CN109585845A - NCM-NCMA positive electrode, preparation method and purposes - Google Patents
NCM-NCMA positive electrode, preparation method and purposes Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The present invention provides a kind of positive electrode material precursor, and the positive electrode material precursor is core-shell structure, and the materials chemistry formula of the core is Ni1‑x‑yCoxMnyCO3, the materials chemistry formula of the shell is Ni1‑r‑s‑ tCorAlsMnt(OH)2, 1-x-y is the numerical value in 0.80 to 0.96 range；X is greater than 0；Y is the numerical value in 0.01 to 0.10 range；1-r-s-t is the numerical value in 0.34 to 0.70 range；R is greater than 0；S is the numerical value in 0.20 to 0.40 range；T is the numerical value in 0.20 to 0.40 range.Cathode material structure of the invention is stablized, and security performance is high, and have extended cycle life, thermal stability it is good.
Description
Technical field
The present invention relates to electrode material fields, and in particular to a kind of NCM-NCMA positive electrode, preparation method and purposes.
Background technique
Lithium ion battery is as a kind of novel green energy resource, with specific energy is high, self discharge is small, open-circuit voltage is high, nothing
Memory effect, have extended cycle life, non-environmental-pollution the advantages that, therefore be widely used as mobile phone, laptop, digital camera etc.
The power supply of electronic product, meanwhile, lithium ion battery is also electric car power supply, and is the accumulation power supply of solar energy renewable energy.
Ion battery positive electrode known to us mainly has cobalt acid lithium, lithium nickelate, LiMn2O4, ternary material and LiFePO4
Deng, but due to cobalt resource scarcity, and be more toxic, cause cobalt acid lithium production cost high, and producing to environment can not
The influence of reverse；Lithium nickelate rich material resources all have advantage in terms of the performance of gram volume and specific energy, but it is recycled
Performance is poor, limits the application of its industrialization；LiMn2O4 is with resourceful, at low cost, pollution-free, safety is good, multiplying power
The advantages that performance is good, but its cycle performance and electrochemical stability are poor, and greatly limit its industrialization；LiFePO 4 material
Safety and cycle life have the advantages that significant, but material itself compacted density is too low, causes battery specific energy not high,
So limiting the space that vehicle is promoted in terms of course continuation mileage；The cost of ternary material is low, is equivalent to the 1/4 of cobalt acid lithium and more
Environmentally protective, other different materials that compare improve the energy density of battery, but its safety at present is not high enough.
Summary of the invention
We are bright to be designed to provide a kind of positive electrode that security performance is excellent；And provide the preparation of the positive electrode
The purposes of method and the positive electrode, to promote lithium ion battery further genralrlization application.
In order to solve the above technical problems, the invention discloses a kind of positive electrode material precursor material, before the positive electrode
Drive body is core-shell structure, and the materials chemistry formula of the core is Ni1-x-yCoxMnyCO3Or Ni1-x-yCoxMny(OH)2, the material of the shell
Material chemical formula is Ni1-r-s-tCorAlsMnt(OH)2, 1-x-y is the numerical value in 0.80 to 0.96 range；
X is greater than 0；
Y is the numerical value in 0.01 to 0.10 range；
1-r-s-t is the numerical value in 0.34 to 0.70 range；
R is greater than 0；
S is the numerical value in 0.20 to 0.40 range；
T is the numerical value in 0.20 to 0.40 range.
In order to solve the above technical problems, the present invention provides a kind of preparation method of positive electrode material precursor, including it is following
Step:
Step (a), presoma core Ni1-x-yCoxMnyCO3Or Ni1-x-yCoxMny(OH)2Preparation
In deionized water by the dissolution of the source Ni, the source Co and the source Mn, the first solution is obtained, by first solution, carbonate
Solution, ammonium hydroxide are mixed, and PH=9-12, and the isothermal reaction 3-12h at 60-90 DEG C are controlled, and are cooled to 25-30 DEG C, filtering
Obtain presoma core Ni1-x-yCoxMnyCO3Or Ni1-x-yCoxMny(OH)2；
Step (b), core-shell structure presoma preparation:
In deionized water by the dissolution of the source Ni, the source Co, the source Mn and the source Al, the second solution is obtained, with presoma core Ni1-x- yCoxMnyCO3Or Ni1-x-yCoxMny(OH)2, ammonium hydroxide and NaOH solution mixing, control PH=10-12, and the constant temperature at 60-65 DEG C
Reaction, filters and obtains the presoma with core-shell structure after washing.
Further, first solution includes nickel sulfate, nickel acetate, nickel chloride, nickel nitrate, manganese sulfate, manganese acetate, chlorine
Change manganese, manganese nitrate, aluminum sulfate, aluminium chloride, aluminum nitrate, cobaltous sulfate, cobalt acetate, cobalt chloride, cobalt nitrate more than one；Second is molten
Liquid include nickel sulfate, nickel acetate, nickel chloride, nickel nitrate, manganese sulfate, manganese acetate, manganese chloride, manganese nitrate, cobaltous sulfate, cobalt acetate,
Cobalt chloride, cobalt nitrate more than one.
Further, in presoma core Ni in step (b)1-x-yCoxMnyCO3Or Ni1-x-yCoxMny(OH)2。
In order to solve the above technical problems, the invention also discloses a kind of positive electrode, the positive electrode
Shown in chemical formula such as formula (I):
(Lia[Ni1-x-yCoxMny]O2)b·(Lia[Ni1-r-s-tCorAlsMnt]O2)1-b (I)
A is the numerical value in 1.01 to 1.07 ranges；
B is the numerical value in 0.70 to 0.95 range；
1-x-y is the numerical value in 0.80 to 0.96 range；
X is greater than 0；
Y is the numerical value in 0.01 to 0.10 range；
1-r-s-t is the numerical value in 0.34 to 0.70 range；
R is greater than 0；
S is the numerical value in 0.20 to 0.40 range；
T is the numerical value in 0.20 to 0.40 range.
Further, including include Lia[Ni1-x-yCoxMny]O2Core and include Lia[Ni1-r-s-tCorAlsMnt]O2's
Shell.
Further, the average-size of the core is between 8 microns and 12 microns.
Further, the average thickness of the shell is between 0.05 micron and 1.1 microns.
In order to solve the above technical problems, the present invention also provides the preparation methods of positive electrode, comprising the following steps:
Step (1), core-shell structure presoma preparation: in presoma core Ni1-x-yCoxMnyCO3Or Ni1-x-yCoxMny
(OH)2The middle source addition Ni, the source Co, the source Al, the source Mn, ammonium hydroxide and NaOH solution are simultaneously mixed, and control PH=10-12, and in 60-
Isothermal reaction at 65 DEG C filters and obtains the presoma with core-shell structure after washing；
Step (2), first sintering: by the step (1) there is the presoma of core-shell structure to be sintered, sintering is completed
Afterwards, then cooling annealing is carried out；
Step (3) is sintered for the second time: lithium source is added in the step (2) sintering gains, water-soluble sintering aid, is mixed
Grinding is closed to be sintered after grinding uniformly, after the completion of sintering, then carry out cooling annealing；
Step (4), third time are sintered: the step (3) sintering gains being sintered, target product anode material is obtained
Material
Further, Li:(Ni+Co+Al+Mn in the step (2)) molar ratio be (0.5~1): 1.
Further, Li:(Ni+Co+Al+Mn in the step (3)) molar ratio=(0.1~0.6): 1.
Further, the method also includes cleaning the product of the step (3), third time burning is carried out after cleaning
Knot.
Further, the cleaning way is to be rinsed with carbon dioxide gas stream.
Further, the cleaning way is to be cleaned with carbonated water.
Further, the sintering time of the third time sintering is 0.5-12 hours, and sintering temperature is 100-1000 DEG C.
Further, in the step (2), sintering time 6-20 hours, 200-1000 DEG C of sintering temperature.
Further, the water-soluble sintering aid is water soluble sulfate, soluble chloride salt dissolving.
Further, in the step (3), sintering time 8-24 hours, 500-1000 DEG C of sintering temperature.
Further, in the step (3), it is 0.01-2.5 DEG C/min that the cooling annealing, which is rate of temperature fall,；Or
Rate of temperature fall is 0.02-1 DEG C/min.
Further, sintering carries out in air or oxygen atmosphere in the step (3).
In order to solve the above technical problems, the present invention also provides a kind of lithium ion battery, including anode, cathode, electrolyte
And diaphragm, the anode include above-mentioned positive electrode or the positive electrode being prepared by the above method.
In order to solve the above technical problems, being prepared the present invention also provides a kind of above-mentioned positive electrode or by the above method
Obtained positive electrode is preparing lithium ion battery, electronic product energy storage, industrial electric power storage energy storage, electric car and electric bicycle
Application in power supply.
The present invention is by first preparing hud typed precursor, and in sintering, the shrinkage rates of core are greater than shell, leads to precursor
Shell rupture, obtains the nickelic ternary material of monocrystalline pattern.Shell ruptures when sintering, and lithium salts is easier in the core for penetrating into precursor
Portion, diffusion mass transfer resistance is smaller, and sintering temperature is lower, and crystal boundary is less when sintering, and dynamic performance is more preferable, thus the DCR of material
It is smaller.The addition of water-soluble sintering aid can further decrease sintering temperature, avoid high temperature sintering to the particle of high-nickel material
The influence of form and performance, meanwhile, annealing process eliminates the oxygen defect that material is formed because of local burning during the sintering process,
The material made has higher crystallinity, and material structure stability is more preferable.Therefore, the anode obtained by this preparation method
Material, structural stability is high, and have extended cycle life,
The present invention is by soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt wiring solution-forming, nickel salt, cobalt
Salt, aluminium salt and manganese salt can be evenly distributed in solution, using be uniformly distributed nickel salt, cobalt salt, aluminium salt and manganese salt solution system
Standby positive electrode material precursor.Since the sedimentation equilibrium constant Ksp of Ni, Co, Al, Mn are different, Ni, Co, Al, Mn will affect in solution
The middle sequence for forming precipitating, the present invention is by the way that reaction temperature, PH, solution concentration, mixing speed is optimized, to technique progress
The consistent of Ni, Co, Al, Mn precipitation sequence is realized in creative improvement, forms homogeneous precipitation, is prepared using this method
Positive electrode material precursor, nickel salt, cobalt salt, aluminium salt and manganese salt are evenly distributed in particle, using the positive electrode material precursor with
Lithium salts mixing, obtains positive electrode by being sintered three times, crystal structure is more uniform, and skeleton structure is stronger, is conducive to material
The performance of energy, the effective capacity and high rate performance for improving positive electrode.In addition, water-soluble sintering aid helps to reduce sintering
Temperature avoids high temperature sintering to the particle shape of high-nickel material and the influence of performance；Meanwhile annealing process eliminates material and is burning
Because the oxygen defect that local burning is formed, the material made have higher crystallinity, material structure stability during knot
More preferably.Therefore, cathode material structure of the invention is stablized, and security performance is excellent, and have extended cycle life, thermal stability it is good.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical scheme and beneficial effects, with reference to embodiments into one
Walk the present invention is described in detail.However, it should be understood that the embodiment of the present invention is not just for the sake of explaining the present invention
The limitation present invention, and the embodiment of the present invention is not limited to the embodiment provided in specification.
Below with reference to embodiment respectively to positive electrode material precursor of the invention and preparation method thereof, positive electrode and its system
Preparation Method is described in detail.
Firstly, illustrating positive electrode material precursor and preparation method thereof of the invention with embodiment.
Embodiment 1
A kind of positive electrode material precursor, the positive electrode material precursor
For core-shell structure, nucleocapsid molar ratio is 0.7:0.3
The materials chemistry formula of the core is Ni0.815Co0.15Mn0.035CO3, the materials chemistry formula of the shell is
Ni0.50Co0.20Al0.15Mn0.15(OH)2, preparation method is:
Step (a), presoma core Ni0.815Co0.15Mn0.035CO3Preparation
Calculate and weigh soluble nickel salt according to the molar ratio Ni:Co:Mn=0.815:0.15:0.035 of each element, can
Dissolubility cobalt salt, aluminum soluble salt and soluble manganese salt；They are added together and carries out being hybridly prepared into 1mol/L in deionized water
The first solution A；
First solution A, ammonium hydroxide, sodium carbonate liquor are mixed, PH=7, and the isothermal reaction 3h at 60 DEG C are controlled, it is cold
But to 30 DEG C, sediment is filtered, wash, is dried, obtain presoma core Ni0.815Co0.15Mn0.035CO3；
Step (b), core-shell structure presoma preparation: by the source Ni, the source Co, the source Al and the source Mn be dissolved in proportion from
In sub- water, the second solution is obtained, with presoma core Ni0.815Co0.15Mn0.035CO3, ammonium hydroxide and NaOH solution mixing, control system
For reaction temperature at 60 DEG C, control mixing speed is 750 revs/min, and the pH for adjusting mixed solution is 7.0, be co-precipitated anti-
After answering 3h, sediment is filtered, wash, is dried, the presoma with core-shell structure is obtained, nucleocapsid molar ratio is 0.7:
0.3。
Embodiment 2
A kind of positive electrode material precursor, the positive electrode material precursor are core-shell structure, and nucleocapsid molar ratio is 0.8:0.2
The materials chemistry formula of the core is Ni0.815Co0.14Mn0.045(OH)2, the materials chemistry formula of the shell is
Ni0.50Co0.20Al0.15Mn0.15(OH)2, preparation method is:
Step (a), presoma core Ni0.815Co0.14Mn0.045(OH)2Preparation
Calculate and weigh soluble nickel salt according to the molar ratio Ni:Co:Mn=0.815:0.14:0.045 of each element, can
Dissolubility cobalt salt, aluminum soluble salt and soluble manganese salt；They are added together and carries out being hybridly prepared into 1mol/L in deionized water
The first solution A；
First solution A, ammonium hydroxide, sodium carbonate liquor are mixed, PH=7, and the isothermal reaction 3h at 60 DEG C are controlled, it is cold
But to 30 DEG C, sediment is filtered, wash, is dried, obtain presoma core Ni0.815Co0.14Mn0.045(OH)2；
Step (b), core-shell structure presoma preparation: by the source Ni, the source Co, the source Al and the source Mn be dissolved in proportion from
In sub- water, the second solution is obtained, with presoma core Ni0.815Co0.14Mn0.045(OH)2, ammonium hydroxide and NaOH solution mixing, control volume
It is reaction temperature at 60 DEG C, control mixing speed is 750 revs/min, and the pH for adjusting mixed solution is 7.0, is co-precipitated
After reacting 3h, sediment is filtered, wash, is dried, obtain the presoma with core-shell structure, nucleocapsid molar ratio is 0.8:
0.2。
Embodiment 3
A kind of positive electrode material precursor, the positive electrode material precursor are core-shell structure, and nucleocapsid molar ratio is 0.9:0.1,
The materials chemistry formula of the core is Ni0.815Co0.16Mn0.025CO3, the materials chemistry formula of the shell is
Ni0.60Co0.20Al0.10Mn0.10(OH)2, preparation method is:
Step (a), presoma core Ni0.815Co0.16Mn0.025CO3Preparation
According to the molar ratio Ni:Co:Mn=0.815:0.16:0.025 of each element
Calculate and weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added together
The first solution A for being hybridly prepared into 1mol/L is carried out in deionized water；
First solution A, ammonium hydroxide, sodium carbonate liquor are mixed, PH=7, and the isothermal reaction 3h at 60 DEG C are controlled, it is cold
But to 30 DEG C, sediment is filtered, wash, is dried, obtain presoma core Ni0.815Co0.16Mn0.025CO3；
Step (b), core-shell structure presoma preparation: by the source Ni, the source Co, the source Al and the source Mn be dissolved in proportion from
In sub- water, the second solution is obtained, with presoma core Ni0.815Co0.16Mn0.025CO3, ammonium hydroxide and NaOH solution mixing, control system
For reaction temperature at 60 DEG C, control mixing speed is 750 revs/min, and the pH for adjusting mixed solution is 7.0, be co-precipitated anti-
After answering 3h, sediment is filtered, wash, is dried, the presoma with core-shell structure is obtained, nucleocapsid molar ratio is 0.9:
0.1。
Embodiment 4
A kind of positive electrode material precursor, the positive electrode material precursor are core-shell structure, and nucleocapsid molar ratio is 0.9:0.1
The materials chemistry formula of the core is Ni0.815Co0.17Mn0.015(OH)2, the materials chemistry formula of the shell is
Ni0.50Co0.20Al0.15Mn0.15(OH)2, preparation method is:
Step (a), presoma core Ni0.815Co0.17Mn0.015(OH)2Preparation
According to the molar ratio Ni:Co:Mn=0.815:0.17:0.015 of each element
Calculate and weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added together
The first solution A for being hybridly prepared into 1mol/L is carried out in deionized water；
First solution A, ammonium hydroxide, sodium carbonate liquor are mixed, PH=7, and the isothermal reaction 3h at 60 DEG C are controlled, it is cold
But to 30 DEG C, sediment is filtered, wash, is dried, obtain presoma core Ni0.815Co0.17Mn0.015(OH)2；
Step (b), core-shell structure presoma preparation: by the source Ni, the source Co, the source Al and the source Mn be dissolved in proportion from
In sub- water, the second solution is obtained, with presoma core Ni0.815Co0.17Mn0.015(OH)2, ammonium hydroxide and NaOH solution mixing, control volume
It is reaction temperature at 60 DEG C, control mixing speed is 750 revs/min, and the pH for adjusting mixed solution is 7.0, is co-precipitated
After reacting 3h, sediment is filtered, wash, is dried, obtain the presoma with core-shell structure, nucleocapsid molar ratio is 0.9:
0.1。
Embodiment 5
A kind of positive electrode material precursor, the positive electrode material precursor are core-shell structure, and nucleocapsid molar ratio is 0.9:0.1
The materials chemistry formula of the core is Ni0.90Co0.05Mn0.05CO3, the materials chemistry formula of the shell is
Ni0.60Co0.20Al0.10Mn0.10(OH)2, preparation method is:
Step (a), presoma core Ni0.90Co0.05Mn0.05CO3Preparation
According to the molar ratio Ni:Co:Mn=0.9:0.05:0.05 of each element
Calculate and weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added together
The first solution A for being hybridly prepared into 1mol/L is carried out in deionized water；
First solution A, ammonium hydroxide, sodium carbonate liquor are mixed, PH=7, and the isothermal reaction 3h at 60 DEG C are controlled, it is cold
But to 30 DEG C, sediment is filtered, wash, is dried, obtain presoma core Ni0.90Co0.05Mn 0.05CO3；
Step (b), core-shell structure presoma preparation: by the source Ni, the source Co, the source Al and the source Mn be dissolved in proportion from
In sub- water, the second solution is obtained, with presoma core Ni0.90Co0.05Mn0.05CO3, ammonium hydroxide and NaOH solution mixing, control system is anti-
Answer temperature at 60 DEG C, control mixing speed is 750 revs/min, and the pH for adjusting mixed solution is 7.0, carries out coprecipitation reaction
After 3h, sediment is filtered, wash, is dried, the presoma with core-shell structure is obtained, nucleocapsid molar ratio is 0.9:0.1.
Embodiment 6
A kind of positive electrode material precursor, the positive electrode material precursor are core-shell structure, and nucleocapsid molar ratio is 0.9:0.1
The materials chemistry formula of the core is Ni0.90Co0.04Mn0.06(OH)2, the materials chemistry formula of the shell is
Ni0.60Co0.20Al0.10Mn0.10(OH)2, preparation method is:
Step (a), presoma core Ni0.90Co0.04Mn0.06(OH)2Preparation
According to the molar ratio Ni:Co:Mn=0.9:0.04:0.06 of each element
Calculate and weigh soluble nickel salt, soluble cobalt, aluminum soluble salt and soluble manganese salt；They are added together
The first solution A for being hybridly prepared into 1mol/L is carried out in deionized water；
First solution A, ammonium hydroxide, sodium carbonate liquor are mixed, PH=7, and the isothermal reaction 3h at 60 DEG C are controlled, it is cold
But to 30 DEG C, sediment is filtered, wash, is dried, obtain presoma core Ni0.90Co0.04Mn0.06(OH)2；
Step (b), core-shell structure presoma preparation: by the source Ni, the source Co, the source Al and the source Mn be dissolved in proportion from
In sub- water, the second solution is obtained, with presoma core Ni0.90Co0.04Mn0.06(OH)2, ammonium hydroxide and NaOH solution mixing, control system
For reaction temperature at 60 DEG C, control mixing speed is 750 revs/min, and the pH for adjusting mixed solution is 7.0, be co-precipitated anti-
After answering 3h, sediment is filtered, wash, is dried, the presoma with core-shell structure is obtained, nucleocapsid molar ratio is 0.9:
0.1。
Embodiment 7
A kind of positive electrode:
(Li1.035(Ni0.815Co0.15Mn0.035)O2)0.70(Li1.02(Ni0.50Co0.20Al0.15Mn0.15)O2)0.3
Preparation method are as follows:
Step (1), the sintering of the positive electrode material precursor for the core-shell structure that embodiment 1 is prepared, are warming up to 500 DEG C instead
It answers 10 hours；
Step (2) after being dried to a hydronium(ion) lithia and losing the crystallization water completely, is sintered gained with the step (1)
Object and water-soluble sintering aid sodium sulphate mixed grinding, the dosage of a hydronium(ion) lithia be Li in a hydronium(ion) lithia with
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in positive electrode material precursor, before the additional amount of water-soluble sintering aid sodium sulphate is
It drives the mass ratio 10% of body to be sintered after grinding uniformly, is warming up to 715 DEG C and is sintered 16.5 hours, then carry out cooling again and move back
Fire processing；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 650 DEG C of sintering 3.5 hours, drop
To room temperature to get arrive target product.
Embodiment 8
A kind of positive electrode,
(Li1.035(Ni0.815Co0.14Mn0.045)O2)0.80(Li1.02(Ni0.50Co0.20Al0.15Mn0.15)O2)0.20
Preparation method are as follows:
Step (1), first sintering: the presoma sintering for the positive electrode core-shell structure that embodiment 2 is prepared rises
Temperature to 600 DEG C react 6.5 hours；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid NaCl mixed grinding, the dosage of a hydronium(ion) lithia is hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid chlorination
The additional amount of sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 775 DEG C of sintering 8 hours, then
Cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 615 DEG C of sintering 5 hours, is down to
Room temperature to get arrive target product.
Embodiment 9
A kind of positive electrode,
(Li1.035(Ni0.815Co0.16Mn0.025)O2)0.90(Li1.05(Ni0.60Co0.20Al0.10Mn0.10)O2)0.10
Preparation method are as follows:
Step (1), first sintering: the positive electrode material precursor sintering for the core-shell structure that embodiment 3 is prepared rises
Temperature to 500 DEG C react 10 hours；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) gains and water-soluble sintering aid Na are sintered2SO4Mixed grinding, the dosage of a hydronium(ion) lithia are hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid sulfuric acid
The additional amount of sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 715 DEG C of sintering 16.5 hours, so
Carry out cooling annealing again afterwards；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 650 DEG C of sintering 3.5 hours, drop
To room temperature；
Step (4), the 4th sintering: the step (3) sintering gains are rinsed with carbonated water, the substance liter after cleaning
Temperature to 350 DEG C be sintered 5 hours, be down to room temperature, obtain target product.
Embodiment 10
A kind of positive electrode,
(Li1.035(Ni0.815Co0.17Mn0.015)O2)0.90(Li1.02(Ni0.50Co0.20Al0.15Mn0.15)O2)0.1
Preparation method are as follows:
Step (1), first sintering: the positive electrode material precursor sintering for the core-shell structure that embodiment 4 is prepared rises
Temperature to 600 DEG C react 6.5 hours；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid NaCl mixed grinding, the dosage of a hydronium(ion) lithia is hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid chlorination
The additional amount of sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 775 DEG C of sintering 8 hours, then
Cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 615 DEG C of sintering 5 hours, is down to
Room temperature；
Step (4), the 4th sintering: the step (3) sintering gains are rinsed with carbon dioxide gas stream, after cleaning
Substance is warming up to 250 DEG C and is sintered 3 hours, is down to room temperature, obtains target product.
Embodiment 11
A kind of positive electrode,
(Li1.035(Ni0.90Co0.05Mn0.05)O2)0.90(Li1.05(Ni0.60Co0.20Al0.10Mn0.10)O2)0.10
Preparation method are as follows:
Step (1), first sintering: the positive electrode material precursor sintering for the core-shell structure that embodiment 5 is prepared rises
Temperature to 500 DEG C react 10 hours；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid sodium sulphate mixed grinding, the dosage of a hydronium(ion) lithia is a hydrated hydroxide
Changing (Ni+Co+Al+Mn) molar ratio in the Li and ternary anode material precursor in lithium is 1.035:1, water-soluble sintering aid sulphur
The additional amount of sour sodium is that the mass ratio 10% of presoma is sintered after grinding uniformly, is warming up to 715 DEG C and is sintered 16.5 hours,
Then cooling annealing is carried out again；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 650 DEG C of sintering 3.5 hours, drop
To room temperature, target product is obtained.
Embodiment 12
A kind of positive electrode,
(Li1.035(Ni0.90Co0.04Mn0.06)O2)0.90(Li1.05(Ni0.60Co0.20Al0.10Mn0.10)O2)0.10
Preparation method are as follows:
Step (1), first sintering: the positive electrode material precursor sintering for the core-shell structure that embodiment 6 is prepared rises
Temperature to 600 DEG C react 6.5 hours；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) it is sintered gains and water-soluble sintering aid NaCl mixed grinding, the dosage of a hydronium(ion) lithia is hydronium(ion) oxidation
(Ni+Co+Al+Mn) molar ratio is 1.035:1 in Li and ternary anode material precursor in lithium, water-soluble sintering aid NaCl
Additional amount be presoma mass ratio 10%, grinding uniformly after, be sintered, be warming up to 775 DEG C be sintered 8 hours, then again
Carry out cooling annealing；Room temperature is down to the rate of temperature fall of 0.3 DEG C/min；
Step (3), third time are sintered: the step (2) sintering being obtained product and is warming up to 615 DEG C of sintering 5 hours, is down to
Room temperature obtains target product.
Comparative example 1
A kind of tertiary cathode material, chemical formula are Li1.035Ni0.815Co0.15Al0.035O2, preparation method are as follows:
Step (1), first sintering: by ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
500 DEG C are reacted 10 hours；Ternary anode material precursor Ni1-x-yCoxAly(OH)2+yIt can be obtained with commercial sources；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, the dosage of a hydronium(ion) lithia are that Li rubs with (Ni+Co+Al) in ternary anode material precursor
Your ratio is 1.035, after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 715 DEG C and reacts 16.5 hours；
Step (3), third time are sintered: the step (2) sintering gains being warming up to 650 DEG C and are sintered 3.5 hours, are down to
Room temperature to get arrive contrast material Li1.035Ni0.815Co0.15Mn0.035O2。
Comparative example 2
A kind of tertiary cathode material, chemical formula are Li1.035Ni0.815Co0.15Al0.035O2, preparation method are as follows:
Step (1), first sintering: by ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering, is warming up to
600 DEG C are reacted 6.5 hours；
Step (2) is sintered for second: a hydronium(ion) lithia being dried to after losing the crystallization water completely, with the step
(1) sintering gains mixing, the dosage of a hydronium(ion) lithia are that Li rubs with (Ni+Co+Al) in ternary anode material precursor
Your ratio is 1.035, after mixed grinding is uniform, is sintered in oxygen atmosphere, is warming up to 775 DEG C and reacts 8 hours；
Step (3), third time are sintered: the step (2) sintering gains being warming up to 615 DEG C and are sintered 5 hours, room is down to
Temperature to get arrive contrast material Li1.035Ni0.815Co0.15Mn0.035O2。
Table 1: embodiment 7~12, to reaction condition and product.
The assembling of CR2032 model button cell:
The tertiary cathode material of the positive electrode, the preparation of comparative example 1~2 that are prepared with embodiment 6~12 is the activity of anode
Object, cathode use metal lithium sheet, and diaphragm uses 2500 diaphragm of Celgard, and electrolyte is Suzhou Fo Sai new material Co., Ltd
Fosai LB-002 electrolyte assembles CR2032 model button cell, assembling sequence by art methods are as follows: positive cover is flat
It puts, places spring leaf, place stainless steel substrates, place positive plate, infuse electrolyte, place diaphragm, place lithium piece, cover cathode
Cap, sealing, is completed.Battery is assembled in the dry glove box full of argon gas.After being completed, to battery progressive
It can test, test result is shown in Table 2.
1, cycle performance
Test equipment title: new prestige battery testing system, model: BTS-5V10mA
Test equipment producer: new Weir Electronics Co., Ltd., Shenzhen；
Test method: at 25 DEG C, with 1C constant-current charge to 4.3V, 4.3V constant pressure to 0.05C, then 1C is discharged to 3V,
100 above-mentioned charge and discharge cycles are repeated, electric discharge when measuring the discharge capacity and the 100th circulation when recycling for the first time is held
Amount, the capacity retention ratio after calculating circulation 100 times, formula are as follows: capacity retention ratio=(putting when the 100th circulation after circulation
Capacitance)/(discharge capacity when recycling for the first time) * 100%.
2, high-temperature storage performance: at 25 DEG C, with 0.5C (=1225mA) constant-current charge to 4.3V, 4.3V constant pressure is extremely
0.05C (=123mA), then 0.5C (=1225mA) is discharged to 3V, records its first time discharge capacity；Then, at 25 DEG C,
With 0.5C (=1225mA) constant-current charge to 4.3V, 4.3V constant pressure to 0.05C (=123mA), the cell thickness before measurement storage；
Then, by the above-mentioned battery completely filled, after being stored 100 days in 60 DEG C of baking ovens, while hot test storage after cell thickness, by with
The comparison of cell thickness before storing, finds out the expansion rate of battery after storage；And will by storage battery core by 0.5C (=
1225mA) constant-current charge is to 4.3V, and 4.3V constant pressure to 0.05C (=123mA), then 0.5C (=1225mA) is discharged to 3V, into
Row five times circulations, record its last discharge capacity, the capacity retention ratio compared with first time discharge capacity, after being stored；
Wherein, after storage battery expansion rate=(thickness of battery before thickness-storage of battery after storage)/(store before battery thickness
Degree) × 100%；Capacity retention ratio=(discharge capacity after storage in 100 days)/(electric discharge appearance when recycling for the first time after storage
Amount) × 100%；
3, security performance is tested: at 25 DEG C, with 0.5C (=1225mA) constant-current charge to 4.3V, 4.3V constant pressure is extremely
0.05C (=123mA)；Battery is dismantled in the glove box of argon gas protection, is cleaned in DMC solution after taking out positive plate；To
After DMC volatilizees completely, lower electrode material is scraped from positive plate surface, the electrode material for weighing 10mg is put into special aluminium crucible,
And it is sealed after the electrolyte of 0.1uL is added；DSC test scanning temperature range be 50~500 DEG C, heating rate be 10 DEG C/
min。
4, surface residual alkali weight testing method: acid-base titration.
(1) it prepares the positive electrode stillness of night: W is weighed with the precision of 0.0001g1The positive material of (30.0000 ± 0.0040g)
Material weighs W with the precision of 0.01g2(100 ± 0.1g) deionized water mixes positive electrode with deionized water, and argon gas displacement is mixed
The air in liquid is closed, is stirred, filtering obtains filtrate, pipettes 50mL filtrate, is put into 100mL beaker, prepares titration；
(2) LiOH content is measured: using phenolphthalein as indicator, with the titration of 0.05mol/L hydrochloric acid standard solution, when titration end-point
Consumed hydrochloric acid standard liquid volume V1；
(3) Li is measured2CO3Content: CO in the clear liquid after argon gas displacement step (2) titration2, then with methyl red indicator,
With the titration of 0.05mol/L hydrochloric acid standard solution, when titration end-point consumed hydrochloric acid standard liquid volume V2；
LiOH content (wt%) calculation formula: ω1=(2V1-V2)*0.05*2.395*W2/W1/50；
Li2CO3Content (wt%) calculation formula: ω2=(V2-V1)*0.05*7.389*W2/W1/50；
2.395: the quality with the comparable LiOH indicated with g of hydrochloric acid standard liquid (1.000mol/L)；
7.389: with the comparable Li indicated with g of hydrochloric acid standard liquid (2.000mol/L)2CO3Quality；
Positive electrode surface residual alkali amount=ω1+ω2。
The performance test results of table 2, embodiment 6~10 and comparative example 1~2.
As can be seen from Table 2:
(1) positive electrode of the invention, the charge-discharge performance at 3.0V~4.3V have obtained significant raising: real
The cycle performance of example 7~12 and comparative example 1~2 is applied it can be found that after 100 circulations, the capacity of positive electrode of the present invention
Conservation rate is higher than tertiary cathode material；For this explanation compared with tertiary cathode material, positive electrode of the present invention has more stable follow
Ring performance.
(2) positive electrode of the present invention, the security performance at 4.3V are significantly improved: 7~12 He of comparative example
Comparative example 1~2 is as can be seen that the lithium ion battery for preparing of positive electrode of the present invention thermal discharge of DSC after charging to 4.3V is low
In tertiary cathode material, the temperature at most strongly exothermic peak is also above tertiary cathode material；This illustrates that positive electrode has stable crystalline substance
Body structure, thermal stability is good, and security performance is excellent, to improve the security performance of battery.
(3) it is compared with embodiment 7,8,11,12 unwashed positive electrodes, the use of embodiment 9~10 carbon dioxide gas stream,
Then the positive electrode of carbonated water cleaning is sintered obtains target product, and surface residual alkali amount is effectively reduced, and helps to reduce in anode
In material configuration process, attack of the alkaline matter on positive electrode surface to binder in positive glue avoids binder from being formed
Double bond improves Painting effect, helps to improve battery core performance.
Those skilled in the art can carry out various modification and variations without departing from spirit and model of the invention to invention
It encloses.In this way, if these modifications and changes of the present invention is within the scope of the claims of the present invention and its equivalent technology, then
The invention is also intended to include including these modification and variations.
Claims (21)
1. a kind of positive electrode material precursor, which is characterized in that the positive electrode material precursor is core-shell structure, the material of the core
Chemical formula is Ni1-x-yCoxMnyCO3Or Ni1-x-yCoxMny(OH)2, the materials chemistry formula of the shell is Ni1-r-s-tCorAlsMnt
(OH)2,
1-x-y is the numerical value in 0.80 to 0.96 range；
X is greater than 0；
Y is the numerical value in 0.01 to 0.10 range；
1-r-s-t is the numerical value in 0.34 to 0.70 range；
R is greater than 0；
S is the numerical value in 0.20 to 0.40 range；
T is the numerical value in 0.20 to 0.40 range.
2. a kind of preparation method of positive electrode material precursor, which comprises the following steps:
Step (a), presoma core Ni1-x-yCoxMnyCO3Preparation
By the source Ni, the source Co and the source Mn dissolution in deionized water, obtain the first solution, by first solution, carbonate solution,
Ammonium hydroxide is mixed, and is controlled PH=9-12, and the isothermal reaction 3-12h at 60-90 DEG C, is cooled to 25-30 DEG C, filters to obtain forerunner
Body core Ni1-x-yCoxMnyCO3；
Step (b), core-shell structure presoma preparation:
In deionized water by the dissolution of the source Ni, the source Co, the source Mn and the source Al, the second solution is obtained, with presoma core Ni1-x- yCoxMnyCO3, ammonium hydroxide and NaOH solution mixing, control PH=10-12, and the isothermal reaction at 60-65 DEG C, after filtering and washing
Obtain the presoma with core-shell structure.
3. method according to claim 2, wherein first solution includes nickel sulfate, nickel acetate, nickel chloride, nitric acid
Nickel, manganese sulfate, manganese acetate, manganese chloride, manganese nitrate, aluminum sulfate, aluminium chloride, aluminum nitrate, cobaltous sulfate, cobalt acetate, cobalt chloride, nitric acid
Cobalt more than one；Second solution includes nickel sulfate, nickel acetate, nickel chloride, nickel nitrate, manganese sulfate, manganese acetate, manganese chloride, nitre
Sour manganese, cobaltous sulfate, cobalt acetate, cobalt chloride, cobalt nitrate more than one.
4. according to the method described in claim 2, it is characterized by: in presoma core Ni in step (b)1-x-yCoxMnyCO3In also
The source M is added, the M is selected from least one of Ti, Ba, Sr, Mg, Cr, Zn, V, Cu.
5. a kind of positive electrode, which is characterized in that shown in the chemical formula of the positive electrode such as formula (I):
(Lia[Ni1-x-yCoxMny]O2)b·(Lia[Ni1-r-s-tCorAlsMnt]O2)1-b (I)
A is the numerical value in 1.01 to 1.07 ranges；
B is the numerical value in 0.70 to 0.95 range；
1-x-y is the numerical value in 0.80 to 0.96 range；
X is greater than 0；
Y is the numerical value in 0.01 to 0.10 range；
1-r-s-t is the numerical value in 0.34 to 0.70 range；
R is greater than 0；
S is the numerical value in 0.20 to 0.40 range；
T is the numerical value in 0.20 to 0.40 range.
6. positive electrode according to claim 5, which is characterized in that the positive electrode is core-shell structure, the core
Chemical formula is Lia[Ni1-x-yCoxMny]O2, the chemical formula of the shell is Lia[Ni1-r-s-tCorAlsMnt]O2。
7. positive electrode according to claim 6, which is characterized in that the average-size of the core is in 8 microns and 12 microns
Between.
8. positive electrode according to claim 6, which is characterized in that the average thickness of the shell is at 0.05 micron and 1.1
Between micron.
9. a kind of preparation method of the described in any item positive electrodes of claim 5 to 8, which comprises the following steps:
Step (1), core-shell structure presoma preparation: in presoma core Ni1-x-yCoxMnyCO3Or the middle source addition Ni, the source Co,
The source Al, the source Mn, ammonium hydroxide and NaOH solution are simultaneously mixed, and control PH=10-12, and the isothermal reaction at 60-65 DEG C, filtering is simultaneously
The presoma with core-shell structure is obtained after washing；
Step (2), first sintering: by the step (1) there is the presoma of core-shell structure to be sintered, after the completion of sintering,
Cooling annealing is carried out again；
Step (3) is sintered for second: the step (2) sintering gains addition lithium source, water-soluble sintering aid, mixing are ground
Mill is sintered after grinding uniformly, after the completion of sintering, then carries out cooling annealing；.
Step (4), third time are sintered: the step (3) sintering gains being sintered, target product positive electrode is obtained.
10. the preparation method of positive electrode as claimed in claim 9, which is characterized in that Li:(Ni+Co+ in the step (2)
Al+Mn molar ratio) is (1~1.01): 1.
11. the preparation method of positive electrode as claimed in claim 9, which is characterized in that the method also includes by the step
Suddenly the product of (3) is cleaned, and third time sintering is carried out after cleaning.
12. the preparation method of positive electrode as claimed in claim 12, which is characterized in that the cleaning way is to use titanium dioxide
Carbon gas washout.
13. the preparation method of positive electrode as claimed in claim 12, which is characterized in that the cleaning way is to use carbonated water
Cleaning.
14. the preparation method of positive electrode as claimed in claim 12, which is characterized in that when the sintering of the third time sintering
Between be 0.5-12 hours, sintering temperature is 100-1000 DEG C.
15. the preparation method of positive electrode as claimed in claim 9, which is characterized in that in the step (2), sintering time
6-20 hours, 200-1000 DEG C of sintering temperature.
16. the preparation method of positive electrode as claimed in claim 9, which is characterized in that the water solubility sintering aid is water
Insoluble sulfates, soluble chloride salt dissolving.
17. the preparation method of positive electrode as claimed in claim 9, which is characterized in that in the step (3), sintering time
8-24 hours, 500-1000 DEG C of sintering temperature.
18. the preparation method of positive electrode as claimed in claim 9, which is characterized in that in the step (3), the cooling
Annealing is that rate of temperature fall is 0.01-2.5 DEG C/min；Or rate of temperature fall is 0.02-1 DEG C/min.
19. the preparation method of positive electrode as claimed in claim 9, which is characterized in that sintering is in air in the step (3)
Or it is carried out in oxygen atmosphere.
20. a kind of lithium ion battery, including anode, cathode, electrolyte and diaphragm, which is characterized in that the anode includes right
It is required that 5 to 8 described in any item positive electrodes or being prepared just by method described in claim 9 to 20 any one
Pole material.
21. described in any item positive electrodes of a kind of claim 5 to 8 or by described in claim 9 to 20 any one
The positive electrode that method is prepared is preparing lithium ion battery, electronic product energy storage, industrial electric power storage energy storage, electric car and electricity
Application in dynamic bicycle electric power.
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| CN112164784A (en) * | 2020-08-27 | 2021-01-01 | 荆门市格林美新材料有限公司 | Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof |
| CN112164784B (en) * | 2020-08-27 | 2022-04-08 | 荆门市格林美新材料有限公司 | Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof |
| CN112599781A (en) * | 2020-12-15 | 2021-04-02 | 荆门市格林美新材料有限公司 | Double-concentration gradient doped lithium ion battery anode material and preparation method thereof |
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