CN107275633A - A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress and preparation method thereof - Google Patents
A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress and preparation method thereof Download PDFInfo
- Publication number
- CN107275633A CN107275633A CN201710446261.XA CN201710446261A CN107275633A CN 107275633 A CN107275633 A CN 107275633A CN 201710446261 A CN201710446261 A CN 201710446261A CN 107275633 A CN107275633 A CN 107275633A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- fluoride
- gradient
- crystal lattice
- tertiary cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- 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
- H01M4/52—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
A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress and preparation method thereof.The invention belongs to field of lithium ion battery, and in particular to a kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress and preparation method thereof.The invention aims to solve at present due in lithium ion battery oxide anode material transition metal ratio change cause produce crystal lattice stress, so that the crystal lattice stress of lithium ion battery oxide anode material is higher, and then the problem of the cyclical stability and high rate performance of influence electrode material.Method：First, hybrid metal saline solution is prepared；2nd, the precipitating reagent aqueous solution is prepared；3rd, complexing agent is prepared water-soluble；4th, fluoride aqueous solution is prepared；5th, persursor material is prepared；6th, cooling down；Seven：Prepare gradient Fluorin doped tertiary cathode material.Ni and F changes of contents is in reverse graded in the gradient Fluorin doped tertiary cathode material of the present invention, reduces crystal lattice stress, improves cycle performance and high rate performance.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of gradient Fluorin doped ternary with low crystal lattice stress is just
Pole material and preparation method thereof.
Background technology
Since realizing commercialization from 1990s lithium ion battery, rapidly become it is most important, be most widely used
Secondary cell.By development for many years, lithium ion battery now has been widely used for all kinds of small-sized portable electronic products
In electric tool, and with attention rate lifting of the countries in the world to the energy in recent years, just gradually largely apply to new energy
Automobile market.Positive electrode is to manufacture one of critical material of lithium ion battery, because the specific capacity of general positive electrode is obvious
Less than negative material so that positive electrode performance directly affects the indices of final battery.So, for opening for positive electrode
Hair seems increasingly important.
Cobalt acid lithium (LiCoO2) it is the positive electrode used in first commercial li-ion battery of Sony companies, at present still
It is the mainstay material in lithium ion battery market now.But because cobalt toxicity is larger, price is higher, and the Li excessively deviate from+It can add
The acute structural instability caused by oxygen layer is repelled, causes cost and safety problem, therefore people always search for preferably
Alternative materials.Layered lithium manganate voltage is higher, and cost is relatively low, but is led in cyclic process due to occurring John-Teller effects
Cause capacity retention undesirable.And the big, reversible capacity that polarized under lithium iron phosphate high multiplying declines fast, depositing the problems such as poorly conductive
It also limit its application.
By contrast, cobalt nickel lithium manganate ternary material (LiNixCoyMnzO2) have and LiCoO2Similar single-phase stratiform knot
Structure.Based on the synergy between transition metal, ternary metal oxide material combines LiCoO2Good high rate performance,
LiNiO2High power capacity and due to Mn4+In the presence of and obtain structural stability.Within this material, Ni is main active matter
The capacity positive correlation of matter, its content and positive electrode；Therefore, develop nickelic ternary material and have become lithium ion battery ternary
The development trend of positive electrode.
But, nickelic ternary material is due to while nickel content height brings high power capacity, also resulting in nickelic material under de- lithium state
The structure and heat endurance of material are undesirable, in addition with the increase of nickel content, cause serious lithium nickel mixing phenomenon, result in material
The cycle performance of material is poor.Therefore, researcher have developed graded ternary material from inside to outside, this functionally gradient material (FGM) because
Change for composition gradient from inside to outside, be provided simultaneously with the advantage that material circulation performance is good and specific capacity is high.
But the nickelic gradient tertiary cathode material of different metal ratio causes material internal because lattice parameter is different
It there is crystal lattice stress so that easy efflorescence during material charge and discharge cycles, broken, and then have impact on the proof stress of electrode material
Intensity, reduces the cyclical stability and high rate performance of material, therefore finds a kind of easy method to improve nickelic gradient three
The proof stress ability of first material is significant.
The content of the invention
The invention aims to solve at present due to transition metal in the oxide anode material of lithium ion battery
Ratio, which changes, to be caused to produce crystal lattice stress, so that the crystal lattice stress of the oxide anode material of lithium ion battery is higher, and then
The problem of influenceing the cyclical stability and high rate performance of electrode material, and a kind of gradient Fluorin doped with low crystal lattice stress is provided
Tertiary cathode material and preparation method thereof.
A kind of chemical formula of gradient Fluorin doped tertiary cathode material with low crystal lattice stress of the present invention is
LiNixCoyMnzM1-x-y-zO2-nFn；Gradient reduces wherein Ni content x from inside to outside, and gradient increases F content n from inside to outside, and 0
＜ x≤1,0 ＜ y≤1,0 ＜ z≤1,0<X+y+z≤1,0<n≤0.15.
A kind of preparation method of gradient Fluorin doped tertiary cathode material with low crystal lattice stress of the present invention presses following step
It is rapid to carry out：
First, hybrid metal saline solution is prepared：1. it is configured to mix after mixing nickel salt, cobalt salt, manganese salt and M salt in molar ratio
Close aqueous metal salt A；The concentration of mixed metal salt is 0.01mol/L~20mol/L in the mixed metal salt water solution A；
Mol ratio is nickel element in the mixed metal salt water solution A：Cobalt element：Manganese element：M element=x1:y1:z1:(1-x1-y1-
z1)；Wherein 0≤x1≤ 1,0≤y1≤ 1,0≤z1≤ 1,0<x1+y1+z1≤1；2. by nickel salt, cobalt salt, manganese salt and M salt by mole
Than being configured to hybrid metal saline solution B after mixing；The concentration of mixed metal salt is in the hybrid metal saline solution B
0.01mol/L~20mol/L；Mol ratio is nickel element in the hybrid metal saline solution B：Cobalt element：Manganese element：M element
=x2:y2:z2:(1-x2-y2-z2)；Wherein 0≤x2≤ 1,0≤y2≤ 1,0≤z2≤ 1,0<x2+y2+z2≤1、x2:y2:z2:(1-
x2-y2-z2)≠x1:y1:z1:(1-x1-y1-z1) and x1With x2It is asynchronously 0, y1With y2It is asynchronously 0, z1With z2It is asynchronously 0；
2nd, the precipitating reagent aqueous solution is prepared：Precipitating reagent is mixed with water, be configured to precipitant concentration for 0.01mol/L~
The 20mol/L precipitating reagent aqueous solution；
3rd, complexing agent aqueous solution is prepared：1. complexing agent is mixed with water, is configured to complexing agent aqueous solution A；The complexing agent
The concentration of water solution A complexing agent is 0.01mol/L~20mol/L；2. complexing agent is mixed with water, is configured to complexing agent water-soluble
Liquid B；The concentration of the complexing agent aqueous solution B complexing agents is 0.01mol/L~10mol/L；
4th, fluoride aqueous solution is prepared：1. fluoride is mixed with water, is configured to fluoride aqueous solution A；The fluoride
The concentration of fluoride is 0.001mol/L~2mol/L in water solution A；2. fluoride is mixed with water, is configured to fluoride water-soluble
