CN103296249B - Doping vario-property lithium nickel cobalt manganese, preparation method and lithium ion battery - Google Patents
Doping vario-property lithium nickel cobalt manganese, preparation method and lithium ion battery Download PDFInfo
- Publication number
- CN103296249B CN103296249B CN201310244150.2A CN201310244150A CN103296249B CN 103296249 B CN103296249 B CN 103296249B CN 201310244150 A CN201310244150 A CN 201310244150A CN 103296249 B CN103296249 B CN 103296249B
- Authority
- CN
- China
- Prior art keywords
- nickel cobalt
- cobalt manganese
- lithium nickel
- doping vario
- property
- 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.)
- Active
Links
Classifications
-
- 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
The invention discloses a kind of doping vario-property lithium nickel cobalt manganese, preparation method and lithium ion batteries, the second particle of doping vario-property lithium nickel cobalt manganese is made of primary particle, second particle is spherical or near-spherical, and the surface non-uniform doping of primary particle has nano-metal-oxide layer;Preparation method is to be doped modification to its dopen Nano metal oxide in the precursor synthesis stage of lithium nickel cobalt manganese.Compared with prior art, using lithium ion battery of the doping vario-property lithium nickel cobalt manganese of the present invention as positive electrode active materials, under the conditions of 4.45V high voltage charge and discharge, with good cyclicity and thermal stability, it can effectively meet the requirement of the high-energy density of lithium ion battery, high power density, long life and high security.
Description
Technical field
The invention belongs to field of lithium ion battery, it is more particularly related to a kind of multivariant oxide positive electrode
And preparation method thereof and using above-mentioned material lithium ion battery.
Background technology
Compared with other traditional secondary batteries, lithium ion battery have it is small, voltage is high, specific capacity is big, energy density
Therefore many advantages, such as high, achieves a series of rapid progresses in consumer electronics fields such as mobile phone, laptops.It is adjoint
Smart mobile phone, the development of ultra-thin notebook and energy-accumulating power station, the demand of electric vehicle, people are to the energy of lithium ion battery
Metric density has requirements at the higher level.At present, the method for lithium ion battery energy density is improved mainly by following several：1) battery is improved
Operating voltage, positive electrode active materials is allowed to deviate from more lithium ions and are participated among electrochemical reaction；2) active material is improved
Mass percentage or increase pole piece thickness, to reduce the mass percentage of inert matter；3) nonactive object is reduced
Matter content, such as reduce isolation film, afflux body thickness；4) positive and negative pole material of the exploitation with higher energy density；Etc..
Many research institutions and enterprise have all been placed on more long-range sight on the voltage for improving material one after another.It is numerous just
In the material of pole, the ternary material LiNi of layer structure1/3Co1/3Mn1/3O2Due to discharge capacity height, having a safety feature, structure
The characteristics of stable, at low cost, it is considered to be one of optimal selection of following anode material for lithium-ion batteries.However, in high voltage
Application process in, LiNi1/3Co1/3Mn1/3O2The presence of surface defect and the strong oxygen of tetravalent Ni, Co, Mn
The property changed aggravates the side reaction of itself and electrolyte, so that contact interface structure is readily broken, transition metal Ni, Mn, Co etc. will
It dissolves out and deposits to anode, the internal resistance of cell is caused to increase, the circulation volume failure of battery is serious；On the other hand, height takes off lithium state
Tertiary cathode material LiNi1/3Co1/3Mn1/3O2It is very unstable in the catalysis lower surface configuration of electrolyte, when running into extruding or high temperature
It is easy to oxygen release and with exothermic phenomenon, is easy to cause battery core thermal runaway, the deterioration of safety of battery.
To solve the above-mentioned problems, LiNi is improved1/3Co1/3Mn1/3O2Performance, most of research at this stage all concentrates on
Ternary material is carried out on bulk phase-doped and surface doping.Existing research shows with Al parts substitution ternary material LiNi1/ 3Co1/3Mn1/3O2In Co elements, the higher material LiNi of thermal stability can be obtained1/3Mn1/3Co(1/3-z)AlzO2, but as z ＞
The gram volume of material will be substantially reduced when 0.1.In addition, there are other researchs that distinct methods are also respectively adopted to tertiary cathode material
Expect surface modification Al2O3And other oxide materials.The result shows that the high voltage cycle capacity of material after doping to battery
Conservation rate plays apparent improvement result really.But these methods there is it is certain the defects of：On the one hand, it is nonactive
The bulk phase-doped capacitance loss that can cause battery of material element；On the other hand, in order to improve the high rate performance of battery and technique
Performance, tertiary cathode material mostly using spherical or spherical second particle, so either in presoma surface doping or
Finished surface adulterates, and can only all be entrained in the surface of second particle, and the primary particle inside second particle is not protected but
Shield is got up, since the surface of second particle can touch electrolyte, the material after doping in charge and discharge process
Cycling and the demand for security of battery can not be met at a higher voltage.
In view of this, a kind of the polynary of cycle performance of battery and thermal stability is not influenced under high pressure it is necessory to provide
Oxide anode material.
The content of the invention
It is an object of the invention to：There is provided one kind does not influence cycle performance of battery and thermal stability under 4.45V high pressures
Multivariant oxide positive electrode and preparation method thereof and the lithium ion battery using the material.
