CN103811727B - A kind of safe lithium ion battery positive plate and preparation method thereof - Google Patents

A kind of safe lithium ion battery positive plate and preparation method thereof Download PDF

Info

Publication number
CN103811727B
CN103811727B CN201310700921.4A CN201310700921A CN103811727B CN 103811727 B CN103811727 B CN 103811727B CN 201310700921 A CN201310700921 A CN 201310700921A CN 103811727 B CN103811727 B CN 103811727B
Authority
CN
China
Prior art keywords
coating
preparation
slurry
sio
positive plate
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.)
Active
Application number
CN201310700921.4A
Other languages
Chinese (zh)
Other versions
CN103811727A (en
Inventor
刘婵
侯敏
曹辉
王东
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.)
Shanghai Aerospace Power Technology Co Ltd
Original Assignee
Shanghai Aerospace Power 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 Shanghai Aerospace Power Technology Co Ltd filed Critical Shanghai Aerospace Power Technology Co Ltd
Priority to CN201310700921.4A priority Critical patent/CN103811727B/en
Publication of CN103811727A publication Critical patent/CN103811727A/en
Application granted granted Critical
Publication of CN103811727B publication Critical patent/CN103811727B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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
    • H01M4/48—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 positive plate of a kind of safe lithium ion battery and preparation method thereof, this positive plate is sandwich construction, and it comprises following active material: lithium manganese phosphate LiMnPO4, nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2(0<x≤0.8,0<y≤0.4,0≤z≤0.4, and x+y+z=1), and, resistant to elevated temperatures nano material Al2O3Or SiO2; The mass percent of above-mentioned active material is: resistant to elevated temperatures Al2O3Or SiO2Ceramic material: LiMnPO4：Li(NixCOyMnz)O2=1%-5%:1%-98%:1%-98%. The preparation method of this positive plate can be the sandwich of sandwich style, can be also by lithium manganese phosphate LiMnPO4With nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2Adopt the form of mechanical mixture to be coated in after aluminium foil surface, apply the resistant to elevated temperatures nano material of one deck on its surface again, the lithium ion battery that the pole piece of this structure is made has good security performance, utilize different activities material contrary unit cell volume variation characteristic in charge and discharge process simultaneously, and Al2O3Or SiO2To the good liquid-keeping property of electrolyte, can significantly improve long cycle performance and the security performance of lithium ion battery.

Description

A kind of safe lithium ion battery positive plate and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, particularly positive plate of a kind of safe lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is the advanced battery growing up phase early 1990s, compare as Ni-MH battery, ickel-cadmium cell, lead-acid battery with traditional secondary cell, there is high-energy-density, high voltage, long-life, high temperature performance is outstanding, self-discharge rate is low and the series of advantages such as memory-less effect. Since it comes out, the market share of lithium ion battery constantly increases, and occupied more than 80% share in civil small-scale secondary cell market, and in new-energy automobile field, lithium ion battery also becomes the first-selection of electrokinetic cell because of above many outstanding advantages.
In new-energy automobile field, flying power, service life and security performance are the competitiveness places of electric automobile maximum, also be the problem that consumer is the most generally concerned about, in order to realize the lightweight of electric automobile and to extend course continuation mileage, car load factory has proposed more and more higher requirement for the energy density of lithium-ion-power cell. In existing domestic new-energy automobile power battery supply system, LiFePO4 system electrokinetic cell is due to its excellent security performance and ripe manufacturing technology, almost in occupation of whole market; But the actual specific capacity of LiFePO 4 material is 130mAh/g left and right only, nominal voltage is 3.2V only, after using in groups automobile, energy density is difficult to higher than 100Wh/kg, causes the course continuation mileage of electric automobile very limited, is greatly restricting technological progress and the market expansion of electric automobile. Ministry of Industry and Information is in " the energy-conservation and new-energy automobile industrial development planning (2012-2020) " formulated on July 9th, 2012, emphatically point out " it is to be greater than 150Wh/kg that the energy density of battery module requires ", this means that the energy density of single power battery must be higher than 170Wh/kg. And existing LiFePO4/graphite system battery specific energy is lower than 120wh/kg, obviously cannot meet the demands, therefore exploitation has the alternative LiFePO4 of positive electrode system of high-energy-density and develops corresponding battery technology, becomes the inexorable trend of following Vehicular dynamic battery.
In the positive electrode that can be applicable to lithium ion battery, nickel-cobalt-manganese ternary material Li (Ni0.5CO0.2Mn0.3)O2Li(NixCOyMnz)O2X+y+z=1 gram volume can reach 160mAh/g, more than nominal voltage 3.6V, can prepare the lithium-ion-power cell of energy density higher than 180wh/kg, but the heat endurance of this material under Charging state is undesirable, such as the test of thermogravimetric-gas chromatograph-mass spectrometer shows, charge to the Li (Ni of 4.2VxCOyMnz)O2, x+y+z=1 tertiary cathode sheet, starts weightlessly at 200 DEG C, and the oxygen content that 250 DEG C of temperature up produce obviously increases, and this illustrates that ternary material is unstable, easily decomposes precipitated oxygen under higher temperature; DSC tests demonstration, charges to the Li (Ni of 4.2VxCOyMnz)O2, x+y+z=1 tertiary cathode sheet can discharge amount of heat between 200 DEG C～250 DEG C, product XRD test shows the existence of NiO crystal, this illustrates that the ternary material of Charging state has very high oxidation activity under higher temperature, at high temperature very dangerous.
Adopt traditional design and processes method, by nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, x+y+z=1 and conductive agent and bonding agent PVDF(Kynoar), decentralized medium NMP is mixed into uniform slurry, then be coated in aluminum foil current collector, through baking, roll-in and film cut into positive plate, then the power lithium-ion battery being prepared into such positive plate, meet with heat abuse, electricity abuse (as overcharges, short circuit) or mechanical abuse (as acupuncture, extruding) time, if internal temperature of battery rises to more than 200 DEG C, positive pole is analysed oxygen and further heat release, just very easily cause the moment catching fire and blast of battery, thereby cause serious security incident, Here it is at present the power lithium-ion battery of China Business still occupy the reason of mainstream market with the LiFePO4 system of low energy densities.
Ceramic material is as SiO2、Al2O3Deng the characteristic with high heat-resisting, electric insulation, chemically-resistant and electrochemical corrosion, its powder granule can be prepared into Nano grade, can be coated with into the thin layer of 1um ~ 10um thickness, is also easy to be coated on the granular materials of micron level. The existing way of this ceramic material being coated to polyolefin micropore barrier diaphragm surface in industry, to improve barrier film antioxygenic property and heat resistance.
Change of distance when positive electrode active materials lithium manganese phosphate discharges and recharges between P-O and Mn-O atom is little, in charge and discharge process, the Volume Changes of this material is less, be about 6%, variation just offsets with the Volume Changes that carbon negative pole occurs at charge and discharge process, therefore has extremely strong structural stability and fatigue durability.
Single by ceramic material Al2O3、SiO2Or positive electrode active materials lithium manganese phosphate and nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, x+y+z=1 is used in conjunction with, and can not effectively solve the security performance of high-energy-density type power lithium-ion battery, is especially applied to the high-capacity dynamical lithium-ion battery in pure electric automobile EV.
Summary of the invention
The object of the invention is to overcome the deficiency of current technology, solve the not good difficult problem of high-energy-density type power lithium-ion battery security performance, a kind of preparation method of the based lithium-ion battery positive plate of taking into account high-energy-density and high security is provided, thereby effectively improve the long cycle performance of battery, played the effect of the course continuation mileage that improves electric automobile.
In order to achieve the above object, the invention provides a kind of positive plate of safe lithium ion battery, this positive plate is sandwich construction, and it comprises following active material: lithium manganese phosphate LiMnPO4, nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, wherein, 0 < x≤0.8,0 < y≤0.4,0≤z≤0.4, and x+y+z=1, and, resistant to elevated temperatures nano material Al2O3Or SiO2; The mass percent of described active material is: resistant to elevated temperatures Al2O3Or SiO2Ceramic material: LiMnPO4：Li(NixCOyMnz)O2=1%-5%：1%-98%：1%-98%。
The positive plate of above-mentioned safe lithium ion battery, wherein, the mass percent of described active material is: resistant to elevated temperatures Al2O3Or SiO2Ceramic material: LiMnPO4：Li(NixCOyMnz)O2=3%-5%：10%-47%：50%-87%。
Three class materials in anodal diaphragm of the present invention, resistant to elevated temperatures nano material, as Al2O3Or SiO2The D50 particle diameter of ceramic material is below 100nm, and the positive active material lithium manganese phosphate D50 particle diameter of security performance excellence is 5um-15um, the positive active material nickel-cobalt-manganese ternary material Li (Ni that security performance is poorxCOyMnz)O2, the average grain diameter of x+y+z=1 is 10um ~ 20um.
