CN104009204A - Lithium ion battery positive pole piece made of lithium-rich manganese-base material and preparing method of lithium ion battery positive pole piece - Google Patents

Lithium ion battery positive pole piece made of lithium-rich manganese-base material and preparing method of lithium ion battery positive pole piece Download PDF

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Publication number
CN104009204A
CN104009204A CN201410283161.6A CN201410283161A CN104009204A CN 104009204 A CN104009204 A CN 104009204A CN 201410283161 A CN201410283161 A CN 201410283161A CN 104009204 A CN104009204 A CN 104009204A
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lithium
pole piece
rich manganese
ion battery
lithium ion
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CN201410283161.6A
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Chinese (zh)
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戴长松
马全新
刘元龙
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哈尔滨工业大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a lithium ion battery positive pole piece made of a lithium-rich manganese-base material and a preparing method of the lithium ion battery positive pole piece and relates to a method for preparing the lithium ion battery positive pole piece with the positive pole made of the lithium-rich manganese-base material. The lithium ion battery positive pole piece and the preparing method solve the technical problems that according to an existing positive pole piece made of the lithium-rich manganese-base material, charging and discharging efficiency are low, rate capability is poor, cycle performance is poor and coulombic efficiency is low in the cycling process. The positive pole piece is formed by an aluminum foil, a positive pole active substance layer and a nanometer metal particle layer, wherein the surface of the aluminum foil is coated with the positive pole active substance layer, and the surface of the positive pole active substance layer is coated with the nanometer metal particle layer. The preparing method includes the steps that positive pole active substance is made into grout and is applied to the aluminum foil, a composite piece is obtained after roasting and pressing, metal nanometer particles are applied or plated to the composite piece, and the lithium ion battery positive pole piece made of the lithium-rich manganese-base material is obtained after pressing and drying. Primary charging and discharging efficiency is improved by 5%-11% after plating, the rate capability is improved by 13%-30%, and the lithium ion battery positive pole piece can be used for lithium batteries.

Description

A kind of lithium-rich manganese-based material lithium ion battery anode pole piece and preparation method thereof

Technical field

The preparation method of the anode slice of lithium ion battery that to the present invention relates to take lithium-rich manganese-based material be positive electrode.

Background technology

The lithium-rich manganese-based material xLi of anode material for lithium-ion batteries 2mnO 3(1-x) LiMO 2(M=Cr, Mn, Fe, Ni, Co etc.) not only specific capacity is high, price is low, fail safe is good, and more friendly to environment, and the reality of this material can utilize capacity to surpass 250mAh/g, is nearly 2 times of current commercial lithium-ion batteries positive electrode capacity.By numerous researchers, be considered as the choosing of the ideal of anode material for lithium-ion batteries of future generation.The Chinese patent that is 200910186311.0 as application number discloses a kind of lithium-rich manganese-based anode material Li[Li (1-2x)/3m ymn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof, take the Li-Ion rechargeable battery that this material is that positive electrode is made, and when it discharges and recharges between 2.5~4.6V, specific discharge capacity is 250mAh/g.

But existing lithium-rich manganese-based material still exist discharge and recharge that coulombic efficiency is low, high rate performance is poor, cycle performance is poor and cyclic process in the weak points such as coulombic efficiency is low, hindered its business application.

Summary of the invention

The present invention seeks to for solve that the efficiency for charge-discharge that anode pole piece that existing lithium-rich manganese-based material makes exists is low, high rate performance is poor, cycle performance is poor and cyclic process in the low technical problem of coulombic efficiency, and provide a kind of lithium-rich manganese-based material lithium ion battery anode pole piece and preparation method thereof.

Lithium-rich manganese-based material lithium ion battery anode pole piece of the present invention is comprised of aluminium foil, positive electrode active material layer and nano metal particles sublayer, and wherein positive electrode active material layer is coated in aluminium foil surface, and nano metal particles sublayer overlays on positive electrode active material layer surface; Positive electrode active material layer is comprised of lithium-rich manganese-based material, conductive agent and binding agent.

