CN104078659A - Composite material, preparation method of composite material, and lithium ion battery comprising composite material - Google Patents

Composite material, preparation method of composite material, and lithium ion battery comprising composite material Download PDF

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CN104078659A
CN104078659A CN201310097680.9A CN201310097680A CN104078659A CN 104078659 A CN104078659 A CN 104078659A CN 201310097680 A CN201310097680 A CN 201310097680A CN 104078659 A CN104078659 A CN 104078659A
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composite material
solution
reactor
preparation
intermediate layer
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CN104078659B (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 invention discloses a composite material, a preparation method of the composite material, and a lithium ion battery comprising the composite material, and belongs to the field of lithium ion battery materials. The composite material is in a core-shell structure. A shell layer of the composite material comprises a middle layer and an outer layer coated outside the middle layer. An inner core of the composite material is Li(NixCoyAlz)O2; the middle layer is Li(Ni1/3Co1/3Mn1/3)O2; the outer layer is LiNi0.5Mn1.5O4; and a molar ratio of the inner core to the middle layer to the outer layer of the composite material is a:b:c, wherein a+b+c=1, b is greater than 0 and less than 0.5, c is greater than 0 and less than 0.5, x+y+z=1, y=0.15, and z is greater than or equal to 0.03 and is less than or equal to 0.05. The composite material has the characteristics of comparatively high capacity, low alkalinity and electrolyte resistance, has good cycling stability and safety performance, has an obvious cost performance advantage, and is more suitable for application of a power battery. Structural precursors of the layers of the composite material are sequentially formed by utilizing a coprecipitation synthesis technology, so that good consistency and good homogeneity are achieved and the layers are tightly connected with each other. Besides, the composite material can be obtained by a single roasting process; and the cost can be lowered effectively.

Description

Composite material and preparation method thereof, containing the lithium ion battery of this composite material
Technical field
The present invention relates to lithium ion battery material field, particularly a kind of for the composite material of lithium ion cell positive and the preparation method of presoma thereof and the battery that uses this composite material.
Background technology
Lithium ion battery is nearly a kind of high-energy battery that fast development is got up during the last ten years, because it has the advantages such as capacity is large, voltage is high, self discharge is little, becomes the power source of the field first-selections such as electric automobile.Therefore, the cycle performance of lithium ion battery and cost etc. all will become the key factor that affects the field commercialization processes such as electric automobile.
Positive electrode is the important component part of lithium ion battery, is also to determine the cycle performance of lithium ion battery and the key component of cost.At present, cobalt acid lithium is the anode material for lithium-ion batteries of widespread commercial.But cobalt expensive and have pollution, therefore, along with the further investigation to anode material for lithium-ion batteries, has produced a lot of new anode material for lithium-ion batteries, for example, with respect to the lower LiNi of cobalt acid lithium cost xco ym 1-x-yo 2series material.
LiNi xco ym 1-x-yo 2nCA material capacity in series material can reach 200mAh/g left and right, but has the shortcoming that electrochemical heat stability is poor and material alkalescence is high, and reason may be due to the Ni in material 3+can mixing in charge and discharge process, simultaneously Ni 4+there is strong oxidizing property, affected the circulation of material and other performance; NCM material initial capacity in this series material only has about 150mAh/g, but advantage be circulate, alkalescence is low.
At present, often by the method with other materials clad anode material, improve the performance of positive electrode each side, thereby solve the defect of emerging anode material for lithium-ion batteries self.As: patent US2010/0310940A1 has reported and has utilized barium titanate and its metal oxide to be coated to improve battery security to anode material for lithium-ion batteries; Patent CN102394295A has reported and has utilized spinelle nickel LiMn2O4 anode material for lithium-ion batteries to be coated to improve cycle life and the high-temperature storage performance of material.
In realizing process of the present invention, inventor finds that prior art at least exists following problem:
Patent US2010/0310940A1 utilizes inorganic matter barium titanate and its metal oxide to be coated positive electrode, can cause the reduction of positive electrode energy density, and also can make the conductivity of positive electrode greatly reduce;
First patent CN102394295A need to synthesize needed positive electrode, now needs to carry out bakes to burn the article; Recycling sol-gal process, at positive electrode surface coating spinelle nickel LiMn2O4, then carries out after baking, forms the positive electrode of coating spinelle nickel LiMn2O4.This mode need to be carried out after baking, can consume large amount of organic, and cost is increased, and exists two kinds of materials to connect the shortcoming of defective tightness simultaneously.
