CN109256537A - A kind of modified nickel cobalt aluminium tertiary cathode material and preparation method thereof - Google Patents
A kind of modified nickel cobalt aluminium tertiary cathode material and preparation method thereof Download PDFInfo
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- CN109256537A CN109256537A CN201810880918.8A CN201810880918A CN109256537A CN 109256537 A CN109256537 A CN 109256537A CN 201810880918 A CN201810880918 A CN 201810880918A CN 109256537 A CN109256537 A CN 109256537A
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Abstract
The present invention provides a kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, include the following steps: the preparation of one) nickel cobalt aluminium tertiary cathode material, two) titanium doped fluorinated graphene, tetrabutyl ammonium hexafluorophosphate are modified the preparation of nickel cobalt aluminium tertiary cathode material altogether.The invention also discloses the modification nickel cobalt aluminium tertiary cathode material being prepared according to the preparation method of the modified nickel cobalt aluminium tertiary cathode material and using the modified nickel cobalt aluminium tertiary cathode material as the lithium ion battery of positive electrode.The modification nickel cobalt aluminium tertiary cathode material that the present invention is prepared is compared with traditional nickel cobalt aluminium tertiary cathode material in the prior art, production cost is cheaper, gram volume, cyclical stability and energy density and bulk density are higher, it conducts electricity very well, avoid the W metal that active material and electrolyte directly result in, the dissolution of Co, Al in the electrolytic solution, causes the generation of capacity attenuation.Service life cycle is longer, uses more safety and stability.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field more particularly to a kind of modified nickel cobalt aluminium tertiary cathode materials
Material and preparation method thereof.
Background technique
Increasingly depleted with fossil energy, energy problem has become the hot spot of concern.Countries in the world are all constantly being sought
Seek the green energy resource of more clean and environmental protection.Wherein, lithium battery is since it is high with energy density, voltage is high, has extended cycle life, certainly
The advantages that discharge rate is low, memory-less effect, discharge voltage are stable, charge and discharge are quick and environmentally friendly is widely used in mobile phone, portable
The fields such as formula computer, camera, video camera, electric vehicle, it is close in energy to lithium ion battery with the continuous extension of application field
More stringent requirements are proposed in terms of degree, high rate performance and cycle life.
Lithium ion battery includes positive electrode, negative electrode material, diaphragm, electrolyte and collector etc..Wherein, positive electrode is very
The performance of battery is determined in big degree.The positive electrode of successful commercialization has cobalt acid lithium, LiMn2O4 and LiFePO4 etc..
But there is the deficiency and defect of itself in these positive electrodes.Nickel cobalt aluminium tertiary cathode material is due to its high discharge capacity, anti-
Answer that good reversibility, large current discharging capability are strong, have preferable cyclical stability and security performance, can fit charging/discharging voltage range
When widening, being not in the safety problem due to caused by overcharge or the structural instability imagination, and the advantages that its small toxicity, becomes
The hot spot of current research.However, the study found that nickel cobalt aluminium tertiary cathode material haves the defects that high temperature cyclic performance is poor, it is living
Property substance and electrolyte contacts, can be corroded under the high temperature conditions by hydrofluoric acid, destroy interfacial structure, and then lead to W metal, Co,
The dissolution of Al in the electrolytic solution, causes the decaying of capacity.
Currently, preparation nickel cobalt aluminium tertiary cathode material is closed mainly using co-precipitation and solid sintering technology by the above method
At material alkalinity it is larger, be easy to absorb moisture and carbon dioxide, be unfavorable for nickel cobalt aluminium tertiary cathode material high rate performance and follow
The ring service life will also be greatly affected, it is difficult to meet the needs of market and industrialized production.
Therefore, a kind of low production cost is developed, high temperature cyclic performance is good, stable structure, uses safe nickel cobalt aluminium three
First positive electrode is imperative.
Summary of the invention
The main purpose of the present invention is to provide a kind of modified nickel cobalt aluminium tertiary cathode material and preparation method thereof, the preparations
Method is simple and easy, of less demanding to equipment and reaction condition, and raw material is easy to get, cheap, the modification nickel cobalt aluminium being prepared
For tertiary cathode material compared with traditional nickel cobalt aluminium tertiary cathode material in the prior art, production cost is cheaper, gram volume,
Cyclical stability and energy density and bulk density are higher, conduct electricity very well, and avoid active material and directly result in electrolyte
W metal, the dissolution of Co, Al in the electrolytic solution causes the generation of capacity attenuation.Service life cycle is longer, using more pacifying
It is complete to stablize.
