CN106711436A - Lithium-rich manganese-based anode material and preparation method thereof - Google Patents
Lithium-rich manganese-based anode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium-rich manganese-based anode material and a preparation method thereof. The lithium-rich manganese-based anode material comprises a lithium-rich manganese-based core material and a coating material coating the core material. The core material has chemical compositions meeting the general formula, namely Li1+xMyO2, wherein M is one or more of manganese, nickel and cobalt and at least contains manganese, x is larger than zero and smaller than or equal to 0.3, y is larger than 0.3 and smaller than 1, and the sum of x and y is equal to 1. The coating material comprises a conducting polymer and a nanometer carbon material, wherein the weight ratio of the nanometer carbon material to the conducting polymer to the core material is (0.01-0.2):(0.01-0.2):1. The anode material is high in density, and meanwhile, the rate capability and the cycle performance of the lithium-rich manganese-based anode material are greatly improved because a nanometer conducting material containing the conducting polymer and the nanometer carbon material coats a lithium-rich manganese-based granular material in a mechanical fusion mode.
Description
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, more particularly to lithium-rich manganese-based anode material and
Its preparation method.
Background technology
In recent years, lithium-rich manganese-based anode material xLi2MnO3·(1-x)LiMO2Due to height ratio capacity (>=250mAh/
G), the advantage such as inexpensive and environment-friendly, it is considered to be most have the lithium ion power battery cathode material of future generation of application prospect,
Receive the extensive concern of people.But lithium-rich anode material is present that irreversible capacity loss first is big, (4.6- under high voltage
The problems such as drop that 4.8V) capacity attenuation is serious, high rate performance is not good enough, voltage declines, this seriously constrains its practicalization.
Because lithium-rich manganese-based anode material needs to charge to competence exertion high power capacity under high potential 4.6-4.8V, and this electricity high
Position has exceeded conventional electrolysis liquid system (such as 1M LiPF6EC/DMC/EMC electrochemical stability window), now electrode and electrolyte
Between occur side reaction cause electrode surface formed thickness SEI films, SEI membrane impedances and Charge-transfer resistance constantly increase with cyclic process
Plus, reversible embedding/de- process of lithium ion is hindered, ultimately result in poor cycle performance.
The electric conductivity of lithium-rich manganese-based anode material is bad, and its lithium ion diffusion coefficient is far below and is both layer structure
LiCoO2, also below LiMn2O4, a little higher than LiFePO4, its electronic conductivity and LiMn2O4, bag carbon LiFePO4It is close.Its
The relatively low electrical conductivity strong influence high rate performance of material, increases the polarization during high current charge-discharge, serious system
About application of the lithium-rich solid-solution material in electrokinetic cell.
The electric conductivity that material is improved by Surface coating treatment is to improve the high rate performance of lithium-rich manganese-based anode material
Effective way, the material of Surface coating high conductivity can avoid electrode material and electrolyte directly contact, prevent material with electricity
The reaction of liquid is solved, while the high rate performance and cycle performance of lithium-rich manganese-based anode material can also be significantly improved.
Conducting polymer has electrical conductivity higher, doping and dedoping characteristic, room-temperature conductivity higher, larger ratio
The features such as surface area and light specific gravity, can be used for can discharge and recharge secondary cell and electrode material.Because conducting polymer is one
Flexible organic conductor is planted, being coated with it can also improve the compacted density of positive electrode, mitigate compacting process to anode material
Destruction.Domestic someone carries out conducting polymer cladding (such as patent to lithium-rich manganese-based anode material with liquid phase coating mode
Application CN 103985853 A), but its preparation method is more complicated, high cost, is unfavorable for large-scale production.
The content of the invention
For above-mentioned background technology and technical problem, the invention provides a kind of lithium-rich manganese-based anode material and its preparation side
Method, to improve the high rate performance and cycle performance of electrode material.
The lithium-rich manganese-based anode material includes lithium-rich manganese-based core material and coats the core material covering material, described
Core material have meet formula Li1+xMyO2Chemical composition, wherein M is one or more in manganese, nickel, cobalt, and is at least wrapped
Containing manganese；0<x≤0.3；0.3<y<1；X+y=1；The covering material includes conducting polymer and nano-scale carbon material, wherein, receive
Meter level carbon material:Conducting polymer:The weight ratio of core material is 0.01-0.2:0.01-0.2:1.
Wherein, the core material is micron particles.
Wherein, the covering material is coated on core material by way of mechanical fusion.
Wherein, the monomer of the conducting polymer includes one or more in aniline, pyrroles or thiophene.
The preparation method of above-mentioned lithium-rich manganese-based anode material, at least comprises the following steps：
Step one, acquisition core material particle；The core material have meet formula Li1+xMyO2Chemical composition, its
Middle M is one or more in manganese, nickel, cobalt, and including at least manganese；0<x≤0.3；0.3<y<1；X+y=1；
Step 2, acquisition covering material source, including obtain conducting polymer and obtain nanoscale carbon source；
Step 3, core material particle and covering material source are added in mixed at high speed-fusion powder handling machine, with
The rotating speed of 500-6000rpm, mixing fusion treatment 0.5-4h so that covering material is coated on core by way of mechanical fusion
On material granule, wherein, nanoscale carbon source:Conducting polymer:The weight ratio of core material is 0.01-0.2:0.01-0.2:1.
Wherein, the step one includes preparing core material particle, specifically includes：Will be with lithium source, manganese source and selected from nickel source
With at least one in cobalt source as raw material, by Li1+xMyO2In mol ratio weigh corresponding raw material, mixing ball is carried out successively
Mill, Ultrafine Grinding, spray drying, roasting, cooling, obtain core material particle.
Wherein, the lithium source includes at least one in lithium hydroxide, lithium carbonate, lithium acetate or lithium nitrate.
Wherein, described manganese source includes at least one in manganese metal, manganese monoxide, manganese dioxide or manganese carbonate.
Wherein, the nickel source includes at least in metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous carbonate
Kind.
Wherein, the cobalt source includes metallic cobalt, cobaltosic oxide, cobalt sesquioxide, cobalt protoxide, cobalt hydroxide, carbonic acid
At least one in cobalt.
Wherein, the ball milling is wet ball grinding.
Wherein, the Ball-milling Time is 0.5-10h, preferably 4-10h, and the ultra-fine time consuming is 1-10h, preferably 1-8h.
Wherein, the equipment of the ball milling includes the one kind in vertical ball mill, horizontal ball mill, vibrator.
Wherein, the equipment of the Ultrafine Grinding includes the one kind in sand mill, high speed ball mill, vibrator.
Wherein, the spray drying is that the slurry after grinding is separated into tiny droplet using atomizer, and is situated between in heat
Rapid drying forms the process of powder in matter.
Wherein, the step of preparing core material particle specifically includes：Will be with lithium source, manganese source and selected from nickel source and cobalt source
At least one as raw material, by Li1+xMyO2In mol ratio weigh corresponding raw material, add deionized water, wet ball grinding
Form slurry within 0.5-10 hours；It is transferred to further Ultrafine Grinding 1-10h in Ultrafine Grinding equipment；Spray drying treatment is carried out to slurry to go
Moisture removal, is made spherical precursor；The spray drying condition is：120-220 DEG C of inlet temperature, 70-100 DEG C of outlet temperature,
And slurry is constantly stirred in spray-drying process, to avoid slurry from being layered；Finally by spherical precursor with 2-5 DEG C/min's
Heating rate is warmed up to 800-1000 DEG C, after constant temperature is processed 4~30 hours, naturally cools to room temperature, obtains core material particle.
Wherein, the step 2 includes preparing conducting polymer, specifically includes：Conducting polymer monomer is added to acid molten
In liquid, then under inert gas shielding, to adding oxidizing agent solution in solution, question response for a period of time after, filtering, washing is done
It is dry, obtain conducting polymer.
Wherein, the acid solution includes hydrochloric acid solution.
Wherein, the conducting polymer monomer includes at least one in aniline, pyrroles and thiophene.
Wherein, the oxidant includes at least one in ammonium persulfate or potassium hyperchlorate.
Wherein, the oxidant and the mol ratio of the conducting polymer monomer are 0.25:1-2:1.
Wherein, the nanoscale carbon source includes that conductive black, acetylene black, CNT, Nano carbon fibers peacekeeping nano-sized carbon are micro-
At least one in ball.
Wherein, the concentration of the hydrochloric acid solution is 0.1-3mol/L, preferably 2mol/L.
Wherein, the step of preparing conducting polymer specifically includes：Conducting polymer monomer is added the hydrochloric acid of 1-3mol/L
In solution, under inert gas shielding, under ambient temperature, lasting stirring, then oxidizing agent solution is slowly added dropwise into foregoing molten
In liquid, after sustained response 1-5 hours, stop stirring, filtering is washed with deionized for several times, dries, and obtains conducting polymer.
A kind of lithium ion battery, it includes above-mentioned lithium-rich manganese-based anode material or is prepared by above-mentioned lithium-rich manganese-based anode material
The lithium-rich manganese-based anode material that method is prepared.
The present invention using the mixed at high speed-fusion powder processing apparatus with special construction and function, make covering material and
Core material rotates in equipment rotor high speed, wall is close under the influence of centrifugal force, between rotor and stator extrusion head
Pass through at a high speed and move in circles；In this moment, two kinds of materials while the effect of be squeezed power and shearing force, grinds in frictional force
Under the reciprocation of power, two kinds of material granule surfaces reach a kind of mechanical fusion state, so as to by the nano level height of high concentration
Conductivity material is coated on micron-sized lithium-rich manganese-based core material.
The present invention includes conducting polymer and nano-scale carbon simultaneously by one layer in lithium-rich manganese-based anode material Surface coating
The nano-level conducting material of material, on the one hand can effectively reduce Charge-transfer resistance, and it is molten on the other hand can to reduce electrolyte
The directly contact of liquid and electrode material, it is to avoid the generation of side reaction between electrolyte solution and electrode material, so as to significantly improve
The high rate performance and cycle performance of material.
Additionally, the present invention is by optimizing preparation technology so that can coat high concentration in lithium-rich manganese-based granular material surface
Include the nano-level conducting material of conducting polymer and nano-scale carbon material simultaneously, lithium-rich manganese-based anode material greatly improved
High rate performance and cycle performance.
Specific embodiment
For a better understanding of the present invention, embodiments of the present invention are introduced in description by the following examples.
Embodiment 1：
By chemical formula Li1.2Co0.13Ni0.13Mn0.54O2In each metallic element mol ratio weigh the MnCO of 5 kilograms of gross mass3、
NiO、Co3O4、Li2CO3Mixed-powder, adds 15L deionized waters, and 4h is ground in ball mill；Mixture paste is transferred to afterwards
Sand mill, adding 20L deionized waters carries out Ultrafine Grinding 6h, and the D50 after Ultrafine Grinding is 0.25 micron；Slurry after Ultrafine Grinding
It is spray-dried, is obtained spray-dried powders.Weigh appropriate powder be placed in Muffle furnace be warming up to 900 DEG C roasting 20h, with stove
Room temperature is cooled to, lithium-rich manganese-based core material is obtained, the powder of acquisition is crossed into 300 mesh sieves.Primary particle particle diameter after sintered
At 0.2-1 microns, the particle diameter D50 of the second particle of formation is 17 microns.
It is the watery hydrochloric acid of 0.2mol/L to prepare 1.6L concentration, by polymer monomer and the mol ratio 1 of Bronsted acid:1 addition is led
Electric polymer monomer aniline 30g is stirred 30 minutes, by oxidant and the mol ratio 0.25 of polymer monomer:1 adds persulfuric acid
Ammonium 18.4g, continues to stir, nitrogen protection, after reacting 10 hours, stops stirring, and then filtering, washing dries, standby.
The lithium-rich manganese-based core material powder that conductive nano carbon black Super-P, polyaniline and abovementioned steps are obtained according to
Weight compares 0.01:0.01:The 1 common 100g of ratio is added in mechanical fusion device, and setting speed is 2500rpm, is not added with other
Grinding aid material, time of fusion 30min obtains the lithium-rich manganese-based anode material of 2wt% conductive blacks and polyaniline-coated.
Button cell is assembled into, in the voltage range of 2~4.8V, discharge capacity is 271.2mAh/g, 3C to 0.1C first
Discharge capacity 218.6mAh/g, 125 weeks capacity of circulation keep 90%.
Embodiment 2：
Lithium-rich manganese-based core material powder is prepared using the identical method of embodiment 1, the conduction added in embodiment 1 is gathered
Monomer adduct aniline is replaced with pyrroles, obtains the polypyrrole of the present embodiment.
The lithium-rich manganese-based core material powder that conductive nano carbon black Super-P, polypyrrole and abovementioned steps are obtained according to
Weight compares 0.02:0.02:The 1 common 100g of ratio is added in mechanical fusion device, and setting speed is 3500rpm, is not added with other
Grinding aid material, time of fusion 1h obtains the lithium-rich manganese-based anode material of 4wt% conductive blacks and polypyrrole cladding.
Button cell is assembled into, in the voltage range of 2~4.8V, discharge capacity is 267.3mAh/g, 3C to 0.1C first
Discharge capacity 220.2mAh/g, 145 weeks capacity of circulation keep 90%.
Embodiment 3：
Lithium-rich manganese-based core material powder and polyaniline are prepared using the identical method of embodiment 1.
The lithium-rich manganese-based core material powder that conductive nano carbon black Super-P, polyaniline and abovementioned steps are obtained according to
Weight compares 0.03:0.03:The 1 common 100g of ratio is added in mechanical fusion device, and setting speed is 5000rpm, is not added with other
Grinding aid material, time of fusion 2h obtains the lithium-rich manganese-based anode material of 6wt% conductive blacks and polyaniline-coated.
Button cell is assembled into, in the voltage range of 2~4.8V, discharge capacity is 261.1mAh/g, 3C to 0.1C first
Discharge capacity 206.6mAh/g, 122 weeks capacity of circulation keep 90%.
Embodiment 4：
Lithium-rich manganese-based core material powder is prepared using the identical method of embodiment 1, the conduction added in embodiment 1 is gathered
Monomer adduct aniline is replaced with pyrroles, obtains the polypyrrole of the present embodiment.
The lithium-rich manganese-based core material powder that conductive nano carbon black Super-P, polypyrrole and abovementioned steps are obtained according to
Weight compares 0.04:0.04:The 1 common 100g of ratio is added in mechanical fusion device, and setting speed is 4500rpm, is not added with other
Grinding aid material, time of fusion 4h obtains the lithium-rich manganese-based anode material of 8wt% conductive blacks and polypyrrole cladding.
Button cell is assembled into, in the voltage range of 2~4.8V, discharge capacity is 271.2mAh/g, 3C to 0.1C first
Discharge capacity 215.3mAh/g, 116 weeks capacity of circulation keep 90%.
Embodiment 5：
Lithium-rich manganese-based core material powder is prepared using the identical method of embodiment 1, the conduction added in embodiment 1 is gathered
Monomer adduct aniline is replaced with pyrroles, obtains the polypyrrole of the present embodiment.
The lithium-rich manganese-based core material powder that carbon nano tube, polypyrrole and abovementioned steps are obtained is according to weight ratio
0.01:0.01:The 1 common 100g of ratio is added in mechanical fusion device, and setting speed is 6000rpm, is not added with other grinding aid things
Matter, time of fusion 3h obtains the lithium-rich manganese-based anode material of 2wt% conductive blacks and polypyrrole cladding.
Button cell is assembled into, in the voltage range of 2~4.8V, discharge capacity is 278.1mAh/g, 3C to 0.1C first
Discharge capacity 200.5mAh/g, 135 weeks capacity of circulation keep 90%.
Embodiment 6：
Lithium-rich manganese-based core material powder and polyaniline are prepared using the identical method of embodiment 1.
The lithium-rich manganese-based core material powder that nanometer carbosphere and polyaniline and abovementioned steps are obtained is according to weight ratio
0.01:0.01:The 1 common 100g of ratio is added in mechanical fusion device, and setting speed is 5000rpm, is not added with other grinding aid things
Matter, time of fusion 2h, obtains lithium-rich manganese-based anode material.
Button cell is assembled into, in the voltage range of 2~4.8V, discharge capacity is 265.6mAh/g, 3C to 0.1C first
Discharge capacity 198.3mAh/g, 125 weeks capacity of circulation keep 90%.
Embodiment 7：
Lithium-rich manganese-based core material powder is prepared using the identical method of embodiment 1, the conduction added in embodiment 1 is gathered
Monomer adduct aniline is replaced with thiophene, obtains the polythiophene of the present embodiment.
The lithium-rich manganese-based core material powder that nanometer carbosphere, polythiophene and abovementioned steps are obtained is according to weight ratio
0.02:The 1 common 100g of ratio is added in mechanical fusion device, and setting speed is 2500rpm, is not added with other grinding aid materials, is melted
Conjunction time 30min, lithium-rich manganese-based anode material.
Button cell is assembled into, in the voltage range of 2~4.8V, discharge capacity is 257.2mAh/g, 3C to 0.1C first
Discharge capacity 206.3mAh/g, 113 weeks capacity of circulation keep 90%.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (11)
1. a kind of lithium-rich manganese-based anode material, including lithium-rich manganese-based core material and the cladding core material covering material, it is special
Levy and be, the core material have meet formula Li1+xMyO2Chemical composition, wherein M be manganese, nickel, cobalt in one kind or many
Kind, and including at least manganese；0<x≤0.3；0.3<y<1；X+y=1；The covering material includes conducting polymer and nano-scale carbon
Material, wherein, nano-scale carbon material:Conducting polymer:The weight ratio of core material is 0.01-0.2:0.01-0.2:1.
2. lithium-rich manganese-based anode material according to claim 1, it is characterised in that the core material is micron order
Grain.
3. lithium-rich manganese-based anode material according to claim 1, it is characterised in that will be described by way of mechanical fusion
Covering material is coated on core material.
4. lithium-rich manganese-based anode material according to claim 1, it is characterised in that the monomer of the conducting polymer includes
One or more in aniline, pyrroles or thiophene.
5. a kind of preparation method of lithium-rich manganese-based anode material, it is characterised in that at least comprise the following steps：
Step one, acquisition core material particle；The core material have meet formula Li1+xMyO2Chemical composition, wherein M is
One or more in manganese, nickel, cobalt, and including at least manganese；0<x≤0.3；0.3<y<1；X+y=1；
Step 2, acquisition covering material source, including obtain conducting polymer and obtain nanoscale carbon source；
Step 3, core material particle and covering material source are added in mixed at high speed-fusion powder handling machine, with 500-
The rotating speed of 6000rpm, mixing fusion treatment 0.5-4h so that covering material is coated on core material by way of mechanical fusion
On particle, wherein, nanoscale carbon source:Conducting polymer:The weight ratio of core material is 0.01-0.2:0.01-0.2:1.
6. the preparation method of lithium-rich manganese-based anode material according to claim 5, it is characterised in that the step one includes
Core material particle is prepared, including：, as raw material, pressed using lithium source, manganese source and selected from least one in nickel source and cobalt source
Li1+xMyO2In mol ratio weigh corresponding raw material, mixing and ball milling, Ultrafine Grinding, spray drying, roasting, cooling are carried out successively, obtain
Obtain core material particle.
7. the preparation method of lithium-rich manganese-based anode material according to claim 5, it is characterised in that the step 2 includes
Conducting polymer is prepared, including：Conducting polymer monomer is added in acid solution, then under inert gas shielding, to solution
Middle addition oxidizing agent solution, question response for a period of time after, filtering, washing, dry, obtain conducting polymer.
8. the preparation method of lithium-rich manganese-based anode material according to claim 7, it is characterised in that the conducting polymer
Monomer includes at least one in aniline, pyrroles and thiophene.
9. the preparation method of lithium-rich manganese-based anode material according to claim 7, it is characterised in that the oxidant includes
At least one in ammonium persulfate or potassium hyperchlorate.
10. the preparation method of lithium-rich manganese-based anode material according to claim 5, it is characterised in that the nano-scale carbon
Source includes at least one in conductive black, acetylene black, CNT, Nano carbon fibers peacekeeping nano-sized carbon microballoon.
A kind of 11. lithium ion batteries, it includes any described lithium-rich manganese-based anode materials of claim 1-4.
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| CN114335543A (en) * | 2021-12-31 | 2022-04-12 | 湖北亿纬动力有限公司 | Preparation method of organic matter supported lithium-rich manganese-based positive electrode material |
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| CN107204461A (en) * | 2017-05-27 | 2017-09-26 | 广东烛光新能源科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN107204461B (en) * | 2017-05-27 | 2019-11-05 | 广东烛光新能源科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN109301192A (en) * | 2018-09-13 | 2019-02-01 | 欣旺达电子股份有限公司 | Lithium ion battery anode slurry preparation method, lithium ion battery negative material and lithium ion battery |
| CN112234203A (en) * | 2020-10-15 | 2021-01-15 | 光鼎铷业(广州)集团有限公司 | Conductive polymer coated rubidium-doped high-nickel ternary lithium battery positive electrode material and preparation method thereof |
| CN114335543A (en) * | 2021-12-31 | 2022-04-12 | 湖北亿纬动力有限公司 | Preparation method of organic matter supported lithium-rich manganese-based positive electrode material |
| CN114400309A (en) * | 2022-01-13 | 2022-04-26 | 蜂巢能源科技股份有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN114400309B (en) * | 2022-01-13 | 2023-08-04 | 蜂巢能源科技股份有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
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Application publication date: 20170524 |