CN106025346B - The battery of lithium ion battery composite cathode material and preparation method thereof and assembling - Google Patents

The battery of lithium ion battery composite cathode material and preparation method thereof and assembling Download PDF

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CN106025346B
CN106025346B CN201610594164.0A CN201610594164A CN106025346B CN 106025346 B CN106025346 B CN 106025346B CN 201610594164 A CN201610594164 A CN 201610594164A CN 106025346 B CN106025346 B CN 106025346B
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lithium
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lithium ion
ion battery
composite cathode
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CN106025346A (en
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吴孟涛
徐宁
张彬
吕菲
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Tianjin B&M Science and Technology Co Ltd
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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
    • 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
    • H01M4/362—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
    • H01M4/36—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses the battery of a kind of lithium ion battery composite cathode material and preparation method thereof and assembling, spinel lithium manganate and anode material for lithium-ion batteries are mixed with composite positive pole；The high energy density lithium ion secondary battery for solving using Si/C as cathode the problems such as coulombic efficiency is low for the first time, utilization rate is low, overdischarge safety is low.Spinel lithium manganate is mixed with anode material for lithium-ion batteries, assembles 18650 batteries with Si/C cathode, electrolyte, diaphragm.The addition of spinel lithium manganate improves coulombic efficiency for the first time, improves battery over-discharge security performance.

Description

The battery of lithium ion battery composite cathode material and preparation method thereof and assembling
Technical field
The present invention relates to a kind of lithium ion battery composite cathode materials, more particularly to lithium ion battery composite cathode material And preparation method thereof and assembling battery.
Background technique
Lithium ion battery is the secondary cell that a kind of energy density is high, function metric density is high, the service life is long, with fossil energy Reduction is serious with environmental pollution, gradually plays irreplaceable role in modern society.With the development of 3C Product, it is desirable that The stand-by time of mobile phone, camera, notebook etc. gradually increases, and requires the energy density of lithium ion secondary battery gradually stringent. The demand of the fast development of the industries such as electric car, smart grid, lithium-ion-power cell steeply rises, while in country ten In three or five planning, new-energy automobile requires the energy density of single battery to be greater than 300Wh/kg, and cycle life is greater than 2000 times.This Just need lithium-ion-power cell that there is the features such as monomer energy density is high, good cycling stability, security performance is excellent.Traditional Graphitic carbon is no longer satisfied the needs of high-energy density as the negative electrode material of lithium ion secondary battery, Si/C cathode lithium from Extensive use in sub- secondary cell has become a kind of trend.
But Si/C has for the first time in use as ion secondary battery cathode material lithium that coulombic efficiency is low, mistake It discharges the disadvantages such as security performance is low, these serious Si/C negative electrode materials that constrain are in high energy density lithium ion secondary battery Application.The existing method for improving Si/C negative electrode material coulombic efficiency for the first time is mainly that cathode mends lithium technology, but the method is deposited In very big security risk, and be not suitable for batch production.Composite positive pole is prepared by the way that additive is added into positive electrode, On the one hand coulombic efficiency for the first time and the safety that Si/C negative electrode material can be improved, on the other hand may be implemented Si/C negative electrode material Extensive use and have simple process, the advantages that safety is good.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of lithium ion battery composite cathode materials and preparation method thereof With the battery of assembling, the coulombic efficiency for the first time and discharge capacity of battery are improved.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: a kind of composite lithium ion battery anode material The preparation method of material, spinel lithium manganate and anode material for lithium-ion batteries are mixed with composite positive pole；
The anode material for lithium-ion batteries includes LiCoO2、LiFePO4、LiMnO2、LiMn2-x-yNixMyO4、 LiNixCoyM1-x-yO2One or more of, wherein LiMn2-x-yNixMyO4In, 0.5≤x≤1,0.01≤y≤0.1, M= Co, Al, Cr, Fe, Mg, Zn, Ti；LiNixCoyM1-x-yO2In 0.3≤x≤0.9,0.05≤y≤0.3, M=Mn, Al, Cr, Fe, Mg, Zn, Ti；
The spinel lithium manganate is Li2Mn2-xMxO4, 0≤x≤0.1, M=Ni, B, Al, Cr, Fe, Mg, Zn, in Ti It is one or more of；Synthetic spinel LiMn2O4 Li2Mn2-xMxO4Method be by lithium compound, manganese compound and doped chemical M Compound mixes in a high speed mixer, and maturing temperature is 400-900 DEG C, and calcining time 2-10h breaks obtained solids Broken, screening obtains finished product；The lithium compound is LiOH, Li2CO3、LiNO3, one or more of lithium acetate；The manganese Close object MnO2、Mn2O3、Mn(OH)2、MnCO3、Mn(NO3)2、MnSO4, one or more of manganese acetate；The doped chemical is One or more of Ni, B, Al, Cr, Fe, Mg, Zn, Ti.
The spinel lithium manganate and anode material for lithium-ion batteries mixing quality ratio are 0.01-0.2:1.
The spinel lithium manganate is Li2Mn2O4。
The anode material for lithium-ion batteries is LiCoO2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2In It is a kind of.
The spinel lithium manganate and anode material for lithium-ion batteries mixing quality ratio are 0.05:1.
The lithium compound is Li2CO3。
The manganese compound is Mn2O3。
The maturing temperature is 800 DEG C, calcining time 10h.
The lithium ion battery composite cathode material of above-mentioned method preparation.
The lithium ion battery composite cathode material of above method preparation is used for and Si/C cathode, diaphragm, organic electrolyte group Dress up 18650 batteries.
The beneficial effects of the present invention are: the present invention is synthetic spinel LiMn2O4 Li first2Mn2-xMxO4, secondly by its with Anode material for lithium-ion batteries mixing matches 18650 batteries of assembling with Si/C cathode, during the charging process 2 Li+From Li2Mn2O4Middle all abjections, only one Li when electric discharge+It is embedded in Mn oxide, generates LiMn2O4, improve the library for the first time of battery Human relations efficiency and discharge capacity, while Li2Mn2O4Addition be conducive to improve 18650 batteries overdischarge security performance.
Detailed description of the invention
Fig. 1 is 18650 batteries discharge curve for the first time in the embodiment of the present invention 1 and comparative example 1.
Fig. 2 is 18650 battery plus-negative plate potential curves in the embodiment of the present invention 1 and comparative example 1.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description:
The preparation method of lithium ion battery composite cathode material of the invention, spinel lithium manganate and lithium ion cell positive Material is mixed with composite positive pole；
The anode material for lithium-ion batteries includes LiCoO2、LiFePO4、LiMnO2、LiMn2-x-yNixMyO4、 LiNixCoyM1-x-yO2One or more of, wherein LiMn2-x-yNixMyO4In, 0.5≤x≤1,0.01≤y≤0.1, M= Co, Al, Cr, Fe, Mg, Zn, Ti；LiNixCoyM1-x-yO2In 0.3≤x≤0.9,0.05≤y≤0.3, M=Mn, Al, Cr, Fe, Mg, Zn, Ti；
The spinel lithium manganate is Li2Mn2-xMxO4, 0≤x≤0.1, M=Ni, B, Al, Cr, Fe, Mg, Zn, in Ti It is one or more of；Synthetic spinel LiMn2O4 Li2Mn2-xMxO4Method be by lithium compound, manganese compound and doped chemical M Compound mixes in a high speed mixer, and maturing temperature is 400-900 DEG C, and calcining time 2-10h breaks obtained solids Broken, screening obtains finished product；The lithium compound is LiOH, Li2CO3、LiNO3, one or more of lithium acetate；The manganese Close object MnO2、Mn2O3、Mn(OH)2、MnCO3、Mn(NO3)2、MnSO4, one or more of manganese acetate；The doped chemical is One or more of Ni, B, Al, Cr, Fe, Mg, Zn, Ti.
The spinel lithium manganate and anode material for lithium-ion batteries mixing quality ratio are 0.01-0.2:1.
It is preferred that the spinel lithium manganate is Li2Mn2O4。
It is preferred that the anode material for lithium-ion batteries is LiCoO2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2 One of.
It is preferred that the spinel lithium manganate and anode material for lithium-ion batteries mixing quality ratio are 0.05:1.
It is preferred that the lithium compound is Li2CO3。
It is preferred that the manganese compound is Mn2O3。
It is preferred that the maturing temperature is 800 DEG C, calcining time 10h.
The lithium ion battery composite cathode material of above-mentioned method preparation.
The lithium ion battery composite cathode material of above method preparation is used for and Si/C cathode, diaphragm, organic electrolyte group Dress up 18650 batteries.
Rich lithium material prepares composite positive pole as anode material for lithium-ion batteries additive, improves with Si/C material The coulombic efficiency for the first time of lithium ion secondary battery as cathode and anti-overdischarge safety improve energy-density lithium ion battery The method of first charge discharge efficiency and safety.Spinel lithium manganate Li2Mn2O4Charging capacity is up to 270mAh/g, during discharge Li+Irreversible insertion forms LiMn2O4Structure spinel, specific discharge capacity 140mAh/g, extra Li+Supplement Si/C Cathode is in charge and discharge process to Li+Loss, improve cathode efficiency.
When lithium ion battery overdischarge, cathode irreversible capacity increases, and voltage quickly increases, the copper on negative current collector Start to dissolve, charge and discharge cycles are deteriorated.Cathode voltage quickly increases during overdischarge in order to prevent, and optimal method is The irreversible capacity for increasing anode, accelerates the decaying of cathode voltage, in order to increase the irreversible capacity of positive electrode, into anode A certain amount of anode additive is added.
Embodiment 1
1.58kg Mn2O3With 0.7537kg Li2CO340min is mixed in a high speed mixer, by uniformly mixed material It is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.By what is prepared Li2Mn2O4With LiCoO25:95 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer.By mixed material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, are stirred evenly and are prepared into anode sizing agent.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm is assembled into 18650 together Battery.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.3V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
From figure 1 it appears that the capacity of Si/C cathode is 632.5mA in embodiment 1, and right in battery discharge procedure Capacity than Si/C cathode in embodiment 1 is 611.2mA, and anode provides extra Li+, the capacity of cathode is improved, and then improve The efficiency of battery；From figure 2 it can be seen that single positive electrode, battery is during overdischarge, Li in comparative example 1 + continue to deviate from from cathode, cathode potential increases, and collector Cu is caused to be precipitated, and battery security reduces, in embodiment 1, Spinelle Li2Mn2O4The Li that comes is provided+, cathode potential is reduced, cathode voltage sharply declines, when battery discharge is to 0V, cathode Current potential is lower, and collector Cu is not precipitated, and improves battery security
Embodiment 2
1.58kg Mn2O3With 0.7537kg Li2CO340min is mixed in a high speed mixer, by uniformly mixed material It is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.By what is prepared Li2Mn2O4With LiCoO21:99 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer.By mixed material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, are stirred evenly and are prepared into anode sizing agent.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm is assembled into 18650 together Battery.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.3V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Embodiment 3
1.58kg Mn2O3With 0.7537kg Li2CO340min is mixed in a high speed mixer, by uniformly mixed material It is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.By what is prepared Li2Mn2O4With LiCoO220:80 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer.By mixed material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, are stirred evenly and are prepared into anode sizing agent.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm is assembled into 18650 together Battery.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.3V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Table 1
Embodiment 4
1.58kg Mn2O3With 0.7537kg Li2CO340min is mixed in a high speed mixer, by uniformly mixed material It is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.By what is prepared Li2Mn2O4With LiNi0.8Co0.1Mn0.1O25:95 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer.After mixing Material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, stir evenly and be prepared into anode sizing agent. In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm is assembled into together 18650 batteries.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.2V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Embodiment 5
1.58kg Mn2O3With 0.7537kg Li2CO340min is mixed in a high speed mixer, by uniformly mixed material It is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.By what is prepared Li2Mn2O4With LiNi0.8Co0.15Al0.05O25:95 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer.It will mixing Material 95% afterwards, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, are stirred evenly and are prepared into positive slurry Material.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm assembles together At 18650 batteries.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.2V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Embodiment 6
1.58kg Mn2O3With 0.7537kg Li2CO340min is mixed in a high speed mixer, by uniformly mixed material It is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.By LiMn2O4With LiNi0.8Co0.15Al0.05O25:95 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer.By mixed material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, are stirred evenly and are prepared into anode sizing agent.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm is assembled into 18650 together Battery.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.2V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Embodiment 7
1.54kg Mn2O3、0.0255kgAl2O3With 0.7537kg Li2CO340min is mixed in a high speed mixer, will be mixed It closes uniform material and is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.It will Li2Mn1.95Al0.05O4With LiNi0.8Co0.15Al0.05O25:95 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer. By mixed material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, are stirred evenly and are prepared into just Pole slurry.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm is together It is assembled into 18650 batteries.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.2V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Embodiment 8
1.54kg Mn2O3, 0.0374kg NiO and 0.7537kg Li2CO340min is mixed in a high speed mixer, will be mixed It closes uniform material and is transferred to bell furnace in 780 DEG C of roasting 10h, after broken, screening for use by the material after roasting.It will Li2Mn1.95Ni0.05O4With LiNi0.8Co0.15Al0.05O25:95 ratio mixes in mass ratio, is uniformly mixed in a high speed mixer. By mixed material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, are stirred evenly and are prepared into just Pole slurry.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), diaphragm is together It is assembled into 18650 batteries.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.2V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Table 2
Comparative example 1
By LiCoO2Material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added in NMP, the system of stirring evenly For at anode sizing agent.In addition, Si/C (si content 30%) cathode, electrolyte (the 1M LiPF containing EC/PC/DEC solute6), every Film is assembled into 18650 batteries together.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.3V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
Comparative example 2
By LiNi0.8Co0.15Al0.05O2Material 95%, 3%SP (conductive agent) and 2%PVDF (binder) are added to NMP In, it stirs evenly and is prepared into anode sizing agent.In addition, Si/C (si content 30%) cathode, electrolyte (contain EC/PC/DEC solute 1M LiPF6), diaphragm is assembled into 18650 batteries together.
Then 18650 batteries assembled are put with 0.2C current density constant-current charge to 4.2V, constant-voltage charge to 0.05C Electricity is to 3.0V.Over-discharge electrical testing: 300mA current discharge to 3.0V, 3mA current discharge to 2.7V, 1mA current discharge to 0V.
In conclusion the contents of the present invention are not limited in the above embodiments, the knowledgeable people in same area can To propose that other embodiments, single this embodiment are included in of the invention easily within technological guidance's thought of the invention In range.

Claims (10)

1. a kind of preparation method of lithium ion battery composite cathode material, which is characterized in that composite positive pole is by lithium-ion electric Pond positive electrode and spinel lithium manganate are mixed with；
The anode material for lithium-ion batteries includes LiCoO2、LiFePO4、LiMnO2、LiMn2-x-yNixMyO4、 LiNixCoyM1-x-yO2One or more of, wherein LiMn2-x-yNixMyO4In, 0.5≤x≤1,0.01≤y≤0.1, M= Co, Al, Cr, Fe, Mg, Zn, Ti；LiNixCoyM1-x-yO2In 0.3≤x≤0.9,0.05≤y≤0.3, M=Mn, Al, Cr, Fe, Mg, Zn, Ti；
The spinel lithium manganate is Li2Mn2-xMxO4, 0≤x≤0.1, M=Ni, B, Al, Cr, Fe, Mg, Zn, one of Ti Or it is several；Synthetic spinel LiMn2O4 Li2Mn2-xMxO4Method be by the chemical combination of lithium compound, manganese compound and doped chemical M Object mixes in a high speed mixer, and maturing temperature is 400-900 DEG C, calcining time 2-10h, obtained solids is broken, Screening obtains finished product；The lithium compound is LiOH, Li2CO3、LiNO3, one or more of lithium acetate；The manganese compound MnO2、Mn2O3、Mn(OH)2、MnCO3、Mn(NO3)2、MnSO4, one or more of manganese acetate；The doped chemical be Ni, B, One or more of Al, Cr, Fe, Mg, Zn, Ti.
2. the preparation method of lithium ion battery composite cathode material according to claim 1, which is characterized in that the spinelle LiMn2O4 and anode material for lithium-ion batteries mixing quality ratio are 0.01-0.2:1.
3. the preparation method of lithium ion battery composite cathode material according to claim 1, which is characterized in that the spinelle LiMn2O4 is Li2Mn2O4。
4. the preparation method of lithium ion battery composite cathode material according to claim 1, which is characterized in that the lithium ion Cell positive material is LiCoO2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2One of.
5. the preparation method of lithium ion battery composite cathode material according to claim 2, which is characterized in that the spinelle LiMn2O4 and anode material for lithium-ion batteries mixing quality ratio are 0.05:1.
6. the preparation method of lithium ion battery composite cathode material according to claim 1, which is characterized in that the lithiumation is closed Object is Li2CO3。
7. the preparation method of lithium ion battery composite cathode material according to claim 1, which is characterized in that the manganese is closed Object is Mn2O3。
8. the preparation method of lithium ion battery composite cathode material according to claim 1, which is characterized in that the roasting temperature Degree is 800 DEG C, calcining time 10h.
9. the lithium ion battery composite cathode material of the method according to claim 1 preparation.
10. the lithium ion battery composite cathode material of the method according to claim 1 preparation is used for negative with Si/C Pole, diaphragm, organic electrolyte are assembled into 18650 batteries.
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