CN109360983A - A kind of nickelic tertiary cathode material of modification and its preparation method and application - Google Patents
A kind of nickelic tertiary cathode material of modification and its preparation method and application Download PDFInfo
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- CN109360983A CN109360983A CN201811267165.XA CN201811267165A CN109360983A CN 109360983 A CN109360983 A CN 109360983A CN 201811267165 A CN201811267165 A CN 201811267165A CN 109360983 A CN109360983 A CN 109360983A
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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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- 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
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- 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
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Abstract
The present invention provides a kind of nickelic tertiary cathode material of modification and its preparation method and application.The nickelic tertiary cathode material of the modification the preparation method comprises the following steps: prepare nickelic ternary interphase solution, obtain acid solution for acid solid is soluble in water；After mixing by above two solution, it after hydro-thermal or solvent thermal reaction, is calcined, cooling obtains being modified nickelic tertiary cathode material after being ground up, sieved.The preparation process of the nickelic tertiary cathode material of modification of the invention is simple, low in cost, and this method can effectively remove the residual alkali on nickelic tertiary cathode material surface, and the nickelic tertiary cathode material of the modification being prepared has excellent cyclical stability；It can be widely applied in the tertiary cathode material of nickel-based battery.
Description
Technical field
The present invention relates to electrochemical technology field, in particular to a kind of nickelic tertiary cathode material of modification and preparation method thereof
And application.
Background technique
With the fast development in power lithium-ion battery market, the positive electrode of battery is increasingly becoming the weight of study on the industrialization
Point, wherein 811 material of ternary nickel cobalt manganese of nickelic component becomes by the feature of high specific discharge capacity (200mAh/g), low cost
The hot spot of next step industrialization.However nickelic ternary material is easy water suction in closing slurry and coating process and causes slurry g., jelly-like,
Make poor processability, and the performance for influencing electrode material plays, and nickel content is higher, material surface residual alkali amount is bigger, influences
Its industrialization.
Currently, mainly starting in terms of four for the excessive processing means of nickelic ternary material surface residual alkali amount: (1) one
As the pH and production environment of presoma are controlled from source, control the temperature, atmosphere and environment temperature of the entire production line, it is stringent to control
Contact of the prepared material with air；(2) mixing lithium sintering stage reduces lithium salts ratio, adjusts sintering schedule, lithium can be diffused rapidly to
Crystals；(3) material is washed, then double sintering reduces surface residual alkali content, but can lose accordingly a part of electrical
Can, this is common method in current business；(4) surface coating modification is also the effective of reduction ternary material surface residual alkali content
Method, nickelic NCM are typically necessary surface cladding.
However, existing in currently available technology for the excessive processing means of nickelic ternary material surface residual alkali amount with loss
Capacity reaches drop residual alkali purpose defect, it would therefore be highly desirable to provide a kind of nickelic tertiary cathode material of modification to improve electrode material
The performance of energy.
Summary of the invention
Based on defect existing in the prior art, the purpose of the present invention is to provide a kind of nickelic tertiary cathode materials of modification
Preparation method, this method can be effectively reduced nickelic tertiary cathode material surface residual alkali amount, and significantly improve its stable circulation
Property；The object of the invention is also to provide the nickelic tertiary cathode materials of modification that the preparation method is prepared；Mesh of the invention
Also reside in application of the nickelic tertiary cathode material of the modification in anode material of lithium battery be provided.
The purpose of the present invention is achieved by the following technical programs:
On the one hand, the present invention provides a kind of preparation method for being modified nickelic tertiary cathode material, and this method includes following step
It is rapid:
Step 1 is configured to solution A for lithium source is soluble in water, by nickel source, manganese source and cobalt source or nickel source, silicon source and cobalt
Source, which is dissolved in deionized water, is configured to solution B；Solution A and B are mixed and reacted；In reaction process, adjusting pH value in reaction is
Alkalescent stirs to get nickelic ternary interphase solution C after reaction；
Step 2 obtains solution D for acid solid is soluble in water；Solution D is added in solution C and is stirred, then
Hydro-thermal reaction or solvent thermal reaction are carried out, is calcined after reaction, cooling obtains being modified nickelic ternary after being ground up, sieved
Positive electrode.
