CN105576233A - Nickel base trinary positive electrode material and preparation method thereof - Google Patents
Nickel base trinary positive electrode material and preparation method thereof Download PDFInfo
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- CN105576233A CN105576233A CN201610120593.4A CN201610120593A CN105576233A CN 105576233 A CN105576233 A CN 105576233A CN 201610120593 A CN201610120593 A CN 201610120593A CN 105576233 A CN105576233 A CN 105576233A
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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
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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
- 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
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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
- H01M4/52—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
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- H—ELECTRICITY
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Abstract
The invention provides a nickel base trinary positive electrode material, which is obtained through compounding coupling agents onto the surface of nickel base materials and then performing heat treatment. The hydrophilic surface property of the nickel base trinary positive electrode material is improved by a compound modification method; the problem that the nickel base trinary positive electrode material is sensitive to the moisture in the environment is effectively solved; the residue lithium content on the surface of the particles is reduced; in addition, the discharging specific capacity loss of the nickel base trinary positive electrode material cannot be caused; the dissolution of transition metal ions on the surfaces of the particles in the long-time circulation process can be inhibited; the corrosion of HF generated in the charging and discharging process on the surface of the materials can be reduced; the electrochemical performance of the materials is improved.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of Ni-based tertiary cathode material and preparation method thereof.
Background technology
Lithium ion battery has that operating voltage is high, specific energy is high, has extended cycle life, lightweight, white electric discharge less, memory-less effect and cost performance ratio, oneself becomes the main alternative of the field rechargeable type power supplys such as high power motor vehicle, artificial satellite, Aero-Space.Therefore lithium ion battery and associated materials thereof become the study hotspot of scientific research personnel.Positive electrode is one of lithium ion battery critical material, decides the performance of lithium ion battery.And the maximum bottleneck of at present limiting lithium ion electrokinetic cell energy density, power density, cycle life and fail safe is positive electrode technology.
In current power lithium-ion battery positive electrode, the ternary layered positive electrode of nickle cobalt lithium manganate, its chemical formula is LiNi
1-x-yco
xmn
yo
2, due to the cooperative effect of Ni, Co and Mn tri-kinds of elements, have that specific discharge capacity is high, energy density is high, cost is lower and advantages of environment protection, become the great positive electrode of world market power lithium-ion battery application increment in recent years.This is Ni-based tertiary cathode material (LiNi wherein
1-x-yco
xmn
yo
2(1-x-y>=0.5)) combine LiCoO
2, LiNiO
2and LiMnO
2the advantage of three kinds of anode material for lithium-ion batteries, its performance is better than above arbitrary one-component positive electrode, there is obvious cooperative effect.In this system, the chemical property of material and physical property different along with the change of these three kinds of transition metal ratios.Introduce Ni, contribute to the capacity improving material, but Ni
2+during too high levels, with Li
+mixing cause cycle performance to worsen.By introduce Co, cation mixing occupy-place can be reduced, the layer structure of effective stabilizing material, reduce resistance value, improve conductivity, but when Co ratio increase to certain limit time can cause a and c reduction and c/a increase, capacity step-down.Introduce Mn, not only can reduce material cost, but also the safety and stability of material can be improved.
But Ni-based tertiary cathode material also also exists defect, is easily corroded and makes cycle life reduce in cyclic process, have impact on the chemical property such as cycle performance and high rate performance, thus limit the large-scale commercial applications of such material; And due to the nickel content of nickel-base material high, when material exposes in atmosphere, very easily with the moisture generation side reaction in air, cause surperficial residual alkali content higher, its main component is Li
2cO
3, some is with Li in addition
2sO
4exist with the form of LiOH, so Ni-based tertiary cathode material is in the moisture of producing and all require in strictly controlled environment in packaging process, had a strong impact on drawing abillity, thus become the yoke that Ni-based tertiary cathode material further develops.
Therefore, how to obtain one and there is better cycle performance and the Ni-based tertiary cathode material of high rate performance, the processability of Ni-based tertiary cathode material can also be promoted simultaneously, become field Nei Ge production firm problem demanding prompt solution.
