CN106803586A - A kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole - Google Patents

A kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole Download PDF

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CN106803586A
CN106803586A CN201710117454.0A CN201710117454A CN106803586A CN 106803586 A CN106803586 A CN 106803586A CN 201710117454 A CN201710117454 A CN 201710117454A CN 106803586 A CN106803586 A CN 106803586A
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positive electrode
indium
tin
positive pole
conducting film
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CN106803586B (en
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任付金
吴小珍
杨顺毅
庞钧友
黄友元
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Shenzhen Battery Nanotechnology Co Ltd
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Shenzhen Battery Nanotechnology 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
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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

A kind of lithium ion battery the invention provides composite positive pole, its preparation method and comprising the composite positive pole.Composite positive pole of the invention includes positive electrode and is completely and homogeneously coated on the conducting film on positive electrode surface.Present invention also offers the preparation method of composite positive pole, the method for the present invention can make conducting film be uniformly coated on the surface of positive electrode, and realization is coated completely.In composite positive pole of the invention, the completely and homogeneously cladding of the conducting film with stronger electric conductivity can intercept the directly contact of electrolyte and positive electrode, reduce the generation of side reaction, additionally it is possible to improve high rate performance, cycle performance and the security performance of battery.Compared to the battery that the positive electrode of uncoated conducting film is made, the 5C high rate performances of composite improve percentage up to 15~28%, and 50 weeks capability retentions of circulation improve percentage up to 7~11%, and exothermic temperature improves 20~30 DEG C, and security performance is improved.

Description

A kind of composite positive pole, its preparation method and the lithium comprising the composite positive pole Ion battery
Technical field
The invention belongs to field of lithium ion battery anode, it is related to a kind of composite positive pole, its preparation method and bag Lithium ion battery containing the composite positive pole, more particularly to a kind of anode composite of ITO nano conductive films clad anode material Material, its preparation method and the lithium ion battery comprising the composite positive pole.
Background technology
With scientific and technological progress and the fast development of human society, industrialized process constantly accelerates, need of the people to the energy Ask constantly growth.The conventional fossil fuels such as coal, oil and natural gas are largely exploited and used so that these non-renewable changes The stone energy is increasingly exhausted, and problem of energy crisis is increasingly severe.In the combustion process of fossil fuel, produce substantial amounts of dust and have Evil gas, causes serious environmental pollution, and the life to ecological environment and people brings huge harm with healthy.
In order to alleviate energy scarcity situation, preserve the ecological environment, it is necessary to change unsustainable energy occupation mode.With The progress of science and technology and the development with society, substantial amounts of portable electronic equipment and electric automobile etc. pour in the life of people In, this is also in the urgent need to the appearance of high performance battery.Traditional secondary cell be all difficult to meet at this stage to electronic product, The demand to battery higher performance such as electricity generation system and new-energy automobile.
Lithium ion battery have energy density higher, power density, operating voltage higher, preferable cycle performance and The advantages of relatively low self-discharge rate, " green power supply " is described as, and optimal chemical energy source is known as by international community, it is wide It is general for electronic products such as mobile phone, notebook computer, electric tool and camcorders.With to current material and battery The improvement of designing technique and the appearance of new material, the range of application of lithium ion battery are constantly expanded, from information industry (mobile electricity Words, PDA and notebook computer) to energy traffic (electric automobile, peak load regulation network), from space (satellite, airship) to (diving under water Ship, underwater robot).Lithium ion battery will serve the mankind as new energy most with prospects, and oneself turns into this century Research and development focus.
For lithium ion battery, positive electrode, negative material and electrolyte are the keys for determining its chemical property Factor, and positive electrode serves as the role of the lithium source in lithium ion battery, is one of important component of lithium ion battery, more It is the key factor for restricting the chemical properties such as lithium ion battery specific energy and specific power.The lithium ion cell positive commonly used at present Material mainly has：The positive electrode of layer structure, including cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMnO2), and two/tri compound layered cathode material (LiNixCoyMnzO2) etc.；The LiMn2O4 of spinel structure (LiMn2O4)；LiFePO4 (the LiFePO of olivine-type structure4) etc..
Although lithium ion battery material has many advantages, such as, for electrokinetic cell, it is also faced with urgent need and solves Problems, such as material circulation performance and security performance be also far not by far up to the mark, under high current the decay of capacity it is serious and The problems such as high rate performance difference.In order to solve these problems, generally material is modified, modified method includes doping and surface Cladding etc. is improving the performance of positive electrode.
Chinese invention patent CN105118963A discloses transparent positive electrode of a kind of lithium ion battery and preparation method thereof. Its structure is made up of the charge transport layer on substrate, substrate and lithium ion storage layer.Also disclose the transparent positive pole of lithium ion battery The preparation method of material, including：Using nano magnetic sputtering, electron beam evaporation or pulsed laser deposition after the cleaning process ITO the or AZO charge transport layers are prepared on substrate；It is heavy using ion aid magnetron sputtering, electron beam evaporation or pulse laser Area method original position on charge transport layer prepares lithium ion storage layer LiV3O8.The transparent positive electrode of lithium ion battery for preparing Visible light wave range mean transmissivity 70~80%, positive pole is prepared using the transparent positive electrode of the lithium ion battery and goes forward side by side one Step is assembled into lithium ion battery, and its charge/discharge capacity is high, good cycling stability, and first charge-discharge specific capacity is 300~350mAh/ G, capacity still may remain in more than 80% after 100 circulations, can be applied to novel transparent field of lithium ion battery.But, Positive electrode prepared by the method is LiV3O8Transparent positive electrode, the material and purposes of invention are respectively provided with limitation.
Chinese invention patent CN103956458A discloses composite lithium ion battery anode and preparation method thereof and is consolidating entirely Application in state lithium ion battery.Composite lithium ion battery anode of the present invention by positive active material, inorganic solid electrolyte and Oxidation conductive additive composition；Positive active material is any in cobalt acid lithium, LiMn2O4, LiFePO4 and nickel-cobalt-manganese ternary material Kind；Inorganic solid electrolyte is at least one of lithium borate, lithium metaborate and lithium fluoride；Oxide conducting additive is indium oxide In tin, indium oxide, tin ash, zinc oxide, nickel oxide and ferroso-ferric oxide any one.The patent also discloses lithium ion battery The preparation method of anode composite, comprises the following steps：(1) by positive active material, inorganic solid electrolyte and oxide conducting Ball milling is carried out after additive mixing, potsherd is pressed into after drying；(2) potsherd sintering is obtained final product into anode composite.It is prepared The anode composite for obtaining has good specific discharge capacity, area specific capacity and cycle performance, can be used to preparing all solid lithium from Sub- battery, and can use at high temperature.But, positive electrode prepared by the method mainly uses solid-phase ball milling method by powder Tin indium oxide mixing is sintered in adding positive electrode, belongs to common doping category.
Therefore, it is lithium-ion electric to invent a kind of high conductivity, forthright high power, high security and coat good positive electrode The technical barrier in pond positive electrode field.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of composite positive pole, its Preparation method and the lithium ion battery comprising the composite positive pole, composite positive pole of the invention include positive electrode and bag The conducting film on positive electrode surface is overlayed on, the completely and homogeneously cladding of the conducting film with stronger electric conductivity can intercept electricity The directly contact of solution liquid and positive electrode, reduces the generation of side reaction, additionally it is possible to improve the high rate performance of battery, cycle performance and Security performance.Compared to the battery that the positive electrode of uncoated conducting film is made, the 5C high rate performances of composite improve percentage Than up to 15%~28%, 50 weeks capability retentions of circulation improve percentage up to 7%~11%, and exothermic temperature improves 20 DEG C~30 DEG C, security performance is improved.
It is that, up to above-mentioned purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of composite positive pole, the composite positive pole include positive electrode and It is coated on the conducting film on the positive electrode surface.
In composite positive pole of the invention, conducting film is coated on the surface of positive electrode completely, and is evenly coated.It is conductive Film has stronger electric conductivity, and conducting film can not only intercept electrolyte and positive electrode with the fully wrapped around structure of positive electrode Directly contact, reduces the generation of side reaction, moreover it is possible to improve high rate performance, cycle performance and the security performance of the battery of assembling.
Preferably, in the composite positive pole positive electrode and the mass ratio of conducting film is 1:(0.001~0.1), Such as 1:0.001、1:0.002、1:0.003、1:0.004、1:0.005、1:0.006、1:0.008、1:0.01、1:0.02、1: 0.03、1:0.04、1:0.06、1:0.07、1:0.08 or 1:0.1 etc..
Preferably, the positive electrode is that chemical composition is LiNixCoyMzO2Positive electrode and/or LiFePO4Positive pole Material, wherein, 0≤x≤1,0≤y≤1,0≤z<1, and x+y+z=1, M are selected from appointing in Mn, Al, Mg, Zr, Zn, Cu or Cr Meaning it is a kind of or at least two combinations.The positive electrode for example can be but be not limited to LiNi1/3Co1/3Mn1/3O2、 LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.15Al0.05O2、LiNi1/3Co1/3Mg1/3O2、LiNi0.5Co0.3Mn0.2O2With LiNi0.8Co0.1Al0.1O2Deng.
In the present invention, chemical composition is LiFePO4Positive electrode refer to lithium iron phosphate cathode material.
Preferably, the thickness of the conducting film is nano conductive film in nanoscale, the then conducting film, and the thickness is preferred Be 0.5nm~200nm, such as 0.5nm, 1nm, 3nm, 7nm, 10nm, 15nm, 20nm, 25nm, 30nm, 34.5nm, 38nm, 40nm、42nm、44nm、46nm、50nm、54nm、58nm、62nm、66nm、70nm、75nm、78nm、80nm、85nm、90nm、 95nm、100nm、110nm、115nm、120nm、125nm、130nm、135nm、140nm、150nm、160nm、175nm、185nm Or 200nm etc..
Preferably, the chemical composition of the conducting film is tin indium oxide (Indium tin oxide, ITO).
Preferably, the tin indium oxide is the indium oxide for mixing tin, and the tin indium oxide is by In2O3And SnO2Composition.
Preferably, the In2O3And SnO2Mass ratio be (3~10):1, for example, 3:1、4:1、4.5:1、5:1、6:1、 6.5:1、7:1、8:1、8.5:1、9:1 or 10:1 etc., preferably 9:1.
Second aspect, the present invention provides a kind of preparation method of composite positive pole as described in relation to the first aspect, methods described For：Using spray pyrolysis in the Surface coating conducting film of positive electrode, composite positive pole is prepared.
Preferably, the conducting film is indium tin oxide conductive film.Indium tin oxide conductive film has stronger electric conductivity, its electricity Resistance rate is 10-3Ω cm~10-5Ω cm, close to the resistivity of metal, the surface that it is completely encapsulated in positive electrode can hinder Every electrolyte and positive electrode directly contact, reduce the generation of side reaction, thus improve the high rate performance of battery, cycle performance and Security performance.
Preferably, the described method comprises the following steps：
(1) conducting film precursor solution is prepared；
(2) positive electrode is added in the conducting film precursor solution that step (1) is obtained, obtains slurry, add thickening Agent adjusts the viscosity of slurry, obtains dispersion liquid；
(3) dispersion liquid obtained using step (2) carries out spray-wall interaction, in the Surface coating conducting film of positive electrode, Obtain composite positive pole.
Preferably, step (1) the conducting film precursor solution is tin indium oxide precursor solution.
Preferably, the process for preparation of the tin indium oxide precursor solution is：Indium sill and tin-based material are dissolved in molten In agent, stirring obtains tin indium oxide precursor solution；
Preferably, the indium sill is any one in indium nitrate, inidum chloride, indium sulfate, indium acetate or oxalic acid indium Or at least two combination, combination typical case but non-limiting examples have：The combination of indium nitrate and inidum chloride, indium nitrate and sulphur The combination of the combination of sour indium, inidum chloride and indium acetate, combination of indium nitrate, inidum chloride and indium acetate etc..But it is not limited to above-mentioned The indium sill enumerated, other indium sills commonly used in the art can also be used for the present invention.
Preferably, the tin-based material is any one in nitric acid tin, stannic chloride, STANNOUS SULPHATE CRYSTALLINE, tin acetate or stannous oxalate Kind or at least two combination, the combination is typical but non-limiting examples have：The combination of nitric acid tin and stannic chloride, nitric acid tin and The combination of STANNOUS SULPHATE CRYSTALLINE, the combination of nitric acid tin and tin acetate, combination of stannic chloride, STANNOUS SULPHATE CRYSTALLINE and tin acetate etc..But it is not limited to The tin-based material enumerated is stated, other tin-based materials commonly used in the art can also be used for the present invention.
Preferably, the mol ratio of the indium sill and tin-based material is (1~20):1, for example, 1:1、2:1、2.5:1、 3.5:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、15:1、16:1、18:1、19:1 or 20:1 etc..
Preferably, the solvent is any one in methyl alcohol, ethanol, phenmethylol or ethylene glycol or at least two group Close.
Preferably, the speed of the stirring is 50r/min~500r/min, such as 50r/min, 75r/min, 100r/ min、120r/min、130r/min、150r/min、175r/min、200r/min、220r/min、245r/min、275r/min、 300r/min, 325r/min, 350r/min, 400r/min, 430r/min, 450r/min or 500r/min etc..
Preferably, the time of the stirring be 30min~300min, for example, 30min, 45min, 60min, 80min, 100min, 120min, 150min, 180min, 200min, 210min, 245min, 260min, 270min, 285min or 300min Deng.
Preferably, the chemical composition of step (2) described positive electrode is LiNixCoyMzO2, wherein, 0≤x≤1,0≤y≤ 1,0≤z<1, and x+y+z=1, M are selected from any one in Mn, Al, Mg, Zr, Zn, Cu or Cr or at least two combination, institute Stating positive electrode for example can be but be not limited to LiNi1/3Co1/3Mn1/3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.15Al0.05O2、 LiNi1/3Co1/3Mg1/3O2、LiNi0.5Co0.3Mn0.2O2And LiNi0.8Co0.1Al0.1O2Deng.
Preferably, with stirring during step (2) adds positive electrode.
Preferably, step (2) add positive electrode after continue stir 10min~120min, for example, 10min, 20min, 30min, 40min, 50min, 60min, 75min, 85min, 100min, 110min or 120min etc., preferably 30min。
Preferably, the solid content of step (2) described slurry be 20wt%~60wt%, for example, 20wt%, 23wt%, 25wt%, 30wt%, 32.5wt%, 35wt%, 38wt%, 40wt%, 43wt%, 45wt%, 47.5wt%, 50wt%, 55wt% or 60wt% etc..
Preferably, step (2) described thickener is solid alcohol thickener FR400.
Preferably, step (2) the conducting film precursor solution and the mass ratio of the thickener are 1:(0.0001~ 0.1), for example, 1:0.0001、1:0.0002、1:0.0003、1:0.0005、1:0.0006、1:0.0008、1:0.001、1: 0.003、1:0.005、1:0.006、1:0.007、1:0.008 or 1:0.01 etc..In the present invention, thickener is preferably starched according to regulation Material viscosity no longer occurs to settle and add to positive electrode.
Preferably, when step (3) carries out spray-wall interaction, dispersion liquid is persistently stirred.
Preferably, when step (3) carries out spray-wall interaction, the carrier gas of spraying is compressed air.
Preferably, when step (3) carries out spray-wall interaction, carrier gas pressure is 3kg/m2~10kg/m2, for example, 3kg/m2、 4kg/m2、5kg/m2、6kg/m2、7kg/m2、8kg/m2、8.5kg/m2、9kg/m2Or 10kg/m2Deng.
Preferably, when step (3) carries out spray-wall interaction, dispersion flow quantity is 5ml/min~500ml/min, for example, 5ml/min、10ml/min、20ml/min、35ml/min、50ml/min、65ml/min、85ml/min、100ml/min、 120ml/min、150ml/min、180ml/min、200ml/min、220ml/min、240ml/min、275ml/min、300ml/ Min, 330ml/min, 360ml/min, 385ml/min, 400ml/min, 425ml/min, 450ml/min or 500ml/min etc..
Preferably, when step (3) carries out spray-wall interaction, the temperature of spraying is 100 DEG C~300 DEG C, for example, 100 DEG C, 125 DEG C, 150 DEG C, 165 DEG C, 180 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 235 DEG C, 250 DEG C, 260 DEG C, 280 DEG C or 300 DEG C etc..
Preferably, when step (3) carries out spray-wall interaction, pyrolysis temperature is 300 DEG C~800 DEG C, for example, 300 DEG C, 325 ℃、350℃、380℃、400℃、420℃、440℃、460℃、480℃、500℃、525℃、550℃、575℃、600℃、 630 DEG C, 660 DEG C, 700 DEG C, 750 DEG C or 800 DEG C etc..
Preferably, when step (3) carries out spray-wall interaction, pyrolysis time be 2h~20h, for example, 2h, 3h, 5h, 6h, 8h, 10h, 12h, 13h, 15h, 16h, 18h or 20h etc..
The third aspect, the present invention provides the preparation method of another composite positive pole as described in relation to the first aspect, the side Method is：Using cladding raw material by chemical vapor deposition (Chemical Vapor Deposition, CVD) method in positive electrode Surface coating conducting film, prepare composite positive pole.
Preferably, the conducting film is indium tin oxide conductive film.It is described when the conducting film is indium tin oxide conductive film Cladding raw material is indium metal organic compound and tin metal organic compound.
Preferably, the indium metal organic compound be Indium Tris acetylacetonate, trimethyl indium, triethylindium, triphenyl indium or In diethacetic acid indium any one or at least two combination, combination typical case but non-limiting examples have：Levulinic The combination of the combination of ketone indium and trimethyl indium, Indium Tris acetylacetonate and triethylindium, the combination of trimethyl indium and diethacetic acid indium, The combination of Indium Tris acetylacetonate, triethylindium and triphenyl indium, combination of Indium Tris acetylacetonate, trimethyl indium and triethylindium etc..But The above-mentioned indium metal organic compound enumerated is not limited to, other indium metal organic compounds commonly used in the art can also be used for this Invention.
Preferably, the chemical composition of the tin metal organic compound is RxSnY, wherein, R is in alkyl or aromatic radical The combination of any one or two kinds, Y is halogen, and x is 0~4 integer.The x is, for example, 0,1,2,3 and 4.
Preferably, the tin metal organic compound is tin trimethyl, tetramethyl tin, tin triethyl, triphenyltin or four In stannic chloride any one or at least two combination.The combination is typical but non-limiting examples have：Tin trimethyl and four The combination of the combination of methyl tin, tin trimethyl and butter of tin, combination of tin trimethyl, tetramethyl tin and tin triethyl etc..But The above-mentioned tin metal organic compound enumerated is not limited to, other tin metal organic compounds commonly used in the art can also be used for this Invention.
Can be gas phase as the indium metal organic compound and tin metal organic compound of cladding raw material in the present invention, It can also be non-gaseous.If cladding raw material is gas phase, the cladding raw material of gas phase is directly introduced into rotary furnace using carrier gas；Such as Fruit cladding raw material is non-gaseous, then be introduced into rotary furnace by carrier gas again after taking certain measure to make cladding feed vaporization.Described Certain measure can be by the way of high temperature evaporation, for example, using diethacetic acid indium and butter of tin as cladding raw material When, the measure for using for：Diethacetic acid indium is placed in the container that temperature is 200 DEG C~400 DEG C, diethacetic acid indium is obtained Steam；Butter of tin is placed in 300 DEG C~500 DEG C of container, the steam of butter of tin is obtained；Make diethacetic acid indium The steam of steam and butter of tin is introduced into reacting furnace by carrier gas respectively.
Preferably, the method using chemical vapour deposition technique in the Surface coating indium tin oxide conductive film of positive electrode includes Following steps：
Positive electrode is placed in rotary furnace, is heated, be passed through reacting gas, respectively had gaseous indium metal using carrier gas Machine compound and gaseous tin metal organic compound are introduced into rotary furnace, chemical vapor deposition are carried out, in the table of positive electrode Bread covers indium tin oxide conductive film, obtains composite positive pole.
Preferably, the chemical composition of the positive electrode is LiNixCoyMzO2, wherein, 0≤x≤1,0≤y≤1,0≤z< 1, and x+y+z=1, M are selected from any one in Mn, Al, Mg, Zr, Zn, Cu or Cr or at least two combination.The positive pole Material for example can be but be not limited to LiNi1/3Co1/3Mn1/3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.15Al0.05O2、LiNi1/ 3Co1/3Mg1/3O2、LiNi0.5Co0.3Mn0.2O2And LiNi0.8Co0.1Al0.1O2Deng.
Preferably, the heating rate during heating is 0.5 DEG C/min~15 DEG C/min, for example, 0.5 DEG C/min, 1 DEG C/ min、2℃/min、3℃/min、3.5℃/min、4℃/min、5℃/min、6℃/min、7℃/min、8℃/min、10℃/ Min, 11 DEG C/min, 12 DEG C/min, 13 DEG C/min, 14 DEG C/min or 15 DEG C/min etc..
Preferably, the reacting gas is oxygen.
Preferably, the speed that is passed through of the reacting gas is 1m3/ h~5m3/ h, for example, 1m3/h、1.2m3/h、1.4m3/ h、1.5m3/h、1.6m3/h、1.7m3/h、1.8m3/h、1.9m3/h、2m3/h、2.5m3/h、3m3/h、3.5m3/h、4m3/ h or 5m3/ H etc..
Preferably, the carrier gas is any one in nitrogen, helium, neon, argon gas, Krypton or xenon or at least two Combination.
Preferably, when gaseous indium metal organic compound being introduced into rotary furnace using carrier gas, carrier gas and gaseous indium are golden Belong to organic compound gaseous mixture flow velocity be 0.1L/min~100L/min, for example, 0.1L/min, 1L/min, 3L/min, 5L/min、8L/min、10L/min、15L/min、20L/min、23L/min、25L/min、30L/min、35L/min、40L/ Min, 45L/min, 50L/min, 60L/min, 65L/min, 70L/min, 80L/min, 85L/min, 90L/min, 95L/min or 100L/min etc., preferably 5L/min~50L/min.
Preferably, when gaseous tin metal organic compound being introduced into rotary furnace using carrier gas, carrier gas and gaseous Sillim Belong to organic compound gaseous mixture flow velocity be 0.1L/min~100L/min, for example, 0.5L/min, 3L/min, 10L/min, 20L/min, 30L/min, 40L/min, 50L/min, 60L/min, 70L/min, 85L/min, 95L/min or 100L/min etc., Preferably 2L/min~20L/min.
Preferably, the rotating speed of the rotary furnace is 0.1r/min~10r/min, such as 0.1r/min, 0.5r/min, 1r/ Min, 2r/min, 3r/min, 4r/min, 5r/min, 6r/min, 7r/min, 8r/min or 10r/min etc..
Preferably, during the chemical vapor deposition, the shared mass concentration in rotary furnace of the reacting gas More than 60%, for example, 60%, 62%, 65%, 67.5%, 70%, 73%, 75%, 77%, 80%, 82%, 85% or 90% etc..
Preferably, the temperature of the chemical vapor deposition be 300 DEG C~1000 DEG C, for example, 300 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 600 DEG C, 625 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C etc..
Preferably, the time of the chemical vapor deposition be 5min~600min, such as 5min, 30min, 45min, 60min、90min、120min、150min、180min、210min、240min、260min、270min、300min、320min、 350min, 380min, 400min, 420min, 450min, 480min, 500min, 520min, 550min, 570min or 600min Deng.
The preparation method of the composite positive pole that second aspect present invention and the third aspect are provided can make conducting film equal The surface of positive electrode is coated on evenly, and can realize coating completely.
Fourth aspect, the present invention provides a kind of positive pole, comprising answering described in first aspect in the raw material components of the positive pole Close positive electrode.
5th aspect, the present invention provides a kind of lithium ion battery, and the lithium ion battery includes answering described in first aspect Close positive electrode.
Compared with the prior art, the present invention has the advantages that：
(1) present invention prepares composite positive pole, the ito film tool of cladding in the Surface coating ito film of positive electrode There is stronger electric conductivity, ITO conduction film resistivities are 10-3Ω cm~10-5Ω cm, close to the resistivity of metal, its is complete Being wrapped in material surface can intercept electrolyte and positive electrode directly contact, reduce the generation of side reaction, additionally it is possible to improve electricity The pond performance of discharge and recharge, high rate performance, cycle performance and security performance under the conditions of big flow, can be applied to 3C lithium ion batteries With electrokinetic cell field.Composite positive pole of the invention is made positive pole and is assembled into battery and can significantly improve high rate performance, follow Ring performance and security performance, compared to the battery that the positive electrode of uncoated conducting film is made, the 5C high rate performances of composite Percentage up to 15%~28% is improved, 50 weeks capability retentions of circulation improve percentage up to 7%~11%, and exothermic temperature improves 20 DEG C~30 DEG C, security performance is improved.
(2) the invention provides spray-wall interaction being respectively adopted and chemical vapor deposition prepares the side of composite positive pole Method, both approaches can realize uniformly and completely cladding of the conducting film on positive electrode surface, and associativity is good, solve Positive electrode current material cladding is uneven and coating is not completely encapsulated in the problem of material surface.And the method for the present invention It is simple to operate, it is easy to industrialized production.
Brief description of the drawings
Fig. 1 is the positive electrode LiNi of embodiment 30.8Co0.15Al0.05O2The anode composite material obtained after cladding ITO conducting films The TEM figures of material.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Conducting performance test：
The positive electrode of composite positive pole and comparative example 1-3 to embodiment 1-8 carries out conducting performance test, weighs 3g ~5g above-mentioned sample, its electrical conductivity is tested using powder conductivity rate instrument.
Assembled battery：
Using the positive electrode of the composite positive pole of embodiment 1-8 and comparative example 1-3 as positive electrode, according to positive pole material Material:Conductive agent:Binding agent mass ratio is 90:5:5 size mixing is coated on aluminium foil as positive pole, and lithium piece is assembled into mould as negative pole Intend battery.
High rate performance is tested：
Different multiplying discharge performance is tested, test condition：Voltage 3.0V~4.3V, 0.5C charging/0.5C electric discharge, 0.5C fill Electricity/1.0C electric discharges, 0.5C charging/2.0C electric discharges, 0.5C charging/5.0C electric discharges.Test result is shown in Table 1.
Cycle performance is tested：
Using the positive electrode of the composite positive pole of embodiment 1-8 and comparative example 1-3 as positive electrode, according to positive pole material Material:Conductive agent:Binding agent mass ratio is 96:2:2 size mixing is coated on aluminium foil as positive pole, and lithium piece is assembled into button as negative pole Formula battery.Charge-discharge performance test is carried out under conditions of 0.5C/1.0C, 3.0-4.2V.
Security performance is tested：
Battery after will be fully charged for the first time is dismantled in drying shed, removes positive plate, with DMC soaking and washing 30min, is dried After carry out DSC tests, DSC test conditions：N2400 DEG C of test heat releases are warmed up to from 40 DEG C with 10 DEG C/min heating rates in atmosphere Peak temperature.
Embodiment 1
Prepare composite positive pole：
(1) 7.82g In (NO are weighed respectively3)3·5H2O and 0.58g SnCl4·5H2O is dissolved in 1000ml methanol solutions, 60min is stirred with the mixing speed of 200r/min, ITO precursor solutions are prepared；
(2) under conditions of stirring, to addition 500g positive electrodes LiNi in above-mentioned solution1/3Co1/3Mn1/3O2, continue to stir Thickener FR400 is added after mixing 30min, regulation slurry viscosity to positive electrode is no longer settled, in the bar of dispersed with stirring liquid Sprayed under part, the carrier gas of spraying is compressed air, and carrier gas pressure is 5kg/m2, dispersion flow quantity is 100ml/min, spraying Temperature is 200 DEG C, and obtaining Surface coating has the positive electrode of ITO precursor films, and 8h is then pyrolyzed at 700 DEG C, and cooling is sieved, Obtain composite positive pole, the composite positive pole is by positive electrode and is coated on the ITO conducting film structures on positive electrode surface Into, and the thickness of ITO conducting films is about 20nm.
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 6.51S/cm.
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 155mAh/g, and efficiency is 89.2% first.
Tested through cycle performance, circulate 50 capability retentions 99.1%, cycle performance is than the LiNi that is coated1/ 3Co1/3Mn1/3O2, conservation rate brings up to 99.1% from 92.6%, and cycle performance is significantly improved, and the percentage of raising is 7%.
Tested through security performance, 256.7 DEG C of Exotherm Onset Temperature, 278.3 DEG C of peak temperature, heat release end temp 296.8 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 221.9 of the composite positive pole than uncoated positive electrode after ITO DEG C, 241.3 DEG C of peak temperature, 258.8 DEG C of heat release end temp) increase, and then improve the security performance of material.
Embodiment 2
Prepare composite positive pole：
(1) 7.82g In (NO are weighed respectively3)3·5H2O and 0.58g SnCl4·5H2O is dissolved in 1000ml methanol solutions, 60min is stirred with the mixing speed of 200r/min, ITO precursor solutions are prepared；
(2) under conditions of stirring, to addition 500g positive electrodes LiNi in above-mentioned solution0.6Co0.2Mn0.2O2, continue to stir Thickener FR400 is added after mixing 30min, regulation slurry viscosity to positive electrode is no longer settled, in the bar of dispersed with stirring liquid Sprayed under part, the carrier gas of spraying is compressed air, and carrier gas pressure is 5kg/m2, dispersion flow quantity is 100ml/min, spraying Temperature is 200 DEG C, and obtaining Surface coating has the positive electrode of ITO precursor films, and 6h is then pyrolyzed at 600 DEG C, and cooling is sieved, Obtain composite positive pole, the composite positive pole is by positive electrode and is coated on the ITO conducting film structures on positive electrode surface Into, and the thickness of ITO conducting films is about 32nm.
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 9.36S/cm.
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 185mAh/g, and efficiency is 90.2% first.
Tested through cycle performance, circulate 50 capability retentions 98.6%, cycle performance is than being coated LiNi0.6Co0.2Mn0.2O2, conservation rate brings up to 98.6% from 90.1%, and cycle performance is significantly improved, and the percentage of raising is 9%.
Tested through security performance, 241.4 DEG C of Exotherm Onset Temperature, 259.3 DEG C of peak temperature, heat release end temp 281.2 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 213.7 of the composite positive pole than uncoated positive electrode after ITO DEG C, 230.1 DEG C of peak temperature, 241.2 DEG C of heat release end temp) increase, and then improve the security performance of material.
Embodiment 3
Prepare composite positive pole：
(1) 5.86g InCl are weighed respectively3·4H2O and 0.37g SnCl2·2H2O is dissolved in 1000ml ethanol solutions, with The mixing speed stirring 60min of 200r/min, prepares ITO precursor solutions；
(2) under conditions of stirring, to addition 1000g positive electrodes LiNi in above-mentioned solution0.8Co0.15Al0.05O2, continue Thickener FR400 is added after stirring 30min, regulation slurry viscosity to positive electrode is no longer settled, in dispersed with stirring liquid Under the conditions of sprayed, the carrier gas of spraying is compressed air, and carrier gas pressure is 5kg/m2, dispersion flow quantity is 80ml/min, spraying Temperature be 150 DEG C, obtaining Surface coating has the positive electrode of ITO precursor films, then 600 DEG C be pyrolyzed 6h, cooling, sieve Point, obtaining composite positive pole, the composite positive pole is by positive electrode and is coated on the ITO conducting films on positive electrode surface Constitute, and the thickness of ITO conducting films is 45nm.
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 0.67 × 102S/cm。
Fig. 1 is the positive electrode LiNi of embodiment 30.8Co0.15Al0.05O2The anode composite material obtained after cladding ITO conducting films The TEM figures of material, as seen from the figure, the thickness of ITO conducting films is 45nm.
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 202mAh/g, and efficiency is 91.5% first.
Tested through cycle performance, circulate 50 capability retentions 98.8%, cycle performance ratio is coated LiNi0.8Co0.15Al0.05O2, conservation rate brings up to 98.8% from 89.2%, and cycle performance is significantly improved, the percentage of raising It is 10%.
Tested through security performance, 228.6 DEG C of Exotherm Onset Temperature, 245.8 DEG C of peak temperature, heat release end temp 258.4 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 208.1 of the composite positive pole than uncoated positive electrode after ITO DEG C, 218.0 DEG C of peak temperature, 236.7 DEG C of heat release end temp) increase, and then improve the security performance of material.
Embodiment 4
Prepare composite positive pole：
(1) 6.19g indium acetates are weighed respectively and 0.33g STANNOUS SULPHATE CRYSTALLINEs are dissolved in 2000ml ethanol solutions, with 350r/min's Mixing speed stirs 120min, prepares ITO precursor solutions；
(2) under conditions of stirring, to addition 3000g positive electrodes LiNi in above-mentioned solution0.8Co0.15Al0.05O2, continue Thickener FR400 is added after stirring 30min, regulation slurry viscosity to positive electrode is no longer settled, in dispersed with stirring liquid Under the conditions of sprayed, the carrier gas of spraying is compressed air, and carrier gas pressure is 8kg/m2, dispersion flow quantity is 150ml/min, spraying Temperature be 200 DEG C, obtaining Surface coating has the positive electrode of ITO precursor films, then 500 DEG C be pyrolyzed 12h, cooling, sieve Point, obtaining composite positive pole, the composite positive pole is by positive electrode and is coated on the ITO conducting films on positive electrode surface Constitute, and the thickness of ITO conducting films is about 52nm.
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 0.22 × 102S/cm。
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 203.7mAh/g, and efficiency is 91.9% first.
Tested through cycle performance, circulate 50 capability retentions 99.0%, cycle performance is than being coated LiNi0.8Co0.15Al0.05O2, conservation rate brings up to 99.0% from 89.2%, and cycle performance is significantly improved, the percentage of raising It is 11%.
Tested through security performance, 231.3 DEG C of Exotherm Onset Temperature, 249.0 DEG C of peak temperature, heat release end temp 262.1 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 208.1 of the composite positive pole than uncoated positive electrode after ITO DEG C, 218.0 DEG C of peak temperature, 236.7 DEG C of heat release end temp) increase, and then improve the security performance of material.
Embodiment 5
First by positive electrode LiNi1/3Co1/3Mn1/3O2It is placed in rotary furnace, is heated up with 5 DEG C/min, while with 2.0m3/ h's Speed is to being passed through oxygen, rotary furnace rotating speed 5r/min in rotary furnace, then trimethyl indium is placed in 300 DEG C of containers, and vaporization is obtained Trimethyl indium steam；Butter of tin is placed in 250 DEG C of containers, vaporization obtains butter of tin steam, the trimethyl indium that will be produced Steam and butter of tin steam are incorporated into rotary furnace by carrier gas nitrogen, and the flow velocity of the gaseous mixture of trimethyl indium steam and carrier gas is The flow velocity of the gaseous mixture of 20L/min, butter of tin steam and carrier gas is 5L/min, in 700 DEG C of chemical vapor deposition 30min, so After be cooled to room temperature, be obtained composite positive pole, the composite positive pole is by positive electrode and is coated on positive electrode surface ITO conducting films constitute, and the thickness of ITO conducting films is about 38nm.
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 1.07 × 10S/cm.
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 158.3mAh/g, and efficiency is 89.5% first.
Tested through cycle performance, circulate 50 capability retentions 99.8%, cycle performance is than the LiNi that is coated1/ 3Co1/3Mn1/3O2, conservation rate brings up to 99.8% from 89.8%, and cycle performance is significantly improved, and the percentage of raising is 11%.
Tested through security performance, 260.4 DEG C of Exotherm Onset Temperature, 282.9 DEG C of peak temperature, heat release end temp 300.8 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 221.9 of the composite positive pole than uncoated positive electrode after ITO DEG C, 241.3 DEG C of peak temperature, 258.8 DEG C of heat release end temp) increase, and then improve the security performance of material.
Embodiment 6
First by positive electrode LiNi0.6Co0.2Mn0.2O2It is placed in rotary furnace, is heated up with 5 DEG C/min, while with 1.0m3/ h's Speed is to being passed through oxygen, rotary furnace rotating speed 5r/min in rotary furnace, then Indium Tris acetylacetonate is placed in 500 DEG C of containers, vaporizes To Indium Tris acetylacetonate steam；Tetramethyl tin is placed in 200 DEG C of containers, vaporization obtains tetramethyl tin steam, the acetyl that will be produced Acetone indium steam and tetramethyl tin steam are incorporated into rotary furnace by carrier gas nitrogen, the gaseous mixture of Indium Tris acetylacetonate steam and carrier gas Flow velocity be 30L/min, the flow velocity of the gaseous mixture of tetramethyl tin steam and carrier gas is 10L/min, in 500 DEG C of chemical vapor depositions 60min, is then cooled to room temperature, and composite positive pole is obtained, and the composite positive pole is by positive electrode and is coated on positive pole The ITO conducting films of material surface are constituted, and the thickness of ITO conducting films is about 55nm..
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 3.89 × 10S/cm.
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 182.1mAh/g, and efficiency is 90.5% first.
Tested through cycle performance, circulate 50 capability retentions 99.3%, cycle performance is than being coated LiNi0.6Co0.2Mn0.2O2, conservation rate brings up to 99.3% from 90.1%, and cycle performance is significantly improved, and the percentage of raising is 10%.
Tested through security performance, 247.5 DEG C of Exotherm Onset Temperature, 264.1 DEG C of peak temperature, heat release end temp 291.5 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 213.7 of the composite positive pole than uncoated positive electrode after ITO DEG C, 230.1 DEG C of peak temperature, 241.2 DEG C of heat release end temp) increase, and then improve the security performance of material.
Embodiment 7
First by positive electrode LiNi0.8Co0.15Al0.05O2It is placed in rotary furnace, is heated up with 5 DEG C/min, while with 1.0m3/h Speed to being passed through oxygen, rotary furnace rotating speed 5r/min in rotary furnace, then trimethyl indium is placed in 300 DEG C of containers, vaporize To trimethyl indium steam；Butter of tin is placed in 250 DEG C of containers, vaporization obtains butter of tin steam, the trimethyl that will be produced Indium steam and butter of tin steam are incorporated into rotary furnace by carrier gas nitrogen, the flow velocity of the gaseous mixture of trimethyl indium steam and carrier gas It is 20L/min, the flow velocity of the gaseous mixture of butter of tin steam and carrier gas is 10L/min, in 600 DEG C of chemical vapor deposition 30min, Then room temperature is cooled to, composite positive pole is obtained, the composite positive pole is by positive electrode and is coated on positive electrode table The ITO conducting films in face are constituted, and the thickness of ITO conducting films is about 70nm.
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 7.59 × 102S/cm。
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 203.7mAh/g, and efficiency is 91.1% first.
Tested through cycle performance, circulate 50 capability retentions 99.2%, cycle performance is than being coated LiNi0.8Co0.15Al0.05O2, conservation rate brings up to 99.2% from 89.2%, and cycle performance is significantly improved, the percentage of raising It is 11%.
Tested through security performance, 232.7 DEG C of Exotherm Onset Temperature, 251.6 DEG C of peak temperature, heat release end temp 279.8 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 208.1 of the composite positive pole than uncoated positive electrode after ITO DEG C, 218.0 DEG C of peak temperature, 236.7 DEG C of heat release end temp) increase, and then improve the security performance of material.
Embodiment 8
First by positive electrode LiNi0.8Co0.15Al0.05O2It is placed in rotary furnace, is heated up with 10 DEG C/min, while with 1.5m3/ The speed of h is to being passed through oxygen, rotary furnace rotating speed 8r/min in rotary furnace, then diethacetic acid indium is placed in 350 DEG C of containers, vapour Change obtains diethacetic acid indium steam, and triphenyltin is placed in 500 DEG C of containers, and vaporization obtains triphenyltin steam, will produce Diethacetic acid indium steam and triphenyltin steam be incorporated into rotary furnace by carrier gas argon gas, diethacetic acid indium steam and load The flow velocity of the gaseous mixture of gas is 10L/min, and the flow velocity of the gaseous mixture of triphenyltin steam and carrier gas is 2L/min, in 700 DEG C of changes Learn vapour deposition 100min, be then cooled to room temperature, be obtained composite positive pole, the composite positive pole by positive electrode and The ITO conducting films for being coated on positive electrode surface are constituted, and the thickness of ITO conducting films is about 92nm.
Through conducting performance test, the electrical conductivity of the composite positive pole of the present embodiment is 2.11 × 102S/cm。
High rate performance test is shown in Table 1.
The battery for preparing positive pole as positive electrode using the composite positive pole of the present embodiment and be assembled into is put first Electric specific capacity is 204.8mAh/g, and efficiency is 91.8% first.
Tested through cycle performance, circulate 50 capability retentions 98.9%, cycle performance is than being coated LiNi0.8Co0.15Al0.05O2, conservation rate brings up to 98.9% from 89.2%, and cycle performance is significantly improved, the percentage of raising It is 11%.
Tested through security performance, 229.1 DEG C of Exotherm Onset Temperature, 250.3 DEG C of peak temperature, heat release end temp 281.1 DEG C, show to coat exothermic temperature (Exotherm Onset Temperature 208.1 of the composite positive pole than uncoated positive electrode after ITO DEG C, 218.0 DEG C of peak temperature, 236.7 DEG C of heat release end temp) increase, and then improve the security performance of material.
Comparative example 1
The positive electrode of this comparative example is the positive electrode LiNi for coat treatment1/3Co1/3Mn1/3O2。
Through conducting performance test, the electrical conductivity of the positive electrode of the present embodiment is 3.63 × 10-3S/cm。
High rate performance test is shown in Table 1.
The ratio of electric discharge first of the battery for positive pole being prepared as positive electrode using the positive electrode of this comparative example and being assembled into Capacity is 158mAh/g, and efficiency is 89.8% first.
Tested through cycle performance, circulate 50 capability retentions 92.6%.
Tested through security performance, 221.9 DEG C of Exotherm Onset Temperature, 241.3 DEG C of peak temperature, heat release end temp 258.8 DEG C, showing that the positive electrode not coated begins to heat release at 221.9 DEG C, heat endurance is poor, and then causes security performance Difference.
Comparative example 2
The positive electrode of this comparative example is the positive electrode LiNi for coat treatment0.6Co0.2Mn0.2O2。
Through conducting performance test, the electrical conductivity of the positive electrode of this comparative example is 6.98 × 10-3S/cm。
High rate performance test is shown in Table 1.
The ratio of electric discharge first of the battery for positive pole being prepared as positive electrode using the positive electrode of this comparative example and being assembled into Capacity is 186.3mAh/g, and efficiency is 90.6% first.
Tested through cycle performance, circulate 50 capability retentions 90.1%.
Tested through security performance, 213.7 DEG C of Exotherm Onset Temperature, 230.1 DEG C of peak temperature, heat release end temp 241.2 DEG C, showing that the positive electrode not coated begins to heat release at 213.7 DEG C, heat endurance is poor, and then causes security performance Difference.
Comparative example 3
The positive electrode of this comparative example is the positive electrode LiNi for coat treatment0.8Co0.15Al0.05O2。
Through conducting performance test, the electrical conductivity of the positive electrode of this comparative example is 1.41 × 10-1S/cm。
High rate performance test is shown in Table 1.
The ratio of electric discharge first of the battery for positive pole being prepared as positive electrode using the positive electrode of this comparative example and being assembled into Capacity is 204.5mAh/g, and efficiency is 92.1% first.
Tested through cycle performance, circulate 50 capability retentions 89.2%.
Tested through security performance, 208.1 DEG C of Exotherm Onset Temperature, 218.0 DEG C of peak temperature, heat release end temp 236.7 DEG C, showing that the positive electrode not coated begins to heat release at 208.1 DEG C, heat endurance is poor, and then causes security performance Difference.
The high rate performance table of table 1
It can be seen from Table 1 that, embodiment 1 and embodiment 5 are to LiNi1/3Co1/3Mn1/3O2After carrying out the cladding of conducting film, High rate performance is significantly improved, 0.5C charging/1.0C discharge-rates performances can bring up to 98.9% from 97.2%；0.5C chargings/ 2.0C discharge-rates performance can bring up to 97.7% from 93.1%；0.5C charging/5.0C discharge-rates performances can be carried from 83.8% Height improves percentage up to 15% to 96.2%.
Embodiment 2 and embodiment 6 are to LiNi0.6Co0.2Mn0.2O2After carrying out the cladding of conducting film, significantly improve forthright again Can, 0.5C charging/1.0C discharge-rates performances can bring up to 98.2% from 96.9%；0.5C charging/2.0C discharge-rate performances 97.0% can be brought up to from 91.9%；0.5C charging/5.0C discharge-rates performances can bring up to 95.8% from 80.3%, improve hundred Divide ratio up to 19%.
Embodiment 3-4 and embodiment 7-8 are to LiNi0.8Co0.15Al0.05O2After carrying out the cladding of conducting film, significantly improve High rate performance, 0.5C charging/1.0C discharge-rates performances can bring up to 99.3% from 94.6%；0.5C charging/2.0C electric discharges times Rate performance can bring up to 98.7% from 90.2%；0.5C charging/5.0C discharge-rates performances bring up to 96.0% from 75.1%, carry High percentage is up to 28%.
Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the present invention not office It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (10)

1. a kind of composite positive pole, it is characterised in that the composite positive pole includes positive electrode and is coated on described The conducting film on positive electrode surface.
2. composite positive pole according to claim 1, it is characterised in that the positive electrode in the composite positive pole It is 1 with the mass ratio of conducting film:(0.001~0.1)；
Preferably, the positive electrode is that chemical composition is LiNixCoyMzO2Positive electrode and/or LiFePO4Positive pole material Material, wherein, 0≤x≤1,0≤y≤1,0≤z<1, and x+y+z=1, M are selected from any in Mn, Al, Mg, Zr, Zn, Cu or Cr It is a kind of or at least two combination；
Preferably, in nanoscale, the thickness is preferably 0.5nm~200nm to the thickness of the conducting film；
Preferably, the chemical composition of the conducting film is tin indium oxide ITO；
Preferably, the tin indium oxide is the indium oxide for mixing tin, and the tin indium oxide is by In2O3And SnO2Composition；
Preferably, the In2O3And SnO2Mass ratio be (3~10):1, preferably 9:1.
3. the preparation method of composite positive pole as claimed in claim 1 or 2, it is characterised in that methods described is：Using spray Mist pyrolysismethod prepares composite positive pole in the Surface coating conducting film of positive electrode；
Preferably, the conducting film is indium tin oxide conductive film.
4. method according to claim 3, it is characterised in that the described method comprises the following steps：
(1) conducting film precursor solution is prepared；
(2) positive electrode is added in the conducting film precursor solution that step (1) is obtained, obtains slurry, add thickener to adjust The viscosity of whole slurry, obtains dispersion liquid；
(3) dispersion liquid obtained using step (2) carries out spray-wall interaction, in the Surface coating conducting film of positive electrode, obtains Composite positive pole.
5. method according to claim 4, it is characterised in that step (1) the conducting film precursor solution is indium oxide Tin precursor solution；
Preferably, the process for preparation of the tin indium oxide precursor solution is：Indium sill and tin-based material are dissolved in solvent, Stirring, obtains tin indium oxide precursor solution；
Preferably, the indium sill be indium nitrate, inidum chloride, indium sulfate, indium acetate or oxalic acid indium in any one or extremely Few two kinds combination；
Preferably, the tin-based material be nitric acid tin, stannic chloride, STANNOUS SULPHATE CRYSTALLINE, tin acetate or stannous oxalate in any one or At least two combination；
Preferably, the mol ratio of the indium sill and tin-based material is (1~20):1；
Preferably, the solvent is any one in methyl alcohol, ethanol, phenmethylol or ethylene glycol or at least two combination；
Preferably, the speed of the stirring is 50r/min~500r/min；
Preferably, the time of the stirring is 30min~300min；
Preferably, the chemical composition of step (2) described positive electrode is LiNixCoyMzO2, wherein, 0≤x≤1,0≤y≤1,0≤ z<1, and x+y+z=1, M are selected from any one in Mn, Al, Mg, Zr, Zn, Cu or Cr or at least two combination；
Preferably, with stirring during step (2) adds positive electrode；
Preferably, step (2) continues to stir 10min~120min, preferably 30min after adding positive electrode；
Preferably, the solid content of step (2) described slurry is 20wt%~60wt%；
Preferably, step (2) described thickener is solid alcohol thickener FR400；
Preferably, step (2) the conducting film precursor solution and the mass ratio of the thickener are 1:(0.0001~0.1)；
Preferably, when step (3) carries out spray-wall interaction, dispersion liquid is persistently stirred；
Preferably, when step (3) carries out spray-wall interaction, the carrier gas of spraying is compressed air；
Preferably, when step (3) carries out spray-wall interaction, carrier gas pressure is 3kg/m2~10kg/m2；
Preferably, when step (3) carries out spray-wall interaction, dispersion flow quantity is 5ml/min~500ml/min；
Preferably, when step (3) carries out spray-wall interaction, the temperature of spraying is 100 DEG C~300 DEG C；
Preferably, when step (3) carries out spray-wall interaction, pyrolysis temperature is 300 DEG C~800 DEG C；
Preferably, when step (3) carries out spray-wall interaction, pyrolysis time is 2h~20h.
6. method according to claim 1 and 2, it is characterised in that methods described is：Chemical gas is passed through using cladding raw material Phase sedimentation prepares composite positive pole in the Surface coating conducting film of positive electrode；
Preferably, the conducting film is indium tin oxide conductive film；
Preferably, when the conducting film is indium tin oxide conductive film, the cladding raw material is indium metal organic compound and tin Metallo-organic compound；
Preferably, the indium metal organic compound is Indium Tris acetylacetonate, trimethyl indium, triethylindium, triphenyl indium or diethyl In guanidine-acetic acid indium any one or at least two combination；
Preferably, the chemical composition of the tin metal organic compound is RxSnY, wherein, R is any in alkyl or aromatic radical One or two combination, Y is halogen, and x is 0~4 integer；
Preferably, the tin metal organic compound is tin trimethyl, tetramethyl tin, tin triethyl, triphenyltin or four chlorinations In tin any one or at least two combination.
7. method according to claim 6, it is characterised in that wrapped on the surface of positive electrode using chemical vapour deposition technique The method for covering indium tin oxide conductive film is comprised the following steps：
Positive electrode is placed in rotary furnace, is heated, be passed through reacting gas, gaseous indium metal is organised respectively using carrier gas Compound and gaseous tin metal organic compound are introduced into rotary furnace, carry out chemical vapor deposition, are wrapped on the surface of positive electrode Indium tin oxide conductive film is covered, composite positive pole is obtained.
8. method according to claim 7, it is characterised in that the chemical composition of the positive electrode is LiNixCoyMzO2, Wherein, 0≤x≤1,0≤y≤1,0≤z<1, and x+y+z=1, M are selected from any one in Mn, Al, Mg, Zr, Zn, Cu or Cr Or at least two combination；
Preferably, the heating rate during heating is 0.5 DEG C/min~15 DEG C/min；
Preferably, the reacting gas is oxygen；
Preferably, the speed that is passed through of the reacting gas is 1m3/ h~5m3/h；
Preferably, the carrier gas is any one in nitrogen, helium, neon, argon gas, Krypton or xenon or at least two group Close；
Preferably, when gaseous indium metal organic compound being introduced into rotary furnace using carrier gas, carrier gas and gaseous indium metal have The flow velocity of the gaseous mixture of machine compound is 0.1L/min~100L/min, preferably 5L/min~50L/min；
Preferably, when gaseous tin metal organic compound being introduced into rotary furnace using carrier gas, carrier gas and gaseous tin metal have The flow velocity of the gaseous mixture of machine compound is 0.1L/min~100L/min, preferably 2L/min~20L/min；
Preferably, the rotating speed of the rotary furnace is 0.1r/min~10r/min；
Preferably, during the chemical vapor deposition, the shared volumetric concentration in rotary furnace of the reacting gas exists More than 60%；
Preferably, the temperature of the chemical vapor deposition is 300 DEG C~1000 DEG C；
Preferably, the time of the chemical vapor deposition is 5min~600min.
9. a kind of positive pole, it is characterised in that comprising the anode composite described in claim 1 or 2 in the raw material components of the positive pole Material.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes the positive pole material described in claim 1 or 2 Material.
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