In above-mentioned preparation method, it is preferable that the lithium source may include lithium hydroxide, lithium carbonate, lithium nitrate, acetic acid
The combination of one or more of lithium, lithium chloride, lithium fluoride, lithium phosphate, lithium hydrogen phosphate and lithium dihydrogen phosphate etc..
In above-mentioned preparation method, it is preferable that the nickel source may include one in nickel sulfate, nickel acetate and nickel nitrate etc.
Kind or a variety of combinations.
In above-mentioned preparation method, it is preferable that the manganese source may include one in manganese sulfate, manganese acetate and manganese nitrate etc.
Kind or a variety of combinations.
Above-mentioned preparation method, it is preferable that source of aluminium may include aluminium oxide, aluminium hydroxide, aluminium salt and meta-aluminate
Deng one of or a variety of combinations.
In above-mentioned preparation method, it is preferable that the cobalt source may include one in cobaltous sulfate, cobalt acetate, cobalt nitrate etc.
Kind or a variety of combinations.
In above-mentioned preparation method, it is preferable that in step 1, the pH value is 7-9；It is further preferred that the pH
Value is adjusted by ammonium hydroxide.
In above-mentioned preparation method, it is preferable that in step 1, the time reacted is 2-4h；Reaction temperature is 50-
85℃；Mixing time after reaction is 30-60min.
In above-mentioned preparation method, it is preferable that adjusting pH value by ammonium hydroxide is alkalescent；It is further preferred that the pH
Value is 7-9.
In above-mentioned preparation method, it is preferable that in step 2, the time of the stirring is 30-60min；Whipping temp
It is 50-85 DEG C.
In above-mentioned preparation method, it is preferable that the hydro-thermal reaction or the reaction temperature of the solvent thermal reaction are
150-200 DEG C, reaction time 12-24h.
In above-mentioned preparation method, it is preferable that further include that centrifuge washing is dry or be evaporated to solidifying before calcining after reaction
The dry step of glue.
In above-mentioned preparation method, it is preferable that solution after reaction stirred under conditions of 60-80 DEG C be evaporated to it is solidifying
It is gluey.
In above-mentioned preparation method, it is preferable that the number of solution centrifugation after reaction is 1-6 times.
In above-mentioned preparation method, it is preferable that the drying is vacuum drying, and vacuum drying temperature is 60-100 DEG C,
Drying time is 6-12h.
In above-mentioned preparation method, it is preferable that the solvent that the solvent thermal reaction uses may include ethyl alcohol, isopropanol,
One of n-butanol, ethylene glycol and acetone etc. or a variety of combinations.
In above-mentioned preparation method, it is preferable that the acid solid is potassium permanganate.Acid solid of the invention takes height
Potassium manganate, potassium permanganate oxidation ability is strong, is not easy to deliquesce, and thermal stability is good, and will not introduce as other acidic materials miscellaneous
Matter ion, wherein Mn element can also play the role of stable tertiary cathode material lattice structure.
In above-mentioned preparation method, it is preferable that the molar ratio of the lithium source, the nickel salt, the cobalt salt and the manganese salt
For 1:x:y:(1-x-y), wherein 1,0 y≤0.2 < 0.8≤x <, and 1-x-y ≠ 0；Alternatively, the lithium source, the nickel salt, institute
The molar ratio for stating cobalt salt and the aluminium salt is 1:x:y:(1-x-y), wherein 1,0 y≤0.2 < 0.8≤x <, and 1-x-y ≠ 0.
In above-mentioned preparation method, it is preferable that the concentration range of acid solid is 0.1mol/L-1mol/ in the solution D
L。
In above-mentioned preparation method, it is preferable that the volumetric usage of the solution D and solution C ratio is 1:5.
In above-mentioned preparation method, it is preferable that in step 2, calcine technology are as follows:
By the mixture obtained after drying under air or oxygen atmosphere, it is heated to the heating rate of 3-5 DEG C/min
400-900 DEG C, keep the temperature 3-16h.
On the other hand, the present invention also provides the nickelic tertiary cathode materials of modification that above-mentioned preparation method is prepared.
In another aspect, the present invention also provides the nickelic tertiary cathode material of above-mentioned modification answering in anode material of lithium battery
With.