Summary of the invention
In view of this, the invention provides a kind of Ni-based tertiary cathode material and preparation method thereof, the technical problem solved is the surface modified method of conventional Ni-based tertiary cathode material, the Ni-based tertiary cathode material that the present invention obtains, there is higher cycle performance and high rate performance, but also there is good post-production performance.Meanwhile, the preparation method that the present invention improves is applicable to large-scale production and application, is easy to the homogenizing and the long term stabilization that realize the preparation of positive electrode batch.
The invention provides a kind of Ni-based tertiary cathode material, heat-treat again after being compounded in nickel-base material surface by coupling agent and obtain.
Preferably, described coupling agent is one or more of titanate coupling agent, aluminate coupling agent and silane coupler.
Preferably, the chemical formula of described nickel-base material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, (1-x-y)>=0.5, x > 0, y > 0;
The mass ratio of described coupling agent and described nickel-base material is (0.005 ~ 0.1): 1.
The invention provides a kind of preparation method of Ni-based tertiary cathode material, comprise the following steps:
1) by after nickel-base material presoma and lithium salts mixed calcining, nickel-base material is obtained;
The chemical formula of described nickel-base material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, (1-x-y)>=0.5, x > 0, y > 0;
2) above-mentioned steps is obtained nickel-base material and coupling agent reacts in organic solvent, then after roasting, obtain Ni-based tertiary cathode material.
Preferably, described nickel-base material presoma is nickel cobalt manganese hydroxide, its chemical formula such as formula shown in (II),
Ni
1-x-yco
xmn
y(OH)
2(II); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
Preferably, described lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate;
The mol ratio of described nickel-base material presoma and described lithium salts is 1:(1.01 ~ 1.10).
Preferably, the temperature of described calcining is 700 ~ 1000 DEG C, and the time of described calcining is 4 ~ 20h.
Preferably, described organic solvent comprises one or more in ethanol, n-butanol, ethylene glycol, isopropyl alcohol and acetone;
The mass ratio of described nickel-base material and organic solvent is 1:(1 ~ 5).
Preferably, the temperature of described reaction is 50 ~ 90 DEG C, and the time of described reaction is 0.5 ~ 5h.
Preferably, the temperature of described roasting is 200 ~ 600 DEG C, and the time of described roasting is 1 ~ 5h.
The invention provides a kind of Ni-based tertiary cathode material, heat-treat again after being compounded in nickel-base material surface by coupling agent and obtain, namely obtaining by heat-treating again after coupling agent finishing nickel-base material.Compared with prior art, the present invention is by the method for modifying of surface recombination, improve the surface nature that Ni-based tertiary cathode material is hydrophilic, efficiently solve Ni-based tertiary cathode material to the more sensitive problem of Environmental Water, reduce the remaining lithium content of particle surface, and the loss of Ni-based tertiary cathode material specific discharge capacity can not be caused, and the dissolving of particle surface transition metal ions in long-term cyclic process can be suppressed, the HF produced in minimizing charge and discharge process, to the corrosion of material surface, improves the chemical property of material.
Experimental result shows, the lithium ion battery first discharge specific capacity of Ni-based tertiary cathode material composition provided by the invention is 183.7mAh/g, and circulate the near 156.2mAh/g of specific capacity after 300 times, and it is 85% that capability retention reaches; Ni-based tertiary cathode material provided by the invention is place after 30 days in the air of 80% in humidity, the first discharge specific capacity of recomposition lithium ion battery is 180.4mAh/g, compared with when not placing, reduced by only the coated rear material of about 3.3mAh/g after circulation 300 times, specific capacity decays to 141.6mAh/g by 180.4mAh/g, and capability retention is 78.5%.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the coated rear Ni-based tertiary cathode material of preparation in embodiment 1;
Fig. 2 is the TEM figure of the not coated and coated rear Ni-based tertiary cathode material of preparation in embodiment 1;
Fig. 3 is the cycle charge-discharge curve chart of the not coated and coated rear Ni-based tertiary cathode material of preparation in embodiment 1;
Fig. 4 is the XPS spectrum figure that the not coated and coated rear Ni-based tertiary cathode material of preparation in embodiment 1 places C element after 30 in atmosphere;
Fig. 5 is that the not coated and coated rear Ni-based tertiary cathode material of preparation in embodiment 1 places the first with 300th charging and discharging curve figure after 30 days in atmosphere;
Fig. 6 is that the not coated and coated rear Ni-based tertiary cathode material of preparation in embodiment 1 places the cycle charge-discharge curve chart after 30 days in atmosphere;
Fig. 7 is the cycle charge-discharge curve chart of the coated rear Ni-based tertiary cathode material of preparation in embodiment 2;
Fig. 8 is the cycle charge-discharge curve chart of the coated rear Ni-based tertiary cathode material of preparation in embodiment 3.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
The all raw materials of the present invention, be not particularly limited its source, commercially buy or prepare according to conventional method well known to those skilled in the art.
The all raw materials of the present invention, are not particularly limited its purity, and the present invention preferably adopts analysis pure.
The invention provides a kind of Ni-based tertiary cathode material, heat-treat again after being compounded in nickel-base material surface by coupling agent and obtain.
The present invention is not particularly limited described nickel-base material, and with Ni-based ternary material for making lithium ion cell positive well known to those skilled in the art or rich nickel cobalt nickel lithium manganate ternary material, its chemical formula is LiNi
1-x-yco
xmn
yo
2, the present invention be preferably Ni-based ternary material, be more preferably rich nickel ternary material, the chemical formula of described nickel-base material preferably such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
The present invention is not particularly limited described coupling agent, with coupling agent well known to those skilled in the art, those skilled in the art can select according to practical condition, combining case and properties of product, the present invention is for ensureing composite effect and positive electrode performance, described coupling agent is preferably one or more of titanate coupling agent, aluminate coupling agent and silane coupler, is more preferably titanate coupling agent, aluminate coupling agent or silane coupler; The present invention is not particularly limited described titanate coupling agent, and with titanate coupling agent well known to those skilled in the art, the present invention is specifically preferably titanate esters DNZ-101 and/or titanate esters DNZ-311; The present invention is not particularly limited described aluminate coupling agent, with aluminate coupling agent well known to those skilled in the art, the present invention is specifically preferably one or more in ester aluminate DL-411, ester aluminate DL-411 AF, ester aluminate DL-411 D and Aluminate ASA; The present invention is not particularly limited described silane coupler, and with silane coupler well known to those skilled in the art, the present invention is specifically preferably Silane coupling agent KH550 and/or silane coupler KH560.
The present invention is not particularly limited described compound, with composite definitions well known to those skilled in the art, the present invention preferably coated, half coated, modify, stacked or generate, be more preferably coated or half coated, most preferably be coated or modify.The present invention to be coatedly not particularly limited described, and coatedly to define with well known to those skilled in the art, the present invention is preferably entirely coated.The mass ratio of the present invention to described coupling agent and described nickel-base material is not particularly limited, those skilled in the art can select according to practical condition, coated situation and properties of product, the mass ratio of coupling agent of the present invention and described nickel-base material is preferably (0.005 ~ 0.1): 1, be more preferably (0.01 ~ 0.09): 1, be more preferably (0.02 ~ 0.08): 1, most preferably be (0.04 ~ 0.06): 1.The present invention is not particularly limited described heat treatment, with heat treatment mode well known to those skilled in the art.
The present invention adopts coupling agent coated or be modified at nickel-base material surface, obtains Ni-based tertiary cathode material, i.e. a kind of surface coating modification or surface modified Ni-based tertiary cathode material.The present invention is directed to existing nickel-base material due to nickel content high, when material exposes in atmosphere, the O in material surface lattice
2 –meeting and the CO in air
2or H
2o reaction generates CO
3 2 –or OH
–, the Li of material surface remnants is (with Li
2o form exist) will and CO
3 2 –or OH
–reaction generates Li
2cO
3or LiOH, these can have a strong impact on the problem of drawing abillity and chemical property at the impurity that material surface is formed.In addition, these impurity also aggravate the decomposition of electrolyte, and the HF of generation causes the corrosion to material granule surface, and then have impact on the defect of cycle performance.The present invention utilizes the hydroxyl generation chemical bonding process of surface functional group in coupling agent and positive electrode particle surface, mainly comprise spontaneous hydrolysis, condensation, formation hydrogen bond or covalent bond, make the coated one deck organic film of the particle surface of material, and then effectively reduce the surface corrosion phenomenon in the impact of nickel-base material surface impurity and use procedure; Further improve the surface nature that Ni-based tertiary cathode material is hydrophilic simultaneously, efficiently solve Ni-based tertiary cathode material to the more sensitive problem of Environmental Water, reduce the remaining lithium content of particle surface
The invention provides a kind of preparation method of Ni-based tertiary cathode material, comprise the following steps, comprise the following steps:
1) by after nickel-base material presoma and lithium salts mixed calcining, nickel-base material is obtained;
The chemical formula of described nickel-base material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, (1-x-y)>=0.5, x > 0, y > 0;
2) above-mentioned steps is obtained nickel-base material and coupling agent reacts in organic solvent, then after roasting, obtain Ni-based tertiary cathode material.
The present invention is to optimum principles such as the selection of described raw material and ratios, and as without dated especially, all consistent with aforementioned Ni-based tertiary cathode material, this is no longer going to repeat them.
First the present invention by after nickel-base material presoma and lithium salts mixed calcining, obtains nickel-base material.
The present invention is not particularly limited described nickel-base material presoma, and with Ni-based ternary anode material precursor well known to those skilled in the art, the present invention is preferably nickel cobalt manganese hydroxide, is more preferably the chemical formula had such as formula shown in (II),
Ni
1-x-yco
xmn
y(OH)
2(II); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
The source of the present invention to described nickel-base material presoma is not particularly limited, and those skilled in the art can be prepared or commercially according to conventional methods, the concrete element ratio of the present invention to described nickel-base material presoma is not particularly limited, with the element of Ni-based ternary anode material precursor well known to those skilled in the art ratio, nickel in the preferred described nickel-base material presoma of the present invention, cobalt and manganese three kinds of elements are preferably 1:(0.1 ~ 1 in the mol ratio of nickel Co-Mn metal respectively): (0.1 ~ 1), be more preferably 1:(0.2 ~ 0.8): (0.2 ~ 0.8), be more preferably 1:(0.3 ~ 0.6): (0.3 ~ 0.6), most preferably be 1:(0.4 ~ 0.5): (0.4 ~ 0.5), exemplary, can be 1:1:1, 2:2:1, 2:1:2, 5:2:3, 3:1:1, 7:1.5:1.5, any one in 8:1:1.
The present invention is not particularly limited described lithium salts, with the lithium salts for the preparation of Ni-based tertiary cathode material well known to those skilled in the art, the present invention be preferably in lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate one or more, be more preferably lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate, most preferably be lithium hydroxide, lithium nitrate or lithium acetate.The mol ratio of nickel-base material presoma of the present invention and described lithium salts is preferably 1:(1.01 ~ 1.10), be more preferably 1:(1.02 ~ 1.09), be more preferably 1:(1.03 ~ 1.08), most preferably be 1:(1.04 ~ 1.07); The molal quantity of the above-mentioned nickel-base material presoma of the present invention calculates in the molal quantity summation of nickel Co-Mn metal, and the molal quantity of above-mentioned lithium salts is the molal quantity calculating of lithium metal meter.
The present invention is not particularly limited described nickel-base material, and with the Ni-based tertiary cathode material of richness well known to those skilled in the art, the present invention is preferably Ni-based tertiary cathode material, and more preferably the chemical formula of described nickel-base material is such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
The condition of the present invention to described mixing is not particularly limited, with the mixing condition of this type of reaction well known to those skilled in the art, those skilled in the art can adjust according to practical condition, raw material condition, the present invention is preferably Homogeneous phase mixing, the time of described mixing is preferably 3 ~ 6h, is more preferably 4 ~ 5h; The mode of the present invention to described mixing is not particularly limited, and with hybrid mode well known to those skilled in the art, the present invention is preferably uniformly mixed.
The condition of the present invention to described calcining is not particularly limited, with the calcination condition of tertiary cathode material well known to those skilled in the art, those skilled in the art can adjust according to practical condition, product situation and performance requirement, the temperature of calcining of the present invention is preferably 700 ~ 1000 DEG C, be more preferably 750 ~ 950 DEG C, most preferably be 800 ~ 900 DEG C; The time of described calcining is preferably 4 ~ 20h, is more preferably 6 ~ 18h, is more preferably 8 ~ 16h, most preferably is 10 ~ 14h; The present invention's other conditions to described calcining are not particularly limited, with calcination condition well known to those skilled in the art.
The present invention subsequently above-mentioned steps is obtained nickel-base material and coupling agent reacts in organic solvent, then after roasting, obtains Ni-based tertiary cathode material.
The present invention is not particularly limited described organic solvent, with organic solvent well known to those skilled in the art, the present invention, be preferably in ethanol, n-butanol, ethylene glycol, isopropyl alcohol and acetone one or more, be more preferably ethanol, n-butanol, ethylene glycol, isopropyl alcohol or acetone, most preferably be ethanol, n-butanol, isopropyl alcohol or acetone.The consumption of the present invention to described organic solvent is not particularly limited, with organic solvent conventional amount used well known to those skilled in the art, the mass ratio of nickel-base material of the present invention and organic solvent is preferably 1:(1 ~ 5), be more preferably 1:(1.5 ~ 4.5), be more preferably 1:(2 ~ 4), most preferably be 1:(2.5 ~ 3.5).
The condition of the present invention to described reaction is not particularly limited, those skilled in the art can adjust according to practical condition, product situation and performance requirement, the temperature of reaction of the present invention is preferably 50 ~ 90 DEG C, is more preferably 65 ~ 85 DEG C, most preferably is 60 ~ 80 DEG C; The time of described reaction is preferably 0.5 ~ 5h, is more preferably 1 ~ 4h, most preferably is 1 ~ 2h.Reactive mode of the present invention is not particularly limited, and the present invention is preferably stirring reaction, and described mixing speed is preferably 300 ~ 700 turns/min, is more preferably 400 ~ 600 turns/min.The present invention is not particularly limited described reacted post processing mode, with conventional post processing mode well known to those skilled in the art, those skilled in the art can adjust according to practical condition, product situation and performance requirement, the present invention is preferably after reaction terminates, carry out filtration step while hot, then carry out the postprocessing working procedures such as washing and drying; The actual conditions of the present invention to postprocessing working procedures such as above-mentioned filtration, washing and dryings is not particularly limited, with the condition of above-mentioned postprocessing working procedures well known to those skilled in the art.
The condition of the present invention to described roasting is not particularly limited, with constant temperature calcining condition well known to those skilled in the art, those skilled in the art can adjust according to practical condition, product situation and performance requirement, the temperature of roasting of the present invention is preferably 200 ~ 600 DEG C, be more preferably 250 ~ 500 DEG C, most preferably be 300 ~ 400 DEG C; The time of described roasting is preferably 1 ~ 5h, is more preferably 1.5 ~ 4.5h, most preferably is 2 ~ 4h; The present invention's other conditions to described roasting are not particularly limited, and with roasting condition well known to those skilled in the art, the present invention is also preferred carries out roasting under protective atmosphere; The present invention is not particularly limited described protective atmosphere, the protective atmosphere commonly used with those skilled in the art, and the present invention is preferably nitrogen or inert gas.
The present invention carries out recombination reaction in non-aqueous system, simple and convenient, without the need to regulating pH and not introducing the technological process of impurity anions, effectively solve in existing coated process, usual employing slaine aqueous systems, precipitation reaction obtains coating, and in precipitation reaction and washing and filtering process, be easy to cause the dissolving of nickel-base material surface metal and the disappearance of lithium, the specific capacity of material is caused to reduce, and operating procedure is loaded down with trivial details, industrialization difficulty is comparatively large, and the problems such as waste water treatment mostly containing remaining anion.
The present invention has prepared Ni-based tertiary cathode material through above-mentioned steps, a kind of Ni-based tertiary cathode material of coupling agent coating modification, the present invention uses coupling agent as compound material, essence is that coupling agent is in coated process, containing two kinds of groups in coupling agent molecule, one is hydrophilic radical, can with inorganic powder surface generation chemical reaction and make inorganic powder surface be coated with one deck organic film, to reduce the surface energy of inorganic particle, change the surface nature that it is hydrophilic; Another kind of group is hydrophobic grouping, can react with high molecular polymer or tangle, between inorganic particle and high molecular polymer, serve as function served as bridge, inorganic particle is combined in high molecular polymer securely.Thus improve the hydrophilic surface nature of Ni-based tertiary cathode material, effectively overcome Ni-based tertiary cathode material due to nickel content high, when material exposes in atmosphere, the Li of material surface remnants can generate alkaline, lithium salt impurity, the defect of drawing abillity and cycle performance and high rate performance can be had a strong impact on, thus solve Ni-based tertiary cathode material to the more sensitive problem of Environmental Water, reduce the remaining lithium content of particle surface, improve later stage processability.
The present invention is after cryogenic thermostat roasting, define the constitutionally stable metal oxide of one deck or lithiated metal oxide composite membrane at particle surface, decrease the phenomenon that positive electrode is easily made cycle life reduce by the hydrolysate HF of electrolyte corrosion in cyclic process.And owing to have employed non-aqueous system, thus the loss of Ni-based tertiary cathode material specific discharge capacity can not be caused, and the dissolving of particle surface transition metal ions in long-term cyclic process can be suppressed, the HF produced in minimizing charge and discharge process, to the corrosion of material surface, improves the chemical property of material.
The present invention carries out Performance Detection to the above-mentioned lithium ion battery be made up of Ni-based tertiary cathode material, experimental result shows, the lithium ion battery first discharge specific capacity of Ni-based tertiary cathode material composition provided by the invention is 183.7mAh/g, circulate the near 156.2mAh/g of specific capacity after 300 times, and it is 85% that capability retention reaches; Ni-based tertiary cathode material provided by the invention is place after 30 days in the air of 80% in humidity, the first discharge specific capacity of recomposition lithium ion battery is 180.4mAh/g, compared with when not placing, reduced by only the coated rear material of about 3.3mAh/g after circulation 300 times, specific capacity decays to 141.6mAh/g by 180.4mAh/g, and capability retention is 78.5%.
In order to understand the present invention further, be described Ni-based tertiary cathode material of one provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
By business-like Ni-based Ni
0.8co
0.1mn
0.1(OH)
2presoma and lithium hydroxide are according to Li:(Ni+Co+Mn) molar ratio of=1.03:1 mix after at 800 DEG C high-temperature calcination 10h, cool, pulverize, sieving obtains not coated nickel-base anode material, is non-clad material.
Not coated nickel-base anode material obtained above is joined in absolute ethyl alcohol, the mass ratio of Ni-based tertiary cathode material and absolute ethyl alcohol is 1:2, after stirring high speed dispersion, the addition being 0.01:1 according to the mass ratio with Ni-based tertiary cathode material adds titanate coupling agent, the reaction temperature of the hierarchy of control is 55 DEG C, mixing speed is 400 turns/min, react and filter while hot after 1 hour, constant temperature calcining 2h at 300 DEG C, the obtained Ni-based tertiary cathode material coated by titanate coupling agent decomposition oxide, is coated rear material.
It is the XRD diffraction pattern of the coated rear Ni-based tertiary cathode material of preparation in embodiment 1 see Fig. 1, Fig. 1; Be the TEM figure of the not coated and coated rear Ni-based tertiary cathode material of preparation in embodiment 1 see Fig. 2, Fig. 2.As shown in Figure 1, the basic and LiNiO of the composite positive pole after coated
2standard diagram coincide, and coated can not having an impact to material structure is described, can keeps former LiNiO
2basic structure.As shown in Figure 2, the constitutionally stable metal oxide of one deck or the lithiated metal oxide composite membrane of 20-50nm is about in coated a layer thickness of the surface uniform of positive electrode.
Using the not coated and coated latter two material of above-mentioned preparation as active material, with lithium sheet for negative pole, in vacuum glove box, be assembled into CR2025 button cell, adopt blue electric battery test system to carry out cycle performance test at 25 DEG C.Its test voltage scope is 2.8 ~ 4.3V, and under charging and discharging currents is 1C, each circulation 300 times, investigates capability retention.
See Fig. 3, Fig. 3 is the cycle charge-discharge curve chart of the not coated and coated rear Ni-based tertiary cathode material of preparation in embodiment 1, shown in the cycle performance of Fig. 3 is tested, non-clad material 1C first discharge specific capacity is 184.7mAh/g, circulate the near 118.6mAh/g of specific capacity after 300 times, and capability retention is only 64.2%; And coated rear material 1C first discharge specific capacity is 183.7mAh/g, circulate the near 156.2mAh/g of specific capacity after 300 times, and it is 85% that capability retention reaches.Visible under this technique, improve the cycle performance of nickel-base material greatly.
For investigating the impact of the present invention on nickel-base material surface texture and shelf characteric, by the non-clad material obtained and coated after material in humidity be all place 30 days in the air of 80% after, adopt the Li of XPS qualitative analysis material surface
2cO
3impurity content, and the non-clad material after placing and coated rear material are assembled into CR2025 button cell according to the method described above and carry out electrochemical property test contrast.
The XPS spectrum figure of 30 rear C element is placed in atmosphere see Fig. 4, Fig. 4 not coated and coated rear Ni-based tertiary cathode material that is preparation in embodiment 1.As shown in the XPS spectrum figure of Fig. 4 carbon, contrast represents material surface Li
2cO
3can finding out in conjunction with energy peak intensity of impurity content, the peak intensity of coated rear material is starkly lower than non-clad material, illustrate after titanate coupling agent coating modification, the inorganic lithium metal-oxide film defining titaniferous at particle surface significantly can avoid moisture in air and particle surface generation side reaction, reduces Li
2cO
3or the generation of the impurity such as LiOH.
The not coated and coated rear Ni-based tertiary cathode material being preparation in embodiment 1 see Fig. 5, Fig. 5 places the first with 300th charging and discharging curve figure after 30 days in atmosphere.As shown in the charging and discharging curve of Fig. 5, after placing the identical time in atmosphere, non-clad material and coated rear material first discharge specific capacity differ larger, the first discharge specific capacity of coated rear material is 180.4mAh/g, compared with when not placing, reduced by only about 4mAh/g, and the first discharge specific capacity of non-clad material is only 160.4mAh/g, reduces amplitude very large.The voltage platform of the charging and discharging curve of the 300th time of non-clad material disappears, and coated rear material still keeps certain discharge voltage plateau.This is because the Li of 30 days rear surfaces placed in atmosphere by non-clad material
2cO
3impurity content is higher, and Charge-transfer resistance is increased greatly, and lithium ion transport is obstructed, and the polarization phenomena causing battery are comparatively serious, and decomposes after oxide coating modification through titanate coupling agent and significantly improve this phenomenon, improves the shelf characteric of material.
The not coated and coated rear Ni-based tertiary cathode material being preparation in embodiment 1 see Fig. 6, Fig. 6 places the cycle charge-discharge curve chart after 30 days in atmosphere.As shown in the test of Fig. 6 cycle performance, after placing the identical time in atmosphere, coated rear material is after circulation 300 times, and specific capacity decays to 141.6mAh/g by 180.4mAh/g, and capability retention is 78.5%.And non-clad material circulates after 300 times, specific capacity decays to 83.2mAh/g by 160.4mAh/g, and capability retention is 51.8%.
Embodiment 2
By business-like Ni-based Ni
0.5co
0.2mn
0.3(OH)
2presoma and lithium carbonate are according to Li:(Ni+Co+Mn) molar ratio of=1.04:1 mix after at 900 DEG C high-temperature calcination 12h, cool, pulverize, sieving obtains nickel-base material.
Nickel-base material obtained above is joined in isopropyl alcohol, the mass ratio of Ni-based tertiary cathode material and isopropyl alcohol is 1:3, after stirring high speed dispersion, the addition being 0.02:1 according to the mass ratio with Ni-based tertiary cathode material adds aluminate coupling agent, the reaction temperature of the hierarchy of control is 60 DEG C, and mixing speed is 500 turns/min, reacts and filters while hot after 1.5 hours, constant temperature calcining 3h at 400 DEG C, the obtained Ni-based tertiary cathode material coated by aluminate coupling agent decomposition oxide.
Using the coated rear Ni-based tertiary cathode material of above-mentioned preparation as active material, with lithium sheet for negative pole, in vacuum glove box, be assembled into CR2025 button cell, adopt blue electric battery test system to carry out cycle performance test at 25 DEG C.Its test voltage scope is 2.7 ~ 4.2V, circulates 500 times under charging and discharging currents is 0.5C, investigates capability retention.
It is the cycle charge-discharge curve chart of the coated rear Ni-based tertiary cathode material of preparation in embodiment 2 see Fig. 7, Fig. 7.As shown in the cycle performance test of Fig. 7, coated rear material 0.5C first discharge specific capacity is 151.3mAh/g, and circulate the near 129.5mAh/g of specific capacity after 500 times, and capability retention is 85.6%.
Embodiment 3
By business-like Ni-based Ni
0.6co
0.2mn
0.2(OH)
2presoma and lithium hydroxide are according to Li:(Ni+Co+Mn) molar ratio of=1.06:1 mix after at 850 DEG C high-temperature calcination 15h, cool, pulverize, sieving obtains Ni-based tertiary cathode material.
Ni-based tertiary cathode material obtained above is joined in ethylene glycol, the mass ratio of Ni-based tertiary cathode material and ethylene glycol is 1:4, after stirring high speed dispersion, the addition being 0.03:1 according to the mass ratio with Ni-based tertiary cathode material adds silane coupler, the reaction temperature of the hierarchy of control is 70 DEG C, and mixing speed is 600 turns/min, reacts and filters while hot after 2 hours, constant temperature calcining 4h at 500 DEG C, the obtained Ni-based tertiary cathode material coated by silane coupler decomposition oxide.
Using the coated rear nickel-base material of above-mentioned preparation as active material, with lithium sheet for negative pole, in vacuum glove box, be assembled into CR2025 button cell, adopt blue electric battery test system to carry out cycle performance test at 25 DEG C.Its test voltage scope is 3.0 ~ 4.3V, circulates 500 times under charging and discharging currents is 0.5C, investigates capability retention.
It is the cycle charge-discharge curve chart of the coated rear Ni-based tertiary cathode material of preparation in embodiment 3 see Fig. 8, Fig. 8.As shown in the cycle performance test of Fig. 8, coated rear material 0.5C first discharge specific capacity is 175.3mAh/g, and circulate the near 148.5mAh/g of specific capacity after 500 times, and capability retention is 84.7%..
Above Ni-based tertiary cathode material of one provided by the invention and preparation method thereof is described in detail; apply specific case herein to set forth principle of the present invention and execution mode; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
Claims (10)
1. a Ni-based tertiary cathode material, is characterized in that, heat-treats again obtain by coupling agent after being compounded in nickel-base material surface.
2. Ni-based tertiary cathode material according to claim 1, is characterized in that, described coupling agent is one or more of titanate coupling agent, aluminate coupling agent and silane coupler.
3. Ni-based tertiary cathode material according to claim 1, is characterized in that, the chemical formula of described nickel-base material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, (1-x-y)>=0.5, x > 0, y > 0;
The mass ratio of described coupling agent and described nickel-base material is (0.005 ~ 0.1): 1.
4. a preparation method for Ni-based tertiary cathode material, is characterized in that, comprises the following steps:
1) by after nickel-base material presoma and lithium salts mixed calcining, nickel-base material is obtained;
The chemical formula of described nickel-base material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, (1-x-y)>=0.5, x > 0, y > 0;
2) above-mentioned steps is obtained nickel-base material and coupling agent reacts in organic solvent, then after roasting, obtain Ni-based tertiary cathode material.
5. preparation method according to claim 4, is characterized in that, described nickel-base material presoma is nickel cobalt manganese hydroxide, its chemical formula such as formula shown in (II),
Ni
1-x-yco
xmn
y(OH)
2(II); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
6. preparation method according to claim 4, is characterized in that, described lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate;
The mol ratio of described nickel-base material presoma and described lithium salts is 1:(1.01 ~ 1.10).
7. preparation method according to claim 4, is characterized in that, the temperature of described calcining is 700 ~ 1000 DEG C, and the time of described calcining is 4 ~ 20h.
8. preparation method according to claim 4, is characterized in that, described organic solvent comprise in ethanol, n-butanol, ethylene glycol, isopropyl alcohol and acetone one or more;
The mass ratio of described nickel-base material and organic solvent is 1:(1 ~ 5).
9. preparation method according to claim 4, is characterized in that, the temperature of described reaction is 50 ~ 90 DEG C, and the time of described reaction is 0.5 ~ 5h.
10. preparation method according to claim 4, is characterized in that, the temperature of described roasting is 200 ~ 600 DEG C, and the time of described roasting is 1 ~ 5h.
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