CN109873140B - Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material - Google Patents
Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 44
- 239000010406 cathode material Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 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 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 230000035484 reaction time Effects 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 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
- 230000008020 evaporation Effects 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 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
- 239000011572 manganese Substances 0.000 description 38
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 19
- 229910016104 LiNi1 Inorganic materials 0.000 description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 15
- 229910013716 LiNi Inorganic materials 0.000 description 14
- 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
- 239000002033 PVDF binder Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229910013100 LiNix Inorganic materials 0.000 description 6
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- XOTUNZWIDVULPE-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] XOTUNZWIDVULPE-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical class [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-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
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- DVLUDLYKHQIGSR-UHFFFAOYSA-N nickel(2+);dinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DVLUDLYKHQIGSR-UHFFFAOYSA-N 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000010586 diagram Methods 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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction 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
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- YQOXCVSNNFQMLM-UHFFFAOYSA-N [Mn].[Ni]=O.[Co] Chemical class [Mn].[Ni]=O.[Co] YQOXCVSNNFQMLM-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 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
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
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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
- 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
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- 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 the technical field of battery materials, and particularly relates to a graphene composite ternary cathode material of a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery is a new generation secondary battery developed on the basis of the primary lithium battery and widely used for small-sized portable electronic communication productsAnd electric vehicles. Currently, lithium ion battery anode materials which are industrialized mainly include lithium cobaltate, modified lithium manganate, lithium iron phosphate, ternary materials and the like. Lithium cobaltate has stable performance, but has high cost and toxic cobalt element, and may cause environmental pollution. Although the spinel type lithium manganate is low in price, the spinel type lithium manganate has poor cycle performance due to Jahn-Teller effect, and the electrochemical performance of the spinel type lithium manganate is rapidly attenuated due to the problem of manganese dissolution at high temperature. Lithium iron phosphate has poor conductivity, poor product batch disposability and poor low-temperature performance, and the problem that the dissolution of trace iron may cause short circuit of the battery exists. Therefore, it was found that LiNi was used as a material for the production of a polymerxCoyMn1-x-yO2The layered nickel oxide cobalt manganese series material (ternary material for short) has the advantages of the materials, overcomes the defects to a certain extent, has the characteristics of high specific capacity, stable cycle performance, relatively low cost, good safety performance and the like, and is considered as an ideal choice for a hybrid power supply. But at the same time, the method also has the defects of lower conductivity, fast capacity attenuation, poor rate capability and the like.
The preparation method of the prior ternary material mainly comprises a high-temperature solid phase method, a coprecipitation method, a sol-gel method, a template method and the like. The invention uses the template method to prepare the nickel-cobalt-manganese-lithium oxide material with uniform particles, thereby simplifying the preparation process. The size of the material prepared by the template method can be controlled, the problem of uneven granularity of the traditional solid phase method is solved, and the prepared material has high purity, small particle size, narrow distribution and good sintering performance.
The ternary positive electrode material integrates LiNiO2、LiCoO2、LiMnO2The advantages of the three positive electrode materials are considered to be one of the most potential widely applied positive electrode materials. The nickel-cobalt-manganese-lithium oxide ternary material has excellent performance which is paid attention to by a plurality of research institutions at home and abroad, is widely used in small electronic products, has a good development trend on large automobile power batteries, and has good application prospect. But simultaneously, the method also has the defects of lower conductivity, quick capacity attenuation, poor rate capability and the like, and in order to obtain a more excellent ternary cathode material, the lithium nickel cobalt manganese oxide is subjected toAnd (4) carrying out row doping and cladding. The crystal lattice is distorted to a certain extent through ion doping, certain defects are generated, and the electronic conductivity and the ion diffusion rate are improved, so that the rate capability and the cycle performance are improved.
Graphene, as a two-dimensional carbon nanomaterial, has a hexagonal honeycomb-shaped cavity structure of a two-dimensional monolayer and excellent physicochemical properties, such as a high specific surface area, a high electronic conductivity, excellent mechanical properties, good chemical stability, and the like, and thus is widely used in lithium ion batteries. In recent years, a lot of researches show that graphene can form a conductive network in a composite cathode material to improve the conductivity of the composite cathode material, and is helpful for shortening the diffusion path of lithium ions and greatly improving the high-rate charge and discharge performance of the cathode material, which are very important for nickel-cobalt-manganese-lithium oxide.
Disclosure of Invention
The invention aims at a ternary layered positive electrode material LiNixCol-x-y-zMnyAlzO2The lithium ion battery graphene composite ternary cathode material has the advantages of poor repeatability and rate capability, simple process, high safety and good stability.
The invention is realized by the following technical scheme:
a lithium ion battery graphene composite ternary cathode material is prepared by putting aluminum element into nickel cobalt manganese lithium oxide crystal lattice to replace Co on partial position3+And then mixing the aluminum-doped nickel-cobalt-manganese-lithium oxide with graphene, and preparing the mixture by a hydrothermal method.
The invention also provides a preparation method of the graphene composite ternary cathode material for the lithium ion battery, which comprises the following steps:
(1) dissolving potassium permanganate in certain deionized water, dropwise adding concentrated hydrochloric acid in a certain molar ratio, stirring for 15 minutes, placing the mixture into a reaction kettle for hydrothermal reaction, cooling, centrifuging, washing and drying to obtain brown manganese dioxide, and then calcining for 6 hours at 350 ℃ in a muffle furnace to obtain a solid product A;
(2) mixing the solid product A obtained in the step 1 with a nickel source, a cobalt source, an aluminum source and lithiumMixing and adding salt into a mixed solution of water and absolute ethyl alcohol according to a certain molar ratio, performing ultrasonic dispersion for 0.5-1 hour, stirring and evaporating to dryness to obtain a solid mixture B, grinding the solid mixture B, putting the ground mixture B into a crucible, and calcining to obtain the aluminum-doped nickel-cobalt-manganese-lithium oxide LiNixCol-x-y- zMnyAlzO2A positive electrode material;
(3) mixing graphene and LiNi prepared in the step 2xCol-x-y-zMnyAlzO2The anode material is put into water/glycol solution with the concentration of 0.01-0.02mol/L, ultrasonically dispersed for 0.5-2 hours, stirred, put into a reaction kettle for hydrothermal reaction, cooled and centrifugally washed to obtain LiNixCol-x-y-zMnyAlzO2 A graphene composite positive electrode material.
The temperature of the hydrothermal reaction in the step 1 is 140-160 ℃, the reaction time is 8-14 hours, the drying time is 8-12 hours, and the calcining temperature rise rate is 2 ℃/min.
In the step 2, the cobalt source is one or more of cobalt nitrate, cobalt acetate and cobalt chloride; the nickel source is one or more of nickel nitrate, nickel acetate and nickel chloride; the aluminum source is one or more of aluminum nitrate and aluminum chloride; the lithium salt is one or more of lithium carbonate, lithium acetate and lithium nitrate.
And 2, dissolving lithium salt, a cobalt source, a nickel source, an aluminum source and brown manganese dioxide in a mixed solution of water and absolute ethyl alcohol according to a certain molar ratio, and keeping the concentration at 0.1-0.15 mol/L.
The volume ratio of water to absolute ethyl alcohol in the mixed solution of water and absolute ethyl alcohol in the step 2 is 1: 0-10.
The evaporation temperature in the step 2 is 60-75 ℃, the calcination process is to heat to 400-500 ℃ for calcination for 5-8h, then to 750-850 ℃ for calcination for 10-20h, and the heating rate is 2 ℃/min.
The aluminum-doped nickel cobalt manganese lithium oxide LiNi obtained in the step 2xCol-x-y-zMnyAlzO2A positive electrode material, wherein 0<x<0.5，0<y<0.5，0<z<0.05。
The dosage of the graphene in the step 3 accounts for LiNixCol-x-y-zMnyAlzO21-10% of the mass, wherein the volume ratio of water to glycol in the mixed solution of water and glycol is 1-2: 1.
the temperature of the hydrothermal reaction in the step 3 is 120-140 ℃, the reaction time is 10-12 hours, the drying temperature is 70-80 ℃, and the drying time is 8-12 hours.
The invention has the advantages that:
1. the composite anode material of the invention is LiNi with better cycle performance and better rate performancexCol-x-y- zMnyAlzO2A graphene composite positive electrode material.
2. The invention is simple and easy to operate, has high production efficiency, reduces the production procedures, saves the production cost, and greatly improves the capacity, the rate capability and the cycle performance of the battery compared with the material which is not modified.
3. Hydrothermal recombination method for improving LiNixCol-x-y-zMnyAlzO2Adhesion to graphene to make LiNixCol-x-y-zMnyAlzO2The graphene sheets are uniformly dispersed among the graphene sheets to form a conductive network, so that the cycle performance and the rate capability of the lithium ion battery can be improved.
Drawings
FIG. 1 shows LiNi1/3Co1/3Mn1/3O2And LiNi1/3Co1/3-0.03Mn1/3Al0.03O2XRD pattern of (a).
FIG. 2 shows LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2Raman spectrum of graphene.
FIG. 3 shows LiNi1/3Co1/3Mn1/3O2、LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/ 3Al0.05O2First charge-discharge curve of graphene at 0.1C.
FIG. 4 shows LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2A cycle performance diagram of the graphene composite anode material.
FIG. 5 shows LiNi prepared in example 41/3Co1/3-0.05Mn1/3Al0.05O2SEM image of/graphene composite cathode material.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
The preparation method of the nickel-cobalt-manganese-lithium oxide cathode material of the lithium ion battery in the embodiment comprises the following steps:
(1) weighing 0.79g of potassium permanganate, dissolving in 50ml of deionized water, stirring for 15 minutes to completely dissolve the potassium permanganate, then dropwise adding 2ml of 37% hydrochloric acid, continuously stirring for 15 minutes, then transferring to a reaction kettle, reacting for 12 hours at 140 ℃, centrifuging, washing, drying for 12 hours at 70 ℃, transferring the obtained product to a crucible, calcining for 6 hours at 350 ℃ in a muffle furnace to obtain the required MnO2；
(2) 0.5481g of lithium nitrate, 0.2174g of manganese dioxide, 0.7276g of cobalt nitrate nonahydrate and 0.7270g of nickel nitrate nonahydrate are weighed and dissolved in a mixed solution of 50ml of water and 50ml of ethanol, and in order to make up for the loss of a lithium source in the calcining process, the lithium nitrate is excessive by 6 percent; performing ultrasonic treatment for 1 hour, continuing stirring for 6 hours, continuing stirring at 70 ℃ until the mixture is dried, grinding the dried solid, putting the ground solid into a crucible, putting the crucible into a muffle furnace, heating to 480 ℃ at a heating rate of 2 ℃/min in the air atmosphere, calcining for 5 hours, continuing heating to 850 ℃, calcining for 16 hours, cooling to room temperature along with the furnace, taking out a sample, and grinding again to obtain LiNi1/3Co1/3Mn1/3O2Powder;
the obtained LiNi1/3Co1/3Mn1/3O2With acetylene black and polyvinylidene fluoride (PVDF) at 8: 1: 1, rolling into a film with the thickness of 120 mu m, and performing vacuum drying at 120 ℃ for 10 hours to obtain the anode of the experimental half cell; using 1mol/L LiPF6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (EC to DMC volume ratio 1: 1) electrolyte, in a dry argon-filled glove box, with a metal lithium sheet as the negative electrode, assembled into a battery. LiNi prepared in this example1/3Co1/ 3Mn1/3O2The button cell which is taken as the anode and takes the lithium sheet as the cathode is charged under constant current-constant voltage under 0.1C multiplying power within the voltage range of 2.5-4.3V, the first discharge specific capacity is 175mAh/g when the battery is discharged under constant current under 0.1C multiplying power, but the capacity is only 157mAh/g after 30 cycles.
Example 2
The preparation method of the aluminum-doped nickel-cobalt-manganese-lithium oxide cathode material for the lithium ion battery in the embodiment comprises the following steps:
(1) weighing 0.79g of potassium permanganate, dissolving in 50ml of deionized water, stirring for 15 minutes to completely dissolve the potassium permanganate, then dropwise adding 2ml of 37% hydrochloric acid, continuously stirring for 15 minutes, then transferring to a reaction kettle, reacting for 12 hours at 140 ℃, centrifuging, washing, drying for 12 hours at 70 ℃, transferring the obtained product to a crucible, calcining for 6 hours at 350 ℃ in a muffle furnace to obtain the required MnO2；
(2) 0.5481g of lithium nitrate, 0.2174g of manganese dioxide, 0.6620g of cobalt nitrate nonahydrate, 0.7270g of nickel nitrate nonahydrate and 0.0844g of aluminum nitrate nonahydrate are weighed and dissolved in a mixed solution of 50ml of water and 50ml of ethanol, and in order to compensate the loss of a lithium source in the calcining process, the lithium nitrate is excessive by 6 percent; performing ultrasonic treatment for 1 hour, continuing stirring for 6 hours, continuing stirring at 70 ℃ until the mixture is dried, grinding the dried solid, putting the ground solid into a crucible, putting the crucible into a muffle furnace, heating to 480 ℃ at a heating rate of 2 ℃/min in the air atmosphere, calcining for 5 hours, continuing heating to 850 ℃, calcining for 16 hours, cooling to room temperature along with the furnace, taking out a sample, and grinding again to obtain LiNi1/3Co1/3-0.03Mn1/3Al0.03O2And (3) powder.
LiNi prepared by experiments1/3Co1/3Mn1/3O2And LiNi1/3Co1/3-0.03Mn1/3Al0.03O2The X-ray diffraction pattern of (A) is shown in FIG. 1. As can be seen from FIG. 1, LiNi was produced1/3Co1/3-0.05Mn1/3Al0.05O2Positive electrode material and undoped LiNi1/3Co1/3Mn1/3O2The XRD patterns of the materials are the same, and no impurity peak appears, which probably means that Al enters LiNi1/3Co1/3Mn1/ 3O2In the lattice, Co is substituted for some positions3+This indicates that the doping does not affect the bulk layer structure.
The obtained LiNi1/3Co1/3-0.03Mn1/3Al0.03O2With acetylene black and polyvinylidene fluoride (PVDF) at 8: 1: 1, rolling into a film with the thickness of 120 mu m, and performing vacuum drying at 120 ℃ for 10 hours to obtain the anode of the experimental half cell; using 1mol/L LiPF6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (EC to DMC volume ratio 1: 1) electrolyte, in a dry argon-filled glove box, with a metal lithium sheet as the negative electrode, assembled into a battery. LiNi prepared in this example1/3Co1/3-0.03Mn1/3Al0.03O2The button cell which is taken as the anode and the lithium sheet as the cathode is charged under constant current-constant voltage at 0.1C multiplying power within the voltage range of 2.5-4.3V, the first discharge specific capacity is 186mAh/g when the battery is discharged under constant current at 0.1C multiplying power, but the capacity is 175mAh/g after 30 cycles.
Example 3
The preparation method of the aluminum-doped nickel-cobalt-manganese-lithium oxide cathode material for the lithium ion battery in the embodiment comprises the following steps:
(1) weighing 0.79g of potassium permanganate, dissolving in 50ml of deionized water, stirring for 15 minutes to completely dissolve the potassium permanganate, then dropwise adding 2ml of 37% hydrochloric acid, continuing stirring for 15 minutes, then transferring to a reaction kettle, reacting at 140 ℃ for 12 hours, centrifuging, washing, drying at 70 ℃ for 12 hours, transferring the obtained product to a crucible, and finally drying in the presence of deionized waterCalcining the mixture for 6 hours in a muffle furnace at 350 ℃ to obtain the required MnO2；
(2) 0.5481g of lithium nitrate, 0.2174g of manganese dioxide, 0.6183g of cobalt nitrate nonahydrate, 0.7270g of nickel nitrate nonahydrate and 0.1406g of aluminum nitrate nonahydrate are weighed and dissolved in a mixed solution of 50ml of water and 50ml of ethanol, and in order to compensate the loss of a lithium source in the calcining process, the lithium nitrate is excessive by 6 percent; performing ultrasonic treatment for 1 hour, continuing stirring for 6 hours, continuing stirring at 70 ℃ until the mixture is dried, grinding the dried solid, putting the ground solid into a crucible, putting the crucible into a muffle furnace, heating to 480 ℃ at a heating rate of 2 ℃/min in the air atmosphere, calcining for 5 hours, continuing heating to 850 ℃, calcining for 16 hours, cooling to room temperature along with the furnace, taking out a sample, and grinding again to obtain LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And (3) powder.
The obtained LiNi1/3Co1/3-0.05Mn1/3Al0.05O2With acetylene black and polyvinylidene fluoride (PVDF) at 8: 1: 1, rolling into a film with the thickness of 120 mu m, and performing vacuum drying at 120 ℃ for 10 hours to obtain the anode of the experimental half cell; using 1mol/L LiPF6Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (EC to DMC volume ratio 1: 1) electrolyte, in a dry argon-filled glove box, with a metal lithium sheet as the negative electrode, assembled into a battery. LiNi prepared in this example1/3Co1/3-0.05Mn1/3Al0.05O2The button cell which is taken as the anode and the lithium sheet as the cathode is charged under constant current-constant voltage at 0.1C multiplying power within the voltage range of 2.5-4.3V, the first discharge specific capacity is 186mAh/g when the battery is discharged under constant current at 0.2C multiplying power, but the capacity is only 178mAh/g after 30 cycles.
Example 4
The preparation method of the aluminum-doped nickel-cobalt-manganese-lithium oxide/graphene positive electrode material for the lithium ion battery in the embodiment comprises the following steps:
(1) weighing 0.79g of potassium permanganate, dissolving in 50ml of deionized water, stirring for 15 minutes to completely dissolve the potassium permanganate, then dropwise adding 2ml of 37% hydrochloric acid, continuing stirring for 15 minutes, then transferring to a reaction kettle, and reacting for 12 hours at 140 DEG CThen, the resulting product was centrifuged, washed, dried at 70 ℃ for 12 hours, transferred to a crucible, and calcined in a muffle furnace at 350 ℃ for 6 hours to obtain the desired MnO2；
(2) 0.5481g of lithium nitrate, 0.2174g of manganese dioxide, 0.6183g of cobalt nitrate nonahydrate, 0.7270g of nickel nitrate nonahydrate and 0.1406g of aluminum nitrate nonahydrate are weighed and dissolved in a mixed solution of 50ml of water and 50ml of ethanol, and in order to compensate the loss of a lithium source in the calcining process, the lithium nitrate is excessive by 6 percent; performing ultrasonic treatment for 1 hour, continuing stirring for 6 hours, continuing stirring at 70 ℃ until the mixture is dried, grinding the dried solid, putting the ground solid into a crucible, putting the crucible into a muffle furnace, heating to 480 ℃ at a heating rate of 2 ℃/min in the air atmosphere, calcining for 5 hours, continuing heating to 850 ℃, calcining for 16 hours, cooling to room temperature along with the furnace, taking out a sample, and grinding again to obtain LiNi1/3Co1/3-0.05Mn1/3Al0.05O2Powder;
(3) weighing the obtained LiNi1/3Co1/3-0.05Mn1/3Al0.05O2Dispersing 0.3g of powder and 0.009g of graphene in a mixed solution of 30ml of deionized water and 20ml of ethylene glycol, ultrasonically dispersing for 1 hour, stirring for 6 hours by a stirrer, then transferring into a reaction kettle to react for 8 hours at 120 ℃, cooling, centrifuging, washing, and drying for 12 hours at 70 ℃ to obtain the LiNi1/ 3Co1/3-0.05Mn1/3Al0.05O2/GR-3wt% material.
The LiNi prepared in example1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2The Raman spectrum of/GR-3 wt% is shown in FIG. 2. As can be seen from FIG. 2, LiNi was produced1/3Co1/3-0.05Mn1/3Al0.05The O positive electrode material does not have a graphene peak, but LiNi compounded with graphene1/3Co1/3-0.05Mn1/3Al0.05O2The Raman diagram of/GR-3 wt% material shows graphene peak, which is probably that graphene is compounded in LiNi1/3Co1/3-0.05Mn1/3Al0.05O positive electrode materialThe surface of the material.
The obtained LiNi1/3Co1/3-0.05Mn1/3Al0.05O2GR-3wt% with acetylene black and polyvinylidene fluoride (PVDF) at 8: 1: 1, rolling into a film with the thickness of 120 mu m, and performing vacuum drying at 120 ℃ for 10 hours to obtain the anode of the experimental half cell; a battery was assembled using 1mol/L LiPF 6/Ethylene Carbonate (EC) -dimethyl carbonate (DMC) (EC to DMC volume ratio 1: 1) electrolyte, and a metal lithium sheet as the negative electrode in a dry argon-filled glove box. LiNi prepared in this example1/3Co1/3-0.05Mn1/3Al0.05O2The button cell with/GR-3 wt% as the positive electrode and the lithium sheet as the negative electrode is charged at constant current-constant voltage under 0.1C multiplying power within the voltage range of 2.5-4.3V, the first discharge specific capacity is 163mAh/g when the battery is discharged at constant current under 0.1C multiplying power, but the capacity is only 158mAh/g after 30 cycles.
Claims (9)
1. The graphene composite ternary cathode material for the lithium ion battery is characterized in that an aluminum element is put into a nickel-cobalt-manganese-lithium oxide crystal lattice to replace Co on partial positions3+Then, mixing aluminum-doped nickel-cobalt-manganese-lithium oxide with graphene, and preparing the mixture by a hydrothermal method;
the preparation method of the graphene composite ternary cathode material for the lithium ion battery comprises the following steps:
(1) dissolving potassium permanganate in certain deionized water, dropwise adding concentrated hydrochloric acid in a certain molar ratio, stirring for 15 minutes, placing the mixture into a reaction kettle for hydrothermal reaction, cooling, centrifuging, washing and drying to obtain brown manganese dioxide, and then calcining for 6 hours at 350 ℃ in a muffle furnace to obtain a solid product A;
(2) mixing the solid product A obtained in the step (1) with a nickel source, a cobalt source, an aluminum source and a lithium salt according to a certain molar ratio, adding the mixture into a mixed solution of water and absolute ethyl alcohol, ultrasonically dispersing for 0.5-1 hour, stirring and evaporating to dryness to obtain a solid mixture B, grinding the solid mixture B, putting the ground mixture B into a crucible, and calcining to obtain the aluminum-doped nickel-cobalt-manganese-lithium oxide LiNixChol-x-y-zMnyAlzO2A positive electrode material;
(3) mixing graphene and the LiNixChol-x-y-zMnyAlzO prepared in the step (2)2The anode material is placed in water/glycol solution with the concentration of 0.01-0.02mol/L, ultrasonically dispersed for 0.5-2 hours, stirred, placed in a reaction kettle for hydrothermal reaction, cooled and centrifugally washed to obtain LiNixChol-x-y-zMnyAlzO2A graphene composite positive electrode material.
2. The preparation method of the graphene composite ternary cathode material for the lithium ion battery as claimed in claim 1, wherein the hydrothermal reaction temperature in the step (1) is 140-.
3. The preparation method of the lithium ion battery graphene composite ternary cathode material according to claim 1, wherein in the step (2), the cobalt source is one or more of cobalt nitrate, cobalt acetate and cobalt chloride; the nickel source is one or more of nickel nitrate, nickel acetate and nickel chloride; the aluminum source is one or more of aluminum nitrate and aluminum chloride; the lithium salt is one or more of lithium carbonate, lithium acetate and lithium nitrate.
4. The method for preparing the graphene composite ternary cathode material for the lithium ion battery according to claim 1, wherein in the step (2), the lithium salt, the cobalt source, the nickel source, the aluminum source and the brown manganese dioxide are dissolved in a mixed solution of water and absolute ethyl alcohol according to a certain molar ratio, and the concentration is kept to be 0.1-0.15 mol/L.
5. The preparation method of the lithium ion battery graphene composite ternary cathode material according to claim 1, wherein the volume ratio of water to absolute ethyl alcohol in the mixed solution of water and absolute ethyl alcohol in the step (2) is 1: 0-10.
6. The preparation method of the graphene composite ternary cathode material for the lithium ion battery according to claim 1, wherein the evaporation temperature in the step (2) is 60-75 ℃, the calcination process comprises heating to 400-.
7. The preparation method of the graphene composite ternary cathode material for the lithium ion battery according to claim 1, wherein the aluminum-doped nickel-cobalt-manganese-lithium oxide LiNixClx-y-zMnyAlzO 2 cathode material obtained in the step (2) is characterized in that x is 0< x <0.5, y is 0< 0.5, and z is 0< z < 0.05.
8. The preparation method of the lithium ion battery graphene composite ternary cathode material according to claim 1, wherein the amount of graphene used in the step (3) accounts for 1-10% of the mass of LiNixCol-x-y-zMnyAlzO2, and the volume ratio of water to ethylene glycol in the mixed solution of water and ethylene glycol is 1-2: 1.
9. the preparation method of the lithium ion battery graphene composite ternary cathode material as claimed in claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 120-140 ℃, the reaction time is 10-12 hours, the drying temperature is 70-80 ℃, and the drying time is 8-12 hours.
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| KR20210064557A (en) * | 2019-11-26 | 2021-06-03 | (주)포스코케미칼 | Positive active materials for rechargable lithium ion battery, preparing method of the same, and and rechargeable lithium ion battery comprising the same |
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| 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 |
| CN112701275B (en) * | 2020-12-28 | 2022-02-22 | 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 |
| CN112599764B (en) * | 2020-12-28 | 2023-03-28 | 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 |
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