To achieve the above objectives, the present invention provides a kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, including such as
Lower step:
1) by cobalt salt, lithium salts, nickel salt, aluminum nitrate is added in citric acid, is made into 4-5molL-1Mixing salt solution, then
Be added ammonium hydroxide, solution PH is adjusted to 10-11, then solution is spray-dried, finally obtain on molecular level be uniformly mixed
Granular precursor；By presoma in atmosphere furnace, it is passed through oxygen, keeps the temperature 3-5 hours at 500~550 DEG C, then be warming up to 700-
It is sintered 12-15 hours at 800 DEG C, naturally cools to room temperature, product is ground, crossed 200-400 mesh and obtaining nickel cobalt aluminium ternary just
Pole material；
2) it disperses fluorinated graphene, 3- chloropropylmethyldimethoxysilane in ethyl alcohol, stirs 1-2 hours, then to
Four (dimethylamino) titaniums are wherein added, are stirred to react at 40-60 DEG C 4-6 hours, it is rear to filter, it is placed in vacuum oven 70-
It is dried 12-15 hours at 80 DEG C, obtains titanium doped fluorinated graphene；
3) it is prepared by the nickel cobalt aluminium tertiary cathode material being prepared by step 1), by step 2) titanium doped
Fluorinated graphene, the mixing of tetrabutyl ammonium hexafluorophosphate are milled 30-60 minutes, first under nitrogen atmosphere, with the liter of 5-10 DEG C/min
Warm speed is warming up at 550-600 DEG C, keeps the temperature 6-8 hours, and natural cooling crushed 200 mesh meshes, obtains modified nickel cobalt aluminium three
First positive electrode.
Preferably, the cobalt salt described in step 1), lithium salts, nickel salt, the molar ratio of aluminum nitrate are 0.3:2:1.7:0.04.
Further, the cobalt salt is soluble cobalt, preferably cobaltous sulfate, cobalt nitrate or cobalt chloride；The lithium salts
Preferably lithium acetate, lithium oxalate or lithium carbonate；The nickel salt is preferably citric acid nickel, nickel nitrate, nickel chloride, nickel acetate or carbon
One or more of sour nickel.
Preferably, fluorinated graphene described in step 2), 3- chloropropylmethyldimethoxysilane, ethyl alcohol, four (diformazan ammonia
Base) titanium mass ratio be (2-3): 0.1:(5-10): (0.1-0.3).
Preferably, nickel cobalt aluminium tertiary cathode material described in step 3), titanium doped fluorinated graphene, tetrabutyl hexafluorophosphoric acid
The mass ratio of ammonium is (1-2): (0.01-0.03): 0.005.
A kind of modified nickel cobalt aluminium tertiary cathode material, using the preparation method system of the modified nickel cobalt aluminium tertiary cathode material
It is standby to obtain.
A kind of lithium ion battery, using the modified nickel cobalt aluminium tertiary cathode material as positive electrode.
Due to the application of the above technical scheme, the invention has the following advantages:
(1) preparation method of modified nickel cobalt aluminium tertiary cathode material disclosed by the invention, it is simple and easy, to equipment and reaction
Condition is of less demanding, and raw material is easy to get, cheap, is suitble to large-scale production.
(2) modified nickel cobalt aluminium tertiary cathode material disclosed by the invention, just with traditional nickel cobalt aluminium ternary in the prior art
Pole material is compared, and production cost is cheaper, and gram volume, cyclical stability and energy density and bulk density are higher, electric conductivity
Can be good, the W metal that active material and electrolyte directly result in is avoided, the dissolution of Co, Al in the electrolytic solution causes capacity to decline
The generation subtracted.Service life cycle is longer, uses more safety and stability.
(3) modified nickel cobalt aluminium tertiary cathode material disclosed by the invention, first prepares Ni-Co-Li-Al presoma, and in material
Expect that surface coats titanium doped fluorinated graphene, improve the stability and chemical property of positive electrode, so that positive electrode has
There are higher energy density, stability and service life cycle, dissolution of the hydrofluoric acid to transition metal can be reduced, prevent to be circulated throughout
The raising of electronics transfer impedance in journey, and can guarantee surface texture of the stabilizing material in charge and discharge process, improve the electricity of material
Chemical property.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Fluorinated graphene used in the embodiment of the present invention is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., Qi Tayuan
Material is purchased from Mo Bei (Shanghai) Biotechnology Co., Ltd.
Embodiment 1
A kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, includes the following steps:
1) by cobaltous sulfate, citric acid nickel, lithium acetate, aluminum nitrate is added in citric acid, is made into 4molL-1Salt-mixture it is molten
Then ammonium hydroxide is added in liquid, solution PH is adjusted to 10, then solution is spray-dried, and finally obtains and mixes on molecular level
Even granular precursor；By presoma in atmosphere furnace, it is passed through oxygen, keeps the temperature 3 hours at 500 DEG C, then be warming up at 700 DEG C
Sintering 12 hours, naturally cools to room temperature, product is ground, and crosses 200 meshes and obtains nickel cobalt aluminium tertiary cathode material；The sulfuric acid
Cobalt, citric acid nickel, lithium acetate, the molar ratio of aluminum nitrate are 0.3:2:1.7:0.04；
2) it disperses fluorinated graphene 20g, 3- chloropropylmethyldimethoxysilane 1g in ethyl alcohol 50g, stirring 1 is small
When, then four (dimethylamino) titanium 1g are added thereto, and it is stirred to react at 40 DEG C 4 hours, it is rear to filter, it is placed in vacuum oven
It is dried 12 hours at 70 DEG C, obtains titanium doped fluorinated graphene；
3) nickel cobalt aluminium tertiary cathode material 10g by be prepared by step 1), the titanium that is prepared by step 2)
Doping fluorinated graphene 0.1g, the tetrabutyl ammonium hexafluorophosphate 0.05g mixing mill 30 minutes, first under nitrogen atmosphere, with 5 DEG C/
The heating rate of min is warming up at 550 DEG C, keeps the temperature 6 hours, and natural cooling crushed 200 mesh meshes, obtains modified nickel cobalt aluminium
Tertiary cathode material.
A kind of modified nickel cobalt aluminium tertiary cathode material, using the preparation method system of the modified nickel cobalt aluminium tertiary cathode material
It is standby to obtain.
A kind of lithium ion battery, using the modified nickel cobalt aluminium tertiary cathode material as positive electrode.
Embodiment 2
A kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, includes the following steps:
1) by cobalt nitrate, lithium carbonate, nickel acetate, aluminum nitrate is added in citric acid, is made into 4.3molL-1Salt-mixture it is molten
Then ammonium hydroxide is added in liquid, solution PH is adjusted to 11, then solution is spray-dried, and finally obtains and mixes on molecular level
Even granular precursor；By presoma in atmosphere furnace, it is passed through oxygen, keeps the temperature 3.5 hours at 510 DEG C, then be warming up to 730 DEG C
Lower sintering 13 hours, naturally cools to room temperature, product is ground, and crosses 250 meshes and obtains nickel cobalt aluminium tertiary cathode material；The nitre
Sour cobalt, lithium carbonate, nickel acetate, the molar ratio of aluminum nitrate are 0.3:2:1.7:0.04.
2) it disperses fluorinated graphene 23g, 3- chloropropylmethyldimethoxysilane 1g in ethyl alcohol 65g, stirring 1.2 is small
When, then four (dimethylamino) titanium 1.5g are added thereto, and it is stirred to react at 45 DEG C 4.5 hours, it is rear to filter, it is dry to be placed in vacuum
It is dried 13 hours at 73 DEG C of dry case, obtains titanium doped fluorinated graphene；
3) nickel cobalt aluminium tertiary cathode material 13g by be prepared by step 1), the titanium that is prepared by step 2)
Doping fluorinated graphene 0.15g, the tetrabutyl ammonium hexafluorophosphate 0.05g mixing mill 40 minutes, first under nitrogen atmosphere, with 7 DEG C/
The heating rate of min is warming up at 570 DEG C, keeps the temperature 6.5 hours, and natural cooling crushed 200 mesh meshes, obtains modified nickel cobalt
Aluminium tertiary cathode material.
A kind of modified nickel cobalt aluminium tertiary cathode material, using the preparation method system of the modified nickel cobalt aluminium tertiary cathode material
It is standby to obtain.
A kind of lithium ion battery, using the modified nickel cobalt aluminium tertiary cathode material as positive electrode.
Embodiment 3
A kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, includes the following steps:
1) by cobalt chloride, lithium oxalate, nickel chloride, aluminum nitrate is added in citric acid, is made into 4.5molL-1Salt-mixture it is molten
Then ammonium hydroxide is added in liquid, solution PH is adjusted to 10, then solution is spray-dried, and finally obtains and mixes on molecular level
Even granular precursor；By presoma in atmosphere furnace, it is passed through oxygen, keeps the temperature 4 hours at 535 DEG C, then be warming up at 750 DEG C
Sintering 13.5 hours, naturally cools to room temperature, product is ground, and crosses 300 meshes and obtains nickel cobalt aluminium tertiary cathode material；The chlorine
Change cobalt, lithium oxalate, nickel chloride, the molar ratio of aluminum nitrate is 0.3:2:1.7:0.04.
2) fluorinated graphene 26g, 3- chloropropylmethyldimethoxysilane 1g is scattered in ethyl alcohol 85g, and stirring 1.5 is small
When, then four (dimethylamino) titanium 2g are added thereto, and it is stirred to react at 50 DEG C 5 hours, it is rear to filter, it is placed in vacuum oven
It is dried 13.5 hours at 76 DEG C, obtains titanium doped fluorinated graphene；
3) nickel cobalt aluminium tertiary cathode material 15g by be prepared by step 1), the titanium that is prepared by step 2)
Doping fluorinated graphene 0.2g, the tetrabutyl ammonium hexafluorophosphate 0.05g mixing mill 50 minutes, first under nitrogen atmosphere, with 8 DEG C/
The heating rate of min is warming up at 580 DEG C, keeps the temperature 7 hours, and natural cooling crushed 200 mesh meshes, obtains modified nickel cobalt aluminium
Tertiary cathode material.
A kind of modified nickel cobalt aluminium tertiary cathode material, using the preparation method system of the modified nickel cobalt aluminium tertiary cathode material
It is standby to obtain.
A kind of lithium ion battery, using the modified nickel cobalt aluminium tertiary cathode material as positive electrode.
Embodiment 4
A kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, includes the following steps:
1) by cobalt salt, lithium salts, nickel salt, aluminum nitrate is added in citric acid, is made into 5molL-1Mixing salt solution, then plus
Enter ammonium hydroxide, solution PH is adjusted to 11, then solution is spray-dried, finally obtains the presoma being uniformly mixed on molecular level
Particle；By presoma in atmosphere furnace, it is passed through oxygen, keeps the temperature 4.5 hours at 545 DEG C, then be warming up at 780 DEG C and be sintered 14.5
Hour, room temperature is naturally cooled to, product is ground, 350 meshes is crossed and obtains nickel cobalt aluminium tertiary cathode material；The cobalt salt, lithium salts,
Nickel salt, the molar ratio of aluminum nitrate are 0.3:2:1.7:0.04；The cobalt salt is cobaltous sulfate, cobalt nitrate, cobalt chloride in mass ratio 1:
2:3 is mixed；The lithium salts is that lithium acetate, lithium oxalate, lithium carbonate 2:3:1 in mass ratio 2:3:3 in mass ratio are mixed；
The nickel salt is that citric acid nickel, nickel nitrate, nickel chloride 3:4:5 in mass ratio are mixed；
2) it disperses fluorinated graphene 28g, 3- chloropropylmethyldimethoxysilane 1g in ethyl alcohol 85g, stirring 1.7 is small
When, then four (dimethylamino) titanium 2.5g are added thereto, and it is stirred to react at 57 DEG C 5.5 hours, it is rear to filter, it is dry to be placed in vacuum
It is dried 14.5 hours at 78 DEG C of dry case, obtains titanium doped fluorinated graphene；
3) nickel cobalt aluminium tertiary cathode material 18g by be prepared by step 1), the titanium that is prepared by step 2)
Doping fluorinated graphene 0.25g, the tetrabutyl ammonium hexafluorophosphate 0.05g mixing mill 55 minutes, first under nitrogen atmosphere, with 9 DEG C/
The heating rate of min is warming up at 590 DEG C, keeps the temperature 7.5 hours, and natural cooling crushed 200 mesh meshes, obtains modified nickel cobalt
Aluminium tertiary cathode material.
A kind of modified nickel cobalt aluminium tertiary cathode material, using the preparation method system of the modified nickel cobalt aluminium tertiary cathode material
It is standby to obtain.
A kind of lithium ion battery, using the modified nickel cobalt aluminium tertiary cathode material as positive electrode.
Embodiment 5
A kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, includes the following steps:
1) by cobalt nitrate, lithium acetate, citric acid nickel, aluminum nitrate is added in citric acid, is made into 5molL-1Salt-mixture it is molten
Then ammonium hydroxide is added in liquid, solution PH is adjusted to 11, then solution is spray-dried, and finally obtains and mixes on molecular level
Even granular precursor；By presoma in atmosphere furnace, it is passed through oxygen, keeps the temperature 5 hours at 550 DEG C, then be warming up at 800 DEG C
Sintering 15 hours, naturally cools to room temperature, product is ground, and crosses 400 meshes and obtains nickel cobalt aluminium tertiary cathode material；The nitric acid
Cobalt, lithium acetate, citric acid nickel, the molar ratio of aluminum nitrate are 0.3:2:1.7:0.04.
2) it disperses fluorinated graphene 30g, 3- chloropropylmethyldimethoxysilane 1g in ethyl alcohol 100g, stirring 2 is small
When, then four (dimethylamino) titanium 3g are added thereto, and it is stirred to react at 60 DEG C 6 hours, it is rear to filter, it is placed in vacuum oven
It is dried 15 hours at 80 DEG C, obtains titanium doped fluorinated graphene；
3) nickel cobalt aluminium tertiary cathode material 20g by be prepared by step 1), the titanium that is prepared by step 2)
Doping fluorinated graphene 0.3g, the tetrabutyl ammonium hexafluorophosphate 0.05g mixing mill 60 minutes, first under nitrogen atmosphere, with 10 DEG C/
The heating rate of min is warming up at 600 DEG C, keeps the temperature 8 hours, and natural cooling crushed 200 mesh meshes, obtains modified nickel cobalt aluminium
Tertiary cathode material.
A kind of modified nickel cobalt aluminium tertiary cathode material, using the preparation method system of the modified nickel cobalt aluminium tertiary cathode material
It is standby to obtain.
A kind of lithium ion battery, using the modified nickel cobalt aluminium tertiary cathode material as positive electrode.
Comparative example
This example provides a kind of nickel cobalt aluminium tertiary cathode material, and raw material and formula are the same as Chinese invention patent CN104900869B
Embodiment 1.
Correlated performance test, test are carried out to nickel-cobalt-manganternary ternary anode material obtained by above-described embodiment 1-5 and comparative example
The results are shown in Table 1, and test method is as follows: by the manganate cathode material for lithium, Super P and PVDF according to mass ratio 8:1:1
Be dissolved in slurrying in N-methyl pyrrolidones (NMP), using automatic film applicator by its film on aluminium foil.After being dried in vacuo 12h,
It is cut into positive plate.It is transferred into the glove box of argon atmosphere and is assembled into metal lithium sheet, diaphragm, electrolyte and imbibition film
2032 button cells.Wherein electrolyte is 1mol L-1LiPF6- EC/DMC (volume ratio 1:1), diaphragm Celgard2400.It adopts
Charge-discharge test is carried out to assembled button cell with LAND test macro, the blanking voltage of test is 3~4.3V.?
CHI660C electrochemical workstation carries out cyclic voltammetry and ac impedance measurement.
Table 1
It is and in the prior art as it can be seen from table 1 modified nickel cobalt aluminium tertiary cathode material disclosed by the embodiments of the present invention
Positive electrode is compared, and has more excellent chemical property.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (9)
1. a kind of preparation method of modified nickel cobalt aluminium tertiary cathode material, which comprises the steps of:
1) by cobalt salt, lithium salts, nickel salt, aluminum nitrate is added in citric acid, is made into 4-5molL-1Mixing salt solution, be then added
Solution PH is adjusted to 10-11, then solution is spray-dried by ammonium hydroxide, finally obtains the forerunner being uniformly mixed on molecular level
Body particle；By presoma in atmosphere furnace, it is passed through oxygen, keeps the temperature 3-5 hours at 500~550 DEG C, then be warming up to 700-800
It is sintered 12-15 hours at DEG C, naturally cools to room temperature, product is ground, crossed 200-400 mesh and obtain nickel cobalt aluminium tertiary cathode material
Material；
2) it disperses fluorinated graphene, 3- chloropropylmethyldimethoxysilane in ethyl alcohol, stirs 1-2 hours, then thereto
Four (dimethylamino) titaniums are added, are stirred to react at 40-60 DEG C 4-6 hours, it is rear to filter, it is placed in 70-80 DEG C of vacuum oven
Lower baking 12-15 hours, obtains titanium doped fluorinated graphene；
3) by the nickel cobalt aluminium tertiary cathode material being prepared by step 1), the titanium doped fluorination being prepared by step 2)
Graphene, the mixing of tetrabutyl ammonium hexafluorophosphate are milled 30-60 minutes, first under nitrogen atmosphere, with the heating speed of 5-10 DEG C/min
Degree is warming up at 550-600 DEG C, keeps the temperature 6-8 hours, and natural cooling crushed 200 mesh meshes, is obtaining modified nickel cobalt aluminium ternary just
Pole material.
2. the preparation method of modified nickel cobalt aluminium tertiary cathode material according to claim 1, which is characterized in that in step 1)
The cobalt salt, lithium salts, nickel salt, the molar ratio of aluminum nitrate are 0.3:2:1.7:0.04.
3. the preparation method of modified nickel cobalt aluminium tertiary cathode material according to claim 1, which is characterized in that the cobalt salt
For soluble cobalt, preferably cobaltous sulfate, cobalt nitrate or cobalt chloride.
4. the preparation method of modified nickel cobalt aluminium tertiary cathode material according to claim 1, which is characterized in that the lithium salts
Preferably lithium acetate, lithium oxalate or lithium carbonate.
5. the preparation method of modified nickel cobalt aluminium tertiary cathode material according to claim 1, which is characterized in that the nickel salt
Preferably one or more of citric acid nickel, nickel nitrate, nickel chloride, nickel acetate or nickelous carbonate.
6. the preparation method of modified nickel cobalt aluminium tertiary cathode material according to claim 1, which is characterized in that in step 2)
The fluorinated graphene, 3- chloropropylmethyldimethoxysilane, ethyl alcohol, four (dimethylamino) titaniums mass ratio be (2-3):
0.1:(5-10):(0.1-0.3)。
7. the preparation method of modified nickel cobalt aluminium tertiary cathode material according to claim 1, which is characterized in that in step 3)
The nickel cobalt aluminium tertiary cathode material, titanium doped fluorinated graphene, tetrabutyl ammonium hexafluorophosphate mass ratio be (1-2):
(0.01-0.03):0.005。
What 8. a kind of preparation method using any one of the claim 1-7 modified nickel cobalt aluminium tertiary cathode material was prepared
Modified nickel cobalt aluminium tertiary cathode material.
9. a kind of using lithium ion battery of the modified nickel cobalt aluminium tertiary cathode material as positive electrode described in claim 8.
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| WO2024091574A1 (en) * | 2022-10-26 | 2024-05-02 | Qiao Quinn | Lithium metal battery architecture |
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| CN107994219A (en) * | 2017-11-27 | 2018-05-04 | 桑顿新能源科技有限公司 | A kind of metal-doped composite positive pole of graphene coated and preparation method thereof |
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| CN104538620A (en) * | 2014-12-28 | 2015-04-22 | 王帅 | Preparation method of fluorinated graphene coated manganese, cobalt and lithium positive electrode material |
| CN106957055A (en) * | 2017-02-27 | 2017-07-18 | 华南师范大学 | A kind of sulphur, nitrogen, transient metal doped graphene and preparation method and application |
| CN107935059A (en) * | 2017-11-17 | 2018-04-20 | 中钢集团安徽天源科技股份有限公司 | A kind of nickel cobalt aluminium ternary material precursor and preparation method thereof |
| CN107994219A (en) * | 2017-11-27 | 2018-05-04 | 桑顿新能源科技有限公司 | A kind of metal-doped composite positive pole of graphene coated and preparation method thereof |
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| WO2024091574A1 (en) * | 2022-10-26 | 2024-05-02 | Qiao Quinn | Lithium metal battery architecture |
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