CN109659534A - A kind of positive electrode, and its preparation method and application - Google Patents

A kind of positive electrode, and its preparation method and application Download PDF

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Publication number
CN109659534A
CN109659534A CN201811550316.2A CN201811550316A CN109659534A CN 109659534 A CN109659534 A CN 109659534A CN 201811550316 A CN201811550316 A CN 201811550316A CN 109659534 A CN109659534 A CN 109659534A
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positive electrode
preparation
oxide
carbon source
carbon
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CN109659534B (en
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谭强强
王鹏飞
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Institute of Process Engineering of CAS
Langfang Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
Langfang Institute of Process Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 present invention relates to a kind of positive electrode, and its preparation method and application, the positive electrode includes basis material and the carbon quantum dot and oxide quantum dots for being set to described matrix material surface.The preparation method of the positive electrode includes the following steps: that (1) mixes carbon source, metal salt and solvent, obtains mixed solution；(2) basis material is added in the mixed solution, obtains precursor solution；(3) precursor solution is subjected to microwave treatment, obtains positive electrode.The present invention modifies substrate material surface using carbon quantum dot and oxide quantum dots, compared with the existing technology in all standing cladding, covering amount of the invention is less, influences on the specific capacity of basis material smaller, and cost is relatively low.

Description

A kind of positive electrode, and its preparation method and application
Technical field
The invention belongs to battery material technical fields, and in particular to a kind of positive electrode, and its preparation method and application.
Background technique
In recent years, the development of lithium ion battery is mainly towards high-energy density and high power density both direction.Nickel cobalt manganese Tertiary cathode material combines the high capacity of lithium nickelate, low cost, the high-pressure solid of cobalt acid lithium, high security, the Gao Wen of LiMn2O4 Qualitative feature obtains extensive research.
Restrict nickel-cobalt-manganternary ternary anode material at present, the principal element of especially nickelic tertiary cathode material development is peace Full property problem, nickel-cobalt-manganternary ternary anode material easily cause battery flatulence since surface alkali content is excessively high, and the safety such as leakage is hidden Suffer from；Simultaneously because the unstability of tertiary cathode material structure, is easy abjection oxygen, oxygen and combustibility a large amount of in battery are organic Electrolyte reaction, causes spontaneous combustion.
CN108428873A discloses a kind of Al2O3The nickel cobalt aluminium ternary anode material for lithium-ion batteries of cladding, including nickel cobalt Aluminic acid lithium material and the Al for being coated on the nickel cobalt aluminic acid lithium material surface2O3, the preparation method of the positive electrode includes: By ternary anode material precursor Ni1-x-yCoxAly(OH)2+ySintering；Lithium source is added in sintering gains to be sintered；Finally add Add covering material Al2O3It is sintered, obtains target product.The positive electrode cycle performance that the preparation method obtains is good, but Its capacity is lower.
CN104393277B discloses lithium ion tertiary cathode material and its preparation of a kind of surface clad oxide Method, the preparation method include the following steps: to mix metal salt solution with positive electrode, and alkali metal hydroxide is then added The aqueous solution of object adjusts the pH value of solution to 7~12, filters, drying, obtain the positive electrode of surface cladding hydroxide, into One step is heat-treated to obtain the tertiary cathode material of surface clad oxide.The positive electrode during the preparation process, hydrogen-oxygen Compound is non-uniform on microcosmic with the flocculation reaction that metal salt occurs, it is difficult to obtain uniform oxide cladding layers, in turn Obtained positive electrode chemical property is poor.
CN108258226A discloses a kind of carbon coating tertiary cathode material and preparation method thereof, and the preparation method includes Organic carbon source: being passed through into reaction chamber by following steps using chemical vapor depsotition equipment, and organic carbon source is decomposed through catalyst converter and given birth to At nano-carbon material, then so that nano-carbon material is deposited on tertiary cathode material surface by vapor deposition, and is made by ball milling Nano-carbon material is evenly distributed on the surface of tertiary cathode material, obtains carbon coating tertiary cathode material, the carbon material is three The covering amount of first material surface is higher, influences the performance of material specific capacity, and preparation process is complicated, higher cost, it is difficult to industry Metaplasia produces.
Therefore, this field needs to develop a kind of positive electrode, makes it have good chemical property, and preparation process It simply, can industrialized production.
Summary of the invention
For the problem that tertiary cathode material stability in the prior art and safety are poor, an object of the present invention exists In providing a kind of positive electrode, the positive electrode includes basis material and the carbon quantum dot for being set to described matrix material surface And oxide quantum dots.
On the one hand the presence of carbon quantum dot in positive electrode of the present invention assigns the good electric conductivity of positive electrode；Separately On the one hand have the function of being passivated grain boundary defects, reduce material surface to the sensibility of moisture and carbon dioxide, and then reduce material Expect surface alkali content, improves the chemical property and security performance of positive electrode.The presence of oxide quantum dots, can be enhanced table The stability of face lattice, further increases the chemical property of positive electrode, and the positive electrode recycles 200 weeks capacity retention ratios >=94.3%, high rate performance is good, specific discharge capacity >=200.2mAh/ under 10C/1C ratio >=80.9%, 0.2C current density g。
The present invention modifies substrate material surface using carbon quantum dot and oxide quantum dots, compared with the existing technology In all standing cladding, covering amount of the invention is less, influences on the specific capacity of basis material smaller, and cost is relatively low.
Preferably, in the positive electrode carbon quantum dot mass percent be 0.1~3%, such as 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8% etc..
When the mass percent of carbon quantum dot is less than 0.1% in positive electrode of the present invention, obtained positive electrode electric conductivity Poor and alkali content is higher, and the positive electrode chemical property obtained from is poor；The quality hundred of carbon quantum dot in positive electrode When dividing than being greater than 3%, because carbon material electro-chemical activity is poor, capacity is lower, and the positive electrode specific capacity obtained from is lower.
Preferably, in the positive electrode oxide quantum dots mass percent be 0.1~3%, such as 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8% etc..
When the mass percent of oxide quantum dots is less than 0.1% in positive electrode of the present invention, obtained positive electrode table Face structural stability is poor；When the mass percent of oxide quantum dots is greater than 3% in positive electrode, because oxide is being circulated throughout Volume expansion in journey is obvious, and when basis material is ternary material, oxide is electric under the charging/discharging voltage of ternary material Chemical activity is poor, and the positive electrode cyclical stability obtained from is poor, and specific capacity is lower.
Preferably, the oxide quantum dots include appointing in aluminium oxide, zirconium oxide, cerium oxide, titanium oxide and vanadium oxide It anticipates a kind of or at least two combination, such as aluminium oxide, zirconium oxide, cerium oxide etc..
Preferably, the partial size of the oxide quantum dots be 0.1~5nm, such as 0.5nm, 1nm, 1.5nm, 2nm, 3nm, 4nm etc..
Preferably, the partial size of the carbon quantum dot is 0.1~5nm, such as 0.5nm, 1nm, 1.5nm, 2nm, 3nm, 4nm Deng.
Preferably, described matrix material includes nickle cobalt lithium manganate tertiary cathode material and/or nickel cobalt lithium aluminate tertiary cathode Material.
Preferably, the partial size of described matrix material is 5~15 μm, such as 6 μm, 7 μm, 8 μm, 10 μm, 12 μm, 13 μm, 14 μ M etc..
The second object of the present invention is to provide a kind of preparation method of positive electrode, the preparation method includes following step It is rapid:
(1) carbon source, metal salt and solvent are mixed, obtains mixed solution；
(2) basis material is added in the mixed solution, obtains precursor solution；
(3) precursor solution is subjected to microwave treatment, obtains positive electrode.
The present invention prepares positive electrode using microwave-heating method, and the precursor solution of liquid phase is carried out microwave treatment, And then carbon source can be decomposed to form carbon quantum dot in substrate material surface, metal salt can be decomposed shape in substrate material surface At oxide quantum dots, liquid phase reaction in-situ can make carbon quantum dot and oxide quantum dots be distributed on the surface of basis material More uniform, obtained positive electrode chemical property is good.
Preferably, the power of step (3) described microwave treatment be 500~3000W, such as 800W, 1000W, 1200W, 1500W, 1800W, 2000W, 2200W, 2500W, 2800W etc..
When the power of microwave treatment of the present invention is less than 500W, carbon source cannot be decomposed shape completely in substrate material surface At carbon quantum dot, metal salt cannot be decomposed to form oxide quantum dots in substrate material surface completely, in turn result in carbon material It is unevenly distributed with oxide, influences the chemical property of positive electrode；When the power of the microwave treatment is greater than 3000W, reaction It is too fast, and then the temperature raising of system is too fast, carbon material is easy to happen excessively oxidation or kindling.
Preferably, the time of the microwave treatment be 10min~60min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min etc..
When the time of microwave treatment of the present invention is less than 10min, carbon source cannot be decomposed completely in substrate material surface Carbon quantum dot is formed, metal salt cannot be decomposed to form oxide quantum dots in substrate material surface completely, in turn result in carbon materials Material and oxide are unevenly distributed, and influence the chemical property of positive electrode；When the time of microwave treatment is greater than 60min, carbon material It is easy to happen excessive oxidation.
Preferably, the temperature of the microwave treatment is 100~300 DEG C, such as 150 DEG C, 200 DEG C, 250 DEG C, 280 DEG C etc..
The present invention is lower using the temperature of microwave treatment, and then guarantees that the metal ion in metal salt will not enter matrix In material lattice, guarantee the stability of matrix material structure, while temperature is lower can prevent carbon material from restoring tertiary cathode material Material；The metal oxide quantum dot on ternary material surface can stablize the lattice surface of tertiary cathode material, prevent ternary material The abjection of middle oxygen, obtained cathode material structure high stability.
Preferably, the atmosphere of the microwave treatment includes air atmosphere and/or oxygen atmosphere.
The atmosphere of the present invention during the preparation process is comprising atmosphere existing for oxygen, and then matrix material in guarantee reaction process Nickel, cobalt, manganese Metal ion in material will not be restored by carbon.
Preferably, the molar concentration of carbon source is 0.01~0.1mol/L in step (1) described mixed solution, such as 0.02mol/L、0.03mol/L、0.04mol/L、0.05mol/L、0.06mol/L、0.07mol/L、0.08mol/L、 0.09mol/L etc..
When the molar concentration of carbon source is less than 0.01mol/L in mixed solution of the present invention, carbon in obtained positive electrode Covering amount is lower, while increasing the energy consumption of microwave, increases the cost of integrated artistic；Mole of carbon source in the mixed solution When concentration is greater than 0.1mol/L, carbon coating is uneven in the positive electrode that is easy to cause.
Preferably, the molar concentration of the metal salt be 0.01~0.1mol/L, such as 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L etc..
When the molar concentration of metal salt is less than 0.01mol/L in mixed solution of the present invention, in obtained positive electrode Oxide covering amount is lower, while increasing the energy consumption of microwave, increases the cost of integrated artistic；Metal in the mixed solution When the molar concentration of salt is greater than 0.1mol/L, oxide cladding is uneven in the positive electrode that is easy to cause.
Preferably, step (1) described carbon source includes organic carbon source, optimization citric acid, succinic acid, lactic acid, acetic acid and formic acid In any one or at least two combination, such as citric acid, succinic acid, lactic acid etc..
Preferably, the metal salt includes metal organic acid salt, preferably aluminium isopropoxide, aluminium citrate, aluminum acetate, isopropanol It is any in zirconium, citric acid zirconium, acetic acid zirconium, tetrabutyl zirconate, cerous acetate, butyl titanate, isopropyl titanate and vanadyl oxalate A kind of or at least two combination, such as citric acid zirconium, aluminium isopropoxide, aluminium citrate, aluminum acetate etc..
Metal salt of the present invention can be dissolved in organic solvent, while be remained after decomposing without anionic group.
Preferably, the solvent includes organic solvent, any one in preferred alcohol, methanol, ethylene glycol and glycerine Or at least two combination, such as ethyl alcohol, methanol, ethylene glycol etc..
Preferably, step (2) described matrix material includes nickel-cobalt-manganternary ternary anode material and/or nickel cobalt aluminium tertiary cathode material Material.
Preferably, the ratio between basis material and carbon source and the gross mass of metal salt are 10~1000 in the precursor solution, It is preferred that 50~200, such as 50,100,300,500,600,800 etc..
When the ratio between basis material and carbon source and the gross mass of metal salt are less than 10 in precursor solution of the present invention, obtain just Carbon quantum dot and oxide quantum dots too high levels in the material of pole, and then positive electrode specific capacity is lower；Base in precursor solution When the ratio between body material and carbon source and the gross mass of metal salt are greater than 1000, carbon quantum dot and oxide amount in obtained positive electrode Son point content it is too low, cannot good covering basis material, the structural stability of basis material is poor, so positive electrode electrification It is poor to learn performance.
As optimal technical scheme, the preparation method of positive electrode of the present invention includes the following steps:
It (1) is 0.01~0.1mol/L by the molar concentration of organic carbon source, the molar concentration of metal organic acid salt is 0.01 Organic carbon source, metal organic acid salt and organic solvent are mixed, obtain mixed solution by~0.1mol/L；
(2) it is 50~200 by the ratio between basis material and carbon source and the gross mass of metal salt, is added in the mixed solution Basis material obtains precursor solution；
(3) microwave treatment that the precursor solution is carried out to 500~3000W power, at a temperature of 100~300 DEG C, oxygen 10min~60min is handled in atmosphere, obtains positive electrode.
The three of the object of the invention are to provide a kind of purposes of positive electrode as described in the first purpose, and the positive electrode is used for Field of batteries is preferred for the positive electrode of lithium ion battery.
The four of the object of the invention are to provide a kind of lithium ion battery, the lithium ion battery include described in the first purpose just Pole material.
Preferably, the positive electrode of the lithium ion battery includes positive electrode described in the first purpose.
Preferably, one of for the purpose of the positive electrode of the lithium ion battery described in positive electrode.
Compared with prior art, the invention has the following beneficial effects:
(1) in positive electrode of the present invention carbon quantum dot presence, on the one hand assign the good electric conductivity of positive electrode； On the other hand have the function of being passivated grain boundary defects, reduce material surface to the sensibility of moisture and carbon dioxide, and then reduce Material surface alkali content improves the chemical property and security performance of positive electrode.The presence of oxide quantum dots, can be enhanced The stability of lattice surface, further increases the chemical property of positive electrode, and the positive electrode recycles 200 weeks capacity and keeps Rate >=94.3%, high rate performance is good, and specific discharge capacity under 10C/1C ratio >=80.9%, 0.2C current density >= 200.2mAh/g。
(2) present invention modifies substrate material surface using carbon quantum dot and oxide quantum dots, relative to existing All standing cladding in technology, covering amount of the invention is less, smaller on the influence of the specific capacity of basis material, and cost is relatively low.
(3) present invention prepares positive electrode using microwave-heating method, and the precursor solution of liquid phase is carried out at microwave Reason, and then carbon source can be decomposed to form carbon quantum dot in substrate material surface, metal salt can be divided in substrate material surface Solution forms oxide quantum dots, and liquid phase reaction in-situ can make carbon quantum dot and oxide quantum dots on the surface of basis material It is distributed more uniform, obtained positive electrode chemical property is good.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of positive electrode includes the following steps:
It (1) is 0.04mol/L by the molar concentration of citric acid, the molar concentration of citric acid zirconium is 0.02mol/L, by lemon Acid, citric acid zirconium and ethyl alcohol mixing, obtain mixed solution；
(2) LiNi is pressed0.9Co0.05Mn0.05O2It is 100 with the ratio between the gross mass of citric acid and citric acid zirconium, in the mixing LiNi is added in solution0.9Co0.05Mn0.05O2, obtain precursor solution；
(3) microwave treatment that the precursor solution is carried out to 1500W power, at a temperature of 200 DEG C, is handled in oxygen atmosphere 25min obtains positive electrode.
Embodiment 2
The difference from embodiment 1 is that the molar concentration of citric acid is 0.01mol/L in step (1).
Embodiment 3
The difference from embodiment 1 is that the molar concentration of citric acid is 0.1mol/L in step (1).
Embodiment 4
The difference from embodiment 1 is that the molar concentration of citric acid is 0.005mol/L in step (1).
Embodiment 5
The difference from embodiment 1 is that the molar concentration of citric acid is 0.15mol/L in step (1).
Embodiment 6
The difference from embodiment 1 is that the molar concentration of citric acid zirconium is 0.01mol/L in step (1).
Embodiment 7
The difference from embodiment 1 is that the molar concentration of citric acid zirconium is 0.1mol/L in step (1).
Embodiment 8
The difference from embodiment 1 is that the molar concentration of citric acid zirconium is 0.005mol/L in step (1).
Embodiment 9
The difference from embodiment 1 is that the molar concentration of citric acid zirconium is 0.15mol/L in step (1).
Embodiment 10
The difference from embodiment 1 is that LiNi in step (2)0.9Co0.05Mn0.05O2It is total with citric acid and citric acid zirconium Mass ratio is 10.
Embodiment 11
The difference from embodiment 1 is that LiNi in step (2)0.9Co0.05Mn0.05O2It is total with citric acid and citric acid zirconium Mass ratio is 1000.
Embodiment 12
A kind of preparation method of positive electrode includes the following steps:
It (1) is 0.04mol/L by the molar concentration of glucose, the molar concentration of aluminum acetate is 0.02mol/L, by grape Sugar, aluminum acetate and ethylene glycol mixing, obtain mixed solution；
(2) LiNi is pressed0.9Co0.05Mn0.05O2It is 100 with the ratio between the gross mass of glucose and aluminum acetate, it is molten in the mixing LiNi is added in liquid0.9Co0.05Mn0.05O2, obtain precursor solution；
(3) microwave treatment that the precursor solution is carried out to 500W power, at a temperature of 300 DEG C, is handled in air atmosphere 60min obtains positive electrode.
Embodiment 13
A kind of preparation method of positive electrode includes the following steps:
(1) be 0.04mol/L by the molar concentration of lactic acid, the molar concentration of aluminium citrate is 0.02mol/L, by lactic acid, Aluminium citrate and methanol mixing, obtain mixed solution；
(2) LiNi is pressed0.9Co0.05Mn0.05O2It is 100 with the ratio between the gross mass of lactic acid and aluminium citrate, it is molten in the mixing LiNi is added in liquid0.9Co0.05Mn0.05O2, obtain precursor solution；
(3) microwave treatment that the precursor solution is carried out to 3000W power, at a temperature of 100 DEG C, is handled in air atmosphere 10min obtains positive electrode.
Comparative example 1
The difference from embodiment 1 is that not adding citric acid in step (1).
Comparative example 2
The difference from embodiment 1 is that not adding citric acid zirconium in step (1).
Comparative example 3
The difference from embodiment 1 is that not adding citric acid zirconium and citric acid in step (1).
Comparative example 4
The difference from embodiment 1 is that the quality of addition citric acid zirconium is addition in step (2) in step (1) LiNi0.9Co0.05Mn0.05O2The 20% of quality, by LiNi0.9Co0.05Mn0.05O2Carry out all standing cladding.
Comparative example 5
The difference from embodiment 1 is that the quality of addition citric acid is addition in step (2) in step (1) LiNi0.9Co0.05Mn0.05O2The 20% of quality, by LiNi0.9Co0.05Mn0.05O2Carry out all standing cladding.
Performance test:
The positive electrode being prepared is performed the following performance tests:
(1) battery assembly: anode pole piece is made in positive electrode produced by the present invention, cathode is metal lithium sheet, and diaphragm is Celgard2400, electrolyte are the LiPF of 1mol/L6/ DMC+DEC is assembled into CR2025 type button cell.The system of anode pole piece Standby process includes: the positive electrode that will be prepared, conductive agent acetylene black, binder PVDF (Kynoar) according to 90:5:5 Mass ratio, with N-Methyl pyrrolidone NMP as solvent be mixed and made into slurry after be coated in aluminium foil on, 120 DEG C drying 12 hours Afterwards, roll and be punched into diameter be 8.4mm disk as anode pole piece.
(2) electro-chemical test: in normal temperature condition, by button cell obtained in Wuhan Jin Nuo Electronics Co., Ltd. LAND electricity It is tested in the test macro of pond, charging/discharging voltage section is 3.0~4.3V, and definition 1C current density is 180mA/g.In 1C electricity It is recycled 200 weeks under current density, test capacity conservation rate, 200 weeks capacity retention ratio=200th week circulation specific discharge capacities/for the first time Specific discharge capacity；High rate performance test: charging to charge cutoff voltage for battery using 0.5C current density, respectively described in test Specific discharge capacity of the battery under 0.2C, 0.5C, 1C, 2C, 5C and 10C current density, calculates the ratio of 10C/1C.
The performance test results are as shown in table 1:
Table 1
It can be seen from Table 1 that being uniformly distributed in matrix using carbon quantum dot and oxide quantum dots in embodiment 1~13 Material LiNi0.9Co0.05Mn0.05O2Surface, obtained positive electrode chemical property is good, recycle 200 weeks capacity retention ratios >=94.3%, high rate performance is good, and discharge under 10C/1C ratio >=80.9%, 0.2C current density specific volume from the data in the table Amount >=200.2mAh/g.
It can be seen from Table 1 that embodiment 4 is kept relative to embodiment 1, high rate performance (10C/1C) and 200 weeks capacity Rate is lower, it may be possible to because the molar concentration of citric acid is too small in embodiment 4, carbon quantum dot content mistake in obtained positive electrode It is small, and then positive electrode electric conductivity is poor, surface alkali content is higher, so embodiment 4 is relative to embodiment 1, high rate performance (10C/1C) and 200 weeks capacity retention ratios are lower.
It can be seen from Table 1 that embodiment 5 is relative to embodiment 1, it is close in 0.2C, 0.5C, 1C, 2C, 5C and 10C electric current Specific discharge capacity under degree is lower, it may be possible to because the molar concentration of citric acid is excessive in embodiment 5, in obtained positive electrode Carbon quantum dot too high levels, because carbon material electro-chemical activity is poor, capacity is lower, the positive electrode specific capacity obtained from compared with It is low, so embodiment 5 is relative to embodiment 1, the specific discharge capacity under 0.2C, 0.5C, 1C, 2C, 5C and 10C current density compared with It is low.
It can be seen from Table 1 that embodiment 8 is kept relative to embodiment 1, high rate performance (10C/1C) and 200 weeks capacity Rate is lower, it may be possible to because the molar concentration of citric acid zirconium is too small in embodiment 8, zirconium oxide quantum dot in obtained positive electrode Content is too small, the hyperoxia that ternary material surface is not combined, and then positive electrode surface texture stability is poor, so implementing For example 8 relative to embodiment 1, high rate performance (10C/1C) and 200 weeks capacity retention ratios are lower.
It can be seen from Table 1 that embodiment 9 is relative to embodiment 1, it is close in 0.2C, 0.5C, 1C, 2C, 5C and 10C electric current Specific discharge capacity under degree is lower, and 200 weeks capacity retention ratios are lower, it may be possible to because of mole of citric acid zirconium in embodiment 9 Concentration is excessive, zirconium oxide quantum dot too high levels in obtained positive electrode, because zirconia electrochemical activity is poor, so implementing For example 9 relative to embodiment 1, the specific discharge capacity under 0.2C, 0.5C, 1C, 2C, 5C and 10C current density is lower, and 200 weeks Capacity retention ratio is lower.
It can be seen from Table 1 that comparative example 1 is relative to 1 high rate performance of embodiment (10C/1C) and 200 weeks capacity retention ratios It is lower, it may be possible to because not adding citric acid in comparative example 1, there is no carbon quantum dot, and then positive material in obtained positive electrode Expect that electric conductivity is poor, surface alkali content is higher, so comparative example 1 is relative to embodiment 1, high rate performance (10C/1C) and 200 weeks Capacity retention ratio is lower.
It can be seen from Table 1 that comparative example 2 is relative to 1 high rate performance of embodiment (10C/1C) and 200 weeks capacity retention ratios It is lower, it may be possible to because citric acid zirconium is not added in comparative example 2, and then positive electrode surface texture stability is poor, so right For ratio 2 relative to embodiment 1, high rate performance (10C/1C) and 200 weeks capacity retention ratios are lower.
It can be seen from Table 1 that comparative example 3 is relative to 1 high rate performance of embodiment (10C/1C) and 200 weeks capacity retention ratios It is lower, it may be possible to which that, because not adding citric acid zirconium and citric acid in comparative example 3, the positive electrode surface texture obtained from is stablized The poor and electric conductivity of property is poor, and surface alkali content is higher, so comparative example 3 is relative to embodiment 1, high rate performance (10C/1C) and Capacity retention ratio is lower within 200 weeks.
It can be seen from Table 1 that comparative example 4 is relative to embodiment 1 in 0.2C, 0.5C, 1C, 2C, 5C and 10C current density Under specific discharge capacity it is lower, it may be possible to because comparative example 4 obtained in positive electrode be oxidized zirconium all standing cladding, because oxidation Zirconium electro-chemical activity is poor, so comparative example 4 is relative to embodiment 1 under 0.2C, 0.5C, 1C, 2C, 5C and 10C current density Specific discharge capacity it is lower.
It can be seen from Table 1 that comparative example 5 is relative to embodiment 1 in 0.2C, 0.5C, 1C, 2C, 5C and 10C current density Under specific discharge capacity it is lower, it may be possible to because comparative example 5 obtained in positive electrode coated by carbon material all standing, because of carbon materials Expect that electro-chemical activity is poor, so comparative example 5 is relative to embodiment 1 under 0.2C, 0.5C, 1C, 2C, 5C and 10C current density Specific discharge capacity it is lower.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention, But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention Within protection scope and the open scope.

Claims (10)

1. a kind of positive electrode, which is characterized in that the positive electrode includes basis material and is set to described matrix material table The carbon quantum dot and oxide quantum dots in face.
2. positive electrode as described in claim 1, which is characterized in that the mass percent of carbon quantum dot in the positive electrode It is 0.1~3%；
Preferably, the mass percent of oxide quantum dots is 0.1~3% in the positive electrode.
3. positive electrode as claimed in claim 1 or 2, which is characterized in that the oxide quantum dots include aluminium oxide, oxidation In zirconium, cerium oxide, titanium oxide and vanadium oxide any one or at least two combination；
Preferably, the partial size of the oxide quantum dots is 0.1~5nm；
Preferably, the partial size of the carbon quantum dot is 0.1~5nm；
Preferably, described matrix material includes nickle cobalt lithium manganate tertiary cathode material and/or nickel cobalt lithium aluminate tertiary cathode material；
Preferably, the partial size of described matrix material is 5~15 μm.
4. a kind of preparation method of the positive electrode as described in one of claim 1-3, which is characterized in that the preparation method includes Following steps:
(1) carbon source, metal salt and solvent are mixed, obtains mixed solution；
(2) basis material is added in the mixed solution, obtains precursor solution；
(3) precursor solution is subjected to microwave treatment, obtains positive electrode.
5. preparation method as claimed in claim 4, which is characterized in that the power of step (3) described microwave treatment be 500~ 3000W；
Preferably, the time of the microwave treatment is 10min~60min；
Preferably, the temperature of the microwave treatment is 100~300 DEG C；
Preferably, the atmosphere of the microwave treatment includes air atmosphere and/or oxygen atmosphere.
6. preparation method as described in claim 4 or 5, which is characterized in that mole of carbon source in step (1) described mixed solution Concentration is 0.01~0.1mol/L；
Preferably, the molar concentration of the metal salt is 0.01~0.1mol/L.
7. the preparation method as described in one of claim 4-6, which is characterized in that step (1) described carbon source includes organic carbon source, In optimization citric acid, succinic acid, lactic acid, acetic acid and formic acid any one or at least two combination；
Preferably, the metal salt includes metal organic acid salt, preferably aluminium isopropoxide, aluminium citrate, aluminum acetate, zirconium iso-propoxide, Any one in citric acid zirconium, acetic acid zirconium, tetrabutyl zirconate, cerous acetate, butyl titanate, isopropyl titanate and vanadyl oxalate Or at least two combination；
Preferably, the solvent includes organic solvent, in preferred alcohol, methanol, ethylene glycol and glycerine any one or extremely Few two kinds of combination；
Preferably, step (2) described matrix material includes nickel-cobalt-manganternary ternary anode material and/or nickel cobalt aluminium tertiary cathode material；
Preferably, the ratio between basis material and carbon source and the gross mass of metal salt are 10~1000 in the precursor solution, preferably 50~200.
8. the preparation method of positive electrode as described in one of claim 4-7, which is characterized in that the preparation method includes as follows Step:
It (1) is 0.01~0.1mol/L by the molar concentration of organic carbon source, the molar concentration of metal organic acid salt is 0.01~ Organic carbon source, metal organic acid salt and organic solvent are mixed, obtain mixed solution by 0.1mol/L；
(2) it is 50~200 by the ratio between basis material and carbon source and the gross mass of metal salt, matrix is added in the mixed solution Material obtains precursor solution；
(3) microwave treatment that the precursor solution is carried out to 500~3000W power, at 100~300 DEG C, in oxygen atmosphere 10min~60min is managed, positive electrode is obtained.
9. a kind of purposes of the positive electrode as described in one of claim 1-3, which is characterized in that the positive electrode is used for battery Field is preferred for the positive electrode of lithium ion battery.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes anode described in one of claim 1-3 Material；
Preferably, the positive electrode of the lithium ion battery includes positive electrode described in one of claim 1-3；
Preferably, the positive electrode of the lithium ion battery is positive electrode described in one of claim 1-3.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111416117A (en) * 2020-03-11 2020-07-14 合肥国轩高科动力能源有限公司 Preparation method of CdTe quantum dot modified lithium battery positive electrode material
CN113921789A (en) * 2021-10-08 2022-01-11 合肥国轩高科动力能源有限公司 Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material
CN114464789A (en) * 2022-01-19 2022-05-10 华中科技大学 Energy storage secondary battery layered positive electrode material and preparation method thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102237517A (en) * 2010-04-20 2011-11-09 深圳市比克电池有限公司 Lithium ion battery, cathode composite material and preparation methods thereof
CN103227317A (en) * 2013-03-26 2013-07-31 武汉理工大学 V205 quantum dot/graphene composite materials and preparation method thereof and application thereof
CN104124430A (en) * 2014-07-18 2014-10-29 武汉理工大学 Ruthenium dioxide quantum dot modified vanadium pentoxide nano material as well as preparation method and application of material
US20150280248A1 (en) * 2014-03-26 2015-10-01 William Marsh Rice University Graphene quantum dot-carbon material composites and their use as electrocatalysts
CN105047866A (en) * 2015-06-15 2015-11-11 西北师范大学 Preparation method of carbon-coating sulfur micron material doped with graphene quantum dots
CN105914353A (en) * 2016-05-06 2016-08-31 复旦大学 Morphology-controlled carbon quantum dot/nickel cobaltate composite electrode material and preparation method
CN106784851A (en) * 2017-03-08 2017-05-31 中国科学院宁波材料技术与工程研究所 A kind of preparation method and applications of graphene quantum dot/mesoporous carbon composite material
CN107431211A (en) * 2014-11-06 2017-12-01 威廉马歇莱思大学 By the method for various carbon sources manufacture graphene quantum dot
KR20170142344A (en) * 2016-06-17 2017-12-28 서울대학교산학협력단 Electrode composite and preparing method thereof
CN107946084A (en) * 2017-10-26 2018-04-20 广东工业大学 A kind of metal oxide/three-dimensional porous graphene composite material and its preparation method and application

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102237517A (en) * 2010-04-20 2011-11-09 深圳市比克电池有限公司 Lithium ion battery, cathode composite material and preparation methods thereof
CN103227317A (en) * 2013-03-26 2013-07-31 武汉理工大学 V205 quantum dot/graphene composite materials and preparation method thereof and application thereof
US20150280248A1 (en) * 2014-03-26 2015-10-01 William Marsh Rice University Graphene quantum dot-carbon material composites and their use as electrocatalysts
CN104124430A (en) * 2014-07-18 2014-10-29 武汉理工大学 Ruthenium dioxide quantum dot modified vanadium pentoxide nano material as well as preparation method and application of material
CN107431211A (en) * 2014-11-06 2017-12-01 威廉马歇莱思大学 By the method for various carbon sources manufacture graphene quantum dot
CN105047866A (en) * 2015-06-15 2015-11-11 西北师范大学 Preparation method of carbon-coating sulfur micron material doped with graphene quantum dots
CN105914353A (en) * 2016-05-06 2016-08-31 复旦大学 Morphology-controlled carbon quantum dot/nickel cobaltate composite electrode material and preparation method
KR20170142344A (en) * 2016-06-17 2017-12-28 서울대학교산학협력단 Electrode composite and preparing method thereof
CN106784851A (en) * 2017-03-08 2017-05-31 中国科学院宁波材料技术与工程研究所 A kind of preparation method and applications of graphene quantum dot/mesoporous carbon composite material
CN107946084A (en) * 2017-10-26 2018-04-20 广东工业大学 A kind of metal oxide/three-dimensional porous graphene composite material and its preparation method and application

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111416117A (en) * 2020-03-11 2020-07-14 合肥国轩高科动力能源有限公司 Preparation method of CdTe quantum dot modified lithium battery positive electrode material
CN113921789A (en) * 2021-10-08 2022-01-11 合肥国轩高科动力能源有限公司 Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material
CN113921789B (en) * 2021-10-08 2022-12-09 合肥国轩高科动力能源有限公司 Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material
CN114464789A (en) * 2022-01-19 2022-05-10 华中科技大学 Energy storage secondary battery layered positive electrode material and preparation method thereof
CN114464789B (en) * 2022-01-19 2023-03-10 华中科技大学 Energy storage secondary battery layered positive electrode material and preparation method thereof

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