CN109873140A - A kind of lithium ion battery graphene composite ternary positive electrode material and preparation method thereof - Google Patents
A kind of lithium ion battery graphene composite ternary positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN109873140A CN109873140A CN201910122074.5A CN201910122074A CN109873140A CN 109873140 A CN109873140 A CN 109873140A CN 201910122074 A CN201910122074 A CN 201910122074A CN 109873140 A CN109873140 A CN 109873140A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium
- cobalt
- silicon
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- 229910013716 LiNi Inorganic materials 0.000 claims description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims 1
- 229940078494 nickel acetate Drugs 0.000 claims 1
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 239000010406 cathode material Substances 0.000 abstract description 6
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 abstract 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 19
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 18
- 229910016104 LiNi1 Inorganic materials 0.000 description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910013100 LiNix Inorganic materials 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种锂离子电池石墨烯复合三元正极材料及其制备方法，该正极材料首先用模板法合成铝掺杂的氧化镍钴锰锂正极材料，然后将铝掺杂的氧化镍钴锰锂正极材料和石墨烯加入去离子水中搅拌均匀，进行水热反应，冷却后离心、洗涤和干燥得到铝掺杂的氧化镍钴锰锂正极材料/石墨烯复合正极材料。本发明通过复合可以综合两种材料的优点，提高电子电导率和离子电导率，提高电池的输出功率密度，而且还可以提高三元材料的结构稳定性，从而得到循环性较好、容量较高、能量密度较大的复合正极材料。
The invention discloses a graphene composite ternary positive electrode material for lithium ion batteries and a preparation method thereof. The positive electrode material firstly uses a template method to synthesize an aluminum-doped nickel-cobalt-manganese-lithium positive electrode material, and then synthesizes the aluminum-doped nickel-cobalt oxide The manganese-lithium cathode material and graphene are added into deionized water and stirred evenly to carry out a hydrothermal reaction. After cooling, centrifugation, washing and drying are performed to obtain an aluminum-doped nickel-cobalt-manganese-lithium cathode material/graphene composite cathode material. The invention can combine the advantages of the two materials, improve the electronic conductivity and the ionic conductivity, improve the output power density of the battery, and can also improve the structural stability of the ternary material, so as to obtain better cyclability and higher capacity. , Composite cathode material with high energy density.
Description
Technical field
The invention belongs to battery material technical field more particularly to a kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary anode materials
Material and preparation method thereof.
Background technique
Lithium ion battery is the secondary cell of new generation developed on the basis of lithium primary cell, is widely used in small portable
Electronic communication product and electric vehicle.The anode material for lithium-ion batteries of current industrialization mainly has cobalt acid lithium, changes
Property LiMn2O4, LiFePO4, ternary material etc..Although cobalt acid lithium performance is stablized, higher cost and cobalt element is toxic, Ke Nengzao
At environmental pollution.Lithium manganate having spinel structure is although cheap, but cause there are Jahn-Teller effect cycle performance compared with
Difference, and its chemical property is decayed because of the problems of dissolution of manganese comparatively fast at high temperature.LiFePO4 poorly conductive, product batch
Secondary disposable poor, poor performance at low temperatures, and there are problems that the dissolution of trace iron may cause battery short circuit.Therefore, the study found that
With LiNixCoyMn1-x-yO2For representative stratiform cobalt nickel oxide manganses series material (abbreviation ternary material) preferably had both it is above-mentioned
The advantages of material, and compensate its defect to a certain extent, there is height ratio capacity, stable cycle performance, advantage of lower cost, peace
The features such as full better performances, it is considered to be the ideal chose for mixed type electrical source of power.But simultaneously it there is also lower electricity
The disadvantages of conductance and capacity attenuation are fast, high rate performance is bad.
The preparation method of ternary material mainly has high temperature solid-state method, coprecipitation, sol-gel method, template etc. at present.
The present invention prepares the uniform cobalt nickel oxide manganses lithium material of particle using template, simplifies preparation process.The material of template preparation
Material can control the size of material, solve the problems, such as that conventional solid-state method granularity is uneven, material purity height, the grain prepared
Diameter is small, narrow distribution and sintering character is good.
Tertiary cathode material set LiNiO2、LiCoO2、LiMnO2Three kinds of positive electrode advantages, it is considered to be most have latent
One of widely applied positive electrode of power.The excellent performance of cobalt nickel oxide manganses lithium ternary material obtains domestic and international many research institutions
Concern, be not only widely used in small-sized electronic product, also there is preferable development trend on full-sized car power battery,
It has a good application prospect.But simultaneously it there is also lower conductivity and capacity attenuation it is fast, high rate performance is bad the disadvantages of,
In order to obtain more excellent tertiary cathode material, nickle cobalt lithium manganate is doped and is coated.Make lattice by ion doping
Certain distortion occurs, generates certain defect, improves electronic conductivity and ion diffusion rates, to improve high rate performance and follow
Ring performance.
Graphene is as two-dimentional carbon nanomaterial, due to the hexagon cellular shape void structure of its two-dimentional monolayer having
And excellent physico-chemical property, such as high specific surface area, high electronic conductivity, superior mechanical property and good chemical stabilization
Property etc., and it is widely used in lithium ion battery.In recent years many are research shows that graphene can be in composite positive pole
It forms conductive network and promotes its electric conductivity, while helping to shorten the diffusion path of lithium ion, fill the big multiplying power of positive electrode
Discharge performance has greatly improved, these are quite important for cobalt nickel oxide manganses lithium.
Summary of the invention
The present invention is directed to ternary layered positive electrode LiNixCol-x-y-zMnyAlzO2Poor repeatability and high rate performance, provide one
The silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and its preparation side that kind technical process is simple, highly-safe, stability is good
Method.
The present invention is achieved by the following technical solutions:
A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, aluminium element is entered in cobalt nickel oxide manganses lithium lattice, is replaced
Co on portion3+, prepared after then mixing aluminium Y-oxides doping cobalt manganese lithium with graphene through hydro-thermal method.
The present invention also provides a kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, including it is following
Step:
(1) potassium permanganate is dissolved in certain deionized water, the concentrated hydrochloric acid of certain mol proportion is added dropwise thereto, stir 15 points
Clock is put into reaction kettle and carries out hydro-thermal reaction, is centrifuged after cooling, washs, be dried to obtain brown manganese dioxide, then in Muffle furnace
It is calcined 6 hours with 350 DEG C, obtains solid product A；
(2) solid product A obtained in step 1 and nickel source, cobalt source, silicon source and lithium salts are mixed to join by certain mol proportion
In the mixed solution of water and dehydrated alcohol, ultrasonic disperse 0.5-1 hours, then it is stirred and is evaporated, obtain solid mixture B,
B is ground, is then placed in crucible, after calcining, the cobalt nickel oxide manganses lithium LiNi of aluminium doping can be obtainedxCol-x-y-zMnyAlzO2
Positive electrode；
(3) LiNi for preparing graphene and step 2xCol-x-y-zMnyAlzO2Positive electrode is placed in water/ethylene glycol solution, dense
Degree is 0.01-0.02mol/L, ultrasonic disperse 0.5-2 hours, is then stirred, and is put into reaction kettle and carries out hydro-thermal reaction, cooling
Centrifuge washing obtains LiNi afterwardsxCol-x-y-zMnyAlzO2 / grapheme composite positive electrode material.
The temperature of hydro-thermal reaction is 140-160 DEG C in the step 1, and the reaction time is 8-14 hours, drying time 8-
12 hours, calcining heating rate was 2 DEG C/min.
Cobalt source is one or more of cobalt nitrate, cobalt acetate, cobalt chloride in the step 2；Nickel source is nickel nitrate, acetic acid
One or more of nickel, nickel chloride；Silicon source is one or more of aluminum nitrate, aluminium chloride；Lithium salts is lithium carbonate, acetic acid
One or more of lithium, lithium nitrate.
In the step 2 lithium salts, cobalt source, nickel source, silicon source and brown manganese dioxide according to certain mol proportion be dissolved in water and
In the mixed solution of dehydrated alcohol, holding concentration is 0.1-0.15mol/L.
The volume ratio of water and dehydrated alcohol is 1:0-10 in the mixed solution of water and dehydrated alcohol in the step 2.
For evaporated temperature at 60-75 DEG C, the calcination process is first to be warming up to 400-500 DEG C of calcining 5-8h in the step 2,
It is warming up to 750-850 DEG C of calcining 10-20h again, heating rate is 2 DEG C/min.
The cobalt nickel oxide manganses lithium LiNi of the doping of aluminium obtained in the step 2xCol-x-y-zMnyAlzO2Positive electrode, wherein 0
< x < 0.5,0 < y < 0.5,0 < z < 0.05.
The dosage of graphene accounts for LiNi in the step 3xCol-x-y-zMnyAlzO2The 1-10% of quality, the water and second two
The volume ratio of water and ethylene glycol is 1-2:1 in the mixed solution of alcohol.
The temperature of hydro-thermal reaction is 120-140 DEG C in the step 3, and the reaction time is 10-12 hours, drying temperature 70-
80 DEG C, the time is 8-12 hours.
The invention has the advantages that
1, composite positive pole of the present invention is the LiNi of a kind of more preferable cycle performance, more preferable high rate performancexCol-x-y-zMnyAlzO2/
Grapheme composite positive electrode material.
2, the invention is simple and feasible, and high production efficiency reduces production process, saves production cost and is not changed
The material of property is compared, and is greatly improved on battery capacity, high rate performance and cycle performance.
3, hydro-thermal method recombination energy improves LiNixCol-x-y-zMnyAlzO2Adhesive force between graphene, makes
LiNixCol-x-y-zMnyAlzO2It is dispersed in one conductive network of formation between graphene sheet layer, so as to improve lithium ion
The cycle performance and high rate performance of battery.
Detailed description of the invention
Fig. 1 show LiNi1/3Co1/3Mn1/3O2And LiNi1/3Co1/3-0.03Mn1/3Al0.03O2XRD spectrum.
Fig. 2 show LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2/ graphene
Raman map.
Fig. 3 show LiNi1/3Co1/3Mn1/3O2、LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/ 3Al0.05O2/ graphene first charge-discharge curve at 0.1C.
Fig. 4 show LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2/ graphene is compound
The cycle performance figure of positive electrode.
Fig. 5 show the LiNi of the preparation of embodiment 41/3Co1/3-0.05Mn1/3Al0.05O2/ grapheme composite positive electrode material
SEM figure.
Specific embodiment
Below in conjunction with specific example, technical scheme is described further:
Embodiment 1
The preparation method of lithium ion battery cobalt nickel oxide manganses lithium anode material in the present embodiment, comprising the following steps:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.7276g are weighed, 0.7270g nine is hydrated nitre
Sour nickel is dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up the loss of lithium source in calcination process, lithium nitrate mistake
Amount 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be put into earthenware after the solid abrasive being evaporated
It in crucible, is placed in Muffle furnace, is warming up to 480 DEG C in air atmosphere with the heating rate of 2 DEG C/min, 5h is calcined, followed by of continuing rising
Temperature calcines 16h to 850 DEG C, then cools to room temperature with the furnace, takes out sample and regrinds to obtain LiNi1/3Co1/3Mn1/3O2Powder
End；
By LiNi obtained1/3Co1/3Mn1/3O2It is mixed with acetylene black and Kynoar (PVDF) by the mass ratio of 8:1:1
It is even, it is rolled into thick 120 μm of film, the anode after 120 DEG C of vacuum drying 10h, as experiment half-cell；Using 1mol/L
LiPF6/ ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC) electrolyte, fills in dry
In the glove box of full argon gas, using metal lithium sheet as cathode, it is assembled into battery.With LiNi prepared by the present embodiment1/3Co1/ 3Mn1/3O2For anode, using lithium piece as the button cell of cathode, in 2.5-4.3V voltage range, with constant current-constant pressure under 0.1C multiplying power
It charges, first discharge specific capacity is 175mAh/g when constant-current discharge under 0.1C multiplying power, but capacity is only after 30 circulations
157mAh/g。
Embodiment 2
The preparation method of lithium ion battery aluminium Y-oxides doping cobalt manganese lithium anode material in the present embodiment, comprising the following steps:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.6620g are weighed, 0.7270g nine is hydrated nitre
Sour nickel, 0.0844g ANN aluminium nitrate nonahydrate are dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up in calcination process
The loss of lithium source, lithium nitrate excessive 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be evaporated
Solid abrasive after be put into crucible, be placed in Muffle furnace, be warming up to 480 in air atmosphere with the heating rate of 2 DEG C/min
DEG C, 5h is calcined, it is further heated up to 850 DEG C, 16h is calcined, then cools to room temperature with the furnace, sample is taken out and regrinds to obtain
LiNi1/3Co1/3-0.03Mn1/3Al0.03O2Powder.
The LiNi that experiment is prepared1/3Co1/3Mn1/3O2And LiNi1/3Co1/3-0.03Mn1/3Al0.03O2X-ray diffraction
Spectrogram is shown in Fig. 1.From figure 1 it appears that the LiNi of preparation1/3Co1/3-0.05Mn1/3Al0.05O2Positive electrode with it is undoped
LiNi1/3Co1/3Mn1/3O2The XRD diagram peak shape of material is identical, miscellaneous peak does not occur, this may be that Al enters LiNi1/3Co1/3Mn1/ 3O2In lattice, replace the Co on portion3+, this illustrates that doping has no effect on main body layer structure.
By LiNi obtained1/3Co1/3-0.03Mn1/3Al0.03O2With acetylene black and Kynoar (PVDF) by 8:1:1's
Mass ratio is uniformly mixed, and is rolled into thick 120 μm of film, the anode after 120 DEG C of vacuum drying 10h, as experiment half-cell；It adopts
With 1mol/L LiPF6/ ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC) electrolyte,
In the dry glove box full of argon gas, using metal lithium sheet as cathode, it is assembled into battery.Prepared by the present embodiment
LiNi1/3Co1/3-0.03Mn1/3Al0.03O2For anode, using lithium piece as the button cell of cathode, in 2.5-4.3V voltage range, with
Constant current-constant-voltage charge under 0.1C multiplying power, first discharge specific capacity is 186mAh/g when constant-current discharge under 0.1C multiplying power, but passes through 30
Capacity is 175mAh/g after secondary circulation.
Embodiment 3
The preparation method of lithium ion battery aluminium Y-oxides doping cobalt manganese lithium anode material in the present embodiment, comprising the following steps:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.6183g are weighed, 0.7270g nine is hydrated nitre
Sour nickel, 0.1406g ANN aluminium nitrate nonahydrate are dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up in calcination process
The loss of lithium source, lithium nitrate excessive 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be evaporated
Solid abrasive after be put into crucible, be placed in Muffle furnace, be warming up to 480 in air atmosphere with the heating rate of 2 DEG C/min
DEG C, 5h is calcined, it is further heated up to 850 DEG C, 16h is calcined, then cools to room temperature with the furnace, sample is taken out and regrinds to obtain
LiNi1/3Co1/3-0.05Mn1/3Al0.05O2Powder.
By LiNi obtained1/3Co1/3-0.05Mn1/3Al0.05O2With acetylene black and Kynoar (PVDF) by 8:1:1's
Mass ratio is uniformly mixed, and is rolled into thick 120 μm of film, the anode after 120 DEG C of vacuum drying 10h, as experiment half-cell；It adopts
With 1mol/L LiPF6/ ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC) electrolyte,
In the dry glove box full of argon gas, using metal lithium sheet as cathode, it is assembled into battery.Prepared by the present embodiment
LiNi1/3Co1/3-0.05Mn1/3Al0.05O2For anode, using lithium piece as the button cell of cathode, in 2.5-4.3V voltage range, with
Constant current-constant-voltage charge under 0.1C multiplying power, first discharge specific capacity is 186mAh/g when constant-current discharge under 0.2C multiplying power, but passes through 30
Capacity is only 178mAh/g after secondary circulation.
Embodiment 4
Lithium ion battery aluminium Y-oxides doping cobalt manganese lithium/graphene anode material preparation method in the present embodiment, including with
Lower step:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.6183g are weighed, 0.7270g nine is hydrated nitre
Sour nickel, 0.1406g ANN aluminium nitrate nonahydrate are dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up in calcination process
The loss of lithium source, lithium nitrate excessive 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be evaporated
Solid abrasive after be put into crucible, be placed in Muffle furnace, be warming up to 480 in air atmosphere with the heating rate of 2 DEG C/min
DEG C, 5h is calcined, it is further heated up to 850 DEG C, 16h is calcined, then cools to room temperature with the furnace, sample is taken out and regrinds to obtain
LiNi1/3Co1/3-0.05Mn1/3Al0.05O2Powder；
(3) resulting LiNi is weighed1/3Co1/3-0.05Mn1/3Al0.05O2Powder 0.3g, graphene 0.009g be dispersed in 30ml go from
It in the mixed solution of sub- water and 20ml ethylene glycol, ultrasonic disperse 1 hour, goes on blender and stirs 6 hours, be then transferred into anti-
It answers in kettle and is reacted 8 hours at 120 DEG C, be centrifuged after cooling, washing, drying 12 hours at 70 DEG C, obtain LiNi1/3Co1/3- 0.05Mn1/3Al0.05O2/ GR-3wt% material.
The LiNi that embodiment is prepared1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2/
The Raman spectrogram of GR-3wt% is shown in Fig. 2.From figure 2 it can be seen that the LiNi of preparation1/3Co1/3-0.05Mn1/3Al0.05O anode material
Expect graphene peak do not occur, but the LiNi of composite graphite alkene1/3Co1/3-0.05Mn1/3Al0.05O2/ GR-3wt% material
There is graphene peak in Raman figure, this may be that graphene is compounded in LiNi1/3Co1/3-0.05Mn1/3Al0.05The table of O positive electrode
Face.
By LiNi obtained1/3Co1/3-0.05Mn1/3Al0.05O2/ GR-3wt% is pressed with acetylene black and Kynoar (PVDF)
The mass ratio of 8:1:1 is uniformly mixed, and is rolled into thick 120 μm of film, after 120 DEG C of vacuum drying 10h, as experiment half-cell
Anode；Using 1mol/L LiPF6/ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC)
Electrolyte using metal lithium sheet as cathode, is assembled into battery in the dry glove box full of argon gas.With the present embodiment institute
The LiNi of preparation1/3Co1/3-0.05Mn1/3Al0.05O2/ GR-3wt% is anode, using lithium piece as the button cell of cathode, in 2.5-
4.3V voltage range, with constant current-constant-voltage charge under 0.1C multiplying power, first discharge specific capacity is when constant-current discharge under 0.1C multiplying power
163mAh/g, but capacity is only 158mAh/g after 30 circulations.
Claims (10)
1. a kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, which is characterized in that aluminium element is entered cobalt nickel oxide manganses
In lithium lattice, replace the Co on portion3+, through hydro-thermal legal system after then aluminium Y-oxides doping cobalt manganese lithium is mixed with graphene
It is standby to obtain.
2. a kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, which comprises the following steps:
(1) potassium permanganate is dissolved in certain deionized water, the concentrated hydrochloric acid of certain mol proportion is added dropwise thereto, stir 15 points
Clock is put into reaction kettle and carries out hydro-thermal reaction, is centrifuged after cooling, washs, be dried to obtain brown manganese dioxide, then in Muffle furnace
It is calcined 6 hours with 350 DEG C, obtains solid product A；
(2) solid product A obtained in step 1 and nickel source, cobalt source, silicon source and lithium salts are mixed to join by certain mol proportion
In the mixed solution of water and dehydrated alcohol, ultrasonic disperse 0.5-1 hours, then it is stirred and is evaporated, obtain solid mixture B,
B is ground, is then placed in crucible, after calcining, the cobalt nickel oxide manganses lithium LiNi of aluminium doping can be obtainedxCol-x-y-zMnyAlzO2
Positive electrode；
(3) LiNi for preparing graphene and step 2xCol-x-y-zMnyAlzO2Positive electrode is placed in water/ethylene glycol solution, dense
Degree is 0.01-0.02mol/L, ultrasonic disperse 0.5-2 hours, is then stirred, and is put into reaction kettle and carries out hydro-thermal reaction, cooling
Centrifuge washing obtains LiNi afterwardsxCol-x-y-zMnyAlzO2 / grapheme composite positive electrode material.
3. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the temperature of hydro-thermal reaction is 140-160 DEG C in the step 1, and the reaction time is 8-14 hours, and drying time is that 8-12 is small
When, calcining heating rate is 2 DEG C/min.
4. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In cobalt source is one or more of cobalt nitrate, cobalt acetate, cobalt chloride in the step 2；Nickel source is nickel nitrate, nickel acetate, chlorine
Change one or more of nickel；Silicon source is one or more of aluminum nitrate, aluminium chloride；Lithium salts is lithium carbonate, lithium acetate, nitric acid
One or more of lithium.
5. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In lithium salts, cobalt source, nickel source, silicon source and brown manganese dioxide are dissolved in water and anhydrous second according to certain mol proportion in the step 2
In the mixed solution of alcohol, holding concentration is 0.1-0.15mol/L.
6. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the volume ratio of water and dehydrated alcohol is 1:0-10 in the mixed solution of water and dehydrated alcohol in the step 2.
7. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In for evaporated temperature at 60-75 DEG C, the calcination process is first to be warming up to 400-500 DEG C of calcining 5-8h, then rise in the step 2
For temperature to 750-850 DEG C of calcining 10-20h, heating rate is 2 DEG C/min.
8. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the cobalt nickel oxide manganses lithium LiNi of the doping of aluminium obtained in the step 2xCol-x-y-zMnyAlzO2Positive electrode, wherein 0 < x <
0.5,0 < y < 0.5,0 < z < 0.05.
9. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the dosage of graphene accounts for LiNi in the step 3xCol-x-y-zMnyAlzO2The 1-10% of quality, the water and ethylene glycol
The volume ratio of water and ethylene glycol is 1-2:1 in mixed solution.
10. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In, in the step 3 temperature of hydro-thermal reaction be 120-140 DEG C, the reaction time be 10-12 hours, 70-80 DEG C of drying temperature,
Time is 8-12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910122074.5A CN109873140B (en) | 2019-02-18 | 2019-02-18 | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910122074.5A CN109873140B (en) | 2019-02-18 | 2019-02-18 | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109873140A true CN109873140A (en) | 2019-06-11 |
| CN109873140B CN109873140B (en) | 2021-09-17 |
Family
ID=66918908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910122074.5A Expired - Fee Related CN109873140B (en) | 2019-02-18 | 2019-02-18 | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109873140B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697798A (en) * | 2019-10-14 | 2020-01-17 | 河南电池研究院有限公司 | A kind of preparation method of graphene-based carbon composite lithium ion battery cathode material |
| CN111530470A (en) * | 2020-05-06 | 2020-08-14 | 合肥工业大学 | The preparation method of manganese dioxide and its composite material and the degradation method of sulfadiazine |
| CN111600002A (en) * | 2020-05-30 | 2020-08-28 | 海宏(唐河)新能源科技有限公司 | Preparation method of aluminum triethoxide coated nickel cobalt lithium manganate modified material |
| CN112599764A (en) * | 2020-12-28 | 2021-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method, product and application of ternary nanowire array @ carbon fiber |
| CN112701275A (en) * | 2020-12-28 | 2021-04-23 | 蜂巢能源科技有限公司 | Graphene-manganese dioxide flower-ball-shaped negative electrode material, and preparation method and application thereof |
| US20210159483A1 (en) * | 2019-11-26 | 2021-05-27 | Posco Chemical Co., Ltd. | Positive active material for rechargeable lithium ion battery, preparing method of the same, and rechargeable lithium ion battery comprising the same |
| CN115036605A (en) * | 2022-06-24 | 2022-09-09 | 云南云天化股份有限公司 | Method for regenerating composite cathode material of retired lithium battery |
| CN117321006A (en) * | 2023-08-23 | 2023-12-29 | 广东邦普循环科技有限公司 | A nickel-cobalt-aluminum ternary cathode material precursor and its preparation method and application |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916837A (en) * | 2015-05-11 | 2015-09-16 | 田东 | Preparation method of aluminum element doped ternary positive electrode material |
| CN105118991A (en) * | 2015-08-27 | 2015-12-02 | 北大先行科技产业有限公司 | Lithium ion secondary battery positive electrode material and preparation method thereof |
| CN105140493A (en) * | 2015-10-14 | 2015-12-09 | 广东天劲新能源科技股份有限公司 | Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof |
| CN105742627A (en) * | 2016-04-15 | 2016-07-06 | 合肥工业大学 | A kind of preparation method of LiNixCoyMnl-x-yBrzO2-z/graphene composite cathode material |
| CN105789706A (en) * | 2016-04-25 | 2016-07-20 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of high-energy-density lithium ion battery |
| CN107204426A (en) * | 2017-06-09 | 2017-09-26 | 合肥工业大学 | A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property |
| CN107611399A (en) * | 2017-09-11 | 2018-01-19 | 福建师范大学 | The method that high dispersive graphene improves the nickel-cobalt-manganese ternary material property of Doped ions |
| CN108011087A (en) * | 2017-11-29 | 2018-05-08 | 华南师范大学 | A kind of manganese dioxide negative material of titanium dioxide modification and preparation method thereof |
| CN108232136A (en) * | 2017-12-18 | 2018-06-29 | 江苏超电新能源科技发展有限公司 | A kind of preparation method of the compound nickel-cobalt lithium manganate material of graphene |
| CN108899604A (en) * | 2018-06-28 | 2018-11-27 | 郑州中科新兴产业技术研究院 | Utilize the method for waste lithium cell anode pole piece preparation ternary anode material precursor |
| CN109256543A (en) * | 2018-08-28 | 2019-01-22 | 凤凰新能源(惠州)有限公司 | A kind of modified nickel cobalt manganese lithium aluminate cathode material and preparation method thereof |
-
2019
- 2019-02-18 CN CN201910122074.5A patent/CN109873140B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916837A (en) * | 2015-05-11 | 2015-09-16 | 田东 | Preparation method of aluminum element doped ternary positive electrode material |
| CN105118991A (en) * | 2015-08-27 | 2015-12-02 | 北大先行科技产业有限公司 | Lithium ion secondary battery positive electrode material and preparation method thereof |
| CN105140493A (en) * | 2015-10-14 | 2015-12-09 | 广东天劲新能源科技股份有限公司 | Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof |
| CN105742627A (en) * | 2016-04-15 | 2016-07-06 | 合肥工业大学 | A kind of preparation method of LiNixCoyMnl-x-yBrzO2-z/graphene composite cathode material |
| CN105789706A (en) * | 2016-04-25 | 2016-07-20 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of high-energy-density lithium ion battery |
| CN107204426A (en) * | 2017-06-09 | 2017-09-26 | 合肥工业大学 | A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property |
| CN107611399A (en) * | 2017-09-11 | 2018-01-19 | 福建师范大学 | The method that high dispersive graphene improves the nickel-cobalt-manganese ternary material property of Doped ions |
| CN108011087A (en) * | 2017-11-29 | 2018-05-08 | 华南师范大学 | A kind of manganese dioxide negative material of titanium dioxide modification and preparation method thereof |
| CN108232136A (en) * | 2017-12-18 | 2018-06-29 | 江苏超电新能源科技发展有限公司 | A kind of preparation method of the compound nickel-cobalt lithium manganate material of graphene |
| CN108899604A (en) * | 2018-06-28 | 2018-11-27 | 郑州中科新兴产业技术研究院 | Utilize the method for waste lithium cell anode pole piece preparation ternary anode material precursor |
| CN109256543A (en) * | 2018-08-28 | 2019-01-22 | 凤凰新能源(惠州)有限公司 | A kind of modified nickel cobalt manganese lithium aluminate cathode material and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697798A (en) * | 2019-10-14 | 2020-01-17 | 河南电池研究院有限公司 | A kind of preparation method of graphene-based carbon composite lithium ion battery cathode material |
| US20210159483A1 (en) * | 2019-11-26 | 2021-05-27 | Posco Chemical Co., Ltd. | Positive active material for rechargeable lithium ion battery, preparing method of the same, and rechargeable lithium ion battery comprising the same |
| US12334537B2 (en) * | 2019-11-26 | 2025-06-17 | Posco Chemical Co., Ltd. | Positive active material for rechargeable lithium ion battery, preparing method of the same, and rechargeable lithium ion battery comprising the same |
| CN111530470A (en) * | 2020-05-06 | 2020-08-14 | 合肥工业大学 | The preparation method of manganese dioxide and its composite material and the degradation method of sulfadiazine |
| CN111530470B (en) * | 2020-05-06 | 2022-03-18 | 合肥工业大学 | The preparation method of manganese dioxide and its composite material and the degradation method of sulfadiazine |
| CN111600002A (en) * | 2020-05-30 | 2020-08-28 | 海宏(唐河)新能源科技有限公司 | Preparation method of aluminum triethoxide coated nickel cobalt lithium manganate modified material |
| CN112599764A (en) * | 2020-12-28 | 2021-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method, product and application of ternary nanowire array @ carbon fiber |
| CN112701275A (en) * | 2020-12-28 | 2021-04-23 | 蜂巢能源科技有限公司 | Graphene-manganese dioxide flower-ball-shaped negative electrode material, and preparation method and application thereof |
| CN115036605A (en) * | 2022-06-24 | 2022-09-09 | 云南云天化股份有限公司 | Method for regenerating composite cathode material of retired lithium battery |
| CN117321006A (en) * | 2023-08-23 | 2023-12-29 | 广东邦普循环科技有限公司 | A nickel-cobalt-aluminum ternary cathode material precursor and its preparation method and application |
| CN117321006B (en) * | 2023-08-23 | 2026-01-02 | 广东邦普循环科技有限公司 | A nickel-cobalt-aluminum ternary cathode material precursor, its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109873140B (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101679066B (en) | Novel titanium oxide, method for producing the same, and lithium secondary battery using the titanium oxide as an active material | |
| CN109873140A (en) | A kind of lithium ion battery graphene composite ternary positive electrode material and preparation method thereof | |
| CN102723481B (en) | High-voltage lithium battery cathode material of a kind of micro-tungsten element that adulterates and preparation method thereof | |
| CN106099098B (en) | A high-voltage cathode material for lithium ion battery LiδCo1-xMgxO2@AlF3 and preparation method thereof | |
| CN103094550A (en) | Preparation method of lithium-rich anode material | |
| CN101771145B (en) | Method for preparing multielement cathode materials for lithium ion batteries | |
| CN104868122A (en) | Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material | |
| CN109119624B (en) | Preparation method of lithium titanium phosphate coated lithium-rich manganese-based positive electrode material | |
| CN107492643A (en) | A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof | |
| CN109904432A (en) | A kind of nickelic tertiary cathode material of W doping vario-property | |
| CN101320806A (en) | A kind of preparation method of rechargeable magnesium battery cathode material manganese magnesium silicate | |
| CN102931383A (en) | Preparation method of composite anode material of lithium-ion power battery | |
| CN104241628B (en) | A kind of preparation method and its obtained product and purposes of the di-iron trioxide microballoon of titanium dioxide modification | |
| CN109713281B (en) | Positive electrode material of lithium ion battery and preparation method thereof | |
| CN106006762A (en) | Preparation of pedal-layered Ni-Co-Mn ternary material precursor and application of precursor as cathode material for lithium ion cell | |
| CN108091863A (en) | Graphene is modified lithium-rich manganese-based anode material and preparation method thereof | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof | |
| CN101859888A (en) | Lithium-manganese composite oxide for positive electrode active material of lithium battery and preparation method thereof | |
| CN104112849A (en) | Light metal element-doped ternary lithium ion battery positive electrode material and synthesis method thereof | |
| CN107204426A (en) | A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property | |
| CN115010186A (en) | High-capacity oxygen valence-variable sodium ion battery positive electrode material and preparation method thereof | |
| CN116081710A (en) | A potassium-doped nickel-manganese-copper ternary layered oxide and its preparation method and application | |
| CN109884100A (en) | A method for judging the performance of lithium-ion battery materials | |
| CN103367733A (en) | Lithium ion battery cathode material and preparation method thereof and lithium ion battery | |
| CN113582253B (en) | Quaternary positive electrode material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210917 |