CN109686970A - A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof - Google Patents

A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof Download PDF

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Publication number
CN109686970A
CN109686970A CN201811607190.8A CN201811607190A CN109686970A CN 109686970 A CN109686970 A CN 109686970A CN 201811607190 A CN201811607190 A CN 201811607190A CN 109686970 A CN109686970 A CN 109686970A
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nma
lithium
tertiary cathode
cobalt
salt
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赵春阳
付烨
钟辉
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Sichuan Wanbang Shenghui Machinery Equipment Co Ltd
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Sichuan Wanbang Shenghui Machinery Equipment Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01BASIC ELECTRIC 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
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01BASIC ELECTRIC 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
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • 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 discloses a kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof.Its chemical formula is Li1+PNi1‑x‑y‑ zMnxAlyMzO2, in which: 0.03 < P <, 0.3,0.1 < X <, 0.6,0.01 < Y < 0.1,0.01 < Z < 0.3, M Ce3+、Ti4+、Zr4+、Mg2+One or more;Its presoma is nano-sheet agglomerated particles, 30-50 nanometers of the thickness of nano-sheet presoma.Main application and advantage of the present invention: replace value valuableness Co with cheap Mn, and by the way that excessive lithium (rich lithium) is added, by stratiform LiNiO2Phase and stratiform LiMnO2A kind of mutually compound NMA positive electrode for having prepared lithium-rich structure.Because being free of cobalt, preparation cost declines 20-30%;The positive electrode capacity reaches 190-200mAh/g, and 100 circulation volume conservation rates are 90-95%.

Description

A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery material preparation, and in particular to a kind of no cobalt richness lithium tertiary cathode material NMA And preparation method thereof.
Background technique
With the high speed development of new energy, high-capacity lithium ion power battery becomes global new energy and produces and scientific and technological development Hot spot.As the positive electrode for influencing lithium battery capacity key component, the emphasis of even more current research of technique, tertiary cathode material NCA has many advantages, such as that capacity is big, voltage platform is high, is the high capacity positive electrode of new generation after tertiary cathode material NCM, is mesh The new hot spot of preceding lithium battery research and development.With technological progress, under the premise of keeping high stability, raising tertiary cathode material (NCA, NCM the content of nickel in) reduces expensive cobalt content, or even is free of cobalt, is the development side of current anode material of lithium battery To all following such as from 333,532,622 (i.e. the Ni:Co:Mn=3:3:3, similarly hereinafter) of former NCM to the NCA811 researched and developed at present The development path that nickel content gradually increases, cobalt content gradually decreases, greatly improve the capacity of tertiary cathode material, cost gradually Decline.
However, nickel content gradually increases in presoma, cobalt content gradually decreases, the layer structure of tertiary cathode material can be made Stability declines in charge and discharge process, and serious cationic mixing easily occurs, and makes the efficiency for charge-discharge, reversible of positive electrode The stability of circulation is greatly reduced.The best NCA of performance is 811 at present, and the ratio between nickel and cobalt are 8:1 (molar ratio), cobalt content Still higher, capacity is also difficult to more than 200mAh/g, this has become the technical bottleneck of tertiary cathode material NCA, becomes current Tertiary cathode material key technical problem urgently to be resolved.
Layered lithium manganate LiMnO2It is a kind of high capacity positive electrode, theoretical charge/discharge capacity reaches 285mAh/g, and difference is not It is mostly currently used lithium manganate having spinel structure LiMn2O42 times of positive electrode.But layered lithium manganate LiMnO2Structure is extremely unstable Fixed, structure is easily collapsed in charge and discharge process, and is changed into the lower spinel-type LiMn of capacity2O4, make cyclical stability Difference, this is also to be difficult to prepare stable layered lithium manganate LiMnO at present2The reason of.
It is well known that the capacity of lithium battery and the lithium content of positive electrode are closely related, theoretically, positive electrode can oneself Higher by the lithium content deviate from, the lithium ion of deintercalation is more in charging, and capacity is higher, and therefore, rich lithium also becomes positive material Material increases one of the means of capacity.But for nickel-base anode material NCA, rich lithium can only be attached to the table of material as lithia Face not can enter material crystal structure, so not can increase its capacity not only, material basicity can be made to increase, and will reduce instead just The cyclical stability of pole material, this is because the Li in positive electrode NCA+Content excessive (i.e. rich lithium) and air contact can give birth to At lithium carbonate and lithium hydroxide, the abjection and insertion activity of Li ion are hindered significantly, declines its capacity and cyclical stability.
Summary of the invention
For deficiency present in background technique, technical problems to be solved are the present invention: providing a kind of high stability, low Cost without cobalt richness lithium tertiary cathode material NMA (three kinds of elements of nickel manganese aluminium compound) and preparation method thereof.
The present invention is in order to solve the above technical problems, the technical solution used are as follows: a kind of no cobalt richness lithium tertiary cathode material Expect that NMA, the chemical formula of the no cobalt richness lithium tertiary cathode material NMA are Li1+PNi1-x-y-zMnxAlyMzO2, presoma chemical formula For Ni1-x-y-zMnxAlyMz(OH)2, in which: 0.03 < P <, 0.3,0.1 < X <, 0.6,0.01 < Y <, 0.1,0.01 < Z < 0.3, M is Ce3+、Ti4+、Zr4+、Mg2+One or more;The presoma is nano-sheet agglomerated particles, the nano-sheet 30-50 nanometers of the thickness of presoma.
A kind of preparation method as described in claim 1 without cobalt richness lithium tertiary cathode material NMA, includes the following steps:
1) by soluble nickel salt, manganese salt, aluminium salt, cerium salt, titanium salt, zirconates, magnesium salts, according to the no cobalt richness lithium tertiary cathode The corresponding stoichiometric ratio mixing of the required ingredient that the presoma chemical formula of material NMA determines;Deionized water is added, gold is made Belong to salting liquid;
2) deionized water dissolving is added in precipitating reagent, is made into precipitant solution;
3) bottom water is added in precipitation reactor, the precipitating reagent that metal salt solution made from step 1), step 2) are made into After each self-heating of solution, cocurrent is injected into precipitation reactor;Then it keeps the temperature, stir progress coprecipitation reaction, coprecipitation reaction Terminate, filter while hot;Deionized water washing, vacuum drying treatment finally are carried out to the sediment filtered out, obtain the no cobalt The presoma of rich lithium tertiary cathode material NMA;
4) presoma of the no cobalt richness lithium tertiary cathode material NMA is uniformly mixed with lithium source, is placed in oxygen atmosphere Calcining, is ground up, sieved after then cooling to room temperature, and is made without cobalt richness lithium tertiary cathode material NMA.
Further, nickel salt described in the step 1) is one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate or more Kind;
The manganese salt is one of manganese nitrate, manganese acetate, manganese chloride and manganese sulfate or a variety of;
The aluminium salt is one of aluminum nitrate, aluminium chloride, aluminum sulfate and aluminum acetate or a variety of;
The cerium salt is one of cerous nitrate, cerous acetate, cerium chloride and cerous sulfate or a variety of;
The titanium salt is one of Titanium Nitrate, acetic acid titanium, cerous sulfate or a variety of;
The zirconates is one of zirconium nitrate, zirconium acetate, zirconium sulfate or a variety of;
The magnesium salts is one of magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride or a variety of;
In the metal salt solution, metal cation concentration is 0.01mol/L~2.0mol/L.
Further, precipitating reagent described in the step 2) is one or both of sodium hydroxide, potassium hydroxide;
Hydroxyl concentration is 0.1mol/L~10mol/L in the precipitant solution.
Further, bottom water additional amount in precipitation reactor described in the step 3), the 20-30% of Zhan Fanying total volume; The coprecipitation reaction carries out under inert atmosphere protection, and reaction temperature is 40-90 DEG C, reaction time 1-3h, reaction system PH value be 7-13.
Further, lithium source described in the step 4) is the one or two of lithium hydroxide, lithium carbonate, in additional amount Lithium meets the mole of the required lithium of the no cobalt richness lithium tertiary cathode material NMA stoichiometric ratio.
Further, the presoma and lithium source are subjected to ball milling mixing in the step 4), in 350-700 degree preroast 2- It 5 hours, takes out preroast product and is ground.
Further, the preroast product after the grinding is sintered in oxygen atmosphere furnace, sintering temperature 700-850 Degree, time are 15-30 hours.
Compared with prior art, the present invention beneficial effect is: (1) replacing valence with cheap Mn in NCA positive electrode It is worth valuableness Co, and by the way that excessive lithium (rich lithium) is added, by stratiform LiNiO2Phase and stratiform LiMnO2It is mutually compound to have prepared a kind of richness The NMA positive electrode of lithium layer structure, to achieve the purpose that improve capacity and stability, reduce cost.
(2) present invention, because being free of cobalt, is greatly reduced its preparation cost, under cost without cobalt richness lithium tertiary cathode material Range of decrease degree reaches 20-30%.
(3) presoma Ni of the present invention without cobalt richness lithium tertiary cathode material1-x-y-zMnxAlyMz(OH)2For nano-sheet reunion Particle has the characteristics that density is small, specific surface area is high, chemical reactivity is high, makes the anode formed in high-temperature burning process Material layer structure is more perfect, and chemical property is more stable.
(4) different from existing ternary anode material precursor synthetic method, the presoma is using coprecipitation in height Concentration, is added without complex ion NH at the low reaction time4 +Under the conditions of carry out, on the one hand, keep each precipitated cationic complete, rate of deposition >= 99.99%, remaining heavy metal ion content < 0.001g/l in filtrate substantially reduce the weight avoided in filtrate recovery processing On the other hand metal ion pollution makes reaction efficiency greatly improve and (improve 200-300%), operating cost declines 40-50%.
(5) obtained without cobalt richness lithium tertiary cathode material, there is very high electro-chemical activity and cyclical stability, capacity Reach 190-200mAh/g, 100 times circulation volume conservation rate reaches 90-95%.
Detailed description of the invention
Fig. 1 is presoma SEM figure of the present invention without cobalt richness lithium tertiary cathode material NMA;
Fig. 2 is SEM figure of the present invention without cobalt richness lithium tertiary cathode material NMA;
Fig. 3 is charge and discharge electrograph (the 100 circulations) curve graph of the present invention without cobalt richness lithium tertiary cathode material NMA.
Specific embodiment
Embodiments of the present invention are described in further detail with reference to the accompanying drawing.
As shown in Fig. 1 to Fig. 3, a kind of no cobalt richness lithium tertiary cathode material NMA, the no cobalt richness lithium tertiary cathode material The chemical formula for expecting NMA is Li1+PNi1-x-y-zMnxAlyMzO2, presoma chemical formula is Ni1-x-y-zMnxAlyMz(OH)2, in which: 0.03 < P <, 0.3,0.1 < X <, 0.6,0.01 < Y < 0.1,0.01 < Z < 0.3, M Ce3+、Ti4+、Zr4+、Mg2+One kind Or it is two or more;The presoma is nano-sheet agglomerated particles, and concrete shape is as shown in Figure 1, the nano-sheet presoma 30-50 nanometers of thickness.The presoma pattern of such no cobalt richness lithium tertiary cathode material NMA, structure have that density is small, compares table The feature that area is high, chemical reactivity is high.The stratiform LiNiO that presoma is formed by high-temperature calcination2Phase and stratiform LiMnO2Phase It is compound, a kind of NMA positive electrode of lithium-rich structure ha