The positive plate of above-mentioned safe lithium ion battery, wherein, this positive plate is by lithium manganese phosphate LiMnPO4, nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, 0 < x≤0.8,0 < y≤0.4,0≤z≤0.4, and x+y+z=1, and, resistant to elevated temperatures nano material Al2O3Or SiO2The sandwich construction of the sandwich style forming.
The present invention also provides a kind of preparation method of positive plate of above-mentioned safe lithium ion battery, and the method comprises:
Step 1, on positive plate collector aluminium foil, coating is by the lithium manganese phosphate LiMnPO of security performance excellence4The slurry of preparation is as the first coating;
Step 2, the slurry that coating is prepared by the poor nickel-cobalt-manganese ternary material of security performance in above-mentioned the first coating is as the second coating;
Step 3 applies slurry prepared by resistant to elevated temperatures nano material as the 3rd coating in the second coating, forms the sandwich construction of sandwich style; Described resistant to elevated temperatures nano material is selected Al2O3Or SiO2Ceramic material.
Above-mentioned preparation method, wherein, the slurry of described the first coating uses binding agent carboxymethyl cellulose (CMC) and the butadiene-styrene rubber (SBR) taking water as decentralized medium, the slurry of described the second coating uses the binding agent Kynoar (PVDF) taking organic solvent 1-METHYLPYRROLIDONE (NMP) as decentralized medium, and the slurry of described the 3rd coating uses the binding agent polyimides PI taking organic solvent 1-METHYLPYRROLIDONE as decentralized medium.
Above-mentioned preparation method, wherein, the preparation method of described the first coating refers to: by lithium manganese phosphate LiMnPO4, binding agent carboxymethyl cellulose and butadiene-styrene rubber, conductive agent (adopting conventional conductive agent) mix with the ratio of 92%～94%:2%～4%:2%～4%, taking deionized water as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on and on plus plate current-collecting body aluminium foil, form the first coating.
Above-mentioned preparation method, wherein, the preparation method of described the second coating refers to: by nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, binding agent Kynoar, conductive agent mix with the ratio of 92%～94%:2%～4%:2%～4%, taking 1-METHYLPYRROLIDONE as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on the first coating, form the second coating.
Above-mentioned preparation method, wherein, the preparation method of described the 3rd coating refers to: by ceramic material Al2O3Or SiO2, binding agent polyimides mixes with the ratio of 90%～95%:5%～10%, taking organic solvent 1-METHYLPYRROLIDONE as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, is coated on the second coating, forms the 3rd coating. Then drying, roll-in, cut and stamping-out, form final positive plate.
The present invention also provides a kind of preparation method of positive plate of above-mentioned safe lithium ion battery, and the method comprises: by lithium manganese phosphate LiMnPO4With nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2Adopt the form of mechanical mixture to be prepared into slurry, be then coated in aluminium foil surface, then apply the resistant to elevated temperatures nano material of one deck on its surface, thereby form safe sandwich construction. Particularly, the method is by modified nickel-cobalt-manganese ternary material, lithium manganese phosphate LiMnPO4, binding agent PVDF, conductive agent mix with the ratio of 73.6%～84.6%:11.4%～18.4%:2%～4%:2%～4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on plus plate current-collecting body aluminium foil and form the first coating, then by ceramic material Al2O3Or SiO2, binding agent PI mixes with the ratio of 90%～95%:5%～10%, taking organic solvent NMP as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, is coated on the first coating, forms the second coating. Then, drying, roll-in, cut and stamping-out, form final positive plate.
In positive plate of the present invention, comprise the positive active material lithium manganese phosphate LiMnPO that security performance is good4, the positive active material nickel-cobalt-manganese ternary material Li (Ni that security performance is poorxCOyMnz)O2, x+y+z=1 and resistant to elevated temperatures nano material, as Al2O3Or SiO2Ceramic material. Positive active material nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, x+y+z=1 provides high-energy-density demand for power lithium-ion battery, and LiFePO4 and ceramic material are for electrokinetic cell provides safety Design demand.
Positive plate of the present invention is sandwich construction (being preferably sandwich style sandwich construction), is positioned at outermost ceramic layer, due to Al2O3Or SiO2Particle is nanoscale size, can on nickel-cobalt-manganese ternary coating, form very thin very fine and close cover layer of while, in the time that battery is overheated, cause positive/negative plate contact, but the ceramic layer on positive plate surface has high-fire resistance, Al even if barrier film shrinks2O3Or SiO2Fusing point more than 2000 DEG C, the fusing point of binding agent polyimides PI is more than 500 DEG C, at high temperature can keep the integrality of coating structure, can stop the nickel-cobalt-manganese ternary of high oxidation activity and the negative pole of high reducing activity directly to contact and form large area internal short-circuit, thereby avoid battery that further thermal runaway occurs. And positive active material lithium manganese phosphate LiMnPO4On plus plate current-collecting body aluminium foil, form the first coating, aluminium foil and nickel-cobalt-manganese ternary coating are kept apart, in the time that battery is overheated, can stop the nickel-cobalt-manganese ternary of high oxidation activity and the comparatively active metallic aluminium release amount of heat that reacts, can reduce equally the security risk of battery.
Three layers of coating of positive plate of the present invention, are respectively the design of water-based/oiliness/oiliness coating, the cementitiousness can effectively improve coating time between two bed boundarys, thus ensure the pole piece adhesion of overbrushing layer pole piece.
Ceramic material Al in positive plate of the present invention2O3Or SiO2Have electrochemistry inertia, shared mass percent is 3%～5%, and little on the energy density impact of electrokinetic cell, this material has stronger polarity simultaneously, and electrolyte is had to good absorption and hold facility, is conducive to improve the long circulation life of electrokinetic cell. Active material nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, x+y+z=1 and lithium manganese phosphate LiMnPO4In charge and discharge process contrary unit cell volume variation characteristic be conducive to eliminate pole piece repeatedly expand the cohesive force that causes decline bad, lithium manganese phosphate LiMnPO simultaneously4Granule can form certain mechanical support effect to nickel-cobalt-manganese ternary bulky grain, thereby effectively improves the long cycle performance of lithium ion battery.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme of the present invention is further described.
Embodiment 1
Nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2, lithium manganese phosphate LiMnPO4With ceramic material Al2O3Or SiO2Mass ratio be 82%:15%:3%.
First by lithium manganese phosphate LiMnPO4, binding agent SBR+CMC, conductive agent mix with the ratio of 92%:4%:4%, taking deionized water as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, be coated on the thick plus plate current-collecting body aluminium foil of 18um and form the first coating. Then by nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2, binding agent PVDF, conductive agent mix with the ratio of 92%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, are prepared into the slurry of certain viscosity through high-speed stirred, are coated on the first coating, form the second coating. Finally by ceramic material Al2O3、SiO2, binding agent PI mixes with the ratio of 45%:45%:10%, taking organic solvent NMP as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, is coated on the second coating, then drying, roll-in, cuts and stamping-out, forms positive plate.
Positive plate, barrier film, negative plate stacked successively and adopt laminated structure to make battery core, welding respectively after positive and negative electrode lug, then through entering shell, laser weld, fluid injection, change into partial volume operation after, be made into lithium ion battery with aluminum shell. Negative plate active material used is graphite, and barrier film is that PP/PE/PP polyolefin three-layer is composite microporous, and electrolyte is with LiPF6For lithium salts, EMC(carbonic acid Methylethyl ester), EC(ethylene carbonate) and DEC(diethyl carbonate) be the organic solution of solvent.
Embodiment 2
Nickel-cobalt-manganese ternary material Li (Ni0.4CO0.2Mn0.4)O2, lithium manganese phosphate LiMnPO4With ceramic material Al2O3+SiO2Mass ratio be 82%:15%:3%.
First lithium manganese phosphate LiMnPO4, binding agent SBR+CMC, conductive agent are mixed with the ratio of 92%:4%:4%, taking deionized water as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on the thick plus plate current-collecting body aluminium foil of 18um and form the first coating. Then by nickel-cobalt-manganese ternary material Li (Ni0.4CO0.2Mn0.4)O2, binding agent PVDF, conductive agent mix with the ratio of 92%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, are prepared into the slurry of certain viscosity through high-speed stirred, are coated on the first coating, form the second coating. Finally by ceramic material Al2O3, SiO2, binding agent PI mix with the ratio of 45%:45%:10%, taking NMP as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, is coated on the second coating, then drying, roll-in, cuts and stamping-out, forms positive plate.
Battery assembling mode is with embodiment 1.
Embodiment 3
Nickel-cobalt-manganese ternary material Li (Ni0.5CO0.2Mn0.3)O2, lithium manganese phosphate LiMnPO4With ceramic material Al2O3+SiO2Mass ratio be 75%:20%:5%.
First by lithium manganese phosphate LiMnPO4, binding agent SBR+CMC, conductive agent mix with the ratio of 92%:4%:4%, taking deionized water as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, be coated on the thick plus plate current-collecting body aluminium foil of 18um and form the first coating. Then by nickel-cobalt-manganese ternary material Li (Ni0.5CO0.2Mn0.3)O2, binding agent PVDF, conductive agent mix with the ratio of 92%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, are prepared into the slurry of certain viscosity through high-speed stirred, are coated on the first coating, form the second coating. Finally by ceramic material Al2O3、SiO2, binding agent PI mixes with the ratio of 45%:45%:10%, taking organic solvent NMP as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, is coated on the second coating, then drying, roll-in, cuts and stamping-out, forms positive plate.
Battery assembling mode is with embodiment 1.
Embodiment 4
First by nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2, lithium manganese phosphate LiMnPO4, binding agent PVDF, conductive agent mix with the ratio of 78.2%:13.8%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on plus plate current-collecting body aluminium foil, form the first coating, then by ceramic material Al2O3, mix with the mass ratio with 97%:3% with binding agent PI, taking NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated in the first coating, form the second coating, then drying, roll-in, cut and stamping-out, form positive plate.
Battery assembling mode is with embodiment 1.
Embodiment 5
First by nickel-cobalt-manganese ternary material Li (Ni0.4CO0.2Mn0.4)O2, lithium manganese phosphate LiMnPO4, binding agent PVDF, conductive agent mix with the ratio of 78.2%:13.8%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on plus plate current-collecting body aluminium foil, form the first coating, then by ceramic material Al2O3、SiO2And PI mixes with the mass ratio of 47%:50%:3%, taking NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated in the first coating, form the second coating, then drying, roll-in, cut and stamping-out, form positive plate.
Battery assembling mode is with embodiment 1.
Embodiment 6:
First by nickel-cobalt-manganese ternary material Li (Ni0.5CO0.2Mn0.3) O2, lithium manganese phosphate LiMnPO4, binding agent PVDF, conductive agent mix with the ratio of 78.2%:13.8%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on plus plate current-collecting body aluminium foil, form the first coating, then by ceramic material Al2O3And PI mixes with the mass ratio of 95%:5%, taking NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated in the first coating, form the second coating, then drying, roll-in, cut and stamping-out, form positive plate.
Battery assembling mode is with embodiment 1.
Comparative example 1
Nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2, lithium manganese phosphate LiMnPO4Mass ratio be 85%:15%.
First by lithium manganese phosphate LiMnPO4, binding agent SBR+CMC, conductive agent mix with the ratio of 92%:4%:4%, taking deionized water as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, be coated on the thick plus plate current-collecting body aluminium foil of 18um and form the first coating. Then by nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2, binding agent PVDF, conductive agent mix with the ratio of 92%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on the first coating, then drying, roll-in, cut and stamping-out, form positive plate.
Battery assembling mode is with embodiment 1.
Comparative example 2
Nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2, ceramic material Al2O3+SiO2Mass ratio be 97%:3%.
First by nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2Binding agent PVDF, conductive agent mix with the ratio of 92%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, are prepared into the slurry of certain viscosity through high-speed stirred, be coated on the thick plus plate current-collecting body aluminium foil of 18um and form the first coating, then by ceramic material Al2O3、SiO2, binding agent PI mixes with the ratio of 45%:45%:10%, organic solvent NMP is decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, is coated on the first coating, then drying, roll-in, cuts and stamping-out, forms positive plate.
Battery assembling mode is with embodiment 1.
Comparative example 3
By nickel-cobalt-manganese ternary material Li (Ni1/3CO1/3Mn1/3)O2Binding agent PVDF, conductive agent mix with the ratio of 92%:4%:4%, taking 1-METHYLPYRROLIDONE NMP as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on the thick plus plate current-collecting body aluminium foil of 18um, then drying, roll-in, cut and stamping-out, form positive plate.
Battery assembling mode is with embodiment 1.
By all test loop performance and security performances by the following method of the power lithium-ion battery of embodiment 1～6 and comparative example 1～3.
Cycle performance: 25 DEG C of room temperatures, by battery 1C constant-current charge to 4.2V, then constant-voltage charge, cut-off current is 0.05C; Subsequently by battery 1C multiplying power constant-current discharge to 2.75V, obtain the initial discharge capacity C of battery0, then according to the above-mentioned system that discharges and recharges, battery is carried out to charge and discharge cycles, the capacitance that obtains battery is Cd, according to L=Cd/C0The discharge capacitance of battery after × 100% method computation cycles.
Over-charge safety performance: battery is full of to electricity to 4.2V in the mode of CC-CV, stops to 8.4V with the electric current constant-current charge of 1C multiplying power.
Safety of acupuncture energy: battery is full of to electricity to 4.2V in the mode of CC-CV, with the high temperature resistant draw point of Φ 3mm ~ Φ 8mm, with the speed of 10mm/s ~ 40mm/s, runs through from the direction perpendicular to accumulator plate, draw point rests on 1h in battery.
Short circuit safety energy: battery is full of to electricity to 4.2V in the mode of CC-CV, adopts the outside line short circuit 10min of internal resistance < 5m Ω.
The result of definition security performance test, " the not blast not on fire of not smoldering " is " outstanding ", and " smolder, have Mars, not blast " is " generally ", and " blast on fire " is " disappointing ".
The power lithium-ion battery test result of embodiment 1～6 and comparative example 1～3 is as shown in table 1:
Table 1: the power lithium-ion battery test result of embodiment 1-6 and comparative example 1-3
From table 1 comparative example 3, with nickel-cobalt-manganese ternary Li (NixCOyMnz)O2, the power lithium-ion battery that x+y+z=1 is prepared, overcharges with acupuncture and all reacts fierce, the phenomenon of blast on fire occurs, the very poor strength of security performance. And from comparative example 1 and 2, single by ceramic material Al2O3、SiO2Or positive electrode active materials lithium manganese phosphate LiMnPO4With nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, x+y+z=1 is used in conjunction with, and also can there is imperfect combustion in battery, occur smoldering and pyrophoric behavio(u)r in the time overcharging with acupuncture, can not effectively solve the safety problem of power lithium-ion battery. The embodiment of the present invention 1～6 is passed through at positive electrode active materials nickel-cobalt-manganese ternary Li (NixCOyMnz)O2, in x+y+z=1, lithium manganese phosphate LiMnPO in a particular manner in right amount arranges in pairs or groups4With ceramic material Al2O3、SiO2After, battery through overcharge with acupuncture after do not smolder and not on firely do not explode, reaction temperature and, security performance be improved significantly, exhibits excellent.
From table 1,500 weeks rear capability retentions of comparative example 3 circulating battery are 92.3%, 500 weeks rear capability retentions of comparative example 1～2 circulating battery are 93%～94%, 500 weeks rear capability retentions of embodiment 1～6 circulating battery are 94%～96%, this explanation adopts after Technological improvement plan of the present invention, and the cycle performance of power lithium-ion battery has also obtained to a certain degree improving.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention. Read after foregoing those skilled in the art, for multiple amendment of the present invention and substitute will be all apparent. Therefore, protection scope of the present invention should be limited to the appended claims.

Claims (7)

1. a positive plate for safe lithium ion battery, is characterized in that, this positive plate is served as reasons and is coated in successively the lithium manganese phosphate LiMnPO on collector aluminium foil4, nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, and, resistant to elevated temperatures nano material Al2O3Or SiO2The sandwich construction of the sandwich style forming, it comprises following active material: lithium manganese phosphate LiMnPO4, nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, wherein, 0 < x≤0.8,0 < y≤0.4,0≤z≤0.4, and x+y+z=1, and, resistant to elevated temperatures nano material Al2O3Or SiO2; The mass percent of described active material is: resistant to elevated temperatures Al2O3Or SiO2Nano material: LiMnPO4：Li(NixCOyMnz)O2=3%-5%：10%-47%：50%-87%。
2. the positive plate of safe lithium ion battery as claimed in claim 1, is characterized in that, described lithium manganese phosphate LiMnPO4D50 particle diameter be 5 μ m-15 μ m; Described nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2D50 particle diameter be 10 μ m ~ 20 μ m; Described Al2O3Or SiO2The D50 particle diameter of nano material is below 100nm.
3. a preparation method for the positive plate of safe lithium ion battery according to claim 1, is characterized in that, the method comprises:
Step 1, on positive plate collector aluminium foil, coating is by the lithium manganese phosphate LiMnPO of security performance excellence4The slurry of preparation is as the first coating;
Step 2, the slurry that coating is prepared by the poor nickel-cobalt-manganese ternary material of security performance in above-mentioned the first coating is as the second coating;
Step 3 applies slurry prepared by resistant to elevated temperatures nano material as the 3rd coating in the second coating, forms the sandwich construction of sandwich style; Described resistant to elevated temperatures nano material is selected Al2O3Or SiO2Nano material.
4. preparation method as claimed in claim 3, it is characterized in that, the slurry of described the first coating is taking water as decentralized medium, taking carboxymethyl cellulose and butadiene-styrene rubber as binding agent, the slurry of described the second coating is taking organic solvent 1-METHYLPYRROLIDONE as decentralized medium, taking Kynoar as binding agent, the slurry of described the 3rd coating is taking organic solvent 1-METHYLPYRROLIDONE as decentralized medium, taking polyimides as binding agent.
5. preparation method as claimed in claim 4, is characterized in that, the preparation method of described the first coating is: by lithium manganese phosphate LiMnPO4, binding agent carboxymethyl cellulose and butadiene-styrene rubber, conductive agent mix with the ratio of 92%～94%:2%～4%:2%～4%, taking deionized water as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on and on plus plate current-collecting body aluminium foil, form the first coating.
6. preparation method as claimed in claim 5, is characterized in that, the preparation method of described the second coating is: by nickel-cobalt-manganese ternary material Li (NixCOyMnz)O2, binding agent Kynoar, conductive agent mix with the ratio of 92%～94%:2%～4%:2%～4%, taking 1-METHYLPYRROLIDONE as decentralized medium, be prepared into the slurry of certain viscosity through high-speed stirred, be coated on the first coating, form the second coating.
7. preparation method as claimed in claim 6, is characterized in that, the preparation method of described the 3rd coating is: by nano material Al2O3Or SiO2, binding agent polyimides mixes with the ratio of 90%～95%:5%～10%, taking organic solvent 1-METHYLPYRROLIDONE as decentralized medium, is prepared into the slurry of certain viscosity through high-speed stirred, is coated on the second coating, forms the 3rd coating.
CN201310700921.4A 2013-12-18 2013-12-18 A kind of safe lithium ion battery positive plate and preparation method thereof Active CN103811727B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310700921.4A CN103811727B (en) 2013-12-18 2013-12-18 A kind of safe lithium ion battery positive plate and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310700921.4A CN103811727B (en) 2013-12-18 2013-12-18 A kind of safe lithium ion battery positive plate and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103811727A CN103811727A (en) 2014-05-21
CN103811727B true CN103811727B (en) 2016-05-25

Family

ID=50708178

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310700921.4A Active CN103811727B (en) 2013-12-18 2013-12-18 A kind of safe lithium ion battery positive plate and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103811727B (en)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617331A (en) * 2015-01-29 2015-05-13 深圳市索阳新能源科技有限公司 Special lithium iron phosphate accumulator for new energy hybrid electric vehicle
JP6439645B2 (en) * 2015-10-08 2018-12-19 株式会社村田製作所 Batteries, battery packs, electronic devices, electric vehicles, power storage devices, and power systems
CN107331861A (en) * 2016-04-28 2017-11-07 万向二三股份公司 A kind of based lithium-ion battery positive plate and preparation method thereof
CN109661739B (en) * 2016-09-21 2021-11-02 宁德时代新能源科技股份有限公司 Secondary battery and cathode pole piece thereof
CN107749457B (en) * 2016-11-18 2020-07-31 万向一二三股份公司 Lithium ion battery containing anode ceramic coating
CN106784621A (en) * 2016-12-23 2017-05-31 惠州拓邦电气技术有限公司 Electrodes of lithium-ion batteries and preparation method thereof, lithium ion battery
CN107146875A (en) * 2017-04-20 2017-09-08 中航锂电（洛阳）有限公司 A kind of heat chemistry blocking-up type composite positive pole, anode pole piece and preparation method thereof, lithium ion battery
CN110212182A (en) * 2019-05-27 2019-09-06 珠海格力电器股份有限公司 Cell positive material and the positive plate comprising it, cell negative electrode material and the negative electrode tab comprising it, lithium ion battery and electrode slurry
CN110350239A (en) * 2019-07-08 2019-10-18 无锡市明杨新能源有限公司 High magnification lithium ion battery with high energy density
CN110504407A (en) * 2019-08-14 2019-11-26 美科新能源(苏州)有限公司 A kind of anode electrode of lithium ion battery, preparation method
CN110707293B (en) * 2019-10-15 2020-12-11 泰州纳新新能源科技有限公司 Preparation method of lithium ion battery cathode
CN110676428B (en) * 2019-10-17 2020-12-15 泰州纳新新能源科技有限公司 Preparation method of mixed anode for lithium ion battery
CN110581255B (en) * 2019-10-18 2020-11-24 宇恒电池有限公司 Lithium ion battery anode and method for preparing lithium ion battery anode
CN112331857A (en) * 2019-12-16 2021-02-05 万向一二三股份公司 Positive pole piece for improving safety of lithium ion battery and high-safety lithium ion battery
CN111430670A (en) * 2020-04-13 2020-07-17 阮弟根 Positive electrode plate, processing method thereof, application of positive electrode plate in preparation of lithium battery, and lithium battery
CN112133887A (en) * 2020-10-09 2020-12-25 昆山宝创新能源科技有限公司 Quasi-solid-state battery pole piece and preparation method and application thereof
CN112531174A (en) * 2020-12-03 2021-03-19 珠海冠宇动力电池有限公司 Positive pole piece and battery
CN112563450B (en) * 2020-12-11 2022-04-12 珠海冠宇电池股份有限公司 Positive plate and battery
CN112736227A (en) * 2020-12-29 2021-04-30 天津国安盟固利新材料科技股份有限公司 Composite cathode and secondary battery using the same
CN113113569B (en) * 2021-04-09 2022-08-23 常州赛得能源科技有限公司 High-rate long-cycle lithium ion battery
CN113517423B (en) * 2021-04-22 2023-02-24 远景动力技术(江苏)有限公司 Positive electrode material, preparation method thereof, pole piece and preparation method thereof
CN113555541A (en) * 2021-07-21 2021-10-26 凤凰新能源(惠州)有限公司 High-energy-density lithium ion battery
CN114024020A (en) * 2021-10-29 2022-02-08 歌尔光学科技有限公司 Electrode assembly, battery and equipment
CN117242598A (en) * 2021-12-17 2023-12-15 宁德时代新能源科技股份有限公司 Positive electrode composite material for lithium ion secondary battery and lithium ion secondary battery
CN114267816A (en) * 2021-12-21 2022-04-01 珠海冠宇电池股份有限公司 Positive plate and battery thereof
CN114335410B (en) * 2021-12-29 2024-02-02 蜂巢能源科技(无锡)有限公司 Dry-method positive electrode containing diaphragm, preparation method and application thereof
CN114335678B (en) * 2021-12-29 2023-11-21 蜂巢能源科技(无锡)有限公司 Battery and preparation method thereof
WO2024011594A1 (en) * 2022-07-15 2024-01-18 宁德时代新能源科技股份有限公司 Positive electrode active material and preparation method therefor, positive pole piece, secondary battery, battery module, battery pack and electrical apparatus
WO2024011595A1 (en) * 2022-07-15 2024-01-18 宁德时代新能源科技股份有限公司 Positive electrode active material and preparation method therefor, positive electrode plate, secondary battery, battery module, battery pack and electric device
CN117673245A (en) * 2022-08-29 2024-03-08 比亚迪股份有限公司 Positive electrode sheet and secondary battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102208644B (en) * 2011-04-28 2014-04-16 宁夏共享集团有限责任公司 Composite lithium manganese phosphate serving as lithium ion battery anode material and preparation method thereof and lithium ion battery

Also Published As

Publication number Publication date
CN103811727A (en) 2014-05-21

Similar Documents

Publication Publication Date Title
CN103811727B (en) A kind of safe lithium ion battery positive plate and preparation method thereof
CN107851832B (en) Nonaqueous electrolyte secondary battery
US9401505B2 (en) Separator including coating layer of inorganic and organic mixture, and battery including the same
CN105428576A (en) Composite ceramic coating, lithium ion battery composite ceramic diaphragm and lithium ion battery
CN103325991A (en) Total temperature-range lithium ion battery
CN113328099B (en) Negative pole piece and secondary battery
JP2014022204A (en) Active material particle for lithium ion secondary battery, and lithium ion secondary battery using the same
CN110556538B (en) Positive plate and lithium ion battery
CN102903914A (en) Active material and method of manufacturing same, and electrode, secondary battery, and battery pack
CN111785925A (en) Pole piece, application and low-temperature-rise safety lithium ion battery containing pole piece
WO2023056825A1 (en) Isolation film, secondary battery containing same, and electrical apparatus
WO2020135110A1 (en) Negative active material, battery and apparatus
CN102427123A (en) Lithium ion secondary battery and anode sheet thereof
CN101924243A (en) Lithium ion battery
CN103094567A (en) Anode material of lithium fast ionic conductor compounded lithium battery and preparation method of anode material
CN101110477B (en) Electro-chemistry energy storing and converting device
CN215896445U (en) Positive pole piece, lithium ion battery and power utilization device
JP2015118815A (en) All solid secondary battery
CN109661739B (en) Secondary battery and cathode pole piece thereof
CN116526069A (en) Separator, battery cell, battery and electricity utilization device
CN115810868A (en) Water-based metal ion battery, preparation method thereof and power utilization device
CN105514354A (en) Power lithium ion battery and positive plate and preparing method thereof
WO2024077493A1 (en) Negative electrode sheet, lithium-ion battery and electric device
WO2023097433A1 (en) Negative electrode plate, secondary battery, battery module, battery pack and electric apparatus
WO2023065128A1 (en) Negative electrode sheet, secondary battery, battery module, battery pack, and electric device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant