CN105552360A - Modified lithium nickel cobalt manganese oxide cathode material and preparation method thereof - Google Patents
Modified lithium nickel cobalt manganese oxide cathode material and preparation method thereof Download PDFInfo
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- 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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Abstract
The invention provides a modified lithium nickel cobalt manganese oxide cathode material which comprises a lithium nickel cobalt manganese oxide material, LiMnPO4 combined on the surface of the lithium nickel cobalt manganese oxide material, and graphene combined on the surface of LiMnPO4. According to the invention, the lithium nickel cobalt manganese oxide material is modified through double combination, wherein a layer of LiMnPO4 coating the surfaces of particles can improve the interface stability of the material under a high cut-off voltage, and graphene coating at the outer layer can improve the electronic conductivity of the material and weak the polarization effect.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, be specifically related to nickel-cobalt lithium manganate cathode material of a kind of modification 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, nickel-cobalt lithium manganate cathode material, the i.e. 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 nickel-cobalt lithium manganate cathode material, the tertiary cathode material of especially rich nickel, i.e. rich nickel nickel-cobalt lithium manganate cathode material, also there is defect, easily be corroded in cyclic process and cycle life is reduced, have impact on the chemical property such as cycle performance and stability, 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 stability, 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 technical problem to be solved in the present invention is Ni-based tertiary cathode material providing a kind of modification and preparation method thereof, composite modified Ni-based tertiary cathode material provided by the invention, has higher high rate performance and cycle performance, but also has 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 nickel-cobalt lithium manganate cathode material of modification, comprise nickel-cobalt lithium manganate material, be compounded in the lithium manganese phosphate on described nickel-cobalt lithium manganate material surface, and be compounded in the Graphene on described lithium manganese phosphate surface;
The chemical formula of described nickel-cobalt lithium manganate material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, x > 0, y > 0,1 > 1-x-y > 0.
Preferably, described nickel-cobalt lithium manganate material is rich nickel tertiary cathode material; The chemical formula of described rich nickel tertiary cathode material such as formula shown in (II),
LiNi
1-x-yco
xmn
yo
2(II); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
Preferably, the mass ratio of described lithium manganese phosphate and described nickel-cobalt lithium manganate material is (0.005 ~ 0.1): 1;
The mass ratio of described Graphene and described nickel-cobalt lithium manganate material is (0.005 ~ 0.1): 1.
The invention provides a kind of preparation method of nickel-cobalt lithium manganate cathode material, comprise the following steps:
1) nickel-cobalt lithium manganate material, manganese nitrate and phosphoric acid are reacted in organic solvent, obtain the composite material that nickel-cobalt lithium manganate material surface recombination has manganese phosphate;
The chemical formula of described nickel-cobalt lithium manganate material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, x > 0, y > 0,1 > 1-x-y > 0;
2) above-mentioned steps is obtained composite material, lithium source and Graphene to mix in a solvent, then after calcination, obtain the nickel-cobalt lithium manganate cathode material of modification.
Preferably, described organic solvent comprises one or more in ethanol, n-butanol, ethylene glycol, isopropyl alcohol and acetone;
The mass ratio of described nickel-cobalt lithium manganate material and described manganese nitrate is 1:(0.006 ~ 0.12);
The mass ratio of described nickel-cobalt lithium manganate material and described phosphoric acid is 1:(0.003 ~ 0.06);
Mass ratio 1:(1 ~ 5 of described nickel-cobalt lithium manganate material and described organic solvent).
Preferably, the temperature of described reaction is 25 ~ 90 DEG C, and the time of described reaction is 0.5 ~ 5h.
Preferably, described step 1) in, also comprise drying steps after described reaction completes;
The temperature of described drying is 80 ~ 120 DEG C, and the time of described drying is 8 ~ 24h.
Preferably, described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate;
Described solvent is water and/or absolute ethyl alcohol.
Preferably, the mass ratio in described composite material and described lithium source is 1:(0.0002 ~ 0.005);
The mass ratio of described composite material and described Graphene is 1:(0.005 ~ 0.1);
The mass ratio of described composite material and described solvent is 1:(1 ~ 5).
Preferably, described calcining for calcine under protective atmosphere;
The temperature of described calcining is 400 ~ 700 DEG C, and the time of described calcining is 2 ~ 6h.
The invention provides a kind of nickel-cobalt lithium manganate cathode material of modification, comprise nickel-cobalt lithium manganate material, be compounded in the lithium manganese phosphate on described nickel-cobalt lithium manganate material surface, and be compounded in the Graphene on described lithium manganese phosphate surface; The chemical formula of described nickel-cobalt lithium manganate material is such as formula shown in (I).Compared with prior art, the present invention, by dual composite modified nickel-cobalt lithium manganate material, is wherein coated on one deck LiMnPO of particle surface
4improve the interface stability of material under high cut-ff voltage; Be coated on the electronic conductivity that outer field Graphene improves material, reduce polarity effect.Experimental result shows, nickle cobalt lithium manganate tertiary cathode material provided by the invention, 2.8 ~ 4.3,4.4 and 4.5V under, charging and discharging currents is that the first discharge specific capacity under 1C is respectively 172.7,181.9 and 190.5mAh/g, after circulating 200 weeks, capability retention is respectively 91.8%, 88.2% and 84% (representative value).At 2.8 ~ 4.3V, charging and discharging currents is that the first discharge specific capacity under 2C, 5C and 10C is respectively 168.3,161.4 and 147mAh/g, and after circulating 100 weeks, capability retention is respectively 91.5%, 89% and 88% (representative value).
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the modified nickel-cobalt lithium manganate cathode material of preparation in embodiment 1;
Fig. 2 is unmodified, single coated LiMnPO of preparation in embodiment 1
4(LMP) afterwards, LiMnPO
4scheme with the dual coated modified nickel-cobalt lithium manganate cathode material SEM of Graphene;
Fig. 3 is the first charge-discharge curve of modified nickel-cobalt lithium manganate cathode material under different cut-ff voltage and the cycle charge-discharge curve chart of preparation in embodiment 1;
Fig. 4 is the cycle charge-discharge curve chart of modified nickel-cobalt lithium manganate cathode material under different charge-discharge magnification of preparation in embodiment 1;
Fig. 5 is the first charge-discharge curve of unmodified and modified nickel-cobalt lithium manganate cathode material under high charge cut-ff voltage 4.5V and the cycle charge-discharge curve chart of preparation in embodiment 2;
Fig. 6 is modified nickel-cobalt lithium manganate cathode material cycle charge-discharge curve chart under high charge-discharge magnification 5C 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 nickel-cobalt lithium manganate cathode material of modification, comprise nickel-cobalt lithium manganate material, be compounded in the lithium manganese phosphate on described nickel-cobalt lithium manganate material surface, and be compounded in the Graphene on described lithium manganese phosphate surface;
The chemical formula of described nickel-cobalt lithium manganate material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, x > 0, y > 0,1 > 1-x-y > 0.
The present invention is not particularly limited described nickel-cobalt lithium manganate material, with the NCM ternary material for making lithium ion cell positive well known to those skilled in the art, the present invention is preferably cobalt nickel lithium manganate ternary material, the chemical formula of described cobalt nickel lithium manganate ternary material is preferably such as formula shown in (I)
LiNi
1-x-yco
xmn
yo
2(I); Wherein, x > 0, y > 0,1 > 1-x-y > 0;
The span of described x is preferably 0.1≤x≤0.6, more preferably 0.1≤x≤0.3; The span of described y is preferably 0.1≤y≤0.6, more preferably 0.1≤y≤0.3; The span of described 1-x-y is preferably 0.1≤1-x-y≤0.9, more preferably 0.3≤1-x-y≤0.6.
Nickel-cobalt lithium manganate material of the present invention is more preferably rich nickel cobalt nickel lithium manganate ternary material (Ni-based ternary material), the chemical formula of described rich nickel tertiary cathode material such as formula shown in (II),
LiNi
1-x-yco
xmn
yo
2(II); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
The present invention is not particularly limited described lithium manganese phosphate, with lithium manganese phosphate material well known to those skilled in the art, the present invention is not particularly limited its concrete property, and those skilled in the art can select according to practical condition, combining case and properties of product.The present invention is not particularly limited described Graphene, with grapheme material well known to those skilled in the art, the present invention is not particularly limited its concrete property, and those skilled in the art can select according to practical condition, combining case and properties of product.
The present invention is not particularly limited described compound, and with composite definitions well known to those skilled in the art, the present invention is preferably coated, half coated, stacked or generate, and is more preferably coated or half coated, most preferably is coated.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 lithium manganese phosphate and described nickel-cobalt lithium manganate 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 lithium manganese phosphate of the present invention and described nickel-cobalt lithium manganate 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 mass ratio of the present invention to described Graphene and described nickel-cobalt lithium manganate 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 Graphene of the present invention and described nickel-cobalt lithium manganate 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 adopts two-coat to carry out coating modification to the surface of nickel-cobalt lithium manganate cathode material, obtains a kind of new modified nickel-cobalt lithium manganate cathode material, i.e. a kind of composite modified Ni-based tertiary cathode material.The present invention is coated on the rich manganese phase LiMnPO of internal layer
4there is the structural stability at 2.5 ~ 4.5V, can weaken under high charge cut-ff voltage (4.4 ~ 4.5V) on the one hand, side reaction between nickelic phase and organic electrolyte, to inhibit on the other hand in cyclic process accessory substance HF to the corrosion of electrode material, play phosphate radical Stability Analysis of Structures advantage, improve high rate performance and the cycle performance of material; The present invention utilizes conductivity and the flexible flake structure of Graphene excellence again, can form the better conductive network of conductivity, reduce resistance and the polarization of battery, substantially increase the high rate performance of material with the conductive carbon in electrodes of lithium-ion batteries.
The invention provides a kind of preparation method of nickel-cobalt lithium manganate cathode material of modification, it is characterized in that, comprise the following steps:
1) nickel-cobalt lithium manganate material, manganese nitrate and phosphoric acid are reacted in organic solvent, obtain the composite material that nickel-cobalt lithium manganate material surface recombination has manganese phosphate;
The chemical formula of described nickel-cobalt lithium manganate material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, x > 0, y > 0,1 > 1-x-y > 0;
2) above-mentioned steps is obtained composite material, lithium source and Graphene to mix in a solvent, then after calcination, obtain the nickel-cobalt lithium manganate cathode material of modification.
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 nickel-cobalt lithium manganate cathode material, this is no longer going to repeat them.
First nickel-cobalt lithium manganate material, manganese nitrate and phosphoric acid react by the present invention in organic solvent, obtain the composite material that nickel-cobalt lithium manganate material surface recombination has manganese phosphate; The chemical formula of described nickel-cobalt lithium manganate material is such as formula shown in (I).
The source of the present invention to described nickel-cobalt lithium manganate material 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-cobalt lithium manganate material is not particularly limited, with the element of nickel-cobalt lithium manganate material well known to those skilled in the art ratio, nickel in the preferred described nickel-cobalt lithium manganate material 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 manganese nitrate, and with the manganese nitrate for the preparation of Ni-based tertiary cathode material well known to those skilled in the art, the present invention is preferably nitric hydrate manganese or 50% manganese nitrate etc.The mass ratio of nickel-cobalt lithium manganate material of the present invention and described manganese nitrate is preferably 1:(0.006 ~ 0.12), be more preferably 1:(0.01 ~ 0.10), be more preferably 1:(0.03 ~ 0.08), most preferably be 1:(0.04 ~ 0.06).
The present invention is not particularly limited described phosphoric acid, and with phosphoric acid well known to those skilled in the art, the present invention is preferably the commercially available phosphoric acid that purity is 85%.The mass ratio of nickel-cobalt lithium manganate material of the present invention and described phosphoric acid is preferably 1:(0.003 ~ 0.06), be more preferably 1:(0.01 ~ 0.05), most preferably be 1:(0.02 ~ 0.04).
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 present invention is not particularly limited described compound, and with composite definitions well known to those skilled in the art, the present invention is preferably coated, half coated, stacked or generate, and is more preferably coated or half coated, most preferably is coated.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 concrete steps of the present invention to described reaction are not particularly limited, with this type of the concrete steps of reaction well known to those skilled in the art, those skilled in the art can adjust according to practical condition, product situation and performance requirement, described nickel-cobalt lithium manganate material preferably first joins in organic solvent by the present invention, after stirring high speed dispersion, add manganese nitrate successively again and phosphoric acid reacts, after having reacted after the postprocessing working procedures such as filtering and dry, obtained MnPO
4h
2the nickel-cobalt lithium manganate material that O is evenly coated, namely nickel-cobalt lithium manganate material surface recombination has the composite material of manganese phosphate.
The condition of the present invention to described reaction is not particularly limited, with the 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 temperature of reaction of the present invention is preferably 25 ~ 90 DEG C, be more preferably 40 ~ 80 DEG C, most preferably be 60 ~ 70 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, and 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 actual conditions of the present invention to postprocessing working procedures such as above-mentioned filtration and dryings is not particularly limited, with the condition of above-mentioned postprocessing working procedures well known to those skilled in the art, the temperature of drying of the present invention is preferably 80 ~ 120 DEG C, be more preferably 90 ~ 110 DEG C, the time of described drying is preferably 8 ~ 24h, be more preferably 10 ~ 20h, most preferably be 12 ~ 18h.
The present invention carries out coating reaction in non-aqueous system, without the need to regulating pH and simple and convenient, is easy to operate the technological process controlled, and first at the rich manganese phase LiMnPO that nickel-cobalt lithium manganate material ternary material Surface coating one deck electrochemical structure is more stable
4material, the existence of this coating layer can be avoided on the one hand when follow-up inert atmosphere high-temperature process, and the existence of carbon causes the reduction of surface transition metal, and rich manganese phase LiMnPO
4there is the structural stability at 2.5 ~ 4.5V, can weaken under high charge cut-ff voltage (4.4 ~ 4.5V), the side reaction between nickelic phase and organic electrolyte, the structural stability of Ni-based ternary material under improving high voltage; Phosphate radical Stability Analysis of Structures advantage can also be played on the other hand, inhibit HF in cyclic process to the corrosion of electrode material, to decrease the side reaction of electrolyte and electrode material, prevent Ni
2+/ Ni
3+, Co
3+and Mn
4+the dissolving of metal ion, thus the impedance reducing battery, improve high rate performance and the cycle performance of material.In addition, rich manganese phase LiMnPO
4material absorption to moisture in air and carbon dioxide in storage process can be extenuated, reduce the remaining lithium content of particle surface, improve materials processing performance and memory property.
Above-mentioned steps is obtained composite material, lithium source and Graphene and mixes in a solvent by the present invention subsequently, then after calcination, obtains the nickel-cobalt lithium manganate cathode material of modification.
The present invention is not particularly limited described lithium source, with the lithium source for the preparation of nickle cobalt lithium manganate 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 mass ratio in composite material of the present invention and described lithium source is preferably 1:(0.0002 ~ 0.005), be more preferably 1:(0.0005 ~ 0.0045), be more preferably 1:(0.001 ~ 0.004), be more preferably 1:(0.002 ~ 0.003).
The present invention is not particularly limited described Graphene, and with the Graphene for the preparation of anode material of lithium battery well known to those skilled in the art, the present invention is preferably commercially available to buy.The mass ratio of composite material of the present invention and described Graphene is preferably 1:(0.005 ~ 0.1), be more preferably 1:(0.01 ~ 0.09), be more preferably 1:(0.03 ~ 0.07), most preferably be 1:(0.04 ~ 0.06).
The present invention is not particularly limited described solvent, and with solvent well known to those skilled in the art, the present invention is preferably water and/or absolute ethyl alcohol.The consumption of the present invention to described solvent is not particularly limited, with solvent conventional amount used well known to those skilled in the art, the mass ratio of composite material of the present invention and 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 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 400 ~ 700 DEG C, be more preferably 450 ~ 650 DEG C, most preferably be 500 ~ 600 DEG C; The time of described calcining is preferably 2 ~ 6h, is more preferably 3 ~ 5h; The present invention's other conditions to described calcining are not particularly limited, and with calcination condition well known to those skilled in the art, the present invention is also preferred to calcine 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, is more preferably nitrogen or argon gas.
The composite material that above-mentioned steps obtains by the present invention, lithium source and Graphene proceed compound, and composite material and lithium source define the manganese phosphate lithium layer on nickel-cobalt lithium manganate material surface, and Graphene forms Graphene skin on manganese phosphate lithium layer surface then.
The present invention utilizes conductivity and the flexible flake structure of Graphene excellence, the better conductive network of conductivity can be formed with the conductive carbon in electrodes of lithium-ion batteries, the electronic conductivity of further raising material, reduces resistance and the polarization of battery, substantially increases the high rate performance of material.
The present invention has prepared the nickel-cobalt lithium manganate cathode material of modification through above-mentioned steps, i.e. a kind of Ni-based tertiary cathode material of double-coated modification, the present invention carries out coating reaction in non-aqueous system, without the need to regulating pH and simple and convenient, is easy to operate the technological process controlled.The present invention is coated on the rich manganese phase LiMnPO of internal layer
4there is the structural stability at 2.5 ~ 4.5V, can weaken under high charge cut-ff voltage (4.4 ~ 4.5V) on the one hand, side reaction between nickelic phase and organic electrolyte, to inhibit on the other hand in cyclic process accessory substance HF to the corrosion of electrode material, play phosphate radical Stability Analysis of Structures advantage, improve high rate performance and the cycle performance of material; The present invention utilizes conductivity and the flexible flake structure of Graphene excellence again, can form the better conductive network of conductivity, reduce resistance and the polarization of battery, substantially increase the high rate performance of material with the conductive carbon in electrodes of lithium-ion batteries.
The present invention carries out Performance Detection to the above-mentioned lithium ion battery be made up of nickel-cobalt lithium manganate cathode material, experimental result shows, nickle cobalt lithium manganate tertiary cathode material provided by the invention, 2.8 ~ 4.3,4.4 and 4.5V under, charging and discharging currents is that the first discharge specific capacity under 1C is respectively 172.7,181.9 and 190.5mAh/g, after circulating 200 weeks, capability retention is respectively 91.8%, 88.2% and 84% (representative value).At 2.8 ~ 4.3V, charging and discharging currents is that the first discharge specific capacity under 2C, 5C and 10C is respectively 168.3,161.4 and 147mAh/g, and after circulating 100 weeks, capability retention is respectively 91.5%, 89% and 88% (representative value).
In order to understand the present invention further, be described nickel-cobalt lithium manganate cathode material of a kind of modification 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 LiNi
0.6co
0.2mn
0.2o
2material positive electrode joins in absolute ethyl alcohol, and the mass ratio of positive electrode and absolute ethyl alcohol is 1:3, and after stirring high speed dispersion, add manganese nitrate and phosphoric acid successively, its addition is according to LiMnPO
4with LiNi
1-x-yco
xmn
yo
2mass ratio be that 0.01:1 calculates respectively, the reaction temperature of the hierarchy of control is 60 DEG C, and mixing speed is 400r/min, after having reacted through filtering, dry, obtained MnPO
4h
2the nickel-cobalt lithium manganate cathode material that O is evenly coated;
Nickel-cobalt lithium manganate cathode material obtained above is fully mixed in deionized water medium with lithium source, Graphene, the addition of its Graphene and LiNi
1-x-yco
xmn
yo
2mass ratio be 0.005:1, be placed in nitrogen atmosphere, at 550 DEG C, calcine 5h.Obtained by LiMnPO
4coated nickel-cobalt lithium manganate cathode material dual with Graphene.
It is the XRD diffraction pattern of the modified nickel-cobalt lithium manganate cathode material of preparation in embodiment 1 see Fig. 1, Fig. 1.Through LiMnPO
4basic and the LiNiO with the XRD diffracting spectrum of the dual coated nickel-cobalt lithium manganate cathode material of Graphene
2standard diagram coincide, and coated can not having an impact to material structure is described, can keeps former LiNiO
2basic structure (see Fig. 1).See unmodified, single coated LiMnPO that Fig. 2, Fig. 2 are preparation in embodiment 1
4(LMP) afterwards, LiMnPO
4scheme with the dual coated modified nickel-cobalt lithium manganate cathode material SEM of Graphene.Schemed by the SEM of modified nickel-cobalt lithium manganate cathode material, material surface originally an apparent crystal grain by coated uniformly film.
Using the modified 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 at 25 DEG C, carry out cycle performance and high rate performance test.
Cycle performance is tested: voltage range is 2.8 ~ 4.3,4.4 and 4.5V, and charging and discharging currents is that 1C respectively circulates 200 times, investigates its capability retention under different cut-ff voltage; See the first charge-discharge curve of modified nickel-cobalt lithium manganate cathode material under different cut-ff voltage and cycle charge-discharge curve chart that Fig. 3, Fig. 3 are preparation in embodiment 1.
High rate performance is tested: voltage range is 2.8 ~ 4.3V each circulation 100 times under charging and discharging currents is 2C, 5C and 10C, investigates its capability retention under different charge-discharge magnification; See the cycle charge-discharge curve chart of modified nickel-cobalt lithium manganate cathode material under different charge-discharge magnification that Fig. 4, Fig. 4 are preparation in embodiment 1.
As can be seen from Fig. 3 (a) and (b), through LiMnPO
4coated modified LiNi dual with Graphene
0.6co
0.2mn
0.2o
2material 2.8 ~ 4.3,4.4 and 4.5V, charging and discharging currents is that the first discharge specific capacity under 1C is respectively 172.7,181.9 and 190.5mAh/g, after circulating 200 weeks, capability retention is respectively 91.8%, 88.2% and 84% (representative value).Visible LiMnPO
4the existence of coating layer inhibits accessory substance HF in long-term cyclic process to the corrosion of electrode material surface, to decrease the side reaction of electrolyte and electrode material, prevents material surface Ni
2+/ Ni
3+, Co
3+and Mn
4+the dissolving of metal ion, reduces the impedance of battery, substantially improves the cycle performance of material.
As seen from Figure 4, through LiMnPO
4coated modified LiNi dual with Graphene
0.6co
0.2mn
0.2o
2material is at 2.8 ~ 4.3V, and charging and discharging currents is that the first discharge specific capacity under 2C, 5C and 10C is respectively 168.3, and 161.4 and 147mAh/g, after circulating 100 weeks, capability retention is respectively 91.5%, 89% and 88% (representative value).The visible existence due to material surface Graphene, defines the better conductive network of conductivity with the conductive carbon in pole piece, reduce further the resistance of battery, greatly enhance the high rate performance of material.
Embodiment 2
By business-like LiNi
0.5co
0.2mn
0.3o
2positive electrode joins in absolute ethyl alcohol, and the mass ratio of positive electrode and absolute ethyl alcohol is 1:4, and after stirring high speed dispersion, add manganese nitrate and phosphoric acid successively, its addition is according to LiMnPO
4with LiNi
1-x-yco
xmn
yo
2mass ratio be that 0.02:1 calculates respectively, the reaction temperature of the hierarchy of control is 70 DEG C, and mixing speed is 500r/min, after having reacted through filtering, dry, obtained MnPO
4h
2the nickel-cobalt lithium manganate cathode material that O is evenly coated;
Nickel-cobalt lithium manganate cathode material obtained above is fully mixed in anhydrous ethanol medium with lithium source, Graphene, the addition of its Graphene and LiNi
1-x-yco
xmn
yo
2mass ratio be 0.01:1, be placed in argon gas atmosphere, at 500 DEG C, calcine 6h.Obtained by LiMnPO
4coated nickel-cobalt lithium manganate cathode material dual with Graphene.
Using the unmodified and modified 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 ~ 4.5V, circulates 200 times under charging and discharging currents is 1C, investigates capability retention.
See the first charge-discharge curve of unmodified and modified nickel-cobalt lithium manganate cathode material under high charge cut-ff voltage 4.5V and cycle charge-discharge curve chart that Fig. 5, Fig. 5 are preparation in embodiment 2.Shown in the cycle performance of Fig. 5 is tested, unmodified material 1C first discharge specific capacity is 178mAh/g, and circulate the near 144mAh/g of specific capacity after 200 times, and capability retention is only 80%; And coated rear material 1C first discharge specific capacity is 183mAh/g, circulate the near 167mAh/g of specific capacity after 200 times, and it is 91.5% that capability retention reaches.Visible through LiMnPO
4dual coated modified with Graphene, significantly improve the specific discharge capacity of material and the cycle performance under high cut-ff voltage.
Embodiment 3
By business-like LiNi
0.8co
0.1mn
0.1o
2positive electrode joins in absolute ethyl alcohol, and the mass ratio of positive electrode and absolute ethyl alcohol is 1:5, and after stirring high speed dispersion, add manganese nitrate and phosphoric acid successively, its addition is according to LiMnPO
4with LiNi
1-x-yco
xmn
yo
2mass ratio be that 0.03:1 calculates respectively, the reaction temperature of the hierarchy of control is 80 DEG C, and mixing speed is 600r/min, after having reacted through filtering, dry, obtained MnPO
4h
2the nickel-cobalt lithium manganate cathode material that O is evenly coated;
Nickel-cobalt lithium manganate cathode material obtained above is fully mixed with lithium source, Graphene Qu Li Shui – absolute ethyl alcohol blending agent, the addition of its Graphene and LiNi
1-x-yco
xmn
yo
2mass ratio be 0.02:1, be placed in argon gas atmosphere, at 600 DEG C, calcine 4h.Obtained by LiMnPO
4coated nickel-cobalt lithium manganate cathode material dual with Graphene.
Using the modified 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, circulates 100 times under charging and discharging currents is 5C, investigates capability retention.
See modified nickel-cobalt lithium manganate cathode material cycle charge-discharge curve chart under high charge-discharge magnification 5C that Fig. 6, Fig. 6 are preparation in embodiment 3.As shown in the cycle performance test of Fig. 6, modified material 0.1C first discharge specific capacity is that 205mAh/g, 5C first discharge specific capacity still maintains 170mAh/g, and circulate the near 159mAh/g of specific capacity after 100 times, and capability retention reaches 93.5%.
Above nickel-cobalt lithium manganate cathode material of a kind of modification 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 nickel-cobalt lithium manganate cathode material for modification, is characterized in that, comprises nickel-cobalt lithium manganate material, is compounded in the lithium manganese phosphate on described nickel-cobalt lithium manganate material surface, and be compounded in the Graphene on described lithium manganese phosphate surface;
The chemical formula of described nickel-cobalt lithium manganate material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, x > 0, y > 0,1 > 1-x-y > 0.
2. nickel-cobalt lithium manganate cathode material according to claim 1, is characterized in that, described nickel-cobalt lithium manganate material is rich nickel tertiary cathode material; The chemical formula of described rich nickel tertiary cathode material such as formula shown in (II),
LiNi
1-x-yco
xmn
yo
2(II); Wherein, (1-x-y)>=0.5, x > 0, y > 0.
3. nickel-cobalt lithium manganate cathode material according to claim 1, is characterized in that, the mass ratio of described lithium manganese phosphate and described nickel-cobalt lithium manganate material is (0.005 ~ 0.1): 1;
The mass ratio of described Graphene and described nickel-cobalt lithium manganate material is (0.005 ~ 0.1): 1.
4. a preparation method for the nickel-cobalt lithium manganate cathode material of modification, is characterized in that, comprises the following steps:
1) nickel-cobalt lithium manganate material, manganese nitrate and phosphoric acid are reacted in organic solvent, obtain the composite material that nickel-cobalt lithium manganate material surface recombination has manganese phosphate;
The chemical formula of described nickel-cobalt lithium manganate material such as formula shown in (I),
LiNi
1-x-yco
xmn
yo
2(I); Wherein, x > 0, y > 0,1 > 1-x-y > 0;
2) above-mentioned steps is obtained composite material, lithium source and Graphene to mix in a solvent, then after calcination, obtain the nickel-cobalt lithium manganate cathode material of modification.
5. 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-cobalt lithium manganate material and described manganese nitrate is 1:(0.006 ~ 0.12);
The mass ratio of described nickel-cobalt lithium manganate material and described phosphoric acid is 1:(0.003 ~ 0.06);
Mass ratio 1:(1 ~ 5 of described nickel-cobalt lithium manganate material and described organic solvent).
6. preparation method according to claim 4, is characterized in that, the temperature of described reaction is 25 ~ 90 DEG C, and the time of described reaction is 0.5 ~ 5h.
7. preparation method according to claim 4, is characterized in that, described step 1) in, also comprise drying steps after described reaction completes;
The temperature of described drying is 80 ~ 120 DEG C, and the time of described drying is 8 ~ 24h.
8. preparation method according to claim 4, is characterized in that, described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate; Described solvent is water and/or absolute ethyl alcohol.
9. preparation method according to claim 4, is characterized in that, the mass ratio in described composite material and described lithium source is 1:(0.0002 ~ 0.005);
The mass ratio of described composite material and described Graphene is 1:(0.005 ~ 0.1);
The mass ratio of described composite material and described solvent is 1:(1 ~ 5).
10. preparation method according to claim 4, is characterized in that, described calcining for calcine under protective atmosphere;
The temperature of described calcining is 400 ~ 700 DEG C, and the time of described calcining is 2 ~ 6h.
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