Beneficial effects of the present invention:
The preparation method simple process of the nickelic tertiary cathode material of modification of the invention, low in cost, this method can have
Effect removes the residual alkali on nickelic tertiary cathode material surface, and the nickelic tertiary cathode material of the modification being prepared has excellent circulation
Stability.
Detailed description of the invention
Fig. 1 is modification LiNi prepared by the embodiment of the present invention 10.8Co0.1Mn0.1O2Positive electrode and other several positive materials
Expect the cycle performance contrast curve chart under 1C multiplying power.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
This implementation provides a kind of modified LiNi0.8Co0.1Mn0.1O2The preparation method of tertiary cathode material comprising following step
It is rapid:
10.7121g lithium acetate is dissolved in the lithium acetate solution that 1mol/L is configured in 100ml deionized water by step 1, point
Not by 19.9072g nickel acetate, 2.4509g manganese acetate, 2.4908g cobalt acetate, which is dissolved in deionized water, is configured to 1mol/L solution,
Two kinds of solution are slowly added into beaker using constant flow pump, adjust pH between 7-8 with ammonium hydroxide in reaction process, reaction terminates
Magnetic agitation 60min afterwards；
Step 2, the potassium permanganate solid for weighing 1.5803g, which is dissolved in deionized water, is settled to 100ml, is configured to
The liquor potassic permanganate of 0.1mol/L；25 DEG C of stirring 1h form uniform, stable liquor potassic permanganate；
The liquor potassic permanganate of the 0.1mol/L of 20ml is added to the mixed reaction solution of step 1 by step 3, is kept
Solution temperature is 55 DEG C, is put into reaction kettle 150 DEG C of progress hydro-thermal reactions for 24 hours after stirring 1h, after reaction, eccentric cleaning 5
Time, it places into vacuum oven and mixture is obtained with the dry 12h of 80 DEG C of temperature；By mixture under oxygen atmosphere, with 5 DEG C/
Min heating rate is heated to 800 DEG C, keeps the temperature 6h at this temperature, is ground up, sieved after being down to room temperature to get modification is arrived
LiNi0.8Co0.1Mn0.1O2Tertiary cathode material.
Comparative example 1
This comparative example provides a kind of commercially available LiNi of modification0.8Co0.1Mn0.1O2The preparation method of positive electrode, including it is following
Step:
Step 1, the potassium permanganate solid for weighing 1.5803g, which is dissolved in deionized water, is settled to 100ml, is configured to
The liquor potassic permanganate of 0.1mol/L；25 DEG C of stirring 1h form uniform, stable liquor potassic permanganate；
Step 2, that weigh 9.728g is commercially available LiNi0.8Co0.1Mn0.1O2Positive electrode is dissolved in 100ml deionized water
Form the nickelic tertiary cathode material solution of 1mol/L；
The liquor potassic permanganate of the 0.1mol/L of 20ml is added in the solution of step 2 by step 3, keeps solution temperature
Degree is 55 DEG C, is put into reaction kettle 150 DEG C of progress hydro-thermal reactions for 24 hours after stirring 1h, after reaction, eccentric cleaning 5 times, then put
Enter in vacuum oven and mixture is obtained with the dry 12h of 80 DEG C of temperature；By mixture under oxygen atmosphere, with 5 DEG C/min heating
Rate is heated to 800 DEG C, keeps the temperature 6h at this temperature, is ground up, sieved after being down to room temperature to get the commercially available of modification is arrived
LiNi0.8Co0.1Mn0.1O2Positive electrode.
Table 1 is modification LiNi prepared by embodiment 10.8Co0.1Mn0.1O2Tertiary cathode material, modification prepared by comparative example 1
Commercially available LiNi0.8Co0.1Mn0.1O2Tertiary cathode material and unmodified commercially available LiNi0.8Co0.1Mn0.1O2Tertiary cathode material
The pH value contrast table of test.
As can be seen from Table 1, the modification LiNi being prepared by embodiment 10.8Co0.1Mn0.1O2Tertiary cathode material pH
Value is reduced to 11.3 from 12.25, than modified commercially available LiNi0.8Co0.1Mn0.1O2Tertiary cathode material reduces by 0.78.