Summary of the invention
In order to solve the problem of prior art, the embodiment of the present invention provides a kind of composite material and preparation method thereof, containing the lithium ion battery of this composite material.Described technical scheme is as follows:
On the one hand, provide a kind of composite material, described composite material is nucleocapsid structure, and the shell of described composite material comprises intermediate layer and be coated on the skin outside intermediate layer, and the kernel of described composite material is Li (Ni xco yal z) O 2, intermediate layer is Li (Ni 1/3co 1/3mn 1/3) O 2, skin is LiNi 0.5mn 1.5o 4the kernel of described composite material, intermediate 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.
A kind of preparation method of composite material is provided on the other hand, and described preparation method comprises:
By coprecipitation reaction, obtain successively the composite material precursor of nucleocapsid structure, the shell of described composite material precursor comprises intermediate layer and is coated on the skin outside intermediate layer, and the kernel of described composite material precursor is (Ni xco yal z) (OH) 2, intermediate layer is (Ni 1/3co 1/3mn 1/3) (OH) 2, skin is Ni 0.25mn 0.75(OH) 2;
After described composite material precursor is mixed according to the ratio of mol ratio 1:1-1.1 with lithium source, at 500-1000 ℃, carry out roasting, then through cooling, broken, sieve that to obtain kernel be Li (Ni xco yal z) O 2, intermediate layer is Li (Ni 1/3co 1/3mn 1/3) O 2, skin is LiNi 0.5mn 1.5o 4composite material, the kernel of described composite material, intermediate 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 that obtains successively nucleocapsid structure by coprecipitation reaction, specifically comprises:
The ratio that is x:y:z according to the mol ratio of Ni, Co, Al is to the ternary salting liquid that drips Ni, Co, Al in the reactor of High Rotation Speed, drips pH value that aqueous slkali controls mixture in reactor for 10-12 carries out coprecipitation reaction simultaneously, and obtaining solid phase is (Ni xco yal z) (OH) 2solidliquid mixture;
As (Ni xco yal z) (OH) 2when particle is enough large, stop dripping the ternary salting liquid of Ni, Co, Al, the ratio that is 1:1:1 according to the mol ratio of Ni, Co, Mn is immediately to the ternary salting liquid that drips Ni, Co, Mn in described reactor, the pH value of controlling mixture in reactor is proceeded coprecipitation reaction for 10-12, at (Ni xco yal z) (OH) 2outside intermediate layer (the Ni that forms of particle 1/3co 1/3mn 1/3) (OH) 2;
After certain thickness intermediate layer forms, stop dripping the ternary salting liquid of Ni, Co, Mn, the ratio that is 0.25:0.75 according to the mol ratio of Ni, Mn is immediately to the binary salt solution that drips Ni, Mn in reactor, control the pH value of mixture in reactor for 10-12 proceeds coprecipitation reaction, extremely in outside, described intermediate layer, form certain thickness outer Ni 0.25mn 0.75(OH) 2, stop reaction;
Solidliquid mixture after reaction is completed, by centrifugation, washs isolated solid matter to neutrality and dry 1-10h at 100-200 ℃, obtains the composite material precursor of nucleocapsid structure.
Described carry out roasting, specifically comprise:
Put into first roasting 2-5 hour at 700-800 ℃ of Muffle furnace, then continue to heat up at 800 ℃-850 ℃ roasting 2-5 hour again, finally continue to be warming up to 850-950 ℃ of roasting 2-5 hour again.
Described lithium source is a kind of in lithium hydroxide, lithium nitrate, lithium carbonate.
The rotating speed of described reactor is 180rps-220rps.
The ternary salting liquid of described Ni, Co, Al is one or more combinations in the acetate solution, nitrate solution, sulfate liquor, chloride solution of Ni, Co, Al, the ternary salting liquid of described Ni, Co, Mn is one or more combinations in the acetate solution, nitrate solution, sulfate liquor, chloride solution of Ni, Co, Mn, 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 aqueous slkali is sodium hydroxide solution or ammoniacal liquor.
A kind of lithium ion battery of just very above-mentioned composite material is provided on the other hand.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
The composite material that the embodiment of the present invention provides is the nucleocapsid structure of multilayer, Core Choice NCA material, and subshell is selected NCM material, and outer shell is selected spinelle lithium nickelate material.Because Shell Materials itself has certain capacity, the inner nuclear material that is coated on high power capacity can not cause inner nuclear material capacity to have larger loss outward, and because Shell Materials alkalescence is low and have good cycle performance, the alkalescence that can reduce composite material after the high inner nuclear material of alkalescence is coated improves the cycle performance of composite material simultaneously, in addition, what outer shell was selected is spinelle lithium nickelate material, the discharge platform of this material is about 4.7-4.8V, discharge platform higher than intermediate layer and kernel, improved the resistance to pressure of material monolithic, simultaneously, because the oxidizability of this material is poor, be difficult for reacting with electrolyte, its internal material does not directly contact with electrolyte because being coated by this material, be difficult for reacting with electrolyte, avoided battery when discharging and recharging, because electrode material reacts the bulging the causing generation of dangerous situation such as even explode with electrolyte, security performance and the stability of battery have been improved.
Therefore, the composite 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 security performance, and superiority of effectiveness is obvious, is more suitable for the application in electrokinetic cell.
The embodiment of the present invention, by utilizing coprecipitation technique to form successively each layer of structured forerunner of composite material, makes to have between good consistency and homogeneity and each layer and connect closely between each layer of composite material.And composite material precursor carries out bakes to burn the article after mixing with lithium source can obtain composite material, can effectively reduce costs.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the discharge curve first of the embodiment of the present invention 3 and comparative example 1,2;
Fig. 2 is the discharge curve first of the embodiment of the present invention 4 and comparative example 1,2;
Fig. 3 is the discharge curve first of the embodiment of the present invention 5 and comparative example 1,2;
Fig. 4 is the discharge curve first of the embodiment of the present invention 6 and comparative example 1,2;
Fig. 5 is the discharge curve first of the embodiment of the present invention 7 and comparative example 1,2;
Fig. 6 is the discharge curve first of the embodiment of the present invention 8 and comparative example 1,2;
Fig. 7 is the discharge curve first of the embodiment of the present invention 9 and comparative example 1,2;
Fig. 8 is the discharge curve first of the embodiment of the present invention 10 and comparative example 1,2;
Fig. 9 is 100 cyclic curve figure of the embodiment of the present invention 5 and comparative example 1,2;
Figure 10 is 100 cyclic curve figure of the embodiment of the present invention 8 and comparative example 1,2.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
Embodiment 1
The embodiment of the present invention provides a kind of composite material, and described composite material is multi-layer core-shell structure, and the shell of described composite material comprises intermediate layer and be coated on the skin outside intermediate layer, and the kernel of described composite material is Li (Ni xco yal z) O 2, intermediate layer is Li (Ni 1/3co 1/3mn 1/3) O 2, skin is LiNi 0.5mn 1.5o 4the kernel of described composite material, intermediate 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 composite material that the embodiment of the present invention provides is the nucleocapsid structure of multilayer, Core Choice NCA material, and subshell is selected NCM material, and outer shell is selected spinelle lithium nickelate material.Because Shell Materials itself has certain capacity, the inner nuclear material that is coated on high power capacity can not cause inner nuclear material capacity to have larger loss outward, and because Shell Materials alkalescence is low and have good cycle performance, the alkalescence that can reduce composite material after the high inner nuclear material of alkalescence is coated improves the cycle performance of composite material simultaneously, in addition, what outer shell was selected is spinelle lithium nickelate material, the discharge platform of this material is about 4.7-4.8V, discharge platform higher than intermediate layer and kernel, improved the resistance to pressure of material monolithic, simultaneously, because the oxidizability of this material is poor, be difficult for reacting with electrolyte, its internal material does not directly contact with electrolyte because being coated by this material, be difficult for reacting with electrolyte, avoided battery when discharging and recharging, because electrode material reacts the bulging the causing generation of dangerous situation such as even explode with electrolyte, security performance and the stability of battery have been improved.
Therefore, the composite 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 security performance, and superiority of effectiveness is obvious, is more suitable for the application in electrokinetic cell.
Embodiment 2
The embodiment of the present invention provides a kind of preparation method of composite material, and described preparation method comprises:
Step 1: obtain successively the composite material precursor of nucleocapsid structure by coprecipitation reaction, the shell of described composite material precursor comprises intermediate layer and be coated on the skin outside intermediate layer, and the kernel of described composite material precursor is (Ni xco yal z) (OH) 2, intermediate layer is (Ni 1/3co 1/3mn 1/3) (OH) 2, skin is Ni 0.25mn 0.75(OH) 2;
Step 2: after described composite material precursor is mixed according to the ratio of mol ratio 1:1-1.1 with lithium source, carry out roasting, then through cooling, broken, sieve that to obtain kernel be Li (Ni xco yal z) O 2, intermediate layer is Li (Ni 1/3co 1/3mn 1/3) O 2, skin is LiNi 0.5mn 1.5o 4composite material, the kernel of described composite material, intermediate 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 embodiment of the present invention, by utilizing coprecipitation technique to form successively each layer of structured forerunner of composite material, makes to have between good consistency and homogeneity and each layer and connect closely between each layer of composite material.And composite material precursor carries out bakes to burn the article after mixing with lithium source can obtain composite material, can effectively reduce costs.
Embodiment of the present invention step 1 specifically comprises:
Step 1a: the ratio that is x:y:z according to the mol ratio of Ni, Co, Al is prepared the ternary salting liquid A of a certain amount of Ni, Co, Al, the ratio that is 1:1:1 according to the mol ratio of Ni, Co, Mn is prepared the ternary salting liquid B of a certain amount of Ni, Co, Mn, the ratio that is 0.25:0.75 according to the mol ratio of Ni, Mn is prepared a certain amount of Ni, Mn binary salt solution C, according to requirements prepares a certain amount of certain density aqueous slkali simultaneously.
Step 1b: prepare the ternary salting liquid A that drips Ni, Co, Al in the reactor of backward High Rotation Speed, drip pH value that aqueous slkali controls mixture in reactor for 10-12 carries out coprecipitation reaction simultaneously, obtaining solid phase is (Ni xco yal z) (OH) 2solidliquid mixture;
As (Ni xco yal z) (OH) 2when particle is enough large, stop dripping the ternary salting liquid A of Ni, Co, Al, to the ternary salting liquid B that drips Ni, Co, Mn in described reactor, the pH value of controlling mixture in reactor is proceeded coprecipitation reaction for 10-12, at (Ni xco yal z) (OH) 2outside intermediate layer (the Ni that forms of particle 1/3co 1/3mn 1/3) (OH) 2;
After certain thickness intermediate layer forms, stop dripping the ternary salting liquid B of Ni, Co, Mn, to the binary salt solution C that drips Ni, Mn in reactor, the pH value of controlling mixture in reactor is proceeded coprecipitation reaction for 10-12, at the certain thickness outer Ni of described intermediate layer outside formation 0.25mn 0.75(OH) 2, stop reaction;
Step 1c: the solidliquid mixture after reaction is completed, by centrifugation, washs isolated solid matter to neutrality and dry 1-10h at 100-200 ℃, obtains the composite material precursor of nucleocapsid structure.
Wherein, (Ni xco yal z) (OH) 2the size of particle, intermediate layer and outer layer thickness all can be according to the selections that needs of specific lithium ion cell electrode; Each solution rate of addition is adjusted according to each layer of particle growth condition.
Described in embodiment of the present invention step 2, carry out roasting, specifically comprise:
Put into first roasting 2-5 hour at 700-800 ℃ of Muffle furnace, then continue to heat up at 800 ℃-850 ℃ roasting 2-5 hour again, finally continue to be warming up to 850-950 ℃ of roasting 2-5 hour again.
Because the material of kernel, subshell, outer shell is different, the speed that temperature is different, lithium ion enters lattice that its lattice forms is also different, therefore, carries out baking inphases under this condition, not only can make each layer better to form lattice, and be conducive to lithium ion and enter fast in each layer crystal lattice.
In the embodiment of the present invention:
Described lithium source is a kind of in lithium hydroxide, lithium nitrate, lithium carbonate, preferably lithium carbonate.
Preferably, the rotating speed of described reactor is 180rps-220rps.
Under this rotating speed, be more conducive to form homogeneous, stable composite material precursor, make to connect between each layer of composite material precursor tightr.
The ternary salting liquid of described Ni, Co, Al is one or more combinations in the acetate solution, nitrate solution, sulfate liquor, chloride solution of Ni, Co, Al, the ternary salting liquid of described Ni, Co, Mn is one or more combinations in the acetate solution, nitrate solution, sulfate liquor, chloride solution of Ni, Co, Mn, 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 aqueous slkali is sodium hydroxide solution or ammoniacal liquor.
Embodiment 3
Ni, Co, Al nitrate solution A that preparation 9L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 0.05L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 1L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, pH value in maintenance reactor is between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor immediately, after 0.1h, solution B is injected reactor completely, then with the speed of 0.5L/h, solution C is added dropwise in reactor immediately, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.9 (Ni 0.8co 0.15al 0.05) (OH) 20.05 (Ni 1/3co 1/3mn 1/3) (OH) 20.1Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.9Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.05Li (Ni 1/3co 1/3mn 1/3) O 20.05LiNi 0.5mn 1.5o 4.
Embodiment 4
Ni, Co, Al chloride solution A that preparation 8L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn chloride solution B that preparation 1L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn chloride solution C that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 2h, solution B is injected reactor completely, finally the speed with 0.5L/h is added dropwise to solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.8 (Ni 0.8co 0.15al 0.05) (OH) 20.1 (Ni 1/3co 1/3mn 1/3) (OH) 20.2Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting obtains the multilayer materials 0.8Li (Ni of modification after fragmentation is sieved 0.8co 0.15al 0.05) O 20.1Li (Ni 1/3co 1/3mn 1/3) O 20.1LiNi 0.5mn 1.5o 4.
Embodiment 5
Ni, Co, Al nitrate solution A that preparation 8L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 1.5L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 1L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor immediately, after 3h, solution B is injected reactor completely, then with the speed of 0.5L/h, dripping solution C immediately enters in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.8 (Ni 0.8co 0.15al 0.05) (OH) 20.15 (Ni 1/3co 1/3mn 1/3) (OH) 20.1Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.8Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.15Li (Ni 1/3co 1/3mn 1/3) O 20.05LiNi 0.5mn 1.5o 4.
Embodiment 6
Ni, Co, Al nitrate solution A that preparation 7L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 1L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 4L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 2h, solution B is injected reactor completely, then the speed with 0.5L/h starts to drip solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.7 (Ni 0.8co 0.15al 0.05) (OH) 20.1 (Ni 1/3co 1/3mn 1/3) (OH) 20.4Ni 0.25mn 0.75(OH) 2composite material precursor.
By the presoma after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.7Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.1Li (Ni 1/3co 1/3mn 1/3) O 20.2LiNi 0.5mn 1.5o 4.
Embodiment 7
Ni, Co, Al nitrate solution A that preparation 7L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 1.5L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 3L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 3h, solution B is injected reactor completely, then the speed with 0.5L/h starts to drip solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.7 (Ni 0.8co 0.15al 0.05) (OH) 20.15 (Ni 1/3co 1/3mn 1/3) (OH) 20.3Ni 0.25mn 0.75(OH) 2composite material precursor.
By the presoma after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.7Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.15Li (Ni 1/3co 1/3mn 1/3) O 20.15LiNi 0.5mn 1.5o 4.
Embodiment 8
Ni, Co, Al nitrate solution A that preparation 7L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 4h, solution B is injected reactor completely, then the speed with 0.5L/h starts to drip solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.7 (Ni 0.8co 0.15al 0.05) (OH) 20.2 (Ni 1/3co 1/3mn 1/3) (OH) 20.2Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.7Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.2Li (Ni 1/3co 1/3mn 1/3) O 20.1LiNi 0.5mn 1.5o 4.
Embodiment 9
Ni, Co, Al nitrate solution A that preparation 6L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 4L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 4h, solution B is injected reactor completely, then the speed with 0.5L/h starts to drip solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.6 (Ni 0.8co 0.15al 0.05) (OH) 20.2 (Ni 1/3co 1/3mn 1/3) (OH) 20.4Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.6Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.2Li (Ni 1/3co 1/3mn 1/3) O 20.2LiNi 0.5mn 1.5o 4.
Embodiment 10
Ni, Co, Al nitrate solution A that preparation 6L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 3L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 6h, solution B is injected reactor completely, then the speed with 0.5L/h starts to drip solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.6 (Ni 0.8co 0.15al 0.05) (OH) 20.3 (Ni 1/3co 1/3mn 1/3) (OH) 20.2Ni 0.25mn 0.75(OH) 2composite material precursor.
By the presoma after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting obtains the multilayer materials 0.6Li (Ni of modification after fragmentation is sieved 0.8co 0.15aL 0.05) O 20.3Li (Ni 1/3co 1/3mn 1/3) O 20.1LiNi 0.5mn 1.5o 4.
Embodiment 11
Ni, Co, Al nitrate solution A that preparation 7L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.82:0.15:0.03; Ni, Co, Mn nitrate solution B that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 4h, solution B is injected reactor completely, then the speed with 0.5L/h starts to drip solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.7 (Ni 0.82co 0.15al 0.03) (OH) 20.2 (Ni 1/3co 1/3mn 1/3) (OH) 20.2Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.7Li (Ni broken, that obtain modification after sieving 0.82co 0.15al 0.03) O 20.2Li (Ni 1/3co 1/3mn 1/3) O 20.1LiNi 0.5mn 1.5o 4.
Embodiment 12
Ni, Co, Al nitrate solution A that preparation 9L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 0.05L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 1L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the ammoniacal liquor of enough 10mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the ammoniacal liquor of 10mol/L simultaneously, pH value in maintenance reactor is between 11-12, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor immediately, after 0.1h, solution B is injected reactor completely, then the speed with 0.5L/h is added dropwise to solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.9 (Ni 0.8co 0.15al 0.05) (OH) 20.05 (Ni 1/3co 1/3mn 1/3) (OH) 20.1Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.1 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.9Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.05Li (Ni 1/3co 1/3mn 1/3) O 20.05LiNi 0.5mn 1.5o 4.
Embodiment 13
Ni, Co, Al chloride solution A that preparation 8L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn chloride solution B that preparation 1L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn chloride solution C that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 2h, solution B is injected reactor completely, finally the speed with 0.5L/h is added dropwise to solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.8 (Ni 0.8co 0.15al 0.05) (OH) 20.1 (Ni 1/3co 1/3mn 1/3) (OH) 20.2Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting obtains the multilayer materials 0.8Li (Ni of modification after fragmentation is sieved 0.8co 0.15al 0.05) O 20.1Li (Ni 1/3co 1/3mn 1/3) O 20.1LiNi 0.5mn 1.5o 4.
Embodiment 14
Ni, Co, Al nitrate solution A that preparation 5L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 4L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 2L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 1L/h progressively drips solution B in reactor immediately, after 4h, solution B is injected reactor completely, then with the speed of 0.5L/h, dripping solution C immediately enters in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.5 (Ni 0.8co 0.15al 0.05) (OH) 20.4 (Ni 1/3co 1/3mn 1/3) (OH) 20.2Ni 0.25mn 0.75(OH) 2composite material precursor.
By the composite material precursor after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.5Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.4Li (Ni 1/3co 1/3mn 1/3) O 20.1LiNi 0.5mn 1.5o 4.
Embodiment 15
Ni, Co, Al nitrate solution A that preparation 5L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Al is 0.8:0.15:0.05; Ni, Co, Mn nitrate solution B that preparation 1L concentration is 1mol/L, wherein, the mol ratio of Ni, Co, Mn is 1:1:1; Ni, Mn nitrate solution C that preparation 8L concentration is 1mol/L, wherein, the mol ratio of Ni, Mn is 0.25:0.75; Prepare the NaOH aqueous slkali of enough 6mol/L.
Solution A be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH aqueous slkali of 6mol/L simultaneously, keep pH value between 10-11, after solution A is dropwised, speed with 0.5L/h progressively drips solution B in reactor, after 2h, solution B is injected reactor completely, then the speed with 0.5L/h starts to drip solution C in reactor, solution C drips rear end reaction, solidliquid mixture after reaction is completed is by centrifugation, wash to neutrality and dry 10h at 100 ℃, making molecular formula is 0.5 (Ni 0.8co 0.15al 0.05) (OH) 20.1 (Ni 1/3co 1/3mn 1/3) (OH) 20.8Ni 0.25mn 0.75(OH) 2composite material precursor.
By the presoma after drying and lithium carbonate in molar ratio 1:1.05 after mixing, put into Muffle furnace, first roasting 3 hours at 750 ℃, then be warming up to 850 ℃ of roastings 5 hours, finally be warming up to 950 ℃ of roastings 2 hours, the material after roasting is through multilayer materials 0.5Li (Ni broken, that obtain modification after sieving 0.8co 0.15al 0.05) O 20.1Li (Ni 1/3co 1/3mn 1/3) O 20.4LiNi 0.5mn 1.5o 4.
Embodiment 16
The present embodiment provides a kind of mobile phone lithium ion battery, the composite material that the positive electrode of described lithium ion battery adopts embodiment 3-15 to provide.
Described lithium ion battery can also be the lithium ion battery for products such as notebook, electric motor cars.
Comparative example 1
Ni, Co, Al salting liquid that preparation 10L concentration is 1mol/L, wherein, the molar ratio of Ni, Co, Al is 0.8:0.15:0.05.
The above-mentioned salting liquid preparing be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH solution of 6mol/L simultaneously, regulate aqueous slkali flow velocity, keep pH value between 10-12.After 10h, salting liquid injects reactor completely, and presoma preparation feedback completes.
Solidliquid mixture after reaction is completed, by centrifugation, washs to neutrality and dry 10h at 100 ℃.By the presoma after drying and lithium carbonate in molar ratio 1:1.05 mix after in Muffle furnace 900 ℃ of roasting 10h, the material after roasting obtains homogeneous LiNi after fragmentation is sieved 0.8co 0.15al 0.05o 2material.
Comparative example 2
Ni, Co, Mn salting liquid that preparation 10L concentration is 1mol/L, wherein, the molar ratio of Ni, Co, Mn is 1:1:1.
The above-mentioned salting liquid preparing be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH solution of 6mol/L simultaneously, regulate aqueous slkali flow velocity, keep pH value between 10-12.After 10h, salting liquid injects reactor completely, and presoma preparation feedback completes.
Solidliquid mixture after reaction is completed, by centrifugation, washs to neutrality and dry 10h at 100 ℃.By the presoma after drying and lithium carbonate in molar ratio 1:1.05 mix after in Muffle furnace 900 ℃ of roasting 10h, the material after roasting obtains homogeneous Li (Ni after fragmentation is sieved 1/3co 1/3mn 1/3) O 2material.
Comparative example 3
Ni, Co, Al salting liquid that preparation 10L concentration is 1mol/L, wherein, the molar ratio of Ni, Co, Al is 0.82:0.15:0.03.
The above-mentioned salting liquid preparing be take to the speed of 1L/h and inject the reactor that rotating speed is 200rps, inject the NaOH solution of 6mol/L simultaneously, regulate aqueous slkali flow velocity, keep pH value between 10-12.After 10h, salting liquid injects reactor completely, and presoma preparation feedback completes.
Solidliquid mixture after reaction is completed, by centrifugation, washs to neutrality and dry 10h at 100 ℃.By the presoma after drying and lithium carbonate in molar ratio 1:1.05 mix after in Muffle furnace 900 ℃ of roasting 10h, the material after roasting obtains the LiNi of homogeneous after fragmentation is sieved 0.82co 0.15al 0.03o 2material.
The material that embodiment of the present invention 3-15 and comparative example 1-3 are provided carries out performance test:
Test event: measure the pH value of the material that embodiment of the present invention 3-15 and comparative example 1-3 provide and material is made to the specific discharge capacity after 2032 button cells;
Capability retention and decomposition temperature after measure portion embodiment and comparative example circulation 100 times.
Test condition or method:
Lower electric discharge specific capacity between 0.1C electric current, 3.0-4.3V voltage;
Between 0.2C electric current, 3.0-4.3V voltage, carry out 100 circulations, capability retention after test loop;
Utilize differential thermal calorimetric scan method to survey the decomposition temperature under 4.3V voltage.
Test result in Table 1, table 2 and Fig. 1-9.
The performance parameter table of the material that table 1 embodiment of the present invention 3-15 and comparative example 1-3 provide
Table 2 embodiment 5, embodiment 8 and comparative example 1, comparative example 2
Capability retention and decomposition temperature after 100 times circulate
? Embodiment 5 Embodiment 8 Comparative example 1 Comparative example 2
Capability retention 87% 88% 74% 84%
Decomposition temperature 248℃ 262℃ 210℃ 257℃
From table 1 and Fig. 1-8, the composite material providing by the embodiment of the present invention is made anodal battery, is sacrificing under the prerequisite of a small amount of capacity, and the alkalescence, the especially embodiment 5 that greatly reduce material still can keep higher capacity 10.9 times in alkalescence; Associative list 2 can be found out, the composite material decomposition temperature that the embodiment of the present invention provides and simple Li (Ni 0.8co 0.15al 0.05) O 2material ratio is greatly improved, so the thermal stability of material is greatly improved, and the decomposition temperature that the composite material that embodiment 8 provides is made after electrode reaches 262 ℃, higher than arbitrary homogenous material; With reference to Fig. 9 and Figure 10, the composite material providing by the embodiment of the present invention is manufactured anodal battery, and the capability retention in circulation after 100 times is higher than the battery of homogenous material electrode, and the capability retention of embodiment 5, embodiment 8 is all higher than 85%.
Therefore, the composite 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 security performance, and superiority of effectiveness is obvious, is more suitable for the application in electrokinetic cell.
The invention described above embodiment sequence number, just to describing, does not represent the quality of embodiment.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a composite material, is characterized in that, described composite material is nucleocapsid structure, and the shell of described composite material comprises intermediate layer and be coated on the skin outside intermediate layer, and the kernel of described composite material is Li (Ni xco yal z) O 2, intermediate layer is Li (Ni 1/3co 1/3mn 1/3) O 2, skin is LiNi 0.5mn 1.5o 4the kernel of described composite material, intermediate 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.
2. a kind of composite material as claimed in claim 1, is characterized in that, a:b:c=0.8:0.15:0.05, x=0.8, z=0.05.
3. a preparation method for composite material, is characterized in that, described preparation method comprises:
By coprecipitation reaction, obtain successively the composite material precursor of nucleocapsid structure, the shell of described composite material precursor comprises intermediate layer and is coated on the skin outside intermediate layer, and the kernel of described composite material precursor is (Ni xco yal z) (OH) 2, intermediate layer is (Ni 1/3co 1/3mn 1/3) (OH) 2, skin is Ni 0.25mn 0.75(OH) 2;
After described composite material precursor is mixed according to the ratio of mol ratio 1:1-1.1 with lithium source, at 500-1000 ℃, carry out roasting, then through cooling, broken, sieve that to obtain kernel be Li (Ni xco yal z) O 2, intermediate layer is Li (Ni 1/3co 1/3mn 1/3) O 2, skin is LiNi 0.5mn 1.5o 4composite material, the kernel of described composite material, intermediate 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 composite material as claimed in claim 3, is characterized in that, the described composite material precursor that obtains successively nucleocapsid structure by coprecipitation reaction, specifically comprises:
The ratio that is x:y:z according to the mol ratio of Ni, Co, Al is to the ternary salting liquid that drips Ni, Co, Al in the reactor of High Rotation Speed, drips pH value that aqueous slkali controls mixture in reactor for 10-12 carries out coprecipitation reaction simultaneously, and obtaining solid phase is (Ni xco yal z) (OH) 2solidliquid mixture;
As (Ni xco yal z) (OH) 2when particle is enough large, stop dripping the ternary salting liquid of Ni, Co, Al, the ratio that is 1:1:1 according to the mol ratio of Ni, Co, Mn is immediately to the ternary salting liquid that drips Ni, Co, Mn in described reactor, the pH value of controlling mixture in reactor is proceeded coprecipitation reaction for 10-12, at (Ni xco yal z) (OH) 2outside intermediate layer (the Ni that forms of particle 1/3co 1/3mn 1/3) (OH) 2;
After certain thickness intermediate layer forms, stop dripping the ternary salting liquid of Ni, Co, Mn, the ratio that is 0.25:0.75 according to the mol ratio of Ni, Mn is immediately to the binary salt solution that drips Ni, Mn in reactor, control the pH value of mixture in reactor for 10-12 proceeds coprecipitation reaction, extremely in outside, described intermediate layer, form certain thickness outer Ni 0.25mn 0.75(OH) 2, stop reaction;
Solidliquid mixture after reaction is completed, by centrifugation, washs isolated solid matter to neutrality and dry 1-10h at 100-200 ℃, obtains the composite material precursor of nucleocapsid structure.
5. the preparation method of composite material as claimed in claim 3, is characterized in that, described carries out roasting, specifically comprises:
Put into first roasting 2-5 hour at 700-800 ℃ of Muffle furnace, then continue to heat up at 800 ℃-850 ℃ roasting 2-5 hour again, finally continue to be warming up to 850-950 ℃ of roasting 2-5 hour again.
6. the preparation method of composite material as claimed in claim 3, is characterized in that, described lithium source is a kind of in lithium hydroxide, lithium nitrate, lithium carbonate.
7. the preparation method of composite material as claimed in claim 4, is characterized in that, the rotating speed of described reactor is 180rps-220rps.
8. the preparation method of composite material as claimed in claim 4, it is characterized in that, described Ni, Co, the ternary salting liquid of Al is Ni, Co, the acetate solution of Al, nitrate solution, sulfate liquor, one or more combinations in chloride solution, described Ni, Co, the ternary salting liquid of Mn is Ni, Co, the acetate solution of Mn, nitrate solution, sulfate liquor, one or more combinations in chloride solution, described Ni, the binary salt solution of Mn is Ni, the acetate solution of Mn, nitrate solution, sulfate liquor, one or more combinations in chloride solution.
9. the preparation method of composite material as claimed in claim 4, is characterized in that, described aqueous slkali is sodium hydroxide solution or ammoniacal liquor.
10. the lithium ion battery of the composite material that just very claim 1 or 2 provides.
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CN106784809A (en) * 2016-11-18 2017-05-31 山东精工电子科技有限公司 A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method
CN109314231A (en) * 2017-02-22 2019-02-05 林奈（中国）新能源有限公司 Core-shell structure copolymer electroactive material
CN109411745A (en) * 2017-08-17 2019-03-01 江苏津谊新能源科技有限公司 A kind of novel tertiary material lithium ion battery
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