The preparation method of above-mentioned lithium-rich manganese-based material lithium ion battery anode pole piece, carries out according to the following steps:

One, positive active material is joined in solvent, be uniformly mixed, obtain slurry; Wherein positive active material is lithium-rich manganese-based material, conductive agent and binding agent;

Two, slurry is coated on aluminium foil, through baking, roll-in, obtains composite sheet;

Three, by bearing in composite sheet, positive active material one side surface is coated with or plating one deck nano metal particles, after roll-in, vacuumize, obtains lithium-rich manganese-based material lithium ion battery anode pole piece.

Lithium-rich manganese-based anode material xLi 2mnO 3(1-x) LiMO 2mechanism of electrochemical behaviors of anhydrous and traditional anode material for lithium-ion batteries LiCoO 2, LiNiO 2or LiMnO 2deng different, lithium-rich manganese-based anode material there will be 2 visibly different steps in initial charge process: when lower than 4.5V, and Li +by transition metal interlayer, deviate from simultaneously transition metal M generation redox reaction, this part and traditional stratified material LiCoO 2, LiNiO 2and LiMnO 2deng reaction mechanism consistent; When charging voltage is during higher than 4.5V, be accompanied by Li +deviate from, component Li 2mnO 3in oxygen element generation oxidation reaction, discharge oxygen.In discharge process subsequently, oxygen generation electrochemical reducting reaction, generates lithium peroxide, lithia and lithium carbonate.Lithium peroxide can participate in redox reaction in circulation, and reversible capacity is provided.The present invention is by being coated with (plating) nano metal particles on lithium-rich manganese-based material anode pole piece surface, nano metal particles adds the electronic conductivity that not only can improve lithium-rich manganese-based anode material, reduce the polarization in charge and discharge process, and redox reaction in the charge and discharge process of the materials such as the lithium peroxide on lithium-rich manganese-based anode material surface, lithia and lithium carbonate is played to catalyst.Thereby improved efficiency for charge-discharge, high rate performance, cryogenic property, the cycle performance of material, also solved voltage attenuation problem in cyclic process.

The present invention adopts lithium-rich manganese-based material 0.5Li 2mnO 30.5LiNi 0.4co 0.2mn 0.4o 2electrode as active substance of lithium ion battery anode, with adopt same material but not the electrode of coated metal compare, when the positive plate of coating does not at room temperature charge 4.75V, under 0.1C (1.0C=250mA/g) multiplying power, discharge capacity reaches 272mAh/g first, while equally at room temperature charging 4.75V after being coated with plating nano-metal, under 0.1C multiplying power, discharge capacity reaches 302~320mAh/g first, and coating positive plate first charge-discharge efficiency is not only 79%, and first charge-discharge efficiency reaches 83~90% after painting plating nano-metal, after coating, first charge-discharge efficiency has improved 5%~11%, be coated with the first charge-discharge coulombic efficiency that plating nano-metal significantly improves material.

The nano material that painting is plated in lithium-rich manganese-based anode pole piece surface is high electronic conductive material, improves the surface conductance performance of positive electrode, lowers polarization of electrode, thereby improves battery first charge-discharge efficiency and high rate performance.While at room temperature charging 4.75V after painting plating nano-metal, under 0.5C multiplying power, discharge capacity reaches 220~248mAh/g, and when coating positive plate does not equally at room temperature charge 4.75V, under 0.5C multiplying power, discharge capacity only has 195mAh/g, after coating, high rate performance improves 13%~30%, significantly improves.

Painting is plated in the nano material on lithium-rich manganese-based anode pole piece surface to the lithia of lithium-rich manganese-based anode material, lithium peroxide, in the charge and discharge process of the materials such as lithium carbonate, redox reaction plays catalyst, thereby improve cycle performance of battery and efficiency for charge-discharge, reduce voltage attenuation in cyclic process.When battery at room temperature charges 4.75V, be coated with the positive plate after plating nano-metal, under 0.1C multiplying power, the 50 weeks capability retentions that circulate reach more than 98%, and 50 weeks capability retentions of coating positive plate only 85% not; After coating, capability retention improves more than 15.3%, and painting plating nano-metal can increase the efficiency for charge-discharge in cyclic process.

Accompanying drawing explanation

Fig. 1 is the first charge-discharge curve chart of lithium ion battery in test 1, and wherein a is the first charge-discharge curve of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; B is the first charge-discharge curve of contrast anode pole piece battery;

Fig. 2 is the high rate performance figure of lithium ion battery in test 1, and wherein ■ is the high rate performance of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; high rate performance for contrast anode pole piece battery;

Fig. 3 is the cycle performance figure of lithium ion battery in test 1; Wherein a is the cycle performance of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; B is the cycle performance of contrast anode pole piece battery.

Fig. 4 is coulombic efficiency figure in the cyclic process of lithium ion battery in test 1; Wherein a is coulombic efficiency in the cyclic process of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; B is coulombic efficiency in the cyclic process of contrast anode pole piece battery.

Embodiment

Embodiment one: the lithium-rich manganese-based material lithium ion battery anode pole piece of present embodiment is comprised of aluminium foil, positive electrode active material layer and nano metal particles sublayer, wherein positive electrode active material layer is coated in aluminium foil surface, and nano metal particles sublayer overlays on positive electrode active material layer surface; Positive electrode active material layer is comprised of lithium-rich manganese-based material, conductive agent and binding agent.

Embodiment two: present embodiment is different from embodiment one is that metal in described nano metal particles sublayer is one or more the combination in ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), gold (Au); Other is identical with embodiment one.

Embodiment three: present embodiment is different from embodiment one or two is that the particle diameter of described metal nanoparticle is 1nm~500nm; Other is identical with embodiment one or two.

Embodiment four: present embodiment is different from one of embodiment one to three is that the particle diameter of described metal nanoparticle is 100nm~200nm; Other is identical with one of embodiment one to three.

Embodiment five: what present embodiment was different from one of embodiment one to four is that described lithium-rich manganese-based material is that general formula is xLi 2mnO 3(1-x) LiMO 2material, or at the coated Al of this material surface 2o 3, RuO 2, ZnO, MgO, CeO 2, ZrO 2, LiNiPO 4, CoPO 4, AlPO 4, a kind of in conducting high polymers thing, carbon, Graphene or wherein several after the material that obtains; xLi 2mnO 3(1-x) LiMO 2middle 0<x<1, M is the one or more combination in Mn, Ni, Co, Cr, Fe, Ti, V, Zn, Mg, Al; Other is identical with one of embodiment one to four.

Embodiment six: present embodiment is different from one of embodiment one to five is that described conductive agent is a kind of in conductive black, acetylene black, electrically conductive graphite, Graphene, carbon nano-tube, carbon fiber, carbosphere or wherein several combination; Other is identical with one of embodiment one to five.

Embodiment seven: present embodiment is different from one of embodiment one to six is that binding agent is a kind of of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), polyolefin, (Kynoar-hexafluoropropylene) copolymer (PVDF-HFP), butadiene-styrene rubber, Viton, Polyurethane, sodium alginate or wherein several combination; Other is identical with one of embodiment one to six.

Embodiment eight: what present embodiment was different from embodiment seven is that polyolefin is polypropylene (PP), polyethylene (PE), poly 1-butene, poly-1-amylene, poly-1-hexene, poly-1-octene or poly(4-methyl-1-pentene); Other is identical with embodiment seven.

Embodiment nine: present embodiment is different from one of embodiment one to eight be in positive electrode active material layer by weight percentage, lithium-rich manganese-based material is 60%~97%, conductive agent is 1%~20%, binding agent is 2%~20%; Other is identical with one of embodiment one to eight.

Embodiment ten: present embodiment is different from one of embodiment one to nine is that the weight of nano metal particles sublayer is 0.0001%~20% of positive electrode active material layer weight; Other is identical with one of embodiment one to nine.

Embodiment 11: the preparation method of the lithium-rich manganese-based material lithium ion battery anode pole piece described in embodiment one, carries out according to the following steps:

One, positive active material is joined in solvent, be uniformly mixed, obtain slurry; Wherein positive active material is lithium-rich manganese-based material, conductive agent and binding agent;

Two, slurry is coated on aluminium foil, through baking, roll-in, obtains composite sheet;

Three, by bearing in composite sheet, positive active material one side surface is coated with or plating one deck nano metal particles, after roll-in, vacuumize, obtains lithium-rich manganese-based material lithium ion battery anode pole piece.

Embodiment 12: what present embodiment was different from embodiment 11 is that the lithium-rich manganese-based material described in step 1 is that general formula is xLi 2mnO 3(1-x) LiMO 2material, or at the coated Al of this material surface 2o 3, RuO 2, ZnO, MgO, CeO 2, ZrO 2, LiNiPO 4, CoPO 4, AlPO 4, a kind of in conducting high polymers thing, carbon, Graphene or wherein several after the material that obtains; xLi 2mnO 3(1-x) LiMO 2middle 0<x<1, M is any one or a few combination in Mn, Ni, Co, Cr, Fe, Ti, V, Zn, Mg, Al; Other is identical with embodiment 11.

Embodiment 13: present embodiment is different from embodiment 11 or 12 is that the conductive agent described in step 1 is a kind of in conductive black, acetylene black, electrically conductive graphite, Graphene, carbon nano-tube, carbon fiber, carbosphere or wherein several combination; Other is identical with embodiment 11 or 12.

Embodiment 14: present embodiment is different from one of embodiment 11 to 13 is that the binding agent described in step 1 is a kind of of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), polyolefin, (Kynoar-hexafluoropropylene) copolymer (PVDF-HFP), butadiene-styrene rubber, Viton, Polyurethane, sodium alginate or wherein several combination; Other is identical with one of embodiment 11 to 13.

Embodiment 15: what present embodiment was different from embodiment 14 is that polyolefin is polypropylene (PP), polyethylene (PE), poly 1-butene, poly-1-amylene, poly-1-hexene, poly-1-octene or poly(4-methyl-1-pentene); Other is identical with embodiment 14.

Embodiment 16: what present embodiment was different from one of embodiment 11 to 15 is in the positive active material described in step 1, by weight percentage, by the conductive agent of 60%~97% lithium-rich manganese-based material, 1%~-20% and 2%~20% binding agent, formed; Other is identical with one of embodiment 11 to 15.

Embodiment 17: what present embodiment was different from one of embodiment 11 to 16 is that the solvent described in step 1 is 1-METHYLPYRROLIDONE (NMP) or deionized water; Other is identical with one of embodiment 11 to 16.

Embodiment 18: what present embodiment was different from one of embodiment 11 to 17 is that the temperature of toasting in step 2 is 120~150 ℃, and baking time is 12~24 hours; Other is identical with one of embodiment 11 to 17.

Embodiment 19: what present embodiment was different from one of embodiment 11 to 18 is that the roll-in described in step 2 refers to employing roll squeezer, between dancer rools press two rollers, gap is 0.5mm~5mm, and roll-in pressure is that 0.1MPa~10MPa carries out roll-in; Other is identical with one of embodiment 11 to 18.

In present embodiment, the object of roll-in is to make positive active material and collector aluminium flake in conjunction with tight.

Embodiment 20: present embodiment is different from one of embodiment 11 to 19 is that in step 3, the metal in nano metal particles is one or more the combination in ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), gold (Au); Other is identical with one of embodiment 11 to 19.

Embodiment 21: present embodiment is different from one of embodiment 11 to 20 is that the particle diameter of nano metal particles in step 3 is 1nm~500nm; Other is identical with one of embodiment 11 to 20.

Embodiment 22: what present embodiment was different from one of embodiment 11 to 21 is in step 3, and the weight of nano metal particles sublayer is 0.0001%~20% of positive electrode active material layer weight; Other is identical with one of embodiment 11 to 21.

Embodiment 23: what present embodiment was different from one of embodiment 11 to 22 is in step 3, the preparation method of overlay coating is plating, chemical plating, hot-dip, ion plating, thermal spraying, evaporation plating, sputter plating, application, electrophoresis or electrostatic spraying; Other is identical with one of embodiment 11 to 22.

With following evidence beneficial effect of the present invention:

Test 1: the preparation method of the lithium-rich manganese-based material lithium ion battery anode pole piece of this test, carries out according to the following steps:

One, take positive active material and join in 1-METHYLPYRROLIDONE (NMP), after being uniformly mixed with 1000r/min speed stirring 30min at a high speed with de-airing mixer, obtain slurry; Wherein positive active material is by weight percentage by 80% lithium-rich manganese-based material 0.5Li 2mnO 30.5LiNi 0.4co 0.2mn 0.4o 2, 10% conductive black and 10% PVDF form;

Two, slurry is coated on aluminium foil, is placed on temperature and is in the baking oven of 120 ℃ and toast 12 hours, then use the roll-in under 8.0MPa pressure of test-type roll squeezer, obtain composite sheet; The object of roll-in is to make positive active material and collector aluminium flake in conjunction with tight;

Three, adopt the method for sputter plating, utilize magnetic control sputtering device to take 99.99% gold medal (Au) and in composite sheet, scribble positive active material one side plating layer of gold (Au) nano particle as target, use again the roll-in under 8.0MPa pressure of test-type roll squeezer, being placed on vacuum degree is that 0.01MPa, temperature are dry 10h in 120 ℃ of vacuum drying chambers again, obtains lithium-rich manganese-based material lithium ion battery anode pole piece.

The lithium-rich manganese-based material 0.5Li described in step 1 wherein 2mnO 30.5LiNi 0.4co 0.2mn 0.4o 2preparation method be: n (Mn): n (Ni): n (Co)=7:2:1 is by MnCl in molar ratio 2, NiSO 4, CoCl 2be added to the water dissolving, obtain mixed solution, then mixed solution, NaOH solution and complexing agent ammoniacal liquor are joined in 5L continuous overflow reactor with certain liquid feeding speed simultaneously, under the protective condition of nitrogen atmosphere, pH value in reaction is 10, temperature is under the condition of 55 ℃, speed with 600r/min stirs, and is precipitated thing; Wherein the liquid feeding speed of mixed solution is 100ml/h, and the liquid feeding speed of alkali lye is 150ml/h, and the liquid feeding speed of ammoniacal liquor is 20ml/h; This sediment suction filtration is washed for three times, in 120 ℃ of vacuum drying chambers, be dried 24 hours, obtain Mn 0.7ni 0.2co 0.1(OH) 2ternary hydroxide precursor; By Mn 0.7ni 0.2co 0.1(OH) 2li/ (Ni+Co+Mn) mol ratio of take with battery-level lithium carbonate is mixed as 1.55:1, take and analyze pure absolute ethyl alcohol as decentralized medium, in ball mill, ball milling is 5 hours, be placed on drying box inner drying, obtain the mixture of presoma and lithium carbonate, then this mixture is placed in resistance furnace, in air atmosphere, resistance furnace rises to the maintenance roasting 16 hours of 850 ℃ with the heating rate of 5 ℃/min, with stove, naturally cool to room temperature, obtains lithium-rich manganese-based material 0.5Li 2mnO 30.5LiNi 0.4co 0.2mn 0.4o 2.

On the lithium-rich manganese-based material lithium ion battery anode pole piece that this test obtains, the particle diameter of golden nanometer particle is about 20nm; The weight of nano metal particles sublayer is 1.0% of positive electrode active material layer weight;

The preparation method of contrast anode pole piece is as a comparison as follows: one, take positive active material and join in 1-METHYLPYRROLIDONE (NMP), after being uniformly mixed at a high speed, obtain slurry with de-airing mixer with 1000r/min speed stirring 30min; Wherein positive active material is by weight percentage by 80% lithium-rich manganese-based material 0.5Li 2mnO 30.5LiNi 0.4co 0.2mn 0.4o 2, 10% conductive black and 10% PVDF form; Two, slurry is coated on aluminium foil, is placed on vacuum degree and is 0.01MPa, temperature and be in 120 ℃ of vacuum drying chambers vacuumize 10 hours, then use the roll-in under 8.0MP pressure of test-type roll squeezer, obtain contrasting anode pole piece.

Lithium-rich manganese-based material lithium ion battery anode pole piece prepared by this test 1 of take respectively and contrast anode pole piece, as anodal, be take metal lithium sheet as negative pole, with 1 mo1L -1liPF 6with EC/DMC (volume ratio 1:1) is electrolyte, prepare lithium ion button cell, carry out battery performance test, the result obtaining is as follows.

Fig. 1 is the first charge-discharge curve chart of lithium ion battery in test 1, and wherein a is the first charge-discharge curve of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; B is the first charge-discharge curve of contrast anode pole piece battery; As can be seen from Figure 1, when contrast anode pole piece battery at room temperature charges 4.75V, under 0.1C (1.0C=250mA/g) multiplying power, discharge capacity reaches 272mAh/g first, and the lithium-rich manganese-based material lithium ion battery anode pole piece battery of test 1 preparation under 0.1C multiplying power first discharge capacity reach 306mAh/g, discharge capacity has improved 12.5% first.

Fig. 2 is the high rate performance figure of lithium ion battery in test 1, and wherein ■ is the high rate performance of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; high rate performance for contrast anode pole piece battery; As can be seen from Figure 2, lithium-rich manganese-based material lithium ion battery anode pole piece battery discharge capacity under 0.5C multiplying power of the preparation of test 1 still reaches 230mAh/g, and contrast anode pole piece battery discharge capacity under 0.5C multiplying power needs only 195mAh/g, more known, be coated in surperficial golden nanometer particle high rate performance is significantly improved.

Fig. 3 is the cycle performance figure of lithium ion battery in test 1; Wherein a is the cycle performance of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; B is the cycle performance of contrast anode pole piece battery.50 weeks capability retentions of lithium-rich manganese-based material lithium ion battery anode pole piece circulating battery of testing as can be seen from Figure 31 preparation under 0.1C multiplying power reach more than 99%, and 50 weeks capability retentions of contrast anode pole piece battery only 85%.

Fig. 4 is coulombic efficiency figure in the cyclic process of lithium ion battery in test 1; Wherein a is coulombic efficiency in the cyclic process of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of the preparation of test 1; B is coulombic efficiency in the cyclic process of contrast anode pole piece battery.As can be seen from Figure 4, under 0.1C multiplying power, after 5 circulations of the lithium-rich manganese-based material lithium ion battery anode pole piece battery of test 1 preparation, in cyclic processes, efficiency for charge-discharge reaches more than 98%, and after 5 circulations of contrast anode pole piece battery in cyclic processes efficiency for charge-discharge be only 95% left and right.Therefrom known, coating nano Au particle can significantly improve in the cyclic process of material and discharge and recharge coulombic efficiency.

Test 2: this test from test 1 different be that positive active material in step 1 is by weight percentage by 90% lithium-rich manganese-based material 0.5Li 2mnO 30.5LiNi 0.4co 0.2mn 0.4o 2, 5% conductive black and 5% PVDF form.Other step is identical with test 1 with parameter.

On the lithium-rich manganese-based material lithium ion battery anode pole piece that this test obtains, the particle diameter of golden nanometer particle is about 20nm; The weight of nano metal particles sublayer is 1.0% of positive electrode active material layer weight; The performance of battery prepared by the lithium-rich manganese-based material lithium ion battery anode pole piece obtaining with this test: while at room temperature charging 4.75V, under 0.1C (1.0C=250mA/g) multiplying power, discharge capacity reaches 296mAh/g first, and first charge-discharge efficiency reaches 83.6%; Under 0.5C multiplying power, discharge capacity still reaches 221mAh/g; Under 0.1C multiplying power, 50 weeks capability retentions of circulating battery reach more than 99%, and after 5 circulations, in cyclic process, efficiency for charge-discharge reaches more than 98%.

Test 3: this test with test 1 different be in step 2, slurry to be coated on aluminium foil, be placed on vacuum degree and be 0.01MPa, temperature and be in the vacuum drying chamber of 80 ℃ and be dried 12 hours.Other step is identical with test 1 with parameter.

On the lithium-rich manganese-based material lithium ion battery anode pole piece that this test obtains, the particle diameter of golden nanometer particle is about 20nm; The weight of nano metal particles sublayer is 1.0% of positive electrode active material layer weight; The performance of battery prepared by the lithium-rich manganese-based material lithium ion battery anode pole piece obtaining with this test is as follows: while at room temperature charging 4.75V, under 0.1C multiplying power, discharge capacity reaches 302mAh/g first, and first charge-discharge efficiency reaches 86%; Under 0.5C multiplying power, discharge capacity still reaches 229mAh/g; Under 0.1C multiplying power, 50 weeks capability retentions of circulating battery reach more than 99%, and after 5 circulations, in cyclic process, efficiency for charge-discharge reaches more than 98%.

Positive active material one side plating layer of gold (Au) nano particle is born in test 4: what this test was different from test 1 is the method that adopts sputter plating in step 3 in composite sheet, and the weight of nano metal particles sublayer is 5.0% of positive electrode active material layer weight.Other step is identical with test 1 with parameter.

On the lithium-rich manganese-based material lithium ion battery anode pole piece that this test obtains, the particle diameter of nano particle is 30~40nm, the performance of the battery of preparing with this positive plate is as follows: while at room temperature charging 4.75V, under 0.1C multiplying power, discharge capacity reaches 320mAh/g first, and first charge-discharge efficiency reaches 90%; Under 0.5C multiplying power, discharge capacity still reaches 251mAh/g; Under 0.1C multiplying power, 50 circulation volumes of battery are undamped, and after 5 circulations, in cyclic process, efficiency for charge-discharge reaches more than 99%.

Positive active material one side plating one deck platinum (Pt) nano particle is born in test 5: what this test was different from test 1 is the method that adopts sputter plating in step 3 in composite sheet, and the weight of nano metal particles sublayer is 1.0% of positive electrode active material layer weight.Other step is identical with test 1 with parameter.

On the lithium-rich manganese-based material lithium ion battery anode pole piece that this test obtains, the particle diameter of nano particle is 15~30nm, the performance of the battery of preparing with this positive plate is as follows: while at room temperature charging 4.75V, under 0.1C multiplying power, discharge capacity reaches 295mAh/g first, and first charge-discharge efficiency reaches 84%; Under 0.5C multiplying power, discharge capacity still reaches 246mAh/g; Under 0.1C multiplying power, 50 weeks capability retentions of circulating battery reach more than 99%, and after 5 circulations, in cyclic process, efficiency for charge-discharge reaches more than 98%.

Test 6: what this test was different from test 1 is the method that adopts ion plating in step 3, utilize accurate etching spraying plating instrument in composite sheet, to bear positive active material one side plating one deck platinum and gold nano stuff and other stuff, the weight of nano metal particles sublayer is 1.0% of positive electrode active material layer weight.Other step is identical with test 1 with parameter.

On the lithium-rich manganese-based material lithium ion battery anode pole piece that this test obtains, the particle diameter of nano particle is 20~30nm, the performance of the battery of preparing with this positive plate is as follows: while at room temperature charging 4.75V, under 0.1C multiplying power, discharge capacity reaches 312mAh/g first, and first charge-discharge efficiency reaches 89%; Under 0.5C multiplying power, discharge capacity still reaches 248mAh/g; Under 0.1C multiplying power, 50 circulation volumes of battery are undamped, and after 5 circulations, in cyclic process, efficiency for charge-discharge reaches more than 99%.

Positive active material one side plating one deck palladium (Pd) nano particle is born in test 7: what this test was different from test 1 is the method that adopts sputter plating in step 3 in composite sheet, and the weight of nano metal particles sublayer is 1.0% of positive electrode active material layer weight.Other step is identical with test 1 with parameter.

On the lithium-rich manganese-based material lithium ion battery anode pole piece that this test obtains, the particle diameter of nano particle is 20~30nm, the performance of the battery of preparing with this positive plate: while at room temperature charging 4.75V, under 0.1C multiplying power, discharge capacity reaches 290mAh/g first, and first charge-discharge efficiency reaches 83.5%; Under 0.5C multiplying power, discharge capacity still reaches 225mAh/g; Under 0.1C multiplying power, 50 weeks capability retentions of circulating battery reach more than 99%, and after 5 circulations, in cyclic process, efficiency for charge-discharge reaches more than 98%.

Claims (10)

1. a lithium-rich manganese-based material lithium ion battery anode pole piece, it is characterized in that this anode pole piece is comprised of aluminium foil, positive electrode active material layer and metal nanoparticle layer, wherein positive electrode active material layer is coated in aluminium foil surface, and metal nanoparticle layer overlays on positive electrode active material layer surface; Positive electrode active material layer is comprised of lithium-rich manganese-based material, conductive agent and binding agent.
2. a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 1, is characterized in that metal in described metal nanoparticle layer is one or more the combination in ruthenium, rhodium, palladium, platinum, gold.
3. a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 1 and 2, is characterized in that the particle diameter of described metal nanoparticle is 1nm~500nm.
4. a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 1 and 2, is characterized in that described lithium-rich manganese-based material is that general formula is xLi 2mnO 3(1-x) LiMO 2material, or at xLi 2mnO 3(1-x) LiMO 2the coated Al in surface 2o 3, RuO 2, ZnO, MgO, CeO 2, ZrO 2, LiNiPO 4, CoPO 4, AlPO 4, a kind of in conducting high polymers thing, carbon, Graphene or wherein several after the material that obtains; xLi 2mnO 3(1-x) LiMO 2middle 0<x<1, M is the one or more combination in Mn, Ni, Co, Cr, Fe, Ti, V, Zn, Mg, Al.
5. a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 1 and 2, is characterized in that described conductive agent is a kind of in conductive black, acetylene black, electrically conductive graphite, Graphene, carbon nano-tube, carbon fiber, carbosphere or wherein several combination.
6. a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 1 and 2, is characterized in that binding agent is a kind of of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethylcellulose, polyolefin, (Kynoar-hexafluoropropylene) copolymer, butadiene-styrene rubber, Viton, Polyurethane, sodium alginate or wherein several combination.
7. a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 1 and 2, it is characterized in that in positive electrode active material layer by weight percentage, lithium-rich manganese-based material is 60%~97%, conductive agent is 1%~20%, and binding agent is 2%~20%.
8. a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 1 and 2, the weight that it is characterized in that metal nanoparticle layer is 0.0001%~20% of positive electrode active material layer weight.
9. the method for preparation a kind of lithium-rich manganese-based material lithium ion battery anode pole piece claimed in claim 1, is characterized in that the method carries out according to the following steps:
One, positive active material is joined in solvent, be uniformly mixed, obtain slurry; Wherein positive active material is lithium-rich manganese-based material, conductive agent and binding agent;
Two, slurry is coated on aluminium foil, through baking, roll-in, obtains composite sheet;
Three, by being covered with in composite sheet, positive active material one side surface is coated with or plating layer of metal nano particle, after roll-in, vacuumize, obtains lithium-rich manganese-based material lithium ion battery anode pole piece.
10. the preparation method of a kind of lithium-rich manganese-based material lithium ion battery anode pole piece according to claim 9, is characterized in that the solvent described in step 1 is 1-METHYLPYRROLIDONE or deionized water.
CN201410283161.6A 2014-06-23 2014-06-23 Lithium ion battery positive pole piece made of lithium-rich manganese-base material and preparing method of lithium ion battery positive pole piece CN104009204A (en)

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CN105789553A (en) * 2014-12-25 2016-07-20 北京有色金属研究总院 Positive electrode of lithium ion battery
CN107644997A (en) * 2016-07-20 2018-01-30 三星环新(西安)动力电池有限公司 A kind of positive electrode surface coating modification method based on sodium carboxymethylcellulose
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CN109686920A (en) * 2018-12-28 2019-04-26 国联汽车动力电池研究院有限责任公司 A kind of high-energy density anode pole piece and its preparation method and application
CN111063864A (en) * 2019-12-12 2020-04-24 桂林理工大学 Coating treatment method for stabilizing high-nickel type positive plate of lithium ion battery
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CN103219492A (en) * 2013-04-09 2013-07-24 中南大学 Manganese positive pole of modified lithium ion battery, and preparation method of manganese positive pole

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CN105789553A (en) * 2014-12-25 2016-07-20 北京有色金属研究总院 Positive electrode of lithium ion battery
CN105355819A (en) * 2015-10-13 2016-02-24 深圳宏泰电池科技有限公司 Lithium-rich manganese-based high-energy-density lithium-ion battery and preparation method thereof
CN107644997A (en) * 2016-07-20 2018-01-30 三星环新(西安)动力电池有限公司 A kind of positive electrode surface coating modification method based on sodium carboxymethylcellulose
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CN109686920A (en) * 2018-12-28 2019-04-26 国联汽车动力电池研究院有限责任公司 A kind of high-energy density anode pole piece and its preparation method and application
CN111063864A (en) * 2019-12-12 2020-04-24 桂林理工大学 Coating treatment method for stabilizing high-nickel type positive plate of lithium ion battery

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