CN104078659B - Matrix material and its preparation method, lithium ion battery containing this matrix material - Google Patents

Matrix material and its preparation method, lithium ion battery containing this matrix material Download PDF

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CN104078659B
CN104078659B CN201310097680.9A CN201310097680A CN104078659B CN 104078659 B CN104078659 B CN 104078659B CN 201310097680 A CN201310097680 A CN 201310097680A CN 104078659 B CN104078659 B CN 104078659B
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matrix material
solution
middle layer
preparation
reactor
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CN104078659A (en
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李鹏
黄庆华
郭健
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NEC China Co Ltd
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NEC China Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/485—Selection 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a kind of matrix material and its preparation method, lithium ion battery containing this matrix material, belongs to field of lithium ion battery material. Described matrix material is nucleocapsid structure, the skin that the shell of described matrix material comprises middle layer and is coated on outside middle layer, and the kernel of described matrix material is Li (NixCoyAlz)O2, middle layer is Li (Ni1/3Co1/3Mn1/3)O2, skin is LiNi0.5Mn1.5O4, the kernel of described matrix material, middle layer, outer field mol ratio are a:b:c, wherein a+b+c=1,0 <b < 0.5,0 < c < 0.5, x+y+z=1, y=0.15,0.03≤z≤0.05. The matrix material that the embodiment of the present invention provides has the feature of higher capacity, low alkalinity, electrolyte resistance, and has better cyclical stability and safety performance, and superiority of effectiveness is obvious, is more suitable for the application of power cell. By utilizing, coprecipitation technique forms each Rotating fields presoma of matrix material to the embodiment of the present invention successively, has and connects closely between good consistence and homogeneity and each layer, and, carry out bakes to burn the article and can obtain matrix material, can effectively reduce costs.

Description

Matrix material and its preparation method, lithium ion battery containing this matrix material
Technical field
The present invention relates to field of lithium ion battery material, in particular to a kind of for the matrix material of lithium ion cell positive and the preparation method of presoma thereof and the battery using this matrix material.
Background technology
Lithium ion battery is nearly a kind of high tension battery that fast development is got up during the last ten years, due to its have that capacity is big, the advantage such as voltage height, self-discharge are little, become the power source of the field first-selections such as electromobile. Therefore, the cycle performance and cost etc. of lithium ion battery all will become the important factor affecting the field commercialization processes such as electromobile.
Positive electrode material is the important component part of lithium ion battery, is also the crucial part of cycle performance and the cost determining lithium ion battery. At present, cobalt acid lithium is the anode material for lithium-ion batteries of most widespread commercial. But cobalt expensive and have pollution, therefore, along with the further investigation to anode material for lithium-ion batteries, create much new anode material for lithium-ion batteries, such as, relative to the cobalt acid lower LiNi of lithium costxCoyM1-x-yO2Series material.
LiNixCoyM1-x-yO2NCA material capacity in series material can reach about 200mAh/g, but there is electrochemical heat stability difference and the alkaline high shortcoming of material, and reason may be due to the Ni in material3+Can mixing in charge and discharge process, simultaneously Ni4+There is strong oxidizing property, have impact on the circulation of material and other performance; NCM material initial capacity in this series material only about 150mAh/g, but advantage be circulate, alkalescence low.
At present, usually through the performance improving positive electrode material each side by the method for other material clad anode materials, thus solve the defect of emerging anode material for lithium-ion batteries self. As: patent US2010/0310940A1 reports and utilizes barium titanate and its metal oxide to improve battery security to anode material for lithium-ion batteries is coated;Patent CN102394295A reports and utilizes spinel nickel lithium manganate that anode material for lithium-ion batteries carries out the coated cycle life and the high-temperature storage performance that improve material.
In the process realizing the present invention, contriver finds that prior art at least exists following problem:
Patent US2010/0310940A1 utilizes inorganics barium titanate and its metal oxide to carry out coated to positive electrode material, can cause the reduction of positive electrode material energy density, and the electroconductibility of positive electrode material also can be made greatly to reduce;
Patent CN102394295A needs first to synthesize required positive electrode material, now needs to carry out bakes to burn the article; Recycling sol-gel method, at positive electrode material Surface coating spinel nickel lithium manganate, then carries out re-baking, forms the positive electrode material of coating spinelle nickel ion doped. This kind of mode needs to carry out re-baking, can consume large amount of organic, and cost is increased, and there is the shortcoming that two kinds of materials connect undertighten simultaneously.
Summary of the invention
In order to solve the problem of prior art, embodiments provide a kind of matrix material and its preparation method, lithium ion battery containing this matrix material. Described technical scheme is as follows:
On the one hand, it provides a kind of matrix material, described matrix material is nucleocapsid structure, the skin that the shell of described matrix material comprises middle layer and is coated on outside middle layer, and the kernel of described matrix material is Li (NixCoyAlz)O2, middle layer is Li (Ni1/3Co1/3Mn1/3)O2, skin is LiNi0.5Mn1.5O4, the kernel of described matrix material, middle layer, outer field mol ratio are a:b:c, wherein a+b+c=1,0 <b < 0.5,0 < c < 0.5, x+y+z=1, y=0.15,0.03≤z≤0.05.