Table 1:
Embodiment 1 and the resulting modified LiNi of comparative example 1 will be passed through respectively0.8Co0.1Mn0.1O2Positive electrode passes through
It is coated and dried, is assembled into fastening lithium ionic cell, carry out 1C constant current charge-discharge test；And be not modified
LiNi0.8Co0.1Mn0.1O2Tertiary cathode material is compared, and the cycle performance of three is as shown in Figure 1.
As shown in Figure 1, modified LiNi in embodiment 10.8Co0.1Mn0.1O2Tertiary cathode material lithium ion battery is in 1C multiplying power
Under capacity retention ratio, compare unmodified LiNi0.8Co0.1Mn0.1O2After tertiary cathode material recycles 50 weeks, the capacity of embodiment 1
Conservation rate is significantly promoted, and is increased to 94.08% by 75.5% before, embodiment 1 is compared to comparative example 1, capacity retention ratio
It is high by 12.13%.
Embodiment 2
The present embodiment provides a kind of modified LiNi0.8Co0.1Mn0.1O2The preparation method of tertiary cathode material, including following step
It is rapid:
10.7121g lithium acetate is dissolved in the lithium acetate solution that 1mol/L is configured in 100ml deionized water by step 1, point
Not by 19.9072g nickel acetate, 2.4509g manganese acetate, 2.4908g cobalt acetate, which is dissolved in deionized water, is configured to 1mol/L solution,
Two kinds of solution are slowly added into beaker using constant flow pump, adjust pH between 7-8 with ammonium hydroxide in reaction process, reaction terminates
Magnetic agitation 60min afterwards；
Step 2, the potassium permanganate solid for weighing 3.1606g, which is dissolved in deionized water, is settled to 100ml, is configured to
The liquor potassic permanganate of 0.2mol/L；25 DEG C of stirring 1h form uniform, stable liquor potassic permanganate；
The liquor potassic permanganate of the 0.2mol/L of 20ml is added to the mixed reaction solution of step 1 by step 3, is kept
Solution temperature is 55 DEG C, and 150 DEG C of progress hydro-thermal reactions in reaction kettle are put into after stirring 1h and for 24 hours, eccentric cleaning 5 times, are placed into true
Mixture is obtained with the dry 12h of 80 DEG C of temperature in empty drying box；By mixture under oxygen atmosphere, with 5 DEG C/min heating rate
800 DEG C are heated to, keeps the temperature 6h at this temperature, is ground up, sieved after being down to room temperature to get modified LiNi is arrived0.8Co0.1Mn0.1O2
Positive electrode.
Embodiment 3
The present embodiment provides a kind of modified LiNi0.8Co0.1Al0.1O2The preparation method of tertiary cathode material, including following step
It is rapid:
7.2397g lithium nitrate is dissolved in the lithium acetate solution that 1mol/L is configured in 100ml deionized water by step 1, point
Not by 23.2648g nickel nitrate, 3.7531g aluminum nitrate, 2.9105g cobalt nitrate, which is dissolved in deionized water, is configured to 1mol/L solution,
Two kinds of solution are slowly added into beaker using constant flow pump, adjust pH between 7-8 with ammonium hydroxide in reaction process, reaction terminates
Magnetic agitation 60min afterwards；
Step 2, the potassium permanganate solid for weighing 3.1606g, which is dissolved in deionized water, is settled to 100ml, is configured to
The liquor potassic permanganate of 0.2mol/L；25 DEG C of stirring 1h form uniform, stable liquor potassic permanganate；
The liquor potassic permanganate of the 0.2mol/L of 20ml is added to the mixed reaction solution of step 1 by step 3, is kept
Solution temperature is 55 DEG C, and 150 DEG C of progress hydro-thermal reactions in reaction kettle are put into after stirring 1h and for 24 hours, eccentric cleaning 5 times, are placed into true
Mixture is obtained with the dry 12h of 80 DEG C of temperature in empty drying box；By mixture under oxygen atmosphere, with 5 DEG C/min heating rate
800 DEG C are heated to, keeps the temperature 6h at this temperature, is ground up, sieved after being down to room temperature to get modified LiNi is arrived0.8Co0.1Al0.1O2
Positive electrode.
Embodiment 4
The present embodiment provides a kind of modified LiNi0.8Co0.1Mn0.1O2The preparation method of tertiary cathode material, including following step
It is rapid:
10.7121g lithium acetate is dissolved in the lithium acetate solution that 1mol/L is configured in 100ml ethyl alcohol by step 1, respectively will
19.9072g nickel acetate, 2.4509g manganese acetate, 2.4908g cobalt acetate, which is dissolved in ethyl alcohol, is configured to 1mol/L solution, molten by two kinds
Liquid is slowly added into beaker using constant flow pump, adjusts pH between 7-8 with ammonium hydroxide in reaction process, magnetic force stirs after reaction
Mix 60min；
Step 2, the potassium permanganate solid for weighing 1.5803g, which is dissolved in ethyl alcohol, is settled to 100ml, is configured to 0.1mol/L
Liquor potassic permanganate；25 DEG C of stirring 1h form uniform, stable liquor potassic permanganate；
The liquor potassic permanganate of the 0.1mol/L of 20ml is added to the mixed reaction solution of step 1 by step 3, is kept
Solution temperature is 55 DEG C, is put into 200 DEG C of progress solvent thermal reaction 12h in reaction kettle after stirring 1h, eccentric cleaning 5 times, places into
Mixture is obtained with the dry 6h of 100 DEG C of temperature in vacuum oven；By mixture under oxygen atmosphere, heated up with 3 DEG C/min fast
Rate is heated to 900 DEG C, keeps the temperature 12h at this temperature, is ground up, sieved after being down to room temperature to get modification is arrived
LiNi0.8Co0.1Mn0.1O2Positive electrode.
Embodiment 5
This implementation provides a kind of LiNi of modification0.9Co0.05Mn0.05O2The preparation method of positive electrode comprising following step
It is rapid:
7.2398g lithium acetate is dissolved in the lithium acetate solution that 1mol/L is configured in 100ml deionized water by step 1, point
Not by 22.3974g nickel acetate, 0.865g manganese acetate, 1.2454g cobalt acetate, which is dissolved in deionized water, is configured to 1mol/L solution,
Two kinds of solution are slowly added into beaker using constant flow pump, adjust PH between 7-8 with ammonium hydroxide in reaction process, reaction terminates
Magnetic agitation 60min afterwards；
Step 2, the potassium permanganate solid for weighing 1.5803g, which is dissolved in deionized water, is settled to 100ml, is configured to
The liquor potassic permanganate of 0.1mol/L；25 DEG C of stirring 1h form uniform, stable liquor potassic permanganate；
The liquor potassic permanganate of the 0.1mol/L of 20ml is added to the mixed reaction solution of step 1 by step 3, is kept
Solution temperature is 55 DEG C, is put into reaction kettle 150 DEG C of progress hydro-thermal reactions for 24 hours after stirring 1h, after reaction, eccentric cleaning 5
Time, it places into vacuum oven and mixture is obtained with the dry 12h of 80 DEG C of temperature；By mixture under oxygen atmosphere, with 5 DEG C/
Min heating rate is heated to 800 DEG C, keeps the temperature 6h at this temperature, is ground up, sieved after being down to room temperature to get modification is arrived
LiNi0.9Co0.05Mn0.05O2Positive electrode.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (10)
1. a kind of preparation method for being modified nickelic tertiary cathode material, which comprises the following steps:
Step 1 is configured to solution A for lithium source is soluble in water, and nickel source, manganese source and cobalt source or nickel source, silicon source and cobalt source is molten
Solution B is configured in deionized water；Solution A and B are mixed and reacted；In reaction process, adjusting pH value in reaction is weak base
Property, nickelic ternary interphase solution C is stirred to get after reaction；
Step 2 obtains solution D for acid solid is soluble in water；Solution D is added in solution C and is stirred, is then carried out
Hydro-thermal reaction or solvent thermal reaction, are calcined after reaction, and cooling obtains being modified nickelic tertiary cathode after being ground up, sieved
Material.
2. preparation method according to claim 1, it is characterised in that: the lithium source includes lithium hydroxide, lithium carbonate, nitric acid
The combination of one or more of lithium, lithium acetate, lithium chloride, lithium fluoride, lithium phosphate, lithium hydrogen phosphate and lithium dihydrogen phosphate；
Preferably, the nickel source includes the combination of one or more of nickel sulfate, nickel acetate and nickel nitrate；
Preferably, the manganese source includes one of manganese sulfate, manganese acetate and manganese nitrate or a variety of combinations；
Preferably, source of aluminium includes one of aluminium oxide, aluminium hydroxide, aluminium salt and meta-aluminate or a variety of combinations；
Preferably, the cobalt source includes one of cobaltous sulfate, cobalt acetate, cobalt nitrate or a variety of combinations.
3. preparation method according to claim 1, it is characterised in that: in step 1, the pH value is 7-9；Further
Preferably, the pH value is adjusted by ammonium hydroxide；
Preferably, the time reacted is 2-4h；Reaction temperature is 50-85 DEG C；Mixing time after reaction is 30-
60min。
4. preparation method according to claim 1, it is characterised in that: in step 2, the time of the stirring is 30-
60min；Whipping temp is 50-85 DEG C；
Preferably, the hydro-thermal reaction or the reaction temperature of the solvent thermal reaction are 150-200 DEG C, reaction time 12-
24h；
Preferably, before calcining after reaction, include the steps that centrifuge washing is dry or it is dry to be evaporated to gel；
Preferably, solution after reaction stirs under conditions of 60-80 DEG C and is evaporated to gel；
Preferably, the number of solution centrifugation after reaction is 1-6 times；
Preferably, the drying is vacuum drying, and vacuum drying temperature is 60-100 DEG C, drying time 6-12h；
Preferably, the solvent that the solvent thermal reaction uses includes one in ethyl alcohol, isopropanol, n-butanol, ethylene glycol and acetone
Kind or a variety of combinations.
5. preparation method according to claim 1, it is characterised in that: the acid solid is potassium permanganate.
6. preparation method according to claim 1 or 2, it is characterised in that: the lithium source, the nickel salt, the cobalt salt and
The molar ratio of the manganese salt is 1:x:y:(1-x-y), wherein 1,0 y≤0.2 < 0.8≤x <, and 1-x-y ≠ 0；Alternatively, described
Lithium source, the nickel salt, the cobalt salt and the aluminium salt molar ratio be 1:x:y:(1-x-y), wherein 0.8≤x <, 1,0 < y≤
0.2, and 1-x-y ≠ 0.
7. preparation method according to claim 1 or 5, it is characterised in that: the concentration range of acid solid in the solution D
For 0.1mol/L-1mol/L；
Preferably, the volumetric usage of the solution D and solution C ratio is 1:5.
8. preparation method according to claim 1, which is characterized in that in step 2, calcine technology are as follows:
By the mixture obtained after drying under air or oxygen atmosphere, 400-900 is heated to the heating rate of 3-5 DEG C/min
DEG C, keep the temperature 3-16h.
9. the nickelic tertiary cathode material of modification that any one of the claim 1-8 preparation method is prepared.
10. application of the modified nickelic tertiary cathode material in anode material of lithium battery described in claim 9.
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Cited By (6)
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| CN111233052A (en) * | 2020-01-17 | 2020-06-05 | 清华大学深圳国际研究生院 | Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery |
| CN111675249A (en) * | 2020-06-11 | 2020-09-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof |
| CN112038613A (en) * | 2020-09-17 | 2020-12-04 | 贵州大学 | Modification method for realizing doped coating of high-nickel ternary cathode material by preprocessing precursor |
| CN112194197A (en) * | 2020-08-27 | 2021-01-08 | 浙江美都海创锂电科技有限公司 | High-nickel ternary positive electrode material with low internal resistance and low flatulence rate as well as preparation method and application thereof |
| CN112499696A (en) * | 2020-11-30 | 2021-03-16 | 蜂巢能源科技有限公司 | Method for reducing residual alkali content of high-nickel material and low-residual alkali high-nickel material prepared by method |
| CN114927682A (en) * | 2022-05-18 | 2022-08-19 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material |
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| CN112499696A (en) * | 2020-11-30 | 2021-03-16 | 蜂巢能源科技有限公司 | Method for reducing residual alkali content of high-nickel material and low-residual alkali high-nickel material prepared by method |
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| CN114927682A (en) * | 2022-05-18 | 2022-08-19 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | LiNi ternary material for increasing high nickel content x Co y Mn 1-x-y O 2 Method for cycling stability and safety of anode material |
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