CN107528050A - Active substance of lithium ion battery anode, positive electrode, positive electrode slurry, positive plate, its preparation method and lithium ion battery - Google Patents

Active substance of lithium ion battery anode, positive electrode, positive electrode slurry, positive plate, its preparation method and lithium ion battery Download PDF

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Publication number
CN107528050A
CN107528050A CN201710672998.3A CN201710672998A CN107528050A CN 107528050 A CN107528050 A CN 107528050A CN 201710672998 A CN201710672998 A CN 201710672998A CN 107528050 A CN107528050 A CN 107528050A
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lithium
ion battery
anode
positive plate
anode material
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叶邦斌
汪小云
杨建国
许俊
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Shanghai Maple Automobile Co Ltd
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Shanghai Maple Automobile 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
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/36—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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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 a kind of active substance of lithium ion battery anode, positive electrode, positive electrode slurry, positive plate, its preparation method and lithium ion battery, it is related to technical field of lithium ion.The active substance of lithium ion battery anode is mainly made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 10~50% and nickle cobalt lithium manganate 50~90%；Iron manganese phosphate for lithium is LiMnxFe1‑xPO4, 0.5<x<1, nickle cobalt lithium manganate is Li (NixCoyMnz)O2, 0<x<1,0<y<1,0<z<1.The pulp layer of graphene layer and positive electrode is sequentially coated with the collector of based lithium-ion battery positive plate.The present invention alleviates that temperature rise under the big multiplying power of traditional lithium battery is too high and safety issue.The present invention not only increases positive electrode heat endurance by improving to positive electrode and electrode chip architecture, and reduces pole piece internal resistance, can meet to use under high magnification, security is good.

Description

Active substance of lithium ion battery anode, positive electrode, positive electrode slurry, positive plate, Its preparation method and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, in particular to a kind of active substance of lithium ion battery anode, Positive electrode, positive electrode slurry, positive plate, its preparation method and lithium ion battery.
Background technology
In recent years although electric automobile industry was quickly grown, but its behind still suffers from larger hidden danger, and maximum of which is asked Topic is the safety problem of lithium battery, influences that lithium ion battery security factor is numerous, and most direct two aspects factor is material Temperature rise during material heat endurance and use causes heat accumulation, and especially under big multiplying power (power) discharge and recharge, temperature rise is in Exponential increase.
Based on national policy and market (consumer) demand, to ensure electric automobile endurance, current major Battery Plant Power lithium-ion battery (the hereinafter referred to as ternary lithium ion using ternary (nickel cobalt manganese NCM) material as positive pole is being researched and developed energetically Battery).But the safety issue of ternary lithium ion battery is not solved thoroughly always, especially the ternary lithium of high nickel content from Sub- battery.Why the security of ternary lithium ion battery is less than batteries such as LiFePO4 and iron manganese phosphate for lithium, wherein most important Some reasons be due to material thermal stability difference：Ternary material is decomposed at 200 DEG C or so, and LiFePO4/phosphorus Sour ferromanganese lithium decomposition temperature is more than 400 DEG C.
Temperature rise causes heat accumulation to be another key factor for influenceing lithium ion battery safety during use.Lithium ion battery Temperature rise during discharge and recharge mostlys come from the internal resistance of cell, and therefore, the reduction internal resistance of cell can reduce the temperature during battery use Elevation amplitude, significantly accumulated so as to reduce heat, avoid thermal runaway.The factor for influenceing the internal resistance of cell is mainly positive electrode and collection Conductive network between fluid is formed.Due to the superior electrical conductivity of negative pole graphite and copper foil, improvement is not so good as anode electrode piece. Current anode electrode piece conductive structure is that anode sizing agent (conductive agent and positive electrode active materials) is coated on aluminium foil, through one after drying Constant-pressure is compacted to ensure electric conductivity.But because metal aluminum foil and powder contact problems, its conductive effect are bad.Percentage of batteries factory Family carries out conductive black on aluminium foil and applied coated with contact effect is improved, and improves electric conductivity, but is limited to conductive black self character, Such a technique is still limited to improving electric conductivity, reduction internal resistance effect.
In view of this, it is special to propose the present invention.
The content of the invention
An object of the present invention is to provide a kind of active substance of lithium ion battery anode, and the positive active material includes Iron manganese phosphate for lithium LiMnxFe1-xPO4(0.5<x<And nickle cobalt lithium manganate Li (Ni 1)xCoyMnz)O2(0<x<1,0<y<1,0<z<1 and x + y+z=1), compounded by the iron manganese phosphate for lithium and nickle cobalt lithium manganate of certain content, improve pure nickel cobalt manganic acid lithium positive pole The decomposition temperature of material, the defects of improving pure nickel-cobalt lithium manganate cathode material thermostabilization difference, pure nickel cobalt mangaic acid can be greatly improved The heat endurance of lithium anode material, improve the security of anode material for lithium-ion batteries.
The second object of the present invention is to provide a kind of anode material for lithium-ion batteries, and the positive electrode includes above-mentioned positive pole Active material, it is good with above-mentioned positive active material identical advantage, the security of positive electrode to have.
The third object of the present invention is to provide a kind of anode material for lithium-ion batteries slurry, the slurry be by above-mentioned lithium from Sub- cell positive material, which is dissolved or dispersed in solvent, to be obtained, and conveniently coats positive electrode on a current collector after slurry is made.
The fourth object of the present invention is to provide a kind of based lithium-ion battery positive plate, first coated on the collector of the positive plate One layer graphene, above-mentioned anode material for lithium-ion batteries slurry is coated with, not only the advantage with anode material for lithium-ion batteries, Obtained positive plate heat endurance is good, and can improve electrode slice electric conductivity by first graphene coated, so as to reduce pole piece Resistance, the based lithium-ion battery positive plate heat endurance and electric conductivity are good, can ensure its security under high-power.
The fifth object of the present invention is to provide a kind of preparation method of based lithium-ion battery positive plate, and this method is first in afflux Above-mentioned anode material for lithium-ion batteries slurry is coated with after a layer graphene is coated on body, between collector and positive electrode slurry There is a layer graphene layer, optimize the conductive network between positive electrode and collector, reduce pole piece resistance, obtained positive plate Heat endurance and electric conductivity are good, and security is good.
The sixth object of the present invention is to provide a kind of lithium ion battery, including above-mentioned lithium ion cell positive active matter Matter, anode material for lithium-ion batteries, anode material for lithium-ion batteries slurry or based lithium-ion battery positive plate, lithium ion battery tool Have with above-mentioned active substance of lithium ion battery anode, anode material for lithium-ion batteries, anode material for lithium-ion batteries slurry, lithium from Sub- battery anode slice identical advantage, the thermal stability of lithium-ion batteries is good, and the internal resistance of cell is low, is used so as to reduce battery Temperature rise in journey, it is that a kind of can take into account high-power and security dynamic lithium battery.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
According to the first aspect of the invention, there is provided a kind of active substance of lithium ion battery anode, lithium ion battery is just Pole active material is mainly made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 10~50% and nickle cobalt lithium manganate 50~ 90%；
The iron manganese phosphate for lithium is LiMnxFe1-xPO4, wherein 0.5<x<1, the nickle cobalt lithium manganate is Li (NixCoyMnz) O2, wherein 0<x<1,0<y<1,0<z<1 and x+y+z=1.
In the present invention, positive active material is compounded to obtain by the iron manganese phosphate for lithium and nickle cobalt lithium manganate of special ratios, with just On the basis of the weight/mass percentage composition of pole active material, the nickel of iron manganese phosphate for lithium and 50~90wt% including 10~50wt% Cobalt manganic acid lithium.
[iron manganese phosphate for lithium]
Iron manganese phosphate for lithium is the phosphate compounds containing iron atom, lithium atom and manganese atom.Wherein, manganese atom and iron are former Sub mutually solid solution, has the crystal structure of orthorhombic olivine-type, has preferable security performance and cycle performance.
Iron manganese phosphate for lithium of the present invention is LiMnxFe1-xPO4, 0.5<x<1.X≤0.5, LiMn can not be ensuredxFe1-xPO4Height Heat endurance and high security.The typical but non-limiting values of x are, for example, 0.51,0.52,0.53,0.54,0.55,0.56, 0.57、0.58、0.59、0.6、0.61、0.62、0.63、0.64、0.65、0.66、0.67、0.68、0.69、0.7、0.71、 0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.8、0.81、0.82、0.83、0.84、0.85、0.86、 0.87th, 0.88,0.89,0.9,0.91,0.92,0.93,0.94,0.95,0.96,0.97,0.98 or 0.99.It is typical but unrestricted The iron manganese phosphate for lithium of property is, for example, LiMn0.6Fe0.4PO4、LiMn0.7Fe0.3PO4、LiMn0.8Fe0.2PO4Or LiMn0.83Fe0.17PO4。
The typical but non-limiting weight/mass percentage composition of iron manganese phosphate for lithium is, for example, 10%, 15%, 20%, 25%, 30%, 35%th, 40%, 45% or 50%.
[nickle cobalt lithium manganate]
Nickle cobalt lithium manganate is tertiary cathode material, and it is to be prepared using nickel salt, cobalt salt, manganese salt as raw material, and product is black Color powder, it, which contains the ratio of nickel cobalt manganese, to be adjusted according to being actually needed.Nickle cobalt lithium manganate is in the layered structure with Ni and Mn Substitute part Co, reduce the dosage of cobalt, reduce cost, improve energy density.Its significant advantage is that cost is low, energy Density is high, good cycle and gram volume are high, but there is also first charge-discharge efficiency is low, structural stability is poor and material simultaneously Heat endurance is not so good as the problem of other unitary and good binary material.
Nickle cobalt lithium manganate of the present invention is Li (NixCoyMnz)O2, 0<x<1,0<y<1,0<z<1 and x+y+z=1.X typical case but Nonrestrictive value is, for example, 0.12,0.14,0.15,0.16,0.18,0.2,0.22,0.24,0.25,0.26,0.28, 0.3、0.32、0.34、0.35、0.36、0.38、0.4、0.42、0.44、0.45、0.46、0.48、0.50、0.52、0.54、 0.55、0.56、0.58、0.6、0.62、0.64、0.65、0.66、0.68、0.7、0.72、0.74、0.75、0.76、0.78、0.8、 0.82nd, 0.84,0.85,0.86,0.88,0.9,0.92,0.94,0.95,0.96 or 0.98.The typical but non-limiting values of y For example, 0.12,0.14,0.15,0.16,0.18,0.2,0.22,0.24,0.25,0.26,0.28,0.3,0.32,0.34, 0.35、0.36、0.38、0.4、0.42、0.44、0.45、0.46、0.48、0.50、0.52、0.54、0.55、0.56、0.58、 0.6、0.62、0.64、0.65、0.66、0.68、0.7、0.72、0.74、0.75、0.76、0.78、0.8、0.82、0.84、0.85、 0.86th, 0.88,0.9,0.92,0.94,0.95,0.96 or 0.98.Z=1-x-y.Typical but non-limiting nickle cobalt lithium manganate example Such as it is Li (Ni1/3Co1/3Mn1/3)O2、Li(Ni0.4Co0.2Mn0.4)O2、Li(Ni0.5Co0.2Mn0.3)O2、Li(Ni0.6Co0.2Mn0.2) O2、Li(Ni0.8Co0.1Mn0.1)O2Or Li (Ni0.85Co0.1Mn0.05)O2。
The typical but non-limiting weight/mass percentage composition of nickle cobalt lithium manganate is, for example, 50%, 55%, 60%, 65%, 70%, 75%th, 80%, 85% or 90%.
" positive active material mainly by " of the present invention, it is intended that positive active material removes the iron manganese phosphate for lithium and nickel Outside cobalt manganic acid lithium, other components can also be included, for example, LiFePO4 etc..Iron manganese phosphate for lithium, nickle cobalt lithium manganate and optionally its His component sum is 100%.In addition, " positive active material mainly by " of the present invention, may be replaced by closing " for " of formula or " by ... form ".
Current major Battery Plant is researching and developing the power lithium-ion battery using ternary (nickel cobalt manganese) material as positive pole energetically, But the safety issue of ternary lithium ion battery is not solved thoroughly always, the especially ternary lithium-ion electric of high nickel content Pond, the security of ternary lithium ion battery is less than batteries such as LiFePO4 and iron manganese phosphate for lithium, and this is mainly due to ternary material Heat endurance is poor, is decomposed at 200 DEG C or so, and LiFePO4/iron manganese phosphate for lithium decomposition temperature is more than 400 DEG C.
The positive active material of anode material for lithium-ion batteries of the present invention is with the iron manganese phosphate for lithium LiMn of special ratiosxFe1- xPO4(0.5<x<And nickle cobalt lithium manganate Li (Ni 1)xCoyMnz)O2(0<x<1,0<y<1,0<z<1 and x+y+z=1) compounded, Due to 0.5<x<LiMn under 1 scopexFe1-xPO4The heat endurance of material is good, by being added in cobalt nickel lithium manganate ternary material Iron manganese phosphate for lithium LiMnxFe1-xPO4(0.5<x<1) material, the heat endurance of pure nickel-cobalt lithium manganate cathode material can be greatly improved, So as to improve the security of anode material for lithium-ion batteries.
Preferably, on the basis of technical scheme provided by the invention, active substance of lithium ion battery anode mainly by with The component composition of lower weight/mass percentage composition：Iron manganese phosphate for lithium 10~40% and nickle cobalt lithium manganate 60~90%；
The iron manganese phosphate for lithium is LiMnxFe1-xPO4, wherein 0.5<x<1, the nickle cobalt lithium manganate is Li (NixCoyMnz) O2, wherein 0.5≤x<1,0<y<0.5,0<z<0.5 and x+y+z=1.
Preferably, on the basis of technical scheme provided by the invention, active substance of lithium ion battery anode mainly by with The component composition of lower weight/mass percentage composition：Iron manganese phosphate for lithium 20~30% and nickle cobalt lithium manganate 70~80%；
The iron manganese phosphate for lithium is LiMnxFe1-xPO4, wherein 0.6≤x≤0.8, the nickle cobalt lithium manganate is Li (NixCoyMnz)O2, wherein 0.6≤x≤0.85,0<y<0.4,0<z<0.4 and x+y+z=1.
By further optimizing the ratio in iron manganese phosphate for lithium in Mn and Fe ratio, nickle cobalt lithium manganate between Ni, Co and Mn Example, and the proportion relation between iron manganese phosphate for lithium and nickle cobalt lithium manganate, can make composite cathode active material heat endurance more It is good, the good anode material for lithium-ion batteries of heat endurance is obtained, ensures its security.
Preferably, on the basis of technical scheme provided by the invention, the D50 of iron manganese phosphate for lithium is 20~30 μm, compares table Area is 20~30m2/g。
D50 is median grain diameter, is exactly median particle diameter, is that the cumulative particle sizes percentile of a sample reaches 50% when institute Corresponding particle diameter.Its physical significance is that particle diameter accounts for 50% more than its particle, and also accounting for 50%, D50 less than its particle commonly uses To represent the particle mean size of powder.
Iron manganese phosphate powder for lithium can be condensed and the offspring that is formed or once grain by primary particle, primary particle The mixture of son and offspring is formed.Iron manganese phosphate for lithium is preferably its primary particle or the average grain diameter of offspring is 20 ~30 μm, for example, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm or 30 μm.
If average grain diameter is too small, it is unfavorable for the coating of later stage material, space is also easy to produce if average grain diameter is excessive, during filling, Decline fillibility.In addition, average grain diameter is more preferably 25~30 μm.
Specific surface area refers to the gross area possessed by unit mass material.
The typical but non-limiting specific surface area of iron manganese phosphate for lithium is, for example, 20m2/g、22m2/g、24m2/g、26m2/g、 28m2/ g or 30m2/g。
Using the iron manganese phosphate for lithium of particular range specific surface area, good processing characteristics can be not only obtained, and material Activity is higher, if specific surface area is excessive, is unfavorable for post-production positive plate, if specific surface area is too small, can reduce the activity of material, It is unfavorable for battery performance performance.
Preferably, on the basis of technical scheme provided by the invention, the D50 of nickle cobalt lithium manganate is 10~15 μm, compares table Area is 0.1~0.3m2/g。
Nickle cobalt lithium manganate powder can also be condensed and the offspring that is formed or once by primary particle, primary particle The mixture of particle and offspring is formed.Nickle cobalt lithium manganate is preferably its primary particle or the average grain diameter of offspring is 10~15 μm, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm.
The nickle cobalt lithium manganate powder of specified particle diameter scope, effect can not only be sufficiently mixed with iron manganese phosphate powder for lithium, and And be advantageous to the coating of later stage material.
Nickle cobalt lithium manganate average grain diameter is more preferably 12~15 μm.
The typical but non-limiting specific surface area of nickle cobalt lithium manganate is, for example, 0.1m2/g、0.15m2/g、0.2m2/g、 0.25m2/ g or 0.3m2/g。
The nickel-cobalt lithium manganate material activity of low specific surface area is high, good conductivity, can be with specified particle diameter and specific surface area Iron manganese phosphate for lithium is engaged, and obtains more preferable fiting effect, can not only lift the heat endurance of pure nickel cobalt lithium manganate material, and And other performances of material are not interfered with.
According to the second aspect of the invention, there is provided a kind of anode material for lithium-ion batteries, lithium ion cell positive material Material includes above-mentioned active substance of lithium ion battery anode.
Positive electrode is largely made up of positive active material, can also include some additives, it is preferable that positive-active Material mass accounts for the 97~98% of anode material for lithium-ion batteries quality.
Positive active material content in positive electrode is higher, positive plate and battery is possessed higher-energy close Degree, possesses preferable performance.
Further, on the basis of technical scheme provided by the invention, anode material for lithium-ion batteries also includes：Conductive agent And binding agent；Conductive agent quality accounts for the 0.5~1% of anode material for lithium-ion batteries quality；Binding agent quality accounts for lithium ion battery The 1.5~2% of positive electrode quality.
Conductive agent is to ensure that electrode has good charge-discharge performance, be usually added into when pole piece makes a certain amount of Conductive materials, play a part of collecting micro-current between active material, between active material and collector, to reduce electrode Contact resistance accelerates the rate travel of electronics, while can also effectively improve migration rate of the lithium ion in electrode material, from And improve the efficiency for charge-discharge of electrode.Conductive agent can select conventional conductive agent, and typical but non-limiting conductive agent is, for example, Conductive black (such as acetylene black, Super P, Super S, 350G or Ketjen black), electrically conductive graphite (such as KS-6, KS-15, SFG-6 or SFG-15), carbon fiber or CNT.
On the basis of the weight/mass percentage composition of anode material for lithium-ion batteries, the typical but non-limiting quality hundred of conductive agent Point content is, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%.
Preferably, conductive agent is the mixture that graphene or graphene are formed with conductive black with any ratio.
Preferably, graphene specific surface area is 36~38m2/g.Conductive agent uses graphene or graphene and conductive black The mixture of composition, because graphene relative to the agent of the conventional conductive such as carbon black, graphite has bigger specific surface area, electric conductivity It is more excellent, therefore the usage amount of conductive agent can be reduced, so as to which activity substance content improves, eliminate addition iron manganese phosphate for lithium pair The negative effect of lithium battery energy density.
Further preferably, conductive agent is the mixture of graphene and conductive black, and wherein graphene quality accounts for conductive agent matter The 45~55% of amount, conductive black quality accounts for the 45~55% of conductive agent quality, such as 45%, 48%, 50% or 55%.
By further optimizing graphene and conductive black ratio, the more preferable conductive agent of electric conductivity can be obtained.
Lithium ion battery binding agent is preferably fluorine-based polymer and/or synthetic rubber, more preferably polyvinyl fluoride, poly- Vinylidene (PVDF), polytetrafluoroethylene (PTFE), SBR type rubber, fluorine class rubber or one kind in ethylene propylene diene rubber or At least two combination, the typical but non-limiting example of combination have：The combination of polyvinyl fluoride and Kynoar, poly- four The combination of PVF and SBR type rubber, the combination of SBR type rubber, fluorine class rubber and ethylene propylene diene rubber, The combination of polytetrafluoroethylene (PTFE), SBR type rubber and fluorine class rubber, polyvinyl fluoride, Kynoar, polytetrafluoroethylene (PTFE) and fourth The combination of benzene rubber-type rubber, Kynoar, polytetrafluoroethylene (PTFE), SBR type rubber, fluorine class rubber and ethylene, propylene two Combination of alkene rubber etc., particularly preferred Kynoar.
On the basis of the weight/mass percentage composition of anode material for lithium-ion batteries, the typical but non-limiting quality hundred of binding agent Point content is, for example, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2%.
Conductive agent and binding agent containing special ratios in anode material for lithium-ion batteries, activity when being advantageous to make pole piece Material can be perfectly adhered on collector, improve the efficiency for charge-discharge of electrode.Conductive agent and binder content are low, further Improve the content of active material.
Preferably, on the basis of technical scheme provided by the invention, a kind of typical anode material for lithium-ion batteries bag Include the following composition of weight/mass percentage composition：Positive active material 97~98%, conductive agent 0.5~1% and binding agent 1.5~2%；
The positive active material is mainly made up of the component of following weight/mass percentage composition：The He of iron manganese phosphate for lithium 10~50% Nickle cobalt lithium manganate 50~90%；The iron manganese phosphate for lithium is LiMnxFe1-xPO4, wherein 0.6≤x≤0.8, the nickle cobalt lithium manganate For Li (NixCoyMnz)O2, wherein 0.6≤x≤0.85,0<y<0.4,0<z<0.4 and x+y+z=1.
On the basis of the weight/mass percentage composition of anode material for lithium-ion batteries, including 97~98wt% positive-active The binding agent of material, 0.5~1wt% conductive agent and 1.5~2wt%.
The typical but non-limiting weight/mass percentage composition of positive active material is, for example, 97%, 97.1%, 97.2%, 97.3%th, 97.4%, 97.5%, 97.6%, 97.7%, 97.8,97.9 or 98%.
The typical but non-limiting weight/mass percentage composition of conductive agent is, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% Or 1%.
The typical but non-limiting weight/mass percentage composition of binding agent is, for example, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% Or 2%.
On the basis of the weight/mass percentage composition of positive active material, the iron manganese phosphate for lithium including 10~50wt% and 50 ~90wt% nickle cobalt lithium manganate.Iron manganese phosphate for lithium is LiMnxFe1-xPO4, 0.6≤x≤0.8；Nickle cobalt lithium manganate is Li (NixCoyMnz)O2, 0.6≤x≤0.85,0<y<0.4,0<z<0.4 and x+y+z=1.
Conductive agent and binding agent refer to above-mentioned conductive agent and binding agent.
The positive active material content of this typical anode material for lithium-ion batteries is high, avoids adding for iron manganese phosphate for lithium Add the negative effect to lithium battery energy density, the heat endurance of obtained positive electrode is high, safe, and will not reduce just Other electric conductivities of pole material.
According to the third aspect of the present invention, there is provided a kind of anode material for lithium-ion batteries slurry, be by lithium-ion electric Pond positive electrode, which is dissolved or dispersed in solvent, to be obtained.
Preferable solvent is any one in water or 1-METHYLPYRROLIDONE.
It is made slurry coating after slurry on a current collector, after solvent volatilization, positive electrode is fixed on collector.
Preferably, the viscosity of anode material for lithium-ion batteries slurry is 5000~7000mPas, and viscosity can pass through tune Save binder content de-regulation.
According to the fourth aspect of the present invention, there is provided a kind of based lithium-ion battery positive plate, based lithium-ion battery positive plate The pulp layer of graphene layer and above-mentioned anode material for lithium-ion batteries slurry is sequentially coated with collector.
Graphene layer is to add grapheme material in solvent, and graphene slurry is made, is coated with lithium ion battery just Formed in the aluminum foil current collector of pole piece.
Here grapheme material refers to containing graphene composition, and typical but non-limiting grapheme material can be pure stone Black alkene or graphene are with carbon black with any mixture than forming.It is preferred that graphene account for grapheme material quality 45~ 55%, carbon black mass accounts for the 45~55% of grapheme material quality.
Dispersant and binding agent can also be added in solvent, is easily produced graphene slurry coated on collector.Coating Dry afterwards and remove solvent, obtain the aluminum foil current collector coated with graphene layer.
Binding agent can select the binding agent of above-mentioned anode material for lithium-ion batteries slurry, and dispersant can select polypropylene The combination of nitrile fiber, triethylene tetramine or polyacrylonitrile fibre and triethylene tetramine arbitrary proportion.
Preferably, the thickness of graphene layer is 0.5~3 μm, such as 0.5 μm, 1 μm, 2 μm or 3 μm.
The based lithium-ion battery positive plate of the present invention first first coats a layer graphene layer in aluminum foil current collector, improves electrode slice Electric conductivity, the internal resistance of cell is reduced, is coated with above-mentioned anode material for lithium-ion batteries slurry, the not only thermostabilization of obtained positive plate Property is good, and can reduce the temperature rise during battery use (under especially big multiplying power), improves its security.
Preferably, on the basis of technical scheme provided by the invention, based lithium-ion battery positive plate is prepared by following methods Obtain：
A) by graphene, optionally binding agent and optionally dispersant add solvent in, obtain graphene slurry；
B) the graphene slurry for first obtaining step a) is dried coated in aluminum foil current collector and removes solvent, forms graphite Alkene layer, then anode material for lithium-ion batteries slurry is coated in and had been coated with the aluminum foil current collector of graphene layer, dry and remove Solvent, obtain based lithium-ion battery positive plate.
Based lithium-ion battery positive plate coated in aluminum foil current collector surface and drying by graphene slurry by removing solvent Afterwards, then by above-mentioned positive electrode slurry coated in aluminum foil current collector surface and drying solvent is removed, by first coating one layer of stone Black alkene layer, to improve electrode slice electric conductivity, pole piece internal resistance is reduced, so as to significantly reduce the temperature rise during battery use, especially It is the temperature rise under big multiplying power, improves pole piece security.The based lithium-ion battery positive plate internal resistance obtained by the method reduces by 30% More than, and the positive electrode heat endurance on positive plate is good, and positive plate is safe.
According to the fifth aspect of the present invention, there is provided a kind of preparation method of based lithium-ion battery positive plate, first by graphite Alkene slurry is coated on the collector of based lithium-ion battery positive plate, then anode material for lithium-ion batteries slurry is coated in into lithium ion On the collector of battery anode slice, based lithium-ion battery positive plate is obtained.
This method is coated with above-mentioned anode material for lithium-ion batteries slurry after first coating a layer graphene on a current collector, collects There is a layer graphene layer between fluid and positive electrode slurry, optimize the conductive network between positive electrode and collector, drop Low pole piece resistance, obtained positive plate heat endurance and electric conductivity is good, and security is good.
Preferably, the preparation method of based lithium-ion battery positive plate comprises the following steps：
A) graphene slurry is prepared：By graphene, optionally binding agent and optionally dispersant add solvent in, stone is made Black alkene slurry；
B) first by graphene slurry made of step a) coated in aluminum foil current collector, after drying again by lithium ion battery just Pole material paste is dried coated in aluminum foil current collector and removes solvent, through roll-in and section, obtain based lithium-ion battery positive plate.
Graphene in step a) refers to above-mentioned grapheme material.
Graphene slurry first is made in grapheme material, coating obtains graphene layer, then graphene layer again on a current collector Upper coating anode material for lithium-ion batteries slurry, to obtain based lithium-ion battery positive plate.
According to the sixth aspect of the invention, there is provided a kind of lithium ion battery, including above-mentioned lithium ion cell positive Active material, anode material for lithium-ion batteries, anode material for lithium-ion batteries slurry or based lithium-ion battery positive plate.
Lithium ion battery is made up of based lithium-ion battery positive plate, anode plate for lithium ionic cell and barrier film etc..Lithium ion battery Negative plate can use traditional lithium-ion battery negative plate, such as graphite cathode piece.
By the full battery assembling of the carry out such as above-mentioned based lithium-ion battery positive plate and ordinary graphite negative electricity pole piece, obtained lithium from The more traditional aluminium foil battery of temperature rise during sub- battery charging and discharging decreases, especially under big multiplying power, than traditional aluminium foil battery temperature rise Low about 20 DEG C.The lithium ion battery can meet to use under high magnification, and security is good.
Compared with the prior art, the present invention has the advantages that：
(1) the iron manganese phosphate for lithium LiMn that the present invention passes through the addition special ratios in cobalt nickel lithium manganate ternary materialxFe1- xPO4(0.5<x<1) material, carry out compounding the positive electrode for being used as lithium ion battery by iron manganese phosphate for lithium and nickle cobalt lithium manganate Active material, the heat endurance of positive electrode can be greatly improved, so as to improve the security of anode material for lithium-ion batteries.
(2) based lithium-ion battery positive plate of the invention coats a layer graphene by elder generation in the aluminum foil current collector of positive plate Layer, anode material for lithium-ion batteries layer being coated with, not only heat endurance is good for obtained positive plate, and by first graphene coated The conductive network that layer can improve between positive electrode and collector is formed, and improves electrode slice electric conductivity, reduces the internal resistance of cell, from And the temperature rise during battery use is significantly reduced, the temperature rise under particularly big multiplying power, improve pole piece security.The lithium-ion electric Pond positive plate heat endurance and electric conductivity are good, can ensure its security under high-power.
(3) present invention to positive electrode and electrode chip architecture by improving, to improve conventional lithium ion battery safety Sex chromosome mosaicism, not only increases the heat endurance of positive electrode, and reduces pole piece internal resistance, during reducing battery use, especially It is the temperature rise under big multiplying power, can meet to use under high magnification, and security is good, and it is high-power and safe to be that one kind can be taken into account The dynamic lithium battery of property.
Brief description of the drawings
After battery full charge after based lithium-ion battery positive plate and graphite cathode the piece assembling that Fig. 1 obtains for embodiment 12 not With the temperature rise figure under multiplying power；
After battery full charge after based lithium-ion battery positive plate and graphite cathode the piece assembling that Fig. 2 obtains for comparative example 8 not With the temperature rise figure under multiplying power.
Icon：A-0.2C multiplying powers；B-0.5C multiplying powers；C-1C multiplying powers；D-3C multiplying powers；E-5C multiplying powers；F-7C multiplying powers；g-10C Multiplying power；H-12C multiplying powers；I-13C multiplying powers；J-14C multiplying powers；K-15C multiplying powers；L-16C multiplying powers.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is The conventional products that can be obtained by commercially available purchase.
Embodiment 1
A kind of active substance of lithium ion battery anode, it is made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 10% and nickle cobalt lithium manganate 90%；
Wherein, iron manganese phosphate for lithium LiMn0.6Fe0.4PO4, D50 is 20 μm, specific surface area 30m2/g；
Nickle cobalt lithium manganate is Li (Ni0.6Co0.2Mn0.2)O2, D50 is 10 μm, specific surface area 0.3m2/g。
Embodiment 2
A kind of active substance of lithium ion battery anode, it is made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 50% and nickle cobalt lithium manganate 50%；
Wherein, iron manganese phosphate for lithium LiMn0.7Fe0.3PO4, D50 is 30 μm, specific surface area 20m2/g；
Nickle cobalt lithium manganate is Li (Ni0.8Co0.1Mn0.1)O2, D50 is 15 μm, specific surface area 0.1m2/g。
Embodiment 3
A kind of active substance of lithium ion battery anode, it is made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 30% and nickle cobalt lithium manganate 70%；
Wherein, iron manganese phosphate for lithium LiMn0.8Fe0.2PO4, D50 is 25 μm, specific surface area 25m2/g；
Nickle cobalt lithium manganate is Li (Ni0.5Co0.2Mn0.3)O2, D50 is 12 μm, specific surface area 0.2m2/g。
Embodiment 4
A kind of active substance of lithium ion battery anode, it is made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 20% and nickle cobalt lithium manganate 80%；
Wherein, iron manganese phosphate for lithium LiMn0.6Fe0.4PO4, D50 is 26 μm, specific surface area 30m2/g；
Nickle cobalt lithium manganate is Li (Ni0.8Co0.1Mn0.1)O2, D50 is 13 μm, specific surface area 0.3m2/g。
Embodiment 5
A kind of active substance of lithium ion battery anode, it is made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 40% and nickle cobalt lithium manganate 60%；
Wherein, iron manganese phosphate for lithium LiMn0.8Fe0.2PO4, D50 is 25 μm, specific surface area 28m2/g；
Nickle cobalt lithium manganate is Li (Ni0.85Co0.1Mn0.05)O2, D50 is 14 μm, specific surface area 0.2m2/g。
Embodiment 6
A kind of active substance of lithium ion battery anode, iron manganese phosphate for lithium LiMn0.55Fe0.45PO4, remaining is formed and content It is same as Example 1.
Embodiment 7
A kind of active substance of lithium ion battery anode, iron manganese phosphate for lithium LiMn0.83Fe0.17PO4, remaining is formed and content It is same as Example 1.
Embodiment 8
A kind of active substance of lithium ion battery anode, nickle cobalt lithium manganate are Li (Ni1/3Co1/3Mn1/3)O2, remaining composition and Content is same as Example 2.
Embodiment 9
A kind of active substance of lithium ion battery anode, nickle cobalt lithium manganate are Li (Ni0.4Co0.2Mn0.4)O2, remaining composition and Content is same as Example 2.
Embodiment 10
A kind of active substance of lithium ion battery anode, iron manganese phosphate for lithium LiMn0.8Fe0.2PO4, D50 is 40 μm, compares surface Product is 15m2/ g, remaining composition and content are same as Example 3.
Embodiment 11
A kind of active substance of lithium ion battery anode, nickle cobalt lithium manganate are Li (Ni0.8Co0.1Mn0.1)O2, D50 is 15 μm, Specific surface area is 1m2/ g, remaining composition and content are same as Example 4.
Comparative example 1
Using iron manganese phosphate for lithium as active substance of lithium ion battery anode, iron manganese phosphate for lithium LiMn0.6Fe0.4PO4, D50 is 20 μm, specific surface area 30m2/g。
Comparative example 2
Using nickle cobalt lithium manganate as active substance of lithium ion battery anode, nickle cobalt lithium manganate is Li (Ni0.6Co0.2Mn0.2) O2, D50 is 10 μm, specific surface area 0.3m2/g。
Comparative example 3
A kind of active substance of lithium ion battery anode, iron manganese phosphate for lithium LiMn0.3Fe0.7PO4, remaining composition and content are equal It is same as Example 1.
Comparative example 4
A kind of active substance of lithium ion battery anode, iron manganese phosphate for lithium LiMn0.4Fe0.6PO4, remaining composition and content are equal It is same as Example 2.
Comparative example 5
A kind of active substance of lithium ion battery anode, iron manganese phosphate for lithium LiMn0.2Fe0.8PO4, remaining composition and content are equal It is same as Example 3.
Comparative example 6
A kind of active substance of lithium ion battery anode, it is made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 5% It is same as Example 4 with nickle cobalt lithium manganate 95%, remaining composition and content.
The active material heat stability testing of test example 1
The active substance of lithium ion battery anode material that embodiment 1~11 and comparative example 1~5 obtain is made into electrode, so It is assembled into button cell respectively afterwards, at room temperature, is charged to later using the circle of CC-CV charge and discharge systems circulation one with C/2 multiplying powers 4.2V, turn 4.2V constant-voltage charges and stop to electric current less than 0.05C, remove battery, be transferred in glove box and disassemble, take out positive pole, will Positive pole, which is put into take out after immersion 8h in fresh DMC, to be dried, and shells the electrode material on plus plate current-collecting body after pole piece dries From taking the electrode material of phase homogenous quantities to carry out thermogravimetric analysis, determine the decomposition temperature of material, as a result as shown in table 1.
The active material heat stability testing result of table 1
Material group Material decomposition temperature DEG C
Embodiment 1 350
Embodiment 2 370
Embodiment 3 360
Embodiment 4 355
Embodiment 5 365
Embodiment 6 315
Embodiment 7 320
Embodiment 8 380
Embodiment 9 380
Embodiment 10 325
Embodiment 11 320
Comparative example 1 420
Comparative example 2 210
Comparative example 3 310
Comparative example 4 305
Comparative example 5 308
Comparative example 6 310
Result of the test shows that the active material of embodiment 1~5 has higher heat decomposition temperature, at 350~370 DEG C Between, heat endurance is good, embodiment 6~7 compared with Example 1, LiMn in embodiment 6xFe1-xPO4Mn ratios 0.5<x< 0.6, the heat endurance of material is obtained be not as good as embodiment 1, LiMn in embodiment 7xFe1-xPO4Mn ratios x>0.8, obtain material The heat endurance of material is good not as embodiment 1, it can thus be seen that as the LiMn using 0.6≤x≤0.8xFe1-xPO4With nickel cobalt manganese The heat endurance of material after sour lithium compounding is better than using 0.5<x<0.6 and 0.8<x<1 LiMnxFe1-xPO4With nickel cobalt manganese The heat endurance of material after sour lithium compounding.
Embodiment 8~9 compared with Example 2, Li (Ni in embodiment 8,9xCoyMnz)O2Ni ratios x<0.5, although Heat endurance to material is good compared with embodiment 2, but x<0.5 Li (NixCoyMnz)O2Energy density is smaller, it is impossible to meet demand.
Compared with Example 3, iron manganese phosphate for lithium specific surface area is smaller for embodiment 10, embodiment 11 compared with Example 4, nickel Cobalt manganic acid lithium specific surface area is larger, and the material heat endurance obtained after compounding has declined.
Comparative example 1 individually uses LiMn0.6Fe0.4PO4As active material, comparative example 2 individually uses Li (Ni0.6Co0.2Mn0.2)O2As active material, LiMn0.6Fe0.4PO4The decomposition temperature of material is at 420 DEG C, and thermostabilization is good, Li (Ni0.6Co0.2Mn0.2)O2Decomposition temperature at 210 DEG C, heat endurance is poor, and this experiment shows, embodiment 1 is answered after both mix It is higher to close the decomposition temperature of active material, and it is LiMn that TGA curves, which are not,0.6Fe0.4PO4With Li (Ni0.6Co0.2Mn0.2)O2 It is simple to add and synergy between the two be present.
Comparative example 3~5 is compared with embodiment 1~3, LiMnxFe1-xPO4Middle Mn ratios x<0.5, compounded with nickle cobalt lithium manganate The heat endurance of material is remarkably decreased afterwards.
Compared with Example 4, iron manganese phosphate for lithium is different from the compound proportion of nickle cobalt lithium manganate, phosphorus in comparative example 6 for comparative example 6 Sour ferromanganese lithium ratio is very few, and the heat endurance of obtained active material material is bad.
It can be seen that only by adding the iron manganese phosphate for lithium of special ratios and specific composition in nickle cobalt lithium manganate, can The heat endurance of material after compounding is significantly improved, ensures the security of battery.
Embodiment 12
A kind of based lithium-ion battery positive plate, is prepared by following methods：
A) grapheme material is added to the water, the graphene slurry that viscosity is 5000mPas is made；
Grapheme material is made up of the component of following weight/mass percentage composition：96% graphene, 2% Kynoar and 2% polyacrylonitrile fibre；
B) anode material for lithium-ion batteries is added to the water, the positive electrode slurry that viscosity is 5000mPas is made；
Anode material for lithium-ion batteries is made up of the composition of following weight/mass percentage composition：The positive active material of embodiment 1 97%th, conductive agent 1% and binding agent 2%；Conductive agent is acetylene black；Binding agent is the combination of polyvinyl fluoride and Kynoar；
C) first by graphene slurry obtained by step a) coated in aluminum foil current collector, 0.5 μm of coating thickness, dry, then will Positive electrode slurry obtained by step b) is dried coated in having been coated with the aluminum foil current collector of graphene layer, through roll-in and section, Obtain based lithium-ion battery positive plate.
Embodiment 13
A kind of based lithium-ion battery positive plate, is prepared by following methods：
A) grapheme material is added in 1-METHYLPYRROLIDONE, the graphene slurry that viscosity is 6000mPas is made；
Grapheme material is made up of the component of following weight/mass percentage composition：98.5% graphene, 1% Kynoar With 0.5% triethylene tetramine；
B) anode material for lithium-ion batteries is added in 1-METHYLPYRROLIDONE, the positive pole that viscosity is 6000mPas is made Material paste；
Anode material for lithium-ion batteries is made up of the composition of following weight/mass percentage composition：The positive active material of embodiment 2 98%th, conductive agent 0.5% and binding agent 1.5%；Conductive agent is carbon fiber；Binding agent is polytetrafluoroethylene (PTFE)；
C) first by graphene slurry obtained by step a) coated in aluminum foil current collector, 3 μm of coating thickness, dry, then will step Rapid b) gained positive electrode slurry, which is coated in, to be had been coated with the aluminum foil current collector of graphene layer, is dried, through roll-in and section, is obtained To based lithium-ion battery positive plate.
Embodiment 14
A kind of based lithium-ion battery positive plate, is prepared by following methods：
A) grapheme material is added in 1-METHYLPYRROLIDONE, the graphene slurry that viscosity is 5500mPas is made；
Grapheme material is made up of the component of following weight/mass percentage composition：98% graphene, 1% Kynoar and 1% polyacrylonitrile fibre；
B) anode material for lithium-ion batteries is added in 1-METHYLPYRROLIDONE, the positive pole that viscosity is 5500mPas is made Material paste；
Anode material for lithium-ion batteries is made up of the composition of following weight/mass percentage composition：The positive active material of embodiment 3 97.5%th, conductive agent 0.5% and binding agent 2%；Conductive agent is CNT；Binding agent is Kynoar.
C) first by graphene slurry obtained by step a) coated in aluminum foil current collector, 1 μm of coating thickness, dry, then will step Rapid b) gained positive electrode slurry, which is coated in, to be had been coated with the aluminum foil current collector of graphene layer, is dried, through roll-in and section, is obtained To based lithium-ion battery positive plate.
Embodiment 15
A kind of based lithium-ion battery positive plate, is prepared by following methods：
A) grapheme material is added to the water, the graphene slurry that viscosity is 5500mPas is made；
Grapheme material is made up of the component of following weight/mass percentage composition：97.5% graphene, 1.5% polyvinylidene fluoride Alkene and 1% triethylene tetramine；
B) anode material for lithium-ion batteries is added to the water, the positive electrode slurry that viscosity is 5500mPas is made；
Anode material for lithium-ion batteries is made up of the composition of following weight/mass percentage composition：The positive active material of embodiment 4 97.5%th, conductive agent 1% and binding agent 1.5%；Conductive agent is Ketjen black；Binding agent is SBR type rubber；
C) first by graphene slurry obtained by step a) coated in aluminum foil current collector, 2 μm of coating thickness, dry, then will step Rapid b) gained positive electrode slurry, which is coated in, to be had been coated with the aluminum foil current collector of graphene layer, is dried, through roll-in and section, is obtained To based lithium-ion battery positive plate.
Embodiment 16
A kind of based lithium-ion battery positive plate, is prepared by following methods：
A) grapheme material is added in 1-METHYLPYRROLIDONE, the graphene slurry that viscosity is 6000mPas is made；
Grapheme material is made up of the component of following weight/mass percentage composition：98% graphene, 1.5% Kynoar With 0.5% polyacrylonitrile fibre；
B) anode material for lithium-ion batteries is added in 1-METHYLPYRROLIDONE, the positive pole that viscosity is 6000mPas is made Material paste；
Anode material for lithium-ion batteries is made up of the composition of following weight/mass percentage composition：The positive active material of embodiment 5 97.4%th, conductive agent 0.8% and binding agent 1.8%；Conductive agent is electrically conductive graphite KS-6；Binding agent is polytetrafluoroethylene (PTFE), butylbenzene The combination of rubber-type rubber and fluorine class rubber；
C) first by graphene slurry obtained by step a) coated in aluminum foil current collector, 1 μm of coating thickness, dry, then will step Rapid b) gained positive electrode slurry, which is coated in, to be had been coated with the aluminum foil current collector of graphene layer, is dried, through roll-in and section, is obtained To based lithium-ion battery positive plate.
Embodiment 17
A kind of based lithium-ion battery positive plate, is prepared by following methods：Grapheme material is by following quality in step a) The component composition of percentage composition：48% graphene, 48% carbon black, 2% Kynoar and 2% polyacrylonitrile are fine Dimension；Remaining step is identical with embodiment 12.
Comparative example 8
A kind of based lithium-ion battery positive plate, is prepared by following methods：
The anode material for lithium-ion batteries of embodiment 12 is added to the water, the positive electrode that viscosity is 5000mPas is made Slurry, coated in aluminum foil current collector, drying, through roll-in and section, obtain based lithium-ion battery positive plate.
Comparative example 9
A kind of based lithium-ion battery positive plate, is prepared by following methods：
The anode material for lithium-ion batteries of embodiment 13 is added in 1-METHYLPYRROLIDONE, viscosity, which is made, is 6000mPas positive electrode slurry, coated in aluminum foil current collector, drying, through roll-in and section, obtain lithium ion battery Positive plate.
Comparative example 10
A kind of based lithium-ion battery positive plate, is prepared by following methods：
The anode material for lithium-ion batteries of embodiment 14 is added in 1-METHYLPYRROLIDONE, viscosity, which is made, is 5500mPas positive electrode slurry, coated in aluminum foil current collector, drying, through roll-in and section, obtain lithium ion battery Positive plate.
Comparative example 11
A kind of based lithium-ion battery positive plate, is prepared by following methods：
The anode material for lithium-ion batteries of embodiment 15 is added to the water, the positive electrode that viscosity is 5500mPas is made Slurry, coated in aluminum foil current collector, drying, through roll-in and section, obtain based lithium-ion battery positive plate.
Comparative example 12
A kind of based lithium-ion battery positive plate, is prepared by following methods：
The anode material for lithium-ion batteries of embodiment 16 is added in 1-METHYLPYRROLIDONE, viscosity, which is made, is 6000mPas positive electrode slurry, coated in aluminum foil current collector, drying, through roll-in and section, obtain lithium ion battery Positive plate.
The pole piece resistance test of test example 2
The based lithium-ion battery positive plate that embodiment 12~17 and comparative example 8~12 are obtained carries out pole piece resistance test, Pole piece takes 100mm is long, 50mm is wide to be tested, and method of testing uses four probe method.Test result is as shown in table 2.
The pole piece resistance test result of table 2
Pole piece group Pole piece resistance (m Ω) Pole piece group Pole piece resistance (m Ω)
Embodiment 12 6.1 Comparative example 8 9.2
Embodiment 13 5.9 Comparative example 9 9.1
Embodiment 14 6.0 Comparative example 10 9.2
Embodiment 15 6.1 Comparative example 11 8.9
Embodiment 16 5.9 Comparative example 12 9.0
Embodiment 17 5.4 - -
As can be seen from Table 2, embodiment 12~16 is first to show to coat a layer graphene layer in collector, is coated with positive pole The pole piece that material paste obtains, and comparative example 8~12 is the pole piece that directly coating positive electrode slurry obtains on a current collector, knot Fruit shows pole piece resistance that embodiment 12~16 obtains between 5.9~6.1m Ω, and the pole piece resistance that comparative example 8~12 obtains Between 8.9~9.2m Ω, the pole piece resistance of the less graphene coated layer of the pole piece coated with graphene layer reduces about 33%. As can be seen here, by the way that first graphene coated layer is coated with positive electrode slurry on a current collector, positive electrode and collection can be improved Conductive network between fluid is formed, and is reduced pole piece internal resistance, is improved electric conductivity.
For embodiment 17 compared with embodiment 12, embodiment 17 is preparing graphene slurry by 1：1 graphene and carbon black structure Into the pole piece resistance obtained after coating is smaller compared with the pole piece resistance of embodiment 12, and electric conductivity is more preferable, it can be seen that, by optimizing stone The composition of black alkene slurry, it can further reduce pole piece resistance.
The internal resistance of cell of test example 3 is tested
The based lithium-ion battery positive plate that embodiment 12~17 and comparative example 8~12 are obtained respectively with ordinary graphite negative pole Electrode slice carries out full battery assembling, and battery capacity 22Ah carries out cell resistance test, and test result is as shown in table 3.
The internal resistance of cell test result of table 3
Battery group The internal resistance of cell (m Ω) Battery group The internal resistance of cell (m Ω)
Embodiment 12 0.8 Comparative example 8 1.2
Embodiment 13 0.7 Comparative example 9 1.3
Embodiment 14 0.9 Comparative example 10 1.2
Embodiment 15 0.8 Comparative example 11 1.3
Embodiment 16 0.7 Comparative example 12 1.3
Embodiment 17 0.6 - -
As can be seen from Table 3, after assembled, the internal resistance of cell that embodiment 12~16 obtains between 0.7~0.9m Ω, and For the internal resistance of cell that comparative example 8~12 obtains between 1.2~1.3m Ω, the battery coated with graphene layer less coats graphite The internal resistance of cell of alkene layer reduces about 33%.As can be seen here, substantially reduced by the internal resistance of cell after graphene coated layer.
Embodiment 17 is compared with embodiment 12, and for embodiment 17 by optimizing the composition of graphene slurry, the internal resistance of cell is more real The reduction of example 12 is applied to become apparent.
From test example 1 and test example 2 as can be seen that by first coating a layer graphene slurry, pole piece can be substantially reduced With the resistance of battery, its electric conductivity is improved.
Battery temperature rise is tested under the different multiplying of test example 4
The based lithium-ion battery positive plate for respectively obtaining embodiment 12 and comparative example 8 assembles with ordinary graphite negative electricity pole piece Battery afterwards is charged, and the temperature rise test under different multiplying is carried out after being full of.As a result as depicted in figs. 1 and 2.
After battery full charge after based lithium-ion battery positive plate and graphite cathode the piece assembling that Fig. 1 obtains for embodiment 12 not With the temperature rise figure under multiplying power；
After battery full charge after based lithium-ion battery positive plate and graphite cathode the piece assembling that Fig. 2 obtains for comparative example 8 not With the temperature rise figure under multiplying power.
It can be seen from Fig. 1 and Fig. 2 under 5C multiplying power dischargings, the temperature rise for the battery that comparative example 8 obtains is higher than embodiment 12 The temperature rise of obtained battery, both differences are at 5 DEG C；And with the raising of multiplying power, both significantly increase temperature rise difference, at 15C times Rate inter-time is different to can reach 20 DEG C, it can be seen that, it is obvious by the temperature rise of the battery of graphene coated layer in use It is low that the temperature rise of the battery of positive electrode slurry layer in use is directly coated than no graphene coated layer, especially big Under conditions of power, this differentiation is more obvious.By coating a layer graphene slurry, during can reducing battery use Temperature rise, can also ensure the security of battery under high-power.
The battery security of test example 5 is tested
The based lithium-ion battery positive plate obtained to embodiment 12~17 and comparative example 8~12 and ordinary graphite negative electrode Battery after piece assembling carries out acupuncture, overcharges and can be tested with short circuit safety.
Safety of acupuncture performance test：By battery in a manner of CC-CV it is fully charged to after 4.2V, it is resistance to Φ 5mm~Φ 8mm High temperature draw point, with 25 ± 5mm/s speed, run through from the direction perpendicular to battery pole plates, draw point stops 1h in the battery.
Overcharge safety can be tested：By battery in a manner of CC-CV it is fully charged to after 4.2V, with the electric current constant current of 1C multiplying powers Charge to 6.3V or charging interval reach 1h after stop.
Short circuit safety can test：By battery in a manner of CC-CV it is fully charged to after 4.2V, using internal resistance<5m Ω's is outer Portion line short circuit 10min.
Define the result of security performance test, " do not smolder not on fire do not explode " is " outstanding ", " smolder, there is Mars, it is not quick-fried It is fried " it is " general ", " blast on fire " is " poor ".
Table 4 is battery safety test result.
The battery safety test result of table 4
As can be seen from Table 4, the battery safety that the present invention obtains is preferable, can be tested by pin prick test, and Other performances such as overcharging during battery use and short circuit are more excellent.
The present invention is asked by improving to positive electrode and electrode chip architecture with improving conventional lithium ion battery security Topic, not only increases the heat endurance of positive electrode, and reduces pole piece internal resistance, during reducing battery use, especially Temperature rise under big multiplying power, can meet to use under high magnification, and security is good, be that a kind of can take into account high-power and security Dynamic lithium battery.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that wrap in the following claims Include all such changes and modifications belonged in the scope of the invention.

Claims (10)

1. a kind of active substance of lithium ion battery anode, it is characterised in that active substance of lithium ion battery anode is mainly by following The component composition of weight/mass percentage composition：Iron manganese phosphate for lithium 10~50% and nickle cobalt lithium manganate 50~90%；
The iron manganese phosphate for lithium is LiMnxFe1-xPO4, wherein 0.5<x<1, the nickle cobalt lithium manganate is Li (NixCoyMnz)O2, its In 0<x<1,0<y<1,0<z<1 and x+y+z=1.
2. according to the active substance of lithium ion battery anode described in claim 1, it is characterised in that lithium ion cell positive activity Material is mainly made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 10~40% and nickle cobalt lithium manganate 60~90%；
The iron manganese phosphate for lithium is LiMnxFe1-xPO4, wherein 0.5<x<1, the nickle cobalt lithium manganate is Li (NixCoyMnz)O2, its In 0.5≤x<1,0<y<0.5,0<z<0.5 and x+y+z=1.
3. according to the active substance of lithium ion battery anode described in claim 1 or 2, it is characterised in that lithium ion cell positive Active material is mainly made up of the component of following weight/mass percentage composition：Iron manganese phosphate for lithium 20~30% and nickle cobalt lithium manganate 70~ 80%；
The iron manganese phosphate for lithium is LiMnxFe1-xPO4, wherein 0.6≤x≤0.8, the nickle cobalt lithium manganate is Li (NixCoyMnz) O2, wherein 0.6≤x≤0.85,0<y<0.4,0<z<0.4 and x+y+z=1.
4. a kind of anode material for lithium-ion batteries, it is characterised in that it is any that anode material for lithium-ion batteries includes claim 1-3 Active substance of lithium ion battery anode described in.
5. according to the anode material for lithium-ion batteries described in claim 4, it is characterised in that anode material for lithium-ion batteries also wraps Include：Conductive agent and binding agent；
Conductive agent quality accounts for the 0.5~1% of anode material for lithium-ion batteries quality；
Binding agent quality accounts for the 1.5~2% of anode material for lithium-ion batteries quality.
6. a kind of anode material for lithium-ion batteries slurry, it is characterised in that anode material for lithium-ion batteries slurry is will by right Ask the anode material for lithium-ion batteries described in 4 or 5 to be dissolved or dispersed in solvent to obtain.
7. a kind of based lithium-ion battery positive plate, it is characterised in that be sequentially coated with stone on the collector of based lithium-ion battery positive plate The pulp layer of anode material for lithium-ion batteries slurry described in black alkene layer and claim 6.
8. according to the based lithium-ion battery positive plate described in claim 7, it is characterised in that be prepared by following methods：
A) by graphene, optionally binding agent and optionally dispersant add solvent in, obtain graphene slurry；
B) the graphene slurry for first obtaining step a) is dried coated in aluminum foil current collector and removes solvent, forms graphene layer, Anode material for lithium-ion batteries slurry is coated in again and had been coated with the aluminum foil current collector of graphene layer, dries and removes solvent, Obtain based lithium-ion battery positive plate.
9. the preparation method of the based lithium-ion battery positive plate described in a kind of claim 7 or 8, it is characterised in that first by graphene Slurry is coated on the collector of based lithium-ion battery positive plate, then the anode material for lithium-ion batteries described in claim 6 is starched On collector of the material coated in based lithium-ion battery positive plate, based lithium-ion battery positive plate is obtained.
A kind of 10. active substance of lithium ion battery anode including described in claim any one of 1-3, described in claim 4 or 5 Anode material for lithium-ion batteries, described in the anode material for lithium-ion batteries slurry described in claim 6 or claim 7 or 8 Based lithium-ion battery positive plate lithium ion battery.
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