CN109817955A - Non-aqueous electrolyte secondary battery nickelic positive electrode and preparation method thereof - Google Patents
Non-aqueous electrolyte secondary battery nickelic positive electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of non-aqueous electrolyte secondary battery nickelic positive electrode and preparation method thereof, the nickelic positive electrode tool general formula LiwNi1‑x‑yCoxMnyMzO2It indicates, average grain diameter D50 is 8-15 μm, is that the big partial size for being 8-18 μm by the D50 small particle for being 2-5 μm and D50 is constituted, and small particle Co content (metal molar ratio；SC) it is higher than large-sized Co content (the metal molar ratio；LC), preferably Co concentration ratio (SC/LC) is in the range of 1.2-2.On the one hand nickelic positive electrode of the invention passes through element doping and cladding stabilizing material structure, on the other hand by improving the cobalt content in small particle come stabilizing material crystal structure, the cycle performance of raising material, small particle and big partial size are mixed according to different proportion finally, improve the tap density of positive electrode and the compacted density of pole piece.
Description
Technical field
The present invention relates to a kind of positive electrode for nonaqueous electrolyte secondary battery materials, more particularly to one kind is by nickelic combined oxidation
The nickelic positive electrode that object is constituted.
Technical background
With the high speed development of new-energy automobile, the demand to power battery is constantly promoted, in recent years, new-energy automobile pair
The requirement of course continuation mileage is higher and higher, also has higher choose to the energy density of lithium ion battery, cycle performance and security performance
War.Nickelic system's positive electrode becomes positive electrode focus of attention, has in power battery field because its capacity is high, at low cost
Boundless market.
Nickelic system's positive electrode is since nickel content is higher, and the radius of lithium ionWith the radius of nickelousRelatively, it is easy to produce lithium nickel mixing, influences the structural stability of material, and then influences its electrochemistry
Energy；The particle diameter distribution of nickelic system's positive electrode is mostly normal distribution currently on the market, and the tap density of this particle diameter distribution material
Lower, the compacted density of manufactured pole piece is lower, this pole piece be easy to cause the broken of second particle, lead to material in roll-in
It is bad with the contact of conductive agent and binder, while Particle Breakage increases the area of material and electrolyte interface, influences its electricity
Chemical property；Big partial size and the particle diameter distribution of small particle mixing are the Non-Gaussian Distribution of two peak shape states, since small size particle can
It is filled into the gap between bulky grain, the tap density of material, the compacted density of pole piece can be effectively improved, but due to small particle
The specific surface area of material is larger, and material and electrolyte generation side reaction are more, and the cyclical stability of material is deteriorated.Application No. is
201710706178.1 washing reduces residual alkali by element doping stabilizing material crystal structure, cladding improves electrochemical stability
And safety, but the method prepare sample tap density it is relatively low；And application No. is 201510545968.7 to pass through difference
The material of partial size precursor preparation different-grain diameter, by different-grain diameter material carry out mixing improve density of material, but to small particle with
Electrolyte reaction is more inconsiderate.The high the two of the good cycle and tap density of material cannot get both, therefore need to develop one kind
Novel nickelic positive electrode, the Lai Gaishan above problem.
Summary of the invention
Aiming at the problems existing in the prior art, also make while the present invention provides one kind with high charge-discharge capacity excellent
Cycle performance and compared with two characteristics of high-tap density and non-aqueous electrolyte secondary battery nickelic positive electrode and its preparation deposited
Method.On the one hand nickelic positive electrode of the invention passes through element doping and cladding stabilizing material structure, on the other hand by mentioning
The cycle performance that cobalt content in high small particle carrys out stabilizing material crystal structure, improves material, finally by small particle and big partial size
It is mixed according to different proportion, improves the tap density of positive electrode and the compacted density of pole piece.
In order to solve the above technical problems, the invention adopts the following technical scheme:
The nickelic positive electrode of a kind of non-aqueous electrolyte secondary battery, with general formula LiwNi1-x-yCoxMnyMzO2It indicates, wherein
M is selected from least one of Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg and Sr element, and 0.98≤w≤1.15,0≤x≤
0.20,0≤y≤0.20,0≤z≤0.02；The average grain diameter D50 of nickelic positive electrode be 8-15 μm, be by D50 be 2-5 μm
The big partial size that small particle and D50 are 8-18 μm is constituted, and the mixed proportion of small particle is 10%-90% by quality ratio, and this is small
The cobalt content of partial size is higher than the large-sized cobalt content.
Nickelic positive electrode of the invention is made of big small particle, wherein small particle Co content (metal molar ratio；SC)
Higher than large-sized Co content (the metal molar ratio；LC), preferably Co concentration ratio (SC/LC) is especially excellent in the range of 1.2-2
It is selected between 1.3-1.7, Co excessive concentration influences the performance of material capacity, and Co element is too low not to have due effect.
The crucial technology of preparing of the nickelic positive electrode of non-aqueous electrolyte secondary battery of the invention is characterized in that, is used
D50 be the 2-5 μm of nickel cobalt manganese hydroxide/oxide different with 8-18 μm of cobalt content, respectively match lithium compound, additive into
Row roasting, then mixed in certain proportion, so that the cobalt content (metal molar ratio: SC) of the small particle is big higher than described
The cobalt content (metal molar ratio: LC) of partial size, to obtain the nickelic anode that the D50 being made of stuff and other stuff is 8-15 μm
Material.
In manufacturing method of the above-mentioned non-aqueous electrolyte secondary battery with nickelic positive electrode, lithium compound is the carbon of LITHIUM BATTERY
Sour lithium or monohydrate lithium hydroxide, the average grain diameter D50 of lithium compound are 5-8 μm, and lithium salts additive amount Li/ (Ni+Co+Mn) exists
(with molar ratio computing) between 1.03-1.15；Additive is selected from the change containing Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg or Sr
The one of which in object is closed, the partial size of additive is between 10-100nm；Nickel cobalt manganese hydroxide/oxide of different-grain diameter is mixed
In the step of closing lithium compound, additive, nickel cobalt manganese hydroxide can first carry out oxidizing roasting and form nickel, cobalt and manganese oxide, then mix
Lithium compound is roasted after can also directly mixing lithium compound, additive mixing, and wherein maturing temperature is 730-900 DEG C, roasting
Time is 8-20h；Material after above-mentioned roasting, can carry out washing reduces residual alkali, then is roasted after mixing with additive, roasts
It is mixed afterwards according still further to certain ratio, obtains the nickelic positive electrode that the D50 of stuff and other stuff composition is 8-15 μm；If material
By washing, then after mix with additive in sintering step, the additive be selected from contain Zr, Mg, Ti, Ce, Mo, W, Nb, B,
F, the one of which in the compound of Ca, Mg or Sr, the partial size of additive is between 10-100nm, sintering temperature 400-700
DEG C, sintering time 3-10h.
In manufacturing method of the above-mentioned non-aqueous electrolyte secondary battery with nickelic positive electrode, additive contain Zr, Mg, Ti,
The elements such as Ce, Mo, W, Nb, B, F, Ca, Mg and Sr, the partial size of additive is between 10-100nm.Additive partial size is excessive, addition
Agent cannot be evenly distributed in material, cause Elemental redistribution in additive uneven, not have the due effect of additive.
Beneficial effects of the present invention: 1, element doping can reduce the mixing of lithium nickel, stable crystal structure, and cladding can reduce material
Side reaction between electrolyte, improves cycle performance, and the structural stability and electrochemistry of material can be improved in element doping and cladding
Performance；Big small particle mixing, small size particle can be filled in the gap between large-size particles and particle, can efficiently use sky
Between, to improve the tap density of material and the compacted density of pole piece；In ternary material cobalt element can stabilizing material stratiform knot
Structure improves cycle performance and high rate performance, by improving the content of cobalt element in small particle, to make up due to small particle specific surface
Long-pending big and the generated cyclical stability difference that reacts with electrolyte problem, to improve the cyclicity of small particle material
Can, and then improve the big mixed cycle performance of small particle.The tap density of this material is high, is made into pole piece and assembles electricity
The compacted density in pond, pole piece is high, the good cycle of battery, to realize high-tap density, high compacted density and cycle performance
It coexists well.2, the nickelic positive electrode of non-aqueous electrolyte secondary battery of the invention has high charge-discharge characteristic and Gao Zhenshi
Density, the lithium ion secondary battery that assembles when using it as anode, the compacted density of positive plate is high and the good cycle of battery.
The lithium ion secondary battery of positive electrode material of the invention has been used as positive electrode, is suitable for hybrid vehicle, electronic vapour
Carrying power supply on automobile representated by vehicle, is also applied in the fields such as energy-storage battery.3, nonaqueous electrolyte two of the invention
The nickelic positive electrode of primary cell has high capacity and high-tap density, and can be properly applied to require have cyclicity
The automobile that energy is good and compacted density is high, which carries, uses large secondary battery, has biggish industrial application value.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of nickelic positive electrode obtained in embodiment 1；
Fig. 2 is the XRD characterization of nickelic positive electrode obtained in embodiment 1；
Fig. 3 is cyclic curve figure of nickelic positive electrode under the conditions of 0.5C obtained in embodiment 1.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The nickelic positive electrode of the non-aqueous electrolyte secondary battery of the present embodiment the preparation method is as follows:
(1) taking D50 is 12 μm of Ni0.80Co0.10Mn0.10(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.03, additive is the nano magnesia of 20nm, and magnesium elements additional amount accounts for
Than after mixing with ball mill being roasted 12 hours under 780 DEG C of oxygen air atmospheres, by the production after roasting for 0.005mol
Object crushed 200 mesh screens, dry after being washed with pure water, take a certain amount of sample, and additive is nano oxidized boron, boron member
Element additional amount accounting be 0.005mol, after mixing under oxygen atmosphere, 450 DEG C roasting 5 hours after be sieved, obtain 12 μm
Li1.03Ni0.80Co0.10Mn0.10Mg0.005B0.005O2Material；
(2) taking D50 is 3 μm of Ni0.80Co0.15Mn0.05(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.03, additive is the nano magnesia of 20nm, and magnesium elements additional amount accounts for
Than after mixing with ball mill being roasted 12 hours under 770 DEG C of oxygen air atmospheres, by the production after roasting for 0.005mol
Object crushed 200 mesh screens, dry after being washed with pure water, take a certain amount of sample, and additive is nano oxidized boron, boron member
Element additional amount accounting be 0.005mol, after mixing under oxygen atmosphere, 450 DEG C roasting 5 hours after be sieved, obtain 3 μm
Li1.03Ni0.80Co0.15Mn0.05Mg0.005B0.005O2Material；
(3) by the Li of preparation1.03Ni0.80Co0.10Mn0.10Mg0.005B0.005O2And Li1.03Ni0.80Co0.15Mn0.05Mg0.00 5B0.005O2According to weight ratio be 2:8 weighed, obtained after mixing in blending tank whole partial size be 10 μm it is nickelic just
Pole material, wherein small particle is 1.5 with large-sized cobalt concentration ratio (SC/LC).
The scanning electron microscope (SEM) photograph of the nickelic positive electrode of the present embodiment is as shown in Figure 1.The nickelic positive electrode that Fig. 2 is exists
0.5C/0.5C cycle performance.Under the conditions of 0.2C, the specific discharge capacity of resulting materials is 193mAh/g, electric discharge ratio with higher
Capacity, after circulation 100 is enclosed, circulation conservation rate is 92%, has preferable cycle performance.The tap density of material is 2.72g/
cm3, the compacted density of pole piece is 3.68g/cm3。
Embodiment 2
The nickelic positive electrode of the non-aqueous electrolyte secondary battery of the present embodiment the preparation method is as follows:
(1) taking D50 is 13 μm of Ni0.83Co0.08Mn0.09(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.04, additive is the nanometer tungsten oxide of 20nm, and wolfram element additional amount accounts for
Than after mixing with ball mill being roasted 12 hours under 770 DEG C of oxygen air atmospheres, by the production after roasting for 0.008mol
Object crushed 200 mesh screens, dry after being washed with pure water, take a certain amount of sample, and additive is nanometer tungsten oxide, tungsten member
Element additional amount accounting be 0.005mol, after mixing under oxygen atmosphere, 500 DEG C roasting 5 hours after be sieved, obtain 13 μm
Li1.04Ni0.83Co0.08Mn0.09W0.013O2Material；
(2) taking D50 is 4 μm of Ni0.83Co0.12Mn0.05(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.05, additive is the nanometer tungsten oxide of 20nm, and wolfram element additional amount accounts for
Than after mixing with ball mill being roasted 12 hours under 790 DEG C of oxygen air atmospheres, by the production after roasting for 0.008mol
Object crushed 200 mesh screens, dry after being washed with pure water, take a certain amount of sample, and additive is nanometer tungsten oxide, tungsten member
Element additional amount accounting be 0.005mol, after mixing under oxygen atmosphere, 500 DEG C roasting 5 hours after be sieved, obtain 3 μm
Li1.05Ni0.83Co0.12Mn0.05W0.013O2Material；
(3) by the Li of above-mentioned preparation1.04Ni0.83Co0.08Mn0.09W0.013O2And Li1.05Ni0.83Co0.12Mn0.05W0.013O2It presses
It is that 6:4 is weighed according to weight ratio, obtains the nickelic positive electrode that whole partial size is 10 μm after mixing in blending tank,
In, small particle and large-sized cobalt concentration ratio (SC/LC) they are 1.5.
Under the conditions of 0.2C, the specific discharge capacity of the nickelic positive electrode of gained is 200mAh/g, electric discharge specific volume with higher
Amount, after circulation 100 is enclosed, circulation conservation rate is 90%, has preferable cycle performance.The tap density of material is 2.70g/cm3,
The compacted density of pole piece is 3.70g/cm3。
Embodiment 3
The nickelic positive electrode of the non-aqueous electrolyte secondary battery of the present embodiment the preparation method is as follows:
(1) taking D50 is 14 μm of Ni0.65Co0.15Mn0.20(OH)2Presoma, lithium source use lithium carbonate, are with molar ratio
The mode of Li/ (Ni+Co+Mn)=1.05 is deployed, and additive is the nano zircite of 20nm, and Zr element additional amount accounting is
0.01mol after mixing with ball mill is roasted 12 hours under 860 DEG C of oxygen air atmospheres, and the product after roasting is crushed
200 mesh screens are crossed, 15 μm of Li is obtained1.05Ni0.65Co0.15Mn0.20Zr0.01O2Material；
(2) taking D50 is 4 μm of Ni0.65Co0.20Mn0.15(OH)2Presoma, lithium source use lithium carbonate, are Li/ with molar ratio
(Ni+Co+Mn)=1.05 mode is deployed, and additive is the nano zircite of 20nm, and Zr element additional amount accounting is
0.01mol after mixing with ball mill is roasted 12 hours under 840 DEG C of oxygen air atmospheres, and the product after roasting is crushed
200 mesh screens are crossed, 5 μm of Li is obtained1.05Ni0.65Co0.20Mn0.15Zr0.01O2Material；
(3) by Li1.05Ni0.65Co0.15Mn0.20Zr0.01O2And Li1.05Ni0.65Co0.20Mn0.15Zr0.01O2It is according to weight ratio
7:3 is weighed, and obtains the nickelic positive electrode that whole partial size is 12 μm after mixing in blending tank, wherein small particle
It is 1.33 with large-sized cobalt concentration ratio (SC/LC).
Under the conditions of 0.2C, the specific discharge capacity of the nickelic positive electrode of gained is 182mAh/g, electric discharge specific volume with higher
Amount, after circulation 100 is enclosed, circulation conservation rate is 94%, has preferable cycle performance, and the tap density of the material is 2.76g/
cm3, the compacted density of pole piece is 3.72g/cm3。
Embodiment 4
The nickelic positive electrode of the non-aqueous electrolyte secondary battery of the present embodiment the preparation method is as follows:
(1) taking D50 is 15 μm of Ni0.82Co0.10Mn0.08(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.03, additive is the nano magnesia of 20nm, and magnesium elements additional amount accounts for
Than after mixing with ball mill being roasted 12 hours under 780 DEG C of oxygen air atmospheres, by the production after roasting for 0.001mol
Object crushed 200 mesh screens, dry after being washed with pure water, take a certain amount of sample, and additive is nano oxidized boron, boron member
Element additional amount accounting be 0.01mol, after mixing under oxygen atmosphere, 450 DEG C roasting 5 hours after be sieved, obtain 12 μm
Li1.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2Material；
(2) taking D50 is 4 μm of Ni0.80Co0.15Mn0.05(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.03, additive is the nano oxidized strontium of 20nm, and strontium element additional amount accounts for
Than after mixing with ball mill being roasted 12 hours under 790 DEG C of oxygen air atmospheres, by the product after roasting for 0.01mol
It crushed 200 mesh screens, take a certain amount of sample, additive is nano oxidized boron, and the additional amount accounting of boron element is
0.01mol, after mixing under oxygen atmosphere, 450 DEG C roasting 5 hours after be sieved, obtain 4 μm of monocrystalline Li1.03Ni0.80
Co0.15Mn0.05Sr0.01B0.01O2Material；
(3) by above-mentioned two sample Li1.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2And Li1.03Ni0.80Co0.15Mn0.05
Sr0.01B0.01O2It is that 2:8 is weighed according to weight ratio, obtaining whole partial size after mixing in blending tank is 13.5 μm
Nickelic positive electrode, wherein small particle is 1.5 with large-sized cobalt concentration ratio (SC/LC).
Under the conditions of 0.2C, the specific discharge capacity of the nickelic positive electrode of gained is 193mAh/g, electric discharge specific volume with higher
Amount, after circulation 50 is enclosed, circulation conservation rate is 96%, has preferable cycle performance.The tap density of material is 2.84g/cm3,
The compacted density of pole piece is 3.73g/cm3。
Embodiment 5
By the sample i in embodiment 41.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2And Li1.03Ni0.80Co0.15Mn0.05
Sr0.01B0.01O2It is that 5:5 is weighed according to weight ratio, obtains the height that whole partial size is 11 μm after mixing in blending tank
Nickel positive electrode, wherein small particle is 1.5 with large-sized cobalt concentration ratio (SC/LC).
Under the conditions of 0.2C, the specific discharge capacity of the nickelic positive electrode of gained is 195mAh/g, electric discharge specific volume with higher
Amount, after circulation 70 is enclosed, circulation conservation rate is 94%, has preferable cycle performance.The tap density of material is 2.83g/cm3,
The compacted density of pole piece is 3.77g/cm3。
Embodiment 6
By the sample i in embodiment 41.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2And Li1.03Ni0.80Co0.15Mn0.05
Sr0.01B0.01O2It is that 8:2 is weighed according to weight ratio, obtaining whole partial size after mixing in blending tank is 9 μm nickelic
Positive electrode, wherein small particle is 1.5 with large-sized cobalt concentration ratio (SC/LC).
Under the conditions of 0.2C, the specific discharge capacity of the nickelic positive electrode of gained is 197mAh/g, electric discharge specific volume with higher
Amount, after circulation 50 is enclosed, circulation conservation rate is 95%, has preferable cycle performance.The tap density of material is 2.86g/cm3,
The compacted density of pole piece is 3.75g/cm3。
Embodiment 7
The nickelic positive electrode of the non-aqueous electrolyte secondary battery of the present embodiment the preparation method is as follows:
(1) taking D50 is 18 μm of Ni0.88Co0.05Mn0.07(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.07, additive is the nanometer tungsten oxide of 20nm, wolfram element additional amount
Accounting is 0.005mol, after mixing with ball mill, is roasted 12 hours under 770 DEG C of oxygen air atmospheres, after roasting
Product crushed 200 mesh screens, dry after being washed with pure water, take a certain amount of sample, additive is nano-titanium oxide, titanium
The accounting of the additional amount of element be 0.01mol, after mixing under oxygen atmosphere, 600 DEG C roasting 5 hours after be sieved, obtain
18 μm of Li1.07Ni0.88Co0.05Mn0.07W0.005Ti0.01O2Material；
(2) taking D50 is 4 μm of Ni0.85Co0.10Mn0.05(OH)2Presoma, lithium source use monohydrate lithium hydroxide, with mole
Than being deployed for the mode of Li/ (Ni+Co+Mn)=1.05, additive is the nano zircite of 20nm, and zr element additional amount accounts for
Than after mixing with ball mill being roasted 12 hours under 750 DEG C of oxygen air atmospheres, by the product after roasting for 0.01mol
It crushed 200 mesh screens, it is dry after being washed with pure water, a certain amount of sample is taken, additive is nano-titanium oxide, titanium elements
Additional amount accounting be 0.005mol, after mixing under oxygen atmosphere, 500 DEG C roasting 5 hours after be sieved, obtain 4 μm
Li1.05Ni0.85Co0.10Mn0.05Zr0.01Ti0.005O2Material；
(3) by Li1.05Ni0.85Co0.10Mn0.05Zr0.01Ti0.005O2And Li1.07Ni0.88Co0.05Mn0.07W0.005Ti0.01O2It presses
It is that 3:7 is weighed according to weight ratio, obtains the nickelic positive electrode that whole partial size is 14 μm after mixing in blending tank,
In, small particle and large-sized cobalt concentration ratio (SC/LC) they are 2.
Under the conditions of 0.2C, the specific discharge capacity of the nickelic positive electrode of gained is 208mAh/g, electric discharge specific volume with higher
Amount, after circulation 50 is enclosed, circulation conservation rate is 93%, has preferable cycle performance.The tap density of material is 2.89g/cm3,
The compacted density of pole piece is 3.80g/cm3。
Comparative example 1
Taking D50 is 14 μm of Ni0.82Co0.10Mn0.08(OH)2Presoma, lithium source uses monohydrate lithium hydroxide, with molar ratio
Mode for Li/ (Ni+Co+Mn)=1.03 is deployed, after mixing with ball mill, under 780 DEG C of oxygen air atmospheres
Roasting 12 hours, crushed 200 mesh screens for the product after roasting, dry after being washed with pure water, take a certain amount of sample,
Additive is nano oxidized boron, and the additional amount accounting of boron element is 0.01mol, after mixing under oxygen atmosphere, 450 DEG C of roastings
It is sieved after burning 5 hours, obtains 14 μm of Li1.03Ni0.82Co0.10Mn0.08B0.01O2Material, the tap density of material are 2.62g/
cm3, the compacted density of pole piece is 3.60g/cm3。
Comparative example 2
Taking D50 is 12 μm of Ni0.65Co0.15Mn0.20(OH)2Presoma, lithium source use lithium carbonate, are Li/ with molar ratio
(Ni+Co+Mn)=1.05 mode is deployed, and additive is the nano zircite of 20nm, and Zr element additional amount accounting is
0.01mol after mixing with ball mill is roasted 12 hours under 860 DEG C of oxygen air atmospheres, and the product after roasting is crushed
200 mesh screens are crossed, Li is obtained1.05Ni0.65Co0.15Mn0.20Zr0.01O2Material, the tap density of material are 2.58g/cm3, pole piece
Compacted density be 3.58g/cm3。
Comparative example 3
Taking D50 is 4 μm of Ni0.80Co0.15Mn0.05(OH)2Presoma, lithium source use monohydrate lithium hydroxide, are with molar ratio
The mode of Li/ (Ni+Co+Mn)=1.03 is deployed, and after mixing with ball mill, is roasted under 790 DEG C of oxygen air atmospheres
It burns 12 hours, the product after roasting be crushed into 200 mesh screens, after washing under oxygen atmosphere, add nano zirconium dioxide, zirconium
Element additional amount accounting be 0.02mol, 450 DEG C roasting 5 hours after be sieved, obtain 4 μm of Li1.03Ni0.80Co0.15Mn0.05Zr0.0 2O2Material, the tap density of material are 2.42g/cm3, the compacted density of pole piece is 3.25g/cm3。
It is above-mentioned that test result is as follows shown in table.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (8)
1. a kind of nickelic positive electrode of non-aqueous electrolyte secondary battery, it is characterised in that: the positive electrode general formula
LiwNi1-x-yCoxMnyMzO2It indicating, M is selected from least one of Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg and Sr element,
0.98≤w≤1.15,0≤x≤0.20,0≤y≤0.20,0≤z≤0.02, average grain diameter D50 are 8-15 μm, are by D50
It is constituted for 2-5 μm of small particle and the D50 big partial size for being 8-18 μm, in mass, the mixed proportion of small particle is 10%-
90%, in terms of metal molar ratio, the cobalt content of small particle is higher than large-sized cobalt content.
2. the nickelic positive electrode of non-aqueous electrolyte secondary battery according to claim 1, it is characterised in that: described small
Partial size Co content (metal molar ratio；SC) it is higher than large-sized Co content (metal molar ratio；LC), Co concentration ratio (SC/LC) exists
In the range of 1.2-2.
3. the non-aqueous electrolyte secondary battery according to claim 1 or 2 preparation method of nickelic positive electrode, feature
It is:
(1) choosing D50 respectively is the 2-5 μm of nickel cobalt manganese hydroxide/oxide different with 8-18 μm of cobalt content；
(2) addition lithium compound, additive are roasted in Xiang Shangshu nickel cobalt manganese hydroxide/oxide, then with certain ratio
Example is mixed, so that the cobalt content (metal molar ratio: SC) of the small particle is higher than the large-sized cobalt content, (metal rubs
That ratio: LC), to obtain the nickelic positive electrode that the D50 being made of stuff and other stuff is 8-15 μm.
4. the non-aqueous electrolyte secondary battery according to claim 3 preparation method of nickelic positive electrode, feature exist
In: the lithium compound in the step (2) is selected from battery-level lithium carbonate or battery-stage monohydrate lithium hydroxide, and lithium compound is averaged
Partial size D50 is 5-8 μm, and with molar ratio computing, lithium salts additive amount Li/ (Ni+Co+Mn) is between 1.03-1.15；The additive
The partial size of one of which in the compound containing Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg or Sr, additive is
Between 10-100 nm.
5. the non-aqueous electrolyte secondary battery according to claim 3 preparation method of nickelic positive electrode, feature exist
In: in the step (2), maturing temperature is 730-900 DEG C, calcining time 8-20h.
6. the non-aqueous electrolyte secondary battery according to claim 3 preparation method of nickelic positive electrode, feature exist
In: to the material after the step (2) roasting, carrying out washing reduces residual alkali, then is roasted after mixing with additive, after roasting
It is mixed according still further to certain ratio.
7. the non-aqueous electrolyte secondary battery according to claim 6 preparation method of nickelic positive electrode, feature exist
In: one of which of the additive in the compound containing Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg or Sr adds
Add the partial size of agent between 10-100 nm.
8. the non-aqueous electrolyte secondary battery according to claim 6 preparation method of nickelic positive electrode, feature exist
In: the sintering temperature is 400-700 DEG C, and sintering time is 3-10 h.
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