In order to realize foregoing invention purpose, present inventor provides a kind of doping vario-property lithium by further investigation
Nickel cobalt manganese, second particle are made of primary particle, the second particle be spherical or near-spherical, the surface of the primary particle
Non-uniform doping has a nano-metal-oxide layer, and the nano oxide layer includes being entrained in once by nano-metal-oxide
The metal-doped layer that the superficial layer of grain is formed and the metal oxide nano particles being attached to outside metal-doped layer.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese of the present invention, the average-size of the primary particle is 0.5~3 μ
M, the average grain diameter of second particle is 7~25 μm.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese of the present invention, the nano metal oxygen of the primary particle surface doping
The thickness of compound layer is 0.1~5 μm.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese of the present invention, the nano metal for being entrained in primary particle surface
Oxide is MgO, Al2O3、CaO、SiO2、ZrO2、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese of the present invention, the molecular formula of the doping vario-property lithium nickel cobalt manganese is
LiNixCoyMn1-x-yMδO2, wherein x, y, δ meet the following conditions：0<x<1,0<y<1,0<1-x-y<1,0.001<δ<0.1, preferably
For x=y=1-x-y=1/3；M is one or more of Al, Ti, Mg, Ca, Si, Zr, Zn, Sn, B, Bi.
The present invention also provides a kind of method for preparing doping vario-property lithium nickel cobalt manganese described in any of the above-described paragraph, including following
Step：
1) prepared by presoma：Presoma is prepared using coprecipitation, by water-soluble metal nickel salt, cobalt salt and manganese salt by predetermined
Ni, Co, Mn molar ratio be made into the mixed solution of suitable concentration, then with different speed together with precipitating reagent, pattern controlling agent
Rate is added drop-wise in reaction vessel simultaneously, the pH value and reaction temperature of control system, in reaction initial period or in the process with appropriate
Speed be added dropwise nano-metal-oxide dispersion liquid, react a period of time after, it is filtered, washing, vacuum drying, obtain nanometer
Presoma (the Ni that doped metallic oxide is modifiedxCoyMn1-x-y)(OH)2/MOz(value of z is determined by the chemical valence of M)；
2) calcine：The precursor powder of nano-metal-oxide doping vario-property is placed in air atmosphere and is roasted；
3) it is made：By the precursor powder after calcining, ball milling mixes by a certain percentage with lithium salts powder, high-temperature calcination
Obtain the modification LiNi of layered crystal structurexCoyMn1-x-yMδO2；
In above-mentioned steps, x, y, δ, z meet the following conditions：0<x<1,0<y<1,0<1-x-y<1,0.001<δ<0.1.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese preparation method of the present invention, the modified LiNixCoyMn1-x-yMδO2
In x, y value be x=1/3, y=1/3；X=0.5, y=0.2；X=0.4, y=0.4；X=0.8, y=0.1；X=0.4, y=
Any one in 0.2, by invention material to be used under the high voltage of 4.45V, and LiNi1/3Co1/3Mn1/3O2Body
Phase structure is more stablized, and has certain anti-high pressure ability, so preferably x=1/3, y=1/3.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese preparation method of the present invention, the water-soluble metal in the step 1)
Nickel salt, cobalt salt and manganese salt are corresponding sulfate, nitrate, acetate, any combination of chlorate；The precipitating reagent is hydrogen-oxygen
Change one or more of sodium solution, potassium hydroxide solution, lithium hydroxide solution；The pattern controlling agent for ammonium hydroxide, ammonium chloride,
One or more of urea and ammonium hydrogen carbonate.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese preparation method of the present invention, the soluble metal in the step 1)
The concentration of nickel cobalt manganese mixed salt solution is 0.2-3.5mol/L, is preferably 0.5-2.0mol/L；Ni, Co, Mn in mixed solution
Molar ratio is 1:1:1、5:2:3、4:4:2、8:1:Any one in 1 is preferably 1:1:1；The concentration of the precipitating reagent is 3-
7mol/L, the concentration of pattern controlling agent is 2-8mol/L；The pH value range of system is 10.5-11.5, reaction temperature 40-60
℃.Its reason is：In this pH and temperature range, Ni, Co, Mn can homogeneous precipitation, and then the other mixing of molecular level；More
It is important that with this condition, crystallization rate is controllable, nanometer oxide particle can be with uniform adsorption in Ni, Co, Mn hydroxide
The surface of crystallization, ultimately forms target product.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese preparation method of the present invention, the nanogold of the middle addition of the step 1)
The mass concentration for belonging to oxidate dispersion solution is 0.01-10%.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese preparation method of the present invention, the presoma in the step 1)
(NixCoyMn1-x-y)(OH)2/MOz, metallic element and the molar ratio of nickel cobalt manganese summation in dopen Nano metal oxide are
0.001-0.1 is preferably 0.005-0.02.Its reason is：If incorporation is excessively high, nano-particle is easily in persursor material table
Dough gathers, and influences the capacity and high rate performance of material after activation.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese preparation method of the present invention, the roasting in the step 2) is in horse
It is not carried out in stove, calcination temperature is 400-600 DEG C, time 5-10h.This is because if temperature is excessively high or overlong time, mix
Miscellaneous depth is too deep, is unable to reach the purpose of surface doping.
As a kind of improvement of doping vario-property lithium nickel cobalt manganese preparation method of the present invention, the lithium salts in the step 3) is carbonic acid
One or more of lithium, lithium hydroxide, lithium acetate.
The present invention also provides a kind of lithium ion batteries, including positive plate, negative plate, electrolyte and are interval in positive and negative anodes
Isolation film between piece, the positive plate include positive electrode, contain the nanogold described in any of the above-described paragraph in positive electrode
Belong to oxide doped and modified lithium nickel cobalt manganese.
The present invention is in synthesis of ternary positive electrode material precursor (NixCoyMn1-x-y)(OH)2While, after surface treatment
Nanometer oxide particle is added thereto simultaneously, since nanometer oxide particle has high surface can, it is easy to adsorb compared with
The grain surface of macrocrystalline hydroxide precursor；Moreover, with unmodified positive electrode Li (NixCoyMn1-x-y)O2It compares,
Presoma (Ni of the present invention after nano-metal-oxide adulteratesxCoyMn1-x-y)(OH)2, in mixed lithium calcination activation into Li
(NixCoyMn1-x-y)O2Afterwards, there is following distinguishing feature：A nanometer oxide particle part for doping can enter Li
(NixCoyMn1-x-y)O2Play the role of stable crystal surface texture inside nucleus, inhibit material phase during high voltage cycle
Become and so on；The nano-metal-oxide of another part doping can be played with forming doping transition zone in material superficial layer
The effect of hydrofluoric acid depleting agents and protective film effectively reduces corrosion and destruction of the electrolyte middle acid substance to positive electrode,
Oxidation of the positive electrode in Xun Huan and thermal runaway to electrolyte is inhibited, improves the stable circulation of material at higher voltages
Property and cycle life.
Description of the drawings
Below in conjunction with the drawings and specific embodiments to doping vario-property lithium nickel cobalt manganese of the present invention, preparation method and lithium-ion electric
Pond is further elaborated.
Fig. 1 is the structure diagram of nano-metal-oxide doping vario-property lithium nickel cobalt manganese of the present invention.
Fig. 2 is the DSC curve of comparative example 1 of the present invention and embodiment 3.
Fig. 3 is the DSC curve of the embodiment of the present invention 5~8.
Specific embodiment
Referring to Fig. 1, be the structure diagram of doping vario-property lithium nickel cobalt manganese of the present invention, wherein, 10 be pure phase ternary material,
12 be M metal-doped layers, and 14 be doping particle MOz。
In order to which the goal of the invention, technical solution and the advantageous effects that make the present invention become apparent from, with reference to embodiments
The present invention is described in further detail with attached drawing, however, it should be understood that the embodiment of the present invention is just for the sake of this hair of explanation
It is bright, the limitation present invention is not intended to, and the embodiment of the present invention is not limited to the embodiment provided in specification.
Embodiment 1
1) molecular formula Li (Ni are pressed1/3Co1/3Mn1/3)O2The ratio of middle transition metal prepares NiSO4、CoSO4、MnSO41:
1:1 mixed aqueous solution makes concentration cationic in mixed solution for 2mo1/L, and is added drop-wise to reaction vessel with the speed of 0.2L/h
In；
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits are added drop-wise to together with mixed solution in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice Al2O3Aqueous dispersions, addition is Al elements and the molar ratio of Ni, Co, Mn element summation is 0.001:After 1, the reaction was continued 4h
Stop charging, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nanometer Al2O3Modified
Nickel cobalt manganese hydroxide precursor powder；
3) modified powder that step 2) obtains is placed in 500 DEG C of roasting 5h in the Muffle furnace of air atmosphere；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
Rice Al2O3Modified LiNi1/3Co1/3Mn1/3Al0.001O2Particle.
Using the distribution of particles of laser particle analyzer characterization powder, using SEM and the microscopic appearance of tem observation powder, obtain
The average second particle size of modified lithium nickel cobalt manganese is 9.329 μm, and primary particle size is about 0.6 μm, adulterates layer thickness
About 0.2 μm.
Embodiment 2
Step 1), 3) with embodiment 1, it is step 2), 4) as follows：
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits are added drop-wise to together with mixed solution in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice Al2O3Aqueous dispersions, addition is Al elements and the molar ratio of Ni, Co, Mn element summation is 0.005:After 1, the reaction was continued 8h
Stop charging, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nanometer Al2O3Modified
Nickel cobalt manganese hydroxide precursor powder；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
Rice Al2O3Modified LiNi1/3Co1/3Mn1/3Al0.005O2Particle.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 8.842 μm, and primary particle size is about
0.5μm。
Embodiment 3
Step 1), 3) with embodiment 1, it is step 2), 4) as follows：
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits are added drop-wise to together with mixed solution in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice Al2O3Aqueous dispersions, addition is Al elements and the molar ratio of Ni, Co, Mn element summation is 0.01:After 1, the reaction was continued 8h
Stop charging, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nanometer Al2O3Modified
Nickel cobalt manganese hydroxide precursor powder；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
Rice Al2O3Modified LiNi1/3Co1/3Mn1/3Al0.01O2Particle.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 8.983 μm, and primary particle size is about
1μm。
Embodiment 4
Step 1), 3) with embodiment 1, it is step 2), 4) as follows：
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits are added drop-wise to together with mixed solution in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice Al2O3Aqueous dispersions, addition is Al elements and the molar ratio of Ni, Co, Mn element summation is 0.02:After 1, the reaction was continued 8h
Stop charging, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nanometer Al2O3Modified
Nickel cobalt manganese hydroxide precursor powder；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
Rice Al2O3Modified LiNi1/3Co1/3Mn1/3Al0.02O2Particle.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 9.813 μm, and primary particle size is about
1.5μm。
Embodiment 5
Step 1), 3) with embodiment 1, it is step 2), 4) as follows：
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits and mixed solution are added drop-wise to jointly in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice MgO aqueous dispersions, addition is Mg elements and the molar ratio of Ni, Co, Mn element summation is 0.01:Stop after 1, the reaction was continued 8h
Only feed, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nickel cobalt that the nano-MgO is modified
Manganese hydroxide precursor powder；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
LiNi modified rice MgO1/3Co1/3Mn1/3Mg0.01O2Particle.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 9.07 μm, and primary particle size is about
1.5μm。
Embodiment 6
Step 1), 3) with embodiment 1, it is step 2), 4) as follows：
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits and mixed solution are added drop-wise to jointly in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice TiO2Aqueous dispersions, addition is Ti elements and the molar ratio of Ni, Co, Mn element summation is 0.01:After 1, the reaction was continued 8h
Stop charging, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nano-TiO2Modified
Nickel cobalt manganese hydroxide precursor powder；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
Rice TiO2Modified LiNi1/3Co1/3Mn1/3Ti0.01O2Particle.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 9.854 μm, and primary particle size is about
2μm。
Embodiment 7
Step 1), 3) with embodiment 1, it is step 2), 4) as follows：
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits and mixed solution are added drop-wise to jointly in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice ZrO2Aqueous dispersions, addition is Zr elements and the molar ratio of Ni, Co, Mn element summation is 0.01:After 1, the reaction was continued 8h
Stop charging, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nanometer ZrO2Modified
Nickel cobalt manganese hydroxide precursor powder；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
Rice ZrO2Modified LiNi1/3Co1/3Mn1/3Zr0.01O2Particle.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 9.789 μm, and primary particle size is about
1μm。
Embodiment 8
Step 1), 3) with embodiment 1, it is step 2), 4) as follows：
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits and mixed solution are added drop-wise to jointly in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；After reacting 12h, it is 1% to receive to add in mass fraction by certain flow rate
Rice Bi2O3Aqueous dispersions, addition is Bi elements and the molar ratio of Ni, Co, Mn element summation is 0.005:After 1, the reaction was continued 8h
Stop charging, and be aged 2 it is small when, after filtered, washing and 120 DEG C of vacuum drying 8h, obtain the nanometer Bi2O3Modified
Nickel cobalt manganese hydroxide precursor powder；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
Be placed in the sintering furnace of air atmosphere, with 900 DEG C sintering 20h after, ground sub-sieve be can obtain layered crystal structure through receiving
Rice Bi2O3Modified LiNi1/3Co1/3Mn1/3Bi0.01O2Particle.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 9.606 μm, and primary particle size is about
2μm。
Comparative example 1
1) molecular formula Li (Ni are pressed1/3Co1/3Mn1/3)O2The ratio of middle transition metal prepares NiSO4、CoSO4、MnSO41:
1:1 mixed aqueous solution makes concentration cationic in mixed solution for 2mo1/L, and is added drop-wise to reaction vessel with the speed of 0.2L/h
In；
2) 2mol/L NaOH solutions, 3mol/L ammonia spirits and mixed solution are added drop-wise to jointly in reaction vessel, controlled
System pH is 11.0 ± 0.2, and heating water bath is to 50 DEG C；Stop charging after reacting 16h, and be aged 2h, after filtered, washing,
In 120 DEG C of drying boxes the hydroxide precursor powder of the material is obtained after dry 8h；
3) powder that step 2) obtains is placed in Muffle furnace, in 500 DEG C of pre-burning 5h, sloughs residual moisture and part lattice
Water；
4) by the precursor powder and Li after calcining2CO3Li/ (Ni+Co+Mn)=1.05 in molar ratio：1 is uniformly mixed, and
It is placed in the sintering furnace of air atmosphere, after 900 DEG C of sintering 20h, ground sub-sieve obtains the pure phase Li of layered crystal structure
(Ni1/3Co1/3Mn1/3)O2Granular product.
By characterization, the average second particle size of modified lithium nickel cobalt manganese is 9.329 μm, and primary particle size is about
0.4μm。
Chemical property is analyzed：
Using the granular product synthesized in comparative example 1 and Examples 1 to 8 as positive electrode active materials sample, respectively with
Conductive carbon, binding agent Kynoar (PVDF) press 90:5:5 mass ratio mixes in N-Methyl pyrrolidone (NMP) solvent
It closes, 12h is stirred under room temperature, scraper is coated on the Al paper tinsel collectors that thickness is 16 μm, and 120 DEG C of vacuum drying 12h are cold-pressed backlash
Into the disk of a diameter of 14.0mm, cathode uses the metal lithium sheet of diameter 15.0mm, and electrolyte uses 1mol/L LiPF6、EC/
EMC=3:7 (V/V), isolation film use polypropylene (PP), are assembled in glove box and obtain CR2430 button cells, detained in LAND
Related electrochemical property test is carried out to it on formula cell tester.
Constant-current charge, charge cutoff voltage 4.45V, 4.45V constant-voltage charge are carried out with the current density of 0.1C to battery
It is 0.05C to current density, then with the current density constant-current discharge of 0.1C to 3.0V, is followed by above-mentioned flow button type battery
Ring test obtains the cycle performance of synthesized each active material.
The gram volume and Xun Huan conservation rate that table 1, comparative example 1 are played with the ternary material synthesized in Examples 1 to 4
Table 1 give with comparative example 1 and Examples 1 to 4 do positive electrode active materials battery discharge capacity for the first time and follow
Capacity retention ratio after ring 50 times.The result shows that when the ratio for mixing nano aluminium oxide is more than 0.01, discharge capacity starts
Now it is substantially reduced；When doping ratio is 0.005, Xun Huan conservation rate is significantly improved compared with comparative example 1.
Table 2 gives the capacity retention ratio after the discharge capacity for the first time of comparative example 1 and embodiment 5~8 and cycle 50 times.Knot
Fruit shows to compare same amount, wherein different types of oxide modifying, TiO2Modification can be obviously improved under 4.45V Xun Huans
Capacity retention ratio.
The gram volume and Xun Huan conservation rate that table 2, comparative example 1 are played with the ternary material synthesized in embodiment 5~8
Thermal stability analysis：
The button cell that material of the comparative example 1 with embodiment 2,5~8 will be used to make, is carried out with the current density of 0.1C
Constant-current charge, charge cutoff voltage 4.45V, 4.45V constant-voltage charge to current density be 0.05C, after in glove box by electricity
Pond is disassembled, and is taken out anode pole piece, is injected a certain amount of fresh electrolyte, is combined with Netzsch STA449F3-QMS403C caloics
Anode pole piece and the exotherm of electrolyte reaction are completely filled in instrument test, as a result as shown in Figures 2 and 3.From the DSC curve in figure
As can be seen that it is modified through nano-oxide, 300 DEG C or so of exothermic peak to high temperature can be elapsed, reduce rate of heat release, carry
High thermal stability between material and electrolyte.
It should be noted that although above-described embodiment 1~8 is only with Li (Ni1/3Co1/3Mn1/3)O2Modification exemplified by this hair
It is bright to illustrate, but the preparation method of the present invention is used to prepare other x, y and meets 0<x<1,0<y<During 1 ternary material, together
Sample can obtain similar effect, and details are not described herein again.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in specific embodiment disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In used some specific terms, but these terms are merely for convenience of description, do not limit the present invention in any way.
Claims (16)
1. a kind of doping vario-property lithium nickel cobalt manganese, second particle are made of primary particle, the second particle is spherical or class ball
Shape, it is characterised in that：The surface non-uniform doping of the primary particle has nano-metal-oxide layer, the nano oxide layer
The metal-doped layer that is formed including the superficial layer that primary particle is entrained in by nano-metal-oxide and it is attached to metal-doped layer
Outer metal oxide nano particles；The molecular formula of the doping vario-property lithium nickel cobalt manganese is LiNixCoyMn1-x-yMδO2, wherein x,
Y, δ meets the following conditions：0<x<1,0<y<1,0<1-x-y<1,0.001<δ<0.1；M for Al, Ti, Mg, Ca, Si, Zr, Zn, Sn,
B, one or more of Bi.
2. doping vario-property lithium nickel cobalt manganese according to claim 1, it is characterised in that：The average-size of the primary particle is
0.5~3 μm, the average grain diameter of second particle is 7~25 μm.
3. doping vario-property lithium nickel cobalt manganese according to claim 1, it is characterised in that：The primary particle surface doping is received
The thickness of rice metal oxide layer is 0.1~5 μm.
4. doping vario-property lithium nickel cobalt manganese according to claim 1, it is characterised in that：The primary particle surface of being entrained in
Nano-metal-oxide is MgO, Al2O3、CaO、SiO2、ZrO2、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of.
5. doping vario-property lithium nickel cobalt manganese according to claim 1, it is characterised in that：Point of the doping vario-property lithium nickel cobalt manganese
Minor LiNixCoyMn1-x-yMδO2In x=y=1-x-y=1/3.
A kind of 6. method of the doping vario-property lithium nickel cobalt manganese prepared any one of claim 1 to 5, which is characterized in that bag
Include following steps：
1) prepared by presoma：Presoma is prepared using coprecipitation, by water-soluble metal nickel salt, cobalt salt and manganese salt by predetermined
Ni, Co, Mn molar ratio are made into the mixed solution of suitable concentration, then with different rates together with precipitating reagent, pattern controlling agent
It is added drop-wise to simultaneously in reaction vessel, the pH value and reaction temperature of control system, in reaction initial period or in the process with appropriate
The dispersion liquid of nano-metal-oxide is added dropwise in speed, and after reacting a period of time, filtered, washing, vacuum drying obtain nanogold
Belong to oxide doped and modified presoma (NixCoyMn1-x-y)(OH)2/MOz；
2) calcine：The precursor powder of nano-metal-oxide doping vario-property is placed in air atmosphere and is roasted；
3) it is made：By the precursor powder after calcining, ball milling mixes by a certain percentage with lithium salts powder, and high-temperature calcination obtains
The modification LiNi of layered crystal structurexCoyMn1-x-yMδO2；
In above-mentioned steps, x, y, δ, z meet the following conditions：0<x<1,0<y<1,0<1-x-y<1,0.001<δ<0.1.
7. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 6, it is characterised in that：The modification
LiNixCoyMn1-x-yMδO2In x, y value be x=1/3, y=1/3；X=0.5, y=0.2；X=0.4, y=0.4；X=0.8, y
=0.1；Any one in x=0.4, y=0.2.
8. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 6, it is characterised in that：In the step 1)
Water-soluble metal nickel salt, cobalt salt and manganese salt are corresponding sulfate, nitrate, acetate, any combination of chlorate；It is described heavy
Shallow lake agent is one or more of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution；The pattern controlling agent is ammonia
One or more of water, ammonium chloride, urea and ammonium hydrogen carbonate.
9. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 6, it is characterised in that：In the step 1)
The concentration of soluble metal nickel cobalt manganese mixed salt solution is 0.2-3.5mol/L；The molar ratio of Ni, Co, Mn are 1 in mixed solution:
1:1、5:2:3、4:4:2、8:1:Any one in 1；The concentration of the precipitating reagent be 3-7mol/L, the concentration of pattern controlling agent
For 2-8mol/L；The pH value range of system is 10.5-11.5, and reaction temperature is 40-60 DEG C.
10. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 9, it is characterised in that：In the step 1)
Soluble metal nickel cobalt manganese mixed salt solution concentration be 0.5-2.0mol/L.
11. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 6, it is characterised in that：In the step 1)
The mass concentration of the nano-metal-oxide dispersion liquid of addition is 0.01-10%.
12. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 6, it is characterised in that：In the step 1)
Presoma (NixCoyMn1-x-y)(OH)2/MOz, metallic element in dopen Nano metal oxide rubs with nickel cobalt manganese summation
You are than being 0.001-0.1.
13. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 12, it is characterised in that：In the step 1)
Presoma (NixCoyMn1-x-y)(OH)2/MOz, metallic element in dopen Nano metal oxide rubs with nickel cobalt manganese summation
You are than being 0.005-0.02.
14. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 6, it is characterised in that：In the step 2)
Roasting be to be carried out in Muffle furnace, calcination temperature be 400-600 DEG C, time 5-10h.
15. the preparation method of doping vario-property lithium nickel cobalt manganese according to claim 6, it is characterised in that：In the step 3)
Lithium salts be lithium carbonate, lithium hydroxide, one or more of lithium acetate.
16. a kind of lithium ion battery, including positive plate, negative plate, electrolyte and the isolation being interval between positive/negative plate
Film, the positive plate include positive electrode, it is characterised in that：Contain any one of claim 1 to 5 institute in the positive electrode
The nano-metal-oxide doping vario-property lithium nickel cobalt manganese stated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310244150.2A CN103296249B (en) | 2013-06-19 | 2013-06-19 | Doping vario-property lithium nickel cobalt manganese, preparation method and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310244150.2A CN103296249B (en) | 2013-06-19 | 2013-06-19 | Doping vario-property lithium nickel cobalt manganese, preparation method and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103296249A CN103296249A (en) | 2013-09-11 |
| CN103296249B true CN103296249B (en) | 2018-05-29 |
Family
ID=49096799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310244150.2A Active CN103296249B (en) | 2013-06-19 | 2013-06-19 | Doping vario-property lithium nickel cobalt manganese, preparation method and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103296249B (en) |
Families Citing this family (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI634695B (en) | 2013-03-12 | 2018-09-01 | 美商蘋果公司 | High voltage, high volumetric energy density li-ion battery using advanced cathode materials |
| CN103441255B (en) * | 2013-09-16 | 2017-02-01 | 宁德新能源科技有限公司 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN103490051B (en) * | 2013-09-18 | 2015-10-28 | 成都晶元新材料技术有限公司 | One is applicable to high-tension multielement cathode lithium electric material and preparation method thereof |
| CN104716315A (en) * | 2013-12-16 | 2015-06-17 | 青岛乾运高科新材料股份有限公司 | Preparation method of lithium ion batteries cathode material solid solution with core-shell structure |
| CN103682316B (en) * | 2013-12-20 | 2016-01-13 | 哈尔滨工业大学 | The preparation method of long-life, high-capacity lithium ion cell tertiary cathode material |
| CN103682319A (en) * | 2013-12-26 | 2014-03-26 | 兰州金里能源科技有限公司 | Constant high temperature circulation NCM 523 (nickel cobalt manganese acid lithium) ternary material and preparation method thereof |
| CN104201366B (en) * | 2014-01-10 | 2017-01-04 | 兰州金里能源科技有限公司 | A kind of preparation method of high security high compacted density nickle cobalt lithium manganate NCM523 ternary material |
| CN103825015B (en) * | 2014-01-10 | 2016-09-07 | 兰州金里能源科技有限公司 | The preparation method of high compacted density nickle cobalt lithium manganate NCM523 ternary material |
| CN103855387A (en) * | 2014-03-25 | 2014-06-11 | 海宁美达瑞新材料科技有限公司 | Modified lithium ion battery ternary positive electrode material and preparation method thereof |
| JP2016033902A (en) * | 2014-07-31 | 2016-03-10 | ソニー株式会社 | Positive electrode active material, positive electrode and battery |
| US9716265B2 (en) | 2014-08-01 | 2017-07-25 | Apple Inc. | High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries |
| JP6655282B2 (en) * | 2014-12-02 | 2020-02-26 | ユミコア | Method for producing nickel-lithium metal composite oxide, nickel-lithium metal composite oxide obtained by the production method, and positive electrode active material comprising the same |
| US10297821B2 (en) | 2015-09-30 | 2019-05-21 | Apple Inc. | Cathode-active materials, their precursors, and methods of forming |
| CN105489856A (en) * | 2015-11-28 | 2016-04-13 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method for zinc oxide-coated lithium nickel manganese cobalt positive electrode material |
| CN105449195B (en) * | 2015-12-28 | 2018-01-30 | 哈尔滨工业大学 | A kind of precursor of lithium ionic cell positive material for interting structure and micron order primary particle with nanotube/rod and preparation method thereof |
| US20180114983A9 (en) | 2016-03-14 | 2018-04-26 | Apple Inc. | Cathode active materials for lithium-ion batteries |
| CN109715561B (en) | 2016-09-20 | 2020-09-22 | 苹果公司 | Cathode active material having improved particle morphology |
| KR102223565B1 (en) * | 2016-09-21 | 2021-03-04 | 애플 인크. | Surface-stabilized cathode material for lithium-ion battery and method for its synthesis |
| CN106410137A (en) * | 2016-09-30 | 2017-02-15 | 江苏翔鹰新能源科技有限公司 | Nanometer silicon carbide coated lithium nickel manganese cobalt cathode material and preparation method thereof |
| CN107302088A (en) * | 2017-06-16 | 2017-10-27 | 惠州亿纬锂能股份有限公司 | A kind of preparation method of anode material for lithium-ion batteries, positive electrode and lithium ion battery |
| CN107579242B (en) * | 2017-08-31 | 2020-09-25 | 福建师范大学 | Method for preparing trivalent cation doped nickel-cobalt-manganese ternary material by direct precipitation |
| CN109004175B (en) * | 2018-02-26 | 2020-09-18 | 宁德新能源科技有限公司 | Positive pole piece and lithium ion battery |
| US11695108B2 (en) | 2018-08-02 | 2023-07-04 | Apple Inc. | Oxide mixture and complex oxide coatings for cathode materials |
| US11749799B2 (en) | 2018-08-17 | 2023-09-05 | Apple Inc. | Coatings for cathode active materials |
| CN109346719B (en) * | 2018-11-09 | 2020-12-01 | 浙江德升新能源科技有限公司 | Method for preparing modified nickel cobalt lithium manganate positive electrode material by aid of additive addition method |
| CN109786689A (en) * | 2018-12-21 | 2019-05-21 | 厦门韫茂科技有限公司 | Anode material of lithium battery presoma, preparation, processing and doping type anode material of lithium battery with film nuclear structure |
| CN111384377B (en) | 2018-12-29 | 2021-09-17 | 宁德时代新能源科技股份有限公司 | Positive electrode material and preparation method and application thereof |
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
| CN112072079A (en) * | 2019-06-10 | 2020-12-11 | 中国科学院物理研究所 | Lithium ion battery positive electrode material and preparation method and application thereof |
| CN110350239A (en) * | 2019-07-08 | 2019-10-18 | 无锡市明杨新能源有限公司 | High magnification lithium ion battery with high energy density |
| US11757096B2 (en) | 2019-08-21 | 2023-09-12 | Apple Inc. | Aluminum-doped lithium cobalt manganese oxide batteries |
| CN112447952B (en) * | 2019-09-02 | 2022-01-28 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof, positive pole piece and lithium ion secondary battery |
| CN112510194B (en) * | 2019-09-16 | 2022-04-15 | 惠州比亚迪实业有限公司 | Ternary cathode material of lithium ion battery, preparation method of ternary cathode material and lithium ion battery |
| CN111326730B (en) * | 2019-12-31 | 2021-08-17 | 广东工业大学 | Surface layer gradient doped lithium-rich layered oxide cathode material and preparation method and application thereof |
| CN111370681B (en) * | 2020-03-20 | 2021-06-01 | 宁德新能源科技有限公司 | Positive electrode active material, electrochemical device, and electronic device |
| CN112794370B (en) * | 2020-12-18 | 2022-02-11 | 北京当升材料科技股份有限公司 | Doped positive electrode material precursor, preparation method and application thereof, doped positive electrode material, preparation method and application thereof |
| CN113258056A (en) * | 2021-04-26 | 2021-08-13 | 浙江帕瓦新能源股份有限公司 | Dual-modified lithium ion battery anode material precursor and anode material |
| CN113328089A (en) * | 2021-06-25 | 2021-08-31 | 骆驼集团资源循环襄阳有限公司 | Boron-doped modified ternary cathode material and preparation method thereof |
| CN113445127B (en) * | 2021-06-28 | 2022-07-15 | 中南大学 | Composite metal oxide doped anode material, preparation method thereof and lithium ion battery |
| KR20230117624A (en) * | 2021-09-28 | 2023-08-08 | 닝더 엠프렉스 테크놀로지 리미티드 | Electrochemical devices and electrical equipment including the electrochemical devices |
| WO2023108361A1 (en) * | 2021-12-13 | 2023-06-22 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN114560510B (en) * | 2022-01-25 | 2023-10-24 | 合肥融捷能源材料有限公司 | Modified 7-series ternary cathode material and preparation method and application thereof |
| CN114481322B (en) * | 2022-03-02 | 2023-07-21 | 湖南长远锂科新能源有限公司 | Spherical-like single crystal positive electrode material and preparation method thereof |
| CN115050937A (en) * | 2022-06-13 | 2022-09-13 | 天津巴莫科技有限责任公司 | Lithium ion battery anode material and preparation method thereof |
| CN116565212A (en) * | 2023-07-11 | 2023-08-08 | 宁德时代新能源科技股份有限公司 | Composite positive electrode material, preparation method thereof, battery and power utilization device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101897061A (en) * | 2007-12-12 | 2010-11-24 | 尤米科尔公司 | Homogeneous nanoparticle core doping of cathode material precursors |
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031715A1 (en) * | 2007-09-06 | 2009-03-12 | Canon Kabushiki Kaisha | Method for producing lithium ion storage/release material, lithium ion storage/release material, electrode structure using the material, and electricity storage device |
| EP2065887A1 (en) * | 2007-11-30 | 2009-06-03 | Hitachi Global Storage Technologies Netherlands B.V. | Method for manufacturing magnetic disk unit |
| CN101944610B (en) * | 2009-07-09 | 2013-08-28 | 河南新飞科隆电源有限公司 | Preparation of stratified lithium ion anode material |
| JP2012113823A (en) * | 2010-11-19 | 2012-06-14 | Nippon Chem Ind Co Ltd | Positive electrode active material for lithium secondary battery, method for manufacturing the same and lithium secondary battery |
| CN102509790B (en) * | 2011-10-20 | 2014-02-12 | 四川天齐锂业股份有限公司 | LiFePO4 (lithium iron phosphate) positive electrode material with specific morphology and structure and lithium secondary battery |
-
2013
- 2013-06-19 CN CN201310244150.2A patent/CN103296249B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101897061A (en) * | 2007-12-12 | 2010-11-24 | 尤米科尔公司 | Homogeneous nanoparticle core doping of cathode material precursors |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103296249A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103296249B (en) | Doping vario-property lithium nickel cobalt manganese, preparation method and lithium ion battery | |
| CN101855755B (en) | Li-Ni-based composite oxide particle powder for rechargeable battery with nonaqueous elctrolyte, process for producing the powder, and rechargeable battery with nonaqueous electrolyte | |
| CN103178258B (en) | Alumina-coated is modified the preparation method of lithium nickel cobalt manganese oxygen positive electrode | |
| CN108091843B (en) | Lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof | |
| CN104979546B (en) | Preparation method of single-crystal-morphology lithium ion battery ternary cathode material | |
| CN103779554B (en) | Modification lithium ion battery with high energy density positive electrode and preparation method thereof | |
| CN102306779B (en) | Lithium ion battery positive electrode material lithium-enriched doped lithium molybdate and preparation method thereof | |
| CN104134790B (en) | A kind of nickle cobalt lithium manganate is material modified and preparation method thereof and application | |
| CN107591519A (en) | Modified lithium nickel cobalt manganese positive electrode material and preparation method thereof | |
| CN105870438B (en) | A kind of lithium secondary battery lithium-rich anode composite material and preparation method | |
| CN106684323A (en) | Ternary lithium-ion battery cathode material improved by active oxide multiply and preparation method thereof | |
| CN108598466A (en) | A kind of preparation method for the nickel-cobalt-manganese ternary material for making constituent content distribution gradient | |
| CN103151511A (en) | Positive active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive active material | |
| CN109256531A (en) | Doping cobalt acid lithium and its preparation method and application with compound coating layer | |
| CN103311513A (en) | High-performance layered solid-solution lithium-battery positive material and preparation method thereof | |
| CN102244260A (en) | Composite metallic-oxide-cladded lithium nickel cobalt manganese oxide anode material and preparation method thereof | |
| CN103000903B (en) | Precursor doped with carbon nanomaterial and preparation method thereof as well as spherical lithium metal oxide anode material and preparation method thereof | |
| CN102208611A (en) | Induced crystallization synthesis method for anode powder material of lithium ion secondary battery | |
| CN106299255B (en) | A kind of preparation method of big partial size spinel-type nickel ion doped | |
| CN109841822A (en) | A kind of preparation method of the modified monocrystalline tertiary cathode material of lithium ion battery | |
| CN109888204A (en) | A kind of lithium battery composite positive pole and the preparation method and application thereof | |
| WO2019041788A1 (en) | Core-shell material | |
| CN113889603A (en) | Sodium ion battery positive electrode material and preparation method thereof | |
| CN101872859A (en) | Lithium cobaltate composite oxide coated by hydrolytic precipitation-roasting method and manufacturing method thereof | |
| CN105826550A (en) | Preparation method of lithium manganate cathode material with ferri-containing compound coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |