CN108172822A - Nickel-cobalt lithium manganate cathode material and preparation method thereof - Google Patents
Nickel-cobalt lithium manganate cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN108172822A CN108172822A CN201711480654.9A CN201711480654A CN108172822A CN 108172822 A CN108172822 A CN 108172822A CN 201711480654 A CN201711480654 A CN 201711480654A CN 108172822 A CN108172822 A CN 108172822A
- Authority
- CN
- China
- Prior art keywords
- nickel
- preparation
- crystal seed
- cathode material
- manganate 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of nickel-cobalt lithium manganate cathode materials and preparation method thereof, and preparation method includes the following steps：Crystal seed is prepared using hydro-thermal method；Crystal seed progress coprecipitation reaction is obtained into NixCoyMn1‑x‑y(OH)2Precursor；The presoma and lithium hydroxide or lithium carbonate are pressed into Li：(Ni+Co+Mn) molar ratio is 1:Mixture, is then sintered, obtains intermediate by 1 1.2 mixing；The intermediate with lithium hydroxide is mixed, then sprays metal-sol, obtains pre-coated object；The pre-coated object is subjected to double sintering to get the nickel-cobalt lithium manganate cathode material.The nickel-cobalt lithium manganate cathode material that above-mentioned preparation method obtains is monocrystalline pattern, and high using the lithium ion battery energy density of the positive electrode, up to 300wh/kg, and cycle life can reach 3000 times.
Description
Technical field
The present invention relates to lithium ion battery material technical field, more particularly to a kind of lithium ion battery nickle cobalt lithium manganate just
Pole material and preparation method thereof.
Background technology
Lithium ion battery as novel green energy resource, have higher than energy, self discharge is small, memory-less effect, the cycle longevity
The advantages that life is long, non-environmental-pollution, is widely used in the electronic products such as mobile phone, laptop；Lithium ion battery is also simultaneously
The accumulation power supply of electric car power supply and the solar energy class renewable sources of energy.
Positive electrode uses the nickle cobalt lithium manganate class positive electrode LiNi of low nickel contentxCoyMn1-x-yO2Such as
LiNi0.5Co0.2Mn0.3O2Deng lithium ion battery, although cycle life can reach 3000 times, batteries of electric automobile 8 can be met
The requirement of year service life, but due to LiNi0.5Co0.2Mn0.3O23.0-4.2V gram volumes only have 160mAh/g or so, 3.0-
4.4V gram volumes also only have 180mAh/g or so, and battery energy density is caused to can only achieve 200wh/kg or so, can not meet electricity
The requirement of electrical automobile single charge continuation of the journey 500km.
The nickel-cobalt lithium manganate cathode material LiNi of high nickel content just in exploitationxCoyMn1-x-yO2Such as
LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.85Co0.1Al0.05O2Deng 3.0-4.2V gram volumes can reach
More than 180mAh/g, the energy density using the lithium ion battery of such positive electrode can reach 300wh/kg, meet electronic
The requirement of automobile single charge continuation of the journey 500km, but its cycle life only has 2000 times, is unable to reach 3000 times.
Therefore, existing nickel-cobalt lithium manganate cathode material LiNixCoyMn1-x-yO2Technology of preparing still has much room for improvement.
Invention content
Based on this, the object of the present invention is to provide a kind of high-energy density and the lithium ion battery nickel cobalt manganese that have extended cycle life
Sour lithium anode material LiNixCoyMn1-x-yO2(0.5<x<1,0.05<y<0.2) preparation method.
Specific technical solution is as follows：
A kind of preparation method of nickel-cobalt lithium manganate cathode material, includes the following steps：
Ni is prepared using hydro-thermal methodxCoyMn1-x-y(OH)2Crystal seed；
Crystal seed progress coprecipitation reaction is obtained into NixCoyMn1-x-y(OH)2Precursor；
The presoma and lithium hydroxide or lithium carbonate are pressed into Li：(Ni+Co+Mn) molar ratio is 1:1-1.2 mixing, so
Mixture is sintered afterwards, obtains intermediate；
The intermediate is mixed with lithium hydroxide, the dosage of lithium hydroxide is the 0.5-1% of the intermediate weight, so
After spray metal-sol, obtain pre-coated object；
The pre-coated object is subjected to double sintering to get the nickel-cobalt lithium manganate cathode material LiNixCoyMn1-x-yO2。
In wherein some embodiments, the hydro-thermal method prepares NixCoyMn1-x-y(OH)2Crystal seed, wherein 0.5<x<1,0.05
<y<0.2, include the following steps：
By nickel acetate, cobalt acetate and manganese acetate by Ni in the crystal seed：Co：The molar ratio mixing of Mn is dissolved in deionized water
In, it then adds in pattern guiding agent and obtains homogeneous phase solution system, the additive amount of the pattern guiding agent is the 1- of nickel acetate dosage
5wt%；
The homogeneous phase solution system is placed in reaction kettle, the constant temperature 3-12h under 120-200 DEG C, 0.2-0.6MPa, then
Cold filtration obtains the NixCoyMn1-x-y(OH)2Crystal seed, the grain size D50 of the crystal seed is 0.5-1.5 μm.
In wherein some embodiments, one kind in water-soluble organic sulfonic acid sodium compound of the pattern guiding agent or
It is several.
In wherein some embodiments, the coprecipitation reaction obtains NixCoyMn1-x-y(OH)2Precursor, including walking as follows
Suddenly：
The crystal seed is added in successive reaction kettle, while by Ni in the crystal seed：Co：The molar ratio of Mn adds in sulfuric acid
Nickel, cobaltous sulfate and manganese sulfate mixed solution, add ammonium hydroxide and NaOH solution, and control system pH value is 10-12, temperature 60-
It 65 DEG C, reacts to D50 for 2-4 μm to get NixCoyMn1-x-y(OH)2Precursor.
In wherein some embodiments, the preparation method of the intermediate includes the following steps：
The presoma presses Li with lithium hydroxide or lithium carbonate：(Ni+Co+Mn) molar ratio is 1:1-1.2 mixing adds in
Sintering aid is mixed after being heat-treated 10-18h under 950-1050 DEG C of oxidizing atmosphere, then is cooled to 700-800 DEG C of heat preservation 2-10h,
Obtain sintered product；
By the sintered product 50-60 DEG C of pure water 10-20min, then drying to water content<0.5wt%, in obtaining
Mesosome.
In wherein some embodiments, one kind in alkali metal compound, boron compound of the sintering aid or
Several, the additive amount of the sintering aid is the 5-20% of forerunner's weight.
In wherein some embodiments, the metal-sol be selected from magnesia colloidal sol, alumina sol, titanium oxide sol and
One or more of zirconia sol；Additive amount is the 1-3% of the intermediate weight.
In wherein some embodiments, the technological parameter of the double sintering is：By the pre-coated object in 550-750 DEG C
3-5h is heat-treated under oxidizing atmosphere, 1-3h is kept the temperature at 950-1000 DEG C.
It is a further object of the present invention to provide above-mentioned preparation methods to be prepared nickel-cobalt lithium manganate cathode material Li
NixCoyMn1-x-yO2。
It is a further object of the present invention to provide a kind of lithium ion battery, including above-mentioned nickel-cobalt lithium manganate cathode material Li
NixCoyMn1-x-yO2。
The preparation method of above-mentioned nickel-cobalt lithium manganate cathode material, can using hydro-thermal method in a manner that coprecipitation is combined
Closely knit little particle presoma (grain size is at 2-4 μm) is obtained with synthesis；Sintering aid (preferably alkali gold is added in sintering step
Belong to one or more of compound, boron compound), which is molten condition at a sintering temperature, is conducive to lithium
Element is preferably combined with presoma；It is coated in encapsulation steps using oxidized metal colloidal sol, can cause metal oxide more
Intermediate is equably coated on, double sintering is by controlling temperature and time that can obtain the crystal form of required metal oxide.
The shape characteristic for the nickel-cobalt lithium manganate cathode material that above-mentioned preparation method obtains is：Monocrystalline pattern, tool metal oxidation
Object clad, relatively low residual lithium amount, gram volume can arrive 200mAh/g, using the lithium ion battery energy density of the positive electrode
Height, up to 300wh/kg, and cycle life can reach 3000 times.
Description of the drawings
Fig. 1 is that embodiment 1 synthesizes the obtained electromicroscopic photograph figure of presoma；
Fig. 2 is that embodiment 1 synthesizes the obtained electromicroscopic photograph figure of nickel-cobalt lithium manganate cathode material；
Fig. 3 is that comparative example 1 synthesizes the obtained electromicroscopic photograph figure of presoma；
Fig. 4 is that comparative example 1 synthesizes the obtained electromicroscopic photograph figure of nickel-cobalt lithium manganate cathode material；
Fig. 5 is the nickel-cobalt lithium manganate cathode material cycle life comparison diagram that embodiment 1 and comparative example 1 obtain.
Specific embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But the present invention can be with perhaps
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make
To the understanding more thorough and comprehensive of the disclosure.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The normally understood meaning of technical staff is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
The arbitrary and all combination of the Listed Items of pass.
Embodiment 1
A kind of preparation method of nickel-cobalt lithium manganate cathode material, includes the following steps：
Ni is prepared using hydro-thermal methodxCoyMn1-x-y(OH)2Crystal seed, wherein x=0.8, y=0.1：
Nickel acetate, cobalt acetate and manganese acetate are pressed into Ni：Co：The molar ratio of Mn is 8:1:1 mixing is dissolved in deionized water,
Then it adds in pattern guiding agent (being specially neopelex) and obtains homogeneous phase solution system, the addition of the pattern guiding agent
Measure the 8wt% for nickel acetate dosage；
The homogeneous phase solution system is placed in reaction kettle, constant temperature 10h, is subsequently cooled to 25 under 150 DEG C, 0.4MPa
DEG C, filter to obtain the NixCoyMn1-x-y(OH)2Crystal seed, the grain size D50 of the crystal seed is 0.5-1.5 μm.
Crystal seed progress coprecipitation reaction is obtained into NixCoyMn1-x-y(OH)2Precursor：
The crystal seed is added in successive reaction kettle, while by Ni：Co：The molar ratio of Mn is 8:1:1 adds in nickel sulfate, sulphur
Sour cobalt and manganese sulfate mixed solution add ammonium hydroxide and NaOH solution, and control system pH value is 10-12, and temperature is 60-65 DEG C,
Reaction is to D50 for 2-4 μm to get NixCoyMn1-x-y(OH)2Precursor (electromicroscopic photograph is as shown in Figure 1).
Prepare intermediate：
The presoma presses Li with lithium hydroxide or lithium carbonate：(Ni+Co+Mn) molar ratio is 1:1-1.2 mixing adds in
(specially mass ratio is 1 to sintering aid:1 LiF and B2O3, additive amount be forerunner's weight 10%), mix after
15h is heat-treated under 1000 DEG C of oxidizing atmospheres, then is cooled to 750 DEG C of heat preservation 8h, obtains sintered product；
The sintered product under atmosphere of inert gases is washed into 10min with 55 DEG C of pure water, is then dried to water content<
0.5wt% obtains intermediate.
The intermediate is mixed with lithium hydroxide, the dosage of lithium hydroxide is the 0.5-1% of the intermediate weight, in
10min is mixed in high-speed mixer, mixes linear velocity>15m/s；Then it (is specially magnesia colloidal sol to spray metal-sol；Addition
Measure 2% for the intermediate weight), then spray anaerobic pure water (addition is the 1-2% of the intermediate weight), time control
It makes in 10-15min, obtains pre-coated object；
The pre-coated object is subjected to double sintering：The pre-coated object is heat-treated 4h under 600 DEG C of oxidizing atmosphere, then
2h is kept the temperature at 950 DEG C.
Up to the nickel-cobalt lithium manganate cathode material Ni0.8Co0.1Mn0.1(OH)2(electromicroscopic photograph is as shown in Figure 2).
Embodiment 2
A kind of preparation method of nickel-cobalt lithium manganate cathode material, includes the following steps：
Ni is prepared using hydro-thermal methodxCoyMn1-x-y(OH)2Crystal seed, wherein x=0.8, y=0.1：
Nickel acetate, cobalt acetate and manganese acetate are pressed into Ni：Co：The molar ratio of Mn is 8:1:1 mixing is dissolved in deionized water,
Then it adds in pattern guiding agent (being specially cetyl benzenesulfonic acid sodium) and obtains homogeneous phase solution system, the addition of the pattern guiding agent
Measure the 10wt% for nickel acetate dosage；
The homogeneous phase solution system is placed in reaction kettle, constant temperature 8h, is subsequently cooled to 30 under 170 DEG C, 0.35MPa
DEG C, filter to obtain the NixCoyMn1-x-y(OH)2Crystal seed, the grain size D50 of the crystal seed is 0.5-1.5 μm.
Crystal seed progress coprecipitation reaction is obtained into NixCoyMn1-x-y(OH)2Precursor：
The crystal seed is added in successive reaction kettle, while by Ni：Co：The molar ratio of Mn is 8:1:1 adds in nickel sulfate, sulphur
Sour cobalt and manganese sulfate mixed solution add ammonium hydroxide and NaOH solution, and control system pH value is 10-12, and temperature is 60-65 DEG C,
Reaction is to D50 for 2-4 μm to get NixCoyMn1-x-y(OH)2Precursor.
Prepare intermediate：
The presoma presses Li with lithium hydroxide or lithium carbonate：(Ni+Co+Mn) molar ratio is 1:1.1 mixing, add in and burn
It (is specially 1 to tie auxiliary agent:1:1 LiF, Na2SO4With B2O3, additive amount is the 8% of forerunner's weight), it mixes after 950
18h is heat-treated under DEG C oxidizing atmosphere, then is cooled to 800 DEG C of heat preservation 5h, obtains sintered product；
The sintered product under atmosphere of inert gases is washed into 20min with 60 DEG C of pure water, is then dried to water content<
0.5wt% obtains intermediate.
The intermediate is mixed with lithium hydroxide, the dosage of lithium hydroxide is the 0.5-1% of the intermediate weight, in
10min is mixed in high-speed mixer, mixes linear velocity>15m/s；Then it (is specially alumina sol to spray metal-sol；Addition
Measure 2% for the intermediate weight), then spray anaerobic pure water (addition is the 1-2% of the intermediate weight), time control
It makes in 10-15min, obtains pre-coated object；
The pre-coated object is subjected to double sintering：The pre-coated object is heat-treated 3h under 750 DEG C of oxidizing atmosphere, then
1h is kept the temperature at 1000 DEG C.
Up to the nickel-cobalt lithium manganate cathode material Ni0.8Co0.1Mn0.1(OH)2。
Comparative example 1
A kind of preparation method of nickel-cobalt lithium manganate cathode material, includes the following steps：
Ni is prepared using coprecipitationxCoyMn1-x-y(OH)2Crystal seed, wherein x=0.8, y=0.1：
Nickel sulfate, cobaltous sulfate and manganese sulfate are pressed into Ni：Co：The molar ratio of Mn is 8:1:1 mixing is dissolved in aqueous solution, with one
Constant speed degree is added in the normal-pressure reaction kettle of nitrogen protection, adds ammonium hydroxide and NaOH solution, control system pH value is 10-12, warm
It is 60-65 DEG C to spend, and is reacted to D50 for 2-4 μm to get NixCoyMn1-x-y(OH)2Precursor (as shown in Figure 3).
With lithium hydroxide or lithium carbonate by Li after the washing of obtained presoma is dried：(Ni+Co+Mn) molar ratio is 1:
1.1 mixing, mix after being heat-treated 18h under 750 DEG C of oxidizing atmosphere, obtain sintered product (as shown in Figure 4).
Comparative example 2
A kind of preparation method of nickel-cobalt lithium manganate cathode material is substantially the same manner as Example 1, and difference lies in do not carry out water
Thermal synthesis, presoma directly use Co deposited synthesis.
Comparative example 3
A kind of preparation method of nickel-cobalt lithium manganate cathode material is substantially the same manner as Example 1, and difference lies in the systems of intermediate
Standby no addition sintering aid.
Comparative example 4
A kind of preparation method of nickel-cobalt lithium manganate cathode material is substantially the same manner as Example 1, and difference lies in the pre- of, intermediate
Cladding is carried out using metal-sol method, but solid phase method is used to carry out.
Performance test results contrast：
| Gram volume (mAh/g) | Cycle life (secondary) | Grain size (μm) | First charge discharge efficiency (%) | |
| Embodiment 1 | 208 | 243 | 4 | 91.7 |
| Embodiment 2 | 211 | 287 | 3 | 92.3 |
| Comparative example 1 | 187 | 120 | 10 | 90.5 |
| Comparative example 2 | 193 | 165 | 4 | 91 |
| Comparative example 3 | 197 | 147 | 2 | 92 |
| Comparative example 4 | 189 | 155 | 3 | 90.8 |
The LiNi prepared using coprecipitation methodxCoyMn1-x-yO2Positive electrode, when 0.5<x<When 1, in lithium ion deintercalation
Cheng Zhong, for material there are serious phase transition phenomenon, this phenomenon can cause the gram volume of material to reduce；Material internal exists simultaneously
Serious stress accumulation phenomenon, this phenomenon can caused by material granule crack, the presence of above-mentioned phenomenon, cause using the material as
The lithium ion battery service life rapid decay of anode is unable to reach the service life of 3000 times.
The method being combined using hydro-thermal method with coprecipitation, grain size smaller, the internal structure that can be prepared are closeer
Real precursor, when being sintered in the presence of sintering aid, sintering aid can provide liquid-phase sintering environment, enable lithium ion
It is enough equably to penetrate into inside precursor, so as to obtain the LiNi of monocrystalline patternxCoyMn1-x-yO2Positive electrode, this pattern
Exist inside positive electrode without crystal boundary, eliminate the stress formed during material preparation, the uniform internal structure of high degree of symmetry
Concentration distribution when making to reduce lithium ion deintercalation eliminates the accumulation of stress, therefore with better cycle life.
Surface cladding processing is carried out using metal-sol, compared to solid phase cladding process, due to metal-sol particle size more
Small, in intermediate surface absorption evenly, evenly, material surface layer phase transition degree is more for the clad obtained after heat treatment
It is small, make material that there is higher gram volume.
Embodiment 1 and the cycle life comparison of comparative example 1 are as shown in Figure 5.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that those of ordinary skill in the art are come
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of nickel-cobalt lithium manganate cathode material, which is characterized in that include the following steps：
Ni is prepared using hydro-thermal methodxCoyMn1-x-y(OH)2Crystal seed；
Crystal seed progress coprecipitation reaction is obtained into NixCoyMn1-x-y(OH)2Precursor；
The presoma and lithium hydroxide or lithium carbonate are pressed into Li：(Ni+Co+Mn) molar ratio is 1:1-1.2 is mixed, and then will
Mixture is sintered, and obtains intermediate；
The intermediate is mixed with lithium hydroxide, the dosage of lithium hydroxide is the 0.5-1% of the intermediate weight, is then sprayed
Metal-sol is drenched, obtains pre-coated object；
The pre-coated object is subjected to double sintering to get the nickel-cobalt lithium manganate cathode material LiNixCoyMn1-x-yO2。
2. preparation method according to claim 1, which is characterized in that the hydro-thermal method prepares NixCoyMn1-x-y(OH)2It is brilliant
Kind, wherein 0.5<x<1,0.05<y<0.2, include the following steps：
By nickel acetate, cobalt acetate and manganese acetate, by Ni in the crystal seed：Co：The molar ratio mixing of Mn is dissolved in deionized water,
Then pattern guiding agent is added in, obtains homogeneous phase solution system, the additive amount of the pattern guiding agent is the 1- of nickel acetate dosage
5wt%；
The homogeneous phase solution system is placed in reaction kettle, constant temperature 3-12h, then cools down under 120-200 DEG C, 0.2-0.6MPa
Filter to obtain the NixCoyMn1-x-y(OH)2Crystal seed, the grain size D50 of the crystal seed is 0.5-1.5 μm.
3. preparation method according to claim 2, which is characterized in that the pattern guiding agent, selected from water-soluble organic sulphur
One or more of sour sodium compound.
4. preparation method according to claim 1, which is characterized in that the coprecipitation reaction obtains NixCoyMn1-x-y
(OH)2Precursor includes the following steps：
The crystal seed is added in successive reaction kettle, while by Ni in the crystal seed：Co：The molar ratio of Mn adds in nickel sulfate, sulphur
Sour cobalt and manganese sulfate mixed solution add ammonium hydroxide and NaOH solution, and control system pH value is 10-12, and temperature is 60-65 DEG C,
Reaction is to D50 for 2-4 μm to get NixCoyMn1-x-y(OH)2Precursor.
5. preparation method according to claim 1, which is characterized in that the preparation method of the intermediate, including walking as follows
Suddenly：
The presoma presses Li with lithium hydroxide or lithium carbonate：(Ni+Co+Mn) molar ratio is 1:1-1.2 is mixed, and adds in sintering
Auxiliary agent is mixed after being heat-treated 10-18h under 950-1050 DEG C of oxidizing atmosphere, then be cooled to 700-800 DEG C of heat preservation 2-10h, must be burnt
Tie product；
By the sintered product 50-60 DEG C of pure water 10-20min, then drying to water content<0.5wt% is obtained intermediate
Body.
6. preparation method according to claim 5, which is characterized in that the sintering aid is selected from alkali metal compound, boron
One or more of class compound, the additive amount of the sintering aid are the 5-20% of forerunner's weight.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that the metal-sol be selected from magnesium colloidal sol,
One or more of Aluminum sol, titanium colloidal sol and zirconium colloidal sol；Additive amount is the 1-3% of the intermediate weight.
8. according to claim 1-6 any one of them preparation methods, which is characterized in that the technological parameter of the double sintering
For：The pre-coated object is heat-treated 3-5h under 550-750 DEG C of oxidizing atmosphere, 1-3h is kept the temperature at 950-1000 DEG C.
9. nickel-cobalt lithium manganate cathode material LiNi is prepared in any one of the claim 1-8 preparation methodsxCoyMn1-x-yO2。
10. a kind of lithium ion battery, which is characterized in that including the nickel-cobalt lithium manganate cathode material described in claim 9
LiNixCoyMn1-x-yO2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711480654.9A CN108172822B (en) | 2017-12-29 | 2017-12-29 | Nickel cobalt lithium manganate positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711480654.9A CN108172822B (en) | 2017-12-29 | 2017-12-29 | Nickel cobalt lithium manganate positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108172822A true CN108172822A (en) | 2018-06-15 |
| CN108172822B CN108172822B (en) | 2020-10-09 |
Family
ID=62516425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711480654.9A Active CN108172822B (en) | 2017-12-29 | 2017-12-29 | Nickel cobalt lithium manganate positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108172822B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378469A (en) * | 2018-11-30 | 2019-02-22 | 清远佳致新材料研究院有限公司 | The preparation method of tertiary cathode material and its tertiary cathode material obtained, lithium ion battery and electric vehicle |
| CN109786731A (en) * | 2018-12-12 | 2019-05-21 | 上海紫剑化工科技有限公司 | Electrode material, lithium ion battery and preparation method thereof, application |
| CN109921009A (en) * | 2019-03-11 | 2019-06-21 | 苏州拉瓦锂能源科技有限公司 | A kind of preparation method of single crystal battery material |
| CN111129443A (en) * | 2018-10-31 | 2020-05-08 | 多氟多化工股份有限公司 | Composite ternary cathode material, preparation method thereof and lithium ion battery |
| WO2020140941A1 (en) * | 2019-01-04 | 2020-07-09 | 散裂中子源科学中心 | Lini0.69mn0.23co0.08o2 compound having a layered structure, synthesis method therefor and application thereof |
| CN111477867A (en) * | 2020-05-21 | 2020-07-31 | 苏州大学 | Modification method of high-nickel ternary cathode material of lithium ion battery |
| CN112142125A (en) * | 2020-09-29 | 2020-12-29 | 山东精工电子科技有限公司 | Method for preparing high-nickel ternary cathode material by secondary growth method |
| CN112366308A (en) * | 2020-11-11 | 2021-02-12 | 江西普瑞美新材料科技有限公司 | Method for rapidly synthesizing nickel-cobalt-manganese positive electrode material precursor |
| WO2021134153A1 (en) * | 2019-12-30 | 2021-07-08 | 荆门市格林美新材料有限公司 | Preparation method for high nickel ternary precursor capable of preferential growth of crystal planes by adjusting and controlling addition amount of seed crystals |
| WO2021156124A1 (en) * | 2020-02-07 | 2021-08-12 | Basf Se | Cathode active material and method for making such cathode active material |
| CN113299905A (en) * | 2021-05-21 | 2021-08-24 | 湖北融通高科先进材料有限公司 | Preparation method of single crystal nickel cobalt lithium manganate ternary material |
| CN114031126A (en) * | 2021-11-11 | 2022-02-11 | 中物院成都科学技术发展中心 | Manganese-rich carbonate precursor and preparation method thereof |
| CN114180645A (en) * | 2020-09-15 | 2022-03-15 | 香港城市大学深圳研究院 | Multi-metal hydroxide and preparation method and application thereof |
| CN114645314A (en) * | 2022-03-09 | 2022-06-21 | 中南大学 | Preparation method of single crystal morphology ternary cathode material |
| WO2024103564A1 (en) * | 2022-11-15 | 2024-05-23 | 广东邦普循环科技有限公司 | Method for preparing high-rate single-crystal positive electrode material from gel mixture, and use thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101355161A (en) * | 2008-09-17 | 2009-01-28 | 长沙矿冶研究院 | Method for preparing lithium ion battery anode material nickel cobalt lithium manganate |
| CN102709538A (en) * | 2012-06-06 | 2012-10-03 | 株洲天地龙电源科技有限公司 | Novel method for synthesizing anode material (LNMC) |
| CN103137962A (en) * | 2013-03-11 | 2013-06-05 | 佛山市邦普循环科技有限公司 | Method for preparing nickel-cobalt-manganese hydroxide |
| CN103296269A (en) * | 2013-05-17 | 2013-09-11 | 太原理工大学 | Green controllable preparation process of lithium nickel cobalt manganese oxide |
| CN104979546A (en) * | 2014-04-01 | 2015-10-14 | 宁德时代新能源科技有限公司 | Preparation method of single-crystal-morphology lithium ion battery ternary positive material |
| CN105006566A (en) * | 2015-08-31 | 2015-10-28 | 宁波金和锂电材料有限公司 | Modified anode material and preparation method thereof as well as lithium ion battery |
| CN105140492A (en) * | 2015-10-14 | 2015-12-09 | 广东天劲新能源科技股份有限公司 | Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method |
| CN105206825A (en) * | 2015-10-22 | 2015-12-30 | 白岩 | Preparation method for nickel-cobalt-lithium manganate |
| CN105390670A (en) * | 2014-08-20 | 2016-03-09 | 旭硝子株式会社 | production method of lithium-containing composite oxide and lithium-containing composite oxide |
| CN106904668A (en) * | 2017-04-14 | 2017-06-30 | 郑州科技学院 | A kind of preparation method of tetrakaidecahedron shape nanometer nickel-cobalt LiMn2O4 |
| CN107369861A (en) * | 2017-06-01 | 2017-11-21 | 吉安市优特利科技有限公司 | The detection method of nickelic ternary material denaturation degrees |
| CN107394164A (en) * | 2017-07-26 | 2017-11-24 | 天津银隆新能源有限公司 | Tertiary cathode material and preparation method thereof |
-
2017
- 2017-12-29 CN CN201711480654.9A patent/CN108172822B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101355161A (en) * | 2008-09-17 | 2009-01-28 | 长沙矿冶研究院 | Method for preparing lithium ion battery anode material nickel cobalt lithium manganate |
| CN102709538A (en) * | 2012-06-06 | 2012-10-03 | 株洲天地龙电源科技有限公司 | Novel method for synthesizing anode material (LNMC) |
| CN103137962A (en) * | 2013-03-11 | 2013-06-05 | 佛山市邦普循环科技有限公司 | Method for preparing nickel-cobalt-manganese hydroxide |
| CN103296269A (en) * | 2013-05-17 | 2013-09-11 | 太原理工大学 | Green controllable preparation process of lithium nickel cobalt manganese oxide |
| CN104979546A (en) * | 2014-04-01 | 2015-10-14 | 宁德时代新能源科技有限公司 | Preparation method of single-crystal-morphology lithium ion battery ternary positive material |
| CN105390670A (en) * | 2014-08-20 | 2016-03-09 | 旭硝子株式会社 | production method of lithium-containing composite oxide and lithium-containing composite oxide |
| CN105006566A (en) * | 2015-08-31 | 2015-10-28 | 宁波金和锂电材料有限公司 | Modified anode material and preparation method thereof as well as lithium ion battery |
| CN105140492A (en) * | 2015-10-14 | 2015-12-09 | 广东天劲新能源科技股份有限公司 | Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method |
| CN105206825A (en) * | 2015-10-22 | 2015-12-30 | 白岩 | Preparation method for nickel-cobalt-lithium manganate |
| CN106904668A (en) * | 2017-04-14 | 2017-06-30 | 郑州科技学院 | A kind of preparation method of tetrakaidecahedron shape nanometer nickel-cobalt LiMn2O4 |
| CN107369861A (en) * | 2017-06-01 | 2017-11-21 | 吉安市优特利科技有限公司 | The detection method of nickelic ternary material denaturation degrees |
| CN107394164A (en) * | 2017-07-26 | 2017-11-24 | 天津银隆新能源有限公司 | Tertiary cathode material and preparation method thereof |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129443A (en) * | 2018-10-31 | 2020-05-08 | 多氟多化工股份有限公司 | Composite ternary cathode material, preparation method thereof and lithium ion battery |
| CN109378469A (en) * | 2018-11-30 | 2019-02-22 | 清远佳致新材料研究院有限公司 | The preparation method of tertiary cathode material and its tertiary cathode material obtained, lithium ion battery and electric vehicle |
| CN109786731A (en) * | 2018-12-12 | 2019-05-21 | 上海紫剑化工科技有限公司 | Electrode material, lithium ion battery and preparation method thereof, application |
| CN109786731B (en) * | 2018-12-12 | 2021-12-10 | 上海紫剑化工科技有限公司 | Electrode material, lithium ion battery, and preparation method and application thereof |
| WO2020140941A1 (en) * | 2019-01-04 | 2020-07-09 | 散裂中子源科学中心 | Lini0.69mn0.23co0.08o2 compound having a layered structure, synthesis method therefor and application thereof |
| CN109921009A (en) * | 2019-03-11 | 2019-06-21 | 苏州拉瓦锂能源科技有限公司 | A kind of preparation method of single crystal battery material |
| WO2021134153A1 (en) * | 2019-12-30 | 2021-07-08 | 荆门市格林美新材料有限公司 | Preparation method for high nickel ternary precursor capable of preferential growth of crystal planes by adjusting and controlling addition amount of seed crystals |
| WO2021156124A1 (en) * | 2020-02-07 | 2021-08-12 | Basf Se | Cathode active material and method for making such cathode active material |
| CN111477867A (en) * | 2020-05-21 | 2020-07-31 | 苏州大学 | Modification method of high-nickel ternary cathode material of lithium ion battery |
| CN114180645A (en) * | 2020-09-15 | 2022-03-15 | 香港城市大学深圳研究院 | Multi-metal hydroxide and preparation method and application thereof |
| CN112142125A (en) * | 2020-09-29 | 2020-12-29 | 山东精工电子科技有限公司 | Method for preparing high-nickel ternary cathode material by secondary growth method |
| CN112366308A (en) * | 2020-11-11 | 2021-02-12 | 江西普瑞美新材料科技有限公司 | Method for rapidly synthesizing nickel-cobalt-manganese positive electrode material precursor |
| CN112366308B (en) * | 2020-11-11 | 2021-12-07 | 江西普瑞美新材料科技有限公司 | Method for rapidly synthesizing nickel-cobalt-manganese positive electrode material precursor |
| CN113299905A (en) * | 2021-05-21 | 2021-08-24 | 湖北融通高科先进材料有限公司 | Preparation method of single crystal nickel cobalt lithium manganate ternary material |
| CN114031126A (en) * | 2021-11-11 | 2022-02-11 | 中物院成都科学技术发展中心 | Manganese-rich carbonate precursor and preparation method thereof |
| CN114645314A (en) * | 2022-03-09 | 2022-06-21 | 中南大学 | Preparation method of single crystal morphology ternary cathode material |
| WO2024103564A1 (en) * | 2022-11-15 | 2024-05-23 | 广东邦普循环科技有限公司 | Method for preparing high-rate single-crystal positive electrode material from gel mixture, and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108172822B (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108172822A (en) | Nickel-cobalt lithium manganate cathode material and preparation method thereof | |
| CN111628157B (en) | Positive electrode material, preparation method thereof and lithium ion battery | |
| CN113955809B (en) | Nickel-cobalt-manganese-lithium aluminate positive electrode material with shell-core structure and preparation method thereof | |
| CN106684369B (en) | Sodium ion battery anode material embedded and coated with sodium fast ion conductor and synthetic method thereof | |
| CN108023078A (en) | A kind of nickelic tertiary cathode material of monocrystalline pattern and preparation method thereof | |
| CN108298599A (en) | The nickelic ternary material precursor of monocrystalline and preparation method, the preparation method of the nickelic ternary material of monocrystalline | |
| CN102623691B (en) | Method for preparing lithium nickel manganese oxide serving as cathode material of lithium battery | |
| CN104300135A (en) | Nickel-rich concentration gradient type lithium nickel cobalt aluminum oxide positive pole material, preparation method thereof and lithium ion battery | |
| CN104810521A (en) | Preparing method of nickel cobalt lithium manganate ternary positive electrode material | |
| CN102646826A (en) | Core-shell lithium manganate composite anode material as well as preparation method and application thereof | |
| CN104916837A (en) | Preparation method of aluminum element doped ternary positive electrode material | |
| CN105958063B (en) | A kind of preparation method of lithium ion battery nickel cobalt aluminium positive electrode | |
| CN110034274B (en) | Modified ternary cathode material, preparation method thereof and lithium ion battery | |
| CN113793927B (en) | Ternary cathode material of lithium ion battery and preparation method thereof | |
| CN110504447A (en) | A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof | |
| CN115498171A (en) | High-nickel ternary cathode material and preparation method and application thereof | |
| CN106684350B (en) | Preparation method of high-voltage positive electrode material lithium nickel manganese oxide | |
| CN105185981B (en) | A kind of LiNixMn2-xO4The preparation method of positive electrode | |
| CN110350171A (en) | A kind of preparation method of the high ni-type tertiary cathode material of rubidium element doping | |
| CN109616652A (en) | Modified complex ternary material and preparation method thereof | |
| CN105489883A (en) | Preparing method for rapidly obtaining ternary anode material of lithium ion battery and anode material | |
| CN111362319B (en) | Method for reducing content of residual lithium on surface of high-nickel ternary nickel cobalt lithium manganate | |
| CN117026359A (en) | Doping modified material, preparation method thereof, single crystal positive electrode material and lithium battery | |
| CN108735981B (en) | Double-conductor modified composite lithium ion battery ternary positive electrode material and preparation method thereof | |
| GB2621290A (en) | Template growth method for preparing lithium cobaltate precursor and use 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 |