CN105140493A - Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof - Google Patents

Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof Download PDF

Info

Publication number
CN105140493A
CN105140493A CN201510659208.9A CN201510659208A CN105140493A CN 105140493 A CN105140493 A CN 105140493A CN 201510659208 A CN201510659208 A CN 201510659208A CN 105140493 A CN105140493 A CN 105140493A
Authority
CN
China
Prior art keywords
graphene
positive pole
composite positive
cnts
lini
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.)
Pending
Application number
CN201510659208.9A
Other languages
Chinese (zh)
Inventor
曾宪武
曾洪华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Tian Jing New Forms Of Energy Science And Technology Co Ltd
Original Assignee
Guangdong Tian Jing New Forms Of Energy Science And Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangdong Tian Jing New Forms Of Energy Science And Technology Co Ltd filed Critical Guangdong Tian Jing New Forms Of Energy Science And Technology Co Ltd
Priority to CN201510659208.9A priority Critical patent/CN105140493A/en
Publication of CN105140493A publication Critical patent/CN105140493A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and a preparation method thereof. The composite cathode materials are composed of LiNi1/3Co1/3Mn1/3O2, Graphene and CNTs, the Graphene and the CNTs account for 0.1%-20% by mass, and the mass ratio of the Graphene to the CNTs is 10:1 to 1:10; the preparation method comprises the steps that stable suspension of the Graphene and the CNTs, acetate or nitrate of nickel, cobalt and manganese and lithium carbonate serve as the raw materials, and the nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials are prepared through a rheologic phase method. The nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials have the advantages of being high in specific discharge capacity, good in rate capability, simple and convenient in preparation technology and the like, and the market prospect is wide when the nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials serve as power lithium-ion battery cathode materials.

Description

A kind of nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole and preparation method thereof
Technical field
The invention belongs to the energy and field of new, relate to a kind of lithium ion secondary battery anode material and preparation method, be specifically related to a kind of nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole (LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs) and preparation method.
Background technology
The pay attention to day by day of the environmental pollution caused for fuel-engined vehicle along with people, lithium ion battery becomes the focus of current people concern gradually as the application of dynamical system in electric automobile (EV) and mixed power electric car (HEV).Tertiary cathode material LiNi 1/3co 1/3mn 1/3o 2because having the features such as height ratio capacity, high voltage platform, low cost, good structural stability and low-temperature characteristics, be considered to one of the material most suitable as power lithium-ion battery positive pole.
Due to the restriction of its preparation technology and self structure performance, LiNi 1/3co 1/3mn 1/3o 2when using as power lithium-ion battery positive electrode, big current, fast charging and discharging performance (multiplying power) are still poor, cannot practical requirement.Cause LiNi 1/3co 1/3mn 1/3o 2the poor main cause of high rate performance have following some: (1) LiNi 1/3co 1/3mn 1/3o 2be a kind of ternary transition metal crystalline composite oxide material with layer structure, the impact by preparation technology easily occurs " cation mixing ", i.e. LiNi 1/3co 1/3mn 1/3o 2part Ni in crystal structure 2+li can be occupied +position, causes crystal partial structurtes to be caved in and resistance to overturning is reduced, affect the high rate performance of material; (2) electrode material surface active material easily dissolves in the electrolyte in charge and discharge process, causes the variation such as capacity, cycle performance and high rate performance; (3) LiNi of existing market 1/3co 1/3mn 1/3o 2tertiary cathode material is in order to ensure tap density, the compacted density of product, and material crystals size is comparatively large, causes the migration path of electronics and ion to increase, and LiNi 1/3co 1/3mn 1/3o 2belong to semi-conducting material, own electronic conductivity is lower, therefore also cause its high rate performance to be deteriorated.
Summary of the invention
The present invention mainly solves LiNi 1/3co 1/3mn 1/3o 2be applied to the problem that high rate performance that power lithium-ion battery positive electrode occurs is poor, a kind of LiNi is provided 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole and preparation method.
First, the invention provides a kind of nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole, concrete technical scheme is:
A kind of nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole, described composite positive pole is by LiNi 1/3co 1/3mn 1/3o 2, Graphene and CNTs composition; Percent mass hundred content shared by Graphene and CNTs be 0.1% ~ 20%, Graphene and CNTs mass ratio be 10:1 ~ 1:10.
Preferably, in described composite positive pole, the mol ratio of lithium and nickel, cobalt, manganese is 3.18:1:1:1; Composite positive pole in the present invention, the excessive object of lithium is to promote LiNi 1/3co 1/3mn 1/3o 2crystal structural stability, suppression " cation mixing "; In described composite positive pole, LiNi 1/3co 1/3mn 1/3o 2it is the crystal with layer structure.
Preferably, in described composite positive pole, percent mass hundred content shared by Graphene and CNTs be 0.15%, Graphene and CNTs mass ratio be 1:1.
Preferably, in described composite positive pole, Graphene size is greater than 5 μm, and the number of plies is 5 ~ 7 layers.
Preferably, in described composite positive pole, CNTs diameter 50nm ~ 70nm, length 3 ~ 5 μm.
The present invention also provides the preparation method of a kind of nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole, and concrete technical scheme is:
A preparation method for nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole, comprises the steps:
(1) taking the nickel containing certain mol proportion, cobalt, the acetic acid of manganese or nitrate joins in secondary deionized water, fully stirs and forms stabilizing solution or the suspending liquid A that concentration is 40g/L ~ 200g/L;
(2) take the carbonate of the lithium containing certain mol proportion, add in solution described in step (1) or suspending liquid A, fully stir that to form stream covert;
(3) stream that step (2) is obtained is in a disguised form at room temperature stirred 1h ~ 3h, then at 85 DEG C ~ 95 DEG C, add thermal agitation 4h ~ 6h, evaporate to dryness moisture content, at being finally placed on 110 DEG C ~ 120 DEG C, heat 5min ~ 10min, obtain dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 5min ~ 15min, then at 800 DEG C ~ 950 DEG C calcining 4h ~ 20h, obtain nickel-cobalt lithium manganate cathode material;
(5) Graphene and CNTs is joined in secondary deionized water, form the suspension-turbid liquid of solid content 1g/L ~ 20g/L, then the polyvinylpyrrolidone (PVP) of certain mass is added as surfactant, ultrasonic process 10min ~ 30min, obtained stable suspension-turbid liquid;
(6) nickel-cobalt lithium manganate cathode material obtained in step (4) is joined in the stable suspension-turbid liquid of Graphene and CNTs obtained in step (5), 80 DEG C ~ 90 DEG C heating 1h ~ 4h, evaporate to dryness moisture content, then heat treatment 1h ~ 2h at 400 DEG C ~ 500 DEG C, in inert atmosphere, prepares nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole.
Preferably, in described step (1) and step (2), the mol ratio of lithium and nickel, cobalt, manganese is 3.18:1:1:1.
Preferably, in described step (5), the amount of surfactant PVP accounts for 0.01% ~ 1% of Graphene and CNTs gross mass.
Preferably, in described step (4), calcining heat is 850 DEG C ~ 900 DEG C, and calcination time is 6 ~ 12h; Mainly because of under higher calcining heat and longer calcination time, although thermal diffusion is more abundant, resulting materials two-dimensional structure stability strengthens, and layer structure is more obvious, may occur excess agglomeration, cause LiNi 1/3co 1/3mn 1/3o 2crystal structure is destroyed, and has influence on chemical property.
Preferably, in described step (6), at 400 DEG C, in inert atmosphere, heat treatment 2h obtains LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole; The heat treatment temperature of 400 DEG C and the heat treatment time of 2h, can ensure the pyrolysis of PVP, removal, and in addition, inert atmosphere can ensure that Graphene and CNTs is not burnt.
In the present invention, in described step (1) when adopting the acetate of nickel, cobalt, manganese, because four acetate hydrate manganese are slightly soluble in water, what therefore formed is suspending liquid A; When adopting the nitrate of nickel, cobalt, manganese, the nitrate of this three metalloid is all soluble in water, and what therefore formed is solution A.
In the present invention, adding dispersant PVP in described step (5) is because it has longer microcosmic chain structure, can be wrapped in the surface of Graphene or CNTs, weaken Van der Waals force, promote its dispersion in secondary deionized water.
Principle of the present invention is as follows:
LiNi is coated on Graphene 1/3co 1/3mn 1/3o 2surface, improve its surface electronic conductivity, suppress LiNi simultaneously 1/3co 1/3mn 1/3o 2surface reactive material dissolving in the electrolyte; CNTs serves as a connection, the LiNi of Surface coating Graphene 1/3co 1/3mn 1/3o 2particle couples together, and builds three-dimensional conductive network, makes LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole shows more excellent high rate performance; In addition, LiNi 1/3co 1/3mn 1/3o 2in preparation process, add excessive lithium salts, can LiNi be promoted 1/3co 1/3mn 1/3o 2the raising of crystal structural stability, suppression " cation mixing ".
The present invention has the following advantages:
(1), the two dimension structure feature of Graphene can be easier to realize LiNi 1/3co 1/3mn 1/3o 2surface coating, thus reach promote LiNi 1/3co 1/3mn 1/3o 2surface electronic conductivity, the object suppressing surface reactive material to dissolve;
(2), the one-dimentional structure feature of CNTs, be convenient to it and play function served as bridge, build three-dimensional conductive network, thus reach and improve LiNi 1/3co 1/3mn 1/3o 2the object of high rate performance;
(3), the use of Rheological Phase Method and PVP surfactant, be convenient to Graphene and CNTs and LiNi 1/3co 1/3mn 1/3o 2effective compound;
(4), Rheological Phase Method simple process, be suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is LiNi in the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2eSEM (SEM) image of/Graphene/CNTs composite positive pole pole piece;
Fig. 2 is LiNi in the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2liNi in/Graphene/CNTs composite positive pole and comparative example 1 1/3co 1/3mn 1/3o 2positive electrode XRD collection of illustrative plates contrast;
Fig. 3 is LiNi in comparative example 2 of the present invention 1/3co 1/3mn 1/3o 2eSEM (SEM) image of/Graphene composite positive pole pole piece;
Fig. 4 is LiNi in comparative example 3 of the present invention 1/3co 1/3mn 1/3o 2eSEM (SEM) image of/CNTs composite positive pole pole piece.
Fig. 5 is LiNi in the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2liNi in/Graphene/CNTs composite positive pole and comparative example 2 1/3co 1/3mn 1/3o 2liNi in/Graphene composite positive pole, comparative example 3 1/3co 1/3mn 1/3o 2the high rate performance of/CNTs composite positive pole compares;
Fig. 6 is LiNi in comparative example 2 of the present invention 1/3co 1/3mn 1/3o 2liNi in/Graphene composite positive pole and comparative example 1 1/3co 1/3mn 1/3o 2the high rate performance of positive electrode compares;
Fig. 7 is LiNi in comparative example 3 of the present invention 1/3co 1/3mn 1/3o 2liNi in/CNTs composite positive pole and comparative example 1 1/3co 1/3mn 1/3o 2the high rate performance of positive electrode compares.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, and protection scope of the present invention is not limited only to the following stated.
embodiment 1
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/Graphene/CNTs composite positive pole, its concrete steps are as follows:
(1) take 2.9574g nickel acetate tetrahydrate, 2.9604g tetra-acetate hydrate cobalt, 2.9129g tetra-acetate hydrate manganese adds in 50ml secondary deionized water, fully stir and form the stable suspension A that concentration is 176.62g/L;
(2) taking 1.4113g lithium carbonate joins in suspending liquid A, fully stirs and forms stream in a disguised form;
(3) stream that step (2) is obtained is in a disguised form at room temperature stirred 2h, then at 90 DEG C, add thermal agitation 4h, evaporate to dryness moisture content, at being finally placed on 120 DEG C, heat 10min, obtain dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 900 DEG C of calcining 6h, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
(5) 68.8mgGraphene and 34.4mgCNTs(preferred size is greater than 5 μm, the number of plies is the Graphene of 5 ~ 7 layers;
Preferred diameter 50nm ~ 70nm, the CNTs that length is 3 μm ~ 5 μm) join in 100ml secondary deionized water, forming solid content is the suspension-turbid liquid of 1.032g/L, then adds the polyvinylpyrrolidone (PVP) of 1.32mg as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 400 DEG C, heat treatment 2h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene and CNTs, and 90 DEG C are heated 2h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole.
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2eSEM (SEM) image of/Graphene/CNTs composite positive pole electrode slice as shown in Figure 1, can be observed Graphene and can be coated on LiNi preferably 1/3co 1/3mn 1/3o 2surface, play improve its surface electronic conductivity and suppress surface reactive material dissolve effect.In addition, CNTs can play function served as bridge, connects the LiNi of coated Graphene 1/3co 1/3mn 1/3o 2particle, in electrode slice, build three-dimensional conductive network.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2the LiNi obtained in/Graphene/CNTs composite positive pole and comparative example 1 1/3co 1/3mn 1/3o 2the XRD collection of illustrative plates of positive electrode as shown in Figure 2.Therefrom can observe, prepared LiNi 1/3co 1/3mn 1/3o 2positive electrode presents good layered crystal structure, cation mixing degree is low, and in addition, the common compound of Graphene and CNTs is not to LiNi 1/3co 1/3mn 1/3o 2the microstructure of positive electrode impacts.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2liNi in/Graphene/CNTs composite positive pole and comparative example 2 1/3co 1/3mn 1/3o 2liNi in/Graphene composite positive pole, comparative example 3 1/3co 1/3mn 1/3o 2the high rate performance of/CNTs composite positive pole more as shown in Figure 5.Therefrom can observe, LiNi 1/3co 1/3mn 1/3o 2the high rate performance of/Graphene/CNTs composite positive pole is obviously better than LiNi 1/3co 1/3mn 1/3o 2/ Graphene and LiNi 1/3co 1/3mn 1/3o 2/ CNTs composite positive pole, illustrates Graphene, CNTs and LiNi 1/3co 1/3mn 1/3o 2common compound than Graphene or CNTs and LiNi 1/3co 1/3mn 1/3o 2single compound better can promote LiNi 1/3co 1/3mn 1/3o 2high rate performance.Reason is, Graphene and CNTs is at LiNi 1/3co 1/3mn 1/3o 2can cooperative effect be played in/CNTs composite positive pole, build three-dimensional conductive network, better promote LiNi 1/3co 1/3mn 1/3o 2the lifting of high rate performance.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole up to 180mAh/g, even if under 3C multiplying power, still can remain on 130mAh/g at the specific discharge capacity of 0.2C.
embodiment 2
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/Graphene/CNTs composite positive pole, its concrete steps are as follows:
(1) take 5.9148g nickel acetate tetrahydrate, 5.9208g tetra-acetate hydrate cobalt, 5.8258g tetra-acetate hydrate manganese adds in 100ml secondary deionized water, fully stir and form the steady suspending liquid A that concentration is 176.61g/L;
(2) taking 2.8300g lithium carbonate joins in suspending liquid A, fully stirs and forms stream in a disguised form;
(3) stream that step (2) is obtained is in a disguised form at room temperature stirred 3h, then at 90 DEG C, add thermal agitation 6h, evaporate to dryness moisture content, at being finally placed on 120 DEG C, heat 10min, obtain dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 15min, then at 900 DEG C of calcining 8h, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
(5) 137.6mgGraphene and 68.8mgCNTs is joined in 200ml secondary deionized water, forming solid content is the suspension-turbid liquid of 1.032g/L, then the polyvinylpyrrolidone (PVP) of 2.10mg is added as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 400 DEG C, heat treatment 2h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene and CNTs, and 90 DEG C are heated 4h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole.
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole up to 183mAh/g, even if under 3C multiplying power, still can remain on 125mAh/g at the specific discharge capacity of 0.2C.
embodiment 3
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/Graphene/CNTs composite positive pole, its concrete steps are as follows:
(1) take 4.7318g nickel nitrate, 4.7366g cobalt nitrate, 4.6606g manganese nitrate be dissolved in 100ml secondary deionized water, fully stir and form the stabilizing solution A that concentration is 141.29g/L;
(2) taking 2.2640g lithium carbonate joins in solution A, fully stirs and forms stream in a disguised form;
(3) stream that step (2) is obtained is in a disguised form at room temperature stirred 2h, then at 90 DEG C, add thermal agitation 5h, evaporate to dryness moisture content, at being finally placed on 120 DEG C, heat 10min, obtain dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 850 DEG C, calcine 12h in air atmosphere, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
(5) 183.4mgGraphene and 91.7mgCNTs is joined in 200ml secondary deionized water, forming solid content is the suspension-turbid liquid of 1.719g/L, then the polyvinylpyrrolidone (PVP) of 2.75mg is added as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 450 DEG C, heat treatment 1h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene and CNTs, and 80 DEG C are heated 4h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole.
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole up to 181mAh/g, even if under 3C multiplying power, still can remain on 126mAh/g at the specific discharge capacity of 0.2C.
embodiment 4
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/Graphene/CNTs composite positive pole, its concrete steps are as follows:
(1) take 3.7710g nickel nitrate, 3.7893g cobalt nitrate, 3.7285g manganese nitrate be dissolved in 100ml secondary deionized water, fully stir and form the stabilizing solution A that concentration is 112.89g/L;
(2) taking 2.2640g lithium carbonate joins in solution A, fully stirs and forms stream in a disguised form;
(3) stream obtained for step (2) is in a disguised form at room temperature stirred 1.5h, then at 85 DEG C, agitating heating 6h, evaporate to dryness moisture content, heats 10min at being finally placed on 110 DEG C, obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 800 DEG C, calcine 10h, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
(5) 234.8mgGraphene and 117.4mgCNTs is joined in 200ml secondary deionized water, forming solid content is the suspension-turbid liquid of 1.761g/L, then the polyvinylpyrrolidone (PVP) of 3.52mg is added as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 400 DEG C, heat treatment 2h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene and CNTs, and 80 DEG C are heated 3h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole.
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole up to 179mAh/g, even if under 3C multiplying power, still can remain on 130mAh/g at the specific discharge capacity of 0.2C.
embodiment 5
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/Graphene/CNTs composite positive pole, its concrete steps are as follows:
(1) take 4.5252g nickel acetate tetrahydrate, 4.5472g tetra-acetate hydrate cobalt, 4.4742g tetra-acetate hydrate manganese adds in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 135.47g/L;
(2) taking 2.7168g lithium carbonate joins in suspending liquid A, fully stirs and forms stream in a disguised form;
(3) stream obtained for step (2) is in a disguised form at room temperature stirred 2h, then at 90 DEG C, agitating heating 6h, evaporate to dryness moisture content, heats 10min at being finally placed on 120 DEG C, obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 850 DEG C, calcine 12h in air atmosphere, roughly obtain the LiNi of 289g 1/3co 1/3mn 1/3o 2positive electrode;
(5) 211.3mgGraphene and 211.3mgCNTs is joined in 200ml secondary deionized water, forming solid content is the suspension-turbid liquid of 2.113g/L, then the polyvinylpyrrolidone (PVP) of 4.23mg is added as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 400 DEG C, heat treatment 2h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene and CNTs, and 90 DEG C are heated 4h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, the accounting of Graphene and CNTs is roughly 0.15%(2 × 211.3mg/289g=0.15%).
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole up to 183mAh/g, even if under 3C multiplying power, still can remain on 127mAh/g at the specific discharge capacity of 0.2C.
embodiment 6
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/Graphene/CNTs composite positive pole, its concrete steps are as follows:
(1) take 3.1676g nickel acetate tetrahydrate, 3.1707g tetra-acetate hydrate cobalt, 3.1120g tetra-acetate hydrate manganese adds in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 94.83g/L;
(2) taking 1.4955g lithium carbonate joins in suspending liquid A, fully stirs and forms stream in a disguised form;
(3) stream obtained for step (2) is in a disguised form at room temperature stirred 2h, then at 90 DEG C, agitating heating 6h, evaporate to dryness moisture content, heats 10min at being finally placed on 120 DEG C, obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 900 DEG C, calcine 6h in air atmosphere, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
(5) 98.6mgGraphene and 197.2mgCNTs is joined in 200ml secondary deionized water, forming solid content is the suspension-turbid liquid of 1.479g/L, then the polyvinylpyrrolidone (PVP) of 2.96mg is added as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 400 DEG C, heat treatment 2h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene and CNTs, and 90 DEG C are heated 4h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole.
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that the present embodiment obtains 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole up to 181mAh/g, even if under 3C multiplying power, still can remain on 124mAh/g at the specific discharge capacity of 0.2C.
comparative example 1
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of positive electrode, its concrete steps are as follows:
(1) take 2.9574g nickel acetate tetrahydrate, 2.9604g tetra-acetate hydrate cobalt, 2.9129g tetra-acetate hydrate manganese adds in 50ml secondary deionized water, fully stir and form the stable suspension A that concentration is 176.62g/L;
(2) taking 1.4113g lithium carbonate joins in suspending liquid A, fully stirs and forms stream in a disguised form;
(3) stream obtained for step (2) is in a disguised form at room temperature stirred 2h, then at 90 DEG C, agitating heating 4h, evaporate to dryness moisture content, heats 10min at being finally placed on 120 DEG C, obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 900 DEG C, calcine 8h in air atmosphere, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2composite positive pole, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, and beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.Under 0.2C, LiNi 1/3co 1/3mn 1/3o 2the first discharge specific capacity of positive electrode can reach 190mAh/g, and however, the specific discharge capacity under its 3.0C is only 20mAh/g, illustrates that its high rate performance is poor.
comparative example 2
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/Graphene composite positive pole, its concrete steps are as follows:
(1) take 2.9574g nickel acetate tetrahydrate, 2.9604g tetra-acetate hydrate cobalt, 2.9129g tetra-acetate hydrate manganese adds in 50ml secondary deionized water, fully stir and form the stable suspension A that concentration is 176.62g/L;
(2) taking 1.4113g lithium carbonate joins in suspending liquid A, fully stirs and forms stream in a disguised form;
(3) stream obtained for step (2) is in a disguised form at room temperature stirred 2h, then at 90 DEG C, agitating heating 4h, evaporate to dryness moisture content, heats 10min at being finally placed on 120 DEG C, obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 900 DEG C, calcine 8h in air atmosphere, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
(5) 103.2mgGraphene is joined in 100ml secondary deionized water, forming solid content is the suspension-turbid liquid of 1.032g/L, then the polyvinylpyrrolidone (PVP) of 1.32mg is added as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 400 DEG C, heat treatment 2h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene, 90 DEG C of heating 2h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole.
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ Graphene composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2eSEM (SEM) image of/Graphene composite positive pole electrode slice as shown in Figure 3, can be observed Graphene and can be coated on LiNi preferably 1/3co 1/3mn 1/3o 2surface, play improve its surface electronic conductivity and suppress surface reactive material dissolve effect.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2liNi in/Graphene composite positive pole and comparative example 1 1/3co 1/3mn 1/3o 2the high rate performance of positive electrode more as shown in Figure 6.Therefrom can observe, LiNi 1/3co 1/3mn 1/3o 2the high rate performance of/Graphene composite positive pole is obviously better than LiNi 1/3co 1/3mn 1/3o 2positive electrode, illustrates Graphene and LiNi 1/3co 1/3mn 1/3o 2compound can promote LiNi 1/3co 1/3mn 1/3o 2high rate performance.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2liNi in/Graphene composite positive pole and embodiment 1 1/3co 1/3mn 1/3o 2the high rate performance of/Graphene/CNTs composite positive pole more as shown in Figure 5.Therefrom can observe, LiNi 1/3co 1/3mn 1/3o 2the high rate performance of/Graphene composite positive pole is not as LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, illustrates that Graphene is at lifting LiNi 1/3co 1/3mn 1/3o 2high rate performance aspect is not so good as Graphene and CNTs and is total to the effective of compound.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2/ Graphene composite positive pole is at the specific discharge capacity of 0.2C up to 190mAh/g, and under 3C multiplying power, specific discharge capacity remains on 110mAh/g.
comparative example 3
A kind of LiNi 1/3co 1/3mn 1/3o 2the preparation method of/CNTs composite positive pole, its concrete steps are as follows:
(1) take 2.9574g nickel nitrate, 2.9604g cobalt nitrate, 2.9129g manganese nitrate be dissolved in 50ml secondary deionized water, fully stir and form the stabilizing solution A that concentration is 176.62g/L;
(2) taking 1.4113g lithium carbonate joins in solution A, fully stirs and forms stream in a disguised form;
(3) stream obtained for step (2) is in a disguised form at room temperature stirred 2h, then at 90 DEG C, agitating heating 4h, evaporate to dryness moisture content, heats 10min at being finally placed on 120 DEG C, obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, then at 900 DEG C, calcine 8h in air atmosphere, obtain LiNi 1/3co 1/3mn 1/3o 2positive electrode;
(5) joined by 103.2mgCNTs in 100ml secondary deionized water, forming solid content is the suspension-turbid liquid of 1.032g/L, then adds the polyvinylpyrrolidone (PVP) of 1.32mg as surfactant, ultrasonic process 30min, obtained stable suspension-turbid liquid;
(6) by LiNi obtained in step (4) 1/3co 1/3mn 1/3o 2then at 400 DEG C, heat treatment 2h in inert atmosphere positive electrode to join in step (5) in the stable suspension-turbid liquid of obtained Graphene, 90 DEG C of heating 2h, evaporate to dryness moisture content, prepares LiNi 1/3co 1/3mn 1/3o 2/ CNTs composite positive pole.
The assembling of battery: the LiNi taking 0.425g gained 1/3co 1/3mn 1/3o 2/ CNTs composite positive pole, add 0.05g acetylene black and make conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, making electrode slurry is evenly being coated on aluminium foil, to beat after sheet in vacuum drying oven, temperature is dry 12h at 70 DEG C, and obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.5V ~ 4.6V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2eSEM (SEM) image of/CNTs composite positive pole electrode slice as shown in Figure 4, can be observed CNTs and can play function served as bridge LiNi 1/3co 1/3mn 1/3o 2particle couples together, but owing to lacking the cooperative effect of Graphene, therefore, cannot build the three-dimensional conductive network of more efficient in electrode slice.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2liNi in/CNTs composite positive pole and comparative example 1 1/3co 1/3mn 1/3o 2the high rate performance of positive electrode more as shown in Figure 7.Therefrom can observe, LiNi 1/3co 1/3mn 1/3o 2the high rate performance of/CNTs composite positive pole is obviously better than LiNi 1/3co 1/3mn 1/3o 2positive electrode, illustrates CNTs and LiNi 1/3co 1/3mn 1/3o 2compound also can promote LiNi 1/3co 1/3mn 1/3o 2high rate performance.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2liNi in/CNTs composite positive pole and embodiment 1 1/3co 1/3mn 1/3o 2the high rate performance of/Graphene/CNTs composite positive pole more as shown in Figure 5.Therefrom can observe, LiNi 1/3co 1/3mn 1/3o 2the high rate performance of/CNTs composite positive pole is not as LiNi 1/3co 1/3mn 1/3o 2/ Graphene/CNTs composite positive pole, illustrates that CNTs is at lifting LiNi 1/3co 1/3mn 1/3o 2high rate performance aspect is not so good as CNTs and Graphene and is total to the effective of compound.
The LiNi that this comparative example obtains 1/3co 1/3mn 1/3o 2/ CNTs composite positive pole is at the specific discharge capacity of 0.2C up to 200mAh/g, and under 3C multiplying power, specific discharge capacity remains on 50mAh/g.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.

Claims (10)

1. nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole, is characterized in that, described composite positive pole is by LiNi 1/3co 1/3mn 1/3o 2, Graphene and CNTs composition; Percent mass hundred content shared by Graphene and CNTs be 0.1% ~ 20%, Graphene and CNTs mass ratio be 10:1 ~ 1:10.
2. composite positive pole according to claim 1, is characterized in that, in described composite positive pole, the mol ratio of lithium and nickel, cobalt, manganese is 3.18:1:1:1.
3. composite positive pole according to claim 1, is characterized in that, in described composite positive pole, percent mass hundred content shared by Graphene and CNTs be 0.15%, Graphene and CNTs mass ratio be 1:1.
4. composite positive pole according to claim 1, is characterized in that, in described composite positive pole, Graphene size is greater than 5 μm, and the number of plies is 5 ~ 7 layers.
5. composite positive pole according to claim 1, is characterized in that, in described composite positive pole, and CNTs diameter 50nm ~ 70nm, length 3 ~ 5 μm.
6. a preparation method for nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole, is characterized in that, comprise the steps:
(1) taking the nickel containing certain mol proportion, cobalt, the acetic acid of manganese or nitrate joins in secondary deionized water, fully stirs and forms stabilizing solution or the suspending liquid A that concentration is 40g/L ~ 200g/L;
(2) take the carbonate of the lithium containing certain mol proportion, add in stabilizing solution described in step (1) or suspending liquid A, fully stir that to form stream covert;
(3) stream that step (2) is obtained is in a disguised form at room temperature stirred 1h ~ 3h, then at 85 DEG C ~ 95 DEG C, add thermal agitation 4h ~ 6h, evaporate to dryness moisture content, at being finally placed on 110 DEG C ~ 120 DEG C, heat 5min ~ 10min, obtain dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 5min ~ 15min, then at 800 DEG C ~ 950 DEG C calcining 4h ~ 20h, obtain nickel-cobalt lithium manganate cathode material;
(5) Graphene and CNTs is joined in secondary deionized water, form the suspension-turbid liquid of solid content 1g/L ~ 20g/L, then add the polyvinylpyrrolidone of certain mass as surfactant, ultrasonic process 10min ~ 30min, obtain and stablize suspension-turbid liquid;
(6) nickel-cobalt lithium manganate cathode material obtained in step (4) is joined in the stable suspension-turbid liquid of Graphene and CNTs obtained in step (5), 80 DEG C ~ 90 DEG C heating 1h ~ 4h, evaporate to dryness moisture content, then heat treatment 1h ~ 2h at 400 DEG C ~ 500 DEG C, in inert atmosphere, prepares nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole.
7. the preparation method of composite positive pole according to claim 6, is characterized in that, in described step (1) and step (2), the mol ratio of lithium and nickel, cobalt, manganese is 3.18:1:1:1.
8. the preparation method of composite positive pole according to claim 6, is characterized in that, in described step (5), the amount of surfactant polyvinylpyrrolidone accounts for 0.01% ~ 1% of Graphene and CNTs gross mass.
9. the preparation method of composite positive pole according to claim 6, is characterized in that, in described step (4), calcining heat is 850 DEG C ~ 900 DEG C, and calcination time is 6 ~ 12h.
10. the preparation method of composite positive pole according to claim 6, is characterized in that, in described step (6), at 400 DEG C, in inert atmosphere, heat treatment 2h obtains nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole.
CN201510659208.9A 2015-10-14 2015-10-14 Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof Pending CN105140493A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510659208.9A CN105140493A (en) 2015-10-14 2015-10-14 Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510659208.9A CN105140493A (en) 2015-10-14 2015-10-14 Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof

Publications (1)

Publication Number Publication Date
CN105140493A true CN105140493A (en) 2015-12-09

Family

ID=54725768

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510659208.9A Pending CN105140493A (en) 2015-10-14 2015-10-14 Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105140493A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105702926A (en) * 2016-02-01 2016-06-22 浙江天能能源科技有限公司 Ternary composite cathode material with three-dimensional network structure and preparation method of ternary composite cathode material
CN105958055A (en) * 2016-06-24 2016-09-21 哈尔滨工业大学 Layered structure nanometer lithium manganate-inlaid graphene-coated positive electrode material for lithium-ion battery, electrode and preparation method
CN106299243A (en) * 2016-08-25 2017-01-04 合肥国轩高科动力能源有限公司 A kind of anode slice of lithium ion battery containing combined conductive agent
CN106549147A (en) * 2016-11-02 2017-03-29 成都新柯力化工科技有限公司 Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application
CN108155358A (en) * 2017-12-11 2018-06-12 浙江天能能源科技股份有限公司 A kind of preparation method of lithium ion battery nickle cobalt lithium manganate anode composite material
CN108198700A (en) * 2018-01-16 2018-06-22 武汉低维材料研究院有限公司 A kind of preparation method and applications of graphene-carbon nano tube/cobalt manganese alloy oxide nano-slice compound
CN108390011A (en) * 2018-03-08 2018-08-10 南京师范大学 A kind of LiMn2O4 and graphene oxide and carbon nanotube composite aerogel and its preparation method and application
CN109873140A (en) * 2019-02-18 2019-06-11 合肥工业大学 A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102694201A (en) * 2012-06-04 2012-09-26 东莞新能源科技有限公司 Lithium ion battery
CN103811757A (en) * 2014-03-11 2014-05-21 中国第一汽车股份有限公司 Graphene composite positive electrode material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102694201A (en) * 2012-06-04 2012-09-26 东莞新能源科技有限公司 Lithium ion battery
CN103811757A (en) * 2014-03-11 2014-05-21 中国第一汽车股份有限公司 Graphene composite positive electrode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
彭辉: "锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2倍率性能提升研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105702926A (en) * 2016-02-01 2016-06-22 浙江天能能源科技有限公司 Ternary composite cathode material with three-dimensional network structure and preparation method of ternary composite cathode material
CN105702926B (en) * 2016-02-01 2018-07-06 浙江天能能源科技股份有限公司 A kind of three-dimensional net structure ternary composite cathode material and preparation method thereof
CN105958055A (en) * 2016-06-24 2016-09-21 哈尔滨工业大学 Layered structure nanometer lithium manganate-inlaid graphene-coated positive electrode material for lithium-ion battery, electrode and preparation method
CN105958055B (en) * 2016-06-24 2018-03-27 哈尔滨工业大学 A kind of laminated structure nano LiMn2O4 inlays the anode material for lithium-ion batteries, electrode and preparation method of graphene coated
CN106299243A (en) * 2016-08-25 2017-01-04 合肥国轩高科动力能源有限公司 A kind of anode slice of lithium ion battery containing combined conductive agent
CN106549147A (en) * 2016-11-02 2017-03-29 成都新柯力化工科技有限公司 Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application
CN108155358A (en) * 2017-12-11 2018-06-12 浙江天能能源科技股份有限公司 A kind of preparation method of lithium ion battery nickle cobalt lithium manganate anode composite material
CN108198700A (en) * 2018-01-16 2018-06-22 武汉低维材料研究院有限公司 A kind of preparation method and applications of graphene-carbon nano tube/cobalt manganese alloy oxide nano-slice compound
CN108390011A (en) * 2018-03-08 2018-08-10 南京师范大学 A kind of LiMn2O4 and graphene oxide and carbon nanotube composite aerogel and its preparation method and application
CN108390011B (en) * 2018-03-08 2020-04-07 南京师范大学 Lithium manganate, graphene oxide and carbon nanotube composite aerogel as well as preparation method and application thereof
CN109873140A (en) * 2019-02-18 2019-06-11 合肥工业大学 A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and preparation method thereof
CN109873140B (en) * 2019-02-18 2021-09-17 合肥工业大学 Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material

Similar Documents

Publication Publication Date Title
CN109980219B (en) Full-gradient nickel-cobalt-manganese positive electrode material, ruthenium oxide coating material and preparation method thereof
Tang et al. Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2
CN105140493A (en) Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof
CN102790217B (en) Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof
CN105226285B (en) A kind of porous Si-C composite material and preparation method thereof
WO2010040285A1 (en) Titanium-containing active material for negative electrodes and its production method and titanium-containing power lithium battery
CN107403913A (en) A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof
CN102244233B (en) Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate
CN101106189A (en) Making method for nano LiFePO4-carbon composite cathode material
CN105406046A (en) Lithium titanate negative electrode material and preparing method of lithium titanate negative electrode material
CN105355908A (en) Composite negative electrode material for lithium ion battery, preparing method thereof, negative electrode using material and lithium ion battery
CN103384001B (en) A kind of graphene combination electrode material and solid catalysis preparation method thereof
CN107482182B (en) Carbon-coated ion-doped manganese phosphate lithium electrode material and preparation method thereof
CN101308926B (en) Lithium ionic cell composite positive pole material coated by orthosilicate and its preparation method
CN103094550A (en) Preparation method of lithium-rich anode material
CN105226267B (en) Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application
CN103928668B (en) Lithium ion battery and preparation method of anode material thereof
CN104218235A (en) Double doped lithium-rich solid solution anode composite material, preparation method thereof, lithium ion battery positive plate and lithium ion battery
CN102315432A (en) A positive electrode material for C/Li2MSiO4-xNy/C (M=Fe, mn, co) composite lithium ion battery and its preparation method
CN104993118A (en) Synthesizing method for lithium-ion negative electrode material of Li4Ti5O12/C
Lin et al. One-step preparation of homogeneous single crystal Li-rich cathode materials with encouraging electrochemical performance
CN114613974B (en) Long-life quick-charging type lithium ion battery cathode material and preparation method thereof
CN112952047A (en) Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery
CN115911610A (en) Anode lithium supplement material, preparation method and application thereof
CN106299344A (en) A kind of sodium-ion battery nickel titanate negative material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20151209

RJ01 Rejection of invention patent application after publication