340785A (en) * 2020-10-26 2021-02-09 广东邦普循环科技有限公司 Doped high-nickel ternary material and preparation method thereof
CN112340785B (en) * 2020-10-26 2022-11-15 广东邦普循环科技有限公司 Doped high-nickel ternary material and preparation method thereof
CN114105209A (en) * 2021-11-22 2022-03-01 江南大学 Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof

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