Preferably, a:b:c=0.8:0.15:0.05, x=0.8, z=0.05.
Providing the preparation method of a kind of matrix material on the other hand, described preparation method comprises:
Being obtained the composite material precursor of nucleocapsid structure successively by coprecipitation reaction, the skin that the shell of described composite material precursor comprises middle layer and is coated on outside middle layer, the kernel of described composite material precursor is (NixCoyAlz)(OH)2, middle layer be (Ni1/3Co1/3Mn1/3)(OH)2, skin be Ni0.25Mn0.75(OH)2;
At 500-1000 DEG C, carry out roasting after being mixed according to the ratio of mol ratio 1:1-1.1 with lithium source by described composite material precursor, then through cooling, broken, sieve that to obtain kernel be Li (NixCoyAlz)O2, middle layer be Li (Ni1/3Co1/3Mn1/3)O2, skin be LiNi0.5Mn1.5O4Matrix material, the kernel of described matrix material, middle layer, outer field mol ratio are a:b:c, wherein a+b+c=1,0 <b < 0.5,0 < c < 0.5, x+y+z=1, y=0.15,0.03≤z≤0.05.
Wherein, the described composite material precursor being obtained nucleocapsid structure successively by coprecipitation reaction, is specifically comprised:
It is that the ratio of x:y:z drips the ternary salts solution adding Ni, Co, Al in the reactor of high speed rotating according to the mol ratio of Ni, Co, Al, drip the pH value adding mixture in alkaline solution control reactor is that 10-12 carries out coprecipitation reaction simultaneously, obtains solid phase for (NixCoyAlz)(OH)2Solidliquid mixture;
As (NixCoyAlz)(OH)2When particle is enough big, stop dripping the ternary salts solution adding Ni, Co, Al, the ratio being 1:1:1 according to the mol ratio of Ni, Co, Mn drips the ternary salts solution adding Ni, Co, Mn immediately in described reactor, in control reactor, the pH value of mixture is that 10-12 proceeds coprecipitation reaction, at (NixCoyAlz)(OH)2Particle outside forms middle layer (Ni1/3Co1/3Mn1/3)(OH)2;
After certain thickness middle layer is formed, stop dripping the ternary salts solution adding Ni, Co, Mn, the ratio being 0.25:0.75 according to the mol ratio of Ni, Mn drips the binary salt solution adding Ni, Mn immediately in reactor, in control reactor, the pH value of mixture is that 10-12 proceeds coprecipitation reaction, to forming certain thickness outer Ni in outside, described middle layer0.25Mn0.75(OH)2, stopped reaction;
By the solidliquid mixture after having reacted by centrifugation, the solid matter isolated washing is dried 1-10h after neutral at 100-200 DEG C, obtains the composite material precursor of nucleocapsid structure.
Described carries out roasting, specifically comprises:
Put into retort furnace first roasting 2-5 hour at 700-800 DEG C, then continue to heat up 800 DEG C-850 DEG C roasting 2-5 hours again, finally continue to be warming up to 850-950 DEG C of roasting 2-5 hour again.
Described lithium source is the one in lithium hydroxide, lithium nitrate, Quilonum Retard.
The rotating speed of described reactor is 180rps-220rps.
The ternary salts solution of described Ni, Co, Al is one or more combinations in the acetate solution of Ni, Co, Al, nitrate solution, sulfate liquor, chloride solution, the ternary salts solution of described Ni, Co, Mn is one or more combinations in the acetate solution of Ni, Co, Mn, nitrate solution, sulfate liquor, chloride solution, and the binary salt solution of described Ni, Mn is one or more combinations in the acetate solution of Ni, Mn, nitrate solution, sulfate liquor, chloride solution.
Described alkaline solution is sodium hydroxide solution or ammoniacal liquor.
On the other hand, it provides the lithium ion battery of a kind of just very above-mentioned matrix material.
The useful effect that the technical scheme that the embodiment of the present invention provides is brought is:
The matrix material that the embodiment of the present invention provides is the nucleocapsid structure of multilayer, Core Choice NCA material, and middle shell selects NCM material, and outer shell layer selects spinel nickel acid lithium material. owing to shell material itself has certain capacity, outside being coated on the inner nuclear material of heavy body, inner nuclear material capacity can not be caused to have bigger loss, and owing to shell material alkalescence is low and have good cycle performance, the alkalescence that can reduce matrix material after coated for inner nuclear material high for alkalescence is improved simultaneously the cycle performance of matrix material, in addition, what outer shell layer was selected is spinel nickel acid lithium material, the discharge platform of this material is about 4.7-4.8V, higher than the discharge platform in middle layer and kernel, improve the resistance to pressure of material entirety, simultaneously, owing to the oxidisability of this material is poor, not easily react with electrolytic solution, its material inside is because of coated and directly do not contact with electrolytic solution by this material, not easily react with electrolytic solution, avoid battery when discharge and recharge, owing to electrode materials and the bulging that causes of electrolytic solution reaction such as are even exploded at the generation of hazardous condition, improve safety performance and the stability of battery.
Therefore, the matrix material that the embodiment of the present invention provides has the feature of higher capacity, low alkalinity, electrolyte resistance, and has better cyclical stability and safety performance, and superiority of effectiveness is obvious, is more suitable for the application of power cell.
By utilizing, coprecipitation technique forms each Rotating fields presoma of matrix material to the embodiment of the present invention successively, makes to have between each layer of matrix material and connects closely between good consistence and homogeneity and each layer. Further, composite material precursor carries out bakes to burn the article after mixing with lithium source can obtain matrix material, can effectively reduce costs.
Accompanying drawing explanation
In order to the technical scheme being illustrated more clearly in the embodiment of the present invention, below the accompanying drawing used required in embodiment being described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the first discharge curve of the embodiment of the present invention 3 with comparative example 1,2;
Fig. 2 is the first discharge curve of the embodiment of the present invention 4 with comparative example 1,2;
Fig. 3 is the first discharge curve of the embodiment of the present invention 5 with comparative example 1,2;
Fig. 4 is the first discharge curve of the embodiment of the present invention 6 with comparative example 1,2;
Fig. 5 is the first discharge curve of the embodiment of the present invention 7 with comparative example 1,2;
Fig. 6 is the first discharge curve of the embodiment of the present invention 8 with comparative example 1,2;
Fig. 7 is the first discharge curve of the embodiment of the present invention 9 with comparative example 1,2;
Fig. 8 is the first discharge curve of the embodiment of the present invention 10 with comparative example 1,2;
Fig. 9 is 100 the cyclic curve figures of the embodiment of the present invention 5 with comparative example 1,2;
Figure 10 is 100 the cyclic curve figures of the embodiment of the present invention 8 with comparative example 1,2.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
Embodiment 1
Embodiments providing a kind of matrix material, described matrix material is multi-layer core-shell structure, the skin that the shell of described matrix material comprises middle layer and is coated on outside middle layer, and the kernel of described matrix material is Li (NixCoyAlz)O2, middle layer is Li (Ni1/3Co1/3Mn1/3)O2, skin is LiNi0.5Mn1.5O4, the kernel of described matrix material, middle layer, outer field mol ratio are a:b:c, wherein a+b+c=1,0 <b < 0.5,0 < c < 0.5, x+y+z=1, y=0.15,0.03≤z≤0.05.
The matrix material that the embodiment of the present invention provides is the nucleocapsid structure of multilayer, Core Choice NCA material, and middle shell selects NCM material, and outer shell layer selects spinel nickel acid lithium material. owing to shell material itself has certain capacity, outside being coated on the inner nuclear material of heavy body, inner nuclear material capacity can not be caused to have bigger loss, and owing to shell material alkalescence is low and have good cycle performance, the alkalescence that can reduce matrix material after coated for inner nuclear material high for alkalescence is improved simultaneously the cycle performance of matrix material, in addition, what outer shell layer was selected is spinel nickel acid lithium material, the discharge platform of this material is about 4.7-4.8V, higher than the discharge platform in middle layer and kernel, improve the resistance to pressure of material entirety, simultaneously, owing to the oxidisability of this material is poor, not easily react with electrolytic solution, its material inside is because of coated and directly do not contact with electrolytic solution by this material, not easily react with electrolytic solution, avoid battery when discharge and recharge, owing to electrode materials and the bulging that causes of electrolytic solution reaction such as are even exploded at the generation of hazardous condition, improve safety performance and the stability of battery.
Therefore, the matrix material that the embodiment of the present invention provides has the feature of higher capacity, low alkalinity, electrolyte resistance, and has better cyclical stability and safety performance, and superiority of effectiveness is obvious, is more suitable for the application of power cell.
Embodiment 2
Embodiments providing the preparation method of a kind of matrix material, described preparation method comprises:
Step 1: the composite material precursor being obtained nucleocapsid structure successively by coprecipitation reaction, the skin that the shell of described composite material precursor comprises middle layer and is coated on outside middle layer, the kernel of described composite material precursor is (NixCoyAlz)(OH)2, middle layer be (Ni1/3Co1/3Mn1/3)(OH)2, skin be Ni0.25Mn0.75(OH)2;
Step 2: carry out roasting after being mixed according to the ratio of mol ratio 1:1-1.1 with lithium source by described composite material precursor, then through cooling, broken, sieve that to obtain kernel be Li (NixCoyAlz)O2, middle layer be Li (Ni1/3Co1/3Mn1/3)O2, skin be LiNi0.5Mn1.5O4Matrix material, the kernel of described matrix material, middle layer, outer field mol ratio are a:b:c, wherein a+b+c=1,0 <b < 0.5,0 < c < 0.5, x+y+z=1, y=0.15,0.03≤z≤0.05.
By utilizing, coprecipitation technique forms each Rotating fields presoma of matrix material to the embodiment of the present invention successively, makes to have between each layer of matrix material and connects closely between good consistence and homogeneity and each layer. Further, composite material precursor carries out bakes to burn the article after mixing with lithium source can obtain matrix material, can effectively reduce costs.
Embodiment of the present invention step 1 specifically comprises:
Step 1a: the ratio being x:y:z according to the mol ratio of Ni, Co, Al prepares the ternary salts solution A of a certain amount of Ni, Co, Al, the ratio being 1:1:1 according to the mol ratio of Ni, Co, Mn prepares the ternary salts solution B of a certain amount of Ni, Co, Mn, the ratio being 0.25:0.75 according to the mol ratio of Ni, Mn prepares a certain amount of Ni, Mn binary salt solution C, according to requirements prepares a certain amount of certain density alkaline solution simultaneously.
Step 1b: prepare the ternary salts solution A dripping in the reactor of backward high speed rotating and adding Ni, Co, Al, drip the pH value adding mixture in alkaline solution control reactor is that 10-12 carries out coprecipitation reaction simultaneously, obtains solid phase for (NixCoyAlz)(OH)2Solidliquid mixture;
As (NixCoyAlz)(OH)2When particle is enough big, stopping dripping the ternary salts solution A adding Ni, Co, Al, drip the ternary salts solution B adding Ni, Co, Mn in described reactor, in control reactor, the pH value of mixture is that 10-12 proceeds coprecipitation reaction, at (NixCoyAlz)(OH)2Particle outside forms middle layer (Ni1/3Co1/3Mn1/3)(OH)2;
After certain thickness middle layer is formed, stop dripping the ternary salts solution B adding Ni, Co, Mn, dripping the binary salt solution C adding Ni, Mn in reactor, in control reactor, the pH value of mixture is that 10-12 proceeds coprecipitation reaction, to forming certain thickness outer Ni in outside, described middle layer0.25Mn0.75(OH)2, stopped reaction;
Step 1c: by the solidliquid mixture after having reacted by centrifugation, dries 1-10h by the solid matter isolated washing at 100-200 DEG C after neutral, obtains the composite material precursor of nucleocapsid structure.
Wherein, (NixCoyAlz)(OH)2The size of particle, middle layer and outer layer thickness all can according to specific lithium ion cell electrode need select; Each solution rate of addition adjusts according to each layer particle growth condition.
Carry out roasting described in embodiment of the present invention step 2, specifically comprise:
Put into retort furnace first roasting 2-5 hour at 700-800 DEG C, then continue to heat up 800 DEG C-850 DEG C roasting 2-5 hours again, finally continue to be warming up to 850-950 DEG C of roasting 2-5 hour again.
Owing to the material of kernel, middle shell, outer shell layer is different, the speed that the temperature that its lattice is formed is different, lithium ion enters lattice is also different, therefore, carries out baking inphases under this condition, each layer not only can be made better to form lattice, and be conducive to lithium ion to enter fast in each layer crystal lattice.
In the embodiment of the present invention:
Described lithium source is the one in lithium hydroxide, lithium nitrate, Quilonum Retard, it is preferable that Quilonum Retard.
Preferably, the rotating speed of described reactor is 180rps-220rps.
Under this rotating speed, be more conducive to forming equal one, stable composite material precursor, make to connect between each layer of composite material precursor tightr.
The ternary salts solution of described Ni, Co, Al is one or more combinations in the acetate solution of Ni, Co, Al, nitrate solution, sulfate liquor, chloride solution, the ternary salts solution of described Ni, Co, Mn is one or more combinations in the acetate solution of Ni, Co, Mn, nitrate solution, sulfate liquor, chloride solution, and the binary salt solution of described Ni, Mn is one or more combinations in the acetate solution of Ni, Mn, nitrate solution, sulfate liquor, chloride solution.
Preferably, described alkaline solution is sodium hydroxide solution or ammoniacal liquor.
Embodiment 3
Preparation 9L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 0.05L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 1L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep the pH value in reactor between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h immediately and add solution B, after 0.1h, solution B injects reactor completely, then with the speed of 0.5L/h, solution C is added dropwise in reactor immediately, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, obtained molecular formula is 0.9 (Ni0.8Co0.15Al0.05)(OH)2·0.05(Ni1/3Co1/3Mn1/3)(OH)2·0.1Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.9Li (Ni of modification0.8Co0.15Al0.05)O2·0.05Li(Ni1/3Co1/3Mn1/3)O2·0.05LiNi0.5Mn1.5O4。
Embodiment 4
Preparation 8L concentration is Ni, Co, Al chloride solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 1L concentration is Ni, Co, Mn chloride solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 2L concentration is Ni, Mn chloride solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 2h, solution B injects reactor completely, finally with the speed of 0.5L/h, solution C is added dropwise in reactor, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.8 (Ni0.8Co0.15Al0.05)(OH)2·0.1(Ni1/3Co1/3Mn1/3)(OH)2·0.2Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally being warming up to 950 DEG C of roastings 2 hours, the material after roasting obtains the multilayer materials 0.8Li (Ni of modification after fragmentation is sieved0.8Co0.15Al0.05)O2·0.1Li(Ni1/3Co1/3Mn1/3)O2·0.1LiNi0.5Mn1.5O4。
Embodiment 5
Preparation 8L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 1.5L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 1L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h immediately and add solution B, after 3h, solution B injects reactor completely, then drip with the speed of 0.5L/h immediately and add solution C and enter in reactor, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.8 (Ni0.8Co0.15Al0.05)(OH)2·0.15(Ni1/3Co1/3Mn1/3)(OH)2·0.1Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.8Li (Ni of modification0.8Co0.15Al0.05)O2·0.15Li(Ni1/3Co1/3Mn1/3)O2·0.05LiNi0.5Mn1.5O4。
Embodiment 6
Preparation 7L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 1L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 4L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 2h, solution B injects reactor completely, then start to drip in reactor to add solution C with the speed of 0.5L/h, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.7 (Ni0.8Co0.15Al0.05)(OH)2·0.1(Ni1/3Co1/3Mn1/3)(OH)2·0.4Ni0.25Mn0.75(OH)2Composite material precursor.
By presoma and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.7Li (Ni of modification0.8Co0.15Al0.05)O2·0.1Li(Ni1/3Co1/3Mn1/3)O2·0.2LiNi0.5Mn1.5O4。
Embodiment 7
Preparation 7L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 1.5L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 3L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 3h, solution B injects reactor completely, then start to drip in reactor to add solution C with the speed of 0.5L/h, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.7 (Ni0.8Co0.15Al0.05)(OH)2·0.15(Ni1/3Co1/3Mn1/3)(OH)2·0.3Ni0.25Mn0.75(OH)2Composite material precursor.
By presoma and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.7Li (Ni of modification0.8Co0.15Al0.05)O2·0.15Li(Ni1/3Co1/3Mn1/3)O2·0.15LiNi0.5Mn1.5O4。
Embodiment 8
Preparation 7L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 2L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1;Preparation 2L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 4h, solution B injects reactor completely, then start to drip in reactor to add solution C with the speed of 0.5L/h, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.7 (Ni0.8Co0.15Al0.05)(OH)2·0.2(Ni1/3Co1/3Mn1/3)(OH)2·0.2Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.7Li (Ni of modification0.8Co0.15Al0.05)O2·0.2Li(Ni1/3Co1/3Mn1/3)O2·0.1LiNi0.5Mn1.5O4。
Embodiment 9
Preparation 6L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 2L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 4L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 4h, solution B injects reactor completely, then start to drip in reactor to add solution C with the speed of 0.5L/h, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.6 (Ni0.8Co0.15Al0.05)(OH)2·0.2(Ni1/3Co1/3Mn1/3)(OH)2·0.4Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.6Li (Ni of modification0.8Co0.15Al0.05)O2·0.2Li(Ni1/3Co1/3Mn1/3)O2·0.2LiNi0.5Mn1.5O4。
Embodiment 10
Preparation 6L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 3L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 2L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 6h, solution B injects reactor completely, then start to drip in reactor with the speed of 0.5L/h and add solution C, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.6 (Ni0.8Co0.15Al0.05)(OH)2·0.3(Ni1/3Co1/3Mn1/3)(OH)2·0.2Ni0.25Mn0.75(OH)2Composite material precursor.
By presoma and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally being warming up to 950 DEG C of roastings 2 hours, the material after roasting obtains the multilayer materials 0.6Li (Ni of modification after fragmentation is sieved0.8Co0.15AL0.05)O2·0.3Li(Ni1/3Co1/3Mn1/3)O2·0.1LiNi0.5Mn1.5O4。
Embodiment 11
Preparation 7L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.82:0.15:0.03; Preparation 2L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 2L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 4h, solution B injects reactor completely, then start to drip in reactor to add solution C with the speed of 0.5L/h, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.7 (Ni0.82Co0.15Al0.03)(OH)2·0.2(Ni1/3Co1/3Mn1/3)(OH)2·0.2Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.7Li (Ni of modification0.82Co0.15Al0.03)O2·0.2Li(Ni1/3Co1/3Mn1/3)O2·0.1LiNi0.5Mn1.5O4。
Embodiment 12
Preparation 9L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 0.05L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 1L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the ammoniacal liquor of enough 10mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the ammoniacal liquor of 10mol/L simultaneously, keep the pH value in reactor between 11-12, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h immediately and add solution B, after 0.1h, solution B injects reactor completely, then with the speed of 0.5L/h, solution C is added dropwise in reactor, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.9 (Ni0.8Co0.15Al0.05)(OH)2·0.05(Ni1/3Co1/3Mn1/3)(OH)2·0.1Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.1 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.9Li (Ni of modification0.8Co0.15Al0.05)O2·0.05Li(Ni1/3Co1/3Mn1/3)O2·0.05LiNi0.5Mn1.5O4。
Embodiment 13
Preparation 8L concentration is Ni, Co, Al chloride solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 1L concentration is Ni, Co, Mn chloride solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1;Preparation 2L concentration is Ni, Mn chloride solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 2h, solution B injects reactor completely, finally with the speed of 0.5L/h, solution C is added dropwise in reactor, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.8 (Ni0.8Co0.15Al0.05)(OH)2·0.1(Ni1/3Co1/3Mn1/3)(OH)2·0.2Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally being warming up to 950 DEG C of roastings 2 hours, the material after roasting obtains the multilayer materials 0.8Li (Ni of modification after fragmentation is sieved0.8Co0.15Al0.05)O2·0.1Li(Ni1/3Co1/3Mn1/3)O2·0.1LiNi0.5Mn1.5O4。
Embodiment 14
Preparation 5L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 4L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 2L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 1L/h immediately and add solution B, after 4h, solution B injects reactor completely, then drip with the speed of 0.5L/h immediately and add solution C and enter in reactor, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.5 (Ni0.8Co0.15Al0.05)(OH)2·0.4(Ni1/3Co1/3Mn1/3)(OH)2·0.2Ni0.25Mn0.75(OH)2Composite material precursor.
By composite material precursor and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.5Li (Ni of modification0.8Co0.15Al0.05)O2·0.4Li(Ni1/3Co1/3Mn1/3)O2·0.1LiNi0.5Mn1.5O4。
Embodiment 15
Preparation 5L concentration is Ni, Co, Al nitrate solution A of 1mol/L, and wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Preparation 1L concentration is Ni, Co, Mn nitrate solution B of 1mol/L, and wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Preparation 8L concentration is Ni, Mn nitrate solution C of 1mol/L, and wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH alkaline solution of enough 6mol/L.
Solution A is injected the reactor of rotating speed as 200rps taking the speed of 1L/h, inject the NaOH alkaline solution of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, progressively drip in reactor with the speed of 0.5L/h and add solution B, after 2h, solution B injects reactor completely, then start to drip in reactor to add solution C with the speed of 0.5L/h, solution C terminates reaction after dripping, solidliquid mixture after having reacted is passed through centrifugation, washing dries 10h after neutral at 100 DEG C, and obtained molecular formula is 0.5 (Ni0.8Co0.15Al0.05)(OH)2·0.1(Ni1/3Co1/3Mn1/3)(OH)2·0.8Ni0.25Mn0.75(OH)2Composite material precursor.
By presoma and the Quilonum Retard after drying in molar ratio 1:1.05 put into retort furnace after mixing, first roasting 3 hours at 750 DEG C, then 850 DEG C of roastings 5 hours it are warming up to, finally be warming up to 950 DEG C of roastings 2 hours, the material after roasting through broken, sieve after obtain the multilayer materials 0.5Li (Ni of modification0.8Co0.15Al0.05)O2·0.1Li(Ni1/3Co1/3Mn1/3)O2·0.4LiNi0.5Mn1.5O4。
Embodiment 16
Present embodiments providing a kind of mobile phone lithium ion battery, the positive electrode material of described lithium ion battery adopts the matrix material of embodiment 3-15 offer.
Described lithium ion battery can also be the lithium ion battery for the product such as notebook, power truck.
Comparative example 1
Preparation 10L concentration is Ni, Co, Al salts solution of 1mol/L, and wherein, the molar ratio of Ni, Co, Al is 0.8:0.15:0.05.
The above-mentioned salts solution prepared is injected rotating speed as the reactor of 200rps taking the speed of 1L/h, injects the NaOH solution of 6mol/L simultaneously, regulate alkaline solution flow velocity, keep pH value between 10-12. After 10h, salts solution injects reactor completely, and precursor power has reacted.
By the solidliquid mixture after having reacted by centrifugation, washing dries 10h after neutral at 100 DEG C. By presoma and the Quilonum Retard after drying in molar ratio 1:1.05 mix after in retort furnace 900 DEG C of roasting 10h, the material after roasting obtains an equal LiNi after fragmentation is sieved0.8Co0.15Al0.05O2Material.
Comparative example 2
Preparation 10L concentration is Ni, Co, Mn salts solution of 1mol/L, and wherein, the molar ratio of Ni, Co, Mn is 1:1:1.
The above-mentioned salts solution prepared is injected rotating speed as the reactor of 200rps taking the speed of 1L/h, injects the NaOH solution of 6mol/L simultaneously, regulate alkaline solution flow velocity, keep pH value between 10-12. After 10h, salts solution injects reactor completely, and precursor power has reacted.
By the solidliquid mixture after having reacted by centrifugation, washing dries 10h after neutral at 100 DEG C. By presoma and the Quilonum Retard after drying in molar ratio 1:1.05 mix after in retort furnace 900 DEG C of roasting 10h, the material after roasting obtains an equal Li (Ni after fragmentation is sieved1/3Co1/3Mn1/3)O2Material.
Comparative example 3
Preparation 10L concentration is Ni, Co, Al salts solution of 1mol/L, and wherein, the molar ratio of Ni, Co, Al is 0.82:0.15:0.03.
The above-mentioned salts solution prepared is injected rotating speed as the reactor of 200rps taking the speed of 1L/h, injects the NaOH solution of 6mol/L simultaneously, regulate alkaline solution flow velocity, keep pH value between 10-12. After 10h, salts solution injects reactor completely, and precursor power has reacted.
By the solidliquid mixture after having reacted by centrifugation, washing dries 10h after neutral at 100 DEG C. By presoma and the Quilonum Retard after drying in molar ratio 1:1.05 mix after in retort furnace 900 DEG C of roasting 10h, the material after roasting obtains the LiNi of equal after fragmentation is sieved0.82Co0.15Al0.03O2Material.
The material that embodiment of the present invention 3-15 and comparative example 1-3 provides is carried out performance test:
Test event: the specific discharge capacity after measuring the pH value of the material that embodiment of the present invention 3-15 and comparative example 1-3 provide and material being made 2032 button cells;
Measure part embodiment and comparative example to circulate capability retention and decomposition temperature after 100 times.
Test condition or method:
Specific discharge capacity is tested under between 0.1C electric current, 3.0-4.3V voltage;
100 circulations are carried out, capability retention after test loop between 0.2C electric current, 3.0-4.3V voltage;
Decomposition temperature under utilizing difference heat heat scan method to survey 4.3V voltage.
Test result is in table 1, table 2 and Fig. 1-9.
The performance perameter table of the material that table 1 embodiment of the present invention 3-15 and comparative example 1-3 provides
Table 2 embodiment 5, embodiment 8 and comparative example 1, comparative example 2
Circulate capability retention and decomposition temperature after 100 times
Embodiment 5 Embodiment 8 Comparative example 1 Comparative example 2
Capability retention 87% 88% 74% 84%
Decomposition temperature 248℃ 262℃ 210℃ 257℃
By table 1 and Fig. 1-8 it will be seen that the matrix material provided by the embodiment of the present invention makees the battery of positive pole, under the prerequisite sacrificing a small amount of capacity, greatly reducing the alkalescence of material, especially embodiment 5 still can keep higher capacity for 10.9 times in alkalescence; Associative list 2 it may be seen that the embodiment of the present invention provide matrix material decomposition temperature and simple Li (Ni0.8Co0.15Al0.05)O2Material ratio is greatly improved, and therefore the thermostability of material is greatly improved, embodiment 8 provide matrix material make electrode after decomposition temperature reach 262 DEG C, higher than arbitrary single-material; With reference to Fig. 9 and Figure 10, the battery of positive pole manufactured by the matrix material provided by the embodiment of the present invention, and the capability retention after circulation 100 times is higher than the battery of single-material electrode, and the capability retention of embodiment 5, embodiment 8 is all higher than 85%.
Therefore, the matrix material that the embodiment of the present invention provides has the feature of higher capacity, low alkalinity, electrolyte resistance, and has better cyclical stability and safety performance, and superiority of effectiveness is obvious, is more suitable for the application of power cell.
Above-mentioned embodiment of the present invention sequence number, just to describing, does not represent the quality of embodiment.
The foregoing is only the better embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment of doing, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (9)

1. a matrix material, it is characterised in that, described matrix material is nucleocapsid structure, the skin that the shell of described matrix material comprises middle layer and is coated on outside middle layer, and the kernel of described matrix material is Li (NixCoyAlz)O2, middle layer is Li (Ni1/3Co1/3Mn1/3)O2, skin is LiNi0.5Mn1.5O4, the kernel of described matrix material, middle layer, outer field mol ratio are a:b:c, wherein a+b+c=1,0 <b < 0.5,0 < c < 0.5, x+y+z=1, y=0.15,0.03≤z≤0.05;
Described matrix material is prepared by following preparation method: described preparation method comprises:
Being obtained the composite material precursor of nucleocapsid structure successively by coprecipitation reaction, the skin that the shell of described composite material precursor comprises middle layer and is coated on outside middle layer, the kernel of described composite material precursor is (NixCoyAlz)(OH)2, middle layer be (Ni1/3Co1/3Mn1/3)(OH)2, skin be Ni0.25Mn0.75(OH)2;
Retort furnace first roasting 2-5 hour at 700-800 DEG C is put into lithium source after being mixed according to the ratio of mol ratio 1:1-1.1 by described composite material precursor, then continue to heat up 800 DEG C-850 DEG C roasting 2-5 hours again, finally continue to be warming up to 850-950 DEG C of roasting 2-5 hour again; Then through cooling, broken, sieving obtains described matrix material.
2. a kind of matrix material as claimed in claim 1, it is characterised in that, a:b:c=0.8:0.15:0.05, x=0.8, z=0.05.
3. the preparation method of a matrix material, it is characterised in that, described preparation method comprises:
Being obtained the composite material precursor of nucleocapsid structure successively by coprecipitation reaction, the skin that the shell of described composite material precursor comprises middle layer and is coated on outside middle layer, the kernel of described composite material precursor is (NixCoyAlz)(OH)2, middle layer be (Ni1/3Co1/3Mn1/3)(OH)2, skin be Ni0.25Mn0.75(OH)2;
Retort furnace first roasting 2-5 hour at 700-800 DEG C is put into lithium source after being mixed according to the ratio of mol ratio 1:1-1.1 by described composite material precursor, then continue to heat up 800 DEG C-850 DEG C roasting 2-5 hours again, finally continue to be warming up to 850-950 DEG C of roasting 2-5 hour again; Then through cooling, broken, sieve that to obtain kernel be Li (NixCoyAlz)O2, middle layer be Li (Ni1/3Co1/3Mn1/3)O2, skin be LiNi0.5Mn1.5O4Matrix material, the kernel of described matrix material, middle layer, outer field mol ratio are a:b:c, wherein a+b+c=1,0 <b < 0.5,0 < c < 0.5, x+y+z=1, y=0.15,0.03≤z≤0.05.
4. the preparation method of matrix material as claimed in claim 3, it is characterised in that, the described composite material precursor being obtained nucleocapsid structure successively by coprecipitation reaction, is specifically comprised:
It is that the ratio of x:y:z drips the ternary salts solution adding Ni, Co, Al in the reactor of high speed rotating according to the mol ratio of Ni, Co, Al, drip the pH value adding mixture in alkaline solution control reactor is that 10-12 carries out coprecipitation reaction simultaneously, obtains solid phase for (NixCoyAlz)(OH)2Solidliquid mixture;
As (NixCoyAlz)(OH)2When particle is enough big, stop dripping the ternary salts solution adding Ni, Co, Al, the ratio being 1:1:1 according to the mol ratio of Ni, Co, Mn drips the ternary salts solution adding Ni, Co, Mn immediately in described reactor, in control reactor, the pH value of mixture is that 10-12 proceeds coprecipitation reaction, at (NixCoyAlz)(OH)2Particle outside forms middle layer (Ni1/3Co1/3Mn1/3)(OH)2;
After certain thickness middle layer is formed, stop dripping the ternary salts solution adding Ni, Co, Mn, the ratio being 0.25:0.75 according to the mol ratio of Ni, Mn drips the binary salt solution adding Ni, Mn immediately in reactor, in control reactor, the pH value of mixture is that 10-12 proceeds coprecipitation reaction, to forming certain thickness outer Ni in outside, described middle layer0.25Mn0.75(OH)2, stopped reaction;
By the solidliquid mixture after having reacted by centrifugation, the solid matter isolated washing is dried 1-10h after neutral at 100-200 DEG C, obtains the composite material precursor of nucleocapsid structure.
5. the preparation method of matrix material as claimed in claim 3, it is characterised in that, described lithium source is the one in lithium hydroxide, lithium nitrate, Quilonum Retard.
6. the preparation method of matrix material as claimed in claim 4, it is characterised in that, the rotating speed of described reactor is 180rps-220rps.
7. the preparation method of matrix material as claimed in claim 4, it is characterized in that, the ternary salts solution of described Ni, Co, Al is more than one in the acetate solution of Ni, Co, Al, nitrate solution, sulfate liquor, the ternary salts solution of described Ni, Co, Mn is more than one in the acetate solution of Ni, Co, Mn, nitrate solution, sulfate liquor, and the binary salt solution of described Ni, Mn is more than one in the acetate solution of Ni, Mn, nitrate solution, sulfate liquor.
8. the preparation method of matrix material as claimed in claim 4, it is characterised in that, described alkaline solution is sodium hydroxide solution or ammoniacal liquor.
9. the lithium ion battery of matrix material that just very claim 1 or 2 provides.
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