Liquid B；The concentration of fluoride is 0mol/L~2mol/L in the fluoride aqueous solution B；
5th, persursor material is prepared：1. step 3 complexing agent aqueous solution B is added to continuously stir in Liquid-phase reactor and made
For reaction bottom liquid, 2. then it is in reaction condition：Inert atmosphere, pH value are 4~14,10~85 DEG C of constant temperature and rotating speed 600r/min
It is under conditions of~1000r/min that mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride is water-soluble
Liquid A is continuously injected into and continuously stirred in Liquid-phase reactor respectively as one-level charging, by hybrid metal while injection one-level charging
Saline solution B and fluoride aqueous solution B is continuously injected into mixed metal salt water solution A respectively as two grades of chargings and fluoride is water-soluble
In liquid A, the additions of one-level charging and two grades of chargings continue whole preparation process, 3. when reaction is to being continuously stirred liquid phase reactor
When solid-liquid mass ratio is 1/40~1/5 in device, rotating speed is lowered by 600r/min~1000r/min, lower modulation is 200r/
0.5h~2h is reacted under min~300r/min, the rotating speed after downward, overflow pipe is 4. opened and starts overflow, spillway discharge is step
3. the inlet amount in time, makes to continuously stir the solution of amount return to step 3. start time of solution in Liquid-phase reactor
Amount, 5. 4. repeat step is 5h~30h to reaction total time, now stops the addition of one-level charging and two grades of chargings, and stop
Heating, completes the preparation of persursor material；
Step 5 1. described in complexing agent aqueous solution B volume be continuously stir Liquid-phase reactor volume 10%~
80%；
Step 5 2. described in the feed rate ratio of four kinds of materials of one-level charging be：The chemical formula of precursor material is
NixCoyMnzM1-x-y-z(OH)2-nFnWhen mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride water
Solution A feed rate ratio is 1:2:1:1；The chemical formula of precursor material is NixCoyMnzM1-x-y-z(CO3)1-0.5nFnWhen mix
Aqueous metal salt A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution A feed rates ratio are 1:1:1:1；
Step 5 2. described in hybrid metal saline solution B it is identical with the feed rate of mixed metal salt water solution A；It is described
One-level charging fluoride aqueous solution B is identical with fluoride aqueous solution A feed rate；
Step 5 2. described in complexing agent aqueous solution A, B complexing agent total mole number and mixed metal salt water solution A, B
The ratio of metal salt total mole number is 0.1~10.0：1；The molal quantity and mixed metal salt of precipitating reagent in the precipitating reagent aqueous solution
The ratio of metal salt total mole number is 0.1~4.0 in water solution A, B：1；Fluoride total mole number in described fluoride aqueous solution A, B
Ratio with metal salt total mole number in mixed metal salt water solution A, B is 0.001~2.0：1；
6th, cooling down：Stirring 1h~3h makes to continuously stir liquid under conditions of rotating speed is 500r/min~1000r/min
Phase reaction device is down to room temperature, obtains persursor material NixCoyMnzM1-x-y-z(OH)2-nFnOr NixCoyMnzM1-x-y-z(CO3)1- 0.5nFn；
7th, gradient Fluorin doped tertiary cathode material is prepared：The persursor material that first step 6 is obtained
NixCoyMnzM1-x-y-z(OH)2-nFnOr NixCoyMnzM1-x-y-z(CO3)1-0.5nFnVacuum drying, dry after under oxygen atmosphere in
Temperature is pre-burning 6h~10h under conditions of 700~800 DEG C, then by persursor material after pre-burning and lithium source according to mol ratio 1：
(1~1.25) it is well mixed, under pure oxygen or air atmosphere, 1h~45h is sintered at temperature is 500~1000 DEG C, after sieving,
Obtain the gradient Fluorin doped tertiary cathode material LiNi with low crystal lattice stressxCoyMnzM1-x-y-zO2-nFn。
Beneficial effects of the present invention：
1st, the present invention is by controlling lithium ion battery gradient Fluorin doped tertiary cathode material LiNixCoyMnzM1-x-y-zO2-nFn
Middle Ni and F changes of contents, the content n for making Ni content x and F are in reverse graded, within the specific limits, Ni constituent contents
Increase can reduce lattice parameter, and because the increase of F elements can increase lattice parameter, make up caused by the reduction of Ni contents
Lattice parameter reduces so that lattice parameter is consistent inside and outside the ternary functionally gradient material (FGM) of gradient Fluorin doped, and Lattice Matching effectively reduces system
The crystal lattice stress of the oxide anode material obtained, therefore internal stress is small.Positive electrode can so be lifted in discharge and recharge
Structural stability in journey, improves the cycle performance and high rate performance of positive electrode.
2nd, by the present invention in that using two-stage feeding manner, and the characteristics of stirred using coprecipitation, while realizing gold
Belong to the uniform gradient change of element and F elements, it is ensured that the controllable precise of materials chemistry composition.
3rd, the tertiary cathode material for the gradient F doping that prepared by the present invention, utilizes the fluxing agent characteristic of metal fluoride, reduction
Ternary gradient anode material solid phase sintering temperature, is more saved.
4th, preparation technology of the invention is simple, lower cost for material, suitable for industrialized production.
Brief description of the drawings
The persursor material Ni that Fig. 1 obtains for one step 6 of experiment0.481Co0.193Mn0.289Li0.075(OH)1.925F0.075's
SEM schemes；
Fig. 2 is the lattice structure contrast schematic diagram for testing the tertiary cathode material in one before and after gradient Fluorin doped；
The gradient Fluorin doped ternary oxide positive electrode with low crystal lattice stress that Fig. 3 is prepared for experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075SEM figure；
The gradient Fluorin doped ternary oxide positive electrode with low crystal lattice stress that Fig. 4 is prepared for experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075XRD；
The gradient Fluorin doped ternary oxide positive electrode with low crystal lattice stress that Fig. 5 is prepared for experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.0750.1C multiplying powers under first charge-discharge curve map；
The gradient Fluorin doped ternary oxide positive electrode with low crystal lattice stress that Fig. 6 is prepared for experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075High rate performance curve map；
The tertiary cathode material for the gradient Fluorin doped with low crystal lattice stress that Fig. 7 is prepared for experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075With control sample gradient tertiary cathode material LiNi0.481Co0.193Mn0.289O21C times
Contrast cycle performance curve map under rate；
The tertiary cathode material for the gradient Fluorin doped with low crystal lattice stress that Fig. 8 is prepared for experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.0751C multiplying powers under circulation 200 times after SEM figure；
Fig. 9 is control sample gradient tertiary cathode material LiNi0.481Co0.193Mn0.289O21C multiplying powers under circulation 200 times after
SEM figure.
Embodiment
Embodiment one：A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress of present embodiment
Chemical formula be LiNixCoyMnzM1-x-y-zO2-nFn；Gradient reduces wherein Ni content x from inside to outside, and F content n is from inside to outside
Gradient increases, 0 ＜ x≤1,0 ＜ y≤1,0 ＜ z≤1,0<X+y+z≤1,0<n≤0.15.
Embodiment two：Present embodiment from unlike embodiment one：The content x of Ni change
Gradient and F content n variable gradient meet 5≤Δx/Δn≤7；Wherein ΔxFor away from Ni content x at centre of sphere different distance
Difference, ΔnFor the difference of F content n at the position corresponding with Ni content x.Other steps and parameter and embodiment one
It is identical.
Embodiment three：Present embodiment from unlike embodiment one or two：The M be Li, Zr,
One kind in Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi or
Several mixtures.Other steps and parameter are identical with embodiment one or two.
Embodiment four：A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress of present embodiment
Preparation method carry out according to the following steps：
First, hybrid metal saline solution is prepared：1. it is configured to mix after mixing nickel salt, cobalt salt, manganese salt and M salt in molar ratio
Close aqueous metal salt A；The concentration of mixed metal salt is 0.01mol/L~20mol/L in the mixed metal salt water solution A；
Mol ratio is nickel element in the mixed metal salt water solution A：Cobalt element：Manganese element：M element=x1:y1:z1:(1-x1-y1-
z1)；Wherein 0≤x1≤ 1,0≤y1≤ 1,0≤z1≤ 1,0<x1+y1+z1≤1；2. by nickel salt, cobalt salt, manganese salt and M salt by mole
Than being configured to hybrid metal saline solution B after mixing；The concentration of mixed metal salt is in the hybrid metal saline solution B
0.01mol/L~20mol/L；Mol ratio is nickel element in the hybrid metal saline solution B：Cobalt element：Manganese element：M element
=x2:y2:z2:(1-x2-y2-z2)；Wherein 0≤x2≤ 1,0≤y2≤ 1,0≤z2≤ 1,0<x2+y2+z2≤1、x2:y2:z2:(1-
x2-y2-z2)≠x1:y1:z1:(1-x1-y1-z1) and x1With x2It is asynchronously 0, y1With y2It is asynchronously 0, z1With z2It is asynchronously 0；
2nd, the precipitating reagent aqueous solution is prepared：Precipitating reagent is mixed with water, be configured to precipitant concentration for 0.01mol/L~
The 20mol/L precipitating reagent aqueous solution；
3rd, complexing agent aqueous solution is prepared：1. complexing agent is mixed with water, is configured to complexing agent aqueous solution A；The complexing agent
The concentration of water solution A complexing agent is 0.01mol/L~20mol/L；2. complexing agent is mixed with water, is configured to complexing agent water-soluble
Liquid B；The concentration of the complexing agent aqueous solution B complexing agents is 0.01mol/L~10mol/L；
4th, fluoride aqueous solution is prepared：1. fluoride is mixed with water, is configured to fluoride aqueous solution A；The fluoride
The concentration of fluoride is 0.001mol/L~2mol/L in water solution A；2. fluoride is mixed with water, is configured to fluoride water-soluble
Liquid B；The concentration of fluoride is 0mol/L~2mol/L in the fluoride aqueous solution B；
5th, persursor material is prepared：1. step 3 complexing agent aqueous solution B is added to continuously stir in Liquid-phase reactor and made
For reaction bottom liquid, 2. then it is in reaction condition：Inert atmosphere, pH value are 4~14,10~85 DEG C of constant temperature and rotating speed 600r/min
It is under conditions of~1000r/min that mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride is water-soluble
Liquid A is continuously injected into and continuously stirred in Liquid-phase reactor respectively as one-level charging, by hybrid metal while injection one-level charging
Saline solution B and fluoride aqueous solution B is continuously injected into mixed metal salt water solution A respectively as two grades of chargings and fluoride is water-soluble
In liquid A, the additions of one-level charging and two grades of chargings continue whole preparation process, 3. when reaction is to being continuously stirred liquid phase reactor
When solid-liquid mass ratio is 1/40~1/5 in device, rotating speed is lowered by 600r/min~1000r/min, lower modulation is 200r/
0.5h~2h is reacted under min~300r/min, the rotating speed after downward, overflow pipe is 4. opened and starts overflow, spillway discharge is step
3. the inlet amount in time, makes to continuously stir the solution of amount return to step 3. start time of solution in Liquid-phase reactor
Amount, 5. 4. repeat step is 5h~30h to reaction total time, now stops the addition of one-level charging and two grades of chargings, and stop
Heating, completes the preparation of persursor material；
Step 5 1. described in complexing agent aqueous solution B volume be continuously stir Liquid-phase reactor volume 10%~
80%；
Step 5 2. described in the feed rate ratio of four kinds of materials of one-level charging be：The chemical formula of precursor material is
NixCoyMnzM1-x-y-z(OH)2-nFnWhen mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride water
Solution A feed rate ratio is 1:2:1:1；The chemical formula of precursor material is NixCoyMnzM1-x-y-z(CO3)1-0.5nFnWhen mix
Aqueous metal salt A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution A feed rates ratio are 1:1:1:1；
Step 5 2. described in hybrid metal saline solution B it is identical with the feed rate of mixed metal salt water solution A；It is described
One-level charging fluoride aqueous solution B is identical with fluoride aqueous solution A feed rate；
Step 5 2. described in complexing agent aqueous solution A, B complexing agent total mole number and mixed metal salt water solution A, B
The ratio of metal salt total mole number is 0.1~10.0：1；The molal quantity and mixed metal salt of precipitating reagent in the precipitating reagent aqueous solution
The ratio of metal salt total mole number is 0.1~4.0 in water solution A, B：1；Fluoride total mole number in described fluoride aqueous solution A, B
Ratio with metal salt total mole number in mixed metal salt water solution A, B is 0.001~2.0：1；
6th, cool：Stirring 1h~3h makes to continuously stir liquid under conditions of rotating speed is 500r/min~1000r/min
Phase reaction device is down to room temperature, obtains persursor material NixCoyMnzM1-x-y-z(OH)2-nFnOr NixCoyMnzM1-x-y-z(CO3)1- 0.5nFn；
7th, gradient Fluorin doped tertiary cathode material is prepared：The persursor material that first step 6 is obtained
NixCoyMnzM1-x-y-z(OH)2-nFnOr NixCoyMnzM1-x-y-z(CO3)1-0.5nFnVacuum drying, dry after under oxygen atmosphere in
Temperature is pre-burning 6h~10h under conditions of 700~800 DEG C, then by persursor material after pre-burning and lithium source according to mol ratio 1：
(1~1.25) it is well mixed, under pure oxygen or air atmosphere, 1h~45h is sintered at temperature is 500~1000 DEG C, after sieving,
Obtain the gradient Fluorin doped tertiary cathode material LiNi with low crystal lattice stressxCoyMnzM1-x-y-zO2-nFn。
Embodiment five：Present embodiment from unlike embodiment four：Nickel salt is described in step one
One kind or wherein several mixtures in nickel sulfate, nickel nitrate, nickel acetate and nickel chloride.Other steps and parameter and specific reality
Apply mode four identical.
Embodiment six：Unlike one of present embodiment and embodiment four or five：The cobalt salt is
One kind or wherein several mixtures in cobaltous sulfate, cobalt nitrate, cobalt acetate and cobalt chloride.Other steps and parameter and specific reality
Apply one of mode four or five identical.
Embodiment seven：Unlike one of present embodiment and embodiment four to six：The manganese salt is
One kind or wherein several mixtures in manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.Other steps and parameter and specific reality
Apply one of mode four to six identical.
Embodiment eight：Unlike one of present embodiment and embodiment four to seven：Institute in step one
It is soluble sulphate, soluble nitrate, soluble acetate, soluble chlorine salt dissolving, soluble citrate and can to state M salt
One kind of dissolubility alkoxide or wherein several mixtures；Wherein described M be Li, Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al,
One or more of mixtures in Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi.Other steps and ginseng
Number is identical with one of embodiment four to seven.
Embodiment nine：Unlike one of present embodiment and embodiment four to eight：In step 2 when
Persursor material is NixCoyMnzM1-x-y-z(OH)2-nFnIn Shi Suoshu precipitating reagents sodium hydroxide, potassium hydroxide and lithium hydroxide
A kind of or wherein several mixture.Other steps and parameter are identical with one of embodiment four to eight.
Embodiment ten：Unlike one of present embodiment and embodiment four to nine：In step 2 when
Persursor material is NixCoyMnzM1-x-y-z(CO3)1-0.5nFnShi Suoshu precipitating reagents are one in sodium carbonate, potassium carbonate and lithium carbonate
Plant or wherein several mixtures.Other steps and parameter are identical with one of embodiment four to nine.
Embodiment 11：Unlike one of present embodiment and embodiment four to ten：In step 3
The complexing agent is ammoniacal liquor, ammonium chloride, ammonium fluoride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, second two
One kind or wherein several mixtures in amine, acetic acid, sodium fluoride, tartaric acid, maleic acid, butanedioic acid, citric acid and malonic acid.
Other steps and parameter are identical with one of embodiment four to ten.
Embodiment 12：Present embodiment from unlike embodiment four to one of 11：Step 4
Described in fluoride be sodium fluoride, one kind of potassium fluoride and ammonium chloride or wherein several mixtures.Other steps and parameter with
Embodiment four to one of 11 is identical.
Embodiment 13：Present embodiment from unlike embodiment four to one of 12：Step 7
Described in lithium source be lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, lithium hydrogen phosphate and carbonic acid
One kind or wherein several mixtures in lithium.Wherein other steps and parameter and the phase of embodiment four to one of 12
Together.
The effect of the present invention is verified with following experiment
Experiment one, a kind of preparation method of gradient Fluorin doped tertiary cathode material with low crystal lattice stress of this experiment are pressed
Following steps are carried out：
First, hybrid metal saline solution is prepared：1. nickel sulfate, cobaltous sulfate, manganese sulfate and lithium sulfate are mixed in molar ratio
After be configured to mixed metal salt water solution A；The concentration of mixed metal salt is 2mol/L in the mixed metal salt water solution A；Institute
It is nickel element to state mol ratio in mixed metal salt water solution A：Cobalt element：Manganese element：Elemental lithium=2.7：0.9：5.4：1；2. will
Nickel sulfate, cobaltous sulfate, manganese sulfate and lithium sulfate are configured to hybrid metal saline solution B after mixing in molar ratio；The mixing gold
The concentration for belonging to mixed metal salt in saline solution B is 2mol/L；Mol ratio is nickel element in the hybrid metal saline solution B：
Cobalt element：Manganese element：Elemental lithium=3：3：3：1；
2nd, the precipitating reagent aqueous solution is prepared：Sodium hydroxide is mixed with water, naoh concentration is configured to and is precipitated for 2mol/L
The agent aqueous solution；
3rd, complexing agent aqueous solution is prepared：1. ammoniacal liquor is mixed with water, is configured to complexing agent aqueous solution A；The complexing agent water
The concentration of ammoniacal liquor is 2.8mol/L in solution A；2. ammoniacal liquor is mixed with water, is configured to complexing agent aqueous solution B；The complexing agent water
The concentration of ammoniacal liquor is 0.3mol/L in solution B；
4th, fluoride aqueous solution is prepared：1. ammonium fluoride is mixed with water, is configured to fluoride aqueous solution A；The fluoride
The concentration of ammonium fluoride is 0.01mol/L in water solution A；2. ammonium fluoride is mixed with water, is configured to fluoride aqueous solution B；It is described
The concentration of ammonium fluoride is 0.15mol/L in fluoride aqueous solution B；
5th, persursor material is prepared：1. step 3 complexing agent aqueous solution B is added to continuously stir in Liquid-phase reactor and made
For reaction bottom liquid, 2. then it is in reaction condition：Inert atmosphere, pH value are 10 ± 0.3,60 DEG C of constant temperature and rotating speed 900r/min
Under the conditions of mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution A is grading as one
Material is continuously injected into respectively to be continuously stirred in Liquid-phase reactor, by hybrid metal saline solution B and fluorine while injection one-level charging
Compound aqueous solution B is continuously injected into mixed metal salt water solution A and fluoride aqueous solution A respectively as two grades of chargings, and one is grading
The addition of material and two grades of chargings continues whole preparation process, 3. after reaction carries out 1h, rotating speed is lowered by 900r/min, lowered
Amplitude is 300r/min, and 2h is reacted under the rotating speed after downward, 4. opens overflow pipe and starts overflow, spillway discharge is the 2h of step 3.
Interior inlet amount, makes to continuously stir the amount of solution of amount return to step 3. start time of solution in Liquid-phase reactor, 5. repeats
4. step is 12h to reaction total time, now stops the addition of one-level charging and two grades of chargings, and stops heating, completes forerunner
The preparation of body material；
Step 5 1. described in complexing agent aqueous solution B volume be continuously stir Liquid-phase reactor volume 72%；Wherein
The volume of the complexing agent aqueous solution B is 720mL, continuously stirs Liquid-phase reactor volume for 1L；
Step 5 2. described in the feed rate ratio of four kinds of materials of one-level charging be：Mixed metal salt water solution A, precipitation
The agent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution A feed rates ratio are 1:2:1:1；
Step 5 2. described in hybrid metal saline solution B it is identical with the feed rate of mixed metal salt water solution A；It is described
One-level charging fluoride aqueous solution B is identical with fluoride aqueous solution A feed rate；
6th, cool：Stirring 3h, which makes to continuously stir Liquid-phase reactor, under conditions of rotating speed is 700r/min is down to room
Temperature, obtains persursor material Ni0.481Co0.193Mn0.289Li0.075(OH)1.925F0.075；
7th, gradient Fluorin doped tertiary cathode material is prepared：The persursor material that first step 6 is obtained
Ni0.481Co0.193Mn0.289Li0.075(OH)1.925F0.075Vacuum drying, in the bar that temperature is 750 DEG C under oxygen atmosphere after drying
Pre-burning 8h under part, then by persursor material Ni after pre-burning0.481Co0.193Mn0.289Li0.075(OH)1.925F0.075Pressed with lithium carbonate
Mol ratio is 1：1.05 are well mixed, under pure oxygen atmosphere, sinter 10h under conditions of temperature is 850 DEG C, after sieving, obtain
The powdered gradient Fluorin doped tertiary cathode material LiNi with low crystal lattice stress0.481Co0.193Mn0.289O1.925F0.075。
(1) the persursor material Ni obtained to one step 6 of experiment0.481Co0.193Mn0.289Li0.075(OH)1.925F0.075Enter
Row SEM is detected, obtains the persursor material Ni that the step 6 of experiment one as shown in Figure 1 is obtained0.481Co0.193Mn0.289Li0.075
(OH)1.925F0.075SEM figures, the average grain diameter of presoma is 7 μm~8 μm as can be seen from Figure 1, be a large amount of sheets once
The ball-type second particle of grain Close stack, even particle size.
(2) the persursor material Ni obtained to one step 6 of experiment0.481Co0.193Mn0.289Li0.075(OH)1.925F0.075Enter
Row spectroscopy detection, obtains spectrum parameters as shown in table 1, it can be seen that content is reduced Ni elements from inside to outside, and F elements are reverse
Change, content increase.
Table 1
(3) lattice structure contrast schematic diagram such as Fig. 2 institutes of the tertiary cathode material in experiment one before and after gradient Fluorin doped
Show；Wherein a is the ternary functionally gradient material (FGM) for not carrying out gradient F doping, and 1 is nickel content upper section, and lattice parameter is big；2 contain for nickel
Amount is compared with lower part, and lattice parameter is small；As can be seen from Figure 2 due to Ni particle radii within the specific limits, Ni constituent contents
Reduction can reduce lattice parameter, and the lattice and mismatch of ternary functionally gradient material (FGM) cause the crystal lattice stress of inside.B is with low
The gradient Fluorin doped ternary functionally gradient material (FGM) of crystal lattice stress, 3 are that nickel content is high and Oil repellent lower part, 4 for nickel content is low and fluorine contains
High part is measured, wherein Ni content x and F content n are in reverse graded, because the increase of F elements can increase lattice parameter,
Make up the lattice parameter caused by the reduction of Ni contents to reduce so that lattice parameter inside and outside the ternary functionally gradient material (FGM) of gradient Fluorin doped
Unanimously, Lattice Matching, effectively reduces the crystal lattice stress of obtained oxide anode material, therefore internal stress is small.So may be used
To lift structural stability of the positive electrode in charge and discharge process, the cycle performance and high rate performance of positive electrode are improved.
(4) the gradient Fluorin doped tertiary cathode material with low crystal lattice stress prepared to experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075SEM detections are carried out, having for the preparation of checking test one as shown in Figure 3 are obtained low
The gradient Fluorin doped tertiary cathode material LiNi of crystal lattice stress0.481Co0.193Mn0.289O1.925F0.075SEM figures, can be with from Fig. 3
It is 7-8 μm to find out positive electrode average grain diameter, is the ball-type second particle of the primary particle composition of graininess Close stack, particle
It is uniform in size.
(5) the gradient Fluorin doped tertiary cathode material with low crystal lattice stress prepared to experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075X-ray diffraction detection is carried out, having for the preparation of experiment one as shown in Figure 4 is obtained
The gradient Fluorin doped tertiary cathode material LiNi of low crystal lattice stress0.481Co0.193Mn0.289O1.925F0.075XRD；Wherein 1 is
Gradient Fluorin doped tertiary cathode material with low crystal lattice stress prepared by experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075, as can be seen from Figure 4 positive electrode there is the layer structure of standard, free from admixture phase
In the presence of showing the material of the present invention has good structure.
(6) the gradient Fluorin doped tertiary cathode material with low crystal lattice stress prepared to experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075Charge-discharge performance detected, obtain tool prepared by experiment one as shown in Figure 5
There is the gradient Fluorin doped tertiary cathode material LiNi of low crystal lattice stress0.481Co0.193Mn0.289O1.925F0.0750.1C multiplying powers under it is first
Secondary charging and discharging curve figure, first charge-discharge curve is typical ternary material charging and discharging curve, initial charge as can be seen from Figure 5
Capacity reaches 170mAh g-1, first efficiency be 85%, show this method synthesis material first capacity and coulombic efficiency all compared with
It is high.
(7) the gradient Fluorin doped tertiary cathode material with low crystal lattice stress prepared to experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075High rate performance detected that obtain prepared by experiment one as shown in Figure 6 has
The gradient Fluorin doped tertiary cathode material LiNi of low crystal lattice stress0.481Co0.193Mn0.289O1.925F0.075High rate performance curve
Figure, the present invention's possesses preferable high rate performance as can be seen from Figure 6.
(8) the gradient Fluorin doped tertiary cathode material with low crystal lattice stress prepared to experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075With control sample gradient tertiary cathode material LiNi0.481Co0.193Mn0.289O21C times
Cycle performance is detected under rate, obtains the gradient Fluorin doped with low crystal lattice stress prepared by experiment one as shown in Figure 7
Tertiary cathode material LiNi0.481Co0.193Mn0.289O1.925F0.075With control sample gradient tertiary cathode material
LiNi0.481Co0.193Mn0.289O21C multiplying powers under contrast cycle performance curve map；Wherein 1 is low for having for the preparation of experiment one
The gradient Fluorin doped tertiary cathode material LiNi of crystal lattice stress0.481Co0.193Mn0.289O1.925F0.075, 2 be control sample gradient ternary
Positive electrode LiNi0.481Co0.193Mn0.289O2；From figure 7 it can be seen that because crystal lattice stress is small, prepared by experiment one has low
The gradient Fluorin doped tertiary cathode material LiNi of crystal lattice stress0.481Co0.193Mn0.289O1.925F0.075Can holding structure stabilization, material
Expect that cycle performance is excellent, capability retention is 98.2% after circulating 100 times.By contrast, control sample gradient tertiary cathode material
LiNi0.481Co0.193Mn0.289O2Cycle performance is poor, and after circulating 100 times, capability retention is 91.6%.
(9) the gradient Fluorin doped gradient tertiary cathode material with low crystal lattice stress prepared to experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075With control sample gradient tertiary cathode material LiNi0.481Co0.193Mn0.289O2At 1C times
ESEM detection is carried out after being circulated 200 times under rate, the ladder with low crystal lattice stress prepared by experiment one as shown in Figure 8 is obtained
Spend Fluorin doped tertiary cathode material LiNi0.481Co0.193Mn0.289O1.925F0.075Under 1C multiplying powers circulate 200 times after SEM figure and
Control sample gradient tertiary cathode material LiNi as shown in Figure 90.481Co0.193Mn0.289O2After being circulated 200 times under 1C multiplying powers
SEM schemes.As can be seen that the gradient Fluorin doped tertiary cathode material with low crystal lattice stress prepared by experiment one
LiNi0.481Co0.193Mn0.289O1.925F0.075After circulation, because crystal lattice stress is small, primary particle reunite second particle according to
It is old complete, and control sample gradient tertiary cathode material LiNi0.481Co0.193Mn0.289O1.925F0.075Second particle hair after circulation
Raw damaged, primary particle bursts second particle because of stress variation.
Experiment two, a kind of preparation method of gradient Fluorin doped tertiary cathode material with low crystal lattice stress of this experiment are pressed
Following steps are carried out：
First, hybrid metal saline solution is prepared：1. nickel sulfate, cobaltous sulfate, manganese sulfate and lithium sulfate are mixed in molar ratio
After be configured to mixed metal salt water solution A；The concentration of mixed metal salt is 2mol/L in the mixed metal salt water solution A；Institute
It is nickel element to state mol ratio in mixed metal salt water solution A：Cobalt element：Manganese element：Elemental lithium=2.7：0.9：5.4：1；2. will
Nickel sulfate, cobaltous sulfate, manganese sulfate and lithium sulfate are configured to hybrid metal saline solution B after mixing in molar ratio；The mixing gold
The concentration for belonging to mixed metal salt in saline solution B is 2mol/L；Mol ratio is nickel element in the hybrid metal saline solution B：
Cobalt element：Manganese element：Elemental lithium=3：3：3：1；
2nd, the precipitating reagent aqueous solution is prepared：Sodium carbonate is mixed with water, concentration of sodium carbonate is configured to for 2mol/L precipitating reagent water
Solution；
3rd, complexing agent aqueous solution is prepared：1. ammoniacal liquor is mixed with water, is configured to complexing agent aqueous solution A；The complexing agent water
The concentration of ammoniacal liquor is 2.8mol/L in solution A；2. ammoniacal liquor is mixed with water, is configured to complexing agent aqueous solution B；The complexing agent water
The concentration of ammoniacal liquor is 0.3mol/L in solution B；
4th, fluoride aqueous solution is prepared：1. ammonium fluoride is mixed with water, is configured to fluoride aqueous solution A；The fluoride
The concentration of ammonium fluoride is 0.01mol/L in water solution A；2. ammonium fluoride is mixed with water, is configured to fluoride aqueous solution B；It is described
The concentration of ammonium fluoride is 0.15mol/L in fluoride aqueous solution B；
5th, persursor material is prepared：1. step 3 complexing agent aqueous solution B is added to continuously stir in Liquid-phase reactor and made
For reaction bottom liquid, 2. then it is in reaction condition：Inert atmosphere, pH value are 10 ± 0.3,60 DEG C of constant temperature and rotating speed 900r/min
Under the conditions of mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution A is grading as one
Material is continuously injected into respectively to be continuously stirred in Liquid-phase reactor, by hybrid metal saline solution B and fluorine while injection one-level charging
Compound aqueous solution B is continuously injected into mixed metal salt water solution A and fluoride aqueous solution A respectively as two grades of chargings, and one is grading
The addition of material and two grades of chargings continues whole preparation process, 3. after reaction carries out 1h, rotating speed is lowered by 900r/min, lowered
Amplitude is 300r/min, and 2h is reacted under the rotating speed after downward, 4. opens overflow pipe and starts overflow, spillway discharge is the 2h of step 3.
Interior inlet amount, makes to continuously stir the amount of solution of amount return to step 3. start time of solution in Liquid-phase reactor, 5. repeats
4. step is 12h to reaction total time, now stops the addition of one-level charging and two grades of chargings, and stops heating, completes forerunner
The preparation of body material；
Step 5 1. described in complexing agent aqueous solution B volume be continuously stir Liquid-phase reactor volume 72%；Wherein
The volume of the complexing agent aqueous solution B is 720mL, continuously stirs Liquid-phase reactor volume for 1L；
Step 5 2. described in the feed rate ratio of four kinds of materials of one-level charging be：Mixed metal salt water solution A, precipitation
The agent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution A feed rates ratio are 1:1:1:1；
Step 5 2. described in hybrid metal saline solution B it is identical with the feed rate of mixed metal salt water solution A；It is described
One-level charging fluoride aqueous solution B is identical with fluoride aqueous solution A feed rate；
6th, cool：Stirring 3h, which makes to continuously stir Liquid-phase reactor, under conditions of rotating speed is 700r/min is down to room
Temperature, obtains persursor material Ni0.481Co0.193Mn0.289Li0.075(CO3)0.9625F0.075；
7th, gradient Fluorin doped tertiary cathode material is prepared：The persursor material that first step 6 is obtained
Ni0.481Co0.193Mn0.289Li0.075(CO3)0.9625F0.075Vacuum drying, after drying under oxygen atmosphere in temperature be 750 DEG C
Under the conditions of pre-burning 8h, then by persursor material Ni after pre-burning0.481Co0.193Mn0.289Li0.075(CO3)0.9625F0.075With lithium carbonate
It is 1 in molar ratio：1 is well mixed, under pure oxygen atmosphere, sinters 10h under conditions of temperature is 850 DEG C, after sieving, obtains powder
Last shape has the gradient Fluorin doped tertiary cathode material LiNi of low crystal lattice stress0.481Co0.193Mn0.289O1.925F0.075。
Experiment three, the difference of this experiment and experiment one are：Precipitating reagent is sodium hydroxide and lithium hydroxide in step 2
The mol ratio of mixture, wherein sodium hydroxide and lithium hydroxide is 1：1.
Experiment four, the difference of this experiment and experiment one are：Step 3 complexing agent is the mixture of ammoniacal liquor and ammonium chloride,
Wherein the mol ratio of ammoniacal liquor and ammonium chloride is 1：1, M is the mixture of magnesium and aluminium, and respectively in the form of magnesium sulfate and aluminum sulfate
In the presence of wherein the mol ratio of magnesium sulfate and aluminum sulfate is 1：1.
Experiment five, the difference of this experiment and experiment one are：Fluoride is the mixing of sodium fluoride and ammonium fluoride in step 4
The mol ratio of thing, wherein sodium fluoride and ammonium fluoride is 1：1.
Experiment six, the difference of this experiment and experiment one are：1. step one plants in the mixed metal salt water solution A mole
Than for nickel element：Cobalt element：Manganese element：The mol ratio of Li elements is 7.2：0.9：0.9：1.
Experiment seven, the difference of this experiment and experiment one are：5. middle reaction total time is 16h to step 5.
Experiment eight, the difference of this experiment and experiment one are：The pH of step 5 2. middle reaction is set as 10.7 ± 0.3.
Experiment nine, the difference of this experiment and experiment one are：The concentration of ammoniacal liquor is in step 3 complexing agent water solution A
M is the mixture of calcium and magnesium in 0.6mol/L, step one, and is existed respectively in the form of calcium nitrate and magnesium sulfate, wherein nitric acid
The mol ratio of calcium and magnesium sulfate is 1：1.
Experiment ten, the difference of this experiment and experiment one are：Nickel salt described in step one is that nickel chloride, cobalt salt are chlorination
Cobalt, manganese salt are manganese chloride.
The difference for testing 11, this experiment and experiment one is：Persursor material and carbonic acid after pre-burning described in step 7
The mol ratio of lithium is 1:1.2.
Claims (10)
1. a kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress, it is characterised in that the ladder with low crystal lattice stress
The chemical formula for spending Fluorin doped tertiary cathode material is LiNixCoyMnzM1-x-y-zO2-nFn；Wherein Ni content x gradients from inside to outside
Reduce, gradient increases F content n from inside to outside, 0 ＜ x≤1,0 ＜ y≤1,0 ＜ z≤1,0<X+y+z≤1,0<n≤0.15.
2. a kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 1, its feature exists
In the content x of the Ni variable gradient and F content n variable gradient meet 5≤Δx/Δn≤7；Wherein ΔxFor away from the centre of sphere
Ni content x difference, Δ at different distancenFor the difference of F content n at the position corresponding with Ni content x.
3. a kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 1, its feature exists
In the M be Li, Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb,
One or more of mixtures in La and Bi.
4. a kind of preparation method of the gradient Fluorin doped tertiary cathode material with low crystal lattice stress, it is characterised in that one kind has
The preparation method of the gradient Fluorin doped tertiary cathode material of low crystal lattice stress is carried out according to the following steps：
First, hybrid metal saline solution is prepared：1. mixing gold is configured to after mixing nickel salt, cobalt salt, manganese salt and M salt in molar ratio
Belong to saline solution A；The concentration of mixed metal salt is 0.01mol/L~20mol/L in the mixed metal salt water solution A；It is described
Mol ratio is nickel element in mixed metal salt water solution A：Cobalt element：Manganese element：M element=x1:y1:z1:(1-x1-y1-z1)；Its
In 0≤x1≤ 1,0≤y1≤ 1,0≤z1≤ 1,0<x1+y1+z1≤1；2. nickel salt, cobalt salt, manganese salt and M salt are mixed in molar ratio
After be configured to hybrid metal saline solution B；The concentration of mixed metal salt is 0.01mol/L in the hybrid metal saline solution B
~20mol/L；Mol ratio is nickel element in the hybrid metal saline solution B：Cobalt element：Manganese element：M element=x2:y2:z2:
(1-x2-y2-z2)；Wherein 0≤x2≤ 1,0≤y2≤ 1,0≤z2≤ 1,0<x2+y2+z2≤1、x2:y2:z2:(1-x2-y2-z2)≠
x1:y1:z1:(1-x1-y1-z1) and x1With x2It is asynchronously 0, y1With y2It is asynchronously 0, z1With z2It is asynchronously 0；
2nd, the precipitating reagent aqueous solution is prepared：Precipitating reagent is mixed with water, precipitant concentration is configured to for 0.01mol/L~20mol/L
The precipitating reagent aqueous solution；
3rd, complexing agent aqueous solution is prepared：1. complexing agent is mixed with water, is configured to complexing agent aqueous solution A；The complexing agent is water-soluble
The concentration of liquid A complexing agents is 0.01mol/L~20mol/L；2. complexing agent is mixed with water, is configured to complexing agent aqueous solution B；
The concentration of the complexing agent aqueous solution B complexing agents is 0.01mol/L~10mol/L；
4th, fluoride aqueous solution is prepared：1. fluoride is mixed with water, is configured to fluoride aqueous solution A；The fluoride is water-soluble
The concentration of fluoride is 0.001mol/L~2mol/L in liquid A；2. fluoride is mixed with water, is configured to fluoride aqueous solution B；
The concentration of fluoride is 0mol/L~2mol/L in the fluoride aqueous solution B；
5th, persursor material is prepared：1. step 3 complexing agent aqueous solution B is added and continuously stirred in Liquid-phase reactor as anti-
Bottom liquid is answered, is 2. then in reaction condition：Inert atmosphere, pH value be 4~14,10~85 DEG C of constant temperature and rotating speed 600r/min~
By mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution under conditions of 1000r/min
A is continuously injected into and continuously stirred in Liquid-phase reactor respectively as one-level charging, by mixed metal salt while injection one-level charging
Aqueous solution B and fluoride aqueous solution B is continuously injected into mixed metal salt water solution A and fluoride aqueous solution respectively as two grades of chargings
In A, the additions of one-level charging and two grades of chargings continue whole preparation process, 3. when reaction is to being continuously stirred Liquid-phase reactor
When middle solid-liquid mass ratio is 1/40~1/5, rotating speed is lowered by 600r/min~1000r/min, lower modulation is 200r/min
0.5h~2h is reacted under~300r/min, the rotating speed after downward, overflow pipe is 4. opened and starts overflow, spillway discharge be step 3.
Inlet amount in time, makes to continuously stir the amount of solution of amount return to step 3. start time of solution in Liquid-phase reactor, 5.
4. repeat step is 5h~30h to reaction total time, now stops the addition of one-level charging and two grades of chargings, and stops heating,
Complete the preparation of persursor material；
Step 5 1. described in complexing agent aqueous solution B volume be continuously stir Liquid-phase reactor volume 10%~80%；
Step 5 2. described in the feed rate ratio of four kinds of materials of one-level charging be：The chemical formula of precursor material is
NixCoyMnzM1-x-y-z(OH)2-nFnWhen mixed metal salt water solution A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride water
Solution A feed rate ratio is 1:2:1:1；The chemical formula of precursor material is NixCoyMnzM1-x-y-z(CO3)1-0.5nFnWhen mix
Aqueous metal salt A, the precipitating reagent aqueous solution, complexing agent aqueous solution A and fluoride aqueous solution A feed rates ratio are 1:1:1:1；
Step 5 2. described in hybrid metal saline solution B it is identical with the feed rate of mixed metal salt water solution A；The one-level
Feed fluoride aqueous solution B identical with fluoride aqueous solution A feed rate；
Step 5 2. described in metal in complexing agent aqueous solution A, B complexing agent total mole number and mixed metal salt water solution A, B
The ratio of salt total mole number is 0.1~10.0：1；The molal quantity and mixed metal salt of precipitating reagent are water-soluble in the precipitating reagent aqueous solution
The ratio of metal salt total mole number is 0.1~4.0 in liquid A, B：1；Fluoride total mole number is with mixing in described fluoride aqueous solution A, B
The ratio for closing metal salt total mole number in aqueous metal salt A, B is 0.001~2.0：1；
6th, cool：Stirring 1h~3h makes to continuously stir liquid phase anti-under conditions of rotating speed is 500r/min~1000r/min
Answer device to be down to room temperature, obtain the persursor material Ni with low crystal lattice stressxCoyMnzM1-x-y-z(OH)2-nFnOr
NixCoyMnzM1-x-y-z(CO3)1-0.5nFn；
7th, gradient Fluorin doped tertiary cathode material is prepared：The persursor material Ni that first step 6 is obtainedxCoyMnzM1-x-y-z
(OH)2-nFnOr NixCoyMnzM1-x-y-z(CO3)1-0.5nFnVacuum drying, dry after under oxygen atmosphere in temperature be 700~800
Pre-burning 6h~10h under conditions of DEG C, then by persursor material after pre-burning and lithium source according to mol ratio 1：(1~1.25) mix equal
It is even, under pure oxygen or air atmosphere, 1h~45h is sintered at temperature is 500~1000 DEG C, after sieving, is obtained with low lattice
The ternary oxide positive electrode LiNi of stressxCoyMnzM1-x-y-zO2-nFn。
5. a kind of preparation side of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 4
Method, it is characterised in that nickel salt described in step one is one kind or wherein several in nickel sulfate, nickel nitrate, nickel acetate and nickel chloride
Mixture；The cobalt salt is one kind or wherein several mixtures in cobaltous sulfate, cobalt nitrate, cobalt acetate and cobalt chloride；Institute
It is one kind or wherein several mixtures in manganese sulfate, manganese nitrate, manganese acetate and manganese chloride to state manganese salt.
6. a kind of preparation side of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 4
Method, it is characterised in that M salt described in step one is soluble sulphate, soluble nitrate, soluble acetate, soluble chlorine
One kind or wherein several mixtures of salt dissolving, soluble citrate and soluble alkoxide；Wherein described M be Li, Zr, Fe,
One kind or several in Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi
The mixture planted.
7. a kind of preparation side of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 4
Method, it is characterised in that precursor material is Ni in step 2xCoyMnzM1-x-y-z(OH)2-nFnShi Suoshu precipitating reagents sodium hydroxide,
One kind or wherein several mixtures in potassium hydroxide and lithium hydroxide；Precursor material is NixCoyMnzM1-x-y-z
(CO3)1-0.5nFnShi Suoshu precipitating reagents are one kind or wherein several mixtures in sodium carbonate, potassium carbonate and lithium carbonate.
8. a kind of preparation side of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 4
Method, it is characterised in that complexing agent described in step 3 is ammoniacal liquor, ammonium chloride, ammonium fluoride, ammonium carbonate, ammonium nitrate, ammonium sulfate, acetic acid
One in ammonium, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, butanedioic acid, citric acid and malonic acid
Plant or wherein several mixtures.
9. a kind of preparation side of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 4
Method, it is characterised in that the fluoride described in step 4 is sodium fluoride, one kind of potassium fluoride and ammonium chloride or wherein several mixing
Thing.
10. a kind of preparation side of gradient Fluorin doped tertiary cathode material with low crystal lattice stress according to claim 4
Method, it is characterised in that lithium source described in step 7 is lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, phosphorus
One kind or wherein several mixtures in sour lithium, lithium hydrogen phosphate and lithium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710446261.XA CN107275633B (en) | 2017-06-13 | 2017-06-13 | Gradient fluorine-doped ternary cathode material with low lattice stress and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710446261.XA CN107275633B (en) | 2017-06-13 | 2017-06-13 | Gradient fluorine-doped ternary cathode material with low lattice stress and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107275633A true CN107275633A (en) | 2017-10-20 |
| CN107275633B CN107275633B (en) | 2020-01-14 |
Family
ID=60066763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710446261.XA Active CN107275633B (en) | 2017-06-13 | 2017-06-13 | Gradient fluorine-doped ternary cathode material with low lattice stress and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107275633B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108400314A (en) * | 2018-05-08 | 2018-08-14 | 北京科技大学 | The method of modifying of high temperature induction yttrium fluoride grade doping lithium-rich manganese-based anode material |
| CN109411718A (en) * | 2018-09-28 | 2019-03-01 | 佛山市德方纳米科技有限公司 | The preparation method of the tertiary cathode material of doping vario-property |
| CN109638279A (en) * | 2018-12-28 | 2019-04-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of nickelic ternary material and products thereof and application |
| CN109860509A (en) * | 2019-01-14 | 2019-06-07 | 中国电力科学研究院有限公司 | A kind of preparation method of the rich lithium manganese base solid solution positive electrode of anion codope |
| CN110112385A (en) * | 2019-04-24 | 2019-08-09 | 南昌大学 | A method of improving tertiary cathode material stability and high rate performance |
| CN111082030A (en) * | 2019-12-31 | 2020-04-28 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
| CN111106343A (en) * | 2019-12-30 | 2020-05-05 | 华南理工大学 | Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof |
| WO2021042987A1 (en) * | 2019-09-02 | 2021-03-11 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method therefor, positive electrode sheet, lithium ion secondary battery, and battery module, battery pack and device containing lithium ion secondary battery |
| CN113437286A (en) * | 2021-07-21 | 2021-09-24 | 天目湖先进储能技术研究院有限公司 | Ternary cathode material and preparation method thereof |
| CN114420920A (en) * | 2022-01-20 | 2022-04-29 | 北京理工大学重庆创新中心 | Fluorine ion gradient doped lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN114506877A (en) * | 2020-11-17 | 2022-05-17 | 松山湖材料实验室 | Method for preparing positive electrode active material, positive electrode, and lithium ion secondary battery |
| CN114914436A (en) * | 2022-02-10 | 2022-08-16 | 中国第一汽车股份有限公司 | High-nickel ternary cathode material and preparation method thereof |
| CN115924995A (en) * | 2022-12-29 | 2023-04-07 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Preparation method of multi-element anode material with gradient composite structure |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683667A (en) * | 2011-12-06 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Lithium-manganese-aluminum oxygen anode material and preparation method thereof |
| CN104241633A (en) * | 2014-09-11 | 2014-12-24 | 北大先行科技产业有限公司 | Gradient-doping positive material of lithium ion battery and preparation method of gradient-doping positive material of lithium ion battery |
| CN106299326A (en) * | 2016-09-26 | 2017-01-04 | 电子科技大学 | A kind of anode material for lithium-ion batteries of ultra high energy density and preparation method thereof |
-
2017
- 2017-06-13 CN CN201710446261.XA patent/CN107275633B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683667A (en) * | 2011-12-06 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Lithium-manganese-aluminum oxygen anode material and preparation method thereof |
| CN104241633A (en) * | 2014-09-11 | 2014-12-24 | 北大先行科技产业有限公司 | Gradient-doping positive material of lithium ion battery and preparation method of gradient-doping positive material of lithium ion battery |
| CN106299326A (en) * | 2016-09-26 | 2017-01-04 | 电子科技大学 | A kind of anode material for lithium-ion batteries of ultra high energy density and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIN-YUN LIAO 等: "Surface-modified concentration-gradient Ni-rich layered oxide cathodes for high-energy lithium-ion batteries", 《JOURNAL OF POWER SOURCES》 * |
| WEIHUA CHEN 等: "Controlled synthesis of concentration gradient LiNi0.84Co0.10Mn0.04Al0.02O1. 90F0.10 with improved electrochemical properties in Li-ion batteries", 《RSC ADV》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108400314A (en) * | 2018-05-08 | 2018-08-14 | 北京科技大学 | The method of modifying of high temperature induction yttrium fluoride grade doping lithium-rich manganese-based anode material |
| CN109411718A (en) * | 2018-09-28 | 2019-03-01 | 佛山市德方纳米科技有限公司 | The preparation method of the tertiary cathode material of doping vario-property |
| CN109638279A (en) * | 2018-12-28 | 2019-04-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of nickelic ternary material and products thereof and application |
| CN109860509B (en) * | 2019-01-14 | 2021-02-26 | 中国电力科学研究院有限公司 | Preparation method of anion co-doped lithium-rich manganese-based solid solution cathode material |
| CN109860509A (en) * | 2019-01-14 | 2019-06-07 | 中国电力科学研究院有限公司 | A kind of preparation method of the rich lithium manganese base solid solution positive electrode of anion codope |
| CN110112385A (en) * | 2019-04-24 | 2019-08-09 | 南昌大学 | A method of improving tertiary cathode material stability and high rate performance |
| WO2021042987A1 (en) * | 2019-09-02 | 2021-03-11 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method therefor, positive electrode sheet, lithium ion secondary battery, and battery module, battery pack and device containing lithium ion secondary battery |
| CN111106343A (en) * | 2019-12-30 | 2020-05-05 | 华南理工大学 | Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof |
| CN111082030A (en) * | 2019-12-31 | 2020-04-28 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
| CN111082030B (en) * | 2019-12-31 | 2023-08-08 | 河北科技大学 | Dual-modified nickel-rich ternary material and preparation method and application thereof |
| CN114506877A (en) * | 2020-11-17 | 2022-05-17 | 松山湖材料实验室 | Method for preparing positive electrode active material, positive electrode, and lithium ion secondary battery |
| CN114506877B (en) * | 2020-11-17 | 2023-12-15 | 松山湖材料实验室 | Preparation method of positive electrode active material, positive electrode and lithium ion secondary battery |
| CN113437286A (en) * | 2021-07-21 | 2021-09-24 | 天目湖先进储能技术研究院有限公司 | Ternary cathode material and preparation method thereof |
| CN114420920A (en) * | 2022-01-20 | 2022-04-29 | 北京理工大学重庆创新中心 | Fluorine ion gradient doped lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN114420920B (en) * | 2022-01-20 | 2023-11-07 | 北京理工大学重庆创新中心 | Fluorine ion gradient doped lithium-rich manganese-based positive electrode material, and preparation method and application thereof |
| CN114914436A (en) * | 2022-02-10 | 2022-08-16 | 中国第一汽车股份有限公司 | High-nickel ternary cathode material and preparation method thereof |
| CN115924995A (en) * | 2022-12-29 | 2023-04-07 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Preparation method of multi-element anode material with gradient composite structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107275633B (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107275633A (en) | A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress and preparation method thereof | |
| CN104934595B (en) | Prepare the nickel cobalt aluminium precursor material being distributed with aluminium element gradient and the method for positive electrode | |
| CN105552327B (en) | Lithium metal oxide composite positive pole with sandwich construction and form persursor material of the material and its preparation method and application | |
| CN106910882B (en) | A kind of preparation method of lithium ion battery large single crystal layered cathode material | |
| CN110518220B (en) | Nickel-cobalt-manganese-aluminum quaternary positive electrode material with high nickel gradient and preparation method thereof | |
| CN110002515A (en) | A kind of high capacity monocrystalline type tertiary cathode material preparation method | |
| CN105355907B (en) | Positive electrode and preparation method prepared by lithium metal oxide persursor material and the material with " annual ring " formula structure | |
| CN108502937A (en) | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application | |
| CN102694166B (en) | Preparation method of lithium-nickel-cobalt-aluminum composite metal oxide | |
| CN106505195A (en) | A kind of nickelic positive electrode and preparation method thereof and lithium ion battery | |
| CN108557905A (en) | A kind of lithium-rich manganese base material presoma and preparation method thereof, lithium-rich manganese-based anode material and preparation method thereof, lithium battery | |
| CN110034297A (en) | A kind of nickelic lithium ion anode material and preparation method thereof | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN103715418A (en) | Preparation method for spherical cobaltosic oxide | |
| CN107968202A (en) | A kind of positive electrode of nickel cobalt manganese core shell structure containing aluminium and preparation method thereof | |
| CN102208607A (en) | Synthesis and surface modification method of lithium excessive laminar oxide anode material | |
| CN109778301A (en) | The preparation of one type monocrystalline lithium-rich oxide material and application | |
| CN108878860B (en) | Nickel-based positive electrode material, precursor thereof, and preparation methods of nickel-based positive electrode material and precursor | |
| CN107123792A (en) | Two-layer composite tertiary cathode material and preparation method thereof | |
| CN110323432A (en) | A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof | |
| CN110085858A (en) | A kind of nickelic tertiary cathode material of niobium-phosphor codoping and its preparation method and application | |
| CN109537054A (en) | A kind of high-rate lithium-rich manganese-based anode material monocrystalline and preparation method thereof | |
| CN114361440A (en) | High-voltage ternary cathode material with core-shell structure and preparation method thereof | |
| CN114843469B (en) | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium ion battery positive electrode material and preparation method thereof | |
| CN109473672A (en) | A kind of lithium-rich